TW201202343A

TW201202343A - Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal display element

Info

Publication number: TW201202343A
Application number: TW100115685A
Authority: TW
Inventors: Atsushi Baba; Katsuhiro Uchiyama
Original assignee: Jsr Corp
Priority date: 2010-05-06
Filing date: 2011-05-05
Publication date: 2012-01-16
Also published as: JP2011237483A; TWI504677B; JP5672762B2; CN102250626A; CN102250626B; KR20110123202A; KR101746042B1

Abstract

The present invention provides a liquid crystal orientating film, a liquid crystal orientating agent being suitable as material for forming the liquid crystal orientating film and a liquid crystal display element provided with the liquid crystal orientating film. The liquid crystal orientating film not only can minimize display quality degradation caused by deterioration in electrical properties even when continuous driving performed for a long time but also can be easily detached in reworking. This invention is a liquid crystal orientating agent which includes [A] at least one polymer selected from the group consisting of polyamic acids and polyimides and [B] imide ring-containing epoxy compounds represented by formula (I).

Description

201202343 六、發明說明：【發明所屬之技術領域】本發明關於適合作爲液晶配向膜的形成材料的液晶配向劑、由該液晶配向劑形成的液晶配向膜以及具有該液晶配向膜的液晶顯示元件。【先前技術】背景技術液晶顯示元件由於具有耗電量小'容易小型化和平板化等優點’所以在從行動電話等小型液晶顯示裝置到液晶電視等大畫面液晶顯示裝置的廣泛的用途中使用。就液晶顯示裝置的驅動模式而言，根據液晶分子的配向狀態的變化’已知具有扭曲向列型（TN型）' 超扭曲向列型（STN型）、面內切換型（IPS型）、垂直配向型（va型）等液晶胞的液晶顯示元件。在任何一種顯示模式中，液晶分子的配向狀態藉由液晶配向膜控制，所以液晶配向膜和成爲該液晶配向膜的材料的液晶配向劑的性質會給液晶顯示元件性質的表現帶來影響。就該液晶配向劑的材料而言，例如在專利文獻〗中公開了聚醯胺酸、聚醯亞胺、聚醯胺、聚酯等樹脂材料，特別是由以聚醯胺酸或聚醯亞胺爲材料的液晶配向劑形成的液晶配向膜和液晶的親和性、耐熱性、機械強度等優異，大量使用在液晶顯示元件中。然而’近年來’液晶顯示元件的利用範圍擴大，要求即使長時間連續驅動’顯示品質也不會降低的液晶顯示元 201202343 件，以目前的聚醯胺酸或聚醯亞胺爲材料的液晶顯示元件，在長時間連續驅動時，由於熱或光，可能會導致液晶配向膜變差，產生電性質變差、液晶分子的配向不佳等。爲了解決該問題，開發出了使用大量包含多官能環氧化合物的液晶配向劑的技術（參照日本第3 7 99 700號專利公報，曰本特開2008-299318號公報）。另一方面，包含了液晶配向膜的製造工序中產生的塗膜的氣孔、塗布不勻等缺陷的基板，爲了再次使用，可能要剝去薄膜（以下，也稱作“重新作業”。），在該重新作業中，要求液晶配向膜對基板有剝離性。然而，如果使用大量包含上述多官能的環氧基的液晶配向劑，則由於烘烤時的環氧基的交聯反應，有可能降低重新作業時液晶配向膜的剝離性。基於這種情況，希望開發出即使長時間連續驅動時，也可以抑制電性質的惡化等引起的顯示品質降低，而且在重新作業時容易剝離的液晶配向膜。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平4-153622號公報 [專利文獻2]日本特開昭60_ 1 07020號公報 [專利文獻3]日本特開昭56_91 277號公報 [專利文獻4]美國第5,928,733號專利公報 [專利文獻5]日本特開昭62-165628號公報 201202343 [專利文獻6 ]日本特開平丨丨_ 2 5 8 6 〇 5號公報 [專利文獻7]日本第3799700號專利 [專利文獻8 ]日本特開2 0 0 8 - 2 9 9 3 1 8號公報【發明内容】本發明是基於上述問題提出的，其目的在於：提供即使長時間連續驅動時，也可以抑制電性質的惡化等引起的顯示品質降低，而且重新作業時容易剝離的液晶配向膜，以及適合作爲形成該配向膜的材料的液晶配向劑，以及具有該液晶配向膜的液晶顯示元件。爲了解決上述問題而提出的本發明是一種液晶配向劑，其包含： [Α]由聚醯胺酸和聚醯亞胺構成的群組中選出的至少一種聚合物（以下，也稱作聚合物[Α])，以及 [Β]下述式（I)所示的含醯亞胺環的環氧化合物（以下，也稱作環氧化合物[Β ])。 Ο[Technical Field] The present invention relates to a liquid crystal alignment agent suitable as a material for forming a liquid crystal alignment film, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] The liquid crystal display device is used in a wide range of applications from a small liquid crystal display device such as a mobile phone to a large-screen liquid crystal display device such as a liquid crystal television, because it has a small power consumption and is easy to be miniaturized and flattened. . Regarding the driving mode of the liquid crystal display device, it is known that there is a twisted nematic (TN type) super twisted nematic (STN type), in-plane switching type (IPS type), depending on the change in the alignment state of the liquid crystal molecules. A liquid crystal display element of a liquid crystal cell such as a vertical alignment type (va type). In any of the display modes, the alignment state of the liquid crystal molecules is controlled by the liquid crystal alignment film, so that the properties of the liquid crystal alignment film and the liquid crystal alignment agent which becomes a material of the liquid crystal alignment film affect the performance of the liquid crystal display element. As the material of the liquid crystal alignment agent, for example, in the patent literature, a resin material such as polyacrylic acid, polyimine, polyamine, or polyester is disclosed, in particular, polyglycine or polyruthenium. The liquid crystal alignment film formed of the liquid crystal alignment agent of the material is excellent in affinity, heat resistance, mechanical strength, and the like of the liquid crystal, and is used in a large amount in liquid crystal display elements. However, the use range of 'liquid crystal display elements' has been expanded in recent years, and it is required to continuously drive the liquid crystal display element 201202343 which does not degrade the display quality even for a long time, and liquid crystal display using current polyaminic acid or polyimine. When the element is continuously driven for a long period of time, heat or light may cause deterioration of the liquid crystal alignment film, deterioration of electrical properties, poor alignment of liquid crystal molecules, and the like. In order to solve this problem, a technique of using a large amount of a liquid crystal alignment agent containing a polyfunctional epoxide has been developed (refer to Japanese Laid-Open Patent Publication No. 2008-299318). On the other hand, a substrate including defects such as pores and uneven coating of the coating film which are generated in the production process of the liquid crystal alignment film may be peeled off for reuse (hereinafter, also referred to as "rework"). In this rework, the liquid crystal alignment film is required to have releasability to the substrate. However, if a large amount of the liquid crystal alignment agent containing the above polyfunctional epoxy group is used, the crosslinking property of the liquid crystal alignment film at the time of rework may be lowered due to the crosslinking reaction of the epoxy group at the time of baking. In view of the above, it is desired to develop a liquid crystal alignment film which is capable of suppressing deterioration in display quality due to deterioration of electrical properties or the like even when continuously driven for a long period of time, and which is easily peeled off during rework. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 62-165628. [Patent Document 8] Japanese Patent Laid-Open Publication No. Hei 2 0 0 8 - 2 9 9 3 1 8 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a continuous driving for a long period of time, It is also possible to suppress a deterioration in display quality due to deterioration of electrical properties, and a liquid crystal alignment film which is easily peeled off during rework, a liquid crystal alignment agent which is suitable as a material for forming the alignment film, and a liquid crystal display element having the liquid crystal alignment film. The present invention proposed to solve the above problems is a liquid crystal alignment agent comprising: [Α] at least one polymer selected from the group consisting of polyproline and polyimine (hereinafter also referred to as a polymer) [Α]), and [Β] an oxime ring-containing epoxy compound represented by the following formula (I) (hereinafter also referred to as an epoxy compound [Β]). Ο

式（I)中，ra是單鍵或碳原子數爲 1〜4的烷二基 (alkanedily)。RB是2價的鏈狀烴基、2價的脂環烴基、2 價的芳香族基、2價的雜環基、或組合它們形成的基。η是〇或1的整數。 201202343 該液晶配向劑藉由含有特定的聚合物[A]和環氧化合物[B]，可以形成：抑制由電性質惡化等導致的顯示品質降低，而且重新作業時容易剝離的液晶配向膜。 .上述式（I)較佳爲由下述式（1-1)和式（1-2)所示的化合物構成的群組中選出的至少一種。In the formula (I), ra is a single bond or an alkanedily having 1 to 4 carbon atoms. RB is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, a divalent heterocyclic group, or a group formed by combining them. η is an integer of 〇 or 1. 201202343 By containing a specific polymer [A] and an epoxide [B], the liquid crystal alignment agent can form a liquid crystal alignment film which is suppressed from deterioration in display quality due to deterioration in electrical properties and the like, and which is easily peeled off during rework. The above formula (I) is preferably at least one selected from the group consisting of compounds represented by the following formula (1-1) and formula (1-2).

(1-2) 式（1-1)和式（1-2)中，RA和上述式（I)的定義相同。Rl、 R2和R3各自獨立，爲可以包含- 〇-、-C〇〇-、-OCO-的碳原子數爲1~2 0的直鏈狀或支鏈狀的烷基。另外’ Rl和r2、或者R 1和R2和R3相互連接，形成氫原子的—部分或全部可以被取代的環結構。η是0或1的整數。藉由選取上述式（I)爲特定的化合物’可以形成：抑制由電性質的惡化等導致顯示品質降低，而且重新作業時容易剝離的液晶配向膜。上述聚合物[Α]較佳爲由聚醯胺酸和將該聚醯胺酸脫水閉環形成的聚醯亞胺構成的群組中選出的至少—種’其中聚醯胺酸使用四羧酸二酐來合成’該四殘酸二野包含由 2,3,5-三羧基環戊基乙酸二酐、3,5,6-三羧基-2-殘甲基降萡 201202343 院-2:3,5:6-二酐和 2，4,6,8-四羧基雙環[3.3.0]-辛烷 -2 :4,6 ·· 8-二酐構成的群組中選出的至少—種。藉由使用這種特定化合物合成的聚合物[A]作爲四羧酸二酐，可以進一步顯現出所希望的性質。上述式（I)的RA較佳爲甲烷二基（methanediyl)。另外，在上述式（1-1)和式（I-2)中，R1和R2較佳係相互連接，形成氫原子的一部分或全部可以被取代的苯環。環氧化合物 [B]藉由具有上述特定結構，可以進一步提高電性質和重新作業時的剝離性。本發明的液晶顯示元件具有由該液晶配向劑形成的液晶配向膜。該液晶顯示元件適合用於各種裝置，例如可以在鐘錶、便攜型遊戲機、文字處理器、筆記型電腦、導航系統、可攜式攝影機、便攜資訊終端、數位相機' 行動電話、各種監視器、液晶電視等顯示裝置中使用。一種聚合物組成物，其包含：[A]由聚醯胺酸和聚醯亞胺構成的群組中選出的至少一種聚合物，以及[B]下述式（I) 所示的含醯亞胺環的環氧化合物。 Ο(1-2) In the formula (1-1) and the formula (1-2), RA is the same as defined in the above formula (I). Rl, R2 and R3 are each independently a linear or branched alkyl group having a carbon number of 1 to 20 which may contain -〇-, -C〇〇-, -OCO-. Further, 'R1 and r2, or R 1 and R 2 and R 3 are bonded to each other to form a ring structure in which a part or all of a hydrogen atom may be substituted. η is an integer of 0 or 1. By selecting the above formula (I) as a specific compound ', it is possible to form a liquid crystal alignment film which suppresses deterioration in display quality due to deterioration in electrical properties and the like, and which is easily peeled off during rework. The above polymer [Α] is preferably at least one selected from the group consisting of polylysine and polyamidene formed by dehydration of the polyglycolic acid. The polyphthalic acid is tetracarboxylic acid. The anhydride is used to synthesize 'the four-residual acid dimer consists of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-resin methyl group 萡201202343 院-2:3, At least one selected from the group consisting of 5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]-octane-2:4,6·8 dianhydride. By using the polymer [A] synthesized by using this specific compound as the tetracarboxylic dianhydride, the desired properties can be further revealed. The RA of the above formula (I) is preferably methanediyl. Further, in the above formula (1-1) and formula (I-2), R1 and R2 are preferably bonded to each other to form a benzene ring in which a part or all of a hydrogen atom may be substituted. The epoxy compound [B] can further improve the electrical properties and the releasability at the time of rework by having the above specific structure. The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent. The liquid crystal display element is suitable for use in various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a navigation system, a camcorder, a portable information terminal, a digital camera, a mobile phone, various monitors, Used in display devices such as LCD TVs. A polymer composition comprising: [A] at least one polymer selected from the group consisting of polyproline and polyimine, and [B] a yttrium represented by the following formula (I) An epoxy compound of an amine ring. Ο

、/η 式U)中，ra是單鍵或碳原子數爲1〜4的烷二基。rb 是2價的鏈狀烴基、2價的脂環烴基、2價的芳香族基、2 201202343 價的雜環基、或組合它們形成的基。η是〇或1的整數。該聚合物組成物適合作爲用於形成液晶配向膜的液晶配向劑等的成分使用。另外’由該聚合物組成物形成的膜還可以作爲電子材料用絕緣膜使用。根據本發明，可以形成：抑制由電性質的惡化等導致顯示品質降低，而且重新剝離時容易剝離的液晶配向膜。該液晶顯示元件適合用於各種裝置，例如可以在鐘錶、便攜型遊戲機、文字處理器、筆記型電腦 '導航系統、可攜式攝影機、便攜資訊終端、數位相機、行動電話、各種監視器、液晶電視等顯示裝置中使用。【實施方式】以下’對本發明的實施方案進行詳細描述。 <液晶配向劑> 本發明的液晶配向劑含有聚合物[Α]和環氧化合物 [Β]。該液晶配向劑藉由含有特定的聚合物[Α]和環氧化合物[Β] ’可以形成：抑制由電性質的惡化等導致之顯示品質降低’且重新剝離時容易剝離的液晶配向膜。此外，只要不損害本發明效果，該液晶配向劑可以含有任意成分。以下’對聚合物[Α]、環氧化合物[Β]和任意成分進行詳細描述。 <聚合物[Α]> 本發明的液晶配向劑中含有的聚合物[Α]是由聚醯胺酸和聚醯亞胺構成的群組中選出的至少一種聚合物。以下’對聚醯胺酸和聚醯亞胺進行詳細描述。 201202343 [聚醯胺酸] 聚醯胺酸可以藉由使四羧酸二酐和二胺化合物反應得到。就四羧酸二酐而言，可以列舉出例如脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。除此以外，還可以使用日本特願2009-157556號中記載的四羧酸二酐。這些四羧酸二酐可以單獨或組合兩種以上使用。就脂肪族四羧酸二酐而言，可以列舉出例如丁四羧酸二酐等。就脂環式四羧酸二酐而言，可以列舉出例如1，2,3,4-環丁四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、 1，3,3&，4,5,915-六氫-5-(四氫-2,5-二氧-3-呋喃基）-萘并 [l，2-c]咲喃-1,3-二嗣、l，3,3a，4,5,9b-六氮-8-甲基- 5- (四氮 -2,5-二氧-3-呋喃基）-萘并[l，2-c]呋喃-1,3-二酮、3-氧雜雙環[3· 2.1]辛-2,4-二酮-6-螺-3’-(四氫呋喃-2，，5，-二酮）、 5-(2,5-二氧四氫-3-呋喃基）-3-甲基-3-環己烯-1，2-二羧酸酐、3,5,6-三羧基-2-羧甲基降萡烷-2:3,5:6-二酐、2,4,6,8-四羧基雙環[3.3.0〕辛烷-2:4,6:8-二酐、4,9-二氧雜三環 [5.3.1.〇2’6]十一碳-3,5,8，10-四酮等。就芳香族四羧酸二酐而言，可以列舉出例如均苯四羧酸二酐等。這些四羧酸二酐中，較佳係脂環式四羧酸二酐、芳香族四羧酸二酐’更佳係2,3,5-三羧基環戊基乙酸二酐、 -10- 201202343 3,5,6-三羧基-2-羧甲基降萡烷-2:3,5:6-二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、1，3,3&，4,5,91)-六氫-8-甲基-5-(四氫-2,5-二氧-3-呋喃基）-萘并[l，2-c]呋喃-1,3-二酮、1,2,3,4 -環丁四羧酸二酐、均苯四羧酸二酐，特佳係 2,3,5·三羧基環戊基乙酸二酐。藉由使用由這種特定化合物合成的聚合物[A]作爲四羧酸二酐，可以進一步顯現出所希望的性質。作爲較佳的四羧酸二酐的用量，相對於全部四羧酸二酐，較佳係含1 0 m ο 1 %以上，更佳爲2 0 m ο 1 %以上，特佳係只使用由2,3,5-三羧基環戊基乙酸二酐、l，3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧-3-呋喃基）-萘并[1,2-c]呋喃 -1,3-二酮、1，2,3,4_環丁四羧酸二酐構成的群組中選出的一種以上。就二胺化合物而言，可以列舉出例如脂肪族二胺、脂環式二胺、二胺基有機矽氧烷、芳香族二胺等。除此以外，還可以使用日本特願2009- 1 5755 6號中記載的二胺化合物。這些二胺化合物可以單獨或組合兩種以上使用。就脂肪族二胺而言，可以列舉出例如1,3-丙二胺、1,4-丁二胺、1，5 -戊二胺、1，6 -己二胺等。就脂環式二睽而言，可以列舉出例如1，4 -二胺基環己院、4,4’-亞甲基雙（環己基胺）、ι，3_雙（胺基甲基）環己院等。就二胺基有機矽氧烷而言，可以列舉出例如1，3 -雙（3 -胺基丙基）-四甲基二矽氧烷等。 -11- 201202343 就芳香族二胺而言，可以列舉出例如對苯二胺、4,4 ’ -二胺基二苯基甲烷、4,4’-二胺基二苯基硫醚、1,5-二胺基萘、2,2’-二甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙（三氟甲基）聯苯、2,7-二胺基芴、4,4’-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基）苯基]丙烷、9,9-雙（4-胺基苯基）芴、 2,2-雙[4-(4-胺基苯氧基）苯基]六氟丙烷、2,2-雙（4-胺基苯基）六氟丙烷、4,4’-(對伸苯二亞異丙基）雙（苯胺）、4,4’-(間伸苯二亞異丙基）雙（苯胺）、I，4-雙（4-胺基苯氧基）苯、3,4-二胺基吡啶、4,4’-雙（4-胺基苯氧基）聯苯、3,6-二胺基咔唑、2，6 -二胺基吡啶、2，4 -二胺基嘧啶、3，6 -二胺基吖啶、 N -甲基-3,6 -二胺基咔唑、N -乙基-3,6 -二胺基昨唑、1,4 -雙 (4-胺基苯基）哌阱、3,5-二胺基苯甲酸、N-苯基- 3,6-二胺基咔唑、Ν,Ν’-雙（4-胺基苯基）-聯苯胺、N，N’-雙（4-胺基苯基）-Ν,Ν’-二甲基聯苯胺、十二烷氧基-2,4-二胺基苯、十四烷氧基-2,4-二胺基苯、十五烷氧基-2,4-二胺基苯、十六烷氧基-2,4 -二胺基苯、十八烷氧基-2,4 -二胺基苯、十二烷氧基-2,5 -二胺基苯、十四烷氧基-2,5 -二胺基苯、十五烷氧基 -2,5-二胺基苯、十六烷氧基-2,5-二胺基苯、十八烷氧基 -2,5-二胺基苯、膽甾烷氧基-3, 5-二胺基苯、膽甾烯氧基 -3,5-二胺基苯、膽甾烷氧基-2,4-二胺基苯、膽甾烯氧基 -2,4-二胺基苯、3，5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、_ 3,6-雙（4-胺基苯甲醯氧基）膽甾烷、3,6-雙（4_胺基苯氧基）膽甾 -12- 201202343 烷、4-(4三氟甲氧基苯甲醯氧基）環己基-3, 5-二胺基苯甲酸酯、4-(4，·三氟甲基苯甲醯氧基）環己基-3,5-二胺基苯甲酸酯、1，1-雙（4-((胺基苯基）甲基）苯基）-4-丁基環己烷、1，1-二（4-((胺基苯基）甲基）苯基）-4-庚基環己烷、1，1-雙（I((胺基苯氧基）甲基）苯基）_4-庚基環己烷、1，1-雙（4-((胺基苯基）甲基）苯基）-4-(4-庚基環己基）環己烷、2,4-二胺基-N，N-二烯丙基苯胺、4-胺基苄基胺、3-胺基苄基胺和下述式（1)所示的二胺化合物等。, /η In the formula U), ra is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Rb is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, a 2 201202343 valent heterocyclic group, or a group formed by combining them. η is an integer of 〇 or 1. The polymer composition is suitably used as a component of a liquid crystal alignment agent or the like for forming a liquid crystal alignment film. Further, the film formed of the polymer composition can also be used as an insulating film for electronic materials. According to the present invention, it is possible to form a liquid crystal alignment film which is suppressed from being deteriorated in display quality due to deterioration in electrical properties and the like, and which is easily peeled off upon re-peeling. The liquid crystal display element is suitable for use in various devices, such as a clock, a portable game machine, a word processor, a notebook computer navigation system, a portable video camera, a portable information terminal, a digital camera, a mobile phone, various monitors, Used in display devices such as LCD TVs. [Embodiment] Hereinafter, embodiments of the invention will be described in detail. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains a polymer [Α] and an epoxy compound [Β]. The liquid crystal alignment agent can be formed by containing a specific polymer [Α] and an epoxide [Β], a liquid crystal alignment film which suppresses deterioration in display quality due to deterioration of electrical properties, and is easily peeled off upon re-peeling. Further, the liquid crystal alignment agent may contain an optional component as long as the effects of the present invention are not impaired. The polymer [Α], the epoxy compound [Β] and optional components are described in detail below. <Polymer [Α]> The polymer [Α] contained in the liquid crystal alignment agent of the present invention is at least one polymer selected from the group consisting of polyglycolic acid and polyimine. The poly-proline and polyimine are described in detail below. 201202343 [Polyuric acid] Polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound. The tetracarboxylic dianhydride may, for example, be an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride. In addition, the tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can also be used. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types. The aliphatic tetracarboxylic dianhydride may, for example, be tetrabutyl carboxylic acid dianhydride or the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3. ,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]pyran-1,3-dioxene, l ,3,3a,4,5,9b-hexanitro-8-methyl-5-(tetrazo-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1 , 3-dione, 3-oxabicyclo[3·2.1]octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5,-dione), 5-(2, 5-dihydrotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane- 2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo [5.3.1.〇2'6] Eleven-3,5,8,10-tetraketone, etc. The aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride or the like. Among these tetracarboxylic dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides. More preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, -10-201202343 3,5,6-Tricarboxy-2-carboxymethylnordecane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2: 4,6:8-dianhydride, 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphtho[l,2-c]furan-1,3-dione, 1,2,3,4-cyclotetracarboxylic dianhydride, pyromellitic dianhydride, especially good 2,3,5 · Tricarboxycyclopentyl acetic acid dianhydride. By using the polymer [A] synthesized from such a specific compound as the tetracarboxylic dianhydride, the desired properties can be further exhibited. The amount of the tetracarboxylic dianhydride to be used is preferably 10 m ο 1 % or more, more preferably 20 ο % or more, based on the total amount of the tetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3- One or more selected from the group consisting of furyl)-naphtho[1,2-c]furan-1,3-dione and 1,2,3,4-cyclotetracarboxylic dianhydride. The diamine compound may, for example, be an aliphatic diamine, an alicyclic diamine, a diamine organosiloxane or an aromatic diamine. In addition to the above, the diamine compound described in Japanese Patent Application No. 2009-155755 can also be used. These diamine compounds can be used individually or in combination of 2 or more types. The aliphatic diamine may, for example, be 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine or hexamethylenediamine. Examples of the alicyclic dioxime include 1,4 -diaminocyclohexan, 4,4'-methylenebis(cyclohexylamine), iota, 3-bis(aminomethyl) The ring home and so on. Examples of the diamine organooxosiloxane include 1,3 -bis(3-aminopropyl)-tetramethyldioxane and the like. -11- 201202343 For the aromatic diamine, for example, p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1, 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl , 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-double (4-Aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylene isopropylidene) bis(aniline), 4,4'-(m-phenylene isopropylidene)bis(aniline), I,4-bis(4-amine Phenoxy)benzene, 3,4-diaminopyridine, 4,4'-bis(4-aminophenoxy)biphenyl, 3,6-diaminocarbazole, 2,6-diamine Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diamine Azole, 1,4-bis(4-aminophenyl)piped, 3,5-diaminobenzoic acid, N-phenyl-3,6-diaminocarbazole, oxime, Ν'-double ( 4-aminophenyl)-biphenyl , N,N'-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2, 4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diamino Benzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecane Oxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3, 5-diaminobenzene, cholesteneoxy-3, 5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl Ester, cholesteryl 3,5-diaminobenzoic acid, lanthanum alkyl 3,5-diaminobenzoic acid, _ 3,6-bis(4-aminobenzylideneoxy) cholate Decane, 3,6-bis(4-aminophenoxy)cholester-12- 201202343 alkane, 4-(4trifluoromethoxybenzyloxy)cyclohexyl-3, 5-diamino Benzoate, 4-(4,·trifluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl) )methyl) Phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(I(I) (aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptyl) Cyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and the formula (1) below Diamine compounds and the like.

或- OCO-°a是〇或1。1)是0~2的整數。c是1〜20的整數。在上述式（1)中，就C<；H2e + 1基的具體例子而言，可以列舉出例如直鏈狀或支鏈狀的甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。就上述式（1)所示的二胺化合物而言，可以列舉出例如下述式（1-1)〜（I-5)所示的化合物等。 -13- 201202343Or - OCO-°a is 〇 or 1. 1) is an integer from 0 to 2. c is an integer from 1 to 20. In the above formula (1), specific examples of the C<;H2e + 1 group include, for example, a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , heptyl, octyl, decyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nineteen Alkyl, eicosyl, and the like. The diamine compound represented by the above formula (1) may, for example, be a compound represented by the following formulas (1-1) to (I-5). -13- 201202343

上述式（1)中，a和b較佳係不同時爲〇。這些二胺化合物中’較佳係芳香族二胺、二胺基有機矽氧烷，更佳係對苯二胺、4,4, _二胺基二苯基甲烷、2，2，-二甲基-4，4’-二胺基聯苯、3,6-二（4-胺基苯甲醯氧基）膽甾烷、3,5-二胺基苯甲酸膽甾烷基酯、膽甾烷氧基-2,4_二胺基苯、1，3-雙（3-胺基丙基）-四甲基二矽氧烷。 [聚醯胺酸的合成] 就聚醯胺酸的合成反應中使用的四羧酸二酐和二胺化合物的使用比例而言，相對於1當量二胺化合物中含有的 -14- 201202343 胺基’四羧酸二酐的酸酐基較佳係0.2當量〜2當量，更佳係0.3當量〜1.2當量。聚醯胺酸的合成反應較佳係在有機溶劑中進行。就反應溫度而言，較佳爲- 20°C〜150°C，更佳爲0°C〜100。(：。就反應時間而言，較佳爲〇. 1小時〜24小時，更佳爲〇.5小時〜1 2小時。就有機溶劑而言，只要是可以溶解合成的聚醯胺酸就沒有特別的限制，可以列舉出例如非質子性極性溶劑、酚及其衍生物、醇類、醚類、鹵化烴類、烴類等。這些有機溶劑可以單獨使用一種或使用將兩種以上一起使用。就非質子性極性溶劑而言，可以列舉出例如醯胺類、酮類、酯類、其他非質子性極性溶劑。就醯胺類而言，可以列舉出例如N -甲基-2 -吡咯啶酮 (NMP)、Ν,Ν-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺等。就酮類而言’可以列舉出例如丙酮、甲乙酮、甲基異丁基酮、環己酮等。就酯類而言’可以列舉出例如乳酸乙酯、乳酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙酯、丙二酸二乙酯、γ-丁內酯 '丙酸異戊基酯、異丁酸異戊基酯等。就其他非質子性極性溶劑而言，可以列舉出例如二甲基亞楓、四甲基脲、八甲基憐酿二胺等。就苯酚衍生物而言，可以列舉出例如間甲酚、二甲苯 •15- 201202343 酣、鹵化苯酣等。就醇類而言，可以列舉出例如甲醇、乙醇、異丙環己醇、乙二醇、丙二醇、1，4_丁二醇、三甘醇、乙單甲基醚、二乙二醇單甲基醚、二乙二醇單乙基醚等就醚類就而言，可以列舉出例如二乙基醚、乙二甲基醚、乙二醇二乙基醚、乙二醇二正丙基醚、乙二異丙基醚、乙二醇二正丁基醚 '乙二醇單乙基醚乙酸二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單醚乙酸酯、二乙二醇單乙基醚乙酸酯、四氫呋喃、二基醚等。就鹵化烴類就而言，可以列舉出例如二氯甲烷、二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯萍就烴類就而言，可以列舉出例如己烷、庚烷、辛苯、甲苯、二甲苯等。在這些有機溶劑中，較佳係非質子性極性溶劑，係ΝΜΡ、γ-丁內酯。相對於四羧酸二酐和二胺化合物的總量（b)與有劑的用量（a)的總量（a + b)，就有機溶劑的用量（a)而言爲0.1重量％~50重星％。反應後得到的聚醯胺酸溶液可以直接用於製備液向劑，也可以在分離反應溶液中包含的聚醯胺酸後，製備液晶配向劑，或者將分離的聚醯胺酸精製後，用備液晶配向劑。就聚醯胺酸的分離方法而言，可以列醇、二醇〇醇二醇二. 酯、甲基異戊 1,2- 等。烷、更佳機溶較佳晶配用於於製舉出 -16- 201202343 大入注；液法㈣方應的反物將出如析例的到法得方燥的乾液下溶壓應減反 ’ 出中劑溶良不的餾壓減器發蒸由藉胺解醯溶聚次爲再作酸。胺等醯法方製精的酸中劑溶機有到聚方的的出出離析分中將劑出溶舉良列不 W在可等劑溶機有出餾壓減器發蒸由藉次多或次 _ ο 行法進方複的重驟 ; 步法的時酸安二醯和聚酐成二合酸在羧四與物合化胺 ’ 合劑聚節型調飾量修子端分末的成當合適，用使以可起的胺明單發、 Η 干才。酉害 } 單損Itt酸不刷如以(ep例可性出 , 布舉物塗列合的以聚劑可型向，飾配一三口修晶而端液劑末善節該改調成步量形一子由進分藉地就。果物效化合物、單異氰酸酯化合物等。就酸單酐而言，可以列舉出例如馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐、正十六烷基琥珀酸酐等。就單胺化合物而言，可以列舉出例如苯胺、環己基胺、正丁胺、正戊胺、正己胺、正庚胺、正辛基胺等。就單異氰酸酯化合物而言，可以列舉出例如異氰酸苯基酯、異氰酸萘基酯等。就分子量調節劑的使用比例而言，相對於四羧酸二酐和二胺總計1 0 0質量份’較佳爲2 0質量份0下’更佳爲 1 0質量份以下。 [聚醯亞胺] -17- 201202343 聚醯亞胺可藉由將上述聚醯胺酸所具有的醯胺酸結_ 脫水閉環醯亞胺化製造" 聚醯亞胺可以是作爲其前質的聚醯胺酸所具有的醯月安酸結構全部脫水閉環的完全醯亞胺化物；也可以只是_月安酸結構的一部分脫水閉環，醯胺酸結構和醯亞胺環結構& 存的部分醯亞胺化物。這裏，醯亞胺環的一部分可以是異醯亞胺環。聚醯亞胺的醯亞胺化率較佳爲 3 0 %以上，更佳爲 40%〜99%。所述的醯亞胺化率，是以百分率表示醯亞胺環結構的數量佔據聚醯亞胺的醯胺酸結構的數量和醯亞胺環結構的數量的總量的比例。另外，醯亞胺化率是將聚_亞胺的溶液投入到純水中，回收得到的沉澱物，在室溫下減壓乾燥後，將其溶解到重氫化二甲基亞颯中，以四甲基砂烷作爲基準物質，從室溫下測定1H-NMR得到的i-NMR 譜圖，藉由下述式（2)所示的式子求得。醯亞胺化率（％) = {IJAWa^xo^xIOO (2) 式（2)中’ A1是來自NH基的質子的峰面積（i〇ppm)。 A2是來自其他質子的峰面積。α是其他質子的個數相對於一個聚醯胺酸中的ΝΗ基的質子的比例。就聚醯亞胺的合成方法而言，可以列舉出例如（i)加熱聚醯胺酸的方法，（ii)將聚醯胺酸溶解在有機溶劑中，在該溶液中添加脫水劑和脫水閉環催化劑，根據需要加熱的方法.(以下，也稱作“方法（ii))等藉由聚醯胺酸的脫水閉環反 -18- 201202343 應進行的方法。這些方法中，較佳係方法（ii)。就方法（i i)中的脫水劑而言，可以列舉出例如乙酸酐、丙酸酐、三氟乙酸酐等酸酐。就脫水劑的用量而言’根據所希望的醯亞胺化率適當選擇，相對於1 m 01聚醯胺酸的醯胺酸結構，較佳爲 O.Olmol〜20mol 0 就方法（ii)中的脫水閉環催化劑而言，可以列舉出例如卩比陡、三甲基卩比陡 '二甲基卩比D定 '三乙胺等第三胺。就脫水閉環催化劑的用量而言，相對於lm〇l含有的脫冰劑，較佳爲0 · 0 1 m ο 1〜1 〇 m ο 1。就方法（ii)中使用的有機溶劑而言，可以列舉出與下述有機溶劑相同的有機溶劑等，該有機溶劑在例如作爲合成聚醯胺酸使用的溶劑而例示。就方法（Π)中的反應溫度而言，較佳爲0 °c〜1 8 0 °c，更佳爲l〇°C 〜150°C。就反應時間而言，較佳爲1.0小時〜120 小時，更佳爲2.0小時〜30小時。藉由使反應條件爲上述範圍，脫水閉環反應充分進行，而且可以使得到的聚醯亞胺的分子量適當。在方法（ii)中，可以得到含有聚醯亞胺的反應溶液。該反應溶液可以直接用於製備液晶配向劑，也可以從反應溶液除去脫水劑和脫水閉環催化劑後，用於製備液晶配向劑；還可以分離聚醯亞胺後，用於製備液晶配向劑；或者將分離的聚醯亞胺精製後，用於製備液晶配向劑。就從反 -19- 201202343 應溶液除去脫水劑和脫水閉環催化劑的方法而言，可以根據公知的方法進行，可以列舉出：例如和例示作爲聚醯胺酸的分離方法和精製方法的同樣的方法等。就以上得到的聚合物[A]的濃度爲10質量％的溶液中的溶液黏度而言，較佳爲20mPa*s~800mPa‘s，更佳爲30mPa •s〜500mPa‘s»聚合物的溶液黏度（mPa_s)是對使用γ-丁內酯或ΝΜΡ製備的濃度10質量％的聚合物溶液，使用Ε型旋轉黏度計，在2 5 °C下測定的値。 <環氧化合物[B]> 本發明的液晶配向劑中含有的環氧化合物[B]是上述式（I)所示的含醯亞胺環的環氧化合物。上述式（I)中，RA是單鍵或碳原子數爲1〜4的烷二基。 RB是2價的鏈狀烴基、2價的脂環烴基、2價的芳香族基、 2價的雜環基、.或組合它們形成的基。η是0或1的整數。作爲碳原子數爲1〜4的烷二基，可以列舉出例如甲烷二基、乙二基、丙二基、丁二基等。它們之中，較佳係單鍵或甲烷二基。上述式（I)較佳爲選自由上述式（1-1)和式（1-2)所示的化合物構成的群組的至少一種。藉由選取上述式（I)爲特定的化合物，可以形成：抑制由電性質的惡化等導致之顯示品質降低，而且重新作業時容易剝離的液晶配向膜。上述式（卜1)和式U·2)中，RA和上述式（I)的定義相同。 R1、R2和R3各自獨立’是可以包含- 〇-、-COO-、-OCO- -20- 201202343 的碳原子數爲idO的直鏈狀或支鏈狀的和R ’或者R1和R 2和R 3可以相互連接，部分或全部被取代的環結構。η是0或1 | 就碳原子數爲1〜2 0的直鏈狀或支鏈狀以列舉出··例如甲基、乙基、丙基、丁基、基、辛基、壬基、癸基、月桂基、十二烷十四烷基、十五烷基、十六烷基、十七烷十九烷基 '二十烷基等。它們之中，較佳丙基。In the above formula (1), a and b are preferably not simultaneously 〇. Among these diamine compounds, 'preferably an aromatic diamine, a diamine organooxane, more preferably a p-phenylenediamine, a 4,4,-diaminodiphenylmethane, a 2,2,-dimethyl group. Base-4,4'-diaminobiphenyl, 3,6-bis(4-aminobenzylideneoxy)cholestane, cholesteryl 3,5-diaminobenzoate, cholesteric Alkoxy-2,4-diaminobenzene, 1,3-bis(3-aminopropyl)-tetramethyldioxane. [Synthesis of Polyamine] The ratio of the use of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyglycine is 14-201202343 amine group contained in 1 equivalent of the diamine compound. The acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 equivalent to 2 equivalents, more preferably 0.3 equivalents to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent. In terms of the reaction temperature, it is preferably - 20 ° C to 150 ° C, more preferably 0 ° C to 100 °. (: In terms of reaction time, it is preferably 〇. 1 hour to 24 hours, more preferably 〇5 hours to 12 hours. In terms of organic solvent, as long as it is a polylysine which can dissolve the synthesis, there is no The specific limitation is, for example, an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. These organic solvents may be used alone or in combination of two or more. Examples of the aprotic polar solvent include guanamines, ketones, esters, and other aprotic polar solvents. Examples of the guanamines include N-methyl-2-pyrrolidine. Ketone (NMP), hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, etc. Examples of the ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and a ring. Examples of the esters include, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Diethyl oxalate, diethyl malonate, γ-butyrolactone, isoamyl propionate, isobutyric acid Examples of the other aprotic polar solvent include dimethyl sulfoxide, tetramethyl urea, and octamethyl phenol diamine. Examples of the phenol derivative include, for example, phenol derivatives. M-cresol, xylene, 15-201202343, hydrazine, etc. Examples of the alcohols include methanol, ethanol, isopropylcyclohexanol, ethylene glycol, propylene glycol, and 1,4-butanediol. And triethylene glycol, ethylene monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc., as the ether, for example, diethyl ether, ethylene glycol ether , ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene diisopropyl ether, ethylene glycol di-n-butyl ether 'ethylene glycol monoethyl ether acetic acid diethylene glycol dimethyl ether , diethylene glycol diethyl ether, diethylene glycol monoether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dialkyl ether, etc. As far as halogenated hydrocarbons are concerned, For example, dichloromethane, dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, and o-dichloropethane are, for example, hexane, Heptane, octylbenzene, toluene, xylene, etc. Among these organic solvents, preferred are aprotic polar solvents, ruthenium, γ-butyrolactone, relative to the total amount of tetracarboxylic dianhydride and diamine compound. (b) The total amount (a + b) of the amount of the agent (a) to be used is 0.1% by weight to 50% by weight based on the amount of the organic solvent (a). The polyaminic acid solution obtained after the reaction can be used. It can be directly used for preparing a liquid-directing agent, or after separating the poly-proline acid contained in the reaction solution, preparing a liquid crystal alignment agent, or purifying the separated polyamic acid, and preparing a liquid crystal alignment agent. For the separation method, an alcohol, a glycol diol diol diester, a methyl isoamyl 1,2-, etc. may be used. The alkane, a better machine is preferably used in the preparation of the crystal - 16 - 201202343 Large injection; liquid method (four) side of the counter object will be out of the sample, such as the dry solution of the dry liquid under the dry solution of the method should be reduced by the 'reducing agent, the dilute pressure reducer is steamed by the amine solution For further acid. An acid-based solvent-solvent machine which is prepared by a method such as an amine, etc., has an elution point to the polymerization of the polymer, and the agent is discharged into a solution. More or less _ ο 法进进 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; When appropriate, use a single amine to make it available.酉 } 单单单 It It It It 单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单 It It 单单单单单单单单The step size is one by one. The fruit effect compound, the monoisocyanate compound, etc. Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, and n-decyl amber. An acid anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, and n-pentane. The amine, n-hexylamine, n-heptylamine, n-octylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, etc. In terms of the ratio of use of the molecular weight modifier With respect to tetracarboxylic dianhydride and diamine, a total of 100 parts by mass 'preferably 20 parts by mass of 0' is more preferably 10 parts by mass or less. [Polyimide] -17- 201202343 The amine can be obtained by the above-mentioned polyaminic acid having a proline sulphate Manufacture " Polyimine can be a complete yttrium imide of the dehydration ring structure of the ruthenium acid structure as a precursor of poly-proline, or it can be only a part of the structure of sulphuric acid dehydration ring closure, 醯Amino acid structure and a quinone ring structure & a partial quinone imide. Here, a part of the quinone ring may be an isoindole ring. The ruthenium imidization ratio of the polyimine is preferably 30. More preferably, it is 40% to 99%. The sulfhydrylation ratio is expressed as a percentage of the number of the ruthenium ring structure of the polyimine and the quinone ring structure. In addition, the ratio of the total amount of ruthenium is obtained by putting a solution of poly-imine into pure water, recovering the obtained precipitate, and drying it under reduced pressure at room temperature, and then dissolving it in the hydrogenation. In the dimethyl hydrazine, an i-NMR spectrum obtained by 1H-NMR measurement at room temperature using tetramethyl sane as a reference material was obtained by the following formula (2). Amination rate (%) = {IJAWa^xo^xIOO (2) In the formula (2), 'A1 is the peak area (i〇ppm) of the proton derived from the NH group. A2 is the peak area from other protons. α is the ratio of the number of other protons to the proton of a mercapto group in a poly-proline. For the synthesis method of polyimine, for example, (i) a method of heating polylysine, (ii) dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. (hereinafter, also referred to as "method (ii) ()) A method to be carried out by dehydration of poly-proline, -18-201202343. Among these methods, the method (ii) is preferred. For the dehydrating agent in the method (ii), for example, Anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. With respect to the amount of the dehydrating agent, 'the ratio of the desired imidization ratio is appropriately selected, and the proline structure of the 1 m 01 poly-proline is preferably O.Olmol to 20 mol 0 in the method (ii). Examples of the dehydration ring-closure catalyst include a third amine such as a rhodium ratio, a trimethyl sulfonium ratio, a steep dimethyl hydrazine ratio, and a D'triethylamine. With respect to the amount of the dehydration ring-closing catalyst, it is preferably 0 · 0 1 m ο 1 〜 1 〇 m ο 1 with respect to the de-icing agent contained in lm〇1. The organic solvent to be used in the method (ii) is exemplified by the same organic solvent as the following organic solvent, and the organic solvent is exemplified, for example, as a solvent used for the synthesis of polyamic acid. The reaction temperature in the method (Π) is preferably from 0 ° C to 1 80 ° C, more preferably from 10 ° C to 150 ° C. In terms of reaction time, it is preferably from 1.0 hour to 120 hours, more preferably from 2.0 hours to 30 hours. By setting the reaction conditions to the above range, the dehydration ring-closure reaction proceeds sufficiently, and the molecular weight of the obtained polyimine can be made appropriate. In the method (ii), a reaction solution containing polyienimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine; or After the isolated polyimine is refined, it is used to prepare a liquid crystal alignment agent. The method of removing the dehydrating agent and the dehydration ring-closure catalyst from the solution of the anti--19-201202343 solution can be carried out according to a known method, and examples thereof include the same method as the separation method and the purification method of poly-proline. Wait. The solution viscosity in a solution having a concentration of the polymer [A] obtained above of 10% by mass is preferably 20 mPa*s to 800 mPa's, more preferably 30 mPa·s to 500 mPa's of a polymer solution. The viscosity (mPa_s) is a ruthenium measured at 25 ° C using a 10% by mass polymer solution prepared using γ-butyrolactone or hydrazine using a Ε-type rotary viscometer. <Epoxy compound [B]> The epoxy compound [B] contained in the liquid crystal alignment agent of the present invention is an oxime ring-containing epoxy compound represented by the above formula (I). In the above formula (I), RA is a single bond or an alkanediyl group having 1 to 4 carbon atoms. RB is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, a divalent heterocyclic group, or a group formed by combining them. η is an integer of 0 or 1. Examples of the alkanediyl group having 1 to 4 carbon atoms include a methane diyl group, an ethylenediyl group, a propylenediyl group, and a butyldiyl group. Among them, a single bond or a methane diyl group is preferred. The above formula (I) is preferably at least one selected from the group consisting of the compounds represented by the above formula (1-1) and formula (1-2). By selecting the above formula (I) as a specific compound, it is possible to form a liquid crystal alignment film which suppresses deterioration in display quality due to deterioration of electrical properties and the like, and which is easily peeled off during rework. In the above formula (Bu 1) and Formula U·2), RA has the same definition as the above formula (I). R1, R2 and R3 are each independently 'linearly or branched and R' or R1 and R 2 and may contain -〇-, -COO-, -OCO- -20- 201202343 having the carbon number idO R 3 may be bonded to each other, partially or completely substituted ring structure. η is 0 or 1 | in the case of a linear or branched chain having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, an octyl group, a decyl group, or a fluorene group. Base, lauryl, dodecyltetradecyl, pentadecyl, hexadecyl, heptadecanecandecyl 'icosyl, and the like. Among them, a propyl group is preferred.

另外’上述式（Ι·1)和（1-2)中的R1、R R1和R2或者R1和R2和R3相互連接，形分或全部被取代的環結構。就環結構而言香環、脂肪族環、雜環、稠環以及組合它們之中’較佳係芳環，更佳係苯環、萘環就可以被取代的環結構所具有的取代例如鹵素原子、羥基、硝基、氰基、烷基、芳基、院氧基、醯基、醯氧基、院氧基鑛鹵烷基等。它們之中，較佳係鹵素原子'傾烷氧基，更佳爲氟原子、氯原子、溴原子基、甲氧基。上述式（1-1)和（1-2)中的η是〇或1的！上述式（I)的^^較佳爲甲烷二基。另外和式（1-2)中，R1和R2較佳係相互連接，形院基。另外，R1 形成氫原子的一 ]整數。的烷基.而言，可戊基、己基、庚基、十三院基、基、十八烷基、係甲基、乙基、 2和R3可以形成成氫原子的一部，可以列舉出芳們形成的環。它〇基，可以列舉出羧基、環烷基、基、氰基院基、 ί基、氰基烷基、、甲基、氰基甲臺數。η較佳係0。 •，在上述式（1-1) 成氫原子的部分 -21- 201202343 或全部可以被取代的苯環。環氧化合物[B]藉由具有上述特定結構，可以進一步提高電性質和重新作業時的剝離性。就上述式（I-1)和Π·2)所示的化合物而言，可以列舉出：例如下述式（ι]·υ〜（ι-卜16)和（卜2·1)〜…2·14)所示的化合物Further, in the above formulas (Ι·1) and (1-2), R1, R R1 and R2 or R1 and R2 and R3 are bonded to each other, and the ring structure is substituted or completely substituted. In terms of ring structure, an aromatic ring, an aliphatic ring, a heterocyclic ring, a fused ring, and a combination thereof are preferably a preferred aromatic ring, and more preferably a ring structure in which a benzene ring or a naphthalene ring may be substituted, such as a halogen. Atom, hydroxyl, nitro, cyano, alkyl, aryl, alkoxy, fluorenyl, decyloxy, alkoxyalkylhalide, and the like. Among them, a halogen atom 'p-alkoxy group is preferred, and a fluorine atom, a chlorine atom, a bromine atom group or a methoxy group is more preferred. η in the above formulas (1-1) and (1-2) is 〇 or 1! The above formula (I) is preferably a methane diyl group. Further, in the formula (1-2), R1 and R2 are preferably connected to each other to form a base. Further, R1 forms an integer of a hydrogen atom. In the case of an alkyl group, a pentyl group, a hexyl group, a heptyl group, a thirteenth compound group, a benzyl group, an octadecyl group, a methyl group, an ethyl group, a group 2 and an R3 group may form a hydrogen atom. The ring formed by the fangs. The thiol group may be exemplified by a carboxyl group, a cycloalkyl group, a phenyl group, a cyano group, a cyano group, a cyano group, a methyl group, and a cyano group. η is preferably 0. • A benzene ring which may be substituted in the part (21) of the above formula (1-1) which forms a hydrogen atom -21 - 201202343. The epoxy compound [B] can further improve the electrical properties and the releasability at the time of rework by having the above specific structure. Examples of the compound represented by the above formula (I-1) and Π·2) include, for example, the following formulas (i), υ~(ι-b 16), and (di 2·1)~...2 ·14) the compound shown

-22- 201202343-22- 201202343

(I'2'5) (1-2-6) (1-2-7) (1-2-8)(I'2'5) (1-2-6) (1-2-7) (1-2-8)

(H9) (1-2-10) (1-2-11) (1-2-12)(H9) (1-2-10) (1-2-11) (1-2-12)

(1-2-14) 上述式（1-1-1)〜（1-1-16)和（1-2-1)〜（1-2-14)中，特佳係 (I -1 -1 )、（【_ i - 4)、（ I -1 - 1 5 )、（ I -1 -1 6 )、（ I - 2 - 6 )，最佳係（I -1 - 4 )、 (1-2-6)。另外，式（I)中的環氧基可以被取代。就取代基而言，可以列舉出例如鹵素原子、羥基、硝基、氰基、烷基、羧基、環烷基、芳基、烷氧基、醯基、醯氧基、烷氧基羰基、氰基烷基、鹵烷基等。就該環氧化合物[B]的合成方法而言，沒有特別的限定’可以組合現有公知的方法進行。另外，還可以使用市 -23- 201202343 場銷售的產品。就環氧化合物[B ]的含有比例而言’ 聚合物[A]，較佳爲0.1質量份~50質量份〜40質量份，特佳係爲3質量份〜3 〇質化合物[B]的含有比例爲上述範圍，可以使長時間驅動時，電性質的惡化也少' 顯示元件的液晶配向膜，同時可以提供業時的剝離性良好的液晶配向劑。 <任意成分> 就任意成分而言，可以列舉出例如等。 [官能性矽烷化合物] 官能性矽烷化合物，可以基於提高對基板表面的黏合性的目的而使用。就官能性矽烷化合物而言，可以列丙基三甲氧基矽烷、3-胺基丙基三乙氧基三甲氧基矽烷、2-胺基丙基三乙氧基: 基）-3-胺基丙基三甲氧基矽烷、N-(2-胺3 甲基二甲氧基矽烷' 3 -脲基丙基三甲氧基三乙氧基矽烷、N -乙氧基羰基-3-胺烷、N-乙氧基羰基-3-胺基丙基三乙氧基甲矽烷基丙基三伸乙基三胺，N-三甲氧乙基三胺、10-三甲氧基甲矽烷基-1，4，' 相對於100質量份份，更佳爲1質量 ‘量份。藉由使環氧提供一種能形成即顯不品質商的液晶形成的膜的重新作官能性矽烷化合物形成的液晶配向膜舉出：例如3 -胺基基矽烷、2-胺基丙砂烷、N-(2-胺基乙 I乙基）-3-胺基丙基基矽烷、3-脲基丙基丙基三甲氧基矽矽烷、N-三乙氧基基矽烷基丙基三伸 7-三吖癸烷、10-三 -24- 201202343 乙氧基矽烷基-1,4,7-三吖癸烷、9-三甲氧基矽烷基-3，6-二吖壬基乙酸酯、9 -三乙氧基矽烷基-3,6 -二吖壬基乙酸酯、 N-苄基-3-胺基丙基三甲氧基矽烷、9-三甲氧基矽烷基-3,6-二吖壬酸甲酯、9-三乙氧基矽烷基-3,6-二吖壬酸甲酯、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、環氧丙氧基甲基三甲氧基矽烷、環氧丙氧基甲基三乙氧基矽烷、2 -環氧丙氧基乙基三甲氧基矽烷、2-環氧丙氧基乙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3_環氧丙氧基丙基三乙氧基矽烷等。就官能性矽烷化合物的使用比例而言，相對於1 00質量份聚合物[A]’較佳爲2質量份以下，更佳爲0.02質量份〜0.2質量份。 <液晶配向劑的製備方法> 該液晶配向劑如上所述，含有聚合物[A ]和環氧化合物 [B] ’根據需要可以含有任意成分，較佳係將各成分溶解到有機溶劑中，調配爲組成物。就有機溶劑而言，可以列舉出ΝΜΡ、γ -丁內酯、γ -丁內醯胺、Ν，Ν-二甲基甲醯胺、Ν，Ν -二甲基乙醯胺、4_羥基 -4-甲基-2-戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚（丁基溶纖素）、乙二醇二甲基醚、乙二醇乙基醚乙 -25- 201202343 酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二異丁基酮、丙酸異戊基酯、異丁酸異戊基酯、二異戊基醚、碳酸伸乙酯、碳酸伸丙二酯等。這些有機溶劑可以單獨使用一種或將兩種以上一起使用。本發明的液晶配向劑的固體成分濃度，也就是液晶配向劑中的溶劑以外的全部成分的質量，佔液晶配向劑的全部質量的比例，考慮黏性、揮發性等而選擇，較佳爲1質量％〜1〇質量％。在固體成分濃度不足1質量％時，由該液晶配向劑形成的液晶配向膜的膜厚過小，可能無法得到良好的液晶配向膜。另一方面，如果固體成分濃度超過10質量％，則塗膜的膜厚過大，可能無法得到良好的液晶配向膜，或者液晶配向劑的黏性增大’塗布性質可能不足。就較佳的固體成分濃度的範圍而言’根據在基板上塗布液晶配向劑時採用的方法而異。例如’在使用旋塗法進行時’ 固體成分濃度較佳爲1·5質量質量％。藉由印刷法進行時，較佳固體成分濃度爲3質量％~9質量％，由此溶液黏度爲12mPa.s~50mPa.s。在使用噴墨法進行時’較佳固體成分濃度爲1質量％〜5質量％的範圍’由此，溶液黏度爲 3mPa.s〜15mPa.s 的範圍。就製備該液晶配向劑時的溫度而言，較佳爲 1 0 t ~ 5 0 °C，更佳爲 2 0 °C ~ 3 〇 °C。 -26- 201202343 <液晶配向膜> 本發明的液晶配向膜由該液晶配向劑形成。因此，該液晶配向膜可以抑制由電性質的惡化等導致之顯示品質降低，而且重新作業時容易剝離。 <液晶配向膜的形成方法> 本發明的液晶配向膜藉由在基板上塗布該液晶配向劑，接著加熱塗布面，而在基板上形成塗膜，根據希望的顯示模式，進一步進行摩擦處理形成。在製造顯示模式爲TN型、STN型或VA型的液晶顯示元件時，將設置了經形成圖案的透明導電膜的兩塊基板形成一對，在它們的各透明性導電膜形成面上，較佳係藉由平版印刷法、旋塗法或噴墨印刷法，分別塗布該液晶配向劑，接著，藉由加熱各塗布面，形成塗膜》就基板而言，可以列舉出：例如包含漂浮玻璃、鈉玻璃等玻璃基材，聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚楓、聚碳酸酯（脂環式烯烴）等塑膠基材的透明基板等。就在基板的一面上設置的透明，導電膜而言，可以列舉出由氧化錫（Sn02)形成的NES A膜（美國PPG公司的注冊商標）、由氧化銦-氧化錫（In203 -Sn02)形成的ITO膜等。就得到經形成圖案的透明導電膜的方法，可以列舉出：例如形成無圖透明導電膜後，藉由光蝕刻形成® @ 方法；形成透明導電膜時，使用具有所希望的圖案的#胃 -27- 201202343 的方法等。塗布液晶配向劑時，爲了使基板表面和透明導電膜與塗膜的黏結性更好，可以在基板表面的形成塗膜的面上’預先塗布官能性矽烷化合物、官能性鈦化合物等進行前處理》在塗布該液晶配向劑後，基於防止液體滴流等目的，較佳係進行預加熱（預烘烤）。就預烘烤的溫度而言，較佳爲 3 0°C ~2 0 0°C ，更佳爲 40°C〜150。(：，特佳係爲 40 °C〜100 °C。就預烘烤的時間而言，較佳爲0.25分鐘〜10 分鐘，更佳係0.5分鐘〜5分鐘。接著’完全除去溶劑，基於根據需要將聚醯胺酸熱醯亞胺化的目的’進行燒結（後烘烤）。就後烘烤的溫度而言，較佳爲8 0 °C〜3 0 0 °C，更佳爲1 2 0。(：〜2 5 0 T：。就後烘烤的時間而言’較佳爲5分鐘〜200分鐘，更佳係1〇分鐘〜1〇〇分鐘。适樣形成的塗膜的膜厚較佳爲10nm~500nm，更佳爲 10nm~200nm 〇在製造顯示模式是IPS型液晶顯示元件時，在設置了形成梳齒型圖案的透明導電膜的基板的導電膜形成面上，和沒有設置導電膜的對向基板的一面上，較佳係藉由平版印刷法、旋塗法或噴墨印刷法塗布該液晶配向劑，接著，藉由加熱各塗布面而.形成塗膜。基板的材質、透明導電膜的材質、透明導電膜的形成圖案方法、基板的前處理以及塗布液晶配向劑後的加熱方法、形成的塗膜的較佳膜厚與 -28- 201202343 製造顯示模式是TN型、STN型或VA型的液晶顯示元件的情形中所列舉的相同。在顯示模式爲VA型的液晶顯示元件時，可以將如上形成的塗膜直接作爲液晶配向膜使用，根據需要也可以進行如下所述的摩擦處理後使用。在製造顯示模式V A型以外的液晶顯示元件時，藉由對如上形成的塗膜進行摩擦處理，形成液晶配向膜。摩擦處理是對如上形成的塗膜面，藉由捲繞例如由尼龍、人造絲、棉花等纖維形成的布的輕，在一定方向摩擦進行。由此，液晶分子的配向能給予塗膜，形成液晶配向膜。然後，對如上形成的液晶配向膜進行處理，藉由使液晶配向膜的每個區域具有不同的液晶配向膜，可以改善所得的液晶顯示元件的視角性質，其中對液晶膜進行的處理包括：例如有如日本特開平6 - 2 2 2 3 6 6號公報或日本特開平 6 - 2 8 1 9 3 7號公報所記載般，對液晶配向膜的一部分照射紫外線，由此改變液晶配向膜的一部分區域的預傾角的處理；以及有如日本特開平5- 1 07544號公報所記載般，對液晶配向膜表面的一部分形成光阻膜後，在和之前的摩擦處理不同的方向上進行摩擦處理後，除去光阻膜的處理。 <液晶顯示元件> 本發明的液晶顯示元件具有該液晶配向膜。該液晶顯示元件適合用於各種裝置，例如可以在鐘錶、便攜型遊戲機、文字處理器、筆記型電腦、導航系統、攝影錄影機、 -29- 201202343 便攜資訊終端、數位相機、行動電話、各種監視器、液晶電視等顯示裝置中使用。 <液晶顯示元件的形成方法> 本發明的液晶顯示元件例如可以如下製造。準備兩塊形成該液晶配向膜的基板，藉由在對向配置的兩塊基板間配置液晶’製造液晶胞。在此，在對塗膜進行摩擦處理時，兩塊基板對向配置，以使各塗膜的摩擦方向相互爲規定角度’例如是正交或逆平行。在製造液晶胞時，可以列舉出例如下述兩種方法。第一種方法是目前已知的方法，首先爲了使各液晶配向膜對向設置’藉由間隙（以下，也稱作“胞間隙”），將兩塊基板對向配置，使用密封劑將兩塊基板的周邊部位貼合’在由基板表面和密封劑分割的胞間隙內注入塡充液晶後’密封注入孔，可以製造液晶胞。第二種方法是稱作〇DF(滴注，One Drop Fill)方式的方法’在形成液晶配向膜的兩塊基板中的一個基板上的規定位置，塗布例如紫外光硬化性密封材料，然後在液晶配向膜面上滴加液晶後’貼合另一個基板並使液晶配向膜對向’然後，在基板的整面照射紫外光，使密封劑硬化，製造液晶胞》在任一種方法的情況下’對如上製造的液晶胞，再加熱到使用的液晶各成爲向同性的溫度後，緩慢冷卻到室溫’除去液晶注入時的流動配向爲宜。然後，藉由在液晶 -30- 201202343 胞的外側表面貼合偏光板，可以得到該液晶顯示元件。就密封劑就而言，可以列舉出例如含有作爲隔片的氧化鋁球和硬化劑的環氧樹脂等。就液晶而言，可以列舉出例如向列型液晶、層列型液晶等。它們之中，較佳係向列型液晶。在爲VA型液晶胞時，較佳係具有負的介電各向異性的向列型液晶。就這種液晶而言，可以列舉出例如二氰基苯類液晶、嗒阱類液晶、西夫鹼類液晶、氧偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶等。爲TN型液晶胞或S TN型液晶胞時，較佳係具有正的介電各向異性的向列型液晶。就這種液晶而言，可以列舉出例如聯苯類液晶、苯基環己烷類液晶、酯類液晶、三聯苯類液晶、聯苯基環己烷類液晶、嘧啶類液晶、二噚烷類液晶、雙環辛烷類液晶、立方烷類液晶等。另外，上述液晶中，可以進一步添加使用例如膽甾醇氯酯、膽甾烯壬酸酯、膽甾烯碳酸酯等膽固醇液晶；以“C-15”、 “CB-15”（Merck公司）銷售的手性試劑；對癸氧基亞苄基-對胺基-2-甲基丁基肉桂酸酯等強介電性液晶等。就貼合到液晶胞外表面的偏光板而言，可以列舉出邊將聚乙烯醇延展配向，邊用醋酸纖維素保護膜夾住吸收碘，稱爲“H膜”的偏光膜形成的偏光板或由Η膜本身形成的偏光板。 <聚合物組成物> 本發明的聚合物組成物包含[Α]由聚醯胺酸和聚醯亞 -31 - 201202343 胺構成的群組中選出的至少一種聚合物，以及[B]上述式（I) 所示的含醯亞胺環的環氧化合物。該聚合物組成物適合作爲用於形成液晶配向膜的液晶配向劑等成分使用。另外，由該聚合物組成物形成的膜還可以作爲電子材料用絕綠膜使用。上述式（I)中，RA是單鍵或碳原子數爲1〜4的烷二基。以是2價的鏈狀烴基、2價的脂環烴基、2價的芳香族基、 2價的雜環基、或組合它們形成的基。η是0或1的整數。 [實施例] 以下，基於實施例，對本發明進行詳細描述，但是該實施例的記載並不是對本發明的限定的解釋。 <聚醯胺酸的合成> [合成例1] 將作爲四羧酸二酐的98g (0.50m〇l) 1，2,3,4-環丁四竣酸二酐和l〇9g (0.50m〇l)均苯四羧酸二野以及作爲二胺化合物的198吕（1.〇111〇1)4,4'-二胺基苯基甲烷溶解到由23〇8 的NMP和2,06 0g的γ-丁內酯形成的混合溶劑中，在4〇〇c 下反應3小時後，追加l，3 5 0g的γ-丁內酯，得到含有1〇質量％聚醯胺酸（P A-1)的溶液。該溶液的溶液黏度爲 1 1 8 m P a _ s。 [合成例2] 將作爲四羧酸二酐的196g (l.Omol) 1，2,3,4-環丁四竣酸二酐和作爲二胺化合物的212g (l.Omol)的2,2，_二甲基 •32- 201202343 -4，4 1 -二胺基聯苯，溶解到由3 7 0 g的Ν Μ P和3，3 0 0 g的γ -丁內酯形成的混合溶劑中，在4 Ο °C下反應3小時，得到含有聚醯胺酸（PA-2)的溶液。該溶液的溶液黏度爲154mPa-s。 <聚醯亞胺的合成> [合成例3] 將作爲四羧酸二酐的224g (l.Omol) 2,3,5-三羧基環戊基乙酸二酐以及作爲二胺化合物的l〇6g (0.9 8 5mol)對苯二胺和7.8g (0.015mol) 3,5_二胺基苯甲酸膽甾烷基酯溶解到3,042g的NMP中，在60°C下反應6小時。得到的聚醯胺酸溶液的溶液黏度爲181mPa_s。接著，在所得的聚醯胺酸溶液中追加3,380g的NMP，添加395g吡啶和306g乙酸酐，在1 1 0 °C下進行4小時脫水閉環。醯亞胺化反應後’ 系統內的溶劑用新的γ - 丁內酯溶劑置換，將吡啶、乙酸酐除去到系統外。這樣，得到含有1 5質量％醯亞胺化率約95% 的聚醯亞胺（ΡΙ-1)的溶液。少量分取所得的聚醯亞胺溶液’ 加入γ-丁內酯，形成聚醯亞胺濃度1 0質量％的溶液’測定的溶液黏度爲102mPa_s。 [合成例4] 將作爲四竣酸二酐的11〇g (0‘50mo1) 2,3,5_三羧基環戊基乙酸二酐和 I60g(〇_5〇mol) l，3,3a，4,5,9b-六氫-8-甲基 -5-(四氫-2,5 -二氧-3-呋喃基）萘并[l，2-c]呋喃-1,3 -二酮、以及作爲二胺化合物的94g(0.87m〇l)對苯二胺、25g(0.10mol) i，3-雙（3-胺基丙基）四甲基二砂氧烷和9.6g (0.015mo1) -33- 201202343 3，6-雙（4_胺基苯甲醯氧基）膽甾烷、作爲單胺的8.ig (0.030mol)十八院基胺，溶解到960g的NMP中，在60°C 下反應6小時。少量分取所得的聚醯胺酸溶液，加入NMP，對固體成分濃度10%的溶液測定黏度，爲58mPa.s。接著，在所得的聚醯胺酸溶液中追加2,700g的NMP，添加400g 吡啶和4 1 0g乙酸酐，在1 1 0°C下進行4小時脫水閉環。醯亞胺化反應後，系統內的溶劑用新的γ-丁內酯溶劑置換，將吡啶、乙酸酐除去到系統外。這樣，得到含有約1 5質量 %醯亞胺化率95%的聚醯亞胺（ΡΙ-2)的溶液。少量分取所得的聚醯亞胺溶液，加入γ-丁內酯，形成聚醯亞胺濃度10 質量％的溶液，測定的溶液黏度爲72mPai。 [合成例5] 將作爲四羧酸二酐的226g (1 .Omol) 2,3,5-三羧基環戊基乙酸二酐以及作爲二胺化合物的 76g (0.80m〇l)對苯二胺、53g (O.lOmol) 3,5-二胺基苯甲酸膽甾烷基酯和100g (0.2mol)膽甾烷氧基-2,4-二胺基苯溶解到l，820g的NMP 中，在60°C下反應6小時。少量分取所得的聚醯胺酸溶液，加入 NMP，對固體成分濃度1 0%的溶液測定黏度，爲 80mPa_s。接著，在所得的聚醯胺酸溶液中追加4,22 5g的 Ν Μ P，添力□ 1 〇 4 g吡啶和1 3 4 g乙酸酐，在1 1 〇 °C下進行4小時脫水閉環。醯亞胺化反應後，系統內的溶劑用新的NMP 溶劑置換，將吡啶 '乙酸酐除去到系統外。這樣’得到含有約15質量％醯亞胺化率66 %的聚醯亞胺（PI-3)的溶液。 -34- 201202343 少量分取所得的聚酿亞胺溶液，加入NMP，形成聚醯亞胺濃度10質量％的溶液，測定的溶液黏度爲98mPa.s。 [合成例6] 將作爲四羧酸二酐的224g (1 .Omol) 2,3,5-三羧基環戊基乙酸二酐以及作爲二胺化合物的87g(0.80m〇l)對苯二胺和99g (0.20mol)膽甾烷氧基-2,4-二胺基苯溶解到l，848g 的NMP中，在60 °C下反應6小時。少量分取所得的聚醯胺酸溶液，加入NMP，對固體成分濃度10%的溶液測定黏度，爲120mPa‘s。接著，在所得的聚醯胺酸溶液中追加3,809g 的NMP，添加79g吡啶和102g乙酸酐，在110°C下進行4 小時脫水閉環。醯亞胺化反應後，系統內的溶劑用新的NMP 溶劑置換，將吡啶、乙酸酐除去到系統外。這樣，得到含有約15質量％醯亞胺化率49%的聚醯亞胺（PI-4)的溶液。少量分取所得的聚醯亞胺溶液，加入NMP，形成聚醯亞胺濃度1〇質量％的溶液，測定的溶液黏度爲155mPa_s。 [合成例7] 將作爲四羧酸二酐的224g (l.Omol) 2,3,5 -三羧基環戊基乙酸二酐以及作爲二胺化合物的76g (0.70mol)對苯二胺、4(^(0.20111〇1)4,4’-二胺基二苯基甲烷和5(^(0.10爪〇1) 膽甾烷氧基_2,4·二胺基苯，溶解到l，556g的NMP中，在 6 0 °C下反應6小時。少量分取所得的聚醯胺酸溶液，加入 NMP，對固體成分濃度10%的溶液測定黏度，爲133mPa_s。接著，在所得的聚醯胺酸溶液中追加3，614g的NMP，添加 -35- 201202343 7 9 g吡啶和1 0 2 g乙酸酐，在1 1 〇°C下進行4小時脫水閉環。脫水閉環反應後，系統內的溶劑用新NMP進行溶劑置換（藉由本操作，將醯亞胺化反應中使用的吡啶、乙酸酐除去到系統外），得到含有約1 5質量％醯亞胺化率爲46%的聚醯亞胺（P 1-5)的溶液。少量分取所得的聚醯亞胺溶液，加入 NMP，形成聚醯亞胺濃度1 0質量％的溶液，測定的溶液黏度爲 133mPa-s。 <液晶配向劑（TN型液晶顯示元件使用）的製備>(1-2-14) In the above formulas (1-1-1) to (1-1-16) and (1-2-1) to (1-2-14), the special system (I-1) 1), ([_ i - 4), (I -1 - 1 5 ), (I -1 -1 6 ), (I - 2 - 6 ), the best system (I -1 - 4 ), (1 -2-6). Further, the epoxy group in the formula (I) may be substituted. The substituent may, for example, be a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, a carboxyl group, a cycloalkyl group, an aryl group, an alkoxy group, a decyl group, a decyloxy group, an alkoxycarbonyl group or a cyanogen group. Alkyl group, haloalkyl group, and the like. The method for synthesizing the epoxy compound [B] is not particularly limited, and can be carried out by a combination of a conventionally known method. In addition, you can also use the products sold in the city -23- 201202343. In terms of the content ratio of the epoxy compound [B ], the polymer [A] is preferably 0.1 parts by mass to 50 parts by mass to 40 parts by mass, particularly preferably 3 parts by mass to 3 parts by mass of the phthalocyanine compound [B]. When the content ratio is in the above range, it is possible to reduce the deterioration of electrical properties when driving for a long period of time. The liquid crystal alignment film of the display element can provide a liquid crystal alignment agent having good peelability at the same time. <Optional component> Examples of the optional component include, for example. [Functional decane compound] The functional decane compound can be used for the purpose of improving the adhesion to the surface of the substrate. In the case of a functional decane compound, propyltrimethoxydecane, 3-aminopropyltriethoxytrimethoxydecane, 2-aminopropyltriethoxy: yl)-3-amino Propyltrimethoxydecane, N-(2-amine 3-methyldimethoxydecane'3-ureidopropyltrimethoxytriethoxydecane, N-ethoxycarbonyl-3-aminene, N -ethoxycarbonyl-3-aminopropyltriethoxycarbenylpropyltriethylamine, N-trimethoxyethyltriamine, 10-trimethoxycarbamimidyl-1,4, It is more preferably 1 mass by weight with respect to 100 parts by mass. A liquid crystal alignment film formed by re-forming a functional decane compound which can form a film formed by liquid crystal which is a non-quality quotient of epoxy is exemplified. For example: 3-amino decane, 2-aminopropane, N-(2-aminoethylethyl)-3-aminopropyl decane, 3-ureidopropylpropyltrimethoxy矽矽, N-triethoxydecylpropyltris-7-trioxane, 10-tri-24- 201202343 ethoxylated alkyl-1,4,7-trioxane, 9-trimethyl Oxyalkylalkyl-3,6-dimercaptoacetate, 9-triethoxy矽alkyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, methyl 9-trimethoxydecyl-3,6-dicaprate, Methyl 9-triethoxydecyl-3,6-dicarboxylate, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Baseline, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, 2-epoxypropane Oxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxy The proportion of the functional decane compound to be used is preferably 2 parts by mass or less, more preferably 0.02 parts by mass to 0.2 parts by mass, per 100 parts by mass of the polymer [A]'. Preparation method of the agent> As described above, the liquid crystal alignment agent contains the polymer [A] and the epoxy compound [B]', and may contain any component as needed, and it is preferred to dissolve the components into an organic solvent to prepare a composition. In terms of organic solvents, Listed as hydrazine, γ-butyrolactone, γ-butyrolactam, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2- Pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, B Glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellulolytic), ethylene glycol dimethyl ether, ethylene glycol ethyl ether B-25-201202343 acid ester, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propylene carbonate, and the like. These organic solvents may be used alone or in combination of two or more. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the mass of all the components other than the solvent in the liquid crystal alignment agent, is a ratio of the total mass of the liquid crystal alignment agent, and is selected in consideration of viscosity, volatility, etc., preferably 1 Mass %~1〇% by mass. When the solid content concentration is less than 1% by mass, the thickness of the liquid crystal alignment film formed of the liquid crystal alignment agent is too small, and a good liquid crystal alignment film may not be obtained. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large, and a good liquid crystal alignment film may not be obtained, or the viscosity of the liquid crystal alignment agent may increase. The coating property may be insufficient. The range of the preferable solid content concentration differs depending on the method employed when the liquid crystal alignment agent is coated on the substrate. For example, when the spin coating method is used, the solid content concentration is preferably 1.5 mass%. When the printing method is carried out, the solid content concentration is preferably from 3% by mass to 9% by mass, whereby the solution viscosity is from 12 mPa·s to 50 mPa·s. When the ink jet method is used, the preferable solid content concentration is in the range of 1% by mass to 5% by mass. Thus, the solution viscosity is in the range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 t to 50 ° C, more preferably from 20 ° C to 3 〇 ° C. -26-201202343 <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is formed of the liquid crystal alignment agent. Therefore, the liquid crystal alignment film can suppress deterioration in display quality due to deterioration of electrical properties and the like, and is easily peeled off during rework. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is further coated with a liquid crystal alignment agent on a substrate, followed by heating the coated surface to form a coating film on the substrate, and further performing rubbing treatment according to a desired display mode. form. When a liquid crystal display element having a display mode of a TN type, an STN type or a VA type is manufactured, a pair of two substrates on which a patterned transparent conductive film is formed is formed, and on each of the transparent conductive film forming surfaces thereof, Preferably, the liquid crystal alignment agent is applied by a lithography method, a spin coating method, or an inkjet printing method, and then each coated surface is heated to form a coating film. The substrate may be, for example, a floating glass. A glass substrate such as soda glass, a transparent substrate of a plastic substrate such as polyethylene terephthalate, polybutylene terephthalate, polyether maple, or polycarbonate (alicyclic olefin). The transparent, conductive film provided on one side of the substrate may, for example, be a NES A film formed of tin oxide (Sn02) (registered trademark of PPG, USA), and formed of indium oxide-tin oxide (In203-Sn02). ITO film, etc. The method of obtaining the patterned transparent conductive film may be, for example, formation of a transparent conductive film without a pattern, and formation of a @@ method by photolithography; when forming a transparent conductive film, using a stomach having a desired pattern. 27-201202343 method, etc. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, it is possible to pre-coat a functional decane compound or a functional titanium compound on the surface of the substrate on which the coating film is formed. After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing liquid dripping. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C. (:, particularly preferred is 40 ° C to 100 ° C. In terms of prebaking time, preferably 0.25 minutes to 10 minutes, more preferably 0.5 minutes to 5 minutes. Then 'completely remove the solvent, based on It is necessary to carry out sintering (post-baking) for the purpose of hot amidation of polyglycine. In terms of the temperature of post-baking, it is preferably 80 ° C to 300 ° C, more preferably 1 2 0. (:~2 5 0 T: In terms of post-baking time, it is preferably 5 minutes to 200 minutes, more preferably 1 minute to 1 minute. The film thickness of the coating film is suitably formed. It is preferably 10 nm to 500 nm, more preferably 10 nm to 200 nm. When the manufacturing display mode is an IPS type liquid crystal display element, the conductive film formation surface of the substrate on which the transparent conductive film forming the comb-tooth pattern is provided is not provided. On one surface of the opposite substrate of the conductive film, the liquid crystal alignment agent is preferably applied by a lithography method, a spin coating method or an inkjet printing method, and then a coating film is formed by heating each coated surface. Material of transparent conductive film, patterning method of transparent conductive film, pretreatment of substrate, and coating liquid crystal alignment The heating method after the agent and the preferred film thickness of the formed coating film are the same as those listed in the case of the TN type, STN type or VA type liquid crystal display element in the case where the manufacturing display mode is -28-201202343. The display mode is VA type. In the case of a liquid crystal display device, the coating film formed as described above can be used as a liquid crystal alignment film as it is, and if necessary, it can be used as a rubbing treatment as described below. When a liquid crystal display element other than the display mode VA type is manufactured, The coating film formed as described above is subjected to a rubbing treatment to form a liquid crystal alignment film. The rubbing treatment is performed on the coating film surface formed as described above by winding a cloth formed of fibers such as nylon, rayon, cotton, etc., in a certain direction. Thereby, the alignment of the liquid crystal molecules can be imparted to the coating film to form a liquid crystal alignment film. Then, the liquid crystal alignment film formed as above is treated, and the liquid crystal alignment film can be improved by making the liquid crystal alignment film have different liquid crystal alignment films in each region. The viewing angle property of the liquid crystal display element, wherein the processing on the liquid crystal film includes, for example, as disclosed in Japanese Patent Laid-Open No. 6-2 2 2 3 6 6 A process of irradiating a part of a liquid crystal alignment film with ultraviolet rays to change a pretilt angle of a partial region of the liquid crystal alignment film, as described in Japanese Unexamined Patent Publication No. Hei No. Hei. In the case where a photoresist film is formed on a part of the surface of the liquid crystal alignment film, the rubbing treatment is performed in a direction different from the previous rubbing treatment, and the photoresist film is removed. [Liquid Crystal Display Element] The liquid crystal display element of the present invention has the liquid crystal alignment film. The liquid crystal display element is suitable for use in various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a navigation system, a video recorder, and -29- 201202343 Used in display devices such as portable information terminals, digital cameras, mobile phones, various monitors, and LCD TVs. <Method of Forming Liquid Crystal Display Element> The liquid crystal display element of the present invention can be produced, for example, as follows. Two substrates for forming the liquid crystal alignment film were prepared, and liquid crystal cells were fabricated by disposing liquid crystal between the two substrates disposed opposite each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are disposed to face each other such that the rubbing directions of the respective coating films are at a predetermined angle ', for example, orthogonal or antiparallel. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a currently known method. First, in order to make the liquid crystal alignment films face each other, the two substrates are arranged oppositely by a gap (hereinafter, also referred to as "cell gap"), and two sealants are used. The peripheral portion of the block substrate is bonded to 'fill the injection hole after injecting the liquid crystal into the cell gap divided by the surface of the substrate and the sealant, and the liquid crystal cell can be manufactured. The second method is a method called a DropDF (One Drop Fill) method, in which a predetermined position on one of two substrates forming a liquid crystal alignment film is coated with, for example, an ultraviolet light-curable sealing material, and then After liquid crystal is dropped on the liquid crystal alignment film surface, 'the other substrate is bonded and the liquid crystal alignment film is opposed to each other', and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing agent to produce a liquid crystal cell. In the case of any method' The liquid crystal cell produced as described above is reheated until the liquid crystals used are each a homogenous temperature, and then slowly cooled to room temperature. It is preferable to remove the liquid alignment at the time of liquid crystal injection. Then, the liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal -30-201202343. The sealant may, for example, be an epoxy resin containing an alumina sphere as a separator and a curing agent. The liquid crystal may, for example, be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferred. In the case of a VA type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferred. Examples of such a liquid crystal include a dicyanobenzene liquid crystal, a helium trap liquid crystal, a Schiff base liquid crystal, an oxy azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, and the like. When it is a TN type liquid crystal cell or a S TN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferred. Examples of such a liquid crystal include a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, and a dioxane. Liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, in the liquid crystal, for example, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl phthalate or cholestyl carbonate may be added, and sold as "C-15" or "CB-15" (Merck). A chiral agent; a strong dielectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. In the case of a polarizing plate which is bonded to the outer surface of the liquid crystal cell, a polarizing plate formed by a polarizing film called "H film" by sandwiching a polyvinyl alcohol with a cellulose acetate protective film and absorbing iodine may be mentioned. Or a polarizing plate formed by the diaphragm itself. <Polymer Composition> The polymer composition of the present invention comprises [Α] at least one polymer selected from the group consisting of poly-proline and poly-Asian-31 - 201202343 amine, and [B] An oxime ring-containing epoxy compound represented by the formula (I). The polymer composition is suitably used as a component such as a liquid crystal alignment agent for forming a liquid crystal alignment film. Further, the film formed of the polymer composition can also be used as an ultra-green film for electronic materials. In the above formula (I), RA is a single bond or an alkanediyl group having 1 to 4 carbon atoms. It is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, a divalent heterocyclic group, or a group formed by combining them. η is an integer of 0 or 1. [Examples] Hereinafter, the present invention will be described in detail based on the examples, but the description of the examples is not intended to limit the invention. <Synthesis of Polylysine> [Synthesis Example 1] 98 g (0.50 m〇l) of 1,4,3,4-cyclobutanetetracarboxylic dianhydride and 10 g of tetracarboxylic dianhydride were used. 0.50m〇l) pyromellitic acid dinorbium and 198 ruthenium (1.〇111〇1) 4,4'-diaminophenylmethane as a diamine compound are dissolved to NMP and 2 by 23〇8, In a mixed solvent of 06 g of γ-butyrolactone, after reacting at 4 ° C for 3 hours, 1,350 g of γ-butyrolactone was added to obtain a polyglycolic acid containing 1 〇 mass% (P). A-1) solution. The solution has a solution viscosity of 1 18 m P a _ s. [Synthesis Example 2] 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride and 212 g (1.0 mol) of 2, 2 as a diamine compound , _ dimethyl • 32- 201202343 -4,4 1 -diaminobiphenyl, dissolved in a mixed solvent of 370 g of Ν Μ P and 3,300 g of γ-butyrolactone The reaction was carried out at 4 ° C for 3 hours to obtain a solution containing poly-proline (PA-2). The solution had a solution viscosity of 154 mPa-s. <Synthesis of Polyimine> [Synthesis Example 3] 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 1 as a diamine compound 6 g (0.9 8 5 mol) of p-phenylenediamine and 7.8 g (0.015 mol) of cholesteryl 3,5-diaminobenzoate were dissolved in 3,042 g of NMP and reacted at 60 ° C for 6 hours. The solution viscosity of the obtained polyaminic acid solution was 181 mPa_s. Next, 3,380 g of NMP was added to the obtained polyamic acid solution, and 395 g of pyridine and 306 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the hydrazine imidization reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and pyridine and acetic anhydride were removed to the outside of the system. Thus, a solution containing 15% by mass of a polyamidimide (ΡΙ-1) having a ruthenium iodide ratio of about 95% was obtained. A small amount of the obtained polyimine solution was added, and γ-butyrolactone was added to form a solution having a polyimine concentration of 10% by mass. The solution viscosity measured was 102 mPa_s. [Synthesis Example 4] 11 〇g (0'50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and I60 g (〇_5〇mol), 3, 3a, which are tetradecanoic dianhydride, 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[l,2-c]furan-1,3-dione, And 94 g (0.87 m〇l) of p-phenylenediamine as a diamine compound, 25 g (0.10 mol) of i,3-bis(3-aminopropyl)tetramethyloxalate and 9.6 g (0.015 mol) -33- 201202343 3,6-bis(4-aminobenzyl methoxy) choline, 8. ig (0.030 mol) as a monoamine, dissolved in 960 g of NMP at 60 The reaction was carried out at ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added, and NMP was added thereto, and the viscosity of the solution having a solid concentration of 10% was measured and found to be 58 mPa·s. Next, 2,700 g of NMP was added to the obtained polyaminic acid solution, 400 g of pyridine and 4 10 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and pyridine and acetic anhydride were removed to the outside of the system. Thus, a solution containing about 15% by mass of polyamidimide (ΡΙ-2) having a ruthenium iodide ratio of 95% was obtained. A small amount of the obtained polyimine solution was added, and γ-butyrolactone was added to form a solution having a polyamidene concentration of 10% by mass, and the measured solution viscosity was 72 mPai. [Synthesis Example 5] 226 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 76 g (0.80 m〇l) of p-phenylenediamine as a diamine compound 53 g (0.1 mol) of 3,5-diaminobenzoic acid cholesteryl ester and 100 g (0.2 mol) of cholestyloxy-2,4-diaminobenzene dissolved in 1,820 g of NMP, The reaction was carried out at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added, and NMP was added thereto, and the viscosity of the solution having a solid concentration of 10% was measured and found to be 80 mPa_s. Next, 4,22 5 g of hydrazine P was added to the obtained polyaminic acid solution, and 力 1 〇 4 g of pyridine and 134 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at 1 1 〇 °C. After the hydrazine imidization reaction, the solvent in the system was replaced with a new NMP solvent, and the pyridine 'acetic anhydride was removed outside the system. Thus, a solution containing about 15% by mass of polyamidimide (PI-3) having a ruthenium iodide ratio of 66% was obtained. -34- 201202343 A small amount of the obtained polyaminin solution was added, and NMP was added to form a solution having a polyamidene concentration of 10% by mass, and the measured solution viscosity was 98 mPa·s. [Synthesis Example 6] 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 87 g (0.80 m〇l) of p-phenylenediamine as a diamine compound And 99 g (0.20 mol) of cholestyloxy-2,4-diaminobenzene was dissolved in 1,848 g of NMP, and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added, NMP was added, and the viscosity of the solution having a solid concentration of 10% was measured to be 120 mPa's. Next, 3,809 g of NMP was added to the obtained polyaminic acid solution, and 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system was replaced with a new NMP solvent, and pyridine and acetic anhydride were removed to the outside of the system. Thus, a solution containing about 15% by mass of a polyamidimide (PI-4) having a ruthenium iodide ratio of 49% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to form a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 155 mPa_s. [Synthesis Example 7] 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 76 g (0.70 mol) of p-phenylenediamine as a diamine compound, 4 (^(0.20111〇1) 4,4'-diaminodiphenylmethane and 5(^(0.10) 1 cholestyloxy-2,4·diaminobenzene dissolved in 1,556g In NMP, the reaction was carried out for 6 hours at 60 ° C. The obtained poly-proline solution was added in small portions, NMP was added, and the viscosity of the solution having a solid concentration of 10% was measured to be 133 mPa s. Next, the obtained poly-proline was used. 3,614 g of NMP was added to the solution, and -35-201202343 7 9 g of pyridine and 10 2 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at 1 1 ° C. After the dehydration ring closure reaction, the solvent in the system was used. NMP was subjected to solvent replacement (by this operation, pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system) to obtain a polyimine (P) containing about 15% by mass of ruthenium imidization ratio of 46%. a solution of 1-5), a small amount of the obtained polyimine solution was added, and NMP was added to form a solution having a concentration of 10% by mass of polyimine, and the measured solution viscosity was 133 mPa-s. The agents (TN-type liquid crystal display element using a) Preparation of >

[實施例U 將作爲聚合物[A]的含聚醯胺（PA-1)的溶液和含聚醯亞胺（PI-1)的溶液混合，並使聚醯胺酸（PA-1):聚醯亞胺 (PI-1) = 80:20(質量比），在其中加入γ-丁內酯、NMP和乙二醇單丁基醚，然後以相對於聚合物[Α]總計1 00質量份，加入相當於10質量份的式（1-1-1)，該式（卜1-1)是作爲環氧化合物[Β]以上述式（1-1)爲例子例舉的式，充分攪拌，形成溶劑組成爲γ-丁內酯：ΝΜΡ:乙二醇單正丁基醚=71:17:12(質量比），固體成分濃度3.5質量％的溶液。該溶液使用孔徑 Ιμηι的過濾器過濾，製備液晶配向劑（S-1)。 [實施例2~13，比較例1〜12] 使聚合物[Α]和環氧化合物[Β]的種類及其使用量分別如表1所示，和實施例1同樣地操作，製備液晶配向劑 (S - 2)〜（S -1 3 )和（C S -1)〜（C S -1 2)，將它們分別作爲實施例 2〜1 3、比較例1〜1 2。 -36- 201202343 另外，比較例中，和環氧化合物[B ]相對應而使用的 (G-1)~(G-3)分別如下所示。另外，表1中的（I-卜4)、 (1-1-15)、' (1-1-16)、（1-2-6)分別是指作爲上述式（1-1)和式 (I - 2 )的例子列舉的化合物。 G-l : Ν，Ν，Ν,’Ν·-四環氧丙基-間二甲苯基二胺 G-2: ^^-四環氧丙基-4,4'-二胺基二苯基甲烷 G-3 :聚氧乙烯（5)苯基環氧丙基醚（Nagase ChemteX 司，EX145) <液晶配向劑（VA型液晶顯示元件用）的製備> [實施例14] 在作爲聚合物[A]的含有聚醯亞胺（PI-3)的溶液中，加入NMP和乙二醇單正丁基醚，然後，以相對[A]聚合物總計100質量份，加入相當於10質量份的上述（1-1-1)作爲環氧化合物[B]，充分攪拌，形成溶劑組成是NMP:乙二醇單正丁基醚=60:40(質量比），固體成分濃度是3.5質量％的溶液。該溶液使用孔徑1 μηι的過濾器過濾，製備液晶配向劑 (S-14)。 [實施例15〜27，比較例13~25] 使聚合物[Α]和環氧化合物[Β]的種類及其使用量分別如表1所示，和實施例14同樣地操作，製備液晶配向劑 (S -1 5 )〜（S - 2 7)和（C S -1 3 )〜（C S - 2 5 ) ’將它們分別作爲實施例 15〜27、比較例13〜25。 <ΤΝ型液晶顯示元件的製造> -37- 201202343 [實施例2 8 ] 藉由旋塗器，將液晶配向劑（S-1)塗布在由ITO膜構成的透明導電膜上，該IT Ο膜設置在厚度1mm的玻璃基板的 —面上，在加熱板上，在80°C下預烘烤1分鐘，接著藉由在200°C下加熱30分鐘，形成膜厚80nm的塗膜。對該塗膜，使用具有捲繞了人造絲布的輥的摩擦器，在輥轉數 500rpm、台板移動速度3cm/s，絨毛壓入長度0.4mm下進行摩擦處理，賦予液晶配向能。之後，在超純水中進行1 分鐘超聲波洗滌，接著，在100 °C的無塵烘箱中乾燥10分鐘，從而得到具有液晶配向膜的基板。重複該操作，得到 —對（兩塊）具有液晶配向膜的基板。接著，在上述一對基板的具有液晶配向膜的各自的外部邊緣，塗布加入了直徑 5.5 μιη的氧化鋁球的環氧樹脂黏合劑後，重合壓接以使液晶配向膜面相對，將黏合劑硬化。接著，從液晶注入口，在一對基板之間，塡充向列型液晶（Merck公司，MLC-62 2 1 ) 後，用丙烯酸類光硬化黏合劑密封液晶注入□，製造液晶胞，將其作爲實施例2 8。 [實施例29~40和比較例26〜37] 使用實施例1〜13的液晶配向劑（S-1)〜（S-13)和比較例 1〜12的液晶配向劑（CS-1)〜（CS-12)，和實施例28同樣地操作，製造液晶顯示元件，將它們作爲實施例29~40和比較例 26~37 。 <VA型液晶顯示元件的製造> -38- 201202343 [實施例4 1 ] 藉由旋塗器，將液晶配向劑（S-14)塗布在ITO膜構成的透明導電膜上，該ITO膜設置在厚度1mm的玻璃基板的 —面上，在加熱板上，在80 °C下’預烘烤1分鐘，接著藉由在210 °C下加熱30分鐘，形成膜厚80nm的塗膜（液晶配向膜）。重複該操作，得到一對（兩塊）具有液晶配向膜的基板。接著，在上述一對基板的具有液晶配向膜的各自的外部邊緣，塗布加入了直徑5.5μιη的氧化鋁球的環氧樹脂黏合劑後，重合壓接以使液晶配向膜面相對’將黏合劑硬化。接著，從液晶注入口，在一對基板之間’塡充向列型液晶 (Merck公司，MLC-6608)後，用丙烯酸類光硬化黏合劑密封液晶注入口，製造液晶胞，將其作爲實施例4 1。 [實施例42〜54和比較例38〜50] 使用液晶配向劑（S -1 4) ~ ( S - 2 7)和比較例1 3 ~ 2 5的液晶配向劑（CS-13)〜（CS-25)，和實施例41同樣地操作，製造液晶顯示元件，將它們作爲實施例42~54和比較例3 8-5 0 ^ <評價> 對實施例1〜2 7和比較例1〜2 5的液晶配向劑以及實施例2 8 ~ 5 4和比較例2 6 ~ 5 0的液晶顯示元件進行下述評價。 [剝離性的測定][Example U] A polyamine-containing (PA-1)-containing solution as the polymer [A] and a solution containing polyiminoimine (PI-1) were mixed, and poly-proline (PA-1) was obtained: Polyimine (PI-1) = 80:20 (mass ratio), to which γ-butyrolactone, NMP and ethylene glycol monobutyl ether were added, and then totaled to 100 mass relative to the polymer [Α] In the formula (1-1-1), which is equivalent to 10 parts by mass, the formula (1-1) is an example in which the epoxy compound [Β] is exemplified by the above formula (1-1). The mixture was stirred to form a solution having a solvent composition of γ-butyrolactone: hydrazine: ethylene glycol mono-n-butyl ether = 71:17:12 (mass ratio), and a solid concentration of 3.5% by mass. This solution was filtered using a filter of pore size Ιμηι to prepare a liquid crystal alignment agent (S-1). [Examples 2 to 13, Comparative Examples 1 to 12] The types of the polymer [Α] and the epoxy compound [Β] and the amounts thereof used were as shown in Table 1, and liquid crystal alignment was prepared in the same manner as in Example 1. The agents (S - 2) - (S - 1 3 ) and (CS - 1) - (CS - 1 2) were used as Examples 2 to 13 and Comparative Examples 1 to 12, respectively. -36-201202343 In addition, in the comparative example, (G-1) to (G-3) used in correspondence with the epoxy compound [B] are as follows. In addition, (I-Bu 4), (1-1-15), '(1-1-16), (1-2-6) in Table 1 mean the above formula (1-1) and the formula, respectively. The compounds listed in the examples of (I - 2 ). Gl : Ν,Ν,Ν,'Ν·-tetraepoxypropyl-m-xylyldiamine G-2: ^^-tetraepoxypropyl-4,4'-diaminodiphenylmethane G -3 : Polyoxyethylene (5) phenylepoxypropyl ether (Nagase ChemteX, EX145) <Preparation of liquid crystal alignment agent (for VA type liquid crystal display element)> [Example 14] As a polymer [ In a solution containing polyimine (PI-3) of A], NMP and ethylene glycol mono-n-butyl ether are added, and then, based on 100 parts by mass of the total [A] polymer, 10 parts by mass is added. The above (1-1-1) was sufficiently stirred as the epoxy compound [B] to form a solvent composition of NMP: ethylene glycol mono-n-butyl ether = 60:40 (mass ratio), and the solid content concentration was 3.5% by mass. Solution. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (S-14). [Examples 15 to 27, Comparative Examples 13 to 25] The types of the polymer [Α] and the epoxy compound [Β] and the amounts thereof used were as shown in Table 1, and liquid crystal alignment was prepared in the same manner as in Example 14. The agents (S -1 5 )~(S - 2 7) and (CS -1 3 )~(CS - 2 5 ) ' were used as Examples 15 to 27 and Comparative Examples 13 to 25, respectively. <Production of ΤΝ-type liquid crystal display element> -37-201202343 [Example 2 8] A liquid crystal alignment agent (S-1) was applied onto a transparent conductive film made of an ITO film by a spin coater, which IT The ruthenium film was placed on the surface of a glass substrate having a thickness of 1 mm, prebaked on a hot plate at 80 ° C for 1 minute, and then heated at 200 ° C for 30 minutes to form a coating film having a film thickness of 80 nm. The coating film was rubbed with a roller having a roll of rayon cloth and a roll speed of 500 rpm, a platen moving speed of 3 cm/s, and a pile press length of 0.4 mm to impart liquid crystal alignment energy. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a dust-free oven at 100 °C for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two) substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive having an alumina ball of 5.5 μm in diameter is applied to each of the outer edges of the pair of substrates having the liquid crystal alignment film, and then the pressure is bonded to make the liquid crystal alignment film face opposite, and the adhesive is bonded. hardening. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-62 2 1 ) between the pair of substrates, and then the liquid crystal injection was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. As Example 2 8. [Examples 29 to 40 and Comparative Examples 26 to 37] The liquid crystal alignment agents (S-1) to (S-13) of Examples 1 to 13 and the liquid crystal alignment agents (CS-1) of Comparative Examples 1 to 12 were used. (CS-12) A liquid crystal display device was produced in the same manner as in Example 28, and these were referred to as Examples 29 to 40 and Comparative Examples 26 to 37. <Production of VA Type Liquid Crystal Display Element> -38-201202343 [Example 4 1] A liquid crystal alignment agent (S-14) was applied onto a transparent conductive film made of an ITO film by a spin coater, the ITO film It was set on the surface of a glass substrate having a thickness of 1 mm, and was prebaked on a hot plate at 80 ° C for 1 minute, and then heated at 210 ° C for 30 minutes to form a coating film having a film thickness of 80 nm (liquid crystal). Orientation film). This operation was repeated to obtain a pair (two pieces) of a substrate having a liquid crystal alignment film. Next, on the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball of 5.5 μm in diameter is applied, and then the pressure bonding is performed so that the liquid crystal alignment film faces are opposite to each other. hardening. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-6608) from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. Example 4 1. [Examples 42 to 54 and Comparative Examples 38 to 50] Using a liquid crystal alignment agent (S -1 4) ~ (S - 2 7) and a liquid crystal alignment agent (CS-13) of Comparative Example 1 3 to 25 (CS-13) -25), liquid crystal display elements were produced in the same manner as in Example 41, and these were used as Examples 42 to 54 and Comparative Examples 3 8 - 5 0 ^ <Evaluation> For Examples 1 to 27 and Comparative Example 1 The liquid crystal display elements of ～25 and the liquid crystal display elements of Examples 2 8 to 5 4 and Comparative Examples 2 6 to 50 were subjected to the following evaluations. [Measurement of peelability]

藉由旋塗器，將實施例1〜27和比較例1~25的各液晶配向劑塗布在由ITO膜構成的透明導電膜上，該ITO膜設置在厚度1mm的玻璃基板的一面上’在加熱板上’在1〇〇 °C -39- 201202343 下，預烘烤90秒鐘，形成膜厚約80ηπι的塗膜。重複該操作’製造兩塊具備塗膜的基板。接著，將得到的基板在氮氣環境下，在2 5 °C的暗室內保管，分別在1 2小時後、7 2 小時後，從暗室取出，在加入了 4(TC的NMP的燒杯中浸漬 2分鐘。2分鐘後，從燒杯取出基板，用超純水洗滌幾次後，藉由吹風’去除表面的水滴，觀察基板，觀察有無殘留塗膜。經過72小時後，從暗室取出，浸漬NMP後沒有殘留塗膜，剝離性良好，記作“ 〇 ” ；經過7 2小時後，從暗室取出的基板無法剝離，但是1 2小時後，從暗室取出的基板，可以剝離的記作“△”，無法剝離的記作“X”。結果在表1中表示。 [電壓保持率的測定] 對和顯示品質降低相關的電性質惡化問題，由液晶顯示元件的電壓保持率評價。對實施例28〜54和比較例26〜50 的各液晶顯示元件，在7 0 °C下以6 0微秒的施加時間、1 6 7 毫秒的間隔施加5V的電壓後，利用TOYO Technica公司製造的VHR-1測定從解除施加到〗67毫秒後的電壓保持率，將該値作爲初期電壓保持率（V Η ! N)。接著，對測定初期電壓保持率後的液晶胞，使用以碳弧爲光源的耐候性試驗儀’光照射1,000小時。對光照射後的液晶顯示元件，藉由和上述同樣的方法，再次測定電壓保持率，將該値作爲照射後的電壓保持率（VHAF)。將由VHlN-VHAF求得的電壓保持率的減少量定義爲ΔΥΗΙΙ計算.。 -40- 201202343 TN型的液晶顯示元件（實施例28〜40和比g 在電壓保持率的減少量 △ V H R小於 7 %時，瓦 “ ◎”；在7%以上且小於10%時，可靠性記作“〇以上的情形下，可靠性記作“ X ”。 VA型的液晶顯示元件（實施例41~54和比® 在電壓保持率的減少量 AVHR不足 2.5 %時，ί “◎” ；在2.5%以上且不足5%時，可靠性記作上的情形下，可靠性記作“ X ”。結果在表2中表例2 6〜3 7) 靠性記作 :在 1 0% 例38〜50) 靠性記作 :在5%以 -41 - 201202343 液晶配向劑組成評價聚合物[A]_ 環氧化合物[B] 剝離性聚醯胺酸聚醯亞胺種類 (質量份）種類用量 (質量份）種類用fl (質量份）责施例1 (S-1) (PA-1) 80 (PI-1) 20 (1-1-1) 10 υ 實施例2 (S-2) (PA-1) 80 (PI-1) 20 (Μ-D 3 U 實施例3 (S-3) (PA-1) 80 (PI-1) 20 (1-1-4) 10 U ft施例4 (S-4) (PA-1) 80 (PI-1) 20 (1-1-4) 1 U 责施例5 (S-5) (PA-1) 80 (PI-1) 20 (M-4) 20 U 责施例6 (S-6) (PA-1) 80 (PI-1) 20 (1-1-4) 30 〇责施例7 (S-7) (PA-1) 80 (PI-1) 20 (1-1-4) 45 U 责施例8 (S-8) (PA-2) 80 (PI-2) 20 (1-1-4) 5 υ 责施例9 (S-9) (PA-2) 80 (PI-2) 20 (1-1-4) 20 U 實施例10 (S-10) (PA-2) 80 (PI-2) 20 (I-2-6) 5 U 實施例11 (S-11) (PA-2) 80 (PI-2) 20 (I-2-6) 30 υ 實施例12 (S-12) (PA-2) 80 (PI-2) 20 (1-1-15) 20 υ 實施例13 (S-13) (PA-2) 80 (PI-2) 20 (1-1-16) 20 υ 比較例1 (CS-1) (PA-1) 80 (PI-2) 20 - - υ 比較例2 (CS-2) (PA-1) 80 (PI-2) 20 G-1 5 Δ 比較例3 (CS-3) (PA-1) 80 (PI-2) 20 G-1 10 X 比較例4 (CS-4) (PA-1) 80 (PI-2) 20 G-1 30 X 比較例5 (CS-5) (PA-1) 80 (PI-2) 20 G-3 5 υ 比較例6 (CS-6) (PA-1) 80 (PI-2) 20 G-3 30 υ 比較例7 (CS-7) (PA-2) 80 (PI-2) 20 - - υ 比較例8 (CS-8) (PA-2) 80 (PI-2) 20 G-1 5 Δ 比較例9 (CS-9) (PA-2) 80 (PI-2) 20 G-1 10 X 比較例10 (CS-10) (PA-2) 80 (PI-2) 20 G-1 30 X 比較例11 (CS-11) (PA-2) 80 (Pi-2) 20 G-2 5 X 比較例12 (CS-12) (PA-2) 80 (PI-2) 20 G-2 30 X 實施例14 (S-14) - - (PI-3) 100 (Μ-D 10 U 賁施例15 (S-15) - - (PI-3) 100 (Μ-D 3 U 賁施例16 (S-16) - - (PI-3) 100 (1-1-4) 10 υ 實施例17 (S-17) - - (PI-4) 100 (1-1-4) 1 υ 賁施例18 (S-18) - - (PI-4) 100 (1-1-4) 10 υ 责施例19 (S-19) - - (PI-4) 100 (1-1-4) 20 υ ft施例20 (S-20) - - (PI-4) 100 (1-1-4) 30 U 责施例21 (S-21) - - (PI-4) 100 (1-1-4) 45 υ 责施例22 (S-22) - - (PI-3)和(PI-5) 80、20 (1-1-4) 5 υ 责施例23 (S-23) - - (PI-3)和(P 卜 5) 80、20 (1-1-4) 20 υ ft施例24 (S-24) - - (Pl-3)和(PI-5) 80、20 (I-2-6) 5 υ 贲施例25 (S-25) - - (PI-3)和(PI-5) 80、20 (I-2-6) 30 υ 實施例26 (S-26) - - (PI-3)和(PI-5) 80、20 (1-1-15) 20 Ο 责施例27 (S-27) - - (PI-3)和(PI-5) 80、20 (1-1-16) 20 U 比較例13 (CS-13) - - (PI-3) 100 - - υ 比較例14 (CS-14) - - (PI-3) 100 G-1 5 Δ 比較例15 (CS-15) - - (PI-3) 100 G-1 30 Δ 比較例16 (CS-16) - - (PI-3) 100 G-2 5 X 比較例17 (CS-17) - - (PI-3) 100 G-2 30 X 比較例18 (CS-18) - 琴 (PI-3) 100 G-3 5 U 比較例19 (CS-19) - - (PI-3) 100 G-3 30 υ 比較例20 (CS-20) - - (PI-3)和(P 卜 5) 80、20 - - U 比較例21 (CS-21) - - (PI-3)和(P 丨-5) 80、20 G-1 5 比較例22 (CS-22) - - (PI-3)和(PI-5) 80、20 G-1 30 Δ 比較例23 (CS-23) - - (PI-3)和(PI-5) 80、20 G-2 5 X 比較例24 (CS-24) - - (PI-3)和(P 卜 5) 80、20 G-3 5 U 比較例25 (CS-25) - - (PL3)和(P 卜 5) 80、20 G-3 30 υ -42- 201202343 [表2]Each of the liquid crystal alignment agents of Examples 1 to 27 and Comparative Examples 1 to 25 was applied onto a transparent conductive film made of an ITO film which was provided on one side of a glass substrate having a thickness of 1 mm by a spin coater. The heating plate was prebaked for 90 seconds at 1 ° C -39 - 201202343 to form a coating film having a film thickness of about 80 η π. This operation was repeated to manufacture two substrates having a coating film. Next, the obtained substrate was stored in a dark room at 25 ° C under a nitrogen atmosphere, and after 12 hours and 72 hours, respectively, it was taken out from the dark room, and immersed in a beaker of 4 (TC NMP). After 2 minutes, the substrate was taken out from the beaker, washed several times with ultrapure water, and the surface water droplets were removed by blowing, and the substrate was observed to observe the presence or absence of a residual coating film. After 72 hours, it was taken out from the dark room and immersed in NMP. There was no residual coating film, and the peeling property was good, and it was described as "〇"; after 72 hours, the substrate taken out from the dark room could not be peeled off, but after 12 hours, the substrate taken out from the dark room was marked as "△". The result of the inability to peel off is shown as "X". The results are shown in Table 1. [Measurement of Voltage Retention Rate] The problem of deterioration of electrical properties related to deterioration in display quality was evaluated by the voltage holding ratio of the liquid crystal display element. 54 and each of the liquid crystal display elements of Comparative Examples 26 to 50 were applied with a voltage of 5 V at an interval of 60 μsec and a distance of 167 ms at 70 ° C, and then measured by VHR-1 manufactured by TOYO Technica Co., Ltd. Unloading The voltage holding ratio after 67 milliseconds is used as the initial voltage holding ratio (V Η ! N). Next, for the liquid crystal cell after the initial voltage holding ratio is measured, a weather resistance tester using a carbon arc as a light source is used. After irradiating for 1,000 hours, the voltage holding ratio was measured again by the same method as described above, and the enthalpy was used as the voltage holding ratio (VHAF) after the irradiation. The voltage obtained by VHlN-VHAF was maintained. The amount of decrease in the rate is defined as ΔΥΗΙΙ.. -40- 201202343 TN type liquid crystal display element (Examples 28 to 40 and ratio g when the voltage retention rate reduction ΔVHR is less than 7%, watt "◎"; at 7 When the value is more than or equal to less than 10%, the reliability is referred to as "〇", and the reliability is referred to as "X". The VA type liquid crystal display element (Examples 41 to 54 and the ratio of the ratio of the voltage retention rate of the ratio AVHR) When it is less than 2.5%, ί "◎"; in the case of 2.5% or more and less than 5%, the reliability is recorded as "X" in the case of reliability. The result is shown in Table 2, Table 2 6~3 7) According to sex: in 10% of cases 38~50) Responsibility is recorded as: 5% -41 - 201202343 Liquid crystal alignment agent composition evaluation polymer [A]_ Epoxy compound [B] Releasable polyglycine polyimine type (parts by mass) Type and amount (parts by mass) Type fl (parts by mass) Example 1 (S-1) (PA-1) 80 (PI-1) 20 (1-1-1) 10 实施 Example 2 (S-2) (PA-1) 80 (PI-1) 20 ( Μ-D 3 U Example 3 (S-3) (PA-1) 80 (PI-1) 20 (1-1-4) 10 U ft Example 4 (S-4) (PA-1) 80 ( PI-1) 20 (1-1-4) 1 U Responsible for Example 5 (S-5) (PA-1) 80 (PI-1) 20 (M-4) 20 U Responsibility Example 6 (S-6 ) (PA-1) 80 (PI-1) 20 (1-1-4) 30 Responsibility Example 7 (S-7) (PA-1) 80 (PI-1) 20 (1-1-4) 45 U Responsibility 8 (S-8) (PA-2) 80 (PI-2) 20 (1-1-4) 5 责 Responsibility Example 9 (S-9) (PA-2) 80 (PI- 2) 20 (1-1-4) 20 U Example 10 (S-10) (PA-2) 80 (PI-2) 20 (I-2-6) 5 U Example 11 (S-11) ( PA-2) 80 (PI-2) 20 (I-2-6) 30 实施 Example 12 (S-12) (PA-2) 80 (PI-2) 20 (1-1-15) 20 实施 Implementation Example 13 (S-13) (PA-2) 80 (PI-2) 20 (1-1-16) 20 υ Comparative Example 1 (CS-1) (PA-1) 80 (PI-2) 20 - - υ Comparative Example 2 (CS-2) (PA-1) 80 (PI-2) 20 G-1 5 Δ Comparative Example 3 (CS-3) (PA-1) 80 (PI-2) 20 G-1 10 X Comparative Example 4 (CS-4) (PA-1) 80 (PI-2) 20 G-1 30 X Comparative Example 5 (CS-5) (PA-1) 80 (PI-2) 20 G-3 5 υ Comparative Example 6 (CS-6) (PA-1) 80 (PI-2) 20 G-3 30 υ Comparative Example 7 (CS-7) (PA-2) 80 (PI-2) 20 - - υ Comparative Example 8 (CS-8) (PA-2) 80 (PI-2) 20 G-1 5 Δ Comparative Example 9 (CS-9) (PA-2) 80 (PI-2) 20 G- 1 10 X Comparative Example 10 (CS-10) (PA-2) 80 (PI-2) 20 G-1 30 X Comparative Example 11 (CS-11) (PA-2) 80 (Pi-2) 20 G- 2 5 X Comparative Example 12 (CS-12) (PA-2) 80 (PI-2) 20 G-2 30 X Example 14 (S-14) - - (PI-3) 100 (Μ-D 10 U Example 15 (S-15) - - (PI-3) 100 (Μ-D 3 U Example 16 (S-16) - - (PI-3) 100 (1-1-4) 10 实施 Implementation Example 17 (S-17) - - (PI-4) 100 (1-1-4) 1 贲 Example 18 (S-18) - - (PI-4) 100 (1-1-4) 10 υ Responsibility Example 19 (S-19) - - (PI-4) 100 (1-1-4) 20 υ ft Example 20 (S-20) - - (PI-4) 100 (1-1-4) 30 U Responsibility Example 21 (S-21) - - (PI-4) 100 (1-1-4) 45 责 Responsibility Example 22 (S-22) - - (PI-3) and (PI-5) 80, 20 (1-1-4) 5 υ Responsibility Example 23 (S-23) - - (PI-3) and (P Bu 5) 80, 20 (1-1-4) 20 υ ft Example 24 (S-24) - - (Pl-3) and (PI-5) 80, 20 (I-2-6) 5 υ 贲 Example 25 (S-25) - - (PI-3) and (PI-5) 80, 20 (I-2-6) 30 实施 Example 26 (S-26 ) - - (PI-3) and (PI-5) 80, 20 (1-1-15) 20 责 Responsible for Example 27 (S-27) - - (PI-3) and (PI-5) 80, 20 (1-1-16) 20 U Comparative Example 13 (CS-13) - - (PI-3) 100 - - υ Comparative Example 14 (CS-14) - - (PI-3) 100 G-1 5 Δ Comparative Example 15 (CS-15) - - (PI-3) 100 G-1 30 Δ Comparative Example 16 (CS-16) - - (PI-3) 100 G-2 5 X Comparative Example 17 (CS-17) - - (PI-3) 100 G-2 30 X Comparative Example 18 (CS-18) - Piano (PI-3) 100 G-3 5 U Comparative Example 19 (CS-19) - - (PI-3) 100 G-3 30 υ Comparative Example 20 (CS-20) - - (PI-3) and (P Bu 5) 80, 20 - - U Comparative Example 21 (CS-21) - - (PI-3) and (P丨-5) 80, 20 G-1 5 Comparative Example 22 (CS-22) - - (PI-3) and (PI-5) 80, 20 G-1 30 Δ Comparative Example 23 (CS-23) - - (PI-3) and (PI-5) 80, 20 G-2 5 X Comparative Example 24 (CS-24) - - (PI-3) and (P Bu 5) 80, 20 G-3 5 U Comparative Example 25 (CS-25) - - (PL3) and (P Bu 5) 80, 20 G-3 30 υ -42- 201202343 [Table 2]

液晶顯示元件使用的液晶配向劑電壓保持率 △VHR(%) 評價 TN型责施例28 (S-1) 6.2 ◎ 實施例29 (S-2) 6.8 ◎ 實施例30 (S-3) 4.2 ◎ 實施例31 (S-4) 7.9 υ 實施例32 (S-5) 4.7 ◎ 實施例33 (S-6) 5.9 ◎ 實施例34 (S-7) 7.2 υ 實施例35 (S-8) 5.8 ◎ 實施例36 (S-9) 5.1 ◎ 實施例37 (S-10) 6.1 ◎ 實施例38 (S-11) 5.9 ◎ 實施例39 (S-12) 7.1 υ 實施例40 (S-13) 6.7 ◎ 比較例26 (CS-1) 18.6 X 比較例27 (CS-2) 16 X 比較例28 (CS-3) 11.6 X 比較例29 (CS-4) 6.8 ◎ 比較例30 (CS-5) 16.8 X 比較例31 (CS-6) 10.9 X 比較例32 (CS-7) 19.6 X 比較例33 (CS-8) 16.2 X 比較例34 (CS-9) 12.7 X 比較例35 (CS-10) 7.7 υ 比較例36 (CS-11) 10.7 X 比較例37 (CS-12) 6.4 ◎ VA型 ft施例41 (S-14) 1.9 ◎ 贲施例42 (S-15) 1.6 ◎ 贲施例43 (S-16) 1 ◎ 责施例44 (S-17) 2.9 υ ft施例45 (S-18) 2.3 ◎ 责施例46 (S-19) 1.4 ◎ 责施例47 (S-20) 1.8 ◎ 责施例48 (S-21) 2.4 ◎ 责施例49 (S-22) 1.6 ◎ 賁施例50 (S-23) 0.8 ◎ 责施例51 (S-24) 1.8 ◎ 责施例52 (S-25) 0.7 ◎ 责施例53 (S-26) 2.4 ◎ 贲施例54 (S-27) 2.2 ◎ 比較例38 (CS-13) 7.1 X 比較例39 (CS-14) 5.1 X 比較例40 (CS-15) 4 υ 比較例41 (CS-16) 3.1 υ 比較例42 (CS-17) 0.7 ◎ 比較例43 (CS-18) 7.4 X 比較例44 (CS-19) 5.9 X 比較例45 (CS-20) 6.8 X 比較例46 (CS-21) 5.1 X 比較例47 (CS-22) 4.2 υ 比較例48 (CS-23) 1.9 ◎ 比較例49 (CS-24) 7.2 X 比較例50 (CS-25) 5.5 X -43- 201202343 如表1和表2的結果所示，由本發明的液晶配向劑形成的液晶配向膜’可以形成重新作業時容易剝離的液晶配向膜。另外，還可知具有該液晶配向膜的本發明的液晶顯示元件’無論在TN型和Va型的哪一種顯示模式下，電壓保持率都良好’電性質不會惡化，可以抑制顯示品質降低。產業上的利用可能性根據本發明，可以形成：抑制由電性質的惡化等顯示品質降低’而且重新作業時容易剝離的液晶配向膜。該液晶顯示元件適合用於各種裝置，例如可以在鐘錶、便攜型遊戲機、文字處理器、筆記型電腦、導航系統、攝影錄影機、便攜資訊終端、數位碼相機、行動電話、各種監視器、液晶電視等顯示裝置中使用。另外，由該聚合物組成物形成的膜還可以作爲電子材料用絕緣膜使用。【圖式簡單說明】 •frrr 無0 【主要元件符號說明】 Αττ 無0 -44-Liquid crystal alignment agent voltage retention rate ΔVHR (%) used for liquid crystal display element Evaluation TN type application 28 (S-1) 6.2 ◎ Example 29 (S-2) 6.8 ◎ Example 30 (S-3) 4.2 ◎ Example 31 (S-4) 7.9 实施 Example 32 (S-5) 4.7 ◎ Example 33 (S-6) 5.9 ◎ Example 34 (S-7) 7.2 实施 Example 35 (S-8) 5.8 ◎ Example 36 (S-9) 5.1 ◎ Example 37 (S-10) 6.1 ◎ Example 38 (S-11) 5.9 ◎ Example 39 (S-12) 7.1 实施 Example 40 (S-13) 6.7 ◎ Comparative Example 26 (CS-1) 18.6 X Comparative Example 27 (CS-2) 16 X Comparative Example 28 (CS-3) 11.6 X Comparative Example 29 (CS-4) 6.8 ◎ Comparative Example 30 (CS-5) 16.8 X Comparative Example 31 (CS-6) 10.9 X Comparative Example 32 (CS-7) 19.6 X Comparative Example 33 (CS-8) 16.2 X Comparative Example 34 (CS-9) 12.7 X Comparative Example 35 (CS-10) 7.7 υ Comparative Example 36 (CS-11) 10.7 X Comparative Example 37 (CS-12) 6.4 ◎ VA type ft application 41 (S-14) 1.9 ◎ 贲 Example 42 (S-15) 1.6 ◎ 贲 Example 43 (S -16) 1 ◎ Responsibility Example 44 (S-17) 2.9 υ ft Example 45 (S-18) 2.3 ◎ Responsibility Example 46 (S-19) 1.4 ◎ Responsibility Example 47 (S-20) 1.8 ◎ Responsibility Example 48 (S-21) 2.4 ◎ Responsibility Example 49 (S-22) 1.6 ◎ 贲 Example 50 (S-23) 0.8 ◎ Responsibility Example 51 (S-24) 1.8 ◎ Responsibility Example 52 (S-25) 0.7 ◎ Responsibility Example 53 (S-26) 2.4 ◎ Example 54 (S-27) 2.2 ◎ Comparative Example 38 (CS-13) 7.1 X Comparative Example 39 (CS-14) 5.1 X Comparative Example 40 (CS-15) 4 υ Comparative Example 41 (CS-16) 3.1 υ Comparative Example 42 (CS-17) 0.7 ◎ Comparative Example 43 (CS-18) 7.4 X Comparative Example 44 (CS-19) 5.9 X Comparative Example 45 (CS-20) 6.8 X Comparative Example 46 (CS-21) 5.1 X Comparative Example 47 (CS-22) 4.2 υ Comparative Example 48 (CS-23) 1.9 ◎ Comparative Example 49 (CS-24) 7.2 X Comparative Example 50 (CS-25) 5.5 X -43- 201202343 As shown in Table 1 and As shown in the results of Table 2, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which is easily peeled off during rework. Further, it is also known that the liquid crystal display element of the present invention having the liquid crystal alignment film has a good voltage holding ratio in either of the TN type and the Va type display mode, and the electrical properties are not deteriorated, and deterioration in display quality can be suppressed. Industrial Applicability According to the present invention, it is possible to form a liquid crystal alignment film which suppresses deterioration in display quality such as deterioration in electrical properties and which is easily peeled off during rework. The liquid crystal display element is suitable for use in various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a navigation system, a video recorder, a portable information terminal, a digital code camera, a mobile phone, various monitors, Used in display devices such as LCD TVs. Further, the film formed of the polymer composition can also be used as an insulating film for electronic materials. [Simple description of the diagram] • frrr no 0 [Description of main component symbols] Αττ No 0 -44-

Claims

201202343 七、申請專利範圍： 1 一種液晶配向劑’其包含： [A] 由聚醯胺酸和聚醯亞胺構成的群組中選出的至少一種聚合物，以及 [B] 下述式（I)所示的含醯亞胺環的環氧化合物， Ο201202343 VII. Patent application scope: 1 A liquid crystal alignment agent comprising: [A] at least one polymer selected from the group consisting of polyproline and polyimine, and [B] the following formula (I) ) an oxime ring-containing epoxy compound, Ο

式（I)中，RA是單鍵或碳原子數爲1〜4的烷二基；汉8是2 價的鏈狀烴基、2價的脂環烴基、2價的芳香族基、2價的雜環基、或組合它們形成的基；n是〇或1的整數。 2,如申請專利範圍第1項的液晶配向劑’其中該式（I)爲由下述式（1-1)和式（1-2)所示的化合物構成的群組中選出的至少一種， 0In the formula (I), RA is a single bond or an alkanediyl group having 1 to 4 carbon atoms; and Han 8 is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, and a divalent group. Heterocyclic groups, or a group in which they are combined; n is an integer of 〇 or 1. 2. The liquid crystal alignment agent of the first aspect of the invention, wherein the formula (I) is at least one selected from the group consisting of compounds represented by the following formulas (1-1) and (1-2) , 0

0 R20 R2

0 式（1-1)和式（1-2)中，RA和該式（I)的定義相同；R1、R 和R3各自獨立，爲可包含-〇-、-C00-、-0C0-的碳原子 -45- 201202343 數爲1~2 0的直鏈狀或支鏈狀的烷基；另外，…和r2、或者R1和R2和R3可以相互連接，形成氫原子的部分或全部可以被取代的環結構；η是0或1的整數。 3 .如申請專利範圍第1或2項的液晶配向劑，其中該[A ]聚合物爲：由聚醯胺酸和將該聚醯胺酸脫水閉環形成的聚醯亞胺構成的群組中選出的至少一種，該聚醯胺酸是使用四羧酸二酐合成，該四羧酸二酐包含由2,3,5 -三羧基環戊基乙酸二酐、3, 5,6-三羧基-2-羧甲基降萡烷-2:3, 5·· 6-二酐和2,4,6，8-四羧基雙環[3.3.0]-辛烷- 2:4,6:8-二酐構成的群組中選出的至少一種。 4.如申請專利範圍第1或2項的液晶配向劑，其中該式（I) 的 RA 是甲院二基（methanediyl)。 5 .如申請專利範圍第2項的液晶配向劑，其中在該式（I -1 ) 和式（1-2)中，R1和R2相互連接，形成部分的氫原子或全部可以被取代的苯環。 6. —種液晶配向膜，其係由申請專利範圍第1至5項中任一項的液晶配向劑所形成。 7 . —種液晶顯示元件，其具備如申請專利範圍第6項的液晶配向膜。 8 . —種聚合物組成物，其包含： [A] 由聚醯胺酸和聚醯亞胺構成的群組中選出的至少一種聚合物，以及 [B] 下述式（I)所示的含醯亞胺環的環氧化合物； -46- 2012023430 In the formula (1-1) and the formula (1-2), RA and the formula (I) have the same definition; R1, R and R3 are each independently, and may include -〇-, -C00-, -0C0- A carbon-45-201202343 number is a linear or branched alkyl group of 1 to 20; in addition, ... and r2, or R1 and R2 and R3 may be bonded to each other, and part or all of a hydrogen atom may be substituted. Ring structure; η is an integer of 0 or 1. 3. The liquid crystal alignment agent of claim 1 or 2, wherein the [A] polymer is in the group consisting of polylysine and polyamidene formed by dehydration of the polyglycolic acid. At least one selected, the polylysine is synthesized using a tetracarboxylic dianhydride comprising 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxyl 2-carboxymethylnorbornane-2:3,5·6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]-octane-2:4,6:8- At least one selected from the group consisting of dianhydrides. 4. The liquid crystal alignment agent according to claim 1 or 2, wherein the RA of the formula (I) is a methanediyl group. 5. The liquid crystal alignment agent of claim 2, wherein in the formula (I-1) and the formula (1-2), R1 and R2 are bonded to each other to form a partial hydrogen atom or all of the benzene which may be substituted. ring. A liquid crystal alignment film formed by the liquid crystal alignment agent of any one of claims 1 to 5. A liquid crystal display element comprising the liquid crystal alignment film of claim 6 of the patent application. 8. A polymer composition comprising: [A] at least one polymer selected from the group consisting of polyproline and polyimine, and [B] represented by the following formula (I) Epoxide compound containing a quinone ring; -46- 201202343

式（I)中，RA是單鍵或碳原子數爲1〜4的烷二基；118是2 價的鏈狀烴基、2價的脂環烴基、2價的芳香族基、2價的雜環基、或組合它們形成的基；η是0或1的整數。 -47- 201202343 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： Μ 。 j» 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：In the formula (I), RA is a single bond or an alkanediyl group having 1 to 4 carbon atoms; 118 is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic group, and a divalent impurity. a ring group, or a group in which they are combined; η is an integer of 0 or 1. -47- 201202343 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ . j» V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: