TW201823436A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element Download PDF

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TW201823436A
TW201823436A TW106131107A TW106131107A TW201823436A TW 201823436 A TW201823436 A TW 201823436A TW 106131107 A TW106131107 A TW 106131107A TW 106131107 A TW106131107 A TW 106131107A TW 201823436 A TW201823436 A TW 201823436A
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crystal alignment
carbon atoms
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石川和典
金信郁
中原翔一朗
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日商日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

A liquid crystal aligning agent which contains the component (A) and the component (B) described below. In the formulae, the symbols are as defined in the description. Component (A): at least one polymer selected from the group consisting of polyimide precursors, which are obtained by reacting a diamine component containing a diamine represented by formula (1) and a tetracarboxylic acid derivative component with each other, and polyimides obtained by closing the rings of the polyimide precursors Component (B): a compound which has two or more partial structures represented by formula (2), while having a molecular weight of 2,500 or less.

Description

液晶配向劑、液晶配向膜及液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

[0001] 本發明為有關新穎的液晶配向劑、液晶配向膜及液晶顯示元件。[0001] The present invention relates to novel liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements.

[0002] 液晶顯示元件，以其為可實現薄型・輕量的顯示裝置，目前已被廣泛地使用。通常，該液晶顯示元件中，就決定液晶的配向狀態之觀點，多使用液晶配向膜予以調整。 　　[0003] 液晶配向膜所使用的聚合物，已知有聚醯亞胺、聚醯胺、聚醯胺醯亞胺等，一般為使用將該些聚合物或其前驅體溶解於溶劑而得的液晶配向劑。 　　[0004] 近年來，大畫面且高精細度之液晶電視，已廣泛地被實用化，而具有該些用途的液晶顯示元件，則被要求可承受長期被使用於嚴苛的使用環境之特性。因此，使用於該環境的液晶配向膜，必須為較以往具有更高的信賴性的物質。因此，針對該些課題，已有提出使用特定添加劑的液晶配向劑之提案(專利文獻1)。 [先前技術文獻] [專利文獻] 　　[0005] 　　[專利文獻1]國際公開第2010／074269號[0002] Liquid crystal display devices have been widely used because they are thin and lightweight display devices. Generally, in this liquid crystal display element, a liquid crystal alignment film is often used for adjustment from the viewpoint of determining the alignment state of the liquid crystal. [0003] Polymers used for liquid crystal alignment films are known as polyimide, polyimide, polyimide, and the like. Generally, these polymers or their precursors are obtained by dissolving them in a solvent. Liquid crystal alignment agent. [0004] In recent years, large-screen and high-definition liquid crystal televisions have been widely used, and liquid crystal display elements having these applications are required to withstand the characteristics of being used in harsh environments for a long time. Therefore, the liquid crystal alignment film used in this environment must be a substance having higher reliability than conventional ones. Therefore, in response to these problems, a proposal for a liquid crystal alignment agent using a specific additive has been proposed (Patent Document 1). [Prior Art Document] [Patent Document] [0005] [Patent Document 1] International Publication No. 2010/074269

[發明所欲解決之問題] 　　[0006] 最近，伴隨液晶顯示元件所使用的背光源(BL)亮度更為提升之狀況，對於液晶配向膜的配向安定性，或對於電氣特性等，亦被要求遠遠超過以往程度的優良耐光性或緩和之特性。 [解決問題之方法] 　　[0007] 本發明者們，經過深入研究結果，發現使用由含有特定構造的二胺之二胺成份與四羧酸衍生物成份進行反應而得的聚醯亞胺前驅體，及使該聚醯亞胺前驅體閉環而得的聚醯亞胺所成之群所選出之聚合物及含有特定構造的化合物之液晶配向劑時，即可達成上述之目標，因而完成本發明。 　　[0008] 可達成上述目的的本發明之第1態樣為，一種含有下述(A)成份及(B)成份之液晶配向劑。 　　(A)成份：由含有下述式(1)之二胺的二胺成份與四羧酸衍生物成份進行反應而得的聚醯亞胺前驅體，及使該聚醯亞胺前驅體進行閉環反應而得的聚醯亞胺所成之群所選出之至少1種的聚合物 　　[0009](式(1)中，R1 表示氫，或1價之有機基；Q1 表示碳數1至5之伸烷基；Cy為表示由氮環丁烷、吡咯啶、哌啶或伸六甲基亞胺所形成之脂肪族雜環的2價之基，該些之環部份可鍵結取代基；R2 及R3 各自獨立為1價之有機基；q及r各自獨立為0～4之整數；但，q與r之合計為2以上時，複數的R2 及R3 ，具有上述之定義)。 　　(B)成份：具有2個以上下述式(2)之構造，且分子量為2,500以下的化合物 　　[0010](式(2)中，R1 為氫原子或碳數1～3之烷基，R2 及R3 各自獨立表示氫原子、碳數1～3之烷基，或＊3 -CH2 -O-R11 (R11 表示氫原子或碳數1～3之烷基，「＊3 」表示與R2 及R3 鍵結的碳原子之鍵結鍵)，「＊1 」及「＊2 」表示與其他原子之鍵結鍵)。 　　[0011] 可達成上述目的之本發明之第2態樣為，如第1態樣之液晶配向劑，其中，前述式(1)之二胺為下述式(3)所表示者； 　　[0012](式(3)中，R1 為氫原子、甲基，或tert-丁氧基羰基；R2 及R3 各自獨立為氫原子或甲基；Q1 為碳數1～5之直鏈伸烷基)。 　　[0013] 可達成上述目的之本發明之第3態樣為，如第1態樣或第2態樣之液晶配向劑，其中，前述式(1)所表示之二胺的含有比例，相對於全二胺成份1莫耳，為1莫耳%～80莫耳%。 　　[0014] 可達成上述目的之本發明之第4態樣為，如第1態樣至第3態樣中任一項之液晶配向劑，其中，前述(B)成份之化合物，為由下述式所選出之至少1種的化合物； 　　[0015][0016] 可達成上述目的之本發明之第5態樣為，如第1態樣至第4態樣之液晶配向劑，其中，(C)成份尚含有含下述式(5)之構造單位的聚醯亞胺前驅體。 　　[0017](式(5)中，X2 為由四羧酸衍生物生成之4價有機基，Y2 為由二胺生成之2價有機基，R4 為氫原子或碳數1～5之烷基，Z1 及Z2 各自獨立為氫原子、可具有取代基的碳數1～10之烷基、碳數2～10之烯基或碳數2～10之炔基)。 　　[0018] 可達成上述目的之本發明之第6態樣為，如第5態樣之液晶配向劑，其中，前述式(5)中之X2 為含有含下述構造的構造單位之聚醯亞胺前驅體。 　　[0019] 可達成上述目的之本發明之第7態樣為，由第1態樣至第6態樣中任一項之液晶配向劑所製得之液晶配向膜。 　　[0020] 可達成上述目的之本發明之第8態樣為，具備第7態樣的液晶配向膜之液晶顯示元件。 [發明之效果] 　　[0021] 本發明之液晶配向劑，可得到具有優良BL耐性、配向安定性、緩和特性之液晶配向膜。 [發明之實施形態] 　　[0022] 本發明之液晶配向劑為含有(A)成份及(B)成份。以下將詳細說明各構成要件。 　　[0023] ＜(A)成份＞ 　　本發明之液晶配向劑所含有之(A)成份為，由含有下述式(1)之二胺(以下，亦稱為特定二胺)的二胺成份與四羧酸衍生物成份進行反應而得的聚醯亞胺前驅體，及使該聚醯亞胺前驅體進行閉環反應而得的聚醯亞胺所成之群所選出之至少1種的聚合物。 　　[0024][0025] 上述式(1)中，R1 表示氫或1價有機基，較佳為氫原子，或碳數1～3之直鏈烷基，更佳為氫原子，或甲基。 　　[0026] 又，R1 可為經由熱而產生解離反應，而取代為氫原子之保護基。就液晶配向劑之保存安定性之觀點，該保護基以於室溫下不會產生解離，較佳為於80℃以上、更佳為100℃以上、特佳為150～200℃間解離，形成氫原子者為佳。例如，1,1-二甲基-2-氯乙氧基羰基、1,1-二甲基-2-氰基乙氧基羰基、tert-丁氧基羰基等，較佳為tert-丁氧基羰基。 　　[0027] Q1 表示碳數1～5之伸烷基，就合成之簡便性而言，較佳為碳數1～5之直鏈伸烷基。Cy表示由氮環丁烷、吡咯啶、哌啶，或伸六甲基亞胺所形成之脂肪族雜環的2價之基，就合成之簡便性而言，以氮環丁烷、吡咯啶，或哌啶為佳。又，該些之環部份可鍵結取代基。 　　[0028] R2 及R3 各自獨立為1價之有機基，q、r各自獨立為0～4之整數；但，q與r之合計為2以上時，複數的R2 及R3 ，具有上述之定義。就合成之簡便性而言，較佳為R2 及R3 皆為甲基。 　　[0029] 又，構成上述二胺的苯環中，胺基的鍵結位置並未有特別限定，胺基可分別鍵結於相對於Cy上的氮原子為3位，或4位，相對於Q1 與R1 鍵結的氮原子為3位，或4位之位置為佳，以相對於Cy上的氮原子為4位，相對於Q1 與R1 鍵結的氮原子為4位之位置為較佳。 　　[0030] 可達成本發明效果之主要原因之一的構造，推測為由上述式(1)之二胺去除2個1級胺基而得之構造(以下，亦稱為特定構造)。因此，即使不使用上述式(1)之二胺，亦可於本發明之液晶配向劑所使用的聚合物中，導入含有2個以上特定構造之二胺化合物，或具有特定構造之四羧酸二酐等的特定構造，但就合成之處理上，仍以使用上述式(1)之二胺為佳。 　　[0031] 本發明之上述式(1)所表示之二胺，以下述式(3)所表示之化合物為佳。 　　[0032][0033] 上述式(3)中，R1 為氫原子、甲基，或tert-丁氧基羰基。R2 及R3 各自獨立為氫原子或甲基。Q1 為碳數1～5之直鏈伸烷基。 　　[0034] 上述式(3)所表示之二胺的具體例，例如，下述式(3-1)～下述式(3-10)所表示之二胺等。下述式中，Boc表示tert-丁氧基羰基。 　　[0035][0036] ＜(B)成份＞ 　　本發明之液晶配向劑所含有之(B)成份為，具有2個以上下述式(2)之構造，且分子量為2,500以下的化合物。 　　[0037][0038] 上述式(2)中，R1 表示氫原子或碳數1～3之烷基。 　　[0039] R2 及R3 各自獨立表示氫原子、碳數1～3之烷基，或＊3 -CH2 -O-R11 (R11 表示氫原子或碳數1～3之烷基，「＊3 」表示與R2 及R3 鍵結的碳原子之鍵結鍵)，「＊1 」及「＊2 」表示與其他原子之鍵結鍵。 　　[0040] R1 及R11 之碳數1～3之烷基，例如甲基、乙基、n-丙基、異丙基等。較佳為氫原子或甲基，更佳為氫原子。又，R1 及R11 可互相為相同或相異皆可。 　　[0041] R2 及R3 之碳數1～3之烷基，可列舉如，上述R1 所例示之基。較佳為氫原子、＊3 -CH2 -OH，或＊3 -CH2 -OCH3 。又，R2 及R3 可互相為相同或相異皆可。 　　[0042] 上述式(2)中，鍵結於氮原子之基(以下，亦稱為「R4 」)，例如，氫原子、1價之有機基，或上述式(2)中的羰基與該氮原子鍵結的2價之有機基等。又，R4 為上述2價之有機基時，上述式(2)中之氮原子及羰基共同形成環構造。 　　[0043] 本發明之(B)成份的化合物中，上述式(2)所表示之構造的數目，只要為2個以上即可，較佳為2個～8個，更佳為2個～6個。化合物(B)所具有的基「＊4 -CH2 -O-R1 (「＊4 」表示與碳原子之鍵結鍵。R1 與上述具有相同之意義)」之數，以每1分子具有2個以上為佳，以3個～8個為較佳，以3個～6個為更佳。 　　[0044] 上述式(2)之構造的較佳具體例，例如下述式(2-1)～下述式(2-6)分別表示之化合物等。 　　[0045][0046] 上述式(2-1)～上述式(2-5)中，「＊1」表示鍵結鍵。式(2-5)中，R5 為碳數1～3之烷基。上述式(2-6)中之「＊1 」及「＊5 」，表示鍵結於上述式(2-6)中之氮原子及羰基共同形成環之基的鍵結鍵。 　　[0047] 化合物(B)之分子量為2,500以下。就對溶劑之溶解性及使液晶配向劑具有良好塗佈性之觀點，該分子量以2,000以下為佳，以1,200以下為更佳。 　　[0048] 化合物(B)之具體例，例如下述式所表示之化合物等。 　　[0049][0050] 化合物(B)之添加比例，相對於液晶配向劑中所含有的聚合物成份之合計100重量份，以0.1重量份～100重量份為佳。化合物(B)的較佳添加比例之下限為，相對於液晶配向劑中所含有的聚合物成份之合計100重量份，為1重量份以上，更佳為3重量份以上。又，該添加比例之上限，較佳為50重量份以下，更佳為20重量份以下。又，化合物(B)，可單獨使用1種或將2種以上組合使用。 　　[0051] ＜聚醯亞胺前驅體及聚醯亞胺＞ 　　本發明之液晶配向劑所含有的聚醯亞胺前驅體為，由含有上述式(1)所表示之二胺的二胺成份與四羧酸衍生物成份進行反應而得之聚醯亞胺前驅體。其中，聚醯亞胺前驅體為聚醯胺酸或聚醯胺酸酯。 　　[0052] 四羧酸衍生物，可列舉如，酸二酐，或二羧酸二酯、二酯二羧酸氯化物等。 　　[0053] 聚醯胺酸，為由二胺成份與酸二酐進行反應而得者，聚醯胺酸酯，為由二胺成份與二羧酸二酯或二酯二羧酸氯化物進行反應而可製得。 　　[0054] 本發明之液晶配向劑所含有的聚醯亞胺為，使該些聚醯亞胺前驅體進行閉環反應而得之聚醯亞胺，其適合作為可製得液晶配向膜之聚合物。 　　[0055] 本發明之液晶配向劑所含有的聚醯亞胺前驅體，為含有下述式(4)所表示之構造單位的聚合物。 　　[0056][0057] 上述式(4)中，X1 為由四羧酸衍生物生成之4價有機基，Y1 為由式(1)之二胺所生成的2價之有機基，R4 為氫原子或碳數1～5之烷基。就經由加熱容易形成醯亞胺化之觀點，R4 以氫原子、甲基或乙基為佳。 　　[0058] 可製得上述聚醯亞胺前驅體之二胺成份中，上述式(1)所表示之二胺的含有比例並沒有限制，以較多者可容易達成本發明之效果。上述式(1)所表示之二胺的比例，相對於全二胺成份1莫耳，以1莫耳%～80莫耳%為佳，更佳為5莫耳%～60莫耳%，更較佳為10莫耳%～40莫耳%。 　　[0059] 只要X1 為4價之有機基時，則未有特別限定之內容。聚醯亞胺前驅體中，X1 可為2種類以上混合存在。 　　[0060] 列舉X1 之具體例時，可列舉如，下述式(X1-1)～下述式(X1-44)之構造。就容易取得之觀點，以下述式(X1-1)～下述式(X1-14)為較佳。 　　[0061][0062][0063][0064][0065][0066][0067] 上述式(X1-1)～上述式(X1-4)中，R5 至R25 ，各自獨立為氫原子、鹵素原子、碳數1～6之烷基、碳數2～6之烯基、碳數2～6之炔基、含有氟原子之碳數1～6的1價之有機基，或苯基，其可相同或相異皆可。就液晶配向性之觀點，R5 至R25 ，以氫原子、鹵素原子、甲基，或乙基為佳，以氫原子，或甲基為較佳。上述式(X1-1)之具體構造，可列舉如，下述式(X1-1-1)～下述式(X1-1-6)所表示之構造。就液晶配向性及光反應的感度之觀點，又以下述式(X1-1-1)為特佳。 　　[0068][0069] 又，本發明之聚醯亞胺前驅體，除上述式(4)以外，於無損本發明效果之範圍中，可含有下述式(5)所表示之構造單位。又，本發明之液晶配向劑，於含有含上述式(4)所表示之構造單位的聚醯亞胺前驅體以外的聚醯亞胺前驅體時，其可為具有下述式(5)所表示之構造單位的聚醯亞胺前驅體。 　　[0070][0071] 上述式(5)中，R4 與上述式(4)之定義相同。X2 為4價之有機基，包含其較佳之例示，其與上述式(4)中之X1 定義為相同。但，本發明之液晶配向劑，除含有上述式(4)所表示之構造單位的聚醯亞胺前驅體以外，尚含有上述式(5)之構造單位的聚醯亞胺前驅體時，就可發現所得液晶配向膜的效果之觀點，以上述式(X1-8)為更佳。Z1 及Z2 各自獨立為氫原子、可具有取代基的碳數1～10之烷基、碳數2～10之烯基或碳數2～10之炔基。 　　[0072] 碳數1～10之烷基的具體例，可列舉如，甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基、雙環己基等。 　　[0073] 碳數2～10之烯基，為存在於上述烷基的1個以上之CH2 -CH2 被CH=CH所取代者。更具體而言，可列舉如，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。 　　[0074] 碳數2～10之炔基為，存在於上述烷基的1個以上之CH2 -CH2 被C≡C所取代者。更具體而言，可列舉如，乙炔基、1-丙炔基、2-丙炔基等。 　　[0075] 上述碳數1～10之烷基、碳數2～10之烯基，及碳數2～10之炔基，可於包含取代基的合計碳數不超過10的範圍內再具有取代基，又，亦可經由取代基而形成環構造。又，經由取代基而形成環構造，係指取代基相互間或取代基與母骨架的一部份經鍵結而形成環構造之意。 　　[0076] 取代基之例，可列舉如，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。 　　[0077] 聚醯亞胺前驅體中，一般若導入巨大構造時，會有降低胺基之反應性或液晶配向性之可能，故Z1 及Z2 以氫原子，或可具有取代基之碳數1～5之烷基為較佳，以氫原子、甲基或乙基為特佳。 　　[0078] 上述式(5)中，Y2 為由上述式(1)以外之二胺成份所生成的二價之有機基，其構造並未有特別之限定。列舉Y2 之具體例時，例如，下述式(Y-1)～下述式(Y-49)及下述式(Y-57)～下述式(Y-114)等。又，二胺成份可以2種以上混合方式存在。 　　[0079][0080][0081][0082][0083][0084][0085][0086][0087][0088][0089][0090][0091][0092][0093][0094][0095][0096][0097][0098] 上述式(Y-158)、上述式(Y-162)～上述式(Y-165)中，n為1～6之整數。 　　[0099][0100] 上述式(Y-174)、上述式(Y-175)、上述式(Y-178)及上述式(Y-179)中之Boc，為表示tert-丁氧基羰基。 　　[0101] ＜聚醯胺酸之製造方法＞ 　　本發明之液晶配向劑所使用的聚醯亞胺前驅體之聚醯胺酸，可由含有本發明之二胺的二胺成份與四羧酸衍生物成份進行反應而製得。 　　[0102] 具體而言為，使四羧酸二酐與二胺，於有機溶劑之存在下進行反應而可合成。 　　[0103] 有機溶劑，只要可溶解所生成的聚醯胺酸時，並未有特別之限定。其具體例，例如，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、γ-丁內酯等。又，聚醯亞胺前驅體之溶解性較高時，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述式(D-1)～下述式(D-3)所示有機溶劑。 　　[0104][0105] 上述式(D-1)中，D1 表示碳數1～3之烷基，上述式(D-2)中，D2 表示碳數1～3之烷基，上述式(D-3)中，D3 表示碳數1～4之烷基。 　　[0106] 該些可單獨使用亦可、混合使用亦可。此外，若為單獨使用無法溶解聚醯胺酸之溶劑時，只要不會使所生成的聚醯胺酸析出之範圍，可與上述溶劑混合使用。又，有機溶劑中之水份會阻礙聚合反應，且為造成所生成的聚醯胺酸產生水解之原因，故有機溶劑以盡可能使用脫水乾燥者為佳。 　　[0107] 於有機溶劑中使二胺成份與四羧酸二酐混合之方法，例如：將二胺分散或溶解於有機溶劑而得之溶液於攪拌中，將四羧酸二酐直接添加，或分散或溶解於有機溶劑後再予添加之方法、於分散或溶解有四羧酸二酐的有機溶劑而得之溶液中，添加二胺之方法、將四羧酸二酐與二胺交互或同時添加於有機溶劑之方法等，而可使用該些中之任一種方法。 　　[0108] 合成聚醯胺酸時之溫度，可選擇於-20℃～150℃中之任意溫度，較佳為-5℃～100℃之範圍，更佳為0℃～80℃。 　　[0109] 又，反應時間只要較可使聚醯胺酸安定地聚合的時間為更長的範圍內，可以任意選擇，較佳為30分鐘～24小時，更佳為1小時～12小時。 　　[0110] 反應可於任意濃度下進行，作為原料之二胺成份與四羧酸二酐的濃度過低時，將無法製得高分子量的聚合物，濃度過高時，將因反應液的黏性過高而不易均勻攪拌，故較佳為1質量%～50質量%、更佳為5質量%～20質量%。亦可於反應初期以高濃度進行，隨後追加有機溶劑亦可。 　　[0111] 聚醯胺酸的合成反應中，相對於二胺成份的莫耳數，四羧酸二酐的莫耳數之比以0.8～1.2為佳。與通常的聚縮合反應相同般，該莫耳比越接近1.0時，所生成的聚醯胺酸之分子量越大。 　　[0112] 依上述方式所製得之聚醯胺酸，經由將反應溶液於充份攪拌中注入貧溶劑後，即可將聚合物析出而回收。又，經進行數次析出、使用貧溶劑洗淨後，經由於常溫或加熱下乾燥結果即可製得純化的聚醯胺酸之粉末。 　　[0113] 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。 　　[0114] ＜聚醯胺酸酯之製造＞ 　　本發明之聚醯亞胺前驅體的聚醯胺酸酯，可依以下所示[1]、[2]或[3]之製法而製得。 　　[0115] [1]由聚醯胺酸製造之情形 　　聚醯胺酸酯，可將依前述方式所製得之聚醯胺酸，經酯化方式而可製得。 　　[0116] 具體而言，為將聚醯胺酸與酯化劑，於有機溶劑之存在下，於-20℃～150℃、較佳為0℃～50℃間，進行30分鐘～24小時、較佳為1小時～4小時反應而可製得。 　　[0117] 酯化劑，以可經由純化而容易去除者為佳，例如，N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三-2-基)-4-甲基嗎啉鎓氯化物等。酯化劑之添加量，相對於聚醯胺酸之重複單位1莫耳，以2莫耳當量～6莫耳當量為佳。 　　[0118] 有機溶劑，例如，N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸或1,3-二甲基-咪唑啉酮等。又，聚醯亞胺前驅體對溶劑具有高溶解性時，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮，或前述式(D-1)～前述式(D-3)所示之溶劑。 　　[0119] 溶劑，可單獨使用亦可、混合使用亦可。若為不會溶解聚醯亞胺前驅體之溶劑時，只要不會使所生成的聚醯亞胺前驅體析出之範圍，亦可與前述溶劑混合使用。又，溶劑中之水份，會阻礙聚合反應，且為造成所生成的聚醯亞胺前驅體水解之原因，故溶劑以使用脫水乾燥者為佳。 　　[0120] 上述反應所使用的溶劑，就聚合物之溶解性而言，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮，或γ-丁內酯為佳，該些可使用1種或將2種以上混合使用。製造時之濃度，就不易引起聚合物之析出，且容易得到高分子量體之觀點，以1質量%～30質量%為佳，以5質量%～20質量%為較佳。 　　[0121] [2]由四羧酸二酯二氯化物與二胺進行反應而製造之情形 　　聚醯胺酸酯，可由四羧酸二酯二氯化物與含有本發明之二胺的二胺成份而製得。 　　[0122] 具體而言為，使四羧酸二酯二氯化物與二胺，於鹼與有機溶劑之存在下，於-20℃～150℃、較佳為0℃～50℃間，進行30分鐘～24小時、較佳為1小時～4小時之反應而可製得。 　　[0123] 鹼，可使用吡啶、三乙胺、4-二甲胺基吡啶等，就可使反應穩定進行之觀點，以使用吡啶為佳。鹼之添加量，就可容易去除之量，且可容易製得高分子量體之觀點，相對於四羧酸二酯二氯化物，以使用2莫耳倍～4莫耳倍為佳，以2莫耳倍～3莫耳倍為較佳。 　　[0124] 上述反應所使用的溶劑，就單體及聚合物的溶解性之觀點，以N-甲基-2-吡咯啶酮，或γ-丁內酯為佳，該些可使用1種或將2種以上混合使用。 　　[0125] 製造時的聚合物濃度，就不易引起聚合物之析出，且容易製得高分子量體之觀點，以1質量%～30質量%為佳，以5質量%～20質量%為較佳。 　　[0126] 又，為防止四羧酸二酯二氯化物之水解，於製造聚醯胺酸酯時所使用的溶劑，以盡可能使用脫水者為佳，又以於氮雰圍中，防止外氣混入者為佳。 　　[0127] [3]由四羧酸二酯與二胺製造之情形 　　聚醯胺酸酯，可由四羧酸二酯與含有本發明之二胺的二胺成份，經聚縮合反應而可製得。 　　[0128] 具體而言，為將四羧酸二酯與二胺，於縮合劑、鹼，及有機溶劑之存在下，於0℃～150℃、較佳為0℃～100℃間，進行30分鐘～24小時、較佳為3小時～15小時之反應而可製得。 　　[0129] 縮合劑，可使用三苯基亞磷酸酯、二環己基碳二醯亞胺、1-乙基-3-(3-二甲胺基丙基)碳二醯亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三基甲基嗎啉鎓、O-(苯併三唑-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯併三唑-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫氧基-3-苯併噁唑基)膦酸(phosphonic acid)二苯酯等。縮合劑之添加量，相對於四羧酸二酯，以2莫耳倍～3莫耳倍為佳，以2莫耳倍～2.5莫耳倍為較佳。 　　[0130] 鹼，可使用吡啶、三乙胺等三級胺。鹼之添加量，就可容易去除之量，且容易製得高分子量體之觀點，相對於二胺成份，以2莫耳倍～4莫耳倍為佳，以2.5莫耳倍～3.5莫耳倍為較佳。 　　[0131] 又，上述反應中，加入路易士酸作為添加劑時，可使反應有效率地進行。路易士酸，例如以氯化鋰、溴化鋰等的鹵化鋰為佳。路易士酸之添加量，相對於二胺成份，以0莫耳倍～1.0莫耳倍為佳，以0莫耳倍～0.7莫耳倍為較佳。 　　[0132] 上述3個聚醯胺酸酯之製造方法中，就可製得高分子量的聚醯胺酸酯之觀點，以上述[1]或上述[2]之製法為特佳。 　　[0133] 依上述方式所得之聚醯胺酸酯之溶液，於充份攪拌中注入貧溶劑時，即可析出聚合物。進行數次之析出，使用貧溶劑洗淨後，於常溫或加熱狀態下乾燥，即可製得純化的聚醯胺酸酯之粉末。貧溶劑，並未有特別之限定，其可為水、甲醇、乙醇、己烷、丁基溶纖劑(cellosolve)、丙酮、甲苯等。 　　[0134] ＜聚醯亞胺之製造方法＞ 　　本發明所使用的聚醯亞胺，可將前述聚醯亞胺前驅體經由醯亞胺化而可製得。 　　[0135] 本發明之聚醯亞胺中，醯胺酸基，或醯胺酸酯基之閉環率(醯亞胺化率)，並非必須為100%，其可配合用途或目的做任意之調整。 　　[0136] 使聚醯亞胺前驅體閉環之方法，可列舉如，不使用觸媒而加熱聚醯亞胺前驅體的熱醯亞胺化，或使用觸媒的觸媒醯亞胺化等方法。 　　[0137] 使聚醯亞胺前驅體熱醯亞胺化時，聚醯亞胺前驅體之溶液，以加熱至100℃～400℃、較佳為120℃～250℃，經由醯亞胺化反應而將所生成之水或醇排除於反應系外之方法為佳。 　　[0138] 聚醯亞胺前驅體的觸媒醯亞胺化，為於聚醯胺酸之溶液中，添加鹼性觸媒與酸酐，於-20℃～250℃、較佳為0℃～180℃間進行攪拌的方式進行。鹼性觸媒之量為醯胺酸基之0.5莫耳倍～30莫耳倍、較佳為2莫耳倍～20莫耳倍，酸酐之量為醯胺酸基之1莫耳倍～50莫耳倍、較佳為3莫耳倍～30莫耳倍。 　　[0139] 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，又以吡啶於反應進行中，可維持適度的鹼性而為較佳。 　　[0140] 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，可容易進行反應結束後的純化，而為較佳。觸媒醯亞胺化之醯亞胺化率，可以調節觸媒量與反應溫度、反應時間等予以控制。 　　[0141] 由聚醯亞胺之反應溶液中，回收聚合物成份時，只要將反應溶液投入貧溶劑，使其沉澱即可。沉澱所使用的貧溶劑，可為甲醇、丙酮、己烷、丁基溶纖劑(cellosolve)、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、水等。投入貧溶劑產生沉澱的聚合物，經過濾、回收後，可於常壓或減壓下，於常溫或加熱下，進行乾燥者為佳。 　　[0142] ＜液晶配向劑＞ 　　液晶配向劑，為製作液晶配向膜時之塗佈液，其主成份為，含有形成樹脂被膜之樹脂成份，溶解該樹脂成份之有機溶劑的組成物。本發明之液晶配向劑，其樹脂成份為，使用上述聚醯亞胺前驅體，及使該聚醯亞胺前驅體進行閉環反應而得的聚醯亞胺所成之群所選出之至少1種的聚合物。 　　[0143] 液晶配向劑中之聚合物濃度，可配合所設定之所欲形成的塗膜厚度，作適當之變更。就可均勻地形成無缺陷的塗膜之觀點，以1質量%以上為佳，就溶液保存安定性之觀點，以10質量%以下為佳。特佳之聚合物濃度，為2質量%～8質量%。 　　[0144] 液晶配向劑中的樹脂成份，可全部為本發明之聚合物亦可，又，亦可與本發明之聚合物以外的其他聚合物混合亦可。該其他聚合物中，二胺成份，可列舉如，使用上述式(1)所表示之以外之二胺而製得的聚醯亞胺前驅體或聚醯亞胺等。 　　[0145] 液晶配向劑所含有的有機溶劑，只要可均勻地溶解聚合物成份時，並未有特別之限定。列舉其具體例時，例如，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。又，即使單獨使用無法均勻地溶解聚合物成份之溶劑時，只要不會析出聚合物之範圍時，亦可與上述之有機溶劑混合。 　　[0146] 液晶配向劑，除可溶解聚合物成份之有機溶劑以外，亦可含有於基板上塗佈液晶配向劑之際，可提高塗膜均勻性之溶劑。該溶劑，一般而言，可使用表面張力較上述有機溶劑為更低表面張力的溶劑。其具體例，可列舉如，乙基溶纖劑(cellosolve)、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、丙二醇-1-單乙醚-2-乙酸酯、丁基溶纖劑乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇二甲醚、二丙酮醇、二乙二醇二乙醚、2,6-二甲基-4-庚醇、二異丁酮、4-甲氧基-4-甲基-2-戊酮、4-羥基-2-丁酮及2-甲基-2-己醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等。該些溶劑，可將2種以上合併使用。 　　[0147] 上述溶劑，可作為樹脂溶解性較低之貧溶劑。該些溶劑，以液晶配向處理劑所含有的有機溶劑的5質量%～60質量%為佳，更佳為10質量%～50質量%。 　　[0148] 液晶配向劑中，上述以外，於無損本發明之效果的範圍內，可添加本發明之聚合物以外的聚合物、改變液晶配向膜之介電係數或導電性等電氣特性為目的之介電體或導電物質、提高液晶配向膜與基板的密著性為目的之矽烷耦合劑、作為液晶配向膜之際可提高膜的硬度或緻密度為目的之交聯性化合物，及燒結塗膜之際，可使聚醯亞胺前驅體有效率地進行醯亞胺化為目的之醯亞胺化促進劑等。 　　[0149] 為含官能性矽烷之化合物或含環氧基之化合物等含交聯性化合物時，其添加量，無論任一者，相對於樹脂成份100質量份，皆以0.1質量%～30質量份為佳，更佳為1質量%～20質量份，特佳為1質量%～10質量份。 　　[0150] ＜液晶配向膜之製造方法＞ 　　液晶配向膜，為將上述液晶配向劑塗佈於基板，經乾燥、燒結而製得之膜。 　　[0151] 塗佈液晶配向劑之基板，只要為具有高透明性之基板時，則並未有特別之限定，而可使用玻璃基板、氮化矽基板、丙烯酸基板、聚碳酸酯基板等的塑膠基板等。特別是，使用形成有可驅動液晶的ITO電極等的基板時，就製程簡單化之觀點為較佳。 　　[0152] 又，反射型的液晶顯示元件中，若僅為單側基板時，亦可使用矽晶圓等的不透明物質，該情形時之電極，亦可使用鋁等可反射光線之材料。 　　[0153] 塗佈液晶配向劑之方法，可列舉如，旋轉塗佈法、印刷法、噴墨法等。其他，使用塗佈液之方法，例如，攪拌塗佈(Dip coating)、輥式塗佈、縫狀塗佈、旋轉塗佈等，而可配合目的予以使用。 　　[0154] 塗佈液晶配向劑後之乾燥、燒結步驟，可選擇任意的溫度與時間。通常，就可充份去除所含有的有機溶劑時，一般以於50℃～120℃、較佳為50℃～80℃間，進行1分鐘～10分鐘、較佳為3分鐘～5分鐘之乾燥，隨後，於150℃～300℃、較佳為200℃～240℃間，進行5分鐘～120分鐘、較佳為10分鐘～40分鐘之燒結處理。 　　[0155] 燒結後之塗膜的厚度，並未有特別之限定，過薄時會有降低液晶顯示元件的信賴性之情形，一般為5nm～300nm，較佳為10nm～200nm。 　　[0156] 使所得液晶配向膜進行配向處理之方法，可列舉如，摩擦法、光配向處理法等。摩擦處理中，可使用嫘縈布、尼龍布、棉布等。垂直配向用的液晶配向膜，使用摩擦處理時將不易達成均勻的配向狀態，故作為垂直配向用液晶配向劑使用時，亦可於不進行摩擦處理下使用。 　　[0157] 光配向處理法的具體例，例如，使用向特定方向偏向的輻射線照射前述塗膜表面，依情況之差異，可再於150℃～250℃的溫度下進行加熱處理，以賦予液晶配向能力之方法等。輻射線，可使用具有波長100nm～800 nm的紫外線及可見光線。其中，又以具有波長100nm～400nm的紫外線為佳，以具有波長200nm～400nm者為特佳。 　　[0158] 又，就改善液晶配向性之觀點，亦可將塗膜基板加熱至50℃～250℃間，照射輻射線亦可。 　　[0159] 輻射線之照射量，以1mJ／cm2 ～10,000mJ／cm2 為佳，以100mJ／cm2 ～5,000mJ／cm2 為特佳。依上述方式所製得之液晶配向膜，可使液晶分子向特定方向安定地形成配向。 　　[0160] 如上所示，亦可於膜照射偏光輻射線之後，隨後，使用含有由水及有機溶劑所選出之至少1種類的溶劑進行接觸處理。 　　[0161] 接觸處理所使用的溶劑，只要為可溶解經由光照射所生成的分解物之溶劑時，則未有特別限定之內容。具體例如，水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、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、乙酸環己酯等。該些溶劑，可將2種以上合併使用。 　　[0162] 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。以使用1-甲氧基-2-丙醇或乳酸乙酯為特佳。 　　[0163] 本發明中，將經偏光輻射線照射後之膜，接觸含有有機溶劑的溶液的處理，可以使用浸漬處理、噴霧(spray)處理等，以使膜與液體得以進行充份接觸之處理為佳。其中，又以於含有有機溶劑的溶液中，將膜進行較佳為10秒～1小時、更佳為1分鐘～30分鐘的浸漬處理之方法為佳。接觸處理，可於常溫或加溫下進行皆可，較佳為10℃～80℃、更佳為20℃～50℃間實施。又，必要時，可施以超音波等提高接觸之手段。 　　[0164] 上述接觸處理之後，就去除所使用的溶液中之有機溶劑為目的時，可使用水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等低沸點溶劑，進行沖洗(洗滌)或乾燥，或同時進行二種處理皆可。 　　[0165] 又，經使用溶劑進行接觸處理後之膜，就使溶劑乾燥及促進膜中的分子鏈再配向等目的時，亦可將其加熱至150℃以上。 　　[0166] 加熱之溫度，以150℃～300℃為佳。溫度越高時，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，加熱溫度以180℃～250℃為較佳，以200℃～230℃為特佳。 　　[0167] 加熱時間，過短時，將會有無法得到本發明效果之可能性，過長時，會有造成分子鏈分解之可能性，故一般以10秒～30分鐘為佳，以1分鐘～10分鐘為較佳。 　　[0168] ＜液晶顯示元件＞ 　　液晶顯示元件為，於製得由本發明之液晶配向劑所得之附有液晶配向膜之基板後，再依已知方法製作液晶晶胞，並使用該液晶晶胞而製得之液晶顯示元件者。 　　[0169] 製作液晶晶胞之方法的一例示，將使用被動元件矩陣構造的液晶顯示元件為例進行說明。又，亦可為構成影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構造之液晶顯示元件。 　　[0170] 首先，準備透明的玻璃製基板，於其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。該些電極例如可作為ITO電極，並形成所期待的影像顯示之圖型。其次，於各基板上，以被覆共用電極與節段電極之方式設置絕緣膜。絕緣膜，例如可為使用凝膠-溶膠法而形成的由SiO2 -TiO2 所形成之膜。 　　[0171] 隨後，於各基板上，形成本發明之液晶配向膜。其次，使一側之基板與另一側之基板，以配向膜面為互相對向之方式重疊，將周邊使用密封材料接著。密封材料中，為控制基板之間隙等目的，通常混入有間隔器。又，未設置密封材料的面內部份，亦以散佈控制基板間隙用的間隔器為佳。並於密封材料之一部份，設置可由外部填充液晶的開口部。 　　[0172] 其次，經由設於密封材料的開口部，將液晶材料注入由2片基板與密封材料所包圍的空間內。隨後，使用接著劑將該開口部密封。注入方法，可使用真空注入法亦可、利用大氣中之毛細管現象之方法亦可。又，亦可將描繪密封材料後的液晶滴下基板上，於減壓下進行貼合之方式，填充液晶亦可。 　　[0173] 液晶材料，可使用正型液晶材料及負型液晶材料中之任一種。特別是，使用於電壓保持率較正型液晶材料為更低的負型液晶材料時，於使用本發明之液晶配向膜時，可得到優良的殘影特性。 　　[0174] 其次，進行偏光板之設置。具體而言，為將與2片基板的液晶層為相反側之面上，貼附一對的偏光板。經以上之步驟，即可製得本發明之液晶顯示元件。該液晶顯示元件中，因液晶配向膜為使用由本發明之液晶配向膜之製造方法所得的液晶配向膜，故具有優良的殘影特性，而適用於高精細度的多功能手提電話(智慧型手機)，或平板型電腦、液晶電視等。[Problems to be Solved by the Invention] Recently, as the brightness of a backlight (BL) used in a liquid crystal display element has been further improved, alignment stability of the liquid crystal alignment film, or electrical characteristics, etc. are also required. Excellent light resistance or relaxation properties far exceeding the previous level. [Solution to Problem] [0007] As a result of intensive research, the present inventors found that a polyfluorene imide precursor obtained by reacting a diamine component containing a diamine having a specific structure and a tetracarboxylic acid derivative component was used. When the polymer selected from the group consisting of polyfluorene imide obtained by closing the polyfluorene imide precursor and the liquid crystal alignment agent containing a compound with a specific structure can achieve the above-mentioned objectives, the present invention is thus completed . [0008] A first aspect of the present invention that can achieve the above object is a liquid crystal alignment agent containing the following components (A) and (B). (A) component: a polyfluorene imide precursor obtained by reacting a diamine component containing a diamine of the following formula (1) with a tetracarboxylic acid derivative component, and ring closing the polyfluorene imine precursor A polymer of at least one selected from the group consisting of polyimide obtained by the reaction [0009] (In formula (1), R 1 Represents hydrogen, or a monovalent organic group; Q 1 Represents an alkylene group having 1 to 5 carbon atoms; Cy is a divalent radical representing an aliphatic heterocyclic ring formed by azetidin, pyrrolidine, piperidine, or hexamethylimine, and these ring portions Can bond substituents; R 2 And R 3 Each is independently a monovalent organic group; q and r are each independently an integer of 0 to 4; however, when the total of q and r is 2 or more, the plural R is 2 And R 3 , With the above definition). (B) Ingredient: a compound having a structure of the following formula (2) and having a molecular weight of 2,500 or less [0010] (In formula (2), R 1 Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 And R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or * 3 -CH 2 -OR 11 (R 11 Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "* 3 '' Means the same as R 2 And R 3 Bonded carbon atoms (bond bond), "* 1 "and"* 2 "Means bonding to other atoms). [0011] A second aspect of the present invention that can achieve the above object is the liquid crystal alignment agent of the first aspect, wherein the diamine of the aforementioned formula (1) is represented by the following formula (3); ] (In formula (3), R 1 Is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group; R 2 And R 3 Each independently a hydrogen atom or a methyl group; Q 1 It is a linear alkylene group having 1 to 5 carbon atoms). [0013] A third aspect of the present invention that can achieve the above object is the liquid crystal alignment agent as in the first aspect or the second aspect, wherein the content ratio of the diamine represented by the above formula (1) is relative to The total diamine content is 1 mole, ranging from 1 mole% to 80 mole%. [0014] A fourth aspect of the present invention that can achieve the above object is the liquid crystal alignment agent according to any one of the first aspect to the third aspect, wherein the compound of the component (B) is as follows At least one compound selected by the formula; [0015] [0016] A fifth aspect of the present invention that can achieve the above object is the liquid crystal alignment agent as in the first aspect to the fourth aspect, wherein the component (C) further contains a structural unit containing the following formula (5) Polyimide precursor. [0017] (In formula (5), X 2 Is a tetravalent organic group generated from a tetracarboxylic acid derivative, Y 2 Is a divalent organic group formed from a diamine, R 4 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z 1 And Z 2 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent). [0018] A sixth aspect of the present invention that can achieve the above object is the liquid crystal alignment agent according to the fifth aspect, wherein X in the foregoing formula (5) 2 It is a polyimide precursor containing a structural unit having the following structure. [0019] A seventh aspect of the present invention that can achieve the above object is a liquid crystal alignment film prepared from the liquid crystal alignment agent of any one of the first aspect to the sixth aspect. [0020] An eighth aspect of the present invention that can achieve the above-mentioned object is a liquid crystal display element including the liquid crystal alignment film of the seventh aspect. [Effects of the Invention] [0021] The liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment film having excellent BL resistance, alignment stability, and relaxation characteristics. [Embodiment of the invention] [0022] The liquid crystal alignment agent of the present invention contains (A) component and (B) component. Each constituent element will be described in detail below. [0023] <(A) component> The (A) component contained in the liquid crystal alignment agent of the present invention is composed of a diamine component containing a diamine of the following formula (1) (hereinafter, also referred to as a specific diamine) and A polyimide precursor obtained by reacting a tetracarboxylic acid derivative component, and at least one polymer selected from the group consisting of polyimide obtained by subjecting the polyimide precursor to a ring closure reaction . [0024] [0025] In the above formula (1), R 1 Represents hydrogen or a monovalent organic group, preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. [0026] R 1 It may be substituted by a protecting group for a hydrogen atom to generate a dissociation reaction via heat. From the standpoint of storage stability of the liquid crystal alignment agent, the protective group does not dissociate at room temperature, preferably at 80 ° C or higher, more preferably at least 100 ° C, and particularly preferably at 150 to 200 ° C, and forms Hydrogen atoms are preferred. For example, 1,1-dimethyl-2-chloroethoxycarbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, tert-butoxycarbonyl, etc., preferably tert-butoxy Carbonyl. [0027] Q 1 The alkylene group having 1 to 5 carbon atoms is preferably a linear alkylene group having 1 to 5 carbon atoms in terms of simplicity of synthesis. Cy represents a divalent radical of an aliphatic heterocyclic ring formed by azetidine, pyrrolidine, piperidine, or hexamethylimine. In terms of simplicity of synthesis, azacyclobutane, pyrrolidine , Or piperidine is preferred. These ring portions may be bonded to a substituent. R 2 And R 3 Each is independently a monovalent organic group, and q and r are each independently an integer of 0 to 4. However, when the total of q and r is 2 or more, the plural R is 2 And R 3 , With the above definition. In terms of simplicity of synthesis, R is preferred 2 And R 3 All are methyl. [0029] In the benzene ring constituting the diamine, the bonding position of the amine group is not particularly limited, and the amine group may be respectively bonded to the 3-position or 4-position with respect to the nitrogen atom on Cy. Q 1 With R 1 The nitrogen atom to be bonded is preferably at the 3 or 4 position, and the nitrogen atom at Cy is the 4 position, relative to the Q 1 With R 1 The position of the bonded nitrogen atom at the 4-position is preferred. [0030] A structure capable of achieving one of the main reasons for the effects of the present invention is presumed to be a structure obtained by removing two primary amine groups from the diamine of the formula (1) (hereinafter, also referred to as a specific structure). Therefore, even if the diamine of the formula (1) is not used, a diamine compound containing two or more specific structures or a tetracarboxylic acid having a specific structure can be introduced into the polymer used in the liquid crystal alignment agent of the present invention. The specific structure of dianhydride and the like, but in terms of synthesis treatment, it is still preferable to use the diamine of the above formula (1). [0031] The diamine represented by the above formula (1) in the present invention is preferably a compound represented by the following formula (3). [0032] [0033] In the above formula (3), R 1 Is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. R 2 And R 3 Each is independently a hydrogen atom or a methyl group. Q 1 It is a linear alkylene group having 1 to 5 carbon atoms. [0034] Specific examples of the diamine represented by the formula (3) include, for example, the diamine represented by the following formula (3-1) to the following formula (3-10). In the following formula, Boc represents a tert-butoxycarbonyl group. [0035] [0036] <(B) Component> The component (B) contained in the liquid crystal alignment agent of the present invention is a compound having a structure of the following formula (2) and having a molecular weight of 2,500 or less. [0037] [0038] In the above formula (2), R 1 Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 2 And R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or * 3 -CH 2 -OR 11 (R 11 Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "* 3 '' Means the same as R 2 And R 3 Bonded carbon atoms (bond bond), "* 1 "and"* 2 "Means bonding to other atoms. R 1 And R 11 Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl. A hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable. Again, R 1 And R 11 It may be the same or different from each other. R 2 And R 3 Examples of the alkyl group having 1 to 3 carbon atoms include the aforementioned R 1 Illustrated base. Preferably a hydrogen atom, * 3 -CH 2 -OH, or * 3 -CH 2 -OCH 3 . Again, R 2 And R 3 It may be the same or different from each other. [0042] In the formula (2), the group bonded to a nitrogen atom (hereinafter, also referred to as “R 4 "), For example, a hydrogen atom, a monovalent organic group, or a divalent organic group in which the carbonyl group in the formula (2) and the nitrogen atom are bonded. Again, R 4 When it is the above-mentioned divalent organic group, the nitrogen atom and the carbonyl group in the above formula (2) together form a ring structure. [0043] In the compound of the component (B) of the present invention, the number of structures represented by the above formula (2) may be 2 or more, preferably 2 to 8 and more preferably 2 to 6. Each. The group "*" in the compound (B) 4 -CH 2 -OR 1 ("＊ 4 "Means a bond to a carbon atom. R 1 It has the same meaning as the above). It is preferable to have 2 or more molecules per molecule, more preferably 3 to 8 molecules, and even more preferably 3 to 6 molecules. [0044] Preferable specific examples of the structure of the above formula (2) include, for example, compounds represented by the following formula (2-1) to the following formula (2-6). [0045] [0046] In the formulas (2-1) to (2-5), "* 1" represents a bonding bond. In formula (2-5), R 5 It is an alkyl group having 1 to 3 carbon atoms. "* In the above formula (2-6) 1 "and"* 5 "" Represents a bonding bond in which the nitrogen atom and the carbonyl group in the formula (2-6) are combined to form a ring group. [0047] The molecular weight of the compound (B) is 2,500 or less. From the viewpoints of solubility in a solvent and good coatability of a liquid crystal alignment agent, the molecular weight is preferably 2,000 or less, and more preferably 1,200 or less. Specific examples of the compound (B) include, for example, a compound represented by the following formula. [0049] [0050] The addition ratio of the compound (B) is preferably 0.1 to 100 parts by weight relative to 100 parts by weight of the total polymer components contained in the liquid crystal alignment agent. The lower limit of the preferable addition ratio of the compound (B) is 1 part by weight or more, more preferably 3 parts by weight or more, based on 100 parts by weight of the total polymer components contained in the liquid crystal alignment agent. The upper limit of the addition ratio is preferably 50 parts by weight or less, and more preferably 20 parts by weight or less. The compound (B) may be used alone or in combination of two or more. [0051] <Polyimide precursor and polyimide> The polyimide precursor contained in the liquid crystal alignment agent of the present invention is a diamine component containing a diamine represented by the above formula (1) and A polyimide precursor obtained by reacting a tetracarboxylic acid derivative component. The polyimide precursor is a polyamidic acid or a polyamidate. [0052] Examples of the tetracarboxylic acid derivatives include acid dianhydrides, dicarboxylic acid diesters, and diester dicarboxylic acid chlorides. [0053] Polyamidic acid is obtained by reacting a diamine component and an acid dianhydride, and polyamidate is a reaction of a diamine component and a dicarboxylic acid diester or a diester dicarboxylic acid chloride. And can be made. [0054] The polyimide contained in the liquid crystal alignment agent of the present invention is a polyimide obtained by subjecting these polyimide precursors to a ring-closing reaction, which is suitable as a polymer capable of preparing a liquid crystal alignment film. . [0055] The polyimide precursor contained in the liquid crystal alignment agent of the present invention is a polymer containing a structural unit represented by the following formula (4). [0056] [0057] In the above formula (4), X 1 Is a tetravalent organic group generated from a tetracarboxylic acid derivative, Y 1 Is a divalent organic group formed from a diamine of formula (1), R 4 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. From the viewpoint of easy formation of amidine by heating, R 4 A hydrogen atom, a methyl group or an ethyl group is preferred. [0058] Among the diamine components of the polyfluorene imide precursor that can be obtained, the content ratio of the diamine represented by the above formula (1) is not limited, and the effect of the present invention can be easily achieved with more. The proportion of the diamine represented by the above formula (1) is preferably 1 mol% to 80 mol%, more preferably 5 mol% to 60 mol%, more preferably 1 mol to the total diamine component. It is preferably 10 mol% to 40 mol%. [0059] As long as X 1 When it is a tetravalent organic group, there is no particular limitation. In polyimide precursors, X 1 Two or more types may be mixed. Enumeration X 1 Specific examples include a structure of the following formula (X1-1) to the following formula (X1-44). From the viewpoint of easy availability, the following formulae (X1-1) to (X1-14) are preferred. [0061] [0062] [0063] [0064] [0065] [0066] [0067] In the formula (X1-1) to the formula (X1-4), R 5 To R 25 , Each independently is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a monovalent one having 1 to 6 carbon atoms having a fluorine atom. Organic groups, or phenyl groups, may be the same or different. From the viewpoint of liquid crystal alignment, R 5 To R 25 Preferably, a hydrogen atom, a halogen atom, a methyl group, or an ethyl group is preferred, and a hydrogen atom or a methyl group is more preferred. Specific structures of the formula (X1-1) include the structures represented by the following formula (X1-1-1) to the following formula (X1-1-6). From the viewpoint of liquid crystal alignment and sensitivity of photoreaction, the following formula (X1-1-1) is particularly preferred. [0068] [0069] In addition to the above formula (4), the polyfluorene imide precursor of the present invention may contain a structural unit represented by the following formula (5) within a range that does not impair the effect of the present invention. In addition, when the liquid crystal alignment agent of the present invention contains a polyimide precursor other than a polyimide precursor containing a structural unit represented by the above formula (4), the liquid crystal alignment agent may have the following formula (5): Representation of the structural unit of polyimide precursors. [0070] [0071] In the above formula (5), R 4 It has the same definition as in the above formula (4). X 2 It is a tetravalent organic group, including a preferable example thereof, which is the same as X in the above formula (4) 1 Defined as the same. However, in the liquid crystal alignment agent of the present invention, in addition to the polyfluorene imide precursor having the structural unit represented by the above formula (4), when the polyfluorene imide precursor having the structural unit of the above formula (5) is contained, From the viewpoint that the effect of the obtained liquid crystal alignment film can be found, the above formula (X1-8) is more preferable. Z 1 And Z 2 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, decyl, cyclopentyl, and cyclohexyl , Dicyclohexyl, etc. [0073] The alkenyl group having 2 to 10 carbon atoms is one or more CH groups present in the alkyl group. 2 -CH 2 Replaced by CH = CH. More specific examples include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-hexene Group, cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. [0074] The alkynyl group having 2 to 10 carbon atoms is one or more CH groups present in the alkyl group. 2 -CH 2 Replaced by C≡C. More specific examples include ethynyl, 1-propynyl, and 2-propynyl. [0075] The alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms may further have substitution in a range where the total carbon number including the substituents does not exceed 10. The group may also form a ring structure through a substituent. In addition, the formation of a ring structure through a substituent means that the substituents are bonded to each other or a part of the parent skeleton to form a ring structure. Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organosilyl group, a fluorenyl group, an ester group, a thioester group, and a phosphoric acid. Esters, amido, alkyl, alkenyl, alkynyl and the like. [0077] Generally, if a polyimide precursor is introduced into a huge structure, the reactivity of the amine group or the alignment of the liquid crystal may be reduced. Therefore, Z 1 And Z 2 A hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is preferable, and a hydrogen atom, a methyl group, or an ethyl group is particularly preferable. [0078] In the above formula (5), Y 2 The structure is not particularly limited as it is a divalent organic group formed from a diamine component other than the above formula (1). List Y 2 Specific examples include, for example, the following formulae (Y-1) to (Y-49) and the following formulae (Y-57) to (Y-114). Moreover, a diamine component may exist in 2 or more types of mixing. [0079] [0080] [0081] [0082] [0083] [0084] [0085] [0086] [0087] [0088] [0089] [0090] [0091] [0092] [0093] [0094] [0095] [0096] [0097] [0098] In the formula (Y-158), the formula (Y-162) to the formula (Y-165), n is an integer of 1 to 6. [0099] [0100] Boc in the formula (Y-174), the formula (Y-175), the formula (Y-178), and the formula (Y-179) represents a tert-butoxycarbonyl group. [0101] <Manufacturing Method of Polyfluorinated Acid> The polyfluorinated acid of the polyfluorinated imide precursor used in the liquid crystal alignment agent of the present invention may be a diamine component containing a diamine of the present invention and a tetracarboxylic acid derivative. Prepared by reacting ingredients. [0101] Specifically, the tetracarboxylic dianhydride and the diamine can be synthesized by reacting them in the presence of an organic solvent. [0103] The organic solvent is not particularly limited as long as it can dissolve the generated polyamic acid. Specific examples thereof include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl Gadolinium, γ-butyrolactone, etc. When the polyimide precursor has high solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula (D -1) to an organic solvent represented by the following formula (D-3). [0104] [0105] In the above 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. [0106] These can be used alone or in combination. When a solvent that does not dissolve polyamic acid is used alone, it can be used in a mixture with the solvent as long as it does not cause precipitation of the generated polyamic acid. In addition, the water in the organic solvent will hinder the polymerization reaction, and for the reason that the generated polyamic acid is hydrolyzed, it is better to use the organic solvent as much as possible for dehydration and drying. A method of mixing a diamine component with a tetracarboxylic dianhydride in an organic solvent, for example, a solution obtained by dispersing or dissolving a diamine in an organic solvent is stirred, and the tetracarboxylic dianhydride is directly added, or A method of dispersing or dissolving in an organic solvent and then adding it, a method of adding a diamine to a solution obtained by dispersing or dissolving an organic solvent in which a tetracarboxylic dianhydride is dispersed, or interacting or simultaneously with a tetracarboxylic dianhydride and diamine Any method may be used as a method of adding to an organic solvent. [0108] The temperature when synthesizing the polyamidic acid can be selected at any temperature from -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C, and more preferably 0 ° C to 80 ° C. [0109] The reaction time may be arbitrarily selected as long as it is longer than the time during which the polyamine can be stably polymerized, and is preferably 30 minutes to 24 hours, and more preferably 1 hour to 12 hours. [0110] The reaction can be carried out at any concentration. When the concentration of the diamine component and the tetracarboxylic dianhydride as raw materials is too low, a polymer having a high molecular weight cannot be obtained. The property is too high to be uniformly stirred, so it is preferably 1% to 50% by mass, and more preferably 5% to 20% by mass. It may be performed at a high concentration in the initial stage of the reaction, and an organic solvent may be added subsequently. [0111] In the synthesis reaction of the polyamic acid, the molar ratio of the tetracarboxylic dianhydride to the molar number of the diamine component is preferably 0.8 to 1.2. As with a normal polycondensation reaction, the closer the Mohr ratio is to 1.0, the larger the molecular weight of the polyamino acid produced. [0112] The polyamidic acid obtained in the above manner can be precipitated and recovered after the reaction solution is poured into the lean solvent with sufficient stirring. In addition, after carrying out precipitation several times, washing with a lean solvent, and drying at room temperature or heating, the powder of purified polyamic acid can be obtained. [0113] The lean solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, and toluene, and water, methanol, and ethanol. And 2-propanol are preferred. [0114] <Production of Polyamidate> The polyamidate of the polyamidate precursor of the present invention can be produced according to the production method of [1], [2], or [3] shown below. [01] In the case of polyamidate, the polyamidate can be obtained by esterifying the polyamidate obtained in the aforementioned manner. [0116] Specifically, in order to combine the polyamidic acid and the esterifying agent in the presence of an organic solvent, the temperature is -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, It is preferably obtained by reacting for 1 to 4 hours. [0117] The esterifying agent is preferably one which can be easily removed by purification, for example, N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal Aldehyde, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t -Butyl acetal, 1-methyl-3-p-tolyl triazene, 1-ethyl-3-p-tolyl triazene, 1-propyl-3-p-tolyl triazene , 4- (4,6-dimethoxy-1,3,5-tri 2-yl) -4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 mol equivalent to 6 mol equivalent relative to the repeating unit of polyamic acid. Organic solvents, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N -Dimethylacetamide, dimethyl sulfenimide, 1,3-dimethyl-imidazolinone, and the like. When the polyfluorene imide precursor has high solubility in a solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the above formula ( D-1) to a solvent represented by the formula (D-3). [0119] The solvent may be used alone or in combination. In the case of a solvent that does not dissolve the polyfluorene imide precursor, as long as it does not cause precipitation of the generated polyfluorene imide precursor, it may be mixed with the solvent and used. In addition, the water in the solvent will hinder the polymerization reaction, and for the reason of the hydrolysis of the produced polyfluorene imide precursor, it is preferable to use dehydration as the solvent. In terms of the solubility of the polymer, the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone These can be used alone or in combination of two or more. The concentration at the time of production is difficult to cause precipitation of a polymer, and from the viewpoint of easily obtaining a high molecular weight body, it is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass. [2] In the case where a polycarboxylic acid ester is produced by reacting a tetracarboxylic acid diester dichloride with a diamine, a tetracarboxylic acid diester dichloride and a diamine component containing the diamine of the present invention can be used. And made. [0122] Specifically, the tetracarboxylic acid diester dichloride and diamine are subjected to a temperature of -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, in the presence of a base and an organic solvent, for 30 minutes. It can be prepared by a reaction of minutes to 24 hours, preferably 1 hour to 4 hours. [0123] As the base, pyridine, triethylamine, 4-dimethylaminopyridine, and the like can be used. From the viewpoint of allowing the reaction to proceed stably, pyridine is preferably used. The addition amount of the base can be easily removed, and the viewpoint of easily producing a high molecular weight body, it is better to use 2 mol times to 4 mol times relative to the tetracarboxylic acid diester dichloride. Molar times-3 Molar times are more preferred. The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and one or more of these can be used. Two or more types are mixed and used. [0125] The polymer concentration at the time of production is less likely to cause precipitation of the polymer, and it is easy to produce a high molecular weight body, preferably 1% to 30% by mass, and more preferably 5% to 20% by mass. . [0126] In order to prevent the hydrolysis of the tetracarboxylic diester dichloride, the solvent used in the production of polyurethane is preferably as dehydrated as possible, and in a nitrogen atmosphere to prevent outside air Mixing is better. [3] In the case of a polycarboxylic acid ester made from a tetracarboxylic acid diester and a diamine, the polycarboxylic acid ester can be prepared from a tetracarboxylic acid diester and a diamine component containing the diamine of the present invention through a polycondensation reaction. . [0128] Specifically, for the tetracarboxylic diester and diamine, in the presence of a condensing agent, a base, and an organic solvent, it is performed at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 30 minutes. It can be prepared by a reaction of minutes to 24 hours, preferably 3 hours to 15 hours. [0129] As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-tri Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethylurea tetrafluoroborate, O- (benzotriazol-1-yl ) -N, N, N ', N'-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-thiooxy-3-benzoxazolyl) phosphonic acid Phenyl esters, etc. The addition amount of the condensing agent is preferably 2 mol times to 3 mol times, and more preferably 2 mol times to 2.5 mol times relative to the tetracarboxylic acid diester. As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of alkali can be easily removed and the high molecular weight body can be easily produced. Compared with the diamine component, it is preferably 2 mol times to 4 mol times, and 2.5 mol times to 3.5 mol times. Times is better. [0131] In the above reaction, when a Lewis acid is added as an additive, the reaction can be efficiently performed. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The added amount of Lewis acid is preferably 0 mol times to 1.0 mol times, and more preferably 0 mol times to 0.7 mol times relative to the diamine component. [0132] In the method for producing the three polyamic acid esters, from the viewpoint that a high molecular weight polyamino acid ester can be obtained, the above-mentioned method [1] or [2] is particularly preferable. [0133] The polymer solution obtained in the manner described above can be precipitated when a poor solvent is injected into the stirring solution. After carrying out precipitation several times, washing with a lean solvent, and drying at normal temperature or under a heating state, a purified polyurethane powder can be obtained. The lean solvent is not particularly limited, and may be water, methanol, ethanol, hexane, cellosolve, acetone, toluene, or the like. [0134] <Production method of polyfluorene imine> The polyfluorene imine used in the present invention can be obtained by fluorinating the aforementioned polyfluorene imine precursor. [0135] In the polyfluorene imine of the present invention, the ring closure rate (fluorine imidization rate) of the amino acid group or the amino acid ester group is not necessarily 100%, and it can be arbitrarily adjusted according to the use or purpose. . [0136] The method of closing the polyfluorene imide precursor includes, for example, a method of heating the polyfluorene imide without using a catalyst, or performing a method such as thermal imidization using a catalyst. . [0137] When the polyfluorene imine precursor is thermally fluorinated, the solution of the polyfluorene imine precursor is heated to 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, through the fluorination reaction. A method of excluding the generated water or alcohol from the reaction system is preferred. [0138] The catalyst of the polyimide precursor is imidized by adding a basic catalyst and an acid anhydride to a solution of the polyimide, at a temperature of -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C. It was carried out by stirring at a temperature of ° C. The amount of alkaline catalyst is 0.5 mol times to 30 mol times of the amino acid group, preferably 2 mol times to 20 mol times of the amino acid group, and the amount of the acid anhydride is 1 mol times to 50 mol of the amino acid group. Molar times, preferably 3 to 30 mole times. [0139] Basic catalysts include, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine can be maintained at a moderate alkalinity while the reaction is progressing, which is preferred. . [0139] Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. When acetic anhydride is used, purification after the reaction can be easily performed, and it is preferable. The rate of catalyst imidization can be controlled by adjusting the amount of catalyst and the reaction temperature and reaction time. [0141] When the polymer component is recovered from the polyimide reaction solution, the reaction solution may be poured into a lean solvent to precipitate it. The lean solvent used for the precipitation may be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which is precipitated by adding a poor solvent is filtered, recovered, and dried at normal temperature or reduced pressure, at normal temperature or under heating. [0142] <Liquid crystal alignment agent> The liquid crystal alignment agent is a coating liquid for producing a liquid crystal alignment film, and its main component is a composition containing a resin component forming a resin film and an organic solvent in which the resin component is dissolved. The liquid crystal alignment agent of the present invention has a resin component of at least one selected from the group consisting of the polyfluorene imide precursor and a polyfluorene imide obtained by subjecting the polyfluorene imide precursor to a ring-closing reaction. Polymer. [0143] The polymer concentration in the liquid crystal alignment agent may be appropriately changed according to the set thickness of the coating film to be formed. From the viewpoint of uniformly forming a defect-free coating film, 1 mass% or more is preferable, and from the viewpoint of storage stability of the solution, 10 mass% or less is preferable. A particularly good polymer concentration is 2% to 8% by mass. [0144] The resin component in the liquid crystal alignment agent may be all of the polymer of the present invention, or it may be mixed with a polymer other than the polymer of the present invention. Examples of the diamine component in the other polymer include polyimide precursors and polyimide prepared using diamines other than those represented by the formula (1). [0145] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer component uniformly. When specific examples are given, for example, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidine Ketone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfinium, dimethylfluorene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, 3-methoxy-N, N-dimethylpropanehydrazone and the like. These can be used singly or in combination of two or more. Furthermore, even when a solvent that does not uniformly dissolve a polymer component is used alone, as long as it does not precipitate a polymer, it can be mixed with the above-mentioned organic solvent. [0146] The liquid crystal alignment agent may contain a solvent that can improve the uniformity of the coating film when the liquid crystal alignment agent is coated on the substrate in addition to the organic solvent capable of dissolving the polymer component. As the solvent, generally, a solvent having a lower surface tension than the above-mentioned organic solvent can be used. Specific examples include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, and 1-methoxyl. 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 2-butoxy-1-propanol, 1-phenoxy-2-propanol Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diacetone alcohol, diethylene glycol diethyl ether, 2,6-dimethyl-4-heptanol, diisobutanone, 4-methoxy-4-methyl Methyl-2-pentanone, 4-hydroxy-2-butanone and 2-methyl-2-hexanol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more kinds. [0147] The above solvents can be used as lean solvents with low resin solubility. These solvents are preferably 5 to 60% by mass, more preferably 10 to 50% by mass of the organic solvent contained in the liquid crystal alignment treatment agent. [0148] In the liquid crystal alignment agent, in addition to the above, as long as the effect of the present invention is not impaired, a polymer other than the polymer of the present invention may be added, and the electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film may be changed. Dielectrics or conductive materials, silane coupling agents for the purpose of improving the adhesion between liquid crystal alignment films and substrates, cross-linking compounds for the purpose of improving the hardness or density of films when used as liquid crystal alignment films, and sintered coating films In this case, a fluorene imidation accelerator for the purpose of allowing a polyfluorene imine precursor to efficiently fluorinate can be used. [0149] When the compound is a crosslinkable compound such as a functional silane-containing compound or an epoxy group-containing compound, the amount of addition is 0.1 to 30% by mass relative to 100 parts by mass of the resin component. It is preferably 1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass. [0150] <Manufacturing Method of Liquid Crystal Alignment Film> The liquid crystal alignment film is a film obtained by applying the above-mentioned liquid crystal alignment agent to a substrate, and drying and sintering it. [0151] The substrate coated with the liquid crystal alignment agent is not particularly limited as long as it is a substrate having high transparency, and plastics such as a glass substrate, a silicon nitride substrate, an acrylic substrate, and a polycarbonate substrate can be used. Substrate, etc. In particular, when a substrate such as an ITO electrode capable of driving liquid crystal is used, it is preferable from the viewpoint of simplifying the manufacturing process. [0152] In a reflective liquid crystal display element, if it is only a single-sided substrate, an opaque substance such as a silicon wafer may be used. In this case, an electrode that can reflect light such as aluminum may also be used. [0153] Examples of the method for applying the liquid crystal alignment agent include a spin coating method, a printing method, and an inkjet method. In addition, the method using a coating liquid, for example, stirring coating (Dip coating), roll coating, slit coating, spin coating, etc., can be used according to the purpose. [0154] The drying and sintering steps after the liquid crystal alignment agent is applied can be selected at any temperature and time. In general, when the organic solvent contained can be sufficiently removed, drying is generally performed at 50 ° C to 120 ° C, preferably 50 ° C to 80 ° C, for 1 minute to 10 minutes, preferably 3 minutes to 5 minutes. Then, a sintering treatment is performed at 150 ° C to 300 ° C, preferably 200 ° C to 240 ° C, for 5 minutes to 120 minutes, preferably 10 minutes to 40 minutes. [0155] The thickness of the coating film after sintering is not particularly limited. When the thickness is too thin, the reliability of the liquid crystal display element may be reduced. The thickness is generally 5 nm to 300 nm, and preferably 10 nm to 200 nm. [0156] Examples of the method for subjecting the obtained liquid crystal alignment film to an alignment treatment include a rubbing method, a photo-alignment treatment method, and the like. In the rubbing treatment, tarpaulin, nylon, cotton, etc. can be used. The liquid crystal alignment film for vertical alignment is difficult to achieve a uniform alignment state when using a rubbing treatment. Therefore, when used as a liquid crystal alignment agent for vertical alignment, it can also be used without rubbing treatment. [0157] A specific example of the photo-alignment treatment method is, for example, irradiating the surface of the coating film with radiation deflected in a specific direction, and depending on the situation, heat treatment may be performed at a temperature of 150 ° C to 250 ° C to impart liquid crystal Method of alignment ability, etc. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 nm to 400 nm are more preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable. [0158] From the viewpoint of improving the alignment of the liquid crystal, the coating film substrate may be heated to a temperature between 50 ° C and 250 ° C, and radiation may be applied. [0159] The amount of radiation is 1 mJ / cm 2 ～ 10,000mJ / cm 2 Preferably at 100mJ / cm 2 ～ 5,000mJ / cm 2 Especially good. The liquid crystal alignment film prepared in the above manner can stably form liquid crystal molecules in a specific direction. [0160] As described above, after the film is irradiated with polarized radiation, the contact treatment may be performed using a solvent containing at least one type selected from water and an organic solvent. [0161] The solvent used for the contact treatment is not particularly limited as long as it is a solvent capable of dissolving a decomposed product generated by light irradiation. Specific examples are 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, cyclohexyl acetate, and the like. These solvents may be used in combination of two or more kinds. [0162] From the viewpoint of versatility or safety, it is preferable to use at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate. . Particularly preferred is the use of 1-methoxy-2-propanol or ethyl lactate. [0163] In the present invention, a process in which the film irradiated with polarized radiation is brought into contact with a solution containing an organic solvent may be a dipping process, a spray process, or the like, so that the film and the liquid are brought into full contact. Better. Among them, it is also preferable that the film is immersed in a solution containing an organic solvent for preferably 10 seconds to 1 hour, and more preferably 1 minute to 30 minutes. The contact treatment may be performed at normal temperature or heating, and it is preferably performed at 10 ° C to 80 ° C, more preferably at 20 ° C to 50 ° C. In addition, if necessary, means such as ultrasound can be used to increase contact. [0164] After the above-mentioned contact treatment, in order to remove the organic solvent in the solution used, a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone and the like can be used for washing ( Washing) or drying, or performing both treatments at the same time. [0165] In the case where the film is subjected to a contact treatment with a solvent, the solvent may be dried and the molecular chain re-alignment in the film may be heated to 150 ° C or higher for the purposes of drying the solvent and promoting the realignment of molecular chains in the film. [0166] The heating temperature is preferably 150 ° C to 300 ° C. When the temperature is higher, the realignment of the molecular chain is promoted, but when the temperature is too high, there is a concern that the molecular chain is decomposed. Therefore, the heating temperature is preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 230 ° C. [0167] If the heating time is too short, the effect of the present invention may not be obtained. If the heating time is too long, the molecular chain may be decomposed. Therefore, generally 10 seconds to 30 minutes is preferred, and 1 minute is preferred. It is preferably 10 minutes. [0168] <Liquid crystal display element> The liquid crystal display element is obtained by preparing a liquid crystal cell-attached substrate obtained from the liquid crystal alignment agent of the present invention, and then preparing a liquid crystal cell according to a known method, and using the liquid crystal cell to Produced liquid crystal display elements. [0169] An example of a method for producing a liquid crystal cell will be described using a liquid crystal display element having a passive element matrix structure as an example. In addition, a liquid crystal display element having an active matrix structure in which each pixel portion constituting an image display is provided with an opening and closing element such as a TFT (Thin Film Transistor) may be used. [0170] First, a transparent glass substrate is prepared. A common electrode is provided on one substrate and a segment electrode is provided on the other substrate. These electrodes can be used, for example, as ITO electrodes, and can form a pattern of a desired image display. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film may be, for example, SiO formed by a gel-sol method. 2 -TiO 2 The formed film. [0171] Subsequently, a liquid crystal alignment film of the present invention is formed on each substrate. Next, the substrate on one side and the substrate on the other side are overlapped so that the alignment film surfaces face each other, and the periphery is sealed with a sealing material. Spacers are often mixed into the sealing material for the purpose of controlling the gap of the substrate. In addition, it is also preferable to use a spacer for controlling the gap between the substrates in which no inner surface portion of the sealing material is provided. An opening portion that can be filled with liquid crystal from the outside is provided on a part of the sealing material. [0172] Next, a liquid crystal material is injected into a space surrounded by the two substrates and the sealing material through an opening provided in the sealing material. Subsequently, the opening is sealed with an adhesive. The injection method may be a vacuum injection method or a method using a capillary phenomenon in the atmosphere. Alternatively, the liquid crystal after the sealing material is drawn may be dropped on the substrate and bonded under reduced pressure, and the liquid crystal may be filled. [0173] As the liquid crystal material, any of a positive type liquid crystal material and a negative type liquid crystal material can be used. In particular, when used in a negative-type liquid crystal material having a lower voltage retention than a positive-type liquid crystal material, when the liquid crystal alignment film of the present invention is used, excellent afterimage characteristics can be obtained. [0174] Next, the polarizing plate is set. Specifically, a pair of polarizing plates is attached to the surface opposite to the liquid crystal layer of two substrates. After the above steps, the liquid crystal display element of the present invention can be obtained. In this liquid crystal display element, since the liquid crystal alignment film is a liquid crystal alignment film obtained by using the liquid crystal alignment film manufacturing method of the present invention, it has excellent afterimage characteristics and is suitable for a high-definition multifunctional mobile phone (smartphone ), Or tablet, LCD TV, etc.

[實施例] 　　[0175] 以下將列舉實施例，對本發明做更具體的說明。但，本發明並不受該些實施例所限定、解釋。以下所使用的化合物之簡稱，及各種特性的測定方法係如以下所示。 ＜化合物之簡稱＞ 　　下述式DA-5及下述式DA-6中，「Boc」為tert-丁氧基羰基。 　　[0176][0177][0178][0179] ＜化合物之簡稱＞ DA-7：1,3-雙(4-胺基苯乙基)脲 DA-8：4-(2-甲胺基乙基)苯胺 NMP：N-甲基-2-吡咯啶酮 BCS：丁基溶纖劑(cellosolve) GBL：γ-丁內酯 　　[0180] ＜黏度＞ 　　合成例中，聚合物溶液之黏度，為使用E型黏度計TVE-22H(東機產業公司製)，依樣品量1.1mL、錐形旋轉器TE-1(1°34’、R24)、溫度25℃下測定者。 　　[0181] ＜液晶顯示元件之製作＞ 　　首先準備附有電極之基板。基板為大小30mm×35mm、厚度0.7mm之玻璃基板。於基板上形成作為構成第1層的對向電極的具備黏稠狀圖型的IZO電極。於第1層的對向電極上的第2層，為形成依CVD法形成膜的SiN(氮化矽)膜。第2層的SiN膜之膜厚為500nm，其具有層間絕緣膜之機能。第2層的SiN膜上，配置有將IZO膜經由圖型形成(Patterning)而形成櫛齒狀畫素電極的第3層，而形成第1畫素及第2畫素等2個畫素。各畫素的尺寸為縱10mm、橫約5mm。此時，第1層的對向電極與第3層的畫素電極間，為經第2層的SiN膜之作用，而形成電氣絕緣狀態。 　　[0182] 第3層的畫素電極，為具有由複數配列的中央部份形成屈曲的「ㄑ」字形狀之電極要素所構成的櫛齒狀形狀。各電極要素的短邊方向之寬度為3μm，電極要素間之間隔為6μm。形成各畫素的畫素電極，因具有由複數配列的中央部份形成屈曲的「ㄑ」字形狀之電極要素所構成，故各畫素的形狀並非長形狀，而為與電極要素相同般，具備中央部份為屈曲的近似粗字「ㄑ」字之形狀。因此，各畫素經由其中央的屈曲部份作為境界，而分割為上下，而具有屈曲部份上側的第1區域與下側的第2區域。 　　[0183] 各畫素的第1區域與第2區域進行比較時，得知構成該些畫素電極的電極要素之形成方向為相異者。即，依後述液晶配向膜的摩擦方向為基準時，畫素的第1區域為依畫素電極的電極要素為＋10°之角度(順時鐘)方式形成，畫素的第2區域為依畫素電極的電極要素為-10°之角度(順時鐘)方式形成。即，各畫素的第1區域與第2區域，為依畫素電極與對向電極之間經由施加電壓所引起的液晶於基板面內的迴轉動作(面內・開閉)的方向為互相相反方向之方式所構成者。 　　[0184] 其次，將所得液晶配向劑使用1.0μm之過濾器過濾後，旋轉塗佈於與所準備的附有上述電極之基板為對向基板之內面形成ITO膜，與具有高4μm之柱狀間隔器的玻璃基板之各者上。其次，於80℃的加熱板上乾燥5分鐘後，經230℃、20分鐘燒結，而於各基板上形成膜厚60nm之塗膜的聚醯亞胺膜。於該聚醯亞胺膜上，使用嫘縈布依特定的摩擦方向進行摩擦(滾筒徑120mm、迴轉數500 rpm、移動速度30mm／sec、擠壓量0.3mm)後，於純水中進行1分鐘超音波照射、於80℃下乾燥10分鐘。 　　[0185] 隨後，使用附有上述液晶配向膜的2種類基板，將其分別以摩擦方向相反之方式組合，留存液晶注入口後，將周圍密封，製得晶胞間隙(Cell Gap)為3.8μm之空晶胞。將液晶(MLC-2041、莫克公司製)於常溫下真空注入該空晶胞後，將注入口密封，而製得反平行配向之液晶晶胞。所得之液晶晶胞，可構成FFS模式液晶顯示元件。隨後，將所得液晶晶胞，於120℃下加熱1小時，放置一晩後，供各評估使用。 　　[0186] ＜蓄積電荷之緩和特性的評估＞ 　　使用以下光學系等進行殘影評估。將所製得之液晶晶胞設置於偏光軸呈垂直交叉配置的2片偏光板之間，於無施加電壓狀態下，將LED背光源點燈，調整液晶晶胞的配置角度，使穿透光線的亮度達最小程度。 　　[0187] 其次，將周波數30Hz的交流電壓施加於該液晶晶胞間，測定其V-T曲線(電壓-穿透率曲線)，算出相對穿透率為23%時的交流電壓作為驅動電壓。 　　[0188] 殘影評估為，施加相對穿透率為23%之周波數30Hz的交流電壓，驅動液晶晶胞過程中，同時施加1V之直流電壓，進行40分鐘之驅動。隨後，使施加的直流電壓值為0V，僅停止直流電壓之施加，並於該狀態下再驅動15分鐘。 　　[0189] 評估為，於開始施加直流電壓的時點起，至45分鐘為止，其相對穿透率降低至25%以下時，則以定義為「良好」之方式進行評估。相對穿透率降低至25%以下需要45分鐘以上時，則以定義為「不良」之方式進行評估。 　　[0190] 又，依上述方法所進行的殘影評估，為於液晶晶胞溫度為23℃之狀態的溫度條件下進行者。 　　[0191] ＜液晶配向安定性評估＞ 　　使用該液晶晶胞，於60℃之恆溫環境下，施加168小時的周波數30Hz的10VPP之交流電壓。隨後，使液晶晶胞的畫素電極與對向電極之間形成短路之狀態，於室溫下放置一日。 　　[0192] 放置後，將液晶晶胞設置於偏光軸呈垂直交叉配置的2片偏光板之間，於無施加電壓之狀態，將背光源點燈，調整液晶晶胞之配置角度，使穿透光線的亮度達最小為止。隨後，算出使液晶晶胞由第1畫素的第2區域中的最暗的角度迴轉至第1區域中最暗的角度為止時的迴轉角度，作為角度Δ。第2畫素亦相同般，比較第2區域與第1區域，同樣地算出角度Δ。隨後，算出第1畫素與第2畫素的角度Δ值之平均值，作為液晶晶胞之角度Δ。該液晶晶胞的角度Δ之值超過0.1度時，則以定義為「不良」之方式進行評估。該液晶晶胞的角度Δ之值未超過0.1度時，則以定義為「良好」之方式進行評估。 　　[0193] ＜BL耐性評估＞ 　　將所製得之液晶晶胞放置於2000nit的BL上，進行1週運轉。運轉後，將晶胞於60℃之溫度下，施加1V的電壓 60μsec，測定100msec後的電壓，並評估其電壓保持率。 　　[0194] 此時，電壓保持率維持80%以上時，則定義為「良好」，未達80%時，則定義為「不良」之方式進行。 　　[0195] ＜耐摩擦性之評估＞ 　　將液晶配向劑塗佈於ITO基板，於預乾燥後，使用230℃之IR式烘箱進行燒結，製得附有液晶配向膜之基板。使用嫘縈布摩擦(輥迴轉數：1000rpm、平台移動速度：20mm／sec、擠壓長度：0.4mm)該液晶配向膜。使用顯微鏡觀察該基板，於膜面未出現因摩擦產生之條紋者，則評估為「良好」，發現條紋者，則評估為「不良」。 　　[0196] ＜合成例＞ (合成例1) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-3 34.36g(0.12mol)後，加入NMP 335.12g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-1 22.77g (0.10mol)，再加入NMP 83.80g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-1)。 　　[0197] (合成例2) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-3 25.20g(0.088mol)，及DA-6 8.77g(0.022mol)後，加入NMP 333.97g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-1 22.96g(0.11mol)，再加入NMP 326g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-2)。 　　[0198] (合成例3) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-3 25.20g(0.088mol)，及DA-5 8.72g(0.022mol)後，加入NMP 334.28g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-1 23.06g(0.11mol)，再加入NMP 83.57g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-3)。 　　[0199] (合成例4) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-4 19.13g(0.096mol)後，加入溶劑(NMP：GBL=50wt%：50wt%)232.72g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-2 14.12g(0.072mol)，再加入溶劑(NMP：GBL=50wt%：50wt%)84.63g後，進行2小時攪拌。隨後投入DA-1 4.76g(0.024mol)後，加入NMP 42.31g，進行攪拌使其溶解。再於水冷下、攪拌間，添加CA-3 9.00g (0.03mol)，再加入溶劑(NMP：GBL=50wt%：50wt%) 326g，進行2小時攪拌後，得聚醯胺酸溶液(PAA-4)。 　　[0200] (合成例5) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-4 23.91g(0.12mol)，及DA-1 5.95g(0.03mol)後，加入NMP 255.76g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-2 6.47g(0.033mol)，再加入NMP 73.01g後，進行2小時攪拌。隨後，投入CA-4 28.15g(0.11mol)後，加入NMP 36.54g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-5)。 　　[0201] (合成例6) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-4 23.91g(0.12mol)，及DA-2 4.56g(0.03mol)後，加入NMP 241.76g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-2 13.71g(0.070mol)，再加入NMP 69.07g後，進行2小時攪拌。隨後，投入CA-4 18.77g(0.075mol)後，加入NMP 34.54g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-6)。 　　[0202] (合成例7) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-4 28.69g(0.144mol)，及DA-1 7.14g(0.036mol)後，加入NMP 296.56g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-2 16.41g(0.084mol)，再加入NMP 84.73g後，進行2小時攪拌。隨後，投入CA-4 22.52g (0.09 mol)後，加入NMP 42.37g，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-7)。 　　[0203] (合成例8) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-5 18.98g(0.048mol)，及DA-7 14.28g(0.048mol)後，加入NMP 312.67g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-1 20.04g(0.092mol)，再加入NMP 78.17g後，於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-8)。 　　[0204] (合成例9) 　　於附有攪拌裝置與氮導入管的500mL燒瓶中，投入DA-7 26.85g(0.09mol)，及DA-8 9.01g(0.06mol)後，加入NMP 289.28g，進行攪拌使其溶解。將此溶液於水冷下、攪拌間，添加CA-2 27.94g(0.14mol)，再加入NMP 72.32g後，進行2小時攪拌，得聚醯胺酸溶液(PAA-9)。 　　[0205] (比較例1) 　　於置有攪拌子的20ml樣品管中，秤取PAA-1 1.51g、PAA-4 6.99g，加入NMP 1.51g、GBL 3.13g、BCS 6.00g、含有1重量%AD-1的GBL溶液0.86g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(A-1)。 　　[0206] (比較例2) 　　於置有攪拌子的20ml樣品管中，秤取PAA-1 1.33g、PAA-5 4.27g，加入NMP 4.40g、GBL 5.36g、BCS 4.00g、含有1重量%AD-1的GBL溶液0.64g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(A-2)。 　　[0207] (比較例3) 　　於置有攪拌子的20ml樣品管中，秤取PAA-2 1.33g、PAA-6 4.27g，加入NMP 4.40g、GBL 5.36g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.64g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(A-3)。 　　[0208] (比較例4) 　　於置有攪拌子的20ml樣品管中，秤取PAA-8 2.00g、PAA-9 6.40g，加入NMP 1.60g、GBL 5.04g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.96g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(A-4)。 　　[0209] (實施例1) 　　於置有攪拌子的20ml樣品管中，秤取PAA-3 1.33g、PAA-6 4.27g，加入NMP 4.40g、GBL 5.36g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.64g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(B-1)。 　　[0210] (實施例2) 　　於置有攪拌子的20ml樣品管中，秤取PAA-3 1.33g、PAA-6 4.27g，加入NMP 4.16g、GBL 5.36g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.64g，含有10重量%AD-3的NMP溶液0.24g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(B-2)。 　　[0211] (實施例3) 　　於置有攪拌子的20ml樣品管中，秤取PAA-3 1.33g、PAA-7 4.27g，加入NMP 4.40g、GBL 5.36g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.64g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(B-3)。 　　[0212] (實施例4) 　　於置有攪拌子的20ml樣品管中，秤取PAA-3 1.33g、PAA-7 4.27g，加入NMP 4.16g、GBL 5.36g、BCS 4.00g、含有1重量%AD-2的GBL溶液0.64g、含有10重量%AD-3的NMP溶液0.24g，使用磁性攪拌子攪拌30分鐘，製得液晶配向劑(B-4)。使用依上述所得的液晶配向劑，進行BL耐性、蓄積電荷緩和特性、液晶配向安定性，及耐摩擦性之評估。其結果係如下述表1所示。 　　[0213][0214] 如以上所述般，本發明之液晶配向膜，無論於耐摩擦性、BL耐性評估、液晶配向安定性評估、殘影消失時間等任一評估，皆顯示出良好的結果。[Examples] [0175] Examples will be listed below to describe the present invention more specifically. However, the present invention is not limited or explained by these examples. The abbreviations of the compounds used below and the methods for measuring various properties are shown below. <Abbreviation of Compound> In the following formula DA-5 and DA-6, "Boc" is a tert-butoxycarbonyl group. [0176] [0177] [0178] <Abbreviation of Compound> DA-7: 1,3-bis (4-aminophenethyl) urea DA-8: 4- (2-methylaminoethyl) aniline NMP: N-methyl- 2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyrolactone [0180] <viscosity> In the synthesis example, the viscosity of the polymer solution is the E-type viscosity meter TVE-22H (Toki Sangyo Co., Ltd. (Manufactured), according to a sample volume of 1.1 mL, a conical spinner TE-1 (1 ° 34 ', R24), and a measurement at a temperature of 25 ° C. [0181] <Production of Liquid Crystal Display Element> First, a substrate with electrodes is prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An IZO electrode having a viscous pattern is formed on the substrate as a counter electrode constituting the first layer. The second layer on the counter electrode of the first layer is a SiN (silicon nitride) film formed by a CVD method. The SiN film of the second layer has a film thickness of 500 nm and has the function of an interlayer insulating film. On the second layer of the SiN film, a third layer in which the IZO film is patterned to form a dentate pixel electrode is arranged to form two pixels such as a first pixel and a second pixel. The size of each pixel is 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. [0182] The pixel electrode of the third layer has a dentate shape composed of electrode elements having a buckled "ㄑ" shape formed in the central portion of the plural array. The width in the short-side direction of each electrode element is 3 μm, and the interval between the electrode elements is 6 μm. The pixel electrodes that form each pixel are composed of electrode elements formed by a central portion of a plurality of rows that are buckled in a "ㄑ" shape. Therefore, the shape of each pixel is not the same as the electrode element. It has the shape of "粗", which is approximately thick and buckled in the center. Therefore, each pixel is divided into an upper part and a lower part with a first region on the upper side and a second region on the lower side through the central buckling part as the realm. [0183] When the first region and the second region of each pixel are compared, it is known that the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the first region of the pixel is formed by an angle (clockwise) of the electrode element of the pixel electrode being + 10 °, and the second region of the pixel is pixel-by-pixel. The electrode elements of the electrode are formed at an angle (clockwise) of -10 °. In other words, the first region and the second region of each pixel are opposite to each other in the direction in which the liquid crystal rotates in the plane of the substrate (in-plane opening / closing) due to the applied voltage between the pixel electrode and the counter electrode. The way the direction is made up. [0184] Next, the obtained liquid crystal alignment agent was filtered with a filter of 1.0 μm, and then spin-coated on the inner surface of the prepared substrate with the above electrode as an opposing substrate to form an ITO film and a pillar having a height of 4 μm. Glass spacers. Next, after drying on a hot plate at 80 ° C. for 5 minutes, and sintering at 230 ° C. for 20 minutes, a polyimide film with a coating thickness of 60 nm was formed on each substrate. After rubbing on the polyimide film with a rubbing cloth in a specific rubbing direction (roller diameter 120 mm, number of revolutions 500 rpm, moving speed 30 mm / sec, extrusion amount 0.3 mm), it was performed in pure water for 1 minute. Ultrasonic irradiation and drying at 80 ° C for 10 minutes. [0185] Subsequently, the two types of substrates with the above-mentioned liquid crystal alignment films were used, and they were combined in opposite directions to rub each other. After the liquid crystal injection port was retained, the surroundings were sealed to obtain a cell gap of 3.8 μm. The empty unit cell. Liquid crystal (MLC-2041, manufactured by Mok) was vacuum-injected into the empty cell at normal temperature, and then the injection port was sealed to prepare an anti-parallel aligned liquid crystal cell. The obtained liquid crystal cell can constitute an FFS mode liquid crystal display element. Subsequently, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour, and left for a while for evaluation. [0186] <Evaluation of Mitigating Characteristics of Accumulated Charge> The afterimage evaluation was performed using the following optical system and the like. The prepared liquid crystal cell is set between two polarizing plates whose polarizing axes are perpendicularly crossed. When no voltage is applied, the LED backlight is turned on, and the arrangement angle of the liquid crystal cell is adjusted to penetrate the light. To a minimum. [0187] Next, an AC voltage having a frequency of 30 Hz was applied between the liquid crystal cells, the VT curve (voltage-transmittance curve) was measured, and the AC voltage at a relative transmittance of 23% was calculated as the driving voltage. [0188] The afterimage was evaluated as follows: an AC voltage of 30 Hz with a relative transmittance of 23% was applied to drive the liquid crystal cell, and a DC voltage of 1 V was applied for 40 minutes. Subsequently, the applied DC voltage value was set to 0V, only the application of the DC voltage was stopped, and the driving was continued for another 15 minutes in this state. [0189] The evaluation is that when the relative transmission rate is reduced to 25% or less from the point when the DC voltage is applied until 45 minutes, the evaluation is performed as “good”. When it takes more than 45 minutes to reduce the relative transmittance to less than 25%, it is evaluated as "bad". [0190] The afterimage evaluation performed by the above method was performed under a temperature condition where the liquid crystal cell temperature was 23 ° C. [0191] <Assessment of Liquid Crystal Alignment Stability> Using this liquid crystal cell, an AC voltage of 10 VPP with a cycle frequency of 30 Hz was applied for 168 hours in a constant temperature environment of 60 ° C. Subsequently, a short circuit is formed between the pixel electrode and the counter electrode of the liquid crystal cell, and the liquid crystal cell is left at room temperature for one day. [0192] After being placed, the liquid crystal cell is placed between two polarizing plates whose polarizing axes are vertically crossed. When no voltage is applied, the backlight is turned on, and the arrangement angle of the liquid crystal cell is adjusted to penetrate. The brightness of the light is minimized. Then, the rotation angle at which the liquid crystal cell is rotated from the darkest angle in the second region of the first pixel to the darkest angle in the first region is calculated as the angle Δ. The second pixel is the same. The second region is compared with the first region, and the angle Δ is calculated in the same manner. Subsequently, the average value of the angle Δ values of the first pixel and the second pixel is calculated as the angle Δ of the liquid crystal cell. When the value of the angle Δ of the liquid crystal cell exceeds 0.1 degree, it is evaluated as "bad". When the value of the angle Δ of the liquid crystal cell does not exceed 0.1 degree, it is evaluated as "good". [0193] <BL Resistance Evaluation> The obtained liquid crystal cell was placed on a 2000 nit BL and operated for one week. After the operation, the unit cell was applied with a voltage of 1 V for 60 μsec at a temperature of 60 ° C., the voltage after 100 msec was measured, and the voltage retention rate was evaluated. [0194] At this time, when the voltage holding ratio is maintained at 80% or more, it is defined as "good", and when it is less than 80%, it is defined as "bad". [0195] <Evaluation of Friction Resistance> A liquid crystal alignment agent was applied to the ITO substrate, and after pre-drying, it was sintered using an IR oven at 230 ° C to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film was rubbed with a rubbing cloth (roller revolution: 1000 rpm, platform moving speed: 20 mm / sec, extrusion length: 0.4 mm). When the substrate was observed with a microscope, if a streak on the film surface did not appear due to friction, it was evaluated as "good", and if a streak was found, it was evaluated as "bad". [Synthesis Example] (Synthesis Example 1) In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 34.36 g (0.12 mol) of DA-3 was added, and then 335.12 g of NMP was added and stirred to dissolve. This solution was stirred under water cooling, 22.77 g (0.10 mol) of CA-1 was added, and 83.80 g of NMP was added, followed by stirring at 50 ° C. for 12 hours to obtain a polyamic acid solution (PAA-1). (Synthesis Example 2) In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 25.20 g (0.088 mol) of DA-3 and 8.77 g (0.022 mol) of DA-6 were added, and then 333.97 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 22.96 g (0.11 mol) of CA-1 was added, and 326 g of NMP was added, followed by stirring at 50 ° C for 12 hours to obtain a polyamic acid solution (PAA-2). [Synthesis Example 3] In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 25.20 g (0.088 mol) of DA-3 and 8.72 g (0.022 mol) of DA-5 were added, and then 334.28 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 23.06 g (0.11 mol) of CA-1 was added, and 83.57 g of NMP was added, followed by stirring at 50 ° C for 12 hours to obtain a polyamic acid solution (PAA-3). (Synthesis Example 4) In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 19.13 g (0.096 mol) of DA-4 was added, and then a solvent (NMP: GBL = 50 wt%: 50 wt%) was added to 232.72 g, Stir to dissolve. This solution was stirred under water cooling, 14.12 g (0.072 mol) of CA-2 was added, and 84.63 g of a solvent (NMP: GBL = 50 wt%: 50 wt%) was added, followed by stirring for 2 hours. Subsequently, 4.76 g (0.024 mol) of DA-1 was added, and 42.31 g of NMP was added, followed by stirring to dissolve. Then, under water cooling and in a stirring room, 9.00 g (0.03 mol) of CA-3 was added, and 326 g of a solvent (NMP: GBL = 50wt%: 50wt%) was added. After stirring for 2 hours, a polyamic acid solution (PAA- 4). (Synthesis Example 5) In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 23.91 g (0.12 mol) of DA-4 and 5.95 g (0.03 mol) of DA-1 were added, and then 255.76 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 6.47 g (0.033 mol) of CA-2 was added, and 73.01 g of NMP was further added, followed by stirring for 2 hours. Subsequently, 28.15 g (0.11 mol) of CA-4 was added, and 36.54 g of NMP was added, followed by stirring at 50 ° C. for 12 hours to obtain a polyamic acid solution (PAA-5). [Synthesis Example 6] In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 23.91 g (0.12 mol) of DA-4 and 4.56 g (0.03 mol) of DA-2 were added, and then 241.76 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 13.71 g (0.070 mol) of CA-2 was added, and 69.07 g of NMP was added, followed by stirring for 2 hours. Subsequently, 18.77 g (0.075 mol) of CA-4 was added, and 34.54 g of NMP was added, followed by stirring at 50 ° C for 12 hours to obtain a polyamic acid solution (PAA-6). [Synthesis Example 7] In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 28.69 g (0.144 mol) of DA-4 and 7.14 g (0.036 mol) of DA-1 were added, and then 296.56 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 16.41 g (0.084 mol) of CA-2 was added, and 84.73 g of NMP was added, followed by stirring for 2 hours. Subsequently, 22.52 g (0.09 mol) of CA-4 was added, and 42.37 g of NMP was added, followed by stirring at 50 ° C. for 12 hours to obtain a polyamic acid solution (PAA-7). [Synthesis Example 8] In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 18.98 g (0.048 mol) of DA-5 and 14.28 g (0.048 mol) of DA-7 were added, and then 312.67 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 20.04 g (0.092 mol) of CA-1 was added, and 78.17 g of NMP was added, followed by stirring at 50 ° C. for 12 hours to obtain a polyamic acid solution (PAA-8). [Synthesis Example 9] In a 500 mL flask equipped with a stirring device and a nitrogen introduction tube, 26.85 g (0.09 mol) of DA-7 and 9.01 g (0.06 mol) of DA-8 were added, and then 289.28 g of NMP was added. Stir to dissolve. This solution was stirred under water cooling, 27.94 g (0.14 mol) of CA-2 was added, and 72.32 g of NMP was added, followed by stirring for 2 hours to obtain a polyamic acid solution (PAA-9). [Comparative Example 1] In a 20 ml sample tube with a stir bar, weigh 1.51 g of PAA-1 and 6.99 g of PAA-4, add 1.51 g of NMP, 3.13 g of GBL, 6.00 g of BCS, and contain 1% by weight. 0.86 g of GBL solution of AD-1 was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (A-1). [Comparative Example 2] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-1 and 4.27 g of PAA-5, add NMP 4.40 g, GBL 5.36 g, BCS 4.00 g, and contain 1% by weight 0.64 g of GBL solution of AD-1 was stirred with a magnetic stir bar for 30 minutes to obtain a liquid crystal alignment agent (A-2). [Comparative Example 3] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-2 and 4.27 g of PAA-6, add NMP 4.40 g, GBL 5.36 g, BCS 4.00 g, and contain 1% by weight 0.64 g of GBL solution of AD-2 was stirred with a magnetic stir bar for 30 minutes to obtain a liquid crystal alignment agent (A-3). [Comparative Example 4] In a 20 ml sample tube equipped with a stir bar, weigh 2.00 g of PAA-8 and 6.40 g of PAA-9, add 1.60 g of NMP, 5.04 g of GBL, 4.00 g of BCS, and contain 1% by weight. 0.96 g of GBL solution of AD-2 was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (A-4). [Example 1] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-3 and 4.27 g of PAA-6, add NMP 4.40 g, GBL 5.36 g, BCS 4.00 g, and contain 1% by weight 0.64 g of GBL solution of AD-2 was stirred with a magnetic stir bar for 30 minutes to obtain a liquid crystal alignment agent (B-1). [Example 2] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-3 and 4.27 g of PAA-6, add 4.16 g of NMP, 5.36 g of GBL, 4.00 g of BCS, and contain 1% by weight 0.64 g of GBL solution of AD-2 and 0.24 g of NMP solution containing 10% by weight of AD-3 were stirred with a magnetic stirrer for 30 minutes to prepare a liquid crystal alignment agent (B-2). [Example 3] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-3 and 4.27 g of PAA-7, add NMP 4.40 g, GBL 5.36 g, BCS 4.00 g, and contain 1% by weight 0.64 g of GBL solution of AD-2 was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (B-3). [Example 4] In a 20 ml sample tube with a stir bar, weigh 1.33 g of PAA-3 and 4.27 g of PAA-7, add 4.16 g of NMP, 5.36 g of GBL, 4.00 g of BCS, and contain 1% by weight 0.64 g of GBL solution of AD-2 and 0.24 g of NMP solution containing 10% by weight of AD-3 were stirred with a magnetic stirrer for 30 minutes to prepare a liquid crystal alignment agent (B-4). Using the liquid crystal alignment agent obtained as described above, evaluations of BL resistance, accumulated charge relaxation characteristics, liquid crystal alignment stability, and abrasion resistance were performed. The results are shown in Table 1 below. [0213] [0214] As described above, the liquid crystal alignment film of the present invention shows good results regardless of any evaluation such as friction resistance, BL resistance evaluation, liquid crystal alignment stability evaluation, and afterimage disappearance time.

Claims (8)

一種液晶配向劑，其特徵為，含有下述(A)成份及(B)成份； 　　(A)成份：由含有下述式(1)之二胺的二胺成份與四羧酸衍生物成份進行反應而得的聚醯亞胺前驅體，及使該聚醯亞胺前驅體進行閉環反應而得的聚醯亞胺所成之群所選出之至少1種的聚合物，(式(1)中，R1 表示氫，或1價之有機基；Q1 表示碳數1至5之伸烷基；Cy為表示由氮環丁烷、吡咯啶、哌啶或伸六甲基亞胺所形成之脂肪族雜環的2價之基，該些之環部份可鍵結取代基；R2 及R3 各自獨立為1價之有機基；q及r各自獨立為0～4之整數；但，q與r之合計為2以上時，複數的R2 及R3 ，具有上述之定義) 　　(B)成份：具有2個以上下述式(2)所表示之部份結構，且分子量為2,500以下的化合物，(式(2)中，R1 為氫原子或碳數1～3之烷基，R2 及R3 各自獨立表示氫原子、碳數1～3之烷基，或＊3 -CH2 -O-R11 (R11 表示氫原子或碳數1～3之烷基，「＊3 」表示與R2 及R3 鍵結的碳原子之鍵結鍵)、「＊1 」及「＊2 」表示與其他原子之鍵結鍵)。A liquid crystal alignment agent, which is characterized by containing the following components (A) and (B); (A) component: a diamine component containing a diamine of the following formula (1) and a tetracarboxylic acid derivative component; A polyimide precursor obtained by the reaction and at least one polymer selected from the group consisting of polyimide obtained by subjecting the polyimide precursor to a ring-closing reaction, (In formula (1), R 1 represents hydrogen, or a monovalent organic group; Q 1 represents an alkylene group having 1 to 5 carbon atoms; Cy represents a group consisting of azetidine, pyrrolidine, piperidine, or hexamethylene A divalent radical of an aliphatic heterocyclic ring formed by an imine, and these ring portions may be bonded to a substituent; R 2 and R 3 are each independently a monovalent organic group; q and r are each independently 0 to An integer of 4; however, when the total of q and r is 2 or more, the plural R 2 and R 3 have the above definition) (B) component: it has 2 or more partial structures represented by the following formula (2) Compounds with a molecular weight below 2,500, (In formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or * 3 -CH 2 -OR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, “* 3 ” represents a bonding bond with a carbon atom to which R 2 and R 3 are bonded), “* 1 ” and “* 2 ” represent and Bonding of other atoms). 如請求項1之液晶配向劑，其中，前述式(1)之二胺為下述式(3)所表示者；(式(3)中，R1 為氫原子、甲基，或tert-丁氧基羰基；R2 及R3 各自獨立為氫原子或甲基；Q1 為碳數1～5之直鏈伸烷基)。The liquid crystal alignment agent according to claim 1, wherein the diamine of the aforementioned formula (1) is represented by the following formula (3); (In formula (3), R 1 is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group; R 2 and R 3 are each independently a hydrogen atom or a methyl group; Q 1 is a straight-chain extension of 1 to 5 carbon atoms. alkyl). 如請求項1或請求項2之液晶配向劑，其中，前述式(1)所表示之二胺的含有比例，相對於全二胺成份1莫耳，為1莫耳%～80莫耳%。The liquid crystal alignment agent according to claim 1 or claim 2, wherein the content ratio of the diamine represented by the aforementioned formula (1) is 1 mole% to 80 mole% relative to 1 mole of the total diamine component. 如請求項1或請求項2之液晶配向劑，其中，前述(B)成份之化合物，為由下述式所選出之至少1種的化合物；。For example, the liquid crystal alignment agent of claim 1 or claim 2, wherein the compound of the component (B) is at least one compound selected from the following formula; . 如請求項1或請求項2之液晶配向劑，其中，(C)成份尚含有含下述式(5)之構造單位的聚醯亞胺前驅體；(式(5)中，X2 為由四羧酸衍生物生成之4價有機基，Y2 為由二胺生成之2價有機基，R4 為氫原子或碳數1～5之烷基，Z1 及Z2 各自獨立為氫原子、可具有取代基的碳數1～10之烷基、碳數2～10之烯基或碳數2～10之炔基)。For example, the liquid crystal alignment agent of claim 1 or claim 2, wherein the component (C) further contains a polyimide precursor containing a structural unit of the following formula (5); (In formula (5), X 2 generated by the tetracarboxylic acid derivative tetravalent organic group, Y 2 is generated for the diamine divalent organic group, R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms of Z 1 and Z 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent). 如請求項5之液晶配向劑，其中，前述式(5)中之X2 為含有含下述構造的構造單位之聚醯亞胺前驅體；。The liquid crystal alignment agent according to claim 5, wherein X 2 in the aforementioned formula (5) is a polyimide precursor containing a structural unit having the following structure; . 一種液晶配向膜，其特徵為，由請求項1至請求項6中任一項之液晶配向劑所製得者。A liquid crystal alignment film, which is prepared by the liquid crystal alignment agent according to any one of claim 1 to claim 6. 一種液晶顯示元件，其特徵為，具備請求項7之液晶配向膜者。A liquid crystal display element comprising a liquid crystal alignment film according to claim 7.
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