1254735 玖、發明說明： 發明所屬之技 本發明係有關一種電學特性良好的液晶配向膜、含有 其原料之聚醯胺酸的液晶配向劑、將該液晶配向劑溶於有 機溶劑所得之塗漆（varmsh)，以及包含該液晶配向膜的液 晶顯示元件。 先前技術 現今之液晶顯示元件係以使用向列型液晶者爲主流， 其包括液晶扭轉角爲90。的扭轉向列型（TN)液晶顯示元 件、扭轉角通常達180。以上的超扭轉向列型（STN)液晶顯 示元件’以及使用薄膜電晶體的薄膜電晶體（TFT)液晶顯 示元件。近年來更提出可改善視角之橫向電場式平面轉動 型(IPS)液晶顯示元件、利用垂直配向狀態調變的垂直配向 型(VA)液晶顯示元件，以及利用彎曲配向狀態調變的光學 補償彎曲型（OCB)或光學補償複折射型（〇CB)液晶顯示元 件等。上述各種液晶顯示元件有些已經實用化，有些則還 在硏究改良中。爲提升液晶顯示元件的特性，不僅有許多 關於其驅動方式的探討，還有許多關於其周邊材料之^良 的硏究。其中，液晶配向膜即是液晶顯笊元件之顯示品質 好壞的重要因素之一。因此’爲提高顯希元件的品質D，液 晶配向膜之改良是很重要的一環。 ' 在本發明中’液曰曰配向劑係表示液晶配向膜所用的聚 醯胺酸或可溶性聚亞醯胺等聚合物。液日自日配向膜係由液晶 配向劑製得，而大多_程係先將液—向劑溶解在有機 11406pif.doc/008 6 1254735 溶劑中形成塗漆，再將其塗布在基板上，然後以加熱等方 式使溶劑蒸發而形成液晶配向膜。當液晶配向劑含有聚醯 胺酸之成分時，再進一步加熱即可產生脫水閉環反應，而 得亞胺化的液晶配向膜。雖然聚亞醯胺以外還有多種液晶 配向膜材料的硏究正在進行中，但其在耐熱性、耐化學物 性（耐液晶材料的特性）、塗布性、液晶配向性、電學特性 及顯示特性等方面都還不足，故現階段無法實用化。 使用聚醯胺酸作爲液晶配向劑的幾個實例簡述如下。 日本專利申請案早期公開公報第平6-222367號揭露，由 具有芳香族或環脂族二撐基的二胺基化合物與具有芳香環 或脂環的四羧酸二酐加成聚合而得之聚醯胺酸。該前案雖 揭露此種聚醯胺酸構成之配向膜其產生擦傷的可能性不受 加熱條件所影響，但卻無具體方法以提高其電學特性。 另外，日本專利申請案早期公開公報第平8-122793 號揭露另一種液晶配向劑，其含有下述聚醯胺酸及其亞醯 胺化聚合物中的至少一種，此聚醯胺酸係由四羧酸二酐之 混合物與有機性二胺反應而得’且此四羧酸二酐混合物含 有70〜95 mol%的特定脂族或環脂族四羧酸二酐與30〜5 mol%的含芳香環的四羧酸二酐。 如該前案所述’此聚醯胺酸所構成之液晶配向劑可以 使摩擦處理（rubbing treatment)產生之靜電迅速被除去，且 其所形成之液晶配向膜表面也不易因摩擦處理而產生損 傷，而可以形成配向能力良好的液晶顯示元件，同時此液 晶配向劑的保存穩定性也很好。不過’該前案還是未揭露 11406pif.doc/008 7 1254735 提升其電學特性的具體方法。舉例來說，該前案之實施例 所提，在酸單元中僅含芳香族四羧酸二酐與環脂族四羧酸 二酐兩者的聚醯胺酸，其電學特性即無明顯提升。另外， 該前案中也沒有揭露使用具多個脂環構造之聚醯胺酸的實 施例。 另一方面，也有許多提升配向膜電學特性的硏究，如 曰本專利申請案早期公開公報第平6-222367號即揭露由 一種聚醯胺酸組成物，其係由可形成電學特性良好之聚亞 醯胺的聚醯胺酸及含有具支鏈二胺的聚醯胺酸所組成者。 使用此種聚醯胺酸組成物之液晶顯示元件的電學特性雖可 達到實用的程度，但隨著液晶配向膜之性能需求逐年提 高，所以業界正積極開發性能更佳之液晶配向膜。 發明內容 由前述內容可知，本發明之目的爲改良對液晶顯示元 件之示特性甚爲重要的液晶配向劑，而提出一種具有適當 的初始傾斜角（pre-tilt angle)及良好的電學特性（特別是電 荷殘留、電壓保持比及殘影等特性）的液晶配向劑，以及 使用此液晶配向劑的液晶顯示元件。. 爲解決前述問題，發明人在深入硏究聚醯胺酸所用之 四羧酸及二胺的分子結構及共聚合比之後發現，如使用含 有下述聚醯胺酸的液晶配向劑來形成液晶顯示元件所用的 液晶配向膜，即可達成前述之目的。 本發明所提出的一種液晶配向劑，包括由下述（a)與(b) 11406pif.doc/008 8 1254735 項之化合物所組成的四羧酸二酐混合物與無長鏈分支的二 胺反應而得之聚醯胺酸（以下簡稱聚醯胺酸(A))，其中（^包 括芳香族四羧酸二酐，含量爲15〜35 mol% ; (b)包括一種 以上的脂族或環脂族四羧酸二酐，含量爲85〜65 mQl%。 在上述液晶配向劑中，該一種以上的脂族或環脂族四 羧酸二酐較佳係由環丁烷四羧酸二酐、環己烷四羧酸二 野、甲基環丁烷四羧酸二酐以及丁烷四羧酸二酐所組成之 族群中所選出者。 亦即，上述一種以上的脂族或環脂族四羧酸二酐可爲 上述族群中所選出的任意2種化合物。 上述一種以上的脂族或環脂族四羧酸二酐亦可爲該族 群中所選出的任意3種化合物。 另外，在本發明其他的較佳實施例中，芳香族四羧酸 二酐亦可爲苯均四酸二酉干(pyromellitic dianhydride)。 此外，在本發明另一較佳實施例中，無長鏈分支的二 胺包括下式（1)所示之二胺： (CE^ (CE^nTechnical Field The present invention relates to a liquid crystal alignment film having good electrical properties, a liquid crystal alignment agent containing polyacrylic acid as a raw material thereof, and a paint obtained by dissolving the liquid crystal alignment agent in an organic solvent ( Varmsh), and a liquid crystal display element including the liquid crystal alignment film. Prior Art Today's liquid crystal display elements are mainly used in the use of nematic liquid crystals, which include a liquid crystal twist angle of 90. The twisted nematic (TN) liquid crystal display element typically has a twist angle of 180. The above super twisted nematic (STN) liquid crystal display element' and a thin film transistor (TFT) liquid crystal display element using a thin film transistor. In recent years, a lateral electric field type planar rotating type (IPS) liquid crystal display element having improved viewing angle, a vertical alignment type (VA) liquid crystal display element using vertical alignment state modulation, and an optical compensation bending type using bending alignment state modulation have been proposed. (OCB) or optically compensated birefringence type (〇CB) liquid crystal display element. Some of the above various liquid crystal display elements have been put to practical use, and some are still being improved. In order to improve the characteristics of liquid crystal display elements, there are many discussions about the driving methods thereof, and there are many studies on the surrounding materials. Among them, the liquid crystal alignment film is one of the important factors for the display quality of the liquid crystal display element. Therefore, in order to improve the quality D of the display element, the improvement of the liquid crystal alignment film is an important part. In the present invention, the liquid helium alignment agent means a polymer such as polylysine or soluble polyamidamide used for the liquid crystal alignment film. The liquid-to-day alignment film is made of a liquid crystal alignment agent, and most of the liquid is first dissolved in an organic solvent of 11406pif.doc/008 6 1254735 to form a paint, and then coated on a substrate, and then coated on the substrate, and then The solvent is evaporated by heating or the like to form a liquid crystal alignment film. When the liquid crystal alignment agent contains a component of polylysine, further heating can be carried out to produce a dehydration ring-closing reaction, thereby obtaining an imidized liquid crystal alignment film. Although there are a variety of liquid crystal alignment film materials in addition to polyamines, heat resistance, chemical resistance (liquid crystal material resistance), coating properties, liquid crystal alignment properties, electrical properties, display properties, etc. The aspects are still insufficient, so it is not practical at this stage. Several examples of the use of polylysine as a liquid crystal alignment agent are briefly described below. Japanese Patent Application Laid-Open No. Hei 6-222367 discloses the addition polymerization of a diamine compound having an aromatic or cycloaliphatic diradical group to a tetracarboxylic dianhydride having an aromatic ring or an alicyclic ring. Polylysine. Although the prior case discloses that the alignment film composed of such polyamic acid has the possibility of causing scratches without being affected by heating conditions, there is no specific method to improve its electrical properties. In addition, Japanese Laid-Open Patent Publication No. Hei 8-122793 discloses another liquid crystal alignment agent containing at least one of the following polyaminic acid and a sulfonamide polymer thereof. A mixture of tetracarboxylic dianhydride and an organic diamine is obtained and the tetracarboxylic dianhydride mixture contains 70 to 95 mol% of a specific aliphatic or cycloaliphatic tetracarboxylic dianhydride and 30 to 5 mol%. An aromatic ring-containing tetracarboxylic dianhydride. As described in the foregoing, the liquid crystal alignment agent composed of the polyamic acid can rapidly remove the static electricity generated by the rubbing treatment, and the surface of the liquid crystal alignment film formed by the liquid crystal alignment film is not easily damaged by the rubbing treatment. Further, a liquid crystal display element having a good alignment ability can be formed, and the liquid crystal alignment agent is also excellent in storage stability. However, the previous case has not revealed the specific method of improving its electrical characteristics. 11406pif.doc/008 7 1254735. For example, as mentioned in the examples of the preceding example, the polyamic acid containing only aromatic tetracarboxylic dianhydride and cycloaliphatic tetracarboxylic dianhydride in the acid unit has no obvious improvement in electrical properties. . Further, the prior art does not disclose an embodiment using a polyaminic acid having a plurality of alicyclic structures. On the other hand, there are also many studies for improving the electrical properties of the alignment film. For example, the disclosure of the patent application laid-open No. Hei 6-222367 discloses a poly-proline composition which is excellent in electrical properties. Polyimide polyisamic acid and polyamine containing a branched diamine. Although the electrical characteristics of the liquid crystal display device using such a polyamic acid composition can be practical, the performance of the liquid crystal alignment film is increasing year by year, and the industry is actively developing a liquid crystal alignment film having better performance. SUMMARY OF THE INVENTION It is apparent from the foregoing that the object of the present invention is to improve a liquid crystal alignment agent which is important for the characteristics of a liquid crystal display element, and to provide an appropriate initial tilt angle and good electrical characteristics (especially A liquid crystal alignment agent which is a property of charge retention, voltage retention ratio, and afterimage, and a liquid crystal display element using the liquid crystal alignment agent. In order to solve the above problems, the inventors have found out that the molecular structure and copolymerization ratio of the tetracarboxylic acid and the diamine used in the polyamic acid are intensively, and it is found that a liquid crystal alignment agent containing the following polylysine is used to form a liquid crystal. The liquid crystal alignment film used for the display element can achieve the aforementioned purpose. The liquid crystal alignment agent of the present invention comprises a tetracarboxylic dianhydride mixture composed of the following compounds (a) and (b) 11406 pif. doc / 008 8 1254735 and reacted with a diamine having no long-chain branching. Poly-proline (hereinafter referred to as poly-proline (A)), wherein (including aromatic tetracarboxylic dianhydride, the content is 15 to 35 mol%; (b) including more than one aliphatic or cycloaliphatic The tetracarboxylic dianhydride has a content of 85 to 65 mQl%. In the above liquid crystal alignment agent, the one or more aliphatic or cycloaliphatic tetracarboxylic dianhydrides are preferably cyclobutane tetracarboxylic dianhydride. a group selected from the group consisting of dicyclohexane tetracarboxylic acid, methylene cyclobutane tetracarboxylic dianhydride, and butane tetracarboxylic dianhydride. That is, one or more of the above aliphatic or cycloaliphatic tetra The carboxylic acid dianhydride may be any two compounds selected from the above group. The above one or more aliphatic or cycloaliphatic tetracarboxylic dianhydrides may also be any three compounds selected from the group. In other preferred embodiments of the invention, the aromatic tetracarboxylic dianhydride may also be pyromellitic dianhydride. Further, in another preferred embodiment of the present invention, the diamine having no long-chain branching includes the diamine represented by the following formula (1): (CE^ (CE^n
其中，x爲碳數1〜3的烴基、氧原子或〉c=o，且p、q各 自介於〇與2之間。 在本發明又一較佳實施例中，無長鏈分支的二胺包括 下式（2)所示之二胺： 11406pif.doc/008 9 1254735 H2N Ri-fSi ——〇)^Si——R1—NH2 式⑵ 其中，h爲碳數1〜5的脂族二撐基或苯二撐基；R2及R3 可相同或不同，且各自爲碳數至少爲1的脂基或碳數至少 爲6的芳香基；而m介於1與20之間。 本發明並提出另一種液晶配向劑，係爲2種或2種以 上之聚醯胺酸的混合物，其中包括聚醯胺酸（A)及聚醯胺 酸(B)作爲必要之成分，其中聚醯胺酸(A)係由下述(a)與(b) 項之化合物所組成的四羧酸二酐混合物與無長鏈分支的二 胺反應而得者，且聚醯胺酸（B)係由四羧酸二酐與包括下 式（3)或（4)所示之二胺在內的二胺反應而得者，其中（a)包 括芳香族四羧酸二酐，含量爲15〜35 mol% ; (b)包括一種 以上的脂族或環脂族四羧酸二酐，含量爲85〜65 mol%。 式（3)爲Wherein x is a hydrocarbon group having 1 to 3 carbon atoms, an oxygen atom or >c=o, and p and q are each between 〇 and 2. In still another preferred embodiment of the present invention, the diamine having no long-chain branching includes the diamine represented by the following formula (2): 11406 pif.doc/008 9 1254735 H2N Ri-fSi ——〇)^Si——R1 —NH 2 Formula (2) wherein, h is an aliphatic di-support or a phenylene support having 1 to 5 carbon atoms; R 2 and R 3 may be the same or different and each have a carbon number of at least 1 or a carbon number of at least 6 Aromatic group; m is between 1 and 20. The present invention also proposes another liquid crystal alignment agent, which is a mixture of two or more kinds of poly-proline, including poly-proline (A) and poly-proline (B) as essential components, wherein The proline (A) is obtained by reacting a mixture of a tetracarboxylic dianhydride composed of the following compounds (a) and (b) with a diamine having no long-chain branching, and poly-proline (B) It is obtained by reacting a tetracarboxylic dianhydride with a diamine including a diamine represented by the following formula (3) or (4), wherein (a) comprises an aromatic tetracarboxylic dianhydride in an amount of 15~ 35 mol%; (b) comprising more than one aliphatic or cycloaliphatic tetracarboxylic dianhydride in an amount of from 85 to 65 mol%. Formula (3) is
其中，R4爲氫或碳數1〜12的烷基，Y爲單鍵或CH2，環 A爲苯環或環己基環，各Z各自表示單鍵、CH2、CH2CH2 或氧原子，r=0〜3，s=0〜5，t=0〜3，且任意苯環或環己基 環上的氫可爲低級烷基所置換，此低級烷基較佳爲碳數1〜4 的直鏈或具支鏈烷基。式(4)爲 11406pif.doc/008 10 1254735Wherein R4 is hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is a single bond or CH2, and ring A is a benzene ring or a cyclohexyl ring, and each Z represents a single bond, CH2, CH2CH2 or an oxygen atom, r=0~ 3, s = 0 to 5, t = 0 to 3, and hydrogen on any benzene ring or cyclohexyl ring may be replaced by a lower alkyl group, and the lower alkyl group is preferably a linear one having a carbon number of 1 to 4 or Branched alkyl. Equation (4) is 11406pif.doc/008 10 1254735
式⑷ Χι - B 广X2-B2-R5Equation (4) Χι - B Guang X2-B2-R5
其中，乂!及X2各自爲單鍵、〇、COO、〇C0、NH、CONH 或碳數1〜12的烷撐基；及B2各自爲單鍵或含有1〜3個 芳香環與/或脂族環的二撐基；R5爲氫、氟、CN、OH、碳 數1〜12的烷基、氟烷基或烷氧基。 在上述液晶配向劑中，除了聚醯胺酸（A)所含之無長 鏈分支的二胺，或聚醯胺(B)所含之式（3)或（4)的二胺以外， 更可使用式（1)與/或（2)所示之二胺。 另外，在上述液晶配向劑中，聚醯胺酸（A)在該聚醯 胺酸混合物中的含量較佳爲85〜99 wt%。 本發明並提出一種塗漆(varnish)，其係由上述任一種 聚醯胺酸溶於有機溶劑而得者，其中聚醯胺酸的濃度爲 0.1〜40 wt%。本發明再提出一種液晶配向膜，係由前述任 一種液晶配向劑或塗漆所製得者。本發明又提出一種液晶 顯示元件，其具有上述之液晶配向膜，且較佳包含一含氟 液晶組成物。此含氟液晶組成物較佳包含1種以上的在分 子中含有氟原子的液晶化合物。 爲讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉較佳實施例作詳細說明如下： 實施方式 本發明之液晶配向劑詳述如下。作爲本發明之液晶配 向劑主要成分的聚醯胺酸可以很容易地在有機溶劑中，由 11406pif.doc/008 11 1254735 大約等莫耳的四羧酸二酐與二胺合成而得。本發明之聚醯 胺酸（A)所含之四羧酸二酐包含一種或一種以上的芳香族 四羧酸二酐，以及二種或二種以上的脂族四羧酸二酐或環 脂族四羧酸二酐，所以總共有三種或三種以上的四羧酸二 酐。 方香族四羧酸二酐之實例包括：苯均四酸二酐、 3,3’，4,4，-聯苯四羧酸二酐、2,2’，3,3’-聯苯四羧酸二酐、 2,3,3’，4、聯苯四羧酸二酐、3,3’，4,4’-二苯甲酮四羧酸二 酐、二（3,4-二羧苯基）醚二酐、二（3,4-二羧苯基）楓二酐、 1，2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、二（二羧苯 基）甲烷二酐、2,2’-二（3,4-二羧苯基）-1，1，1，3,3,3-六氟丙烷 二酐等等。上述各種四羧酸二酐可單獨使用或多種組合使 用，其中尤以苯均四酸二酐爲佳。 另外，脂族四羧酸二酐或環脂族四羧酸二酐之實例包 括：環丁烷四羧酸二酐、環己烷四羧酸二酐、甲基化環丁 烷四羧酸二酐、丁烷四羧酸二酐、環戊烷四羧酸二酐、二 環己烷四羧酸二酐、二環戊烷四羧酸二酐、二（二羧環己 基）醚二酐、二（二羧環己基）楓二酐、二（二羧環己基）甲烷 二酐、1,2-二羧基-4-琥珀酸-1，2,3,4-四氫化萘二酐、1，2-二 羧基-4-甲基-4-琥珀酸-1，2,3,4-四氫化萘二酐、1，4-環己烷-二丁二酸、4-(2,5-二氧雜四氫呋喃-3-基）-1，2,3,4-四氫化萘 -1，2-二羧酸酐、2,3,5-三羧基環戊烷乙酸二酐、5,6-二羧基 -：μ甲基琥珀酸-1-環己烷二酐，以及2,3,5,6-四羧基二環 [2.2.1]環戊院二酐等等。 11406pif.doc/008 12 1254735 上述各種四羧酸二酐中較佳者爲環丁烷四羧酸二酐、 環己烷四羧酸二酐、甲基化環丁烷四羧酸二酐，以及丁烷 四羧酸二酐。正因爲使用了 2種或2種以上的脂族或環脂 族四羧酸二酐，所以本發明之液晶配向劑可具有良好的電 學特性。 此處所用之2種或2種以上的脂族或環脂族四羧酸二 酐可全爲脂族或全爲環脂族，或是混用此二者。具體來說， 當使用2種脂族或環脂族四羧酸二酐之組合時，其較佳者 爲環丁烷四羧酸二酐與甲基化環丁烷四羧酸二酐之組合、 環丁烷四羧酸二酐與環己烷四羧酸二酐之組合、環丁院四 羧酸二酐與丁烷四羧酸二酐之組合、丁烷四羧酸二酐與環 己烷四羧酸二酐之組合，以及丁烷四羧酸二酐與甲基化環 丁烷四羧酸二酐之組合。 當使用3種脂族或環脂族四羧酸二酐之組合時，其較 佳者爲環丁烷四羧酸二酐、環己烷四羧酸二酐與丁烷四竣 酸二酐之組合；環丁烷四羧酸二酐、甲基化環丁烷四竣酸 二酐與丁烷四羧酸二酐之組合；以及環己烷四羧酸二酐、 甲基化環丁烷四羧酸二酐與丁烷四羧酸二酐之組合等。當 然，本發明之範圍並不限於上述之各種組合，只要在不損 及配向劑之特性，則亦可採用3種以上丁烷四羧酸二酐的 組合。 另外，上述各種四羧酸二酐中多少有羧基位置或取代 基位置不同的，或是立體結構不同的數種異構物，而這些 異構物當然亦包含在本發明之範圍中。 11406pif.doc/008 13 1254735 在聚醯胺酸（A)中，芳香族四羧酸二酐之含量爲全部 四羧酸二酐的15〜35 mol%，較佳爲17〜30 mol%。當芳香 族四羧酸二酐之含量低於15 mol%時，殘留電荷的絕値會 增加，使其電壓保持比下降；而當其含量高於35 mol%時， 對本發明特徵之電學特性改良的效果並不顯著。另外，當 脂族或環脂族四羧酸二酐中有1者爲環丁烷四羧酸二酐 時，其含量較佳爲全部四羧酸二酐的20〜60 mol% 用來合成聚醯胺酸（A)的二胺可以是無長鏈分支的二 胺，其包括主鏈上完全無分支之取代基者，以及主鏈上有 甲基、苯基或鹵素原子等短取代基者，而所有具有此結構 的習知二胺皆可使用於本發明中。 不過，該二胺中較佳者還是之前通式（1)所示之二胺， 其包括：二（4-胺基苯基）醚、4,45-二胺基二苯甲烷、3,3’-二胺基二苯甲烷、4,4’-二胺基-3,3’-二甲基二苯甲烷、4,4’-二胺基-2,2、二甲基二苯甲烷、4,4’-二胺基-3,3’，5,5’-四甲 基二苯甲烷、1，2-二（4-胺基苯基）乙烷、1，2-二（4-胺基-2-甲基苯基）乙烷、4,4’-二胺基二苯基-2,2-丙烷、2,2’-二胺 基二苯甲酮、4,4’-二胺基二苯甲酮、3,4-二胺基二苯甲酮 等等。 另外，上述無長鏈分支之二胺的其他適當實例爲之前 通式（2)所示之二胺基矽酮化合物。雖然前述式（2)中的R, 爲碳數1〜5的脂族官能基或碳數6 (或以上）的芳香基，但 考量獲得之便利性，則以亞甲基、乙撐基、丙撐基或苯撐 基爲佳。另外，雖然前述式（2)之心及R3可爲相同或不同 11406pif.doc/008 14 1254735 的一價脂族官能基或芳香基，但較佳爲碳數1〜6的烷基或 苯基，更佳爲甲基、乙基、正丙基、異丙基、正丁基、異 丁基、三級丁基或苯基。m介於1與20之間，但較佳爲1。 此種二胺基矽酮的具體實例包括：1，3-二（3-胺基甲基）-1，1，3,3 -四本基_^砂氧;|兀、1，3 -一*(3-胺基乙基）-1，1，3,3 -四苯 基二矽氧烷、1，3-二（3-胺基丙基）-1，1，3,3-四苯基二矽氧 烷、1，3-二（3-胺基丁基）-1，1，3,3-四苯基二矽氧烷、1，3-二（3-胺基甲基）-1，1，3,3-四甲基二矽氧烷、1,3-二（3-胺基乙基）_ 1,1，3,3-四甲基二矽氧烷、1，3_二（3-胺基丙基）-1，1，3,3-四甲 基二矽氧烷、1，3-二（3-胺基丁基）-1，1，3,3-四甲基二矽氧 烷、1，3-二（3-胺基甲基)-1，1，3,3-四（2-丙基）二矽氧烷、1，3-二（3-胺基乙基）-1，1，3,3-四（2-丙基）二矽氧烷，以及1，3-二（3-胺基丙基）-1，1，3,3-四（2-丙基）二矽氧烷等等。 該二胺基矽酮化合物的適當含量如下：當配向劑僅使 用聚醯胺酸(A)時，其含量佔全部二胺（100 mol%)的0.5〜10 mol% ;而當配向劑組合使用聚醯胺酸(A)及（B)時，該二胺 基矽酮化合物較佳使用於聚醯胺酸(B)中，此時聚醯胺酸(B) 中該二胺基矽酮化合物的含量相對於全部二胺〇〇〇 mol%) 而言即爲0.5〜20 mol%。 上述通式⑴與（2)所示之二胺以外的二胺的實例包 括：對苯二胺、間苯二胺、鄰苯二胺、二（4-胺基苯基)楓、 二（4-胺基苯基）亞楓、二（4-(3-胺基苯氧基）苯基）楓、2,2-二（4-(4-胺基苯氧基）苯基）丙烷、二（4-(4-二胺基苯氧基）苯 基）楓、聯苯胺、2,2-二（4-胺基苯基)丙烷、1，5-二胺基萘' 11406pif.doc/008 15 1254735 2,2-二（4-胺基苯基）-1，1，1，3,3,3-六氟丙烷、2,2-二（4-(4-胺 基苯氧基）苯基）-U，l，3,3,3-六氟丙烷、4,4’-二（4-胺基苯氧 基）聯苯、1，3-二（4-(4-胺基苯甲基）苯基）丙烷、1，4-二（4-胺 基苯氧基）苯、二對胺基苯基苯胺等周知的二胺，其可作 爲聚醯胺酸（A)及聚醯胺酸(B)的二胺成分。 上述無長鏈分支的二胺中特佳者包括：二（4-胺基苯基) 醚、4,4’-二胺基二苯甲烷與1，2-二（4-胺基苯基）乙烷，以 及1，3-二（3-胺基丙基）-1，1，3,3-四甲基二矽氧烷等等。 上述無長鏈分支的二胺亦可倂用2種或2種以上，此 時較佳由二（4-胺基苯基）醚、4,4’-二胺基二苯甲烷、1，2-二 (4-胺基苯基）乙烷，以及1，3-二（3-胺基丙基）-1，1，3,3-四甲 基二矽氧烷中選出2種或2種以上倂用。 以上述方式所得之聚醯胺酸（A)可單獨用作配向劑， 但爲易於調整液晶的初始傾斜角，其較佳與下述之聚醯胺 酸(B)混合使用。 另一方面，作爲聚醯胺酸（B)之原料的二胺必須含有 前述通式（3)及(4)所示之二胺中的1種或1種以上。 通式（3)之化合物的實例包括：U-二（4-(4-胺基苯氧 基）苯基）環己烷、1，1_二（4-(4-胺基苯氧基）苯基）-4-丙基環 己烷、1,1-二（4-(4-胺基苯甲基）苯基）環己烷，以及4-正丁 基-1,1-二（4-(4-胺基苯甲基）苯基）環己烷等等。另外，通式 (4)之化合物的實例包括：4-正丙基環己基-3’，5’-二胺基二 苯甲烷與4-(4-正丙基環己基）環己基-3’,5’-二胺基二苯甲 烷等等。 11406pif.doc/008 16 1254735 聚醯胺酸（B)亦可含有上述二胺以外的其他二胺，其 種類並無特別限制，而可爲聚醯胺酸（八)之相關說明中所 舉出之各種無長鏈分支的二胺，脂族二胺或環脂族二胺等 等。 上述脂族二胺或環脂族二胺之實例包括：三亞甲基二 胺、四亞甲基二胺、六亞甲基二胺、1，12-十二院二胺、M-二胺基環己烷、4,4，-二胺基二環己基甲烷、4,4，_二胺基-3,3 甲基二環己基甲院、丨，4-二胺基丁基苯、丨，心二 胺基-2-十二烷氧苯，以及4,4，_二胺基辛基二苯甲烷等 等。 在上述各種無長鏈分支的二胺及其以外的芳香族二 胺、脂族二胺及環脂族二胺中，式（3)或（4)所示之二胺較 f土爲4,4-二胺基二苯甲烷、L2-二（4-胺基苯基）乙烷或n 二（3-胺基丙基）_u，3,3_四甲基二矽氧烷；如所使用者爲式 (3)及（4)所代表之二胺混合物時，其較佳由該數種化合物 中运出2種或2種上。 @醯胺酸（B)所用之四羧酸二酐亦無特別限制，而可 爲習知的四竣酸二酐，亦即可爲聚醯胺酸（A)之相關說明 中所舉出的芳香族、脂族或環脂族四羧酸二酐。該些四羧 酸二酐可以單獨使用或選擇多種倂用，其中尤以苯均四酸 二酐 '環丁烷四羧酸二酐、丁烷四羧酸二酐及其組合爲佳。 使前述四羧酸二酐與二胺反應而得聚醯胺酸的方法可 以是習用的方法，例如是以下所述者：首先將有機溶劑、 四羧酸二酐及二胺裝入反應器中，令其於—1(TC〜100。(：、 11406pif.doc/008 17 1254735 通入惰性氣體且攪拌的條件下反應1〜60小時，即可得黏 稠的聚醯胺酸溶液。 再者，在本發明之聚醯胺酸的製造過程中，除了上述 四羧酸二酐與二胺之外，更可適度添加單胺與/或單羧酸 酐，以作爲聚醯胺酸的反應終止劑，這些單胺與/或單羧 酸將位在聚醯胺酸的尾端。另外，爲提高與基板的密著性 或耐摩擦性，本發明之液晶配向劑中亦可加入有機矽化 物，其例如爲：胺丙基三甲氧基矽烷、胺丙基三乙氧基矽 院、乙儲基二甲氧基砂院、N-(2-胺基乙基）-3-胺丙基甲基 二甲氧基矽烷、N-(2-胺基乙基）-3-胺丙基三甲氧基矽烷、 乙烯基三乙氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽 烷、3-縮水甘油氧丙基三甲氧基矽烷、3-縮水甘油氧丙基 甲基二甲氧基矽烷，以及2-(3,4-環氧環己基）乙基三甲氧 基矽烷等矽烷耦合劑；或是二甲基聚矽氧烷、聚二甲基矽 氧烷及聚二苯基矽氧烷等矽酮油。 本發明所含之聚醯胺酸的分子量以膠體穿透層析法 (GPC)所得之聚苯乙烯換算重量平均分子量（Mw)爲 10000〜500000，較佳爲20000〜200000，而其與數量平均 分子量之比（即聚合分散度Mw/Mn)爲1.2〜3.6。 在以上述方式所得之聚醯胺酸（聚醯胺酸（A)或（B)) 中’聚醯胺酸（A)適合作爲本身即具有良好電學特性之橫 向電場驅動型（水平轉動型）液晶顯示元件的液晶配向膜的 原料。但是，僅使用聚醯胺酸（A)並無法得到大初始傾斜 角的配向膜。因此，對必須控制初始傾斜角的扭轉向列型 11406pif.doc/008 18 1254735 (ΤΝ)、光學補償彎曲型（OCB)及垂直配向型（VA)元件所用 的液晶配向劑而言，其較佳倂用聚醯酸（A)與對初始傾斜 角控制性較佳的聚醯胺酸（B)。聚醯胺酸（B)所用之具支鏈 的二胺可以是之前所舉出的各種通式爲（3)或（4)的二胺。 在本發明之通式（3)所示之二胺的具體實例中，R4、Y、環 A、Z、r、s及t的各種組合係顯示於表1〜14中，其中化 合物的環(A)記爲B時即表示苯環，而記爲Ch時即表示環 己基環。 表1 編號 r4 環A Y z r s t 1 氬 - - - 0 - 0 2 ch3 - - 0 - 0 3 c2h5 - - - 0 - 0 4 n-C3H7 - - - 0 - 0 5 η - C4H9 _ - - 0 - 0 6 n-C5Hn - - 0 - 0 7 n-C6H13 - - - 0 - 0 8 n-C7H15 - - - 0 - 0 9 n-C8H17 - - - 0 - 0 10 - - - 0 - 0 11 n-C10H21 - - - 0 - 0 12 n-CnH23 - - - 0 - 0 13 n-C12H25 - - - 0 - 0 11406pif.doc/008 19 1254735 表2 編號 r4 環A Y Z r s t 14 氫 Ch - - 1 0 0 15 ch3 Ch - - 1 0 0 16 c2h5 Ch - - 1 0 0 17 n-C3H7 Ch - - 1 0 0 18 n-C4H9 Ch - - 1 0 0 19 n-C5Hu Ch - - 1 0 0 20 n-C6H13 Ch - - 1 0 0 21 n-C7H15 Ch - - 1 0 0 22 n-C8H17 Ch - - 1 0 0 23 11-C9H19 Ch - - 1 0 0 24 n-C10H21 Ch - 1 0 0 25 n-CnH23 Ch - - 1 0 0 26 n-C12H25 Ch - - 1 0 0 表3 編號 r4 環A Y Z r s t 27 氣 B - - 1 0 0 28 ch3 B - - 1 0 0 29 c2h5 B - - 1 0 0 30 n-C3Hv B 爾 - 1 0 0 31 n-C4H9 B - - 1 0 0 32 n-C5Hn B - - 1 0 0 33 n-C6H13 B - - 1 0 0 34 n-C7H15 B - - 1 0 0 35 n-C8H17 B - - 1 0 0 36 n-C9H19 B 麵 1 0 0 37 n-C10H21 B - - 1 0 0 38 n-CnH23 B - - 1 0 0 39 n-C12H25 B - - 1 0 0 11406pif.doc/008 20 1254735 表4 編號 r4 環A Y z r s t 40 氫 Ch ch2 - 1 1 0 41 ch3 Ch ch2 - 1 1 0 42 c2h5 Ch ch2 - 1 1 0 43 n-C3H7 Ch ch2 - 1 1 0 44 n-C4H9 Ch ch2 - 1 1 0 45 n-C5Hu Ch ch2 - 1 1 0 46 n-C6H13 Ch ch2 - 1 1 0 47 n-C7H15 Ch ch2 - 1 1 0 48 n-C8H17 Ch ch2 - 1 1 0 49 Ch ch2 - 1 1 0 50 n-C10H21 Ch ch2 - 1 1 0 51 n-CuH23 Ch ch2 - 1 1 0 52 n-C12H25 Ch ch2 - 1 1 0 表5 編號 r4 環A Y z r s t 53 氫 B ch2 - 1 1 0 54 ch3 B ch2 - 1 1 0 55 c2h5 B ch2 - 1 1 0 56 n-C3H7 B ch2 - 1 1 0 57 n-C4H9 B ch2 - 1 1 0 58 n-C5Hu B ch2 - 1 1 0 59 n-C6H13 B ch2 - 1 1 0 60 n-C7H15 B ch2 - 1 1 0 61 n-C8H17 B ch2 - 1 1 0 62 n_CgH B ch2 - 1 1 0 63 n-C10H21 B ch2 - 1 1 0 64 n-CnH23 B ch2 - 1 1 0 65 n-C12H25 B ch2 - 1 1 0 11406pif.doc/008 21 1254735 表6 編號 r4 環A Y z r S t 66 氫 - - 氧 0 - 1 67 ch3 - - 氧 0 _ 1 68 c2h5 - - 氧 0 - 1 69 n-C3H7 - - 氧 0 - 1 70 n-C4H9 - - 氧 0 - 1 71 n-C5Hn - - 氧 0 - 1 72 n-C6H13 - - 氧 0 _ 1 73 n-C7H15 - - 氧 0 - 1 74 n-C8H17 - - 氧 0 - 1 75 - - 氧 0 - 1 76 n-C10H21 - - 氧 0 - 1 77 n-CuH23 - - 氧 0 - 1 78 n-C12H25 - 讎 氧 0 - 1 表7 編號 r4 環A Y z r S t 79 氣 Ch - 氧 1 0 1 80 ch3 Ch - 氧 1 0 1 81 C2H5 Ch - 氧 1 0 1 82 n-C3H7 Ch - 氧 1 0 1 83 n-C4H9 Ch - 氧 1 0 1 84 n-C5Hn Ch - 氧 1 0 1 85 n-C6H13 Ch - 氧 1 0 1 86 n-C7H15 Ch - 氧 1 0 1 87 n-C8H17 Ch - 氧 1 0 1 88 Ch - 氣 1 0 1 89 n-C10H21 Ch - 氧 1 0 1 90 n-CnH23 Ch - 氧 1 0 1 91 n-C12H25 Ch - 氧 1 0 1 11406pif.doc/008 22 1254735 表8 編號 r4 環A Y z r S t 92 氫 Ch ch2 氧 1 2 1 93 ch3 Ch ch2 氧 1 2 1 94 c2h5 Ch ch2 氧 1 2 1 95 n-C3H7 Ch ch2 氧 1 2 1 96 n-C4H9 Ch ch2 氧 1 2 1 97 n-C5Hn Ch ch2 氧 1 2 1 98 n-C6H13 Ch ch2 氧 1 2 1 99 11-C7H15 Ch ch2 氧 1 2 1 100 n-C8H17 Ch ch2 氧 1 2 1 101 11-C9H19 Ch ch2 氧 1 2 1 102 n-C10H21 Ch ch2C] ί氧 1 2 1 103 n-CuH23 Ch 2氧 1 2 1 104 n-C12H25 Ch ch2 氧 1 2 1 表9 編號 r4 環A Y Z r S t 105 氫 B - 氧 1 0 1 106 ch3 B - 氧 1 0 1 107 c2h5 B - 氧 1 0 1 108 n-C3H7 B - 氧 1 0 1 109 n-C4H9 B - 氧 1 0 1 110 n，C5Hu B - 氧 1 0 1 111 n~C6H13 B - 氧 1 0 1 112 n-C7H15 B - 氧 1 0 1 113 n-C8H17 B - 氧 1 0 1 114 B - 氧 1 0 1 115 n-C10H21 B - 氧 1 0 1 116 n-CnH23 B - 氧 1 0 1 117 n-C12H25 B - 氧 1 0 1 11406pif.doc/008 23 1254735 表ίο 編號 r4 環A Y z r s t 118 氫 - - ch2 0 - 1 119 ch3 - - ch2 0 雨 1 120 c2h5 - - ch2 0 - 1 121 n-C3H7 - - ch2 0 - 1 122 n-C4H9 - - ch2 0 - 1 123 n-C5Hu - - ch2 0 - 1 124 n-C6H13 - - ch2 0 - 1 125 n-C7H15 - - ch2 0 - 1 126 n-C8H17 - - ch2 0 - 1 127 11-C9H19 _ - ch2 0 - 1 128 n-C10H21 - - ch2 0 - 1 129 n-CnH23 - - ch2 0 - 1 130 n-C12H25 - - ch2 0 睡 1 表11 編號 r4 環A Y z Γ s t 131 氣 Ch - ch2 1 0 1 132 ch3 Ch - ch2 1 0 1 133 c2h5 Ch - ch2 1 0 1 134 n-C3H7 Ch - ch2 1 0 1 135 n-C4H9 Ch - ch2 1 0 1 136 n_C5Hu Ch - ch2 1 0 1 137 n-C6H13 Ch - ch2 1 0 1 138 n-C7H15 Ch - ch2 1 0 1 139 n-C8H17 Ch - ch2 1 0 1 140 11-C9H19 Ch - ch2 1 0 1 141 n-C10H21 Ch - ch2 1 0 1 142 n-CuH23 Ch - ch2 1 0 1 143 n-C12H25 Ch - ch2 1 0 1 11406pif.doc/008 24 1254735 表12 編號 r4 環A Y z r s t 144 氫 Ch ch2 ch2 1 2 1 145 ch3 Ch ch2 ch2 1 2 1 146 c2h5 Ch ch2 ch2 1 2 1 147 η - C3H7 Ch ch2 ch2 1 2 1 148 n - C4H9 Ch ch2 ch2 1 2 1 149 n-C5Hu Ch ch2 ch2 1 2 1 150 n-C6H13 Ch ch2 ch2 1 2 1 151 n-C7H15 Ch ch2 ch2 1 2 1 152 n-C8H17 Ch ch2 ch2 1 2 1 153 Ch ch2 ch2 1 2 1 154 n-C10H21 Ch ch2 ch2 1 2 1 155 n-CnH23 Ch ch2 ch2 1 2 1 156 n~C12H25 Ch ch2 ch2 1 2 1 表13 編號 r4 環A Y Z r s t 157 氫 B - ch2 1 0 1 158 ch3 B - ch2 1 0 1 159 C2H5 B ch2 1 0 1 160 n-C3H7 B 画 ch2 1 0 1 161 n-C4H9 B - ch2 1 0 1 162 n-C5Hn B - ch2 1 0 1 163 n-C6H13 B - ch2 1 0 1 164 n-C7H15 B — ch2 1 0 1 165 n-C8H17 B - ch2 1 0 1 166 B - ch2 1 0 1 167 n-C10H21 B - ch2 1 0 1 168 n-C丨丨H23 B - ch2 1 0 1 169 n-C12H25 B - ch2 1 0 1 11406pif.doc/008 25 1254735 表14 編號 r4 環A Y z Γ s t 170 氫 B ch2 ch2 1 1 1 171 ch3 B ch2 ch2 1 1 1 172 C2H5 B ch2 ch2 1 1 1 173 n-C3H7 B ch2 ch2 1 1 1 174 n-C4H9 B ch2 ch2 1 1 1 175 n_C5Hu B ch2 ch2 1 1 1 176 n-C6H13 B ch2 ch2 1 1 1 177 11-C7H15 B ch2 ch2 1 1 1 178 n-C8H17 B ch2 ch2 1 1 1 179 B ch2 ch2 1 1 1 180 n-C10H21 B ch2 ch2 1 1 1 181 n-CnH23 B ch2 ch2 1 1 1 182 n-C12H25 B ch2 ch2 1 1 1 本發明之式（3)所代表的二胺並不僅限於上述各者，只 要能達成本發明之目的，其可以有各式各樣的變化。另外， 該些一胺可以單獨使用或數種倂用。在該些二胺中，r = 0 且：R4爲氫或短鏈烷基者的初始傾斜角比較小，而當1〜3 時，即使R4爲氫，初始傾斜角也比較大。 當初始傾斜角小時，其比較適用於水平轉動型液晶顯 示元件；而當初始傾斜角爲3°〜V時，其比較適用於扭轉 向列型液晶顯示元件。另外，對超扭轉向列型（STN)、垂 直配向型（VA)與光學補償彎曲型（OCB)等需要更大初始傾 斜角的液晶顯示元件而言，則較佳使用具有較長支鏈的成 分。 另外，在本發明之通式（4)所示之二胺的具體實例中， 11406pif.doc/008 26 1254735Wherein, 乂! and X2 are each a single bond, hydrazine, COO, 〇C0, NH, CONH or an alkylene group having 1 to 12 carbon atoms; and B2 is each a single bond or contains 1 to 3 aromatic rings and/or fats. a diradical group of a family ring; R5 is hydrogen, fluorine, CN, OH, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group or an alkoxy group. In the above liquid crystal alignment agent, in addition to the diamine having no long-chain branch contained in the poly-proline (A), or the diamine of the formula (3) or (4) contained in the polyamine (B), A diamine represented by the formula (1) and/or (2) can be used. Further, in the above liquid crystal alignment agent, the content of the polyamic acid (A) in the polyamic acid mixture is preferably from 85 to 99% by weight. The present invention also proposes a varnish obtained by dissolving any of the above polylysines in an organic solvent, wherein the concentration of the polyproline is 0.1 to 40% by weight. The present invention further provides a liquid crystal alignment film which is obtained by any of the foregoing liquid crystal alignment agents or paints. The present invention further provides a liquid crystal display element having the above liquid crystal alignment film, and preferably comprising a fluorine-containing liquid crystal composition. The fluorine-containing liquid crystal composition preferably contains one or more liquid crystal compounds containing a fluorine atom in the molecule. The above and other objects, features, and advantages of the present invention will become more apparent from the following description. Polylysine which is a main component of the liquid crystal alignment agent of the present invention can be easily synthesized from an organic solvent in an organic solvent from about 11406 pif.doc/008 11 1254735 to about a molar amount of a tetracarboxylic dianhydride and a diamine. The tetracarboxylic dianhydride contained in the poly-proline (A) of the present invention contains one or more aromatic tetracarboxylic dianhydrides, and two or more aliphatic tetracarboxylic dianhydrides or cyclic lipids. Group tetracarboxylic dianhydride, so there are three or more tetracarboxylic dianhydrides in total. Examples of the Fangxiang tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4,-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetra Carboxylic dianhydride, 2,3,3',4,biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxylate) Phenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)leaf dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, bis(dicarboxyphenyl)methane dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, and the like. The above various tetracarboxylic dianhydrides may be used singly or in combination of two or more, and in particular, pyromellitic dianhydride is preferred. Further, examples of the aliphatic tetracarboxylic dianhydride or the cycloaliphatic tetracarboxylic dianhydride include: cyclobutane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, methylated cyclobutane tetracarboxylic acid II Anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, dicyclohexane tetracarboxylic dianhydride, dicyclopentane tetracarboxylic dianhydride, di(dicarboxycyclohexyl)ether dianhydride, Di(dicarboxycyclohexyl)amphoteric anhydride, bis(dicarboxycyclohexyl)methane dianhydride, 1,2-dicarboxy-4-succinic acid-1,2,3,4-tetrahydronaphthalene dianhydride, 1, 2-Dicarboxy-4-methyl-4-succinic acid-1,2,3,4-tetrahydronaphthalene dianhydride, 1,4-cyclohexane-disuccinic acid, 4-(2,5-di Oxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxycyclopentane acetic acid dianhydride, 5,6-dicarboxyl -: μmethylsuccinic acid-1-cyclohexane dianhydride, and 2,3,5,6-tetracarboxybicyclo[2.2.1]cyclopentanic anhydride and the like. 11406pif.doc/008 12 1254735 Preferred among the above various tetracarboxylic dianhydrides are cyclobutane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, methylated cyclobutane tetracarboxylic dianhydride, and Butane tetracarboxylic dianhydride. Since two or more kinds of aliphatic or cycloaliphatic tetracarboxylic dianhydrides are used, the liquid crystal alignment agent of the present invention can have good electrical properties. The two or more aliphatic or cycloaliphatic tetracarboxylic dianhydrides used herein may be all aliphatic or wholly cycloaliphatic or may be used in combination. Specifically, when a combination of two aliphatic or cycloaliphatic tetracarboxylic dianhydrides is used, it is preferably a combination of a cyclobutane tetracarboxylic dianhydride and a methylated cyclobutane tetracarboxylic dianhydride. a combination of cyclobutane tetracarboxylic dianhydride and cyclohexane tetracarboxylic dianhydride, a combination of cyclobutylene tetracarboxylic dianhydride and butane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride and cyclohexane A combination of an alkanetetracarboxylic dianhydride and a combination of butane tetracarboxylic dianhydride and methylated cyclobutane tetracarboxylic dianhydride. When a combination of three aliphatic or cycloaliphatic tetracarboxylic dianhydrides is used, it is preferably cyclobutane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. Combination; cyclobutane tetracarboxylic dianhydride, methylated cyclobutane tetraphthalic acid dianhydride and butane tetracarboxylic dianhydride; and cyclohexane tetracarboxylic dianhydride, methylated cyclobutane IV A combination of a carboxylic acid dianhydride and a butane tetracarboxylic dianhydride. Of course, the scope of the present invention is not limited to the above various combinations, and a combination of three or more kinds of butanetetracarboxylic dianhydrides may be employed as long as the properties of the alignment agent are not impaired. Further, among the above various tetracarboxylic dianhydrides, there are some different carboxyl groups or substituent positions, or a plurality of isomers having different steric structures, and these isomers are of course included in the scope of the present invention. 11406pif.doc/008 13 1254735 In the polyamic acid (A), the content of the aromatic tetracarboxylic dianhydride is 15 to 35 mol%, preferably 17 to 30 mol%, based on the total tetracarboxylic dianhydride. When the content of the aromatic tetracarboxylic dianhydride is less than 15 mol%, the absolute charge of the residual charge increases, and the voltage retention ratio thereof decreases; and when the content thereof exceeds 35 mol%, the electrical characteristics of the present invention are improved. The effect is not significant. Further, when one of the aliphatic or cycloaliphatic tetracarboxylic dianhydrides is a cyclobutane tetracarboxylic dianhydride, the content thereof is preferably from 20 to 60 mol% of the total tetracarboxylic dianhydride for synthesizing the poly The diamine of the proline (A) may be a long-chain-free diamine including a completely unbranched substituent in the main chain, and a short substituent such as a methyl group, a phenyl group or a halogen atom in the main chain. And all of the conventional diamines having this structure can be used in the present invention. However, preferred of the diamine is a diamine represented by the above formula (1), which comprises: bis(4-aminophenyl)ether, 4,45-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-2,2, dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 1,2-bis(4-aminophenyl)ethane, 1,2-di(4- Amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl-2,2-propane, 2,2'-diaminobenzophenone, 4,4'-di Aminobenzophenone, 3,4-diaminobenzophenone, and the like. Further, other suitable examples of the above-mentioned long-chain-free diamine are the diaminofluorenone compounds represented by the above formula (2). Although R in the above formula (2) is an aliphatic functional group having 1 to 5 carbon atoms or an aromatic group having 6 or more carbon atoms, considering the convenience of obtaining a methylene group or an ethylene group, Propylene or phenylene is preferred. Further, although the core of the above formula (2) and R3 may be the same or different monovalent aliphatic functional group or aromatic group of 11406pif.doc/008 14 1254735, it is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group or a phenyl group. m is between 1 and 20, but is preferably 1. Specific examples of such a diamino fluorenone include: 1,3-bis(3-aminomethyl)-1,1,3,3-tetra-based oxalate;|兀, 1,3 -1 *(3-Aminoethyl)-1,1,3,3-tetraphenyldioxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetraphenyl Dioxazane, 1,3-bis(3-aminobutyl)-1,1,3,3-tetraphenyldioxane, 1,3-bis(3-aminomethyl)- 1,1,3,3-tetramethyldioxane, 1,3-bis(3-aminoethyl)-1 1,1,3,3-tetramethyldioxane, 1,3_ Bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane, 1,3-bis(3-aminobutyl)-1,1,3,3-tetramethyl Dioxazane, 1,3-bis(3-aminomethyl)-1,1,3,3-tetrakis(2-propyl)dioxane, 1,3-bis(3-amino) Ethyl)-1,1,3,3-tetrakis(2-propyl)dioxane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetrazide (2) -propyl)dioxane and the like. The appropriate content of the diamine-based fluorenone compound is as follows: when the alignment agent uses only poly-proline (A), the content thereof is 0.5 to 10 mol% of the total diamine (100 mol%); and when the alignment agent is used in combination In the case of poly-proline (A) and (B), the diamine-based fluorenone compound is preferably used in poly-proline (B), in which case the diamine fluorenone compound in poly-proline (B) The content is 0.5 to 20 mol% relative to the entire diamine oxime mol%). Examples of the diamine other than the diamines represented by the above formulas (1) and (2) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, bis(4-aminophenyl) maple, and di(4). -aminophenyl) yafeng, bis(4-(3-aminophenoxy)phenyl) maple, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, two (4-(4-Diaminophenoxy)phenyl) maple, benzidine, 2,2-bis(4-aminophenyl)propane, 1,5-diaminonaphthalene' 11406pif.doc/008 15 1254735 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)benzene -U,l,3,3,3-hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-(4-aminophenyl) a well-known diamine such as phenyl)propane, 1,4-bis(4-aminophenoxy)benzene, or di-p-aminophenylaniline, which can be used as polyglycine (A) and polydecylamine. The diamine component of the acid (B). Particularly preferred among the above-mentioned long chain-free diamines include: bis(4-aminophenyl)ether, 4,4'-diaminodiphenylmethane and 1,2-bis(4-aminophenyl). Ethane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane, and the like. The diamine having no long-chain branching may be used in combination of two or more kinds. In this case, it is preferably bis(4-aminophenyl)ether, 4,4'-diaminodiphenylmethane, 1,2. -2 (4-aminophenyl)ethane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane are selected from 2 or 2 The above is applicable. The polyamic acid (A) obtained in the above manner can be used alone as an alignment agent, but in order to easily adjust the initial tilt angle of the liquid crystal, it is preferably used in combination with the polyamic acid (B) described below. On the other hand, the diamine which is a raw material of the polyamic acid (B) must contain one or more of the diamines represented by the above formulas (3) and (4). Examples of the compound of the formula (3) include: U-bis(4-(4-aminophenoxy)phenyl)cyclohexane, 1,1-di(4-(4-aminophenoxy) Phenyl)-4-propylcyclohexane, 1,1-bis(4-(4-aminobenzyl)phenyl)cyclohexane, and 4-n-butyl-1,1-di(4) -(4-Aminobenzyl)phenyl)cyclohexane and the like. Further, examples of the compound of the formula (4) include: 4-n-propylcyclohexyl-3',5'-diaminodiphenylmethane and 4-(4-n-propylcyclohexyl)cyclohexyl-3' , 5'-diaminodiphenylmethane and the like. 11406pif.doc/008 16 1254735 Polyamine (B) may also contain other diamines other than the above diamine, and the kind thereof is not particularly limited, but may be exemplified in the related description of polyglycine (VIII). Various diamines having no long chain branching, aliphatic diamines or cycloaliphatic diamines and the like. Examples of the above aliphatic diamine or cycloaliphatic diamine include: trimethylene diamine, tetramethylene diamine, hexamethylene diamine, 1,12-dial diamine, M-diamine Cyclohexane, 4,4,-diaminodicyclohexylmethane, 4,4,-diamino-3,3 methyldicyclohexylmethyl, anthracene, 4-diaminobutylbenzene, anthracene, Heart diamino-2-dodecyloxybenzene, and 4,4,-diaminooctyldiphenylmethane and the like. In the above various long chain-free diamines and other aromatic diamines, aliphatic diamines and cycloaliphatic diamines, the diamine represented by the formula (3) or (4) is 4, compared with the f soil. 4-diaminodiphenylmethane, L2-bis(4-aminophenyl)ethane or n-di(3-aminopropyl)-u,3,3-tetramethyldioxane; as used When it is a mixture of diamines represented by the formulas (3) and (4), it is preferred to carry out two or two kinds of the compounds. The tetracarboxylic dianhydride used for the protonic acid (B) is also not particularly limited, and may be a conventional tetraruthenic dianhydride, that is, the related description of the poly-proline (A). Aromatic, aliphatic or cycloaliphatic tetracarboxylic dianhydride. These tetracarboxylic acid dianhydrides may be used singly or in combination of various hydrazines, and among them, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, and a combination thereof are particularly preferable. The method for reacting the above tetracarboxylic dianhydride with a diamine to obtain a polyamic acid may be a conventional method, for example, as follows: First, an organic solvent, a tetracarboxylic dianhydride, and a diamine are charged into a reactor. Let it be fused to a solution of -1 (TC~100. (:, 11406pif.doc/008 17 1254735) under an inert gas and stirred for 1 to 60 hours to obtain a viscous polyamine solution. In the process for producing the polyproline of the present invention, in addition to the above tetracarboxylic dianhydride and diamine, a monoamine and/or a monocarboxylic anhydride may be appropriately added to serve as a reaction terminator of polyglycine. These monoamines and/or monocarboxylic acids will be located at the end of the polyamic acid. In addition, in order to improve the adhesion to the substrate or the abrasion resistance, an organic telluride may be added to the liquid crystal alignment agent of the present invention. For example: amine propyl trimethoxy decane, amine propyl triethoxy oxime, ethyl storage dimethoxy sand, N-(2-aminoethyl)-3-aminopropyl methyl two Methoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropenyloxypropane Trimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy a decane coupling agent such as decane; or an fluorenone oil such as dimethyl polyoxane, polydimethyl siloxane or polydiphenyl siloxane. The molecular weight of the poly phthalic acid contained in the present invention is colloidal. The polystyrene-equivalent weight average molecular weight (Mw) obtained by the permeation chromatography (GPC) is 10,000 to 500,000, preferably 20,000 to 200,000, and the ratio thereof to the number average molecular weight (i.e., the polymerization dispersity Mw/Mn) is 1.2. ~3.6. In the poly-proline (polylysine (A) or (B)) obtained in the above manner, 'polyglycine (A) is suitable as a transverse electric field driven type which has good electrical properties itself (horizontal The material of the liquid crystal alignment film of the liquid crystal display element of the rotary type. However, the alignment film having a large initial tilt angle cannot be obtained by using only the polyamic acid (A). Therefore, the twisted nematic 11406pif which must control the initial tilt angle is used. Doc/008 18 1254735 (ΤΝ), optically compensated bending type (OCB) and vertical alignment type For the liquid crystal alignment agent used for the VA) element, it is preferably a polyphthalic acid (A) and a polylysine (B) which is preferably controlled to an initial tilt angle. The polyalginic acid (B) is used. The branched diamine may be the various diamines of the formula (3) or (4) exemplified above. In the specific example of the diamine represented by the formula (3) of the present invention, R4, Y, The various combinations of the rings A, Z, r, s and t are shown in Tables 1 to 14, wherein the ring (A) of the compound represents B as a benzene ring, and the Ch represents a cyclohexyl ring. 1 No. r4 Ring AY zrst 1 Argon - - 0 - 0 2 ch3 - - 0 - 0 3 c2h5 - - - 0 - 0 4 n-C3H7 - - - 0 - 0 5 η - C4H9 _ - - 0 - 0 6 n-C5Hn - - 0 - 0 7 n-C6H13 - - - 0 - 0 8 n-C7H15 - - - 0 - 0 9 n-C8H17 - - - 0 - 0 10 - - - 0 - 0 11 n-C10H21 - - - 0 - 0 12 n-CnH23 - - - 0 - 0 13 n-C12H25 - - - 0 - 0 11406pif.doc/008 19 1254735 Table 2 No. r4 Ring AYZ rst 14 Hydrogen Ch - - 1 0 0 15 ch3 Ch - - 1 0 0 16 c2h5 Ch - - 1 0 0 17 n-C3H7 Ch - - 1 0 0 18 n-C4H9 Ch - - 1 0 0 19 n-C5Hu Ch - - 1 0 0 20 n-C6H13 Ch - - 1 0 0 21 n-C7H15 Ch - - 1 0 0 22 n-C8H17 Ch - - 1 0 0 23 11-C9H19 Ch - - 1 0 0 24 n-C10H21 Ch - 1 0 0 25 n-CnH23 Ch - - 1 0 0 26 n-C12H25 Ch - - 1 0 0 Table 3 No. r4 Ring AYZ rst 27 Gas B - - 1 0 0 28 ch3 B - - 1 0 0 29 c2h5 B - - 1 0 0 30 n-C3Hv B - 1 0 0 31 n-C4H9 B - - 1 0 0 32 n-C5Hn B - - 1 0 0 33 n-C6H13 B - - 1 0 0 34 n-C7H15 B - - 1 0 0 35 n-C8H17 B - - 1 0 0 36 n-C9H19 B face 1 0 0 37 n-C10H21 B - - 1 0 0 38 n-CnH23 B - - 1 0 0 39 n-C12H25 B - - 1 0 0 11406pif.doc/008 20 1254735 4 No. r4 Ring AY zrst 40 Hydrogen Ch ch2 - 1 1 0 41 ch3 Ch ch2 - 1 1 0 42 c2h5 Ch ch2 - 1 1 0 43 n-C3H7 Ch ch2 - 1 1 0 44 n-C4H9 Ch ch2 - 1 1 0 45 n-C5Hu Ch ch2 - 1 1 0 46 n-C6H13 Ch ch2 - 1 1 0 47 n-C7H15 Ch ch2 - 1 1 0 48 n-C8H17 Ch ch2 - 1 1 0 49 Ch ch2 - 1 1 0 50 n- C10H21 Ch ch2 - 1 1 0 51 n-CuH23 Ch ch2 - 1 1 0 52 n-C12H25 Ch ch2 - 1 1 0 Table 5 No. r4 Ring AY zrst 53 Hydrogen B ch2 - 1 1 0 54 ch3 B ch2 - 1 1 0 55 c2h5 B ch2 - 1 1 0 56 n-C3H7 B ch2 - 1 1 0 57 n-C4H9 B ch2 - 1 1 0 58 n-C5Hu B ch2 - 1 1 0 59 n-C6H13 B ch2 - 1 1 0 60 n-C7H15 B ch2 - 1 1 0 61 n-C8H17 B ch2 - 1 1 0 62 n_CgH B ch2 - 1 1 0 63 n-C10H21 B ch2 - 1 1 0 64 n-CnH23 B ch2 - 1 1 0 65 n-C12H25 B ch2 - 1 1 0 11406pif.doc/008 21 1254735 Table 6 Number R4 ring AY zr S t 66 hydrogen - - oxygen 0 - 1 67 ch3 - - oxygen 0 _ 1 68 c2h5 - - oxygen 0 - 1 69 n-C3H7 - - oxygen 0 - 1 70 n-C4H9 - - oxygen 0 - 1 71 n-C5Hn - - Oxygen 0 - 1 72 n-C6H13 - - Oxygen 0 _ 1 73 n-C7H15 - - Oxygen 0 - 1 74 n-C8H17 - - Oxygen 0 - 1 75 - - Oxygen 0 - 1 76 n- C10H21 - - Oxygen 0 - 1 77 n-CuH23 - - Oxygen 0 - 1 78 n-C12H25 - Oxygen 0 - 1 Table 7 No. r4 Ring AY zr S t 79 Gas Ch - Oxygen 1 0 1 80 ch3 Ch - Oxygen 1 0 1 81 C2H5 Ch - oxygen 1 0 1 82 n-C3H7 Ch - oxygen 1 0 1 83 n-C4H9 Ch - oxygen 1 0 1 84 n-C5Hn Ch - oxygen 1 0 1 85 n-C6H13 Ch - oxygen 1 0 1 86 n-C7H15 Ch - Oxygen 1 0 1 87 n-C8H17 Ch - Oxygen 1 0 1 88 Ch - Gas 1 0 1 89 n-C10H21 Ch - Oxygen 1 0 1 90 n-CnH23 Ch - Oxygen 1 0 1 91 n- C12H25 Ch - Oxygen 1 0 1 11406pif.doc/008 22 125 4735 Table 8 No. r4 Ring AY zr S t 92 Hydrogen Ch ch2 Oxygen 1 2 1 93 ch3 Ch ch2 Oxygen 1 2 1 94 c2h5 Ch ch2 Oxygen 1 2 1 95 n-C3H7 Ch ch2 Oxygen 1 2 1 96 n-C4H9 Ch ch2 Oxygen 1 2 1 97 n-C5Hn Ch ch2 oxygen 1 2 1 98 n-C6H13 Ch ch2 oxygen 1 2 1 99 11-C7H15 Ch ch2 oxygen 1 2 1 100 n-C8H17 Ch ch2 oxygen 1 2 1 101 11-C9H19 Ch ch2 Oxygen 1 2 1 102 n-C10H21 Ch ch2C] 氧 Oxygen 1 2 1 103 n-CuH23 Ch 2 Oxygen 1 2 1 104 n-C12H25 Ch ch2 Oxygen 1 2 1 Table 9 No. r4 Ring AYZ r S t 105 Hydrogen B - Oxygen 1 0 1 106 ch3 B - oxygen 1 0 1 107 c2h5 B - oxygen 1 0 1 108 n-C3H7 B - oxygen 1 0 1 109 n-C4H9 B - oxygen 1 0 1 110 n, C5Hu B - oxygen 1 0 1 111 n~C6H13 B - oxygen 1 0 1 112 n-C7H15 B - oxygen 1 0 1 113 n-C8H17 B - oxygen 1 0 1 114 B - oxygen 1 0 1 115 n-C10H21 B - oxygen 1 0 1 116 n-CnH23 B - Oxygen 1 0 1 117 n-C12H25 B - Oxygen 1 0 1 11406pif.doc/008 23 1254735 Table ίο No. r4 Ring AY zrst 118 Hydrogen - - ch2 0 - 1 119 ch3 - - ch2 0 Rain 1 120 c2h5 - - Ch2 0 - 1 121 n-C3H7 - - ch2 0 - 1 122 n-C4H9 - - ch2 0 - 1 123 n-C5Hu - - ch2 0 - 1 124 n-C6H13 - - Ch2 0 - 1 125 n-C7H15 - - ch2 0 - 1 126 n-C8H17 - - ch2 0 - 1 127 11-C9H19 _ - ch2 0 - 1 128 n-C10H21 - - ch2 0 - 1 129 n-CnH23 - - Ch2 0 - 1 130 n-C12H25 - - ch2 0 Sleep 1 Table 11 No. r4 Ring AY z Γ st 131 Gas Ch - ch2 1 0 1 132 ch3 Ch - ch2 1 0 1 133 c2h5 Ch - ch2 1 0 1 134 n- C3H7 Ch - ch2 1 0 1 135 n-C4H9 Ch - ch2 1 0 1 136 n_C5Hu Ch - ch2 1 0 1 137 n-C6H13 Ch - ch2 1 0 1 138 n-C7H15 Ch - ch2 1 0 1 139 n-C8H17 Ch - ch2 1 0 1 140 11-C9H19 Ch - ch2 1 0 1 141 n-C10H21 Ch - ch2 1 0 1 142 n-CuH23 Ch - ch2 1 0 1 143 n-C12H25 Ch - ch2 1 0 1 11406pif.doc/008 24 1254735 Table 12 No. r4 Ring AY zrst 144 Hydrogen Ch ch2 ch2 1 2 1 145 ch3 Ch ch2 ch2 1 2 1 146 c2h5 Ch ch2 ch2 1 2 1 147 η - C3H7 Ch ch2 ch2 1 2 1 148 n - C4H9 Ch ch2 ch2 1 2 1 149 n-C5Hu Ch ch2 ch2 1 2 1 150 n-C6H13 Ch ch2 ch2 1 2 1 151 n-C7H15 Ch ch2 ch2 1 2 1 152 n-C8H17 Ch ch2 ch2 1 2 1 153 Ch ch2 ch2 1 2 1 154 n-C10H21 Ch ch2 ch2 1 2 1 155 n-CnH23 Ch ch2 ch2 1 2 1 156 n~C12H25 Ch ch2 ch2 1 2 1 13 No. r4 Ring AYZ rst 157 Hydrogen B - ch2 1 0 1 158 ch3 B - ch2 1 0 1 159 C2H5 B ch2 1 0 1 160 n-C3H7 B Draw ch2 1 0 1 161 n-C4H9 B - ch2 1 0 1 162 n-C5Hn B - ch2 1 0 1 163 n-C6H13 B - ch2 1 0 1 164 n-C7H15 B — ch2 1 0 1 165 n-C8H17 B - ch2 1 0 1 166 B - ch2 1 0 1 167 n-C10H21 B - ch2 1 0 1 168 nC丨丨H23 B - ch2 1 0 1 169 n-C12H25 B - ch2 1 0 1 11406pif.doc/008 25 1254735 Table 14 No. r4 Ring AY z Γ st 170 Hydrogen B ch2 ch2 1 1 1 171 ch3 B ch2 ch2 1 1 1 172 C2H5 B ch2 ch2 1 1 1 173 n-C3H7 B ch2 ch2 1 1 1 174 n-C4H9 B ch2 ch2 1 1 1 175 n_C5Hu B ch2 ch2 1 1 1 176 n-C6H13 B Ch2 ch2 1 1 1 177 11-C7H15 B ch2 ch2 1 1 1 178 n-C8H17 B ch2 ch2 1 1 1 179 B ch2 ch2 1 1 1 180 n-C10H21 B ch2 ch2 1 1 1 181 n-CnH23 B ch2 ch2 1 1 1 182 n-C12H25 B ch2 ch2 1 1 1 The diamine represented by the formula (3) of the present invention is not limited to the above, and various changes can be made as long as the object of the present invention can be attained. In addition, the monoamines may be used singly or in combination. Among these diamines, the initial tilt angle of r = 0 and R4 is hydrogen or short-chain alkyl is relatively small, and when 1 to 3, even if R4 is hydrogen, the initial tilt angle is relatively large. When the initial tilt angle is small, it is more suitable for the horizontally rotating liquid crystal display element; and when the initial tilt angle is 3 ° to V, it is more suitable for the twisted nematic liquid crystal display element. In addition, for a liquid crystal display element requiring a larger initial tilt angle such as a super twisted nematic (STN), a vertical alignment type (VA), and an optically compensated bend type (OCB), it is preferred to use a longer branch. ingredient. Further, in a specific example of the diamine represented by the formula (4) of the present invention, 11406 pif.doc/008 26 1254735
Xi、X2、Bi、：82及R5的各種組合係列示在下表15〜27中。 在表15〜21所列出的化合物中，B係表示苯環，且Ch表 示環己烷環。h與B2之苯環或環己烷環係以1，4-位置與 其他官能基鍵結，二胺基苯的兩個胺基位在1，3-位置，且 Xi係與二胺基苯的5-位鍵結。另外，當&記爲B-Ch時， 表示Xi與I的苯環鍵結，且X2與&的環己烷環鍵結； 而當B2記爲B-Ch時，表示乂2與B2的苯環鍵結，且心與 B2的環己烷環鍵結。 表15 編號 X, B, X2 Rs 183 單鍵 單鍵 單鍵 單鍵 n-C5H丨丨 184 單鍵 單鍵 單鍵 單鍵 n-C12H25 185 單鍵 單鍵 單鍵 單鍵 n-C5Fu 186 單鍵 單鍵 單鍵 單鍵 n-C12F25 187 0 單鍵 單鍵 單鍵 n-C5Hu 188 0 單鍵 單鍵 單鍵 n-C12H25 189 0 單鍵 單鍵 單鍵 n-C5Fu 190 0 單鍵 單鍵 單鍵 n_C12F25 191 COO 單鍵 單鍵 單鍵 n-C5Hu 192 COO 單鍵 單鍵 單鍵 n-CI2H25 193 COO 單鍵 單鍵 單鍵 n-C5F丨丨 194 COO 單鍵 單鍵 單鍵 n-C 丨 2F25 195 OCO 單鍵 單鍵 單鍵 n-QH!丨 196 OCO 單鍵 單鍵 單鍵 n-C12H25 197 OCO 單鍵 單鍵 單鍵 n-QFi 丨 198 OCO 單鍵 單鍵 單鍵 n_C12F25 199 NH 單鍵 單鍵 單鍵 n-C5Hn 200 NH 單鍵 單鍵 單鍵 n-Cl2H25 201 NH 單鍵 單鍵 單鍵 n-C5F丨丨 202 NH 單鍵 單鍵 單鍵 n-C12F25 203 CONH 單鍵 單鍵 單鍵 n-C5H丨丨 204 CONH 單鍵 單鍵 單鍵 n-C 丨 2H25 205 CONH 單鍵 單鍵 單鍵 n-C5Fn 206 CONH 單鍵 單鍵 單鍵 n-C12F25 11406pif.doc/008 27 1254735 表16 編號 Xl X, R, 207 單鍵 B 單鍵 單鍵 n-C5H" 208 單鍵 B 單鍵 單鍵 n-C12H25 209 單鍵 Ch 單鍵 單鍵 n-C5H 丨 1 210 單鍵 Ch 單鍵 單鍵 n-C12H25 211 單鍵 B-B 單鍵 單鍵 n-C5Hn 212 單鍵 B-B 單鍵 單鍵 n-C,2H25 213 單鍵 B-Ch 單鍵 單鍵 n-C5Hn 214 單鍵 B-Ch 單鍵 單鍵 n~C12H25 215 單鍵 Ch-B 單鍵 單鍵 n-C5Hn 216 單鍵 Ch-B 單鍵 單鍵 n-C12H25 217 單鍵 Ch-Ch 單鍵 單鍵 n-C5Hu 218 單鍵 Ch-Ch 單鍵 單鍵 n-C 丨 2H25 219 單鍵 B-B-B 單鍵 單鍵 n-C5Hn 220 單鍵 B-B-B 單鍵 單鍵 n-C 丨 2H25 221 單鍵 B-B-Ch 單鍵 單鍵 n-C5Hn 222 單鍵 B-B-Ch 單鍵 單鍵 n-C12H25 223 單鍵 B-Ch-Ch 單鍵 單鍵 n-C5Hu 224 單鍵 B-Ch-Ch 單鍵 單鍵 n-C12H25 225 單鍵 Ch-Ch-Ch 單鍵 單鍵 n-C5Hu 226 單鍵 Ch-Ch-Ch 單鍵 單鍵 n-C,2H25 表17 編號 X, B, x, R, 227 0 B 單鍵 單鍵 n-C5Hn 228 〇 B 單鍵 單鍵 n-C12H25 229 〇 Ch 單鍵 單鍵 n-C5H丨丨 230 〇 Ch 單鍵 單鍵 n-C 丨 2H25 231 0 B-B 單鍵 單鍵 n-C5Hu 232 0 B-B 單鍵 單鍵 n-C12H25 233 0 B-Ch 單鍵 單鍵 n-C5H| 丨 234 0 B-Ch 單鍵 單鍵 n-C12H25 235 0 Ch-B 單鍵 單鍵 n-C5Hn 236 0 Ch-B 單鍵 單鍵 n-Cl2H25 237 〇 Ch-Ch 單鍵 單鍵 n-C5Hn 238 0 Ch-Ch 單鍵 單鍵 n-C 丨 2H25 239 〇 B-B-B 單鍵 單鍵 n-C5Hu 240 〇 B-B-B 單鍵 單鍵 n-C 丨 2H25 241 0 B-B-Ch 單鍵 單鍵 n-C5Hu 242 0 B-B-Ch 單鍵 單鍵 n-C丨2H25 243 0 B-Ch-Ch 單鍵 單鍵 n-C5Hn 244 〇 B-Ch-Ch 單鍵 單鍵 n-CI2H25 245 0 Ch-Ch-Ch 單鍵 單鍵 n-C5Hn 246 0 Ch-Ch-Ch 單鍵 單鍵 11406pif.doc/008 28 1254735 表18 表19 編號 X, B, X, R, 267 ch2 B 單鍵 單鍵 n-CA丨 268 ch2 B 單鍵 單鍵 n-C12H25 269 ch2 Ch 單鍵 單鍵 n-C5Hu 270 ch2 Ch 單鍵 單鍵 n-Cl2H25 271 ch2 B-B 單鍵 單鍵 n-C5Hu 272 ch2 B-B 單鍵 單鍵 n-C12H25 273 ch2 B-Ch 單鍵 單鍵 n-C5H丨丨 274 ch2 B-Ch 單鍵 單鍵 n-C12H25 275 ch2 Ch-B 單鍵 單鍵 n-C5Hn 276 ch2 Ch-B 單鍵 單鍵 n-C12H25 277 ch2 Ch-Ch 單鍵 單鍵 n-C5H丨丨 278 ch2 Ch-Ch 單鍵 單鍵 n-CI2H25 279 ch2 B-B-B 單鍵 單鍵 n-QH丨丨 280 ch2 B-B-B 單鍵 單鍵 n-C12H25 281 ch2 B-B-Ch 單鍵 單鍵 n-C5H丨丨 282 ch2 B-B-Ch 單鍵 單鍵 n-C 丨 2H25 283 ch2 B-Ch-Ch 單鍵 單鍵 n-C5Hu 284 ch2 B-Ch-Ch 單鍵 單鍵 n-Cl2H25 285 ch2 Ch-Ch-Ch 單鍵 單鍵 n-C5Hn 286 CH, Ch-Ch-Ch 單鍵 單鍵 n-C12H25 編號 X, B, X, R, 247 COO B 單鍵 單鍵 n-C5H丨丨 248 coo B 單鍵 單鍵 n-C12H25 249 coo Ch 單鍵 單鍵 n-C5H丨丨 250 coo Ch 單鍵 單鍵 n-C12H25 251 coo B-B 單鍵 單鍵 n-C5H丨丨 252 coo B-B 單鍵 單鍵 n-C12H25 253 coo B-Ch 單鍵 單鍵 n-C5Hn 254 coo B-Ch 單鍵 單鍵 n-C12H25 255 coo Ch-B 單鍵 單鍵 n-C5Hn 256 coo Ch-B 單鍵 單鍵 n-C 丨 2H25 257 coo Ch-Ch 單鍵 單鍵 n-C5H丨丨 258 coo Ch-Ch 單鍵 單鍵 n-C12H25 259 coo B - B-B 單鍵 單鍵 n-C5Hu 260 coo B-B-B 單鍵 單鍵 n-C12H25 261 coo B-B-Ch 單鍵 單鍵 n-C5H丨丨 262 coo B-B-Ch 單鍵 單鍵 n-C12H25 263 coo B-Ch-Ch 單鍵 單鍵 n-C5Hn 264 coo B-Ch-Ch 單鍵 單鍵 n-C12H25 265 coo Ch-Ch-Ch 單鍵 單鍵 n-C5Hu 266 coo Ch-Ch-Ch 單鍵 單鍵 n-C12H25 29 11406pif.doc/008 1254735 表20 表21 編號 X| B, X, Rs 307 COO 單鍵 ch2ch2 B n-C5Hu 308 coo 單鍵 ch2ch2 B n-Cl2H25 309 coo 單鍵 ch2ch2 Ch n-C5H丨丨 310 coo 單鍵 ch2ch2 Ch n-C12H25 311 coo 單鍵 ch2ch2 B-B n-C5Hn 312 coo 單鍵 ch2ch2 B-B n-C12H25 313 coo 單鍵 ch2ch2 B-Ch n-QH丨丨 314 coo 單鍵 ch2ch2 B-Ch n-C12H25 315 coo 單鍵 ch2ch2 Ch-B n-C5Hu 316 coo 單鍵 ch2ch2 Ch-B n-C 丨 2H25 317 coo 單鍵 ch2ch2 Ch-Ch r>C5H丨丨 318 coo 單鍵 ch2ch2 Ch-Ch n-C12H25 319 coo 單鍵 ch2ch2 B-B-B n-C5Hn 320 coo 單鍵 ch2ch2 B-B-B n-C12H25 321 coo 單鍵 ch2ch2 B-B-Ch n-C5Hn 322 coo 單鍵 ch2ch2 B-B-Ch n-C12H25 323 coo 單鍵 ch2ch2 B-Ch-Ch n-C5Hn 324 coo 單鍵 ch2ch2 B-Ch-Ch n-C12H25 325 coo 單鍵 ch2ch2 Ch-Ch-Ch n-C5H丨丨 326 coo 單鍵 ch,ch9 Ch-Ch-Ch n-C,2H25 編號 X, B, X, R, 287 0 單鍵 ch2ch2 B n-C5H丨丨 288 0 單鍵 ch2ch2 B n-C,2H25 289 〇 單鍵 ch2ch2 Ch n-C5Hn 290 〇 單鍵 ch2ch2 Ch n-C 丨 2H25 291 〇 單鍵 ch2ch2 B-B n-C5Hu 292 〇 單鍵 ch2ch2 B-B n-C12H25 293 〇 單鍵 ch2ch2 B-Ch n-C5Hn 294 〇 單鍵 ch2ch2 B-Ch n-CI2H25 295 〇 單鍵 ch2ch2 Ch-B n-C5Hu 296 〇 單鍵 ch2ch2 Ch-B n-C12H25 297 〇 單鍵 ch2ch2 Ch-Ch n-C5Hu 298 0 單鍵 ch2ch2 Ch-Ch n-C12H25 299 〇 單鍵 ch2ch2 B - B-B n-C5Hn 300 〇 單鍵 ch2ch2 B-B-B n-Cl2H25 301 0 單鍵 ch2ch2 B-B-Ch n-C5Hu 302 0 單鍵 ch2ch2 B-B-Ch n-C12H25 303 0 單鍵 ch2ch2 B-Ch - Ch n-C5Hu 304 0 單鍵 ch2ch2 B-Ch-Ch n-C12H25 305 0 單鍵 ch2ch2 Ch-Ch-Ch n-C5Hu 306 0 單鍵 ch?ch9 Ch-Ch-Ch n-C12H25 30 11406pif.doc/008 1254735 表22 編號 X, B, X, R, 327 單鍵 B ch2ch2 B n-C5Hu 328 單鍵 B ch2ch2 Ch n-C5Hn 329 單鍵 B ch2ch2 B-B n-C5Hn 330 單鍵 B ch2ch2 B-Ch n-C5Hn 331 單鍵 B ch2ch; Ch-B n-C5Hn 332 單鍵 B ch2ch2 Ch-Ch n-C5Hn 333 單鍵 Ch ch2ch2 B n-C5Hn 334 單鍵 Ch ch2ch2 Ch n-C5Hu 335 單鍵 Ch ch2ch2 B-B n-C5Hu 336 單鍵 Ch ch2ch2 B-Ch n-C5Hn 337 單鍵 Ch ch2ch2 Ch-B n-C5Hn 338 單鍵 Ch ch2ch2 Ch-Ch n-C5Hu 339 單鍵 B-B ch2ch2 B n-C5Hn 340 單鍵 B-B ch2ch2 Ch n-C5Hn 341 單鍵 B-Ch ch2ch2 B n-C5Hn 342 單鍵 B-Ch ch2ch2 Ch n-C5Hn 343 單鍵 Ch-B ch2ch2 B n-C5Hn 344 單鍵 Ch-B ch2ch2 Ch n_C5Hu 345 單鍵 Ch-Ch ch2ch2 B n-C5Hu 346 單鍵 Ch-Ch CH?CH, Ch 表23 編號 X, B, X, R, 347 o B ch2ch2 B n-C5Hu 348 〇 B ch2ch2 Ch n-C5Hu 349 o B ch2ch2 B-B n-C5Hn 350 o B ch2ch2 B-Ch n-C5Hn 351 o B ch2ch2 Ch-B n-C5Hu 352 o B ch2ch2 Ch-Ch n-C5Hn 353 o Ch ch2ch2 B n-C5Hu 354 o Ch ch2ch2 Ch n-C5Hn 355 o Ch ch2ch2 B-B n-C5Hn 356 o Ch ch2ch2 B-Ch n-C5Hn 357 〇 Ch ch2ch2 Ch-B n-C5Hn 358 〇 Ch ch2ch2 Ch-Ch n-C5Hu 359 〇 B-B ch2ch2 B n-C5H 丨 i 360 o B-B ch2ch2 Ch n-C5Hu 361 o B-Ch ch2ch2 B n-C5Hn 362 〇 B-Ch ch2ch2 Ch n-C5Hn 363 〇 Ch-B ch2ch2 B n-C5Hn 364 〇 Ch-B ch2ch2 Ch i>C5H丨i 365 o Ch-Ch ch2ch2 B n_C5Hu 366 〇 Ch-Ch CH?CH, Ch n-CsHn 31 11406pif.doc/008 1254735 表24 表25 編號 X, B, X, Rs 387 ch2 B ch2ch2 B n-C5Hn 388 ch2 B ch2ch2 Ch n-C5Hn 389 ch2 B ch2ch2 B-B n-C5Hu 390 ch2 B ch2ch2 B-Ch n-C5Hu 391 ch2 B ch2ch2 Ch-B n-C5Hu 392 ch2 B ch2ch2 Ch-Ch n-C5Hu 393 ch2 Ch ch2ch2 B n-C5Hn 394 ch2 Ch ch2ch2 Ch n-C5Hu 395 ch2 Ch ch2ch2 B-B n-C5Hn 396 ch2 Ch ch2ch2 B-Ch n-C5Hn 397 ch2 Ch ch2ch2 Ch-B n-C5Hn 398 ch2 Ch ch2ch2 Ch-Ch n-C5Hn 399 ch2 B-B ch2ch2 B n-QH丨丨 400 ch2 B-B ch2ch2 Ch n-C5Hu 401 ch2 B-Ch ch2ch2 B n-QH丨丨 402 ch2 B-Ch ch2ch2 Ch n - C5Hn 403 ch2 Ch-B ch2ch9 B n-C5Hn 404 ch2 Ch-B ch2ch2 Ch n-C5Hn 405 ch2 Ch-Ch ch2ch2 B n-C5Hn 406 CH? Ch-Ch ch7ch7 Ch n-C,Hn 編號 X, X, R, 367 COO B ch2ch2 B n-C5Hn 368 coo B ch2ch2 Ch n-C5Hu 369 coo B ch2ch2 B-B n-C5Hu 370 coo B ch2ch2 B-Ch n-C5Hn 371 coo B ch2ch; Ch-B n-C5Hn 372 coo B ch2ch2 Ch-Ch n-C5Hu 373 coo Ch ch2ch2 B n-C5HM 374 coo Ch ch2ch2 Ch n-C5Hn 375 coo Ch ch2ch2 B-B n-C5Hn 376 coo Ch ch2ch2 B-Ch n-C5Hn 377 coo Ch ch2ch2 Ch-B n-C5Hu 378 coo Ch ch2ch2 Ch-Ch n-C5Hn 379 coo B-B ch2ch2 B n-C5Hu 380 coo B-B ch2ch2 Ch n-C5H丨丨 381 coo B-Ch ch2ch2 B n-C5Hu 382 coo B-Ch ch2ch2 Ch n-C5H 丨 i 383 coo Ch-B ch2ch2 B n-C5Hu 384 coo Ch-B ch2ch2 Ch n-C5Hn 385 coo Ch-Ch ch2ch2 B n-C5Hu 386 coo Ch-Ch CH,CH, Ch n_C5H" 32 11406pif.doc/008 1254735 表26 表27 編號 Χι B, X, R, 427 〇 單鍵 ch2ch2 B-B 氫 428 〇 單鍵 ch2ch2 B-B 氫 429 0 單鍵 ch2ch2 B-B F 430 0 單鍵 ch2ch2 B-B F 431 〇 單鍵 ch2ch2 B-B CN 432 〇 單鍵 ch2ch2 B-B CN 433 〇 單鍵 ch2ch2 B-B OH 434 〇 單鍵 ch2ch2 B-B OH 435 0 單鍵 ch2ch2 B-B 〇-c2h5 436 0 單鍵 ch2ch2 B-B o-c2h5 437 coo 單鍵 ch2ch2 B-B 氫 438 coo 單鍵 ch2ch2 B-B 氫 439 coo 單鍵 ch2ch2 B-B F 440 coo 單鍵 ch2ch2 B-B F 441 coo 單鍵 ch2ch2 B-B CN 442 coo 單鍵 ch2ch2 B-B CN 443 coo 單鍵 ch2ch2 B-B OH 444 coo 單鍵 ch2ch2 B-B OH 445 coo 單鍵 ch2ch2 B-B 〇-c2h5 446 coo 單鍵 ch?ch7 B-B 0-C?Hs 編號 Χι B, X, Rs 407 0 單鍵 單鍵 B-B 氫 408 0 單鍵 單鍵 B-B 氫 409 〇 單鍵 單鍵 B-B F 410 ο 單鍵 單鍵 B-B F 411 0 單鍵 單鍵 B-B CN 412 〇 單鍵 單鍵 B-B CN 413 ο 單鍵 單鍵 B-B OH 414 〇 單鍵 單鍵 B-B OH 415 ο 單鍵 單鍵 B-B 〇-c2h5 416 〇 單鍵 單鍵 B-B 0-c2h5 417 coo 單鍵 單鍵 B-B 氫 418 coo 單鍵 單鍵 B-B 氫 419 coo 單鍵 單鍵 B-B F 420 coo 單鍵 單鍵 B-B F 421 coo 單鍵 單鍵 B-B CN 422 coo 單鍵 單鍵 B-B CN 423 coo 單鍵 單鍵 B-B OH 424 coo 單鍵 單鍵 B-B OH 425 coo 單鍵 單鍵 B-B 〇-c2h5 426 coo 單鍵 單鍵 B-B 〇-C?H, 33 11406pif.doc/008 1254735 本發明之式（3)所代表的二胺並不僅限於上述各者，只 要能達成本發明之目的，其可以有各式各樣的變化。另外’ 該些二胺皆可單獨使用或數種倂用。 上述式（3)與/或式（4)所示之具支鏈的二胺可以單獨進 行反應，也可以與其他二胺組合使用，其中各二胺的比例 可任意設定調整，以得到預定的初始傾斜角。 在本發明之由電學特性良好的聚醯胺酸（A)與可適當 調整初始傾斜角的聚醯胺酸（B)組合而成的液晶配向劑 中，（A)與(B)的重量比爲99/1〜80/20。當（B)的比例低於1% 時，即無增加初始傾斜的效果；而當（B)的比例高於20% 時’初始傾斜角即不再繼續增加。 另外，當使用本發明之聚醯胺酸作爲液晶配向劑時， 在不損及本發明之效果的前提下，亦可在聚醯胺之外倂用 其他的高分子化合物。特別是在倂用聚醯胺、可溶性聚亞 醯胺與聚醯胺亞胺時，配向膜的電學特性可進一步地提 升。 另外，在不損及本發明效果的前提下，本發明之聚醯 胺酸可以可溶性聚亞醯胺或聚醯胺酸酯等型態來使用。如 前所述，在將可用於本發明之液晶配向劑塗布於基板上之 後，會進行加熱處理以使其亞醯胺化。因此，可對作爲本 發明之液晶配向劑成分的聚醯胺酸的全部或一部分，以無 水乙酸/吼啶等觸媒催化而形成可溶性聚亞醯胺，或是預 先令其與醇類反應而得聚醯胺酸酯，之後再於液晶顯示元 件製程中進行加熱處理，即可形成以聚亞醯胺爲主成分之 11406pif.doc/008 34 1254735 液晶配向膜，其當可達到本發明之效果。 本發明第3項特徵之塗漆（varnish)係將上述聚醯胺 酸，或是可溶性聚亞醯胺或聚醯胺酸酯等聚醯胺酸衍生物 (以下簡稱高分子化合物）所構成的液晶配向劑溶於有機溶 劑中而得者。爲將液晶配向膜形成在已配置透明電極的基 板上，常見的作法即是將該高分子化合物溶於有機溶劑中 形成塗漆，再加以使用，此時塗漆中聚醯胺酸的濃度爲 0.1〜40 wt%，且較佳爲0·5〜10 wt%。在將液晶配向劑塗布 於基板上之前，爲調整膜厚，可預先以有機溶劑稀釋塗漆； 而爲了能以旋塗法或印刷法製得品質良好的（即平坦且厚 度均勻）薄膜，稀釋後的濃度通常須在10 wt%以下。對其 他的塗布方法而言，如浸泡塗布法，亦可使用低於10 wt% 的低濃度。 另一方面，當聚醯胺酸的濃度不到0.1 wt%時，即容 易產生液晶配向膜厚度過薄的問題。因此，在使用一般的 旋塗法或印刷法進行塗布時，塗漆中高分子化合物的濃度 係在〇·1 wt%以上，且較佳爲0.5〜10 wt%。但是，對使用 塗漆的塗布法而言，更低或更高的濃度也是可行的。 與作爲液晶配向劑之高分子化合物共用的溶劑並無特 別限制，只要其可以溶解該高分子化合物即可。這些溶劑 包括該高分子化合物之製程或使用時所常用者，其範圍很 廣，而可視使用目的作適當選擇。 這些溶劑例如是非質子極性有機溶劑，其可作爲聚醯 胺酸、可溶性聚亞胺、聚醯胺酸酯及可能倂用之其他高分 11406pif.doc/008 35 1254735 子的良好溶劑(good solvent)者。實例包括：N-甲基-2-11比略 醒、一甲基雑茂酮（dimethyl-imidazolidinone)、N-甲基己 內醯胺、N-甲基丙醯胺、N，N-二甲基乙醯胺、二甲亞楓 (DMSO)、N，N-二甲基甲醯胺、N，N-二乙基甲醯胺、二乙 基乙醯胺，或是广丁內酯等等。另外，爲改善溶液的塗布 性，亦可倂用其他的溶劑，如乳酸烷酯、3-甲基-3-甲氧基 丁醇、四氫化萘、異佛爾酮l(Isophorone)、乙二醇單丁基醚 等乙二醇單烷基醚、二乙二醇單乙基醚等二乙二醇單烷基 醚、乙二醇單烷基或單苯基酮、三乙二醇單烷基醚、丙二 醇單丁基醚等丙二醇單烷基醚、丙二酸二乙酯等丙二酸二 烷酯、二丙二醇單甲基醚等二丙二醇單烷基醚，或是其乙 酸酯等酯類化合物等等。 另外，在倂用2種或2種以上的有機溶劑時，各種溶 劑的混合比例係依照溶液所需之表面張力、黏度、印刷性、 塗布性、潤濕性，以及形成薄膜之均勻性等液晶配向膜所 需的其他特性來作調整設定。其中，如以溶解性、印刷性、 塗布性，以及薄膜均勻性爲考量，則較佳由N-甲基-2-¾ 咯酮、二甲基雜茂酮、广丁內酯及乙二醇單丁基醚中選出 2種或2種以上來使用。 本發明之液晶配向劑亦可視需要加入各種添加劑。舉 例來說，爲提高塗布性，可添加界面活性劑；爲提高防靜 電學特性，可加入防靜電劑；而爲提高與基板的密著性’ 可添加矽烷類耦合劑或鈦化合物類的耦合劑。另外，對光 學補償彎曲型（OCB)或垂直配向型（VA)等需具備核心區域 11406pif.doc/008 36 1254735 (domain)的液晶顯示元件而言，可適量加入由無機或有機 微粒子所構成的核形成材料。 雖然上述所得之液晶配向劑較佳是用來形成主動矩陣 式的薄膜電晶體用液晶配向膜，如扭轉向列型（TN)、水平 轉動型（IPS)、垂直配向型（VA)及光學補償彎曲型（〇CB)元 件等，但因其可造成所需之初始傾斜角，所以亦可用來形 成被動矩陣式之扭轉向列型液晶顯示元件、超扭轉向列型 液晶顯示元件及強介電型或反強介電型液晶顯示元件的液 晶配向膜。再者，由於此種液晶顯示元件的電學特性良好， 所以亦可作爲保護層或絕緣層。 此處液晶顯示元件可以習知的方法製得，首先使本發 明之液晶配向劑在基板上形成液晶配向膜，並令其與另一 基板上相同或不同之液晶配向膜相對配置，然後在其中注 入液晶，而成爲具液晶夾層的基板。液晶配向膜之製程如 下：首先將液晶配向劑塗布在基板上，再進行後續之乾燥 步驟，然後進行加熱處理以發脫水-閉環反應，即完成了 液晶顯示元件。此時，亦可在配置透明電極的一或二基板 上適當形成濾光片、上塗層（over-coating)、層間緣緣層或 突起物。 塗布方法中的旋塗法、印刷法、浸泡法或滴落法係爲 一般所知之方法，其亦可用於本發明之中。另外，進行乾 燥步驟及脫水-閉環反應所需之加熱處理時，一般係以熱 爐或紅外線爐來加熱，或是使用加熱板來加熱，其亦可適 用於本發明中。 11406pif.doc/008 37 1254735 乾燥步驟之溫度可使溶劑蒸發，但以較低者爲佳，其 範例如爲50〜100。(：；而加熱處理較佳在150〜30(TC之溫 度範圍內進行。 本發明之液晶顯示元件較佳使用以下的液晶組成物。 舉例來說，用在超扭轉向列型液晶顯示元件之液晶組成物 可以是日本專利申請案早期公開公報第平8-157828號、 第平8-231960號、第平9-241644號及第平9-302346號所 列舉者。另外，用在薄膜電晶體液晶顯示元件（TN、IPS、 VA及OCB型元件）之液晶組成物可以是日本專利第 3086228號、第2635435號、日本專利第平5_501735號、 曰本專利申請案早期公開公報第平8-199168號、第平9-235552號、第平9-241643號、第平9-255956號、第平 10-204016 號、第平 10-204436 號、第平 ι〇·231482 號、 第 2000-087040 號、第 2001-48822 號，以及第 2001-192657 號所列舉者。 由本發明之液晶配向劑所製得的液晶配向膜與上述公 報所揭露之薄膜電晶體液晶顯示元件用液晶組成物所組成 的液晶顯示元件，特別適用於需要高電壓保持比的產品 中，同時其改善殘影問題的效果也很高。詳言之，本發明 之液晶配向劑特別適合與前述各專利案所揭露之具有高電 壓保持比的含氟液晶組合物合用，此含氟液晶組合物係尾 端有-OCF3官能基的化合物，或是含有1〜3個（或更多）氣 原子的化合物。另外，前述液晶組成物中亦可含有1種(或 以上）的光學活性化合物，並沒有任何問題。 11406pif.doc/008 38 1254735 實例= 以下舉出數個實例以說明本發明，其並非用以限制本 發明之範圍。在具體說明該些實施例之前，各合成範例、 實例及比較例所用之材料與其縮寫，以及評量之方法先行 詳述如下。 1.材料與其縮寫 (1) 各種四羧酸二酐 苯均四酸二酐（PMD A) 1，2,3,4-環丁烷四羧酸二酐(CBDA) 1，2,4,5-環己烷四羧酸二酐(CHDA) 1，2,3,4-丁烷四羧酸二酐^0八） 甲基化環丁烷四羧酸二酐（甲基化程度達1.5) (CMDA) (2) 各種二胺 4,4’-二胺基二苯甲烷(DPM) 1，2-二（4-胺基苯基）乙烷(DPEt) 4,4’-二胺基二苯醚（DPE) 1,1-二{4-[(4-胺基苯基）甲基]苯基}-4-丁基環己烷(4Ch) 5-{4-[4-(4-戊基環己基）環己基]苯基}甲基-1，3-二胺基苯 (5Ch) 1，3-二（3-胺基丙基）-l，l，3,3-四甲基二矽氧烷(APDS) (3) 各種溶劑 N-甲基-2-吼咯酮(NMP) 乙二醇單丁基醚（butyl cellosolve，BC) 丁內酯（GBL) 11406pif.doc/008 39 1254735 (4)各種液晶組成物 此處所用之液晶組成物的組成如下所示，此組成物的向 列-等向相變（NI)溫度爲100.(TC，且複折射率爲0.093 ◦ 。2取—~Ο~ 17wt.% C3H7~^Z)O~F 17wt.°yC C5Hn^^-〇H^F 16wt·% C2H5 -^^F 10wt.% C3H7一一 5wt.% C5H11 ~。2心~^〇~ 10wt.% C2H5—~F 6wt·% c3H7-〇^〇^^r 6wt·% CsHn-〇-H〇K^-F 13wt.% 11406pif.doc/008 40 1254735 2.評量方法 2-1:垂直電場型液晶顯示元件的評量方法 (1) 殘留電荷之測量 將頻率30Hz、振幅2V的方波與3V的直流電壓重疊 施加在元件上達1小時，然後立刻測量閃爍消除電壓 (flicker elimination voltage)，並在 30 分之後再測定一次 閃爍消除電壓，其値的絕對値即爲殘留電荷。當殘留電荷 愈小時，殘影即愈少，所以殘留電荷愈小愈好。 (2) 電壓保持比之測量 此測量係依照水嶋等人於第14屆液晶硏討會預稿集 Ρ·78所發表的方法來進行，其測定條件如下：閘電壓寬度 (gate width)爲69//S、頻率60Hz、波峰高度±4.5V，且測定 溫度爲60°C。電壓保持比愈高則電學特性愈好。 (3) 初始傾斜角的測量方法 此處液晶的初始傾斜角係以晶體旋轉法（crystal rotation)加以測定。 (4) 配向能力的評量 此評量係以偏光顯微鏡觀察液晶，並由觀察者判斷有 無配向不良的現象。配向性佳者即標爲Ο，不佳者則爲X。 2-2.橫向電場型液晶顯示元件的評量方法 (1) DC殘影的測定 將各實例與比較例所製作之元件置於設定在60°C的 熱爐中，並在其上施加l〇〇mV、1kHz之正弦波交流電壓， 且重疊施加由0V升到10V (以IV爲單位在3秒內階梯式 11406pif.doc/008 41 1254735Various combinations of Xi, X2, Bi, 82, and R5 are shown in Tables 15 to 27 below. Among the compounds listed in Tables 15 to 21, B represents a benzene ring, and Ch represents a cyclohexane ring. The benzene ring or cyclohexane ring system of h and B2 is bonded to other functional groups at the 1,4-position, and the two amine positions of the diaminobenzene are at the 1,3-position, and the Xi system and the diaminobenzene are 5-bit bond. In addition, when & is denoted as B-Ch, it represents a benzene ring bond of Xi and I, and X2 is bonded to a cyclohexane ring of & and when B2 is denoted as B-Ch, it represents 乂2 and B2. The benzene ring is bonded and the core is bonded to the cyclohexane ring of B2. Table 15 No. X, B, X2 Rs 183 One button One button One button One button n-C5H丨丨184 One button One button One button One button n-C12H25 185 One button One button One button One button n-C5Fu 186 One button One button single button single button n-C12F25 187 0 One button single button single button n-C5Hu 188 0 One button single button single button n-C12H25 189 0 One button single button single button n-C5Fu 190 0 One button single button single button n_C12F25 191 COO One button One button One button n-C5Hu 192 COO One button One button One button n-CI2H25 193 COO One button One button One button n-C5F丨丨194 COO One button One button One button nC 丨2F25 195 OCO Single Key single button single button n-QH!丨196 OCO One button single button single button n-C12H25 197 OCO One button single button single button n-QFi 丨198 OCO One button single button single button n_C12F25 199 NH One button single button single button n-C5Hn 200 NH One button One button Single button n-Cl2H25 201 NH One button One button One button n-C5F丨丨202 NH One button One button One button n-C12F25 203 CONH One button One button One button n-C5H丨丨204 CONH One-touch One-touch single button nC 丨2H25 205 CONH One-touch single-button single button n-C5Fn 206 CONH One-touch single-button single button n-C12F25 11406pif.doc/008 27 12547 35 Table 16 No. Xl X, R, 207 One-touch B One-touch single button n-C5H" 208 One-touch B One-touch single button n-C12H25 209 One-touch Ch One-touch single button n-C5H 丨1 210 One-button Ch single Key single button n-C12H25 211 One button BB One button single button n-C5Hn 212 One button BB One button single button nC, 2H25 213 One button B-Ch One button single button n-C5Hn 214 One button B-Ch One button single Key n~C12H25 215 One-button Ch-B One-touch single button n-C5Hn 216 One-button Ch-B One-touch single button n-C12H25 217 One-button Ch-Ch One-touch single button n-C5Hu 218 One-button Ch-Ch single Key single key nC 丨2H25 219 One button BBB One button single button n-C5Hn 220 One button BBB One button single button nC 丨2H25 221 One button BB-Ch One button single button n-C5Hn 222 One button BB-Ch One button single Key n-C12H25 223 Single button B-Ch-Ch One-touch single button n-C5Hu 224 One-button B-Ch-Ch One-touch single button n-C12H25 225 One-button Ch-Ch-Ch One-touch single button n-C5Hu 226 One-button Ch-Ch-Ch One-touch single button nC, 2H25 Table 17 No. X, B, x, R, 227 0 B One-touch single button n-C5Hn 228 〇B One-touch single button n-C12H25 229 〇Ch single button Single button n-C5H丨丨230 〇Ch One-touch single button nC 丨2H2 5 231 0 BB One-touch single button n-C5Hu 232 0 BB One-touch single button n-C12H25 233 0 B-Ch One-touch single button n-C5H| 丨234 0 B-Ch One-touch single button n-C12H25 235 0 Ch -B One-touch single button n-C5Hn 236 0 Ch-B One-touch single button n-Cl2H25 237 〇Ch-Ch One-touch single button n-C5Hn 238 0 Ch-Ch One-touch single button nC 丨2H25 239 〇BBB single button Single button n-C5Hu 240 〇BBB Single button Single button nC 丨2H25 241 0 BB-Ch One-touch single button n-C5Hu 242 0 BB-Ch One-touch single button nC丨2H25 243 0 B-Ch-Ch One-touch single button n-C5Hn 244 〇B-Ch-Ch single bond single bond n-CI2H25 245 0 Ch-Ch-Ch single button single button n-C5Hn 246 0 Ch-Ch-Ch single button single button 11406pif.doc/008 28 1254735 18 Table 19 No. X, B, X, R, 267 ch2 B One-touch single button n-CA丨268 ch2 B One-touch single button n-C12H25 269 ch2 Ch One-touch single button n-C5Hu 270 ch2 Ch One-touch single button n-Cl2H25 271 ch2 BB single button single button n-C5Hu 272 ch2 BB single button single button n-C12H25 273 ch2 B-Ch single button single button n-C5H丨丨274 ch2 B-Ch single button single button n-C12H25 275 Ch2 Ch-B One-touch single button n-C5Hn 276 ch2 Ch-B One-touch single button n-C12H25 277 ch 2 Ch-Ch One-touch single button n-C5H丨丨278 ch2 Ch-Ch One-touch single button n-CI2H25 279 ch2 BBB One-touch single button n-QH丨丨280 ch2 BBB One-touch single button n-C12H25 281 ch2 BB -Ch single button single button n-C5H丨丨282 ch2 BB-Ch single button single button nC 丨2H25 283 ch2 B-Ch-Ch single button single button n-C5Hu 284 ch2 B-Ch-Ch single button single button n- Cl2H25 285 ch2 Ch-Ch-Ch One-touch single button n-C5Hn 286 CH, Ch-Ch-Ch One-touch single button n-C12H25 No. X, B, X, R, 247 COO B One-touch single button n-C5H丨丨248 coo B One-touch single button n-C12H25 249 coo Ch One-touch single button n-C5H丨丨250 coo Ch One-touch single button n-C12H25 251 coo BB One-touch single button n-C5H丨丨252 coo BB single button Single button n-C12H25 253 coo B-Ch One button single button n-C5Hn 254 coo B-Ch One button single button n-C12H25 255 coo Ch-B One button single button n-C5Hn 256 coo Ch-B One button single button nC 丨2H25 257 coo Ch-Ch One-touch single button n-C5H丨丨258 coo Ch-Ch One-touch single button n-C12H25 259 coo B - BB One-touch single button n-C5Hu 260 coo BBB One-touch single button n- C12H25 261 coo BB-Ch One-touch single button n-C5H丨丨262 coo BB-Ch single button Single button n-C12H25 263 coo B-Ch-Ch One-touch single button n-C5Hn 264 coo B-Ch-Ch One-touch single button n-C12H25 265 coo Ch-Ch-Ch One-touch single button n-C5Hu 266 coo Ch -Ch-Ch Single button single button n-C12H25 29 11406pif.doc/008 1254735 Table 20 Table 21 No. X| B, X, Rs 307 COO Single bond ch2ch2 B n-C5Hu 308 coo Single bond ch2ch2 B n-Cl2H25 309 coo Single bond ch2ch2 Ch n-C5H丨丨310 coo Single bond ch2ch2 Ch n-C12H25 311 coo Single bond ch2ch2 BB n-C5Hn 312 coo Single bond ch2ch2 BB n-C12H25 313 coo Single bond ch2ch2 B-Ch n-QH丨丨314 Coo single bond ch2ch2 B-Ch n-C12H25 315 coo single bond ch2ch2 Ch-B n-C5Hu 316 coo single bond ch2ch2 Ch-B nC 丨2H25 317 coo single bond ch2ch2 Ch-Ch r>C5H丨丨318 coo single bond ch2ch2 Ch-Ch n-C12H25 319 coo single bond ch2ch2 BBB n-C5Hn 320 coo single bond ch2ch2 BBB n-C12H25 321 coo single bond ch2ch2 BB-Ch n-C5Hn 322 coo single bond ch2ch2 BB-Ch n-C12H25 323 coo single bond Ch2ch2 B-Ch-Ch n-C5Hn 324 coo single bond ch2ch2 B-Ch-Ch n-C12H25 325 coo single bond ch2ch2 Ch-Ch-Ch n-C5H丨丨326 coo single bond ch,ch9 Ch-Ch-Ch nC , 2H25 number X, B, X, R, 287 0 Single key ch2ch2 B n-C5H丨丨288 0 Single key ch2ch2 B nC, 2H25 289 Single key ch2ch2 Ch n-C5Hn 290 Single key ch2ch2 Ch nC 丨2H25 291 Single key ch2ch2 BB n-C5Hu 292 〇 single bond ch2ch2 BB n-C12H25 293 〇 single bond ch2ch2 B-Ch n-C5Hn 294 〇 single bond ch2ch2 B-Ch n-CI2H25 295 〇 single bond ch2ch2 Ch-B n-C5Hu 296 〇 single bond ch2ch2 Ch-B n-C12H25 297 〇 single bond ch2ch2 Ch-Ch n-C5Hu 298 0 single bond ch2ch2 Ch-Ch n-C12H25 299 〇 single bond ch2ch2 B - BB n-C5Hn 300 〇 single bond ch2ch2 BBB n-Cl2H25 301 0 Single bond ch2ch2 BB-Ch n-C5Hu 302 0 Single bond ch2ch2 BB-Ch n-C12H25 303 0 Single bond ch2ch2 B-Ch - Ch n-C5Hu 304 0 Single bond ch2ch2 B-Ch-Ch n-C12H25 305 0 Single button Ch2ch2 Ch-Ch-Ch n-C5Hu 306 0 Single key ch?ch9 Ch-Ch-Ch n-C12H25 30 11406pif.doc/008 1254735 Table 22 No. X, B, X, R, 327 Single key B ch2ch2 B n- C5Hu 328 Single bond B ch2ch2 Ch n-C5Hn 329 Single bond B ch2ch2 BB n-C5Hn 330 Single bond B ch2ch2 B-Ch n-C5Hn 331 Single bond B ch2ch; Ch-B n-C5Hn 332 Single bond B ch2ch2 Ch-Ch n-C5Hn 333 single key Ch ch2 Ch2 B n-C5Hn 334 single bond Ch ch2ch2 Ch n-C5Hu 335 single bond Ch ch2ch2 BB n-C5Hu 336 single bond Ch ch2ch2 B-Ch n-C5Hn 337 single bond Ch ch2ch2 Ch-B n-C5Hn 338 single bond Ch ch2ch2 Ch-Ch n-C5Hu 339 Single Key BB ch2ch2 B n-C5Hn 340 Single Key BB ch2ch2 Ch n-C5Hn 341 Single Key B-Ch ch2ch2 B n-C5Hn 342 Single Key B-Ch ch2ch2 Ch n-C5Hn 343 Single Key Ch -B ch2ch2 B n-C5Hn 344 Single bond Ch-B ch2ch2 Ch n_C5Hu 345 Single bond Ch-Ch ch2ch2 B n-C5Hu 346 Single key Ch-Ch CH?CH, Ch Table 23 No. X, B, X, R, 347 o B ch2ch2 B n-C5Hu 348 〇B ch2ch2 Ch n-C5Hu 349 o B ch2ch2 BB n-C5Hn 350 o B ch2ch2 B-Ch n-C5Hn 351 o B ch2ch2 Ch-B n-C5Hu 352 o B ch2ch2 Ch-Ch n-C5Hn 353 o Ch ch2ch2 B n-C5Hu 354 o Ch ch2ch2 Ch n-C5Hn 355 o Ch ch2ch2 BB n-C5Hn 356 o Ch ch2ch2 B-Ch n-C5Hn 357 〇Ch ch2ch2 Ch-B n-C5Hn 358 〇Ch Ch2ch2 Ch-Ch n-C5Hu 359 〇BB ch2ch2 B n-C5H 丨i 360 o BB ch2ch2 Ch n-C5Hu 361 o B-Ch ch2ch2 B n-C5Hn 362 〇B-Ch ch2ch2 Ch n-C5Hn 363 〇Ch-B Ch2ch2 B n-C5Hn 364 〇Ch-B ch2ch2 Ch i>C5H丨i 365 o Ch-Ch ch2ch2 B n_C5Hu 366 〇Ch-Ch CH?CH, Ch n-CsHn 31 11406pif.doc/008 1254735 Table 24 Table 25 No. X, B, X, Rs 387 ch2 B ch2ch2 B n-C5Hn 388 ch2 B ch2ch2 Ch n-C5Hn 389 ch2 B ch2ch2 BB n-C5Hu 390 ch2 B ch2ch2 B-Ch n-C5Hu 391 ch2 B ch2ch2 Ch-B n-C5Hu 392 ch2 B ch2ch2 Ch-Ch n-C5Hu 393 ch2 Ch ch2ch2 B n-C5Hn 394 ch2 Ch ch2ch2 Ch n-C5Hu 395 ch2 Ch ch2ch2 BB n-C5Hn 396 ch2 Ch ch2ch2 B-Ch n-C5Hn 397 ch2 Ch ch2ch2 Ch-B n-C5Hn 398 ch2 Ch ch2ch2 Ch-Ch n-C5Hn 399 ch2 BB ch2ch2 B n-QH丨丨400 ch2 BB ch2ch2 Ch n-C5Hu 401 ch2 B-Ch ch2ch2 B n-QH丨丨402 ch2 B-Ch ch2ch2 Ch n - C5Hn 403 ch2 Ch-B ch2ch9 B n-C5Hn 404 ch2 Ch- B ch2ch2 Ch n-C5Hn 405 ch2 Ch-Ch ch2ch2 B n-C5Hn 406 CH? Ch-Ch ch7ch7 Ch nC, Hn No. X, X, R, 367 COO B ch2ch2 B n-C5Hn 368 coo B ch2ch2 Ch n-C5Hu 369 coo B ch2ch2 BB n-C5Hu 370 coo B ch2ch2 B-Ch n-C5Hn 371 coo B ch2ch; Ch-B n-C5Hn 372 coo B ch2ch2 Ch-Ch n-C5Hu 373 coo Ch ch2ch2 B n-C5HM 374 coo Ch Ch2ch2 Ch n-C5Hn 375 coo Ch ch2ch2 BB n- C5Hn 376 coo Ch ch2ch2 B-Ch n-C5Hn 377 coo Ch ch2ch2 Ch-B n-C5Hu 378 coo Ch ch2ch2 Ch-Ch n-C5Hn 379 coo BB ch2ch2 B n-C5Hu 380 coo BB ch2ch2 Ch n-C5H丨丨381 Coo B-Ch ch2ch2 B n-C5Hu 382 coo B-Ch ch2ch2 Ch n-C5H 丨i 383 coo Ch-B ch2ch2 B n-C5Hu 384 coo Ch-B ch2ch2 Ch n-C5Hn 385 coo Ch-Ch ch2ch2 B n- C5Hu 386 coo Ch-Ch CH,CH, Ch n_C5H" 32 11406pif.doc/008 1254735 Table 26 Table 27 No. Χι B, X, R, 427 〇 Single bond ch2ch2 BB Hydrogen 428 〇 Single bond ch2ch2 BB Hydrogen 429 0 Single bond Ch2ch2 BB F 430 0 single key ch2ch2 BB F 431 single key ch2ch2 BB CN 432 single key ch2ch2 BB CN 433 single key ch2ch2 BB OH 434 single key ch2ch2 BB OH 435 0 single key ch2ch2 BB 〇-c2h5 436 0 single Key ch2ch2 BB o-c2h5 437 coo single bond ch2ch2 BB hydrogen 438 coo single bond ch2ch2 BB hydrogen 439 coo single bond ch2ch2 BB F 440 coo single bond ch2ch2 BB F 441 coo single bond ch2ch2 BB CN 442 coo single bond ch2ch2 BB CN 443 coo Single bond ch2ch2 BB OH 444 coo single bond ch2ch2 BB OH 445 coo single bond ch2ch2 BB 〇-c2h5 4 46 coo One-touch ch?ch7 BB 0-C?Hs No. Χι B, X, Rs 407 0 One-touch single button BB Hydrogen 408 0 One-touch single button BB Hydrogen 409 〇 One-touch single button BB F 410 ο One-touch single button BB F 411 0 One-touch single button BB CN 412 〇 One-touch single button BB CN 413 ο One-touch single button BB OH 414 〇 One-touch single button BB OH 415 ο One-touch single button BB 〇-c2h5 416 〇 One-touch single button BB 0-c2h5 417 coo One button single button BB Hydrogen 418 coo One button single button BB Hydrogen 419 coo One button single button BB F 420 coo One button single button BB F 421 coo One button single button BB CN 422 coo One button single button BB CN 423 coo single button single button BB OH 424 coo single button single button BB OH 425 coo single button single button BB 〇-c2h5 426 coo single button single button BB 〇-C?H, 33 11406pif.doc/008 1254735 The present invention The diamine represented by the formula (3) is not limited to the above, and various changes can be made as long as the object of the present invention can be attained. Further, these diamines may be used singly or in combination. The branched diamine represented by the above formula (3) and/or formula (4) may be reacted alone or in combination with other diamines, wherein the ratio of each diamine may be arbitrarily set to be adjusted to obtain a predetermined Initial tilt angle. The weight ratio of (A) to (B) in the liquid crystal alignment agent obtained by combining the polyamic acid (A) having good electrical properties and the polylysine (B) which can appropriately adjust the initial tilt angle of the present invention It is from 99/1 to 80/20. When the ratio of (B) is less than 1%, there is no effect of increasing the initial inclination; and when the ratio of (B) is higher than 20%, the initial inclination angle does not continue to increase. Further, when the polyglycolic acid of the present invention is used as a liquid crystal alignment agent, other polymer compounds may be used in addition to the polyamine without impairing the effects of the present invention. In particular, when polyamine, soluble polyamine and polyamidimide are used, the electrical properties of the alignment film can be further improved. Further, the polyamine acid of the present invention can be used in a form of a soluble polyamidamine or a polyamidite, without impairing the effects of the present invention. As described above, after the liquid crystal alignment agent usable in the present invention is applied onto a substrate, heat treatment is performed to imidize it. Therefore, all or a part of the polyamic acid which is a component of the liquid crystal alignment agent of the present invention can be catalyzed by a catalyst such as anhydrous acetic acid/acridine to form a soluble polyamidene, or it can be reacted with an alcohol in advance. The polyphthalate is obtained, and then heat-treated in the process of liquid crystal display element to form a liquid crystal alignment film of 11406pif.doc/008 34 1254735 which is mainly composed of polyamidamine, which can achieve the effect of the invention. . The varnish of the third feature of the present invention comprises the polylysine or a poly-proline derivative such as a soluble polyamidamine or a polyamidite (hereinafter referred to as a polymer compound). The liquid crystal alignment agent is dissolved in an organic solvent. In order to form a liquid crystal alignment film on a substrate on which a transparent electrode is disposed, a common practice is to dissolve the polymer compound in an organic solvent to form a lacquer, and then use it. At this time, the concentration of the poly-proline in the lacquer is 0.1 to 40 wt%, and preferably 0.5 to 10 wt%. Before the liquid crystal alignment agent is applied onto the substrate, in order to adjust the film thickness, the paint may be diluted with an organic solvent in advance; and in order to obtain a good quality (ie, flat and uniform thickness) film by spin coating or printing, after dilution The concentration must usually be below 10 wt%. For other coating methods, such as immersion coating, low concentrations of less than 10 wt% can also be used. On the other hand, when the concentration of the polyamic acid is less than 0.1% by weight, the problem that the thickness of the liquid crystal alignment film is too thin is liable to occur. Therefore, when the coating is carried out by a general spin coating method or a printing method, the concentration of the polymer compound in the paint is 〇·1 wt% or more, and preferably 0.5 to 10 wt%. However, lower or higher concentrations are also possible for coating processes using lacquering. The solvent to be used in common with the polymer compound as the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer compound. These solvents include those which are commonly used in the preparation or use of the polymer compound, and have a wide range and can be appropriately selected depending on the intended use. These solvents are, for example, aprotic polar organic solvents which act as good solvents for polyglycines, soluble polyimines, polyampamates and other high scores of 11406pif.doc/008 35 1254735 which may be used. By. Examples include: N-methyl-2-11 ratio awake, dimethyl-imidazolidinone, N-methyl caprolactam, N-methylpropionamide, N,N-dimethyl Ethylamine, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, or butyl lactone, etc. . In addition, in order to improve the coating property of the solution, other solvents such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene may be used. Ethylene glycol monoalkyl ether such as alcohol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or monophenyl ketone, triethylene glycol monoalkane a propylene glycol monoalkyl ether such as a propylene glycol monoalkyl ether or a propylene glycol monobutyl ether; a dialkyl glycol monoalkyl ether such as dimalonate monomethyl ether; or an acetate thereof. Ester compounds and the like. Further, when two or more kinds of organic solvents are used, the mixing ratio of the various solvents depends on the surface tension, viscosity, printability, coatability, wettability, and uniformity of film formation required for the solution. Other characteristics required for the alignment film are used to make adjustment settings. Among them, N-methyl-2-3⁄4 phenol, dimethyl ketone, butyl lactone and ethylene glycol are preferred in terms of solubility, printability, coatability, and film uniformity. Two or more types of monobutyl ether are used for use. The liquid crystal alignment agent of the present invention may also be added with various additives as needed. For example, in order to improve the coating property, a surfactant may be added; in order to improve the antistatic property, an antistatic agent may be added; and in order to improve the adhesion to the substrate, a coupling of a decane-based coupling agent or a titanium compound may be added. Agent. In addition, for liquid crystal display elements such as optical compensation bend type (OCB) or vertical alignment type (VA) that require a core region of 11406pif.doc/008 36 1254735 (domain), an appropriate amount of inorganic or organic fine particles may be added. Nuclear forming materials. Although the liquid crystal alignment agent obtained above is preferably used to form an active matrix type liquid crystal alignment film for a thin film transistor, such as a twisted nematic (TN), a horizontally rotating (IPS), a vertical alignment type (VA), and an optical compensation. A curved (〇CB) component, etc., but it can also be used to form a passive matrix twisted nematic liquid crystal display element, a super twisted nematic liquid crystal display element, and a ferroelectric dielectric because it can cause a desired initial tilt angle. A liquid crystal alignment film of a type or anti-strong dielectric type liquid crystal display element. Further, since such a liquid crystal display element has good electrical characteristics, it can also function as a protective layer or an insulating layer. Here, the liquid crystal display element can be obtained by a conventional method. First, the liquid crystal alignment agent of the present invention forms a liquid crystal alignment film on a substrate, and is disposed opposite to the same or different liquid crystal alignment film on the other substrate, and then in which The liquid crystal is injected to form a substrate with a liquid crystal interlayer. The process of the liquid crystal alignment film is as follows: first, a liquid crystal alignment agent is coated on a substrate, followed by a subsequent drying step, and then heat treatment is performed to perform a dehydration-closed ring reaction, that is, the liquid crystal display element is completed. At this time, a filter, an over-coating, an interlayer edge layer or a protrusion may be appropriately formed on one or both of the substrates on which the transparent electrodes are disposed. The spin coating method, the printing method, the immersion method or the dropping method in the coating method is a generally known method, and it can also be used in the present invention. Further, when the drying step and the heat treatment required for the dehydration-ring closure reaction are carried out by heating in a hot or infrared furnace or by heating with a hot plate, it is also applicable to the present invention. 11406pif.doc/008 37 1254735 The temperature of the drying step allows the solvent to evaporate, but it is preferably the lower one, for example 50 to 100. (:; and the heat treatment is preferably carried out in a temperature range of 150 to 30 (TC). The liquid crystal display element of the present invention preferably uses the following liquid crystal composition. For example, it is used in a super twisted nematic liquid crystal display element. The liquid crystal composition may be those listed in Japanese Laid-Open Patent Publication No. Hei 8-157828, No. Hei 8-231960, No. Hei 9-241644, and No. Hei 9-302346. The liquid crystal composition of the liquid crystal display element (TN, IPS, VA, and OCB type elements) may be Japanese Patent No. 3086228, No. 2635435, Japanese Patent No. Hei 5-501735, Japanese Patent Application Laid-Open No. Hei 8-199168 No. 9-235552, No. 9-241643, No. 9-255956, No. 10-204016, No. 10-204436, No. ping 〇 231482, No. 2000-087040 The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention and the liquid crystal composition composed of the liquid crystal composition for a thin film transistor liquid crystal display element disclosed in the above publication are the same as those listed in the above. Display component, special It is suitable for products requiring high voltage retention ratio, and its effect of improving the image sticking problem is also high. In detail, the liquid crystal alignment agent of the present invention is particularly suitable for the high voltage retention ratio disclosed in the aforementioned patents. The fluoroliquid crystal composition is a compound having a -OCF3 functional group at the tail end or a compound having 1 to 3 (or more) gas atoms. Further, the liquid crystal composition may also contain 1 (or more) of the optically active compound without any problem. 11406 pif.doc/008 38 1254735 Example = Several examples are given below to illustrate the invention, which is not intended to limit the scope of the invention. Prior to these examples, the materials used in the various synthetic examples, examples, and comparative examples, along with the abbreviations and methods of evaluation, are described in detail below. 1. Materials and abbreviations (1) Various tetracarboxylic dianhydride pyromellitic dianhydrides ( PMD A) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA) 1,2,3,4-butyl Alkanetetracarboxylic dianhydride ^0 VIII) methylated cyclobutane tetracarboxylic dianhydride (methylation process) Degrees up to 1.5) (CMDA) (2) Various diamines 4,4'-diaminodiphenylmethane (DPM) 1,2-bis(4-aminophenyl)ethane (DPEt) 4,4'- Diaminodiphenyl ether (DPE) 1,1-bis{4-[(4-aminophenyl)methyl]phenyl}-4-butylcyclohexane (4Ch) 5-{4-[4 -(4-pentylcyclohexyl)cyclohexyl]phenyl}methyl-1,3-diaminobenzene (5Ch) 1,3-bis(3-aminopropyl)-l,l,3,3 -Tetramethyldioxane (APDS) (3) Various solvents N-methyl-2-furanosone (NMP) Ethylene glycol monobutyl ether (BC) Butyrolactone (GBL) 11406pif. Doc/008 39 1254735 (4) Various liquid crystal compositions The composition of the liquid crystal composition used herein is as follows, and the nematic-isotropic phase transition (NI) temperature of this composition is 100. (TC, and complex refractive index It is 0.093 ◦. 2 take - ~ Ο ~ 17wt.% C3H7 ~ ^ Z) O ~ F 17wt. ° yC C5Hn ^ ^ - 〇 H ^ F 16wt · % C2H5 - ^ ^ F 10wt.% C3H7 - 1 5wt.% C5H11 ~. 2心~^〇~ 10wt.% C2H5—~F 6wt·% c3H7-〇^〇^^r 6wt·% CsHn-〇-H〇K^-F 13wt.% 11406pif.doc/008 40 1254735 2. Comment Method 2-1: Evaluation method of vertical electric field type liquid crystal display element (1) Measurement of residual charge A square wave of frequency 30 Hz and amplitude of 2 V is superimposed on a component with a DC voltage of 3 V for 1 hour, and then the flicker elimination is measured immediately. The flicker elimination voltage is measured again after 30 minutes, and the absolute enthalpy of enthalpy is the residual charge. When the residual charge is smaller, the residual image is less, so the smaller the residual charge, the better. (2) Voltage-holding ratio measurement This measurement was carried out in accordance with the method published by Minamata et al. in the 14th Liquid Crystal Forum Pre-Collection Ρ78. The measurement conditions are as follows: gate width is 69 //S, frequency 60 Hz, peak height ± 4.5 V, and the measured temperature is 60 ° C. The higher the voltage holding ratio, the better the electrical characteristics. (3) Method of measuring initial tilt angle Here, the initial tilt angle of the liquid crystal is measured by crystal rotation. (4) Evaluation of alignment ability This measurement is based on a polarizing microscope to observe the liquid crystal, and the observer judges whether there is a poor alignment. Those with good alignment are marked as Ο, and those who are not good are marked as X. 2-2. Evaluation method of transverse electric field type liquid crystal display element (1) Measurement of DC residual image The elements produced in the respective examples and comparative examples were placed in a hot furnace set at 60 ° C, and a l was applied thereto. 〇〇mV, 1kHz sinusoidal AC voltage, and overlap applied from 0V to 10V (in IV) stepped in 3 seconds 11406pif.doc/008 41 1254735
地升高電壓），然後以此電壓驅動30分鐘。之後，以IV 爲單位，在3秒內階梯式地將直流成分的電壓由10V降到 0V。由於殘留電荷會在液晶元件之電容中佔一定比例’所 以測量直流電壓施加前後的電容差値，即得殘留電荷。此 殘留電荷之値愈小，直流電殘影即愈少。 (2) 交流電殘影的測量（配向性評量） 將各實例與比較例所製作之元件置於設定在60°C的 熱爐中，並在其上施加1kHz之正弦波交流電壓，其振幅 在3秒內由0.1 V升高到10.1 V，其間電壓每升高IV即測 一次電容。在以10.1V的電壓驅動一小時後，在3秒內將 其振幅由10.IV降到0.IV，其間電壓每降低IV即測一次 電容。之後計算升壓及降壓時2.IV〜3.1V之間的電容積分 値，再取其差値的一半，即爲平均遲滯値(mean hysteresis)， 其値愈小表示配向性愈好。 (3) 電壓保持比的測量 此測量方法係以2-1縱向電場元件的評量方法爲準。 合成例1 [聚醯胺酸之合成】 準備具有溫度計、攪拌器與反應物入口以及氮氣導入 口的100ml四口燒瓶，再於其中投入2.4849克DPM與55.0 克脫水NMP，並在乾燥氮氣環境下攪拌溶解之。接著將反 應系統的溫度保持在2(TC以下，依序於其中加入0.4921 克 PMDA、1.2781 克 CBDA 及 0.7449 克 BDA，再反應 30 小時，然後加入40.0克BC，即得聚合物濃度爲5 wt%的 11406pif.doc/008 42 1254735 聚醯胺酸（PA1)溶液。在此反應中，如因反應放熱而導致 系統溫度升高，則須將反應溫度控制在70°C以下。另外， 所得之聚合物的重量平均分子量爲56000，且黏度爲30cp。 合成例2〜13 該些合成例係以下表28所示之比例，使用四羧酸二 酐與二胺來合成聚醯胺酸，其方法係以合成例1所述者爲 準。這些合成例與合成例1之結果皆列示於表28中。 表28 聚合 物縮 寫 莫耳分率（mol%) 莫耳分率（mol%) 重暈平均 分子量 四 羧酸二酐 二胺 PM DA CB DA BD A CH DA CM DA DP Μ DPE t DPE 4Ch 5Ch 合成 例1 PA1 18 52 30 100 56,000 合成 例2 PA2 25 25 50 80 20 68,000 合成 例3 PA3 30 40 30 80 20 78,000 合成 例4 PA4 20 40 20 20 100 65,000 合成 例5 PA5 20 45 20 10 5 100 66,000 合成 例6 PB1 100 50 50 80,000 合成 例7 PB2 100 30 70 52,000 . 合成 例8 PB3 50 50 25 25 50 58,000 合成 例9 PB4 100 80 20 70,000 合成 例10 PB5 30 70 40 60 77,000 合成 例11 PA6 30 70 100 79,000 合成 例12 PA7 100 100 50,000 合成 例13 PA8 70 10 20 100 65,000 43 11406pif.doc/008 1254735 合成例14 準備具有溫度計、攪拌器與反應物入口以及氮氣導入 口的1000ml四口燒瓶，再於其中投入2屯4658克DDEt與 200克脫水NMP，並在乾燥氮氣環境下攪拌溶解之。接著 將反應系統的溫度保持在20°C以下，依序於其中加入 9.1578 克 PMDA、7.0758 克 CBDA 及 8_3185 克 BDA，再 反應30小時，然後加入550克GBL與200.0克BC，即得 聚合物濃度爲5 wt%的聚醯胺酸(PA14)溶液。在此反應中， 如因反應放熱而導致系統溫度升高，則須將反應溫度控制 在70°C以下。另外，所得之聚合物的重量平均分子量爲 70000，且黏度爲4〇cp。 合成例15〜23 該些合成例係以下表29所示之比例，使用四羧酸二 酐與二胺來合成聚醯胺酸，其方法係以合成例14所述者 爲準。這些合成例與合成例14之結果皆列示於表29中。 11406pif.doc/008 44 1254735 表29 聚合 物縮 寫 莫耳分率（mol%) 莫耳分率（mol%) 四羧酸二酐 二胺 PM DA CB DA BD A CH DA CM DA DP Μ DPE t DPE AP DS 4Ch 合成 例14 PA9 35 30 35 100 合成 例15 PA10 30 30 40 30 70 合成 例16 ΡΑ11 20 50 30 30 70 合成 例17 ΡΑ12 16 44 40 30 70 合成 例18 ΡΑ13 35 25 40 40 50 10 合成. 例19 ΡΒ6 100 20 20 60 合成 例20 ΡΒ7 80 20 30 10 60 合成 例21 ΡΒ8 50 50 40 5 55 合成 例22 ΡΒ9 50 50 40 1 59 合成 例23 ΡΑ14 5 95 100 實例1 (縱向電場元件之製作與評量）Ground the voltage) and then drive it for 30 minutes. Thereafter, the voltage of the DC component is stepped down from 10 V to 0 V in steps of 3 in units of IV. Since the residual charge accounts for a certain ratio in the capacitance of the liquid crystal cell, the difference in capacitance before and after the application of the DC voltage is measured, that is, the residual charge is obtained. The smaller the residual charge, the less DC residual image. (2) Measurement of AC residual image (alignment evaluation) The components fabricated in each example and comparative example were placed in a furnace set at 60 ° C, and a 1 kHz sine wave AC voltage was applied thereto, and the amplitude thereof was applied. It rises from 0.1 V to 10.1 V in 3 seconds, and the capacitance is measured every time the voltage is raised. After driving at a voltage of 10.1 V for one hour, the amplitude was reduced from 10.IV to 0. IV in 3 seconds, and the capacitance was measured every time the voltage was lowered. Then calculate the capacitance integral between 2.IV and 3.1V during boost and buck, and then take half of the difference, which is the mean hysteresis. The smaller the hysteresis, the better the alignment. (3) Measurement of voltage holding ratio This measurement method is based on the evaluation method of 2-1 vertical electric field component. Synthesis Example 1 [Synthesis of Polylysine] A 100 ml four-necked flask equipped with a thermometer, a stirrer and a reactant inlet, and a nitrogen inlet was prepared, and then 2.4849 g of DPM and 55.0 g of dehydrated NMP were placed therein, and dried under a nitrogen atmosphere. Stir and dissolve. Then, the temperature of the reaction system was maintained at 2 (TC or less, and 0.4921 g of PMDA, 1.2781 g of CBDA, and 0.7449 g of BDA were sequentially added thereto, and further reacted for 30 hours, and then 40.0 g of BC was added to obtain a polymer concentration of 5 wt%. 11406pif.doc/008 42 1254735 Polylysine (PA1) solution. In this reaction, if the temperature of the system rises due to the exothermic reaction, the reaction temperature must be controlled below 70 ° C. In addition, the resulting polymerization The weight average molecular weight of the material was 56,000, and the viscosity was 30 cp. Synthesis Examples 2 to 13 These synthesis examples are the ratios shown in Table 28 below, and the tetracarboxylic dianhydride and the diamine were used to synthesize the polyamic acid. The results of the synthesis examples are as follows. The results of these synthesis examples and Synthesis Example 1 are shown in Table 28. Table 28 Polymer abbreviated molar fraction (mol%) Molar fraction (mol%) Average molecular weight tetracarboxylic dianhydride diamine PM DA CB DA BD A CH DA CM DA DP Μ DPE t DPE 4Ch 5Ch Synthesis Example 1 PA1 18 52 30 100 56,000 Synthesis Example 2 PA2 25 25 50 80 20 68,000 Synthesis Example 3 PA3 30 40 30 80 20 78,000 Synthesis Example 4 PA4 20 40 20 20 100 65,000 Synthesis Example 5 PA5 20 45 20 10 5 100 66,000 Synthesis Example 6 PB1 100 50 50 80,000 Synthesis Example 7 PB2 100 30 70 52,000 . Synthesis Example 8 PB3 50 50 25 25 50 58,000 Synthesis Example 9 PB4 100 80 20 70,000 Synthesis Example 10 PB5 30 70 40 60 77,000 Synthesis Example 11 PA6 30 70 100 79,000 Synthesis Example 12 PA7 100 100 50,000 Synthesis Example 13 PA8 70 10 20 100 65,000 43 11406 pif.doc/008 1254735 Synthesis Example 14 Preparation with thermometer, stirrer A 1000 ml four-necked flask with a reactant inlet and a nitrogen inlet was charged with 2, 4,658 g of DDEt and 200 g of dehydrated NMP, and dissolved by stirring under a dry nitrogen atmosphere. Then, the temperature of the reaction system was kept below 20 ° C, and 9.1578 g of PMDA, 7.0758 g of CBDA and 8_3185 g of BDA were sequentially added thereto, and further reacted for 30 hours, and then 550 g of GBL and 200.0 g of BC were added to obtain a polymer concentration. It is a 5 wt% polylysine (PA14) solution. In this reaction, if the temperature of the system rises due to the exothermic reaction, the reaction temperature must be controlled below 70 °C. Further, the obtained polymer had a weight average molecular weight of 70,000 and a viscosity of 4 〇 cp. Synthesis Examples 15 to 23 These synthesis examples were obtained by synthesizing polyamic acid using tetracarboxylic dianhydride and diamine in the proportions shown in the following Table 29, in the manner as described in Synthesis Example 14. The results of these synthesis examples and Synthesis Example 14 are shown in Table 29. 11406pif.doc/008 44 1254735 Table 29 Polymer abbreviations Molar fraction (mol%) Molar fraction (mol%) Tetracarboxylic dianhydride diamine PM DA CB DA BD A CH DA CM DA DP Μ DPE t DPE AP DS 4Ch Synthesis Example 14 PA9 35 30 35 100 Synthesis Example 15 PA10 30 30 40 30 70 Synthesis Example 16 ΡΑ11 20 50 30 30 70 Synthesis Example 17 ΡΑ12 16 44 40 30 70 Synthesis Example 18 ΡΑ13 35 25 40 40 50 10 Synthesis. Example 19 ΡΒ6 100 20 20 60 Synthesis Example 20 ΡΒ7 80 20 30 10 60 Synthesis Example 21 ΡΒ8 50 50 40 5 55 Synthesis Example 22 ΡΒ9 50 50 40 1 59 Synthesis Example 23 ΡΑ14 5 95 100 Example 1 (Production of a longitudinal electric field element and Assessment)
首先混合合成例1所得之固形物濃度5 wt%的聚醯胺 酸（A)的溶液（PA1)與合成例6所得之聚醯胺酸（B)的溶液 (PB1)，二者之重量比爲90:10，再以重量比1/1的NMP/BC 混合溶劑稀釋使固形物濃度降爲3 wt%，即得液晶配向劑。 接著以旋塗法將此液晶配向劑塗布在已形成透明電極（ITO) 的基板上，再於80°C下乾燥5分鐘，然後於220°C下加 熱處理30分鐘，以使聚醯胺酸轉爲聚亞醯胺，即可得一 45 11406pif.doc/008 1254735 配向膜。接著進行配向處理，其係以摩擦裝置對已形成配 向膜的基板表面進行摩擦處理。接著以乙醇洗淨基板，再 於12〇°C下乾燥之，然後於其上散布一些尺寸7//m的間 隙材料，再將形成配向膜的一面朝內，而以環氧樹脂硬化 劑封住其周邊，並留下液晶的注入孔，如此即得胞間隙爲 7仰1的反平行（anti_paranel)液晶胞。接著在液晶胞中注入 前述液晶組成物，再以光硬化劑密封注入口，而後以紫外 光照射以使液晶注入口的光硬化劑硬化。接著於11〇。〇下 加熱處理30分鐘（等向化處理），即得液晶顯示元件，其各 種電學特性將以前述之方法加以評量。另外，再使用尺寸 2(^m的間隙材料製作間隙20//m的逆平行液晶胞，然後 進行前述製程，即得胞間隙20/mi的液晶顯示元件，其初 始傾斜角係以前述方法加以測量，其結果顯示於表30中。 實例2〜14、比較例i〜5 該些例子係以表30所示之聚醯胺酸溶液及其比例， 而以實例1所述之方法製造液晶配向劑。接著使用此液晶 配向劑製作電學特性評量用的液晶顯示元件與初始傾斜角 測量用的液晶顯示元件，再進行更種評量，其結果顯示於 表30中。 11406pif.doc/008 46 1254735 表30First, a solution (PA1) of a polyglycine (A) having a solid concentration of 5 wt% obtained in Synthesis Example 1 and a solution (PB1) of polylysine (B) obtained in Synthesis Example 6 were mixed, and the weight ratio therebetween At 90:10, the solid concentration was reduced to 3 wt% by diluting with a 1/1 by weight NMP/BC mixed solvent to obtain a liquid crystal alignment agent. Then, the liquid crystal alignment agent was coated on the substrate on which the transparent electrode (ITO) was formed by spin coating, and then dried at 80 ° C for 5 minutes, and then heat treated at 220 ° C for 30 minutes to make polylysine. Conversion to polyamidoamine gives a 45 11406 pif.doc/008 1254735 alignment film. Next, an alignment treatment is performed which rubs the surface of the substrate on which the alignment film has been formed by a rubbing device. Then, the substrate is washed with ethanol, and then dried at 12 ° C, and then some gap material of 7 / / m is spread thereon, and the side forming the alignment film is turned inward, and the epoxy resin hardener is used. The surrounding area is sealed, and the injection hole of the liquid crystal is left, so that an anti-paranel liquid crystal cell having a cell gap of 7 is obtained. Then, the liquid crystal composition is injected into the liquid crystal cell, and the injection port is sealed with a light hardener, and then irradiated with ultraviolet light to harden the light hardener of the liquid crystal injection port. Then at 11 〇. The heat treatment was carried out for 30 minutes (isotropic treatment) to obtain a liquid crystal display element, and various electrical characteristics thereof were evaluated by the aforementioned methods. In addition, an anti-parallel liquid crystal cell having a gap of 20/m is formed by using a gap material of size 2 (m), and then the foregoing process is performed, that is, a liquid crystal display element having a cell gap of 20/mi is obtained, and the initial tilt angle is obtained by the aforementioned method. The results are shown in Table 30. Examples 2 to 14 and Comparative Examples i to 5 These examples are based on the polylysine solution shown in Table 30 and the ratio thereof, and the liquid crystal alignment was produced by the method described in Example 1. Then, the liquid crystal display element for electric property measurement and the liquid crystal display element for initial tilt angle measurement were prepared using this liquid crystal alignment agent, and further evaluation was performed, and the results are shown in Table 30. 11406pif.doc/008 46 1254735 Table 30
聚醯胺 酸(A) 聚醯胺 酸⑼ ㈧/(B) 初期殘 留電荷 (mV) 30分 後殘留 電荷 (mV) 電壓保 持比 (%) 初始傾 斜角 (°) 配向性 實例 1 PA1 PB1 90/10 12 0 98.6 5.5 〇 實例 2 PA2 PB2 90/10 15 0 98.6 8.8 〇 實例 3 PA3 PB3 95/5 16 0 98.4 13 〇 實例 4 PA4 PB4 90/10 20 0 98.8 10.1 〇 實例 5 PA5 PB5 90/10 21 0 98.3 6.6 〇 實例 6 PA1 PB5 90/10 13 0 98.5 6.8 〇 實例 7 PA2 PB4 85/15 14 0 98.6 11.0 〇 實例 [8 PA3 PB3 95/5 19 0 98.4 12.8 〇 實例 [9 PA4 PB2 90/10 22 0 98.4 9.1 〇 實例 10 PA5 PB1 90/10 20 0 98.8 5.3 〇 實例 11 PA1 PB6 90/10 15 0 99.0 7.0 〇 實例 12 PA1 PB7 90/10 16 0 98.9 7.0 〇 實例 13 PA4 PB8 90/10 12 0 98.8 6.2 〇 實例 14 PA3 PB9 90/10 8 0 99.2 6.7 〇 比較例 1 PA6 PB1 90/10 48 2 98.0 5.5 〇 比較例 2 PA7 PB2 90/10 102 8 98.3 8.3 X 比較例 3 PA8 PB1 90/10 113 7 98.3 16.8 X 比較例 4 PA6 — 100/0 250 20 97.5 1.2 〇 比較例 5 PA7 — 100/0 288 126 98.0 1.1 X 實例15 (橫向電場元件之製作與評量） 首先以重量比1/1的NMP/BC混合溶劑稀釋合成例14 所得之固形物濃度5 wt%的聚醯胺酸（A)的溶液（PA9)，以 使固形物濃度降爲3 wt%，即得液晶配向劑。接著以旋塗 法將此液晶配向劑塗布在已形成弧形透明電極（ITO)的基 板上，再於80°C下乾燥5分鐘，然後於220°C下加熱處 理30分鐘，以使聚醯胺酸轉爲聚亞醯胺，即可得一配向 47 11406pif.doc/008 1254735 膜。另一方面，對相對之已形成透明電極的基板進行同樣 的塗布··加熱處理，即得同樣的配向膜。接著進行配向處 理’其係以摩擦裝置對已形成配向膜的基板表面進行朝電 極傾斜15。(即與電場方向夾75。)的摩擦處理。另一方面， 對相對之基板亦進行同樣的摩擦處理。接著以乙醇洗淨基 板’再於12(TC下乾燥之，然後於其上散布一些尺寸4//m 的間隙材料，再將形成配向膜的一面朝內，而以環氧樹脂 硬化劑封住其周邊，並留下液晶的注入孔，如此即得胞間 隙爲的平行(parallel)液晶胞。接著在液晶胞中注入前 述液晶組成物，再以光硬化劑密封注入口，而後以紫外光 照射以使液晶注入口的光硬化劑硬化。接著於U〇°C下加 熱處理30分鐘(等向化處理），即得液晶顯示元件’其各種 電學特性將以前述之方法加以評量，結果顯示於表31中。 實例16〜19、比較例6 該些例子係使用表31所示之聚醯胺酸溶液，以實例I5 所述之方法製造液晶顯示元件，再對其進行各種評量，其 結果顯示於表31中。 表31 聚醯胺酸(A) DC殘影（pF) AC殘影（pF) 電壓保持比 (%) 實例15 PA9 43 0.065 98.3 實例16 PA10 45 0.083 98.0 實例17 53 0.109 98.4 實例18 PAl2 55 0.096 98.1 一一 實例19 PA13 14 0.102 比較例6 PA14 102 1.355 97.3 11406pif.doc/008 48 1254735 由實例1〜14的結果可見，使用本發明之液晶配向劑 的液晶顯示元件之特性較佳，其具有適當的初始傾斜角’ 初期殘留電荷量小，且30分鐘後即無電荷殘留，同時電 壓保持比也在98%以上。由此可知此液晶配向劑具有良好 的電學特性，其即表示製得之液晶配向膜具有良好的配向 性。另一方面，比較例1〜5的初期殘留電荷量大，且30 分鐘後仍有殘留電荷。再者，其電壓保持比或配向性也不 佳。 接著，由實例15〜19的結果可見，使用本發明之液晶 配向劑的液晶顯示元件之特性較佳，其施加直流電（DC)負 載時的電荷殘留量小，而施加交流電(AC)負載時幾乎不會 殘留電荷。另外，由於電壓保持比高，所以液晶配向膜的 配向性高而不會有殘影，亦即具有良好的電學特性。另一 方面，由比較例6的結果可知，其直流電操作模式及交流 電操作模式的特性皆不佳。 由上可知，使用本發明之聚醯胺酸的實施例所得之液 晶配向劑的特性明顯優於比較例。詳言之，在習知技藝中， 不論是由「僅含芳香族四羧酸二酐與脂族（或脂環族）四羧 酸二酐2種酸成分的聚醯胺酸」製得的液晶配向劑（比較 例1與4)，還是由「僅含脂族(或脂環族）四羧酸二酐作爲 酸成分的聚醯胺酸」製得的液晶配向劑（比較例2與5)， 或是由組成比在本發明申S靑專利範圍以外的相同材料所得 者（比較例3與6)，其電學特性皆明顯較差。 11406pif.doc/008 49 1254735 發明之效里 如上所述，如使用含本發明之聚醯胺酸的液晶配向劑 來製作液晶配向膜，即可得到具有適當初始傾斜角、配向 性良好、殘留電荷量小，且電壓保持比高的液晶顯示元件。 因此，儘管其特別適合應用在TFT液晶顯示元件(TN型、 IPS型、VA型及OCB型），但因其電學特性良好且初始傾 斜角可任意調整，所以同樣適合使用在超扭轉向列型、強 介電型及反強介電型液晶顯示元件中。另外，由本發明之 液晶配向劑所構成之薄膜具有良好的電學特性，所以也可 以作爲保護層或絕緣層。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍內，當可作各種之更動與潤飾，因此本發明之保護 車E圍當視後附之申請專利範圍所界定者爲準。 11406pif.doc/008 50Polylysine (A) Polylysine (9) (8) / (B) Initial residual charge (mV) Residual charge after 30 minutes (mV) Voltage retention ratio (%) Initial tilt angle (°) Alignment example 1 PA1 PB1 90 /10 12 0 98.6 5.5 〇 Example 2 PA2 PB2 90/10 15 0 98.6 8.8 〇 Example 3 PA3 PB3 95/5 16 0 98.4 13 〇 Example 4 PA4 PB4 90/10 20 0 98.8 10.1 〇 Example 5 PA5 PB5 90/10 21 0 98.3 6.6 〇 Example 6 PA1 PB5 90/10 13 0 98.5 6.8 〇 Example 7 PA2 PB4 85/15 14 0 98.6 11.0 〇 Example [8 PA3 PB3 95/5 19 0 98.4 12.8 〇 Example [9 PA4 PB2 90/10 22 0 98.4 9.1 〇 Example 10 PA5 PB1 90/10 20 0 98.8 5.3 〇 Example 11 PA1 PB6 90/10 15 0 99.0 7.0 〇 Example 12 PA1 PB7 90/10 16 0 98.9 7.0 〇 Example 13 PA4 PB8 90/10 12 0 98.8 6.2 〇 Example 14 PA3 PB9 90/10 8 0 99.2 6.7 〇Comparative Example 1 PA6 PB1 90/10 48 2 98.0 5.5 〇Comparative Example 2 PA7 PB2 90/10 102 8 98.3 8.3 X Comparative Example 3 PA8 PB1 90/10 113 7 98.3 16.8 X Comparative Example 4 PA6 — 100/0 250 20 97.5 1.2 〇Comparative Example 5 PA7 — 100/0 288 126 98.0 1.1 X Example 15 (Transverse electric field component Preparation and Evaluation) First, a solution (PA9) of a polyglycine (A) having a solid concentration of 5 wt% obtained in Synthesis Example 14 was diluted with a NMP/BC mixed solvent in a weight ratio of 1/1 to lower the solid concentration. It is 3 wt%, which is a liquid crystal alignment agent. Then, the liquid crystal alignment agent is coated on the substrate on which the curved transparent electrode (ITO) has been formed by spin coating, and then dried at 80 ° C for 5 minutes, and then heat treated at 220 ° C for 30 minutes to make the polyfluorene. The conversion of the amine to polyamidamine gives a 45 47406 pif.doc/008 1254735 film. On the other hand, the same coating/heat treatment was applied to the substrate on which the transparent electrode was formed, that is, the same alignment film was obtained. Next, the alignment treatment is carried out. The surface of the substrate on which the alignment film has been formed is tilted toward the electrode 15 by a rubbing device. (ie, rubbing against the direction of the electric field 75). On the other hand, the same rubbing treatment is applied to the opposite substrate. Then, the substrate was washed with ethanol and then dried at 12 (TC), and then some gap material of 4/m size was spread thereon, and the side on which the alignment film was formed was turned inward, and sealed with epoxy resin hardener. The surrounding area is left, and the injection hole of the liquid crystal is left, so that the parallel liquid crystal cell with the cell gap is obtained. Then, the liquid crystal composition is injected into the liquid crystal cell, and the injection port is sealed with a light hardener, and then ultraviolet light is used. Irradiation to harden the light hardener of the liquid crystal injection port, followed by heat treatment at U 〇 ° C for 30 minutes (isotropic treatment), that is, the liquid crystal display element's various electrical characteristics will be evaluated by the aforementioned method, and the result is as follows. The results are shown in Table 31. Examples 16 to 19, Comparative Example 6 These examples were produced by using the polylysine solution shown in Table 31, and the liquid crystal display element was produced by the method described in Example I5, and then subjected to various evaluations. The results are shown in Table 31. Table 31 Polylysine (A) DC afterimage (pF) AC afterimage (pF) Voltage retention ratio (%) Example 15 PA9 43 0.065 98.3 Example 16 PA10 45 0.083 98.0 Example 17 53 0.109 98.4 Example 18 PAl2 55 0.096 98.1 One An example 19 PA13 14 0.102 Comparative Example 6 PA14 102 1.355 97.3 11406 pif.doc/008 48 1254735 It can be seen from the results of Examples 1 to 14 that the liquid crystal display element using the liquid crystal alignment agent of the present invention has better characteristics and has an appropriate initial The tilting angle 'the initial residual charge amount is small, and no charge remains after 30 minutes, and the voltage holding ratio is also 98% or more. It is understood that the liquid crystal alignment agent has good electrical properties, which means that the obtained liquid crystal alignment film On the other hand, in Comparative Examples 1 to 5, the initial residual charge amount was large, and residual charge remained after 30 minutes. Further, the voltage holding ratio or the alignment property was not good. As a result of ～19, it is found that the liquid crystal display element using the liquid crystal alignment agent of the present invention has better characteristics, and the charge residual amount when a direct current (DC) load is applied is small, and almost no charge remains when an alternating current (AC) load is applied. Further, since the voltage holding ratio is high, the alignment of the liquid crystal alignment film is high without image sticking, that is, it has good electrical characteristics. On the other hand, by Comparative Example 6 As a result, it is understood that the characteristics of the direct current operation mode and the alternating current operation mode are not good. From the above, the characteristics of the liquid crystal alignment agent obtained by using the polyamic acid of the present invention are significantly superior to those of the comparative example. In the prior art, it is a liquid crystal alignment agent prepared by "polyamic acid containing only two kinds of acid components of aromatic tetracarboxylic dianhydride and aliphatic (or alicyclic) tetracarboxylic dianhydride" (comparative Examples 1 and 4) are liquid crystal alignment agents (Comparative Examples 2 and 5) prepared by "polyamic acid containing only aliphatic (or alicyclic) tetracarboxylic dianhydride as an acid component", or by The electrical properties of the same materials (Comparative Examples 3 and 6) which are outside the range of the patent application of the present invention are significantly inferior. 11406pif.doc/008 49 1254735 In the effect of the invention, as described above, if a liquid crystal alignment film is prepared using a liquid crystal alignment agent containing the polyamic acid of the present invention, a suitable initial tilt angle, good alignment, and residual charge can be obtained. A liquid crystal display element having a small amount and a high voltage holding ratio. Therefore, although it is particularly suitable for use in TFT liquid crystal display elements (TN type, IPS type, VA type, and OCB type), it is also suitable for use in the super twisted nematic type because of its good electrical characteristics and the initial tilt angle can be arbitrarily adjusted. , strong dielectric type and anti-strong dielectric type liquid crystal display elements. Further, since the film composed of the liquid crystal alignment agent of the present invention has good electrical properties, it can also serve as a protective layer or an insulating layer. While the present invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The protection vehicle E is subject to the definition of the patent application scope attached to it. 11406pif.doc/008 50