TW200804936A

TW200804936A - Vertical alignment mode liquid crystal alignment agent and vertical alignment mode liquid crystal display device

Info

Publication number: TW200804936A
Application number: TW096117023A
Authority: TW
Inventors: Tsutomu Kumagai; Satoshi Fukuma; Michinori Nishikawa
Original assignee: Jsr Corp
Priority date: 2006-05-17
Filing date: 2007-05-14
Publication date: 2008-01-16
Also published as: CN101075043A; KR20070111354A

Abstract

The present invention provides a vertical alignment mode liquid crystal alignment agent that shows a high voltage holding ratio and a good coating property to substrate. The vertical alignment mode liquid crystal alignment agent is made of polymer which includes from amic acid repeating unit and/or imide repeating unit. The group of the above-mentioned repeating unit being from diamine contains the after-mentioned two groups, for example, one is at least one selected from dodecanoxyl-2,4-diaminobenzene or a specific diamine with steroid structure, and the other is another kind of specific diamine like 1,4-bis(aminemethyl)-bicyclo[2.2.1] heptane.

Description

200804936 九、發明說明：【發明所屬之技術領域】本發明涉及垂直配向型液晶配向劑和具有垂直配向型液晶配向膜的液晶顯示元件。更具體地說，涉及顯示良好印刷性、且各種電特性優良的垂直配向型液晶配向劑和具有垂直配向型液晶配向膜的液晶顯示元件。【先前技術】目前，作爲液晶顯示元件已知具有所謂TN型（Twisted ί Nematic)液晶胞的TN型液晶顯示元件，該元件在設置透明導電膜的基板表面上形成具有聚醯胺酸、聚醯亞胺等所形成的液晶配向膜作爲液晶顯示元件用基板，將2片該基板對向配置，在其間隙內形成具有正介電各向異性的向列型液晶層，構成夾層（sandwich)結構的晶胞，液晶分子的長軸從一片基板向另一片基板連續地扭轉90度。並且，還開發了對比度比TN型液晶顯示元件高、視角依賴性少的STN(Super Twisted Nematic)型液晶顯示元件和 ® 垂直配向型液晶顯示元件。該STN型液晶顯示元件在向列型液晶中摻合光學活性物質之手性劑作爲液晶使用，並利用通過使液晶分子的長軸在基板間處於連續扭轉180度以上的狀態而產生的雙折射效應。並且近年來，新型液晶顯示元件的開發也很活躍，作爲其中之一，提出了一種橫電場型液晶顯示元件，其驅動液晶的2個電極在一側基板上以梳齒狀設置，產生與基板 200804936 面平行的電場，控制液晶分子。該元件通常被稱爲平面切換型（IPS型），已知其廣視角性能優異。並且最近通過使用光學補償膜使廣視角性能進一步提高，使其具備獲得與無色調反轉和色調變化的陰極射線管匹敵的廣視角的顯赫特徵。作爲上述以外的液晶顯示元件，提出了具有負介電各向異性的液晶分子在基板上垂直配向的被稱作爲 MVA(Multi domain Vertical Alignment)型或 PVA(Patterned V e r t i c a 1 A1 i g n m e n t)型的垂直配向型液晶顯示元件。這些 ΜVA型或PVA型液晶顯示元件不僅視角·對比度優良，而且在形成液晶配向膜的過程中也可以不需要進行磨刷 (Rubbing)處理等，在製造工程方面也是優良的。以前，作爲這些液晶配向膜，由於耐熱性、與液晶的親和性或者機械強度優良，在任何一種顯示方式中，都將聚醯胺酸或其脫水閉環的聚醯亞胺用於很多液晶顯示元件。目前，垂直配向型液晶顯示元件的液晶配向膜，如專利文獻1中所述，將液晶配向劑塗敷於基板上而形成，作爲基本性能，必需有能使液晶垂直配向的垂直配向性。近年來，隨著垂直配向型液晶顯示元件普及率的擴大，藉由垂直型液晶配向膜可達成的顯示品質提高和生產力提高的要求水準不斷提高。對配向膜要求的特性也是多種多樣的，其中作爲最重要的特性，如專利文獻1〜4所述，可以 200804936 舉出對高電壓保持性能和對基板的良好塗敷性的改進。通常爲了達到高電壓保持性能，已知，如專利文獻5所述，使配向膜中使用的聚醯亞胺具有高醯亞胺化率的方法。但是，由於醯亞胺化率的提高使其在溶劑中的溶解性下降，因而使可以使用的溶劑範圍受到限制，結果，難以實現良好的塗敷性。這樣，能夠產生高電壓保持特性的醯亞胺化率的提高，由於使塗敷性大大變差，因而成爲折衷選擇 (trade-off)的關係，而成問題。【專利文獻1】日本特開2002 — 32705 8號公報【專利文獻2】日本特開2002 — 1 62630號公報【專利文獻3】日本特開2004 — 67 5 89號公報【專利文獻4】日本特開2005 — 30 8 924號公報【專利文獻5】日本特開2004 - 1 63724號公報【發明内容】發明所欲解決之課題本發明的目的是提供具有高電壓保持特性，同時具有對基板的良好塗敷性的垂直配向型液晶配向劑。本發明的另一目的是提供具有由本發明上述液晶配向劑形成的液晶配向膜，並顯示高電壓保持特性的垂直配向型液晶顯示元件。本發明的其他目的和優點，可以由以下的說明看出。爲解決課題之手段根據本發明，本發明的上述目的和優點，第1，由一 200804936 式（I - 1)表示的醯胺酸重複單元和下述式（I - 2)表示的醯亞胺重複單元的至少一種重複單元的聚合物，上述式（I - 1) 中的Q1和上述式（I — 2)中的Q2含有下述式（II — 1)和（II — 2) 各自表示的二價有機基團中的至少一種，以及下述式（III 1)表示的二價有機基團中的至少一種。200804936 Nineth, the invention relates to a vertical alignment type liquid crystal alignment agent and a liquid crystal display element having a vertical alignment type liquid crystal alignment film. More specifically, it relates to a vertical alignment type liquid crystal alignment agent which exhibits good printability and is excellent in various electrical characteristics, and a liquid crystal display element having a vertical alignment type liquid crystal alignment film. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (Twisted ί Nematic) liquid crystal cell is known, which is formed on the surface of a substrate on which a transparent conductive film is provided with poly-proline, polyfluorene A liquid crystal alignment film formed of an imide or the like is used as a substrate for a liquid crystal display element, and two substrates are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The unit cell, the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element and a ? vertical alignment type liquid crystal display element having a higher contrast ratio than the TN type liquid crystal display element and having less viewing angle dependency have been developed. The STN-type liquid crystal display device uses a chiral agent in which a photoactive material is mixed in a nematic liquid crystal as a liquid crystal, and uses birefringence generated by causing a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. effect. In recent years, the development of new liquid crystal display elements has also been active. As one of them, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving liquid crystals are arranged in a comb shape on one side substrate to generate a substrate. 200804936 Parallel electric field, controlling liquid crystal molecules. This element is generally called a planar switching type (IPS type) and is known to have excellent wide viewing angle performance. And recently, the use of an optical compensation film has further improved the wide viewing angle performance, and it has a remarkable feature of obtaining a wide viewing angle which is comparable to a cathode ray tube which has no tone inversion and color tone change. As a liquid crystal display element other than the above, it is proposed that a liquid crystal molecule having a negative dielectric anisotropy is vertically aligned on a substrate, and is referred to as a MVA (Multi domain Vertical Alignment) type or a PVA (Patterned V ertica 1 A1 ignment) type. Alignment type liquid crystal display element. These ΜVA type or PVA type liquid crystal display elements are not only excellent in viewing angle and contrast, but also need not be subjected to rubbing treatment in forming a liquid crystal alignment film, and are excellent in terms of manufacturing engineering. Conventionally, as these liquid crystal alignment films, polyacetamide or a dehydrated ring-closed polyimine is used for many liquid crystal display elements in any of various display modes because of heat resistance, affinity with liquid crystals, or mechanical strength. . At present, a liquid crystal alignment film of a vertical alignment type liquid crystal display element is formed by applying a liquid crystal alignment agent onto a substrate as described in Patent Document 1. As a basic property, it is necessary to have a vertical alignment property which enables vertical alignment of liquid crystals. In recent years, with the expansion of the vertical alignment type liquid crystal display element, the demand for improvement in display quality and productivity improvement by the vertical type liquid crystal alignment film has been increasing. The characteristics required for the alignment film are also various. Among them, as the most important characteristics, as described in Patent Documents 1 to 4, an improvement in high voltage holding performance and good coating property to a substrate can be cited. In order to achieve high voltage holding performance, it is known that the polyimine used in the alignment film has a high sulfhydryl imidization ratio as described in Patent Document 5. However, since the solubility of the hydrazine imidization is lowered in the solvent, the range of the solvent which can be used is limited, and as a result, it is difficult to achieve good coatability. As described above, the improvement of the imidization ratio of the high voltage holding property can be caused, and the coating property is greatly deteriorated, which is a trade-off relationship. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-32705 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a high voltage holding characteristic while having a good substrate. A coated vertical alignment type liquid crystal alignment agent. Another object of the present invention is to provide a vertical alignment type liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent of the present invention and exhibiting high voltage holding characteristics. Other objects and advantages of the invention will be apparent from the description which follows. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention, the first, the proline repeating unit represented by the formula (I-1) of 200804036 and the quinone imine represented by the following formula (I-2) a polymer of at least one repeating unit of the repeating unit, Q1 in the above formula (I-1) and Q2 in the above formula (I-2) each having the following formulas (II-1) and (II-2) At least one of a divalent organic group and at least one of a divalent organic group represented by the following formula (III 1).

HOOC COOH / \ / \ P1 、 / \ —^HNOC CONH-Q1* (1 -Ί) 這基機有價四的酸羧四成構示表表 Q1 且 )ο MHC CUH ο 團基、，機 ο nncG Η ο If// 有 N 價 //_|_—\二的胺二成構示 Ρ2: Ν·HOOC COOH / \ / \ P1 , / \ --^HNOC CONH-Q1* (1 -Ί) This base machine has a value of four acid carboxylic acid four-fold construction table Q1 and) ο MHC CUH ο 团基 , , machine ο nncG Η ο If// There is an amine II composition of N valence / / _ | _ - \ two Ρ 2: Ν ·

2 Q 裏構示基機有價四的酸竣四成構示表基機有價二的胺表 2 Q 且 -8- 2008049362 Q shows that the base has a price of four acid 竣 40% of the structure of the base of the valence of the amine 2 2 and -8- 200804936

(上式中，X 爲單鍵、·〇-、-CO-、-COO-、·〇(]〇-、-NHC〇-、 -C〇NH·、·3_、伸甲基、碳原子數爲2〜ό的伸烷基或伸苯 g 基’ R是碳原子數爲10〜20的院基、具有碳原子數爲4〜 40的脂環式骨架的一價有機基團或者碳原子數爲6〜20的含氟原子的一價有機基團，R2是具有碳原子數爲4〜40的脂環式骨架的二價有機基團或者碳原子數爲5〜30的含氟原子的二價有機基團）。 —X2—R3—X2— (I I I - 1) (上式中，X2爲伸甲基或碳原子數爲2〜20的伸烷 • 基，R3爲具有含芳香環骨架、有機矽氧烷骨架、 -R-(〇-C2H4)n-〇-R-表示的二價有機基團（R表市碳原子數爲2〜5的伸烷基，η表示1〜100)、-R-(〇-C3H6)n-〇-R· 表示的二價有機基團（R表示碳原子數爲2〜5的伸烷基，η表示1〜50)、具有碳原子數爲4〜40脂環式環狀骨架的二價有機基團，式中多個存在的χ2各自可以相同，也可以不同）。 200804936 根據本發明，本發明的上述目的和優點，第2，由一種垂直配向型液晶配向劑達成，其特徵在於，上述式 (I 一 1)中的P1和（I — 2)中的P2含有下述式（IV — 1)〜（IV 一 6)各自表示的四價有機基團中的至少一種，(In the above formula, X is a single bond, 〇-, -CO-, -COO-, 〇(]〇-, -NHC〇-, -C〇NH·, ·3_, methyl group, carbon number Is an alkylene group of 2 to fluorene or a phenyl group of the benzene group. R is a monovalent organic group having a carbon atom number of 10 to 20, an alicyclic skeleton having an alicyclic skeleton having 4 to 40 carbon atoms, or a carbon number. a monovalent organic group of 6 to 20 fluorine atom, R 2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a fluorine atom having 5 to 30 carbon atoms; Valence organic group) - X2 - R3 - X2 - (III - 1) (In the above formula, X2 is a methyl group or an alkylene group having 2 to 20 carbon atoms, and R3 has an aromatic ring skeleton, An organooxane skeleton, a divalent organic group represented by -R-(〇-C2H4)n-〇-R- (R represents an alkylene group having 2 to 5 carbon atoms, and η represents 1 to 100), -R-(〇-C3H6)n-〇-R· represents a divalent organic group (R represents an alkylene group having 2 to 5 carbon atoms, η represents 1 to 50), and has a carbon number of 4 to 4 a divalent organic group of 40 alicyclic cyclic skeleton, wherein each of the plurality of oxime 2 present in the formula may be the same or different) 200804936 According to the present invention, the above objects and advantages of the present invention, and second, are achieved by a vertical alignment type liquid crystal alignment agent characterized in that P1 in the above formula (I-1) and P2 in (I-2) contain At least one of the tetravalent organic groups represented by the following formulas (IV-1) to (IV-6),

(I V — 1)(I V — 1)

(其中，R5、R6、R7、R8和R9各自獨立地爲氫原子或一價有機基團）。根據本發明，本發明的上述目的和優點，第3，由一種垂直配向型液晶配向劑達成，其特徵在於，上述式 (I 一 1)中的pi和（I 一 2)中的P2相對於全部四價有機基團 -10- 200804936 (pi+p2)含有5 0莫耳％以上上述式（IV — 5)和（IV — 6)各自表示的四價有機基團中的至少一種。根據本發明，本發明的上述目的和優點，第4，由一種垂直配向型液晶配向劑達成，其特徵在於，上述式 (III 一 1)表示的二價有機基團含有下述式（V - 1)〜（V-5)各自表示的二價有機基團中的至少一種，(wherein R5, R6, R7, R8 and R9 are each independently a hydrogen atom or a monovalent organic group). According to the present invention, the above objects and advantages of the present invention, and third, are achieved by a vertical alignment type liquid crystal alignment agent characterized in that P2 in the above formula (I-1) and P2 in (I-2) are relative to All tetravalent organic groups-10-200804936 (pi+p2) contain 50% by mole or more of at least one of the tetravalent organic groups represented by the above formulas (IV-5) and (IV-6). According to the present invention, the above object and advantages of the present invention, in a fourth aspect, are achieved by a vertical alignment type liquid crystal alignment agent, characterized in that the divalent organic group represented by the above formula (III-1) contains the following formula (V - 1) at least one of divalent organic groups represented by each of (V-5),

-^Rh-^Rh

(V-1) (¥-2)，Rb^^*Rb、 (V-3) / (V — 4)(V-1) (¥-2), Rb^^*Rb, (V-3) / (V-4)

Ra r ip， (V — 5) 一 Rb—Si--O一 Si* • Rb- (其中，Ra表示氫原子或一價的有機基團，Rb爲碳原子數爲1〜20的伸烷基，多個Ra和Rb各自可以相同，也可以不同，P爲1〜99的整數，q爲1〜20的整數）。根據本發明，本發明的上述目的和優點，第5，由一種垂直配向型液晶配向劑達成，其特徵在於，上述聚合物爲相對於上述式（I 一 1)表示的醯胺酸重複單元和上述式（I - 2)表示的醯亞胺重複單元的合計量，該所述醯亞胺重複單元佔40莫耳％以上的醯亞胺化聚合物。根據本發明，本發明的上述目的和優點，第6，由一 -11- 200804936 種垂直配向型液晶配向劑達成，其特徵在於，相對於1 00 重量份聚合物，進一步含有1〜50重量份選自下述式（VI -1)和（VI— 2)各自表示的分子內至少具有2個環氧基的化合物所組成的群中的至少一種含環氧基化合物，Ra r ip, (V — 5) A Rb—Si—O—Si* • Rb— (wherein Ra represents a hydrogen atom or a monovalent organic group, and Rb is an alkylene group having 1 to 20 carbon atoms) A plurality of Ra and Rb may be the same or different, and P is an integer of 1 to 99, and q is an integer of 1 to 20. According to the present invention, the above objects and advantages of the present invention, in a fifth aspect, are achieved by a vertical alignment type liquid crystal alignment agent, characterized in that the polymer is a repeating unit of lysine represented by the above formula (I-1) The total amount of the quinone imine repeating unit represented by the above formula (I-2), wherein the quinone imine repeating unit accounts for 40 mol% or more of the quinone imidized polymer. According to the present invention, the above objects and advantages of the present invention, the sixth aspect, are achieved by a vertical alignment type liquid crystal alignment agent of -11-200804936, characterized in that it further contains 1 to 50 parts by weight with respect to 100 parts by weight of the polymer. At least one epoxy group-containing compound selected from the group consisting of compounds having at least two epoxy groups in the molecule represented by the following formulas (VI-1) and (VI-2),

(這裏式中，s爲2〜6的整數，t爲1〜4的整數，：T 爲s價的有機基團，。爲t價的有機基團）。根據本發明，本發明的上述目的和優點，第7，由一種垂直配向型液晶顯示元件達成，其特徵在於具有由本發明的上述液晶配向劑形成的垂直配向型液晶配向膜。發明之效果由本發明的液晶配向劑形成的垂直液晶配向膜，其垂直配向性優良，爲可獲得具有高電壓保持性能、同時具有優良的基板塗敷性的最佳液晶配向膜。本發明液晶顯示元件可有效地用於各種裝置，例如可適合作爲桌上型計算機、手錶、座鐘、行動電話、計數顯示幕、文字處理器、個人電腦、液晶電視機等顯示裝置使用。【實施方式】 -12-(In the formula, s is an integer of 2 to 6, and t is an integer of 1 to 4, and T is an organic group having an s-valent value, and is an organic group having a t-valence). According to the present invention, the above objects and advantages of the present invention are attained by a vertical alignment type liquid crystal display device characterized by comprising a vertical alignment type liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. EFFECTS OF THE INVENTION The vertical liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is excellent in vertical alignment property, and is an optimum liquid crystal alignment film which can have high voltage holding performance and excellent substrate coating properties. The liquid crystal display element of the present invention can be effectively used for various devices, and can be suitably used, for example, as a display device such as a desktop computer, a watch, a desk clock, a mobile phone, a counter display screen, a word processor, a personal computer, or a liquid crystal television. [Embodiment] -12-

200804936 實施發明之最佳形態以下，對本發明進行詳細的說明。本發明的垂直配向型液晶配向劑（以下，也稱爲明液晶配向劑”），如上所述，爲包括含有醯胺酸重和/或醯亞胺重複單元的聚合物。上述重複單元中，胺酸重複單元的聚合物（以下，也稱爲“聚醯胺酸聚通過例如使四羧酸二酸酐與二胺化合物在有機溶劑而製得。另外，含有醯亞胺重複單元的聚合物（以下爲“醯亞胺化聚合物”）爲通過使聚醯胺酸聚合物酸部分脫水閉環而製得。本發明中所用的含醯胺酸兀和/或醯亞胺重複單元的聚合物可以將聚醯胺酸與醯亞胺化聚合物倂用，也可以是同一聚合物中含酸重複單元和醯亞胺重複單元的聚合物。以下，對本發明的聚醯胺酸聚合物、醯亞胺化聚合物的製備行說明。 [四羧酸二酸酐] 作爲可以用於構成本發明液晶配向劑的聚醯胺物和/或聚醯亞胺聚合物的四羧酸二酸酐，可以舉例四羧酸二酸酐、下述式（IV - y)表示的環丁烷四羧酸 “本發複單元含有醯合物，，）中反應，也稱的醯胺重複單聚合物有醯胺可用於方法進酸聚合如丁烷二酸酐200804936 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The vertical alignment type liquid crystal alignment agent (hereinafter, also referred to as a bright liquid crystal alignment agent) of the present invention, as described above, is a polymer including a repeating unit containing a valeric acid heavy and/or a quinone imine. A polymer of an amine acid repeating unit (hereinafter, also referred to as "polyglycine polymerization" is produced, for example, by using a tetracarboxylic acid dianhydride and a diamine compound in an organic solvent. In addition, a polymer containing a quinone imine repeating unit ( The following is a "deuterated imidized polymer") which is obtained by partially dehydrating a polyamic acid polymer acid. The polymer containing a repeating unit of guanidinium amide and/or quinone imine used in the present invention may be The polyaminic acid and the ruthenium iodide polymer may be used as a polymer containing an acid repeating unit and a quinone imine repeating unit in the same polymer. Hereinafter, the polyproline polymer of the present invention, 醯亚The preparation of the aminated polymer is described. [Tetracarboxylic acid dianhydride] As the tetracarboxylic dianhydride which can be used for the polyamine and/or the polyimine polymer which constitutes the liquid crystal alignment agent of the present invention, four can be exemplified. Carboxylic acid dianhydride, the following (IV - y) represents a reaction of cyclobutane tetracarboxylic acid "the present compound contains a chelating compound,"), also known as a guanamine repeating single polymer having a guanamine which can be used in a method of acid polymerization such as butane Anhydride

-13- 200804936 (其中，R5、R6、R7和R8相互獨立地爲氫原子、鹵素原子或一價有機基團）、 1，2,3,4-環戊烷四羧酸二酸酐、1，2,4,5-環己烷四羧酸二酸酐、3,3’ ，4,4’ -二環己基四羧酸二酸酐、2,3,5-三羧基環戊基醋酸二酸酐、1，2,4-三羧基環戊基醋酸二酸酐、雙環 [2,2，1]庚烷-2,3,5,6-四羧酸二酸酐、3,5,6-三羧基降冰片烷 -2-醋酸二酸酐、四環[4,4,0，12,5，17，10]十二烷-3,4,8,9-四羧酸二酸酐、2,3，4,5-四氫呋喃四羧酸二酸酐、下述式（IV — 6°) 表示的二羧酸二酸酐 R9-13- 200804936 (wherein R5, R6, R7 and R8 are each independently a hydrogen atom, a halogen atom or a monovalent organic group), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1 , 2,4-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2,2,1]heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, tetracyclo[4,4,0,12,5,17,10]dodecane-3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic acid dianhydride, dicarboxylic acid dianhydride R9 represented by the following formula (IV-6°)

(其中，R9爲氫原子或一價有機基團）、5-(2,5-二氧代四氫呋喃）-3 -甲基-3-環己烯-1,2-二羧酸二酸酐、雙環 [2,2,2]-辛-4-烯-2,3,5,6-四羧酸二酸酐、雙環[2,2,2]-辛-7-烯-2,3,5,6-四羧酸二酸酐、下式（1)和（2)表示的化合物等脂肪族和脂環式四羧酸二酸酐； 14- 200804936(wherein R9 is a hydrogen atom or a monovalent organic group), 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, double ring [2,2,2]-oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6 - an aliphatic or alicyclic tetracarboxylic dianhydride such as a tetracarboxylic dianhydride or a compound represented by the following formulas (1) and (2); 14- 200804936

ο ο (式中，R1C)和R12表示具有芳香環的2價有機基團， I R"和R13表示氫原子或者烷基，複數存在的R11和R13 各自可以相同，也可以不同）；均苯四酸二酸酐、3,3’ ，4,4’ -二苯基酮四羧酸二酸酐、3,3’ ，4,4’ -二苯基礪四羧酸二酸酐、1，4,5,8-萘四羧酸二酸酐、2,3,6,7-萘四羧酸二酸酐、3,3’ ，4,4’ -二苯基醚四羧酸二酸酐、3,3’ ，4,4’ -二甲基二苯基矽烷四羧酸二酸酐、3,3’ ，4,4’ -四苯基矽烷四羧酸二酸酐、 1，2,3,4-呋喃四羧酸二酸酐、4,4’ -二（3,4·二羧基苯氧基） • 二苯基硫醚二酸酐、4,4’ ·二（3,4-二羧基苯氧基）二苯基颯二酸酐、4，4’ -二（3，4-二羧基苯氧基）二苯基丙烷二酸酐、3,3’ ，4,4’ -全氟異亞丙基二苯二甲酸二酸酐、 3,3’ ，4,4’ -聯苯四羧酸二酸酐、二（苯二甲酸）苯膦氧化物二酸酐、乙二醇-二（脫水偏苯三酸酯）、丙二醇-二（脫水偏苯三酸酯）、1，4-丁二醇-二（脫水偏苯三酸酯）、1，6-己二醇-二（脫水偏苯三酸酯）、1，8-辛二醇-二（脫水偏苯 •15- 200804936 三酸酯）、2,2-二（4-羥苯基）丙烷-二（脫水偏苯三酸酯）、下述式（3)〜（6)表示的化合物等芳香族四羧酸二酸酐。它們可以1種單獨或者2種以上組合使用。 /CH3ο ο (wherein R1C) and R12 represent a divalent organic group having an aromatic ring, I R" and R13 represent a hydrogen atom or an alkyl group, and a plurality of R11 and R13 may be the same or different); Tetraic acid dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic acid dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylnonanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid Diacid anhydride, 4,4'-bis(3,4.dicarboxyphenoxy) • Diphenyl sulfide dianhydride, 4,4′·bis(3,4-dicarboxyphenoxy)diphenylphosphonium Diacid anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, di(phthalic acid)benzenephosphine oxide dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene Alcohol-di(hydrogen trimellitate), 1,4-butanediol-di(hydrogen trimellitate), 1,6-hexanediol-di(hydrogen trimellitate), 1, 8-octanediol-di(dehydrated phenyl•15-200804936 triester), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), the following formula (3) An aromatic tetracarboxylic acid dianhydride such as a compound represented by (6). They may be used alone or in combination of two or more. /CH3

0 作爲上述式（IV — 1°)表示的環丁烷四羧酸二酸酐，可以 -16- 200804936 舉例如1，2,3,4-環丁烷四羧酸二酸酐、1，2-二甲基-1，2,3,4-環丁烷四羧酸二酸酐、1，2-二乙基-1，2,3，4-環丁烷四羧酸二酸酐、1，3-二甲基-1，2,3,4-環丁烷四羧酸二酸酐、1，3-二乙基-1，2,3,4-環丁烷四羧酸二酸酐、1，3-二氯-1，2,3,4-環丁烷四羧酸二酸酐、1，2,3,4-四甲基-i，2,3,4-環丁烷四羧酸二酸酐00 is a cyclobutane tetracarboxylic acid dianhydride represented by the above formula (IV-1°), and may be -16-200804936, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-di Methyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-two Methyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-two Chloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-i,2,3,4-cyclobutanetetracarboxylic acid dianhydride 0

作爲上述式（IV - 6°)表示的二羧酸二酸酐，可以舉例如 1，3,3&，4,5,91)-六氫-5-(四氫-2,5-二氧代-3-呋喃基）-萘 [l，2-c]-呋喃-1，3-二酮、1，3,3&，4,5,913-六氫-5-甲基-5-(四氫 ·2,5·二氧代-3-呋喃基）-萘[l，2-c]-肤喃-1,3-二酮、 1，3,3&，4,5,91>-六氫-5-乙基-5-(四氫-2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃-1,3-二酮、1，3,3&，4,5,91)-六氫-7-甲基-5-(四氫-2,5 -二氧代-3 -呋喃基）-萘[l，2-c] -呋喃-1，3 -二酮、 1，3,3&，4,5,91)-六氫-7-乙基-5-(四氫-2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃-1，3-二酮、l，3,3a，4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基）-萘[1，2<]-呋喃-1，3-二酮、 1，3,3&，4,5,91)-六氫-8-乙基-5-(四氫-2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃-1，3-二酮、1，3,3&，4,5,9士-六氫-5,8-二甲基 -5-(四氫- 2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃-1，3-二酮。其中，相對於全部四羧酸二酸酐，較佳含有50莫耳％以上選自上述式（IV — 1°)表示的環丁烷四羧酸二酸酐，例如 1，2,3,4-環丁烷四羧酸二酸酐、1，2-二甲基-1，2,3,4-環丁烷四羧酸二酸酐、1，2·二乙基-1,2,3,4-環丁烷四羧酸二酸酐、1，3- -17- 200804936 二甲基-1，2,3,4-環丁烷四羧酸二酸酐、1，3·二乙基-1，2,3,4-環丁烷四羧酸二酸酐、1，3-二氯-1，2,3,4-環丁烷四羧酸二酸酐、1，2,3,4_四甲基-1，2,3,4-環丁烷四羧酸二酸酐；雙環 [2.2.1]庚烷-2,3,5,6-四羧酸二酸酐；1，2,3,4-環戊烷四羧酸The dicarboxylic acid dianhydride represented by the above formula (IV-6°) may, for example, be 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo. -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro- 2,5·dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro- 5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3& 4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3 - Diketone, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan Naphthyl)-naphthalene [1,2<]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,9-hexahydro-5,8 -Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione. Wherein, with respect to all of the tetracarboxylic dianhydride, it is preferred to contain 50 mol% or more of a cyclobutane tetracarboxylic acid dianhydride represented by the above formula (IV-1), for example, a 1,2,3,4-ring Butane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2·diethyl-1,2,3,4-ring Butane tetracarboxylic acid dianhydride, 1,3- -17- 200804936 dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3·diethyl-1,2,3 , 4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic acid dianhydride; bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride; 1,2,3,4-cyclopentane IV carboxylic acid

二酸酐；1，2,4,5-環己烷四羧酸二酸酐；上述式（IV 一 6。）表示的四羧酸二酸野，例如l，3,3a，4,5,9b-六氫-5-(四氫-2,5-一氧代-3-呋喃基）-萘[i，2-c]·呋喃-1，3-二酮、l，3,3a，4,5,9b-六氫-5·甲基- 5-(四氫-2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃 -1，3-二酮、l，3,3a，4,5,9b-六氫-5-乙基·5-(四氫-2,5-二氧代 -3-呋喃基）-萘[l，2-c]-呋喃-1，3-二酮、1，3,3&，4,5,91)-六氫-7-甲基-5-(四氫-2,5-二氧代_3-呋喃基）_萘[1，2<]-呋喃-1，3-二酮、l，3,3a，4,5,9b-六氫-7-乙基-5-(四氫-2,5-二氧代-3-呋喃基）-萘[l，2-c]-呋喃·ι，3-二酮、六氫-8-甲基 -5-(四氫·2,5-二氧代-3-呋喃基呋喃- l，3-二酮、 l，3,3a，4,5,9b-/\ 氫-8_ 乙基-5-(四氫-2,5•二氧代 _3-呋喃基）· 奈[1，2 - c ] _ 呋喃-1，3 -二酮、；[，3，3 a，4，5，9 b -六氫 _ 5，8 -二甲基 -5-(四氫-2,5 -二氧代-3-呋喃基）·萘[u-c] -呋喃-1,3 -二酮； 2,3,5 -二羧基環戊基醋酸二酸酐的至少一種四羧酸二酸酐，從提高性能的角度考慮，更佳7 〇莫耳％以上。上述式（I — 1)和（1一 2)表示的重複單元中（^和Q2各自代表的上述式（Π〜丨)、(Π〜2)和（III 一 1)所表示的基團是來源於一胺的基團’相當於由二胺除去2個胺基所得的殘基。 -18- 200804936 上述式（II — 1)中，作爲R1表示的碳原子數爲10〜20 的烷基，可以舉例如正癸基、正十二烷基、正十五烷基、正十六烷基、正十八烷基、正二十烷基等。另外，作爲具有碳原子數爲4〜40的脂環式骨架的一價有機基團，可以舉例如具有來源於環丁烷、環戊烷、環己烷、環癸烷等環烷的脂環式骨架；降冰片烯、金剛烷等有橋脂環式骨架；膽甾醇、膽甾烷醇等甾體骨架的一價有機基團等。上述具有脂環式骨架的一價有機基團任選可被鹵素原子、較佳氟原子取代。此外，作爲碳原子數爲6〜20的含氟原子的一價有機基圑，可以列舉例如正己基、正辛基、正癸基等碳原子數爲6〜20的直鏈烷基；環己基、環辛基等碳原子數爲6〜20的脂環式烴基；苯基、聯苯基等碳原子數爲6〜20 的芳香族烴基等有機基團的氫原子一部分或全部被氟原子或氟代烷基取代的基團。另外，上述式（II 一 1)中，X1表示的基團爲單鍵、·0-、-CO-、-C〇〇-、-OCO-、-NHCO-、- CONH-、 -S-、亞甲基、碳原子數爲2~6的伸烷基或伸苯基，其中，作爲特佳的，可以列舉-〇-、-CO-、-COO-、-〇C〇·表币的基團。作爲具有上述式（II - 1)表示的基團的二胺的具體例子，較佳的可以舉出十二院氧基· 2，4 -二胺基苯、十五院氧基-2,4· 一胺基苯、十六院氧基-2,4 - —女基本、十八丨兀氣基 -2,4-二胺基苯、下述式（7)〜（21)表示的化合物。 -19- 200804936 ocoDiacid anhydride; 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride; tetracarboxylic acid diacid field represented by the above formula (IV-6), for example, 1,3,3a,4,5,9b- Hexahydro-5-(tetrahydro-2,5-monooxy-3-furanyl)-naphthalene [i,2-c]·furan-1,3-dione, l,3,3a,4,5 , 9b-hexahydro-5.methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-5-ethyl·5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan- 1,3-diketone, 1,3,3&,4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [l,2-c]-furan·ι,3-dione, hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl Furan-l,3-dione, l,3,3a,4,5,9b-/\ hydrogen-8_ethyl-5-(tetrahydro-2,5•dioxo-3-furanyl)·na [1,2 - c ] _ furan-1,3 -dione, [,3,3 a,4,5,9 b -hexahydro-5,8-dimethyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)·naphthalene [uc]-furan-1,3-dione; 2,3,5 -two The at least one tetracarboxylic acid dianhydride of carboxycyclopentyl acetic acid dianhydride is more preferably 7 〇 mol% or more from the viewpoint of improving performance. In the repeating unit represented by the above formulas (I-1) and (1-2) The group represented by the above formula (Π~丨), (Π~2) and (III-1) represented by (^ and Q2 is a group derived from a monoamine' corresponding to removal of two amine groups from a diamine In the above formula (II-1), the alkyl group having 10 to 20 carbon atoms represented by R1 may, for example, be n-decyl, n-dodecyl or n-pentadecane. a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, and may be derived, for example, as a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. An alicyclic skeleton of a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a bridged ring skeleton such as norbornene or adamantane; a steroid skeleton such as cholesterol or cholestyl alcohol; a monovalent organic group or the like. The above monovalent organic group having an alicyclic skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. Examples of the monovalent organic fluorene of a fluorine atom having 6 to 20 carbon atoms include straight-chain alkyl groups having 6 to 20 carbon atoms such as n-hexyl, n-octyl and n-decyl groups; cyclohexyl groups and rings; An alicyclic hydrocarbon group having 6 to 20 carbon atoms such as an octyl group; a hydrogen atom of an organic group such as an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a biphenyl group, or a fluorine atom or a fluorine atom Alkyl substituted group. Further, in the above formula (II-1), the group represented by X1 is a single bond, ·0-, -CO-, -C〇〇-, -OCO-, -NHCO-, -CONH-, -S-, a methylene group, an alkylene group having 2 to 6 carbon atoms or a phenyl group, wherein, as a particularly preferred one, a group of -〇-, -CO-, -COO-, -〇C〇·ecoin can be cited. group. Specific examples of the diamine having a group represented by the above formula (II-1) include tetradecyloxy-2,4-diaminobenzene and fifteen-epoxy-2,4. A monoaminobenzene, a hexadecanthoyloxy-2,4-anthracene, an octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (7) to (21). -19- 200804936 oco

CHa H3Cch{ch2)3chC"CH3 ch3 (7)CHa H3Cch{ch2)3chC"CH3 ch3 (7)

oco—k«ΛίOco—k«Λί

CH3 CH3 1 ^CHa H ( CH2)2CH=C ch3 (9)CH3 CH3 1 ^CHa H ( CH2)2CH=C ch3 (9)

CH3 H3〇CH(CH2)2 CH=C^ CHa CHsCH3 H3〇CH(CH2)2 CH=C^ CHa CHs

H(CHzhCn /CH3 ch3 (11) coo-H(CHzhCn /CH3 ch3 (11) coo-

ch3 H39 CH(CH2>2 ch=c zCH3 ch3 !3C CHl H2ir、^-NH2 (13)Ch3 H39 CH(CH2>2 ch=c zCH3 ch3 !3C CHl H2ir, ^-NH2 (13)

：H ( CH2)3CH (12) ch3 /CHa ch3 (14) CH3:H ( CH2)3CH (12) ch3 /CHa ch3 (14) CH3

H ( CH2)3CH ^*ch3 ch3 (15)H ( CH2)3CH ^*ch3 ch3 (15)

H2N h2n h2nH2N h2n h2n

〇〇〇-〇-〇〇〇-ό (19)〇〇〇-〇-〇〇〇-ό (19)

H2N\ {^^COOH^^OOOH2N\ {^^COOH^^OOO

(2 0) (2 1) 接下來，上述式（II - 2)中，作爲R2表示的具有碳原子數爲4〜40的脂環式骨架的二價有機基團，可以舉例如具 -20- 200804936 有來源於環丁烷、環戊烷、環己烷、環癸烷等源於環烷的脂環式骨架；降冰片烯、金剛烷等有橋脂環式骨架；膽甾醇、膽甾烷醇等甾體骨架的二價有機基團等。上述具有脂. 環式骨架的二價有機基團任選可被鹵素原子、較佳爲氟原子取代。作爲具有上述式（II - 2)表示的基團的二胺的具體例子，較佳的可以舉出下述式（22)〜（26)表示的化合物。(2 0) (2 1) In the above formula (II-2), the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R2 may, for example, be -20. - 200804936 There are alicyclic skeletons derived from cyclohexane, such as cyclobutane, cyclopentane, cyclohexane, cyclodecane, etc.; norbornane, adamantane, etc., having a bridged ring skeleton; cholesterol, cholesteric A divalent organic group such as a steroid skeleton such as an alkanol. The above divalent organic group having a lipid ring skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. Specific examples of the diamine having a group represented by the above formula (II-2) include compounds represented by the following formulas (22) to (26).

^ch3^ch3

Q-co H2NQ-co H2N

本發明的聚醯胺酸聚合物和/或聚醯亞胺聚合物中，上述式（II 一 1)和（Π 一 2)各自表示的二價有機基團的比率，從垂直配向性的角度考慮’相對於全部二胺的量，較佳爲7 莫耳％以上，更佳爲莫耳％以上。接下來，在上述式（III 一 1)中，作爲R3表示的具有含芳 •21- 200804936 香環骨架的二價有機基團，可以舉例如伸苯基、伸聯苯基、伸萘基、伸甲基二伸苯基、氧基二伸苯基。這些含芳香環骨架中的芳香環的任意的氫任選可被鹵素或碳原子數爲1 〜5的烷基取代。作爲具有有機矽氧烷骨架的二價有機基團，可以舉例如四甲基二矽氧烷基等。另外，作爲具有碳原子數爲4〜40的脂環式骨架的二價有機基團，可以舉例如具有來源於環丁烷、環戊烷、環己烷、環癸烷等源於環院的脂環式骨架；降冰片烯、金剛院等有橋脂環式骨架的 # 二價有機基團等。上述具有脂環式骨架的二價有機基團任選可被鹵素原子、較佳爲氟原子取代。作爲具有上述式（III 一 υ表示的基團的二胺的具體例子’較佳的可以舉出1，4-二（胺基甲基）-雙環[2,2,1]庚烷、 1，4-二（胺基丙基）-雙環[2,2，1]庚烷、異佛爾酮二胺、1，3-二 (氨基甲基）環己烷、1，4-二（胺基甲基）環己烷、1，3-二（氨基丙基）環己烷、間二甲苯二胺、對二甲苯二胺、3,3’ -(六甲基三矽氧烷-1，3-二基）二（丙胺）、下述式（27)、（28)表示的化籲合物等。 Η2Ν · CH2CH2{〇-CH2CH2+0-CH2CH2· NH2 (27) Η2Ν· CH2CH2CH2+0-CH2CH2l〇-CH2CH2CH2· ΝΗ2 (28) (上式中，η爲1〜100的整數）。本發明的聚醯胺酸聚合物和/或聚醯亞胺聚合物中，上述式（III - 1)表示的二價有機基團的比率，從提高聚合物溶 -22- 200804936 解性的角度考慮，相對於全部二胺的量，較佳爲2 %以上，更佳爲5 %以上。在本發明中所用的聚醯胺酸聚合物和/或聚醯亞胺聚合物的合成中，在不損害本發明效果的範圍內，可以聯用其他的二胺化合物。作爲其他的二胺化合物，可以舉例如對苯一胺、2 -甲基-1，4 -苯二胺、2 -乙基-1，4 -苯二胺、2，5 · 二甲基_1，4-苯二胺、2,5-二乙基-丄肛苯二胺、2,3,5,6•四甲基-1，4-苯二胺、間苯二胺、4,4，-二胺基二苯基甲烷、4,4，_ _ 二胺基二苯乙烷、4,4’ -二胺基二苯硫醚、4,4，-二胺基二苯基颯、2,2’ -二甲基-4,4’ -二胺基聯苯、2,2，-二（三氟甲基）-4,4，-二胺基聯苯、2,2，-二乙基_4,4，-二胺基聯苯、3,3’ _二甲基-4,4, ·二胺基聯苯、3,3，_二（三氟甲基）·4,4 -一胺基聯本、3,3 -二乙基- 4,4’ -二胺基聯苯、 4，4 -二胺基苯甲醯苯胺、4,4 -二胺基二苯基醚、丨，％二胺基奈、2,2’ _二甲基-4,4’ -二胺基聯苯、5-胺基-1·(4，_胺基本基）-1，3,3-二甲基印滿、6·胺基_胺基苯基）·ι 3,3_ 春二甲基茚滿、3，4 ’ -二胺基二苯基醚、3，3，-二胺基二苯酮、3,4’ _ 二胺基二苯酮、4,4，·二胺基二苯酮、2,2•二[4·(4· 胺基苯氧基）苯基]丙烷、2,2·二[4-(4-胺基苯氧基）苯基]六氟丙烷、2,2·二（4-胺基苯基）丙烷、2,2_二（4_胺基苯基）六氟丙烷、2,2-二[4-(4-胺基苯氧基）苯基]颯、丨，扣二（4·胺基苯氧基）苯、1，3-二（4-胺基苯氧基）苯、ι，3-二（3·胺基苯氧基）苯、 9,9-二（4-胺基苯基）-10-氫蒽、2,7-二胺基芴、9,9-二（4-胺基 -23- 200804936 苯基）¾、4,4’ -伸甲基-二（2-氯苯胺）、2,2，，5,5，·四氯 -4,4，·二胺基聯苯、2,2，_二氯_4,4, ·二胺基乃，5，·二甲氧基聯苯、3,3’ ·二甲氧基-4,4’ -二胺基聯苯、1，4,4，-(對 -伸苯基異亞丙基）二苯胺、4,4’ -(間-伸苯基異亞丙基）二苯胺、2,2’ -二[4-(4-胺基-2三氟甲基苯氧基）苯基]六氟丙院、4,4’ -二胺基-2,2，-二（三氟甲基）聯苯、4,4，-二[(4- 胺基-2-三氟甲基）苯氧基]-八氟聯苯、心(4-正庚基環己基苯氧基-2,4-二胺基苯等芳香族二胺； 1，3-丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺、壬二胺、4,4_二胺基庚二胺等脂肪族二胺； 2,3·二胺基吡啶、2,6-二胺基吡啶、3,4-二胺基吡啶、 2,4-二胺基嘧啶、5,6-二胺基- 2,3-二氰基毗嗪、5,6-二胺基 • 2,4-二羥基嘧啶、2,4-二胺基-6-二甲氨基-1，3，5-三嗪、2,4-二胺基-6-異丙氧基-1，3,5-三嗪、2,4-二胺基-6-甲氧基 -1，3,5-三嗪、2,4-二胺基-6-苯基-1，3,5-三嗪、2,4-二胺基-6-甲基-s-三嗪、2,4-二胺基-1，3,5-三嗪、4,6-二胺基-2-乙烯基 -s-三嗪、2,4-二胺基-5·苯基噻哩、2,6-二胺基嘌呤、5,6-二胺基-1，3 -二甲基尿嘧啶、3，5 -二胺基-1，2，4 -***、6，9 -二胺基-2-乙氧基吖啶乳酸酯、3,8-二胺基-6-苯基菲啶、1,4-二胺基呱嗪、3,6-二胺基吖啶、二（4·氨基苯基）苯基胺等分子內具有2個1級胺基以及該1級胺基以外的氮原子的二胺；可舉出下述式（29)和（30)表示的化合物等。這些二胺化合物可以單獨或者2種以上組合使用。 -24- 200804936In the poly-proline polymer and/or polyimine polymer of the present invention, the ratio of the divalent organic group represented by each of the above formulas (II-1) and (Π-2) is from the viewpoint of vertical alignment. It is considered that 'relative to the amount of all diamines, preferably 7 mol% or more, more preferably more than mol%. Next, in the above formula (III-1), as the divalent organic group having an aromatic ring containing an aromatic 21-200804936 represented by R3, for example, a phenyl group, a biphenyl group, a naphthyl group, Methyldiphenyl, oxydiphenyl. Any of these hydrogens containing an aromatic ring in the aromatic ring skeleton may be optionally substituted by halogen or an alkyl group having 1 to 5 carbon atoms. The divalent organic group having an organic siloxane skeleton may, for example, be tetramethyldimethoxyalkyl or the like. Further, the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms may, for example, be derived from cyclopentane, cyclopentane, cyclohexane or cyclodecane. An alicyclic skeleton; a divalent organic group having a bridged ring skeleton such as norbornene or a Donkey Kong. The above divalent organic group having an alicyclic skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. The specific example of the diamine having the group represented by the above formula (III) is preferably 1,4-bis(aminomethyl)-bicyclo[2,2,1]heptane, 1, 4-bis(aminopropyl)-bicyclo[2,2,1]heptane, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-di(amino) Methyl)cyclohexane, 1,3-bis(aminopropyl)cyclohexane, m-xylenediamine, p-xylenediamine, 3,3'-(hexamethyltrioxane-1,3 -diyl)di(propylamine), a compound represented by the following formulas (27), (28), etc. Η2Ν · CH2CH2{〇-CH2CH2+0-CH2CH2· NH2 (27) Η2Ν· CH2CH2CH2+0-CH2CH2l 〇-CH2CH2CH2·ΝΗ2 (28) (In the above formula, η is an integer of 1 to 100.) In the polyproline polymer and/or polyimine polymer of the present invention, the above formula (III-1) represents The ratio of the divalent organic group is preferably 2% or more, more preferably 5% or more, relative to the total amount of the diamine, from the viewpoint of improving the solubility of the polymer solution-22-200804936. In the present invention In the synthesis of polyaminic acid polymers and/or polyimine polymers used, Other diamine compounds may be used in combination within the scope of the effects of the present invention. As other diamine compounds, for example, p-phenylamine, 2-methyl-1,4-phenylenediamine, 2-ethyl- 1,4-phenylenediamine, 2,5 · dimethyl-1,4-phenylenediamine, 2,5-diethyl-anthraquinone, 2,3,5,6•tetramethyl- 1,4-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,_diaminodiphenylethane, 4,4'-diaminodiphenyl Thioether, 4,4,-diaminodiphenylanthracene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2,-bis(trifluoromethyl)-4 , 4,-diaminobiphenyl, 2,2,-diethyl-4,4,-diaminobiphenyl, 3,3'-dimethyl-4,4,diaminobiphenyl, 3,3,_bis(trifluoromethyl)·4,4-amino-amine, 3,3-diethyl-4,4′-diaminobiphenyl, 4,4-diaminobenzene Toluidine aniline, 4,4-diaminodiphenyl ether, hydrazine, % diaminone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1 · (4, _ amine basic group) -1,3,3-dimethyl-imprinted, 6-amino-aminophenyl) · ι 3,3_ spring dimethyl indane, 3,4 ' - two amine Diphenyl ether, 3,3,-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4,diaminobenzophenone, 2,2•2 [4· (4·Aminophenoxy)phenyl]propane, 2,2·bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2·bis(4-aminophenyl) ) propane, 2,2-di(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, anthracene, ketone (4.amine) Phenoxy group) benzene, 1,3-bis(4-aminophenoxy)benzene, iota, 3-bis(3.aminophenoxy)benzene, 9,9-bis(4-aminobenzene) Base)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-amino-23-200804936 phenyl) 3⁄4, 4,4'-methyl-di(2-chloro Aniline), 2,2,5,5,·tetrachloro-4,4,diaminobiphenyl, 2,2,-dichloro-4,4,diamino,5,·dimethyl Oxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4,-(p-phenylphenylidene)diphenylamine, 4,4 '-(m-phenylphenylisopropylene)diphenylamine, 2,2'-bis[4-(4-amino-2trifluoromethylphenoxy)phenyl]hexafluoropropane, 4, 4'-Diamino-2,2,-bis(trifluoromethyl)biphenyl 4,4,-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, heart (4-n-heptylcyclohexylphenoxy-2,4-diamine An aromatic diamine such as benzene; 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, etc. Aliphatic diamine; 2,3·diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2 , 3-dicyanopyrazine, 5,6-diamino 2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 2, 4-Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-di Amino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-three Pyrazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazide, 2,6-diaminopurine, 5,6-diamine 1,3 - dimethyl uracil, 3,5 -diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridine lactate, 3, 8-Diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4·aminobenzene) ) Of diphenylamine molecule having two amine groups and a diamine Level 1 nitrogen atom other than the stage 1 group; the following compounds of formula (29) and (30) can be exemplified. These diamine compounds may be used singly or in combination of two or more kinds. -24- 200804936

2 (2 9)2 (2 9)

(式中，y爲2〜12的整數，z爲i〜5的整數）。其中，作爲較佳的例子，可以舉出對苯二胺、2_甲基 _1，4_苯二胺、2-乙基-1，4·苯二胺、2,5-二甲基_丨，扣苯二胺、 Φ 2,5-二乙基_1，4-苯二胺、2,3,5,6-四甲基_1，4_苯二胺、4,4,_ 二胺基二苯基甲院、2,2 -一甲基_4,4’ -二胺基聯苯、 2，2 ’ -二.（三氟甲基）-4，4 ’ -二胺基聯苯、2，2，_二乙基 -4,4’ -二胺基聯本、3,3 -—甲基-4,4’ -二胺基聯苯、 3，3 ’ -二乙基-4，4 ’ -二胺基聯苯、3，3 ’ -二（三氣甲基）-4,4’ -二胺基聯苯、4,4’ -二胺基二苯基醚、4,4，-二胺基二苯酮、2,2-二（4-胺基苯基）丙烷、2,2、二（4-胺基苯基）六氟丙烷、2，6 -二胺基吡啶、3，4 ·二氨基吡b定等。 ® [聚醯胺酸的合成] 供給聚醯胺酸合成反應的四羧酸二酸軒與比率’較佳相對於1當量二胺的胺基，使四竣酸二酸肝的酸酐基爲0.2〜2.0當量的比率，更佳使其爲〇·8〜12當量的比率。聚醯胺酸的合成反應，在有機溶劑中，較佳於_2〇〜150它、更佳於〇〜i〇〇°c的溫度條件下進行。這裏’作爲有機溶劑，只要能夠溶解合成的聚醯胺酸， -25- 200804936 則對其沒有特別的限製，可以例示例如i-甲基-2-吡咯烷酮、N，N-二甲基乙醯胺、N，N-二甲基甲醯胺、二甲基亞颯、 7 -丁內酯、四甲基脲、六甲基磷醯三胺等非質子極性溶劑；間甲酚、二甲苯酚、苯酚、鹵代苯酚等酚類溶劑。此外，有機溶劑的用量（α )較佳爲使四羧酸二酸酐與二胺化合物的總量（沒）相對於反應溶液的總量（α + /3 )爲0. 1〜30 重量％的量。另外，在不使生成的聚醯胺酸析出的範圍內，上述有 ® 機溶劑中還可以聯用聚醯胺酸的不良溶劑之醇類、酮類、 ϋ類 '醚類、鹵代烴類、烴類等。作爲這種不良溶劑的具體例子’可以舉例如甲醇、乙醇、異丙醇、環己醇、4_羥基-4-甲基戊酮、乙二醇、丙二醇、丨，4_丁二醇、三甘醇、乙二醇單甲醚、乳酸乙酯、乳酸丁酯、丙酮、甲基乙基酮、甲S異丁基酮、環己酮、醋酸甲酯、醋酸乙酯、醋酸丁酯、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、二***、乙二醇甲醚、乙二醇***、乙二醇正丙 ® 醚、乙二醇異丙醚、乙二醇正丁醚、乙二醇二甲基醚、乙二醇***乙酸酯、二甘醇二甲醚、二甘醇二***、二甘醇單甲醚、二甘醇單***、二甘醇單甲醚乙酸酯、二甘醇單 ***乙酸酯、四氫呋喃、二氯甲烷、1，2-二氯乙烷、1，4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、辛烷、苯、甲苯、二甲苯等。如上所述，得到溶解了聚醯胺酸的反應溶液。然後， -26- 200804936 將該反應溶液投入到大量的不良溶劑中，得到析出物，通過減壓乾燥該析出物可得聚醯胺酸。並且，使該聚醯胺酸再次溶解於有機溶劑中，然後用不良溶劑使其析出，通過進行一次或者幾次此製程，可以精製聚醯胺酸。 [醯亞胺化聚合物的合成] 構成本發明液晶配向劑的醯亞胺化聚合物可以通過將上述聚醯胺酸脫水閉環而合成。本發明中所用的醯亞胺化聚合物，還可以是醯亞胺化率不足100%的部分脫水閉環的 Φ 聚合物。這裏所謂的“醯亞胺化率”是指在聚合物的全部重複單元中，具有醯亞胺環或異醯亞胺環的重複單元的比率用百分率表示的値。本發明中所用的聚醯胺酸聚合物和/ 或醯亞胺化聚合物的醯亞胺化率較佳爲40%以上，從電壓保持率的角度考慮，更佳爲70%以上。聚醯胺酸的脫水閉環可以採用通過⑴加熱聚醯胺酸的方法，或者（ii)將聚醯胺酸溶解於有機溶劑中，向該溶液中加入脫水劑和脫水閉環催化劑並根據需要加熱的方法使其縮合而合成的方法。 φ 在上述⑴加熱聚醯胺酸的方法中，反應溫度較佳爲50 〜2 00°C，更佳爲60〜170°C。當反應溫度不足50°C時，則脫水閉環反應不能進行完全，如果反應溫度超過200°C，則會出現所得醯亞胺化聚合物的分子量下降的情況。另一方面，上述（ii)的在聚醯胺酸溶液中添加脫水劑和脫水閉環催化劑的方法中，作爲脫水劑，可以使用例如醋酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的用量，根據 -27- 200804936 所需醯亞胺化率而定，較佳相對於1莫耳聚醯胺酸的重複單元，爲0·01〜20莫耳。另外，作爲脫水閉環催化劑，可以使用例如吡啶、三甲吡啶、二甲基吡啶、三乙胺等三級胺。但是，並不局限於這些。脫水閉環催化劑的用量，相對於1莫耳所用脫水劑，較佳爲（Κ01〜10莫耳。上述脫水劑、脫水閉環劑的用量越多，則可使醯亞胺化率越高。此外，作爲脫水閉環反應中使用的有機溶劑，可以舉例與作爲聚醯胺酸合成中所用溶劑而例示的相同的有機溶劑。並 # 且，脫水閉環反應的反應溫度較佳爲0〜180°C，更佳爲10 〜1 5 0 °C。此外，通過對如此得到的反應溶液進行與聚醯胺酸精製方法同樣的操作，可以精製醯亞胺化聚合物。 [末端修飾型聚合物] 本發明的聚醯胺酸/醯亞胺化聚合物還可以是進行了分子量調節的末端修飾型聚合物。通過使用該末端修飾型聚合物，可以在不損害本發明效果的前提下改善液晶配向劑的塗敷特性等。這種末端修飾型聚合物可以通過在聚醯 ® 胺酸的合成時，向反應體系中加入一元酸酐、單胺化合物、單異氰酸酯化合物等而合成。其中，作爲一元酸酐，可以舉例如馬來酸酐、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。此外，作爲單胺化合物，可以舉例如苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一烷胺、正十二烷胺、正十三烷胺、 -28- 200804936 正十四烷胺、正十五烷胺、正十六烷胺、正十七烷胺、正十八烷胺、正二十烷胺等。此外’作爲單異氰酸酯化合物，可以舉例如異氰酸苯酯、異氰酸萘基酯等。 [聚合物的對數粘度] 如上所得的聚醯胺酸和/或醯亞胺化聚合物，其對數粘度（W 1 η)値較佳爲〇 . 〇 5〜1 0 d 1 / g ’更佳爲0 · 0 5〜5 d 1 / g。本發明中對數粘度（7? In)値是通過使用N-甲基-2-吡咯烷酮作爲溶劑，在30°C下對濃度爲0.5g/100ml的溶液進行 ® 粘度測定，.由下式⑴求得的値。 _加(溶液流下時間/溶劑流下時間） % =— 一 (聚合物的重量濃度) [聚合物的醯亞胺化率] 如上所得醯亞胺化聚合物，其醯亞胺化率從提高電壓保持性能的角度考慮，較佳爲50〜100%，更佳爲65〜 100%，特佳爲75〜100%。本發明中的醯亞胺化聚合物的醯亞胺化率的値，是將 • 醯亞胺化聚合物在60:C減壓乾燥後，使其溶於氘代二甲亞颯中，以四甲基矽烷爲基準物，在室溫下測定1H-NMR，由下述式（ii)所示的公式求出的値。醯亞胺化率（％) = (1 — Α1/Α2χ α )χ100 ...... (ii) A1:源於NH基質子的峰面積（lOppm) A2:源於芳香環質子的峰面積（7〜8ppm) α :相對於聚合物前驅物（聚醯胺酸）中的i個NH基質 -29- ,200804936 子，源於芳香環的質子的個數比率。 [垂直配向型液晶配向劑] 爲了製得本發明的液晶配向劑，較佳將上述聚醯胺酸聚合物和/或醯亞胺化聚合物溶解含於有機溶劑中而構成。另外調製本發明液晶配向劑時的溫度較佳爲〇°C〜200 °C，更佳爲20°C〜60°C。作爲構成本發明液晶配向劑的有機溶劑，例如，可以列舉N-甲基-2-吡咯烷酮、r -丁內酯、r -丁內醯胺、N，N-• 二甲基甲醯胺、N，N-二甲基乙醯胺、4-羥基-4-甲基-2·戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇***、乙二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚（丁基溶纖劑）、乙二醇二甲基醚、乙二醇***乙酸酯、二甘醇二甲醚、二甘醇二***、二甘醇單甲醚、二甘醇單***、二甘醇單甲醚乙酸酯、二甘醇單***乙酸酯等。其中作爲較佳的溶劑組成，是將上述溶劑組合所得的組成.，而且是在配向劑中聚 ® 合物不會析出，並且使配向劑的表面張力爲30〜40mN/m 範圍的組成。本發明的液晶配向劑中固體含量濃度考慮粘性、揮發性等而進行選擇，較佳爲1〜1 0重量％的範圍。也就是說，本發明液晶配向劑塗敷於基板表面，形成作爲液晶配向膜的樹脂膜，當固體含量濃度不足1重量％時，將導致該樹脂膜的厚度過小，從而不能得到良好的液晶配向膜；當固體 -30- 200804936 含量濃度超過ίο重量％時，將導致樹脂膜厚度過厚，從而不能得到良好的液晶配向膜，並且，液晶配向劑的粘性增大，塗敷特性變差。另外，特佳的固體含量濃度範圍根據對基板塗敷液晶配向劑時所用的方法而不同。例如，當爲旋塗法時，特佳在1 · 5〜4 · 5重量％的範圍。在印刷法的場合，特佳使固體含量濃度爲4〜10重量％的範圍，這樣，這樣可以使溶液粘度落在10〜50mPa.s的範圍。當採用噴墨法時，特佳使固體含量濃度爲2〜5重量％的範圍，這樣可以使溶液粘度落在5〜15mPa，s的範圍。本發明的液晶配向劑在不損害目的物性的範圍內，還可以含有下述式（VI — 1)和（VI - 2)表示的含環氧基化合物。(wherein y is an integer of 2 to 12, and z is an integer of i to 5). Among them, preferred examples thereof include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-benzenediamine, and 2,5-dimethyl group.丨, phenylenediamine, Φ 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4, _ Aminodiphenylmethyl, 2,2-monomethyl-4,4'-diaminobiphenyl, 2,2'-di.(trifluoromethyl)-4,4 '-diamine linkage Benzene, 2,2,-diethyl-4,4'-diamino-based, 3,3-methyl-4,4'-diaminobiphenyl, 3,3'-diethyl- 4,4 '-diaminobiphenyl, 3,3 '-bis(trismethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4, 4,-Diaminobenzophenone, 2,2-bis(4-aminophenyl)propane, 2,2, bis(4-aminophenyl)hexafluoropropane, 2,6-diaminopyridine , 3,4 · diaminopyridine, etc. ® [Synthesis of poly-proline] The tetracarboxylic acid diacid and the ratio of the poly-proline synthesis reaction are preferably relative to the amine group of 1 equivalent of the diamine, so that the anhydride group of the tetradecanoic acid diacid is 0.2. A ratio of ~2.0 equivalents is more preferably made to a ratio of 〜·8 to 12 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at a temperature of from _2 〜 to 150 °, more preferably at a temperature of from 〇 to i 〇〇 °c. Here, 'as an organic solvent, as long as it can dissolve the synthesized polyaminic acid, -25-200804936, it is not particularly limited, and examples thereof include i-methyl-2-pyrrolidone and N,N-dimethylacetamide. , aprotic polar solvents such as N,N-dimethylformamide, dimethylhydrazine, 7-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-cresol, xylenol, A phenolic solvent such as phenol or halogenated phenol. 1〜30重量重量的重量。 The amount of the total amount of the tetracarboxylic acid dianhydride and the diamine compound (n) relative to the total amount of the reaction solution (α + /3) is 0. 1~30% by weight the amount. Further, in the range in which the produced polyamine acid is not precipitated, the alcohol, the ketone, the anthracene' ether, and the halogenated hydrocarbon in which the poor solvent of the polyamic acid is further used in the above-mentioned solvent may be used. , hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methylpentanone, ethylene glycol, propylene glycol, hydrazine, 4-butanediol, and the like. Glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl S isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, A Methyl oxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene Alcohol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane , chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which polylysine was dissolved was obtained. Then, -26-200804936, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the poly-proline is redissolved in an organic solvent, and then precipitated with a poor solvent, and the poly-proline is purified by performing one or several processes. [Synthesis of ruthenium iodide polymer] The ruthenium iodide polymer constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydration ring closure of the above polyglycine. The ruthenium iodide polymer used in the present invention may also be a partially dehydrated ring-closing Φ polymer having a ruthenium iodide ratio of less than 100%. The "yttrium imidation ratio" as used herein means the ratio of the ratio of the repeating unit having a quinone ring or an isoindole ring in all repeating units of the polymer expressed as a percentage. The polyaminic acid polymer and/or the ruthenium iodide polymer used in the present invention preferably has a ruthenium amination ratio of 40% or more, and more preferably 70% or more from the viewpoint of voltage retention. The dehydration ring closure of polylysine may be carried out by (1) heating poly-proline, or (ii) dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as needed. A method of synthesizing it by condensation. φ In the above method (1) of heating poly-proline, the reaction temperature is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be completed. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is determined according to the desired imidization ratio of -27-200804936, preferably 0. 01 to 20 moles relative to the repeating unit of 1 mole of polyamic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst to be used is preferably (Κ01 to 10 mol) with respect to the dehydrating agent used for 1 mol. The more the amount of the dehydrating agent and the dehydration ring-closure agent, the higher the niobium amination rate. The organic solvent used in the dehydration ring-closure reaction may, for example, be the same organic solvent as exemplified as the solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C. It is preferably 10 to 150 ° C. Further, the ruthenium iodide polymer can be purified by performing the same operation as the polyaminic acid purification method on the reaction solution thus obtained. [End Modification Polymer] The present invention The polyglycolic acid/quinone imidized polymer may also be a terminal modified polymer having a molecular weight adjusted. By using the terminal modified polymer, the coating of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The characteristics of the coating, etc. The terminal modified polymer can be added to the reaction system by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound, etc. in the synthesis of polyfluorene® amine acid. Among them, as the monobasic acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecane Further, as the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and n- Monoalkylamine, n-dodecylamine, n-tridecylamine, -28- 200804936 n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, Further, as the monoisocyanate compound, for example, phenyl isocyanate or naphthyl isocyanate may be mentioned. [Logarithmic Viscosity of Polymer] Polylysine and/or yttrium obtained as above The aminated polymer preferably has a logarithmic viscosity (W 1 η) 〇. 〇 5 〜 1 0 d 1 / g 'more preferably 0 · 0 5 〜 5 d 1 / g. Logarithmic viscosity in the present invention (7) In) 値 is determined by using N-methyl-2-pyrrolidone as a solvent at a concentration of 0.5 g/100 ml at 30 ° C.値 obtained by the following formula (1) _ addition (solution flow time / solvent flow time) % = - one (weight concentration of polymer) [polymerization yield of ruthenium iodide] The ruthenium imidization ratio in the present invention is preferably from 50 to 100%, more preferably from 65 to 100%, particularly preferably from 75 to 100%, from the viewpoint of improving voltage retention performance. The hydrazine imidization rate is obtained by dissolving the hydrazine imidized polymer in a reduced pressure of 60: C, and dissolving it in deuterated dimethyl hydrazine, using tetramethyl decane as a reference, in the chamber. 1H-NMR was measured at a temperature, and 値 was obtained by the formula shown by the following formula (ii): 醯 imidization ratio (%) = (1 - Α1/Α2χ α ) χ 100 ...... (ii) A1: Peak area derived from NH proton (10 ppm) A2: Peak area derived from aromatic ring protons (7 to 8 ppm) α: Relative to i NH matrix-29 in polymer precursor (polyglycine) - , 200804936, the ratio of the number of protons derived from the aromatic ring. [Vertically oriented liquid crystal alignment agent] In order to obtain the liquid crystal alignment agent of the present invention, it is preferred to dissolve the above polyamic acid polymer and/or ruthenium iodide polymer in an organic solvent. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, N,N-•dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2. pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene Alcohol ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Wait. Among them, a preferred solvent composition is a composition obtained by combining the above solvents, and the composition is not precipitated in the alignment agent, and the surface tension of the alignment agent is in the range of 30 to 40 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility and the like, and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a resin film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the resin film is too small, so that a good liquid crystal alignment cannot be obtained. When the content of the solid -30-200804936 is more than 5% by weight, the thickness of the resin film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is deteriorated. Further, the particularly preferable solid content concentration range differs depending on the method used for coating the substrate with the liquid crystal alignment agent. For example, when it is a spin coating method, it is particularly preferably in the range of 1 · 5 to 4 · 5 % by weight. In the case of the printing method, the solid content concentration is preferably in the range of 4 to 10% by weight, so that the viscosity of the solution falls within the range of 10 to 50 mPa.s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 2 to 5% by weight, so that the viscosity of the solution falls within the range of 5 to 15 mPa, s. The liquid crystal alignment agent of the present invention may further contain an epoxy group-containing compound represented by the following formulas (VI-1) and (VI-2) within a range not impairing the physical properties of the object.

Rc-tO IRc-tO I

<? (V I - 1) (VI-2) (迫裏式中，s爲2〜6的整數，！爲i〜4的整數，rc 爲s價的有機基團，Rd· t價的有機基團）。作爲迫種含環氧基化合物，可以舉例如乙二醇二縮水甘油醚、聚乙一醇一縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1，6 -己二醇二縮水甘油醚、甘油二縮水甘 -31- 200804936 油醚、2,2-二溴新戊二醇二縮水甘油醚、1，3,5,6-四縮水甘油基-2,4-己二醇、N，N，N’，N’-四縮水甘油基-P-苯二胺、 N，N，N’，N，-四縮水甘油基-m-二甲苯二胺、N，N，N，，N’-四縮水甘油基-2,2’-二甲基-4,4’-二胺基聯苯、2,2-二[4-(N，N-二縮水甘油基-4-胺基苯氧基）苯基]丙烷、Ν，Ν，Ν’，N5-四縮水甘油基- 4,4’-二胺基二苯基甲院、1，3 -二（N，N-二縮水甘油基胺基甲基）環己烷、1，4-二（N，N-二縮水甘油基胺基甲基）環己烷、1，3-二（N，N-二縮水甘油基胺基甲基）苯、N,N，N’，N’-四 # 縮水甘油基-m-間二甲苯二胺等。這種含環氧基化合物的含量，相對於100重量份聚合物，較佳含有1〜50重量份，更佳5〜45重量份。另外，本發明的液晶配向劑中，從提高對基板表面粘合性的角度考慮，在不損害目的物性的範圍內，還可以含有含官能性矽烷的化合物。作爲這種含官能性矽烷的化合物，可以舉例如3-胺基丙基三甲氧基矽烷、3·胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙 ® 氧基矽烷、N-(2-胺基乙基）-3-胺基丙基三甲氧基矽烷、N-(2-月女基乙基）-3 -胺基丙基甲基一*甲氧基砂院、3 -脈基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧羰基-3-胺基丙基三甲氧基矽烷、N-乙氧羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三亞乙基三胺、N_三甲氧基矽烷基丙基三亞乙基三胺、10 -三甲氧基矽烷基-1，4，7 -三氮雜癸烷、10-三乙氧基矽烷基-1，4,7·三氮雜癸烷、9-三甲氧基 -32- 200804936 矽烷基-3，6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基砍院、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、N-二（氧乙烯基）-3 -胺基丙基三甲氧基砂院、N -二（氧乙烯基）-3 -胺基丙基三乙氧基矽烷、3-(N-烯丙基-N_縮水甘油基）胺基丙基三甲氧基矽烷、3-(N，N-二縮水甘油基）胺基丙基三甲氧基矽烷等。 • [採用液晶配向劑的顯示元件的製造] 採用本發明垂直配向型液晶配向劑的液晶顯示元件可以通過例如以下的方法製造。 (1)通k例如輥塗法、旋塗法、印刷法、噴墨法等方法，將本發明液晶配向劑塗敷在設有形成圖案的透明導電膜的基板一面上，接著，通過對塗敷面進行加熱形成塗膜。這裏，作爲基板，可以使用例如浮法玻璃、鈉鈣玻璃等玻璃；聚對苯二甲酸乙酯、聚對苯二甲酸丁酯、聚醚颯、聚碳酸 ® 酯等塑膠製透明基板。作爲基板一面上所設置的透明導電膜，可以使用氧化錫（Sn〇2)製的NESA膜（美國PPG公司注冊商標）、氧化銦一氧化錫（In2〇3 — Sn〇2)製的ITO膜等。這些透明導電膜圖案的形成，可以採用光蝕刻法和預先使用遮罩（mask)的方法。在液晶配向劑的塗敷時，爲了進一步改善基板表面與樹脂膜的粘著性，還可以預先塗敷例如含官能性矽烷的化合物、含官能性鈦的化合物等。塗敷液晶 -33- 200804936 配向劑後的加熱溫度較佳爲80〜300°C，更佳爲120〜250 °C。另外，本發明液晶配向劑，通過塗敷後除去有機溶劑，形成作爲配向膜的樹脂膜，在還沒有完全進行醯亞胺化時，還可以通過進一步加熱進行脫水閉環，形成進一步醯亞胺化的樹脂膜。形成的樹脂膜的厚度較佳爲0.001〜 Ιμπι，更佳爲 0.005 〜0.5/zm。 (2)製造2片如上所述形成垂直液晶配向膜的基板，將 2片基板通過間隙（晶胞間隙（cell gap))對向配置，將2片基 • 板周邊部位用密封劑進行貼合，向由基板表面和密封劑分割出的晶胞間隙內注充液晶，封閉注入孔，構成液晶晶胞。然後，在液晶晶胞的外表面，即構成液晶晶胞的透明基板側配置偏光片，製得液晶顯示元件。這裏，作爲密封劑，可以使用例如作爲固化劑和間隙物（spacer)的含氧化鋁球的環氧樹脂等。作爲液晶，可以舉出向列型液晶和碟型液晶。其中較佳爲向列型液晶，可以使用例如希夫氏鹼類液晶、氧化偶 ® 氮基類液晶、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、二氧陸圜類液晶、雙環辛烷類液晶、立方烷類液晶等。此外，這些液晶中還可以添加例如氯化膽甾醇、膽甾醇壬酸酯、膽甾醇碳酸酯等膽甾型液晶和以商品名「C-15」、「CB-15」 (默克公司製）銷售的手性劑等而進行使用。並且，還可以使用對癸氧基苯亞甲基-P-胺基-2-甲基丁基肉桂酸酯等鐵 -34- .200804936 電性液晶。此外，作爲液晶盒外表面上貼合的偏光片，可以舉出使一邊將聚乙烯醇延伸配向一邊吸收碘所得的稱作爲Η膜的偏光膜夾在醋酸纖維素保護膜中而製成的偏光板或者Η 膜本身製成的偏光板。實施例以下通過實施例對本發明進行更具體的說明，但本發明並不局限於這些實施例。 # 另外，實施例和比較例中的各種測定按照以下的方法進行。 (1) 垂直配向性的評價在由上述方法製作的垂直配向型液晶顯示元件無電壓施加時和施加8V交流電壓（峰-峰）時，通過十字尼科耳棱鏡從垂直方向對液晶顯示元件進行目測觀察，當沒有漏光等顯示不佳、爲白顯示時，評價爲「良好」。 (2) 電壓保持率的測定 ® 在60°C下，給液晶顯示元件施加5V的電壓，電壓施加時間爲60微秒，施加期間（span)爲16.7微秒，然後，測定從電壓解除至16.7毫秒後的電壓保持率。 (3) 聚合物溶解性的評價調製成粘度爲15〜25 mPa· sec (固體含量濃度爲6·〇重量 %〜8·0重量％)、溶劑組成爲··全部溶劑量爲i〇〇，r _丁內酯：N-甲基-2-吡咯烷酮：丁基溶纖劑=40·· (60 — A): A (重量比 -35- 200804936 時，目測觀察有無混濁，在不良溶劑丁基溶纖劑的爲3 0以上時，也無混濁的情況下，評價爲「良好」 (4)印刷性評價對上述（3)的“聚合物溶解性評價”中爲良好的液，用該調製溶液通過印刷法塗敷·焙燒後，目測觀膜。對於塗膜，沒有凹陷或塗敷不勻的評價爲“良合成例1〜25、比較合成例1〜6 將表1和表2中所示的組成以二胺、四羧酸二| # 中，表示爲“酸酐”）的順序加入到N-甲基-2-吡咯中，配成固體含量濃度爲20重量％的溶液，使其在應4小時，得到聚醯胺酸聚合物。向所得聚醯胺酸中相對於聚醯胺酸聚合物的總量加入表1中所示莫吡啶和醋酸酐後，在1 1 〇°C加熱4小時進行脫水閉_ 將所得溶液在二***中再次沉澱後，回收並減壓乾到如表1和表2所示對數粘度、醯亞胺化率的醯亞合物（A — 1)〜（A — 25)和（a— 1)〜（a — 6)。<? (VI - 1) (VI-2) (In the forced formula, s is an integer of 2 to 6, ! is an integer of i to 4, rc is an organic group of s, and organic of Rd·t Group). Examples of the seed-containing epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl. Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl-31- 200804936 oil ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-P-phenylenediamine, N,N,N',N,-tetraglycidyl Base-m-xylylenediamine, N,N,N,,N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-di[ 4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, hydrazine, hydrazine, hydrazine, N5-tetraglycidyl-4,4'-diaminodiphenyl A hospital, 1,3 -di(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1 ,3-di(N,N-diglycidylaminomethyl)benzene, N,N,N',N'-tetra# glycidyl-m-m-xylene Amine. The content of the epoxy group-containing compound is preferably from 1 to 50 parts by weight, more preferably from 5 to 45 parts by weight, per 100 parts by weight of the polymer. Further, in the liquid crystal alignment agent of the present invention, a compound containing a functional decane may be contained in a range which does not impair the target physical properties from the viewpoint of improving the adhesion to the surface of the substrate. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amine can be mentioned. Propyltriethyloxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-moon-glycolyl)-3-aminopropyl Methyl-methoxylate, 3-propylpropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10 -trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxy-32- 200804936 decane Base-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Baseline, N-benzyl-3-aminopropyltriethoxysulfate, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Triethoxy decane, N-bis(oxyvinyl)-3-aminopropyltrimethoxy sand, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3- (N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. [Manufacture of display element using liquid crystal alignment agent] The liquid crystal display element using the vertical alignment type liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) Applying a liquid crystal alignment agent of the present invention to a substrate provided with a patterned transparent conductive film by a method such as a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, followed by coating The surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate carbonate can be used. As the transparent conductive film provided on one side of the substrate, an ITO film made of tin oxide (Sn〇2), a NESA film (registered trademark of PPG, USA), or indium tin oxide (In2〇3 — Sn〇2) can be used. Wait. These transparent conductive film patterns can be formed by photolithography and a method of using a mask in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the resin film, for example, a compound containing a functional decane, a compound containing a functional titanium, or the like may be applied in advance. The heating temperature after coating the liquid crystal -33- 200804936 is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. Further, in the liquid crystal alignment agent of the present invention, after the application, the organic solvent is removed to form a resin film as an alignment film, and when the imidization is not completely performed, the dehydration ring closure can be further carried out by further heating to form further ruthenium iodization. Resin film. The thickness of the formed resin film is preferably 0.001 to Ιμπι, more preferably 0.005 to 0.5/zm. (2) Two substrates in which a vertical liquid crystal alignment film is formed as described above are produced, and two substrates are arranged to face each other through a gap (cell gap), and the peripheral portions of the two base plates are bonded together with a sealant. The liquid crystal gap is filled into the cell gap separated by the surface of the substrate and the sealant, and the injection hole is closed to form a liquid crystal cell. Then, a polarizer is disposed on the outer surface of the liquid crystal cell, that is, on the transparent substrate side constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like which is a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and disc liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized even nitrogen liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a combination can be used. Phenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl choline, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-15" and "CB-15" (manufactured by Merck) may be added. It is used by selling chiral agents and the like. Further, an iron-34-.200804936 electro-optical liquid crystal such as p-methoxybenzylidene-P-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called a ruthenium film obtained by absorbing iodine while extending the polyvinyl alcohol may be immersed in a cellulose acetate protective film. A polarizing plate made of a plate or a film itself. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. # Further, various measurements in the examples and comparative examples were carried out in the following manner. (1) Evaluation of the vertical alignment property When the vertical alignment type liquid crystal display element produced by the above method is applied without a voltage and when an AC voltage (peak-peak) of 8 V is applied, the liquid crystal display element is vertically viewed by a crossed Nicol prism. It was visually observed that when there was no light leakage or the like and the display was white, the evaluation was "good". (2) Measurement of voltage holding ratio ® A voltage of 5 V was applied to the liquid crystal display element at 60 ° C, the voltage application time was 60 μsec, the application period was 16.7 μs, and then the voltage was released to 16.7. The voltage holding ratio after milliseconds. (3) The solubility of the polymer was adjusted to have a viscosity of 15 to 25 mPa·sec (solid content concentration of 6·〇% by weight to 8·0% by weight), and the solvent composition was ··all the amount of the solvent was i〇〇, r _butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40 · · (60 - A): A (weight ratio -35-200804936, visual observation of turbidity, in the poor solvent butyl cellosolve When it is 30 or more, it is evaluated as "good" in the case of no turbidity. (4) Printability evaluation is a good liquid in the "polymer solubility evaluation" of the above (3), and the printing solution is used for printing. After coating and baking, the film was visually observed. The evaluation of the coating film without depression or unevenness of coating was "good synthesis examples 1 to 25, and comparative synthesis examples 1 to 6. The compositions shown in Tables 1 and 2 were The order of the diamine, tetracarboxylic acid II|#, denoted as "anhydride") was added to N-methyl-2-pyrrole, and a solution having a solid content concentration of 20% by weight was prepared, and it was allowed to stand for 4 hours. A poly-proline polymer was obtained. The mopyridine shown in Table 1 was added to the total amount of the poly-proline acid polymer relative to the obtained poly-proline acid. After the acid anhydride, it was heated at 11 ° C for 4 hours to carry out dehydration. After the precipitate was reprecipitated in diethyl ether, it was recovered and dried under reduced pressure to a logarithmic viscosity and a ruthenium imidation rate as shown in Tables 1 and 2. Bismuth (A-1)~(A-25) and (a-1)~(a-6).

含量A 溶，察塗好，，。酸酐（表烷酮 60〇C 反聚合物耳數的 I反應。燥，得胺化聚 -36- .200804936The content A is dissolved, and it is well coated. An acid anhydride (I-reaction of the paraffin 60 〇C anti-polymer ear number. Dry, aminated poly-36-.200804936

醯亞胺化聚合物 1~1 I < CNJ 1 < A-3 寸 1 < uo 1 c VO 1 c A-7 oo ! < ON ! < o T < \ < 1 * 1 < csi I! < 醯亞胺化聚合物醯亞胺化率 wn oo JO oo oo oo VQ 醯亞胺化聚合物對數粘度〇〇 o 卜卜 oo 卜卜 oo MD 醋酸酐 (莫耳數） VO S CN VO o4 s 吡陡 (莫耳數） CN wo o4 VO 酸酐 (mmol) 1-2(100) 1-2(100) T-2(100) T-2(100) 1-2(100) ! 7-2(100) 1-2(100) T^2(100) T-2(100) T-2(100) T-K20), T-2(80) 1-2(50), T-4(50) 二胺化合物 (mmol) D-l(10)，D-5(20), D-10(70) D-l(lO), D-5(10), D-6(10), D-10(70) D-l(10), D-5(20), D-6(20), D-10(50) D-l(10), D-5(10), D-6(10), D-10(70) D-l(10), D-6(20), D-10(70) : D-l(10), D-6(20), D-10(70) D-l(10), D-6(20), D-10(50), D-ll(20) D-l(10), D-6(20), D-10(50), D-ll(20) D-l(10), D-6(20), D-7(20), D-10(50) D-l(10), D-6(20), D-12(70) D-l(lO), D-6(20), D-10(40), D>12(30) D-l(lO), D-6(20), D-10(50), D-13(20) 合成例 oo m 寸 VO v〇卜 OO σ\ O t—4 CN .200804936醯imitized polymer 1~1 I < CNJ 1 < A-3 inch 1 < uo 1 c VO 1 c A-7 oo ! < ON ! < o T < \ < 1 * 1 < csi I! < 醯i-imidized polymer 醯 imidization rate wn oo JO oo oo oo VQ 醯 imidization polymer logarithmic viscosity 〇〇o 卜 oo 卜 oo MD acetic anhydride (mole number) VO S CN VO o4 s Pyridox (mole number) CN wo o4 VO Anhydride (mmol) 1-2(100) 1-2(100) T-2(100) T-2(100) 1-2(100 ) 7-2(100) 1-2(100) T^2(100) T-2(100) T-2(100) T-K20), T-2(80) 1-2(50), T-4(50) diamine compound (mmol) Dl(10), D-5(20), D-10(70) Dl(lO), D-5(10), D-6(10), D -10(70) Dl(10), D-5(20), D-6(20), D-10(50) Dl(10), D-5(10), D-6(10), D -10(70) Dl(10), D-6(20), D-10(70) : Dl(10), D-6(20), D-10(70) Dl(10), D-6 (20), D-10(50), D-ll(20) Dl(10), D-6(20), D-10(50), D-ll(20) Dl(10), D-6 (20), D-7(20), D-10(50) Dl(10), D-6(20), D-12(70) Dl(lO), D-6(20), D-10 (40), D>12(30) Dl(lO), D-6(20), D-10(50), D-13(20) Synthesis example oo m inch VO v〇卜 OO σ\ O t— 4 CN .200804936

CO y '< I < T < in i 'i 1 < ν〇丁 < T < οο ι—Ι 1 < σ\ T < 1 c 1 < 1 c 1 C 1 < 1 < oo oo g g oo vq VO l〇 as ΙΟ vq r-； r-； ON c4 u〇 r4 ι〇〇4 un CN c^ m oi cs l〇 w^i o4 un o4 CN Cvj w^> o4 l〇 o4 〇j to i cn S g cn 〇 yTy h N gN o OO oo ci H I ·< 1—-< VO S v—^ 弇 Q <〇 1 i Q o Q r < Q § VO VO © c— § OO s s 2 o 2 CNl \ i r—( Q Q ά t Q ά Q Q Q Q Q ά τ·Η A Q s 豸 g 豸 g o § i—4 芬轉 ά ά Ν〇 ά W^> Ό ώ oo Q 1 < Q 卜 Q VO Q v〇 Q oo Q VO Q ， H δ & 完 Q δ CN Q Q Q Q ά Q Q Q Q Q Q Q i—^ Q CO 寸【 to i2 Γ^· OO 2 S 200804936CO y '< I < T < in i 'i 1 <ν〇丁< T < οο ι—Ι 1 < σ\ T < 1 c 1 < 1 c 1 C 1 < 1 < oo oo gg oo vq VO l〇as ΙΟ vq r-; r-; ON c4 u〇r4 ι〇〇4 un CN c^ m oi cs l〇w^i o4 un o4 CN Cvj w^> O4 l〇o4 〇j to i cn S g cn 〇yTy h N gN o OO oo ci HI ·<1—-< VO S v-^ 弇Q <〇1 i Q o Q r < Q § VO VO © c— § OO ss 2 o 2 CNl \ ir—( QQ ά t Q ά QQQQQ ά τ·Η AQ s 豸g 豸go § i—4 芬转ά ά Ν〇ά W^> Ό ώ oo Q 1 < Q Bu Q VO Q v〇Q oo Q VO Q , H δ & Finish Q δ CN QQQQ ά QQQQQQQ i—^ Q CO inch [to i2 Γ^· OO 2 S 200804936

醯亞胺化聚合物 a—1 a—2 CO Γ a—4 a—5 a—6 醯亞胺化聚合物醯亞胺化率 οο o 〇〇〇醯亞胺化聚合物對數粘度〇〇 CO 醋酸酐 (莫耳數） p p p p 吡啶 (莫耳數） m p p p p 酸酐(mmol) T-2(100) T-2(100) T-2(100) T-3(50), T-5(50) T-3(50), T-5(50) T-3(50), T-5(50) 二胺化合物(mmol) D-l(15), D-10(85) D-l(lO), D-10(50), D-13(40) D-l(20), D-5(20), D-10(60) D-l(20), D-5(20), D-10(60) D-3(30), D-9(10), D-10(60) D-4(30), D-9(10), D-10(60) 比較合成例 τ—^ CS] cn 寸 vn醯i-imidized polymer a-1 a-2 CO Γ a-4 a-5 a-6 醯i-imidized polymer 醯 imidization rate οο o 〇〇〇醯i-imidized polymer logarithmic viscosity 〇〇CO Acetic anhydride (mole number) pppp pyridine (mole number) mpppp anhydride (mmol) T-2 (100) T-2 (100) T-2 (100) T-3 (50), T-5 (50) T-3(50), T-5(50) T-3(50), T-5(50) Diamine compound (mmol) Dl(15), D-10(85) Dl(lO), D- 10(50), D-13(40) Dl(20), D-5(20), D-10(60) Dl(20), D-5(20), D-10(60) D-3 (30), D-9(10), D-10(60) D-4(30), D-9(10), D-10(60) Comparative Synthesis Example τ—^ CS] cn inch vn

σ\ CO 200804936 在表1和表2中，對於二胺化合物和酸酐，括弧內的數字表示含量比率，表中符號的含義如下： <二胺化合物> D — 1 :上述式（10)表示的二胺 D- 2 :上述式（11)表示的二胺 D — 3 :上述式（14)表示的二胺 D— 4:上述式（20)表示的二胺 D— 5: 1，4-二（胺基甲基）-二環[2·2·1]庚烷 φ D- 6 : 1,3-二（胺基甲基）-環己烷 D — 7 :間二甲苯二胺 D— 8 : 3,3’-(四甲基二矽氧烷-1,3-二基）二（丙胺） D- 9:上述式（28)表示的二胺（平均分子量1000) D - 1 0 :對苯二胺 D — 11: 4,4、二胺基二苯基甲烷 D— 12 : 4,4’-二胺基二苯基醚 D— 13: 2,2’-二甲基-4,4’-二胺基聯苯 ® 〈四羧酸二酸酐〉 Τ 一 1: 1，2,4,5-環己烷四羧酸二酸酐 Τ 一 2: 2,3,5-三羧基環戊基醋酸二酸酐 Τ—3: 1,2,3,4-環丁烷四羧酸二酸酐丁一4:1，3,3&，4,5,913-六氫-8-甲基-5-(四氫-2,5-二氧代 -3-呋喃基）-萘[1，2<]-呋喃-1，3-二酮 Τ一 5:均苯四酸二酸酐 -40- 200804936 實施例1 將合成例1中製得的醯亞胺化聚合物（a — 1)溶於 r -丁內酯/N-甲基_2_吡咯烷酮/丁基溶纖劑的混合溶液（重量比40/30/3 0)中，相對於100重量份聚合物溶解20重量份聚乙二醇二縮水甘油醚（分子量約400 ;添加劑A)，製成固體成分濃度爲6重量％的溶液。目測觀察該溶液，獲得無混濁的透明溶液，因此確認其顯示良好的溶解性。接著用孔徑爲0.2 /z m的濾器過濾，調製出本發明的膜形成用組合物 • 後，進行印刷性的評價，塗膜上未見凹陷和塗敷不勻，確認具有良好的印刷性。然後，除了配成固體成分濃度爲4%以外，與上述同樣地調製本發明的膜形成用組合物。接著，將該膜形成用組合物用旋塗機塗布於設置在厚度爲1mm的玻璃基板一面上的ITO膜製透明導電膜上，在 200°C下乾燥60分鐘，形成乾燥膜厚爲0.08 μ m的覆膜。接著，在一對透明電極/透明電極基板的上述液晶配向 ® 膜塗敷基板的帶有液晶配向膜的各外緣上，塗敷加入直徑爲3.5 // m的氧化鋁球的環氧樹脂粘合劑後，使液晶配向膜面相向重合並壓接，再使粘合劑固化。接着，通過液晶注入口向基板之間塡充向列型液晶（默克社製，MLC-6608) 後，用丙烯酸類光固化粘合劑將液晶注入口封閉，在基板外側的兩面上貼合偏光片，製作出液晶顯示元件。對所得液晶顯示元件進行垂直配向性評價，爲良好。並且測定電 -41- 200804936 壓保持率，爲99%以上，顯示良好的電廳保持性能。整理結果而列於表3。實施例2〜67，比較例1〜1 1 按照下述表3、4中所示的配方，與實施例1同樣地調製固體成分濃度爲6 %的膜形成用組合物，評價溶解性和印刷性。並且同樣地調製固體成分濃度爲4 %的膜形成用組合物，製作液晶顯示元件。然後，評價垂直配向性和測定電壓保持率，結果倂列於表3、4和5中。 -42- 200804936σ\ CO 200804936 In Tables 1 and 2, for the diamine compound and the acid anhydride, the numbers in parentheses indicate the content ratio, and the symbols in the table have the following meanings: <Diamine compound> D - 1 : Formula (10) above Diamine D-2 represented by the above formula (11): diamine D-3 represented by the above formula (14): diamine D-5: 1, 4 represented by the above formula (20) - bis(aminomethyl)-bicyclo[2·2·1]heptane φ D- 6 : 1,3-bis(aminomethyl)-cyclohexane D-7 : m-xylenediamine D — 8 : 3,3′-(tetramethyldioxane-1,3-diyl)di(propylamine) D-9: diamine represented by the above formula (28) (average molecular weight: 1000) D - 1 0 : p-phenylenediamine D — 11: 4, 4, diaminodiphenylmethane D-12: 4,4'-diaminodiphenyl ether D-13: 2,2'-dimethyl-4 , 4'-Diaminobiphenyl® <Tetracarboxylic acid dianhydride> Τ A 1: 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride Τ A 2: 2,3,5-tricarboxyl ring Amyl phthalic acid anhydride Τ-3: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride 4:1,3,3&,4,5,913-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2< ]-furan-1,3-dione oxime-5: pyromellitic dianhydride-40-200804936 Example 1 The ruthenium iodide polymer (a-1) obtained in Synthesis Example 1 was dissolved in r - In a mixed solution of butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 40/30/30), 20 parts by weight of polyethylene glycol diglycidyl ether is dissolved relative to 100 parts by weight of the polymer. (Molecular weight: about 400; additive A), a solution having a solid concentration of 6 wt% was prepared. The solution was visually observed to obtain a turbid transparent solution, and thus it was confirmed that it showed good solubility. Subsequently, the film-forming composition of the present invention was prepared by filtration using a filter having a pore size of 0.2 /z m. Then, the printability was evaluated, and no unevenness or unevenness in coating was observed on the coating film, and it was confirmed that the film had good printability. Then, the film-forming composition of the present invention was prepared in the same manner as above except that the solid content concentration was 4%. Next, the film-forming composition was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by a spin coater, and dried at 200 ° C for 60 minutes to form a dry film thickness of 0.08 μ. The film of m. Next, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhered to an alumina ball having a diameter of 3.5 // m is applied. After the mixture is mixed, the liquid crystal alignment film faces are gradually combined and pressure-bonded, and the adhesive is cured. Next, the nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Ltd.) was filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port was closed with an acrylic photocurable adhesive, and bonded to both sides of the substrate. A polarizer is used to produce a liquid crystal display element. The vertical alignment property of the obtained liquid crystal display element was evaluated to be good. And measured the electric -41- 200804936 pressure retention rate, more than 99%, showing good electrical office retention performance. The results are summarized in Table 3. Examples 2 to 67, Comparative Examples 1 to 1 1 A film-forming composition having a solid content concentration of 6% was prepared in the same manner as in Example 1 according to the formulations shown in the following Tables 3 and 4, and the solubility and printing were evaluated. Sex. Further, a film-forming composition having a solid concentration of 4% was prepared in the same manner to prepare a liquid crystal display element. Then, the vertical alignment property and the measured voltage retention ratio were evaluated, and the results are shown in Tables 3, 4 and 5. -42- 200804936

表3 固體成分電壓保持率實施例聚合物添加劑(重量%) 溶解性印刷性垂直配向性 (%) 1 A-1 添加劑A⑽ 良好良好良好 >99 2 A-1 添加劑· 良好良好良好 >99 3 A— 1 添加劑C(10) 良好良好良好 >99 4 A-1 添加劑C(40) 良好良好良好 >99 5 A— 1 添加劑D(20) 良好良好良好 >99 6 A-1 添加劑E⑽ 良好良好良好 >99 7 A— 1 添加劑F(10) 良好良好良好 >99 8 A-1 添加劑F(30) 良好良好良好 >99 9 A—2 添加劑BU〇) 良好良好良好 >99 10 A—2 添加劑C(20) 良好良好良好 >99 11 A—2 添加劑D⑽ 良好良好良好 >99 12 A-2 添加劑E(10) 良好良好良好 >99 13 A-2 添加劑F⑽ 良好良好良好 >99 14 A-3 添加劑D⑽ 良好良好良好 >99 15 A—3 添加劑D⑽ 良好良好良好 >99 16 A-3 添加劑F⑽ 良好良好良好 >99 17 A-4 添加劑E⑽ 良好良好良好 >99 18 A-5 添加劑A_ 良好良好良好 >99 19 A-5 添加劑C⑽ 良好良好良好 >99 -43- 200804936 20 A-5 添加劑1X40) 良好良好良好 >99 21 A-5 添加劑F(20) 良好良好良好 >99 22 A-6 添加劑A⑽ 良好良好良好 >99 23 A—6 添加劑B(5) 良好良好良好 >99 24 A-7 添加劑D(10) 良好良好良好 >99 25 A-7 添加劑D(40) 良好良好良好 >99 26 A-7 添加劑E(30) 良好良好良好 >99 27 A-7 添加劑F⑽ 良好良好良好 >99 28 A-8 添加劑A(20) 良好良好良好 >99 29 A-9 添加劑B⑽ 良好良好良好 >99 30 A-10 添加劑D(20) 良好良好良好 >99 31 A-ll 添加劑A(20) 良好良好良好 >99 32 A-ll 添加劑B(10) 良好良好良好 >99 33 A-ll 添加劑B⑽ 良好良好良好 >99 34 A-ll 添加劑_ 良好良好良好 >99 35 A-ll 添加劑D(5) 良好良好良好 >99 36 A-ll 添加劑卿）良好良好良好 >99 37 A-12 添加劑F⑽ 良好良好良好 >99 38 A —13 添加劑D⑽ 良好良好良好 >99 39 A-13 添加劑D⑽ 良好良好良好 >99 40 A-13 添加劑E⑽ 良好良好良好 >99 41 A-13 添加劑F(5) 良好良好良好 >99 42 A-14 添加劑A(20) 良好良好良好 >99 -44- 200804936Table 3 Solid content voltage holding ratio Example Polymer additive (% by weight) Solubility printability Vertical alignment (%) 1 A-1 Additive A (10) Good good and good> 99 2 A-1 Additive · Good good and good> 99 3 A-1 Additive C(10) Good & Good >99 4 A-1 Additive C(40) Good Good &Good>99 5 A-1 Additive D(20) Good & Good >99 6 A-1 Additive E(10) Good Good &Good>99 7 A-1 Additive F(10) Good Good &Good>99 8 A-1 Additive F(30) Good Good Good >99 9 A-2 Additive BU〇) Good Good &Good> 99 10 A-2 Additive C(20) Good Good &Good>99 11 A-2 Additive D(10) Good Good &Good>99 12 A-2 Additive E(10) Good Good &Good>99 13 A-2 Additive F(10) Good Good & Good 99 14 A-3 Additive D(10) Good Good &Good>99 15 A-3 Additive D(10) Good Good &Good>99 16 A-3 Additive F(10) Good Good &Good>99 17 A-4 Additive E(10) Good & Good >99 18 A-5 Additive A _Good good and good>99 19 A-5 Additive C(10) Good good and good>99 -43- 200804936 20 A-5 Additive 1X40) Good good and good>99 21 A-5 Additive F(20) Good good and good> 99 22 A-6 Additive A(10) Good Good &Good>99 23 A-6 Additive B(5) Good Good &Good>99 24 A-7 Additive D(10) Good Good &Good>99 25 A-7 Additive D( 40) Good and good >99 26 A-7 Additive E(30) Good & Good >99 27 A-7 Additive F(10) Good Good &Good>99 28 A-8 Additive A(20) Good Good &Good>99 29 A-9 Additive B(10) Good Good &Good>99 30 A-10 Additive D(20) Good Good &Good>99 31 A-ll Additive A(20) Good Good &Good>99 32 A-ll Additive B (10 Good and good >99 33 A-ll Additive B(10) Good & Good >99 34 A-ll Additives _ Good Good &Good>99 35 A-ll Additive D(5) Good Good &Good>99 36 A-ll Additives) Good and good >99 37 A-12 Additive F(10) Good and good Good >99 38 A —13 Additive D(10) Good Good &Good>99 39 A-13 Additive D(10) Good Good &Good>99 40 A-13 Additive E(10) Good Good &Good>99 41 A-13 Additive F(5) Good Good & Good 99 T14 A-14 Additive A(20) Good Good &Good>99 -44- 200804936

43 A-14 添加劑D⑽ 良好良好良好 >99 44 A-15 良好良好良好 >99 45 A —16 添加劑D⑽ 良好良好良好 >99 46 A —16 添加劑E(30) 良好良好良好 >99 47 A —17 添加劑B(30) 良好良好良好 >99 48 A-17 添加劑D(5) 良好良好良好 >99 49 A-17 添加劑D⑽ 良好良好良好 >99 50 A-17 添加劑E(30) 良好良好良好 >99 51 A-18 添加劑F⑽ 良好良好良好 >99 表4 固體成分電壓保持率實施例聚合物添加劑(重量%) 溶解性印刷性垂直配向性 (%) 52 A-19 添加劑F(20) 良好良好良好 >99 53 A-20 添加劑D⑽ 良好良好良好 >99 54 A-20 添加劑W0) 良好良好良好 >99 55 A-21 添加劑A⑽ 良好良好良好 >99 56 A-21 添加劑B(20) 良好良好良好 >99 57 A—21 添加劑D⑽ 良好良好良好 >99 58 A-22 添加劑B⑽ 良好良好良好 >99 59 A-22 添加劑D(20) 良好良好良好 >99 60 A-22 添加劑D(40) 良好良好良好 >99 61 A—22 添加劑E(30) 良好良好良好 >99 -45- 200804936 62 A—23 添加劑E(30) 良好良好良好 >99 63 A-24 添加劑⑽ 良好良好· 不好 98 64 A-25 添加劑A⑽ 良好良好良好 96 65 A - 25 添加劑D⑽ 良好良好良好 94 66 A-25 添加劑E(10) 良好良好良好 93 67 A-25 添加劑F(20) 良好良好良好 96 表5 固體成分電壓保持率比較例聚合物添加劑(重量％) 溶解性印刷性垂直配向性 (%) 1 a—1 添加劑B(10) 不好 _ 良好 99 2 a-1 添加劑C⑽ 不好 _ 良好 >99 3 a—1 添加劑EG〇) 不好一良好 >99 4 a—1 添加劑E⑽ 不好 — 良好 >99 5 a-2 添加劑D⑽ 不好 _ 良好 >99 6 a—2 添加劑F⑽ 不好一良好 99 7 a—3 添加劑Da〇) 良好良好良好 93 8 a—4 添加劑_ 良好良好良好 90 9 a—5 添加劑A(30) 良好良好良好 92 10 a—5 添加劑E(10) 良好良好良好 93 11 a—6 添加劑C⑽ 良好良好良好 91 表3、表4和表5中，對於添加劑，括弧內的數字表示43 A-14 Additive D(10) Good & Good >99 44 A-15 Good & Good >99 45 A -16 Additive D(10) Good Good &Good>99 46 A -16 Additive E(30) Good Good &Good>99 47 A-17 Additive B(30) Good & Good >99 48 A-17 Additive D(5) Good Good &Good>99 49 A-17 Additive D(10) Good Good &Good>99 50 A-17 Additive E(30) Good Good &Good>99 51 A-18 Additive F(10) Good Good &Good>99 Table 4 Solid Composition Voltage Retention Examples Polymer Additives (% by Weight) Solubility Printability Vertical Alignment (%) 52 A-19 Additive F (20) Good and good >99 53 A-20 Additive D(10) Good Good &Good>99 54 A-20 Additive W0) Good Good &Good>99 55 A-21 Additive A(10) Good Good &Good>99 56 A-21 Additive B(20) Good & Good >99 57 A-21 Additive D(10) Good Good &Good>99 58 A-22 Additive B(10) Good Good &Good>99 59 A-22 Additive D(20) Good Good &Good>99 60 A-22 Tim Agent D (40) Good Good &Good>99 61 A-22 Additive E (30) Good Good &Good>99 -45- 200804936 62 A-23 Additive E(30) Good & Good >99 63 A-24 Additive (10) Good and good · Bad 98 64 A-25 Additive A(10) Good Good Good 96 65 A - 25 Additive D(10) Good Good Good 94 66 A-25 Additive E(10) Good Good Good 93 67 A-25 Additive F(20) Good Good and good 96 Table 5 Solid content voltage retention ratio Comparative example Polymer additive (% by weight) Solubility printability Vertical alignment (%) 1 a-1 Additive B (10) Not good _ Good 99 2 a-1 Additive C(10) No Good _ Good >99 3 a-1 Additive EG〇) Not good one good >99 4 a-1 Additive E(10) Bad - Good >99 5 a-2 Additive D(10) Bad _ Good >99 6 a- 2 Additive F(10) Not good one good 99 7 a-3 Additive Da〇) Good good good 93 8 a-4 Additive _ Good good good 90 9 a-5 Additive A(30) Good good good 92 10 a-5 Additive E ( 10) Good good and good 93 11 a-6 Add C⑽ 91 Good Good Good Good Table 3, Table 4 and Table 5, the additives, the numbers in parentheses represent

含量比率，表中的符號含義如下： -46- 200804936 <添加劑> 添加劑A :聚乙二醇二縮水甘油醚（分子量約400) 添加劑B : 1，6-己二醇二縮水甘油醚添加劑C : N，N，N’，N’-四縮水甘油基-2,2’-二甲基-4,4’-二胺基聯苯添加劑D: N，N，N’，N’-四縮水甘油基-4,4’-二胺基二苯基甲烷添加劑E : 1,3-二（N，N-二縮水甘油基胺基甲基）環己烷 φ 添加劑F : N，N，N’，N’-四縮水甘油基-m-二甲苯二胺【圖式簡單說明】並〇【主要元件符號說明】 ΛΕ 〇 y ϊ vn -47·The content ratio, the symbols in the table have the following meanings: -46- 200804936 <Additives> Additive A: Polyethylene glycol diglycidyl ether (molecular weight about 400) Additive B: 1,6-hexanediol diglycidyl ether additive C : N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl additive D: N,N,N',N'-four Glycidyl-4,4'-diaminodiphenylmethane additive E: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane φ Additive F : N, N, N ',N'-tetraglycidyl-m-xylylenediamine [Simple description of the diagram] 〇 [Main component symbol description] ΛΕ 〇y ϊ vn -47·

Claims

200804936200804936

十、申請專利範圍： 1· 一種垂直配向型液晶配向劑，其特徵在於包括具有下述式（I - 1)表示的醯胺酸重複單元和下述式（I 一 2)表示的醯亞胺重複單元的至少一種重複單元的聚合物，上述式（I 一1)中的Q1和上述式（I— 2)中的Q2含有下述式（II — 1)和 (II - 2)各自表示的二價有機基團中的至少一種以及下述式（III 一 1)表示的二價有機基團中的至少一種，HOOC COOH / \ / pi / \-^HNOC CONH -Q1X. Patent application scope: 1. A vertical alignment type liquid crystal alignment agent characterized by comprising a repeating unit of a proline having the following formula (I-1) and a quinone imine represented by the following formula (I-2) The polymer of at least one repeating unit of the repeating unit, Q1 in the above formula (I-1) and Q2 in the above formula (I-2) contain each of the following formulas (II-1) and (II-2) At least one of a divalent organic group and at least one of the divalent organic groups represented by the following formula (III-1), HOOC COOH / \ / pi / \-^HNOC CONH -Q1

中其胺二成構基機有價四的酸竣厂四基成機o=c 構有示價表二 P1的示表 Q1 且 /N\ cyo o nnc \\ 2 Q I N 、 ▲ P2 CHO (其中，p2表示構成四羧酸的四價有機基團，且Q2表示構成二胺的二價有機基團）；The amine sulphide plant has a price of four. The acid bismuth plant has a four-base machine o=c. It has a price list of two P1 tables Q1 and /N\ cyo o nnc \\ 2 QIN , ▲ P2 CHO (where p2 Represents a tetravalent organic group constituting a tetracarboxylic acid, and Q2 represents a divalent organic group constituting a diamine);

-48- 200804936 (上式中，X1 爲單鍵、-0-、-CO-、-COO-、-OCO-、-NHC〇-、 •C〇NH_、-S_、伸甲基、碳原子數爲2 — 6的伸烷基或伸苯基，R1是碳原子數爲10〜20的烷基、具有碳原子數爲4 〜40的脂環式骨架的一價有機基團或者碳原子數爲6〜 20的含氟原子的一價有機基團，R2是具有碳原子數爲4 〜40的脂環式骨架的二價有機基團或者碳原子數爲5〜 30的含氟原子的二價有機基團）；-48- 200804936 (In the above formula, X1 is a single bond, -0-, -CO-, -COO-, -OCO-, -NHC〇-, •C〇NH_, -S_, methyl group, carbon number a 2 to 6 alkyl or phenyl group, R 1 is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, or a carbon number of a monovalent organic group of 6 to 20 fluorine atoms; R 2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a divalent fluorine atom having 5 to 30 carbon atoms; Organic group);

(I I I -1)(I I I -1)

(上式中，X2爲伸甲基或碳原子數爲2〜20的伸烷基， R3爲具有含芳香環骨架、有機矽氧烷骨架、 1-(0-(：2114)^〇-1^表示的二價有機基團（11表示碳原子數爲2〜5的伸烷基，n表示1〜1〇〇)、·Κ-(〇·ί：3Η6)η-〇-ίΙ-表不的一價有機基團（R表示碳原子數爲2〜5的伸院基，η 表示1〜50)、具有碳原子數爲4〜40脂環式環狀骨架的二價有機基團，式中多個存在的X2各自可以相同，也可以不同）。 2 ·如申請專利範圍第1項之垂直配向型液晶配向劑，其中上述式（I 一 1)中的Ρ1和（I 一 2)中的Ρ2含有下述式（IV - 1) 〜（IV — 6)各自表示的四價有機基團中的至少一種， R5 R5(In the above formula, X2 is a methyl group or an alkylene group having 2 to 20 carbon atoms, and R3 has an aromatic ring skeleton, an organic decane skeleton, and 1-(0-(:2114)^〇-1 The divalent organic group represented by ^ (11 represents an alkylene group having 2 to 5 carbon atoms, n represents 1 to 1 fluorene), Κ-(〇·ί: 3Η6)η-〇-ίΙ- a monovalent organic group (R represents a stretching group having 2 to 5 carbon atoms, η represents 1 to 50), and a divalent organic group having an alicyclic ring skeleton having 4 to 40 carbon atoms. Each of the plurality of X2s present may be the same or different.) 2. The vertical alignment type liquid crystal alignment agent of the first aspect of the patent application, wherein Ρ1 and (I-2) in the above formula (I-1) Ρ2 contains at least one of the tetravalent organic groups represented by the following formulas (IV-1) to (IV-6), R5 R5

R7 R8 -49- 200804936R7 R8 -49- 200804936

XX 资XX： (IV— 2) (IV— 3)· (IV— 4)XX XX: (IV-2) (IV-3)· (IV-4)

(IV-5) (IV-6)(IV-5) (IV-6)

(其中，R5、R6、R7、R8和R9各自獨立地；! 價有機基團）。 3. 如申請專利範圍第2項之垂直配向型液晶配上述式（I 一 1)中的Ρ1和（I 一 2)中的P2相對於名基團（P、P2)含有50莫耳％以上之上述式（IV-各自表示的四價有機基團中的至少一種。 4. 如申請專利範圍第1項之垂直配向型液晶配上述式（III 一 1)表示的二價有機基團含有下矣 (V_5)各自表示的二價有機基團中的至少一〉氫原子或一向劑，其中 ί部四價有機 5)和（IV - 6) 向劑，其中 ί式（V— 1)〜種， -50- 200804936(wherein R5, R6, R7, R8 and R9 are each independently; valence organic group). 3. The vertical alignment type liquid crystal according to item 2 of the patent application range contains P2 in the above formula (I-1) and P2 in (I-2) contains 50 mol% or more relative to the group (P, P2). At least one of the tetravalent organic groups represented by the above formula (IV). 4. The vertical alignment type liquid crystal of the first aspect of the patent application is formulated with the divalent organic group represented by the above formula (III-1) At least one of a divalent organic group represented by 矣(V_5)> a hydrogen atom or a direct agent, wherein ί a tetravalent organic 5) and (IV-6) agent, wherein ί (V-1)~ , -50- 200804936

R〇r. -2> (V—3) Rb^^Rb〜（V—3) (V - 4)R〇r. -2> (V-3) Rb^^Rb~(V—3) (V - 4)

(V — 5) (其中，Ra表示氫原子或一價的有機基團，Rb·碳原子數爲1〜2〇的伸烷基，多個Ra和Rb各自可以相同，也可以不同，p爲1〜99的整數，q爲i〜20的整數）。 5 ·如申請專利範圍第1項之垂直配向型液晶配向劑，其中上述聚合物爲相對於上述式（I 一丨）表示的醯胺酸重複單元和上述式（I - 2)表示的醯亞胺重複單元的合計量，該醯亞胺重複單元佔40莫耳％以上的醯亞胺化聚合物。 6·如申請專利範圍第1項之垂直配向型液晶配向劑，相對於100重量份聚合物，進一步含有1〜50重量份選自下述式（VI— 1)和（VI - 2)各自表示的分子內至少具有2個環氧基的化合物所組成的群中的至少一種含環氧基化合物，(V-5) (wherein, Ra represents a hydrogen atom or a monovalent organic group, Rb·alkylene group having 1 to 2 carbon atoms, and each of Ra and Rb may be the same or different, and p is An integer from 1 to 99, q is an integer from i to 20). 5. The vertical alignment type liquid crystal alignment agent of claim 1, wherein the polymer is a repeating unit of a proline which is represented by the above formula (I) and a formula represented by the above formula (I-2) The total amount of the amine repeating unit, the quinone imine repeating unit accounts for 40 mol% or more of the quinone imidized polymer. 6. The vertical alignment type liquid crystal alignment agent of claim 1, further comprising 1 to 50 parts by weight, based on 100 parts by weight of the polymer, each selected from the group consisting of the following formulas (VI-1) and (VI-2) At least one of the group consisting of a compound having at least two epoxy groups in the molecule, comprising an epoxy group-containing compound,

-51- 200804936 Rd —N <? (VI-2) (這裏式中，s爲2〜6的整數，t爲1〜4的整數爲s價的有機基團，Rd爲t價的有機基團）。 7.—種垂直配向型液晶顯示元件，其特徵在淤具有如專利範圍第1至6項中任一項之垂直配向型液晶配所形成的垂直配向型液晶配向膜。，Rc 3請 ]劑 -52- 200804936 七、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 〇 /\\\ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：-51- 200804936 Rd —N <? (VI-2) (In the formula, s is an integer of 2 to 6, an integer of 1 to 4 is an s-valent organic group, and Rd is a t-valent organic group. group). A vertical alignment type liquid crystal display element characterized by having a vertical alignment type liquid crystal alignment film formed by a vertical alignment type liquid crystal according to any one of claims 1 to 6. , Rc 3 please ] Agent -52- 200804936 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 /\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: