201243461 六、發明說明： 【發明所屬之技術領域】 本·明涉及邊緣電％開關模式（Fringe Field Switching Mode，以下，也稱作r FFS模式」）的液晶顯 示元件以及在其中使用的液晶配向劑以及液晶配向膜的 形成方法。更詳細地，涉及驅動時的光線透射率高，沒 有產生顯示不佳的FFS模式的液晶顯示元件。 【先前技術】 作為液晶顯示元件的顯示模式，目前已知TN模式 (Twisted Nematic Mode,扭曲向列模式）、STN 模式 (Super Twisted Nematic Mode,超扭曲向列模式）、乂八模 式（Vertical Alignment M〇de，垂直配向模式）等所謂的 縱電場方式，這方式分別以下述方式驅動液晶：在由具 有電極的兩塊基板所構成的一對基板間夾住液晶，在相 對基板面垂直的方向產生電場。這些縱電場方式的液晶 顯示元件具有視角窄的問題。作為在維持縱電場方式的 同時改善視角問題的模式提出了 MVA模式 (Multi-Domain Vertical AHgnment，多重垂直配向模式） 〇 與此不同地，作為橫電場方式的液晶顯示元件提出 了 IPS模式（In_Plane Switching M〇de，面内切換模式）的 液日日顯不7L件（參照專利文獻丨〜3和非專利文獻1 )。該 模式的液晶顯示元件為T述方式：只在夾住液晶層的一 對基板中之一個上分別形成具有梳型形狀的一對電極， 在相對基板面水平的方向產生電場，驅動液晶。橫電場 201243461 式的液晶顯示元件由於液晶分子只在和A L ^ ^ 暴板平行的方向 上響應電場’所以液晶分子的長軸方向 w的折射率變化沒 有問題’即使改變視角時’觀察者確認 j野比度和顯示 顏色的濃度變化也少，因此，可以不限相A ， _ 个丨氏说角地高品質顯 示。然而，由於在IPs模式的液晶顯示元件的電極上（梳 型電極的梳齒上部）’液晶不進行電場響應，所以與縱電 場方式的液晶顯示元件相比，具有開口率低的問題’。 作為在維持IPS模式的視角性質的同時、解決開口率 問題的方式，提出了 FFS模式的液晶顯示元件（專^文獻 4〜6)。該FFS模式只在夹住液晶層的—對基板中的一個上 具有依次形成共用電極、絕緣層和信號電極的結構，可 以說是層疊一對電極而構成的。於此，信號電極例如可 以是透過一定的間隙排列之具有多個梳齒的梳狀電極。 然而，如果在這些電極間施加電壓，則在共用電極中的 上方沒有存在梳齒的區域與梳齒間，產生通過液晶層的 拱形電場，藉此驅動液晶。因此，FFS模式由於液晶在信 號電極上進行電場響應，所以可以解決lps模式中的開口 率問題。 然而，FFS模式中，由於驅動時產生了光線透射率變 低的現象，所以可能產生顯示不佳的情況，需要解決該 問題。 [先前技術文獻] [專利文獻] [專利文獻1]美國專利第5928733號說明書 [專利文獻2]日本特開昭5 6_9丨277號公報 201243461 [專利文獻3]曰本特開2008-46 184號公報 [專利文獻4]日本特開2007-26423 1號公報 [專利文獻5]日本特開2008_5 1846號公報 [專利文獻6]日本特開2009-1 16334號公報 [非專利文獻] [非專利文獻 l]“Liq. Cryst.，，，vol. 22，p379(1996) 【發明内容】 [發明欲解決之課題] 本發明之目的是解決FFS模式的上述問題。即，本發 明的目的在於’提供驅動時的光線透射率高、不會產生 顯示不佳的FFS模式的液晶顯示元件。 [解決課題之手段] 下 子 題 由 依 本發明人等查明FFS模式驅動時的光線透射率低 現象是由於h號電極附近的液晶配向膜界面的浠 _ %日日分· 的相反預傾斜不佳引起的，從而獲得不會產生這種 的液晶顯示元件。即，本發明的上述目的和優點 1糸藉 FFS模式的液晶顯示元件而實現，其特徵在於： 由於一對基板間夾住液晶層而形成； 在前述一對基板中之一的前述液晶層側之面上 次形成共用電極、絕緣層、信號電極和液晶配向犋 前述液晶層係由正型液晶所形成， 而且，刖述液晶配向膜的預傾角是〇 2〇以下 [發明之效果] 、没有 根據本發明，提供在驅動時的光線透射率高 產生顯示不佳的FFS模式的液晶顯示元件。 201243461 本發明的液晶顯示元件由於視角廣而且顯示品質極 為優異，可以抑制顯示不佳的產生，所以適合在例如液 晶電視、手提信息終端等中使用。 【實施方式】 [實施發明之形態] 本發明的液晶顯示元件是FFS模式的液晶顯示元件。 本發明的液晶顯示元件係於一對基板間夾住液晶層 而形成。作為這裡所使用的基板，可以使用例如由浮式 玻璃、納玻璃等玻璃；聚對苯二甲酸乙二酯、聚對苯二 曱酸丁二酯、聚醚砜、聚碳酸酯、聚（脂環式烯烴）、聚（ 脂環式烯烴）的氫化物等塑料形成的透明基板等。作為基 板的厚度較佳為0.3〜2mm ’更佳為〇.5〜1 mm。 在本發明的液晶顯示元件中的一對基板中之一的液 晶層側之面上，依次形成共用電極、絕緣層、信號電極 和液晶配向膜。 作為上述共用電極，可以使用例如由氧化錫（Sn〇2) 所形成的NESA膜（美國ppg公司的註冊商標）、由氧化銦_ 氧化錫（IkOrSnO2)所形成的IT0膜等。作為該共用電極 的形狀可以是不具有在基板的一面上形成的圖案之所謂 的「β膜」，或者可以是具有任意圖案的圖案狀電極。作 為共用電極的厚度較佳為10〜200nm，更佳為2〇〜1〇〇1^。 共用電極可以藉由周知的方法，例如濺射法等在基板上 形成。 土 作為上述絕緣層，可以是例如由氮化矽等所形成。 作為絕緣層的厚度較佳為丨⑼〜丨，〇〇〇nm，更佳為丨5〇〜75〇 201243461 例如化學氣相蒸鍍法 nm。絕緣層可以藉由周知的方法 等在共用電極上形成。 上述信號電極可w L , ^ 和上述用電極相同的材料所 形成。信號電極可以θ μ, β ^ ' ^ - UU # ^ ^ 疋1八有多個梳齒的梳狀電極》 等。 刀別可以具有例如直線狀、「<」狀 以下’參照附圖 號電極之較佳的形狀 的梳齒形狀的例子。 ’對本發明的液晶顯示元件中的信 進行說明。圖1和圖2表示梳狀電極 圖1的信號電極是星右夕/ /、有夕個由共通的背部1所產生之 梳齒2的梳狀信號電極 蚀圖1的销唬電極的梳齒2具有直線 狀的形狀。梳齒2的各個官译a ^来R ' 谷個寬度a和鄰接的2個梳齒兩個間 距離b的比a/b較佳為〇1〜5，# 更佳為0.5〜2。本發明的液晶 顯示元件由於液晶瓦。 狀 了以在梳齒2上進行電場響應，所以儘 官比a/b的值沒有過小，.一 J 也了以顯不尚開口率的晝面。a 和㈣各個值應當根據畫面大小和像素的精度適當設定 ，例如可以是1〜20_，進而可以是5〜1〇μιη。從背部磕 生梳齒2的部分的角度ω可以是例如7〇〜11〇。匚，較佳 75~l〇5°C » ‘、、' 梳齒2的長度L和數量，應根據顯示面積、像素數量 等適當設定。 圖2的彳s號電極和圖1的信號電極大致相同，值是在 從背部1產生的梳齒2具有「<」形的形狀方面是不同的 。圖2的信號電極中的梳齒2從背部j略微朝向右側產生， 在長度L中間，其方向略微向左側改變，在整體中具有「 201243461 〈」形的形狀。妆呰# , * 攸皆部1產生梳齒2的部分 L的中間改變方向的Α |刀的角度0和長度 万向的部分的角度δ分別如下所示。 角度Θ較佳為, 住為90〜11〇。，更佳為92 ， 佳為160〜180。，f #达 们且角度δ較 且自18Λ。 5〜178。，其中不包括角度9是9〇。 且角度δ疋180〇;或者 角度β較佳為7〇„ 為180〜200。，更佳為 且角度δ是180。。 90° ’更佳為75〜88。，且角度δ較佳 182〜195°，其中不包括角度Θ是9〇。 圖2的信號電極中的梳齒2較佳在長度l的中間改變 方向的位置可以是長度L的40〜60❶/。的部分，較佳為 45〜55%的部分。 π 圖2的信號電極中的a、b和L的值以及梳齒2的數量和 圖1的情形相同。 為了形成這種具有梳狀圖案的信號電極，可以藉由 例如形成無圖電極膜後，通過光蝕刻以形成圖案的方法 ;形成信號電極時，使用具有所希望的圖案之光罩的方 法等得到。 本發明的液晶顯示元件中的液晶配向膜在將其應用 於後述的正型液晶時，預傾角是〇. 2。以下。於此，所述 的預傾角是〇. 2。以下是指藉由該液晶配向膜，正型液晶 分子實質上在和膜面f行地配向’是允許液晶配向暝形 成面的凹凸等引起的不玎避免的液晶分子的少量傾斜的 含義。該預傾角較佳為0·1。以下’更佳為0.05。以下，最 佳為0^ 這種顯示出低預傾角的液晶配向膜可以由例如由聚 201243461 醢胺酸、聚醯胺酸的醯亞胺化聚合物、丙烯酸系樹脂和 聚有機矽氧烷所構成的群組中選出之至少一種有機高分 子所形成。作為本發明中的液晶配向膜較佳為由包：： 聚醯胺酸和聚酿胺酸的酿亞胺化聚合物所構成的群組令 選出之至乂一種有機高分子所形成的液曰曰日配向膜。 液晶配向膜可以藉由經過在基板上塗布包含上述較佳的 有機尚分子的液晶配向劑，形成 的步驟形成。 - 《者加熱該塗膜 以下對用於形成本發明中較佳的潘曰 晶配向劑進行說明。 日日配向膜的液 上述聚酿胺酸可以藉由使四叛酸 得到。藉由將該聚酿胺酸脫水閉 和二胺反應而 胺化聚合物。 Λ得到上述醯亞 作為上述四羝舱_ 硬馱一酐，可以列舉出 酸二針、脂環式四羧酸二酐、芳香族：脂肪族四羧 為該等之具體的例子，分別是作為脂肪族夂二針等。作 可以列舉出例如丁四羧酸二酐等； 、四羧酸二酐， 作為脂環式四竣酸二酐，可以列舉出偏 丁四缓酸二奸、2,3,5_三幾基環戊彳如1，2,3,4-環 l，3,3a，4,5,9b-六氳四氫_2,5_二側氣=乙酸二肝' [1，2-cKm鋼、i，3,3a,4,5,9b4 夫喃基）-蔡并 d!]辛·2,4.二嗣 _6_螺_3，（四氳^，3-二銅、3- )、5_(2,5-二側氧四氫_3_呋。南基㈠甲 -2’，5 -一酮 二甲酸酐、3，5,6-二游其9鉍田甘々土、3~環己烯-1，2- 一羧基-2-羧甲基降莰烷 一 St ' 201243461 2,4,6,8-四羧基二環[3·3‘〇]辛烷 _2:4,6:8-二酐、4,9-二吖三 環[5.3.1.〇2,6]十一烷_3,5,8，1〇_四酮等； 作為芳香族四羧酸二酐，可以列舉出例如均苯四酸 二酐等。 文 作為用於合成上述聚醯胺酸的四羧酸二酐，較佳為 5亥等之中包含脂環式四綾酸二酐的四羧酸二酐，進—步 較佳為包含由2,3,5_三綾基環戊基乙酸二酐和i 2 3 4产 ::缓酸二肝所構成的群組中選出之至少一種的四’二 作為用於合& 4 w 部四羧酸二醉成上述聚醯胺酸的四羧酸二酐，相對全 9Λ 較佳為包含1 Omol%以上、更佳*勺人 2〇m〇l%以上的 一 文佳為包含 環丁四羧酸，广二羧基環戊基乙酸二酐和1，2,3,4- 為只由從2,3,5-三：成：群組中選出之至少-種；最佳 羧酸二酐所構 基環戊基乙酸二酐和1，2,3,4-環丁四 作為上述Γ組中選出之至少-種所構成。 ----^胺，—p 、 、具有9，1〇_二备 W以列舉出例如具有薙結構的二胺 胺、芳香族二胺'了構的二胺、脂肪族二胺、脂環式二 分別是，作A〜胺基有機矽氧烷等。 例如2,7-二胺基寒 ^八有第結構的二胺，可以列舉出 作為具有9l〇下述式（1)所示的化合物等； 下述式（2)所示沾π〜氫蒽結構的二胺，可以列舉出例如 的化合物等。 -10- 201243461201243461 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal display element of a Fringe Field Switching Mode (hereinafter, also referred to as r FFS mode) and a liquid crystal alignment agent used therein And a method of forming a liquid crystal alignment film. More specifically, it relates to a liquid crystal display element which has a high light transmittance at the time of driving and which does not produce a poor display FFS mode. [Prior Art] As the display mode of the liquid crystal display element, TN mode (Twisted Nematic Mode), STN mode (Super Twisted Nematic Mode), and Super Alignment M (Vertical Alignment M) are currently known. In the so-called vertical electric field mode, the liquid crystal is driven in such a manner that liquid crystal is sandwiched between a pair of substrates composed of two substrates having electrodes, and is generated in a direction perpendicular to the surface of the substrate. electric field. These vertical electric field type liquid crystal display elements have a problem that the viewing angle is narrow. In the mode of improving the viewing angle while maintaining the vertical electric field method, the MVA mode (Multi-Domain Vertical AHgnment) is proposed. In contrast, the IPS mode is proposed as the horizontal electric field type liquid crystal display element (In_Plane Switching). In the case of the M〇de, the in-plane switching mode, the liquid is not 7L (see Patent Documents 丨 to 3 and Non-Patent Document 1). The liquid crystal display element of this mode is a T-type in which a pair of electrodes having a comb shape are formed on only one of a pair of substrates sandwiching the liquid crystal layer, and an electric field is generated in a horizontal direction with respect to the surface of the substrate to drive the liquid crystal. In the liquid crystal display element of the horizontal electric field 201243461, since the liquid crystal molecules respond to the electric field only in the direction parallel to the AL ^ ^ blast plate, there is no problem in the refractive index change of the long-axis direction w of the liquid crystal molecules 'even if the viewing angle is changed', the observer confirms j There is also a small change in the concentration of the wild scale and the display color. Therefore, it is possible to display a high-quality display without a phase A or _. However, since the liquid crystal does not undergo an electric field response on the electrode of the liquid crystal display element of the IPs mode (the comb-shaped upper portion of the comb-shaped electrode), it has a problem that the aperture ratio is low as compared with the liquid crystal display element of the vertical-field type. As a method of solving the problem of the aperture ratio while maintaining the viewing angle property of the IPS mode, a liquid crystal display element of the FFS mode (documents 4 to 6) has been proposed. This FFS mode has a structure in which a common electrode, an insulating layer and a signal electrode are sequentially formed on only one of the pair of substrates sandwiching the liquid crystal layer, and it can be said that a pair of electrodes are laminated. Here, the signal electrodes may be, for example, comb electrodes having a plurality of comb teeth arranged through a certain gap. However, if a voltage is applied between the electrodes, an arc-shaped electric field passing through the liquid crystal layer is generated between the region where the comb teeth are present and the comb teeth above the common electrode, thereby driving the liquid crystal. Therefore, the FFS mode can solve the aperture ratio problem in the lps mode because the liquid crystal responds to the electric field on the signal electrode. However, in the FFS mode, since the light transmittance is lowered at the time of driving, a poor display may occur, and the problem needs to be solved. [PRIOR ART DOCUMENT] [Patent Document 1] US Pat. No. 5,929,333, [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. [Non-patent document] [Non-patent document] [Non-patent literature] [Non-patent literature] [Non-patent document] [Non-patent document] [Non-patent document] [Non-patent document] [Non-patent document] l] "Liq. Cryst.,,, vol. 22, p379 (1996) [Summary of the Invention] [Problem to be Solved by the Invention] An object of the present invention is to solve the above problems of the FFS mode. That is, the object of the present invention is to provide The light transmittance at the time of driving is high, and the liquid crystal display element of the FFS mode which does not display poorly is not produced. [Means for Solving the Problem] The lower sub-question is based on the fact that the inventors have found that the low light transmittance when driving in the FFS mode is due to h. The liquid crystal alignment film near the surface of the liquid crystal alignment film is caused by the poor pre-tilt of 浠_% 日日·, thereby obtaining a liquid crystal display element which does not occur. That is, the above objects and advantages of the present invention Mode LCD display The element is formed by: sandwiching a liquid crystal layer between a pair of substrates; forming a common electrode, an insulating layer, a signal electrode, and a liquid crystal alignment layer on a surface of the liquid crystal layer side of one of the pair of substrates The liquid crystal layer is formed of a positive liquid crystal, and the pretilt angle of the liquid crystal alignment film is 〇2 〇 or less [effect of the invention], and according to the present invention, the light transmittance at the time of driving is high, resulting in poor display. In the liquid crystal display device of the FFS mode, the liquid crystal display device of the present invention has a wide viewing angle and excellent display quality, and can suppress the occurrence of poor display. Therefore, it is suitable for use in, for example, a liquid crystal television, a portable information terminal, or the like. [Mode for Carrying Out the Invention] The liquid crystal display device of the present invention is a liquid crystal display device of the FFS mode. The liquid crystal display device of the present invention is formed by sandwiching a liquid crystal layer between a pair of substrates. As the substrate used herein, for example, Glass such as floating glass or nano glass; polyethylene terephthalate, polybutylene terephthalate, a transparent substrate formed of a plastic such as polyethersulfone, polycarbonate, poly(alicyclic olefin) or poly(alicyclic olefin), etc. The thickness of the substrate is preferably 0.3 to 2 mm. 5 to 1 mm. The common electrode, the insulating layer, the signal electrode, and the liquid crystal alignment film are sequentially formed on the liquid crystal layer side surface of one of the pair of substrates in the liquid crystal display device of the present invention. For example, a NESA film (registered trademark of ppg Corporation, USA) formed of tin oxide (Sn〇2), an ITO film formed of indium oxide-tin oxide (IkOrSnO2), or the like. The shape of the common electrode may be a so-called "β film" having no pattern formed on one surface of the substrate, or may be a pattern electrode having an arbitrary pattern. The thickness of the common electrode is preferably from 10 to 200 nm, more preferably from 2 to 1 〇〇1. The common electrode can be formed on the substrate by a known method such as sputtering. Soil The insulating layer may be formed, for example, of tantalum nitride or the like. The thickness of the insulating layer is preferably 丨(9)~丨, 〇〇〇nm, more preferably 丨5〇~75〇 201243461 For example, chemical vapor deposition method nm. The insulating layer can be formed on the common electrode by a known method or the like. The above signal electrode can be formed by the same material as the above electrode. The signal electrode can be θ μ, β ^ ' ^ - UU # ^ ^ 疋 1 eight comb electrodes with a plurality of comb teeth, and the like. The blade may have, for example, a linear shape, a "<" shape, or an example of a comb shape which is a preferred shape of the reference electrode. The letter in the liquid crystal display element of the present invention will be described. 1 and 2 show the comb electrode of Fig. 1. The signal electrode of Fig. 1 is a comb-shaped signal electrode of the comb tooth 2 generated by the common back 1 and has a comb electrode of the pin electrode of Fig. 1. 2 has a linear shape. The ratio a/b of each of the widths a of the comb teeth 2 and the width b of the adjacent two comb teeth is preferably 〇1 to 5, and more preferably 0.5 to 2. The liquid crystal display element of the present invention is a liquid crystal tile. In order to make an electric field response on the comb teeth 2, the value of the a/b ratio is not too small, and the J is also used to show the surface of the opening ratio. The values of a and (4) should be appropriately set according to the screen size and the accuracy of the pixel, and may be, for example, 1 to 20 mm, and further may be 5 to 1 〇 μιη. The angle ω of the portion of the comb tooth 2 from the back may be, for example, 7 〇 to 11 。.匚, preferably 75~l〇5°C » The length L and the number of the ',,' comb teeth 2 should be set as appropriate according to the display area, the number of pixels, and so on. The 彳s electrode of Fig. 2 is substantially the same as the signal electrode of Fig. 1, and the value is different in the shape in which the comb teeth 2 generated from the back 1 have a "<" shape. The comb teeth 2 in the signal electrode of Fig. 2 are generated slightly from the back j toward the right side, and the direction is slightly changed to the left side in the middle of the length L, and has a shape of "201243461 <" in the whole. Makeup 呰 # , * 攸 All parts 1 produce the part of the comb 2 The middle of the L changes direction Α | The angle 0 of the knife and the length δ of the part of the universal direction are as follows. The angle Θ is preferably, and the living is 90 to 11 inches. More preferably 92, preferably 160~180. , f #达达 and angle δ is more than 18Λ. 5 to 178. , which does not include the angle 9 is 9 〇. And the angle δ 疋 180 〇; or the angle β is preferably 7 〇 „ is 180 to 200. More preferably, the angle δ is 180. 90° 'more preferably 75 to 88., and the angle δ is preferably 182~ 195°, wherein the angle Θ is not included. The position of the comb teeth 2 in the signal electrode of FIG. 2 preferably in the middle of the length l may be a portion of the length L of 40 to 60 ❶/, preferably 45. ～55% of the part π The values of a, b and L in the signal electrode of Fig. 2 and the number of comb teeth 2 are the same as in the case of Fig. 1. In order to form such a signal electrode having a comb pattern, for example, by A method of forming a pattern by photolithography after forming a non-graph electrode film; a method of forming a signal electrode using a photomask having a desired pattern, etc. The liquid crystal alignment film in the liquid crystal display element of the present invention is applied thereto. In the positive liquid crystal described later, the pretilt angle is 〇. 2 or less. Here, the pretilt angle is 〇. 2. The following means that the positive liquid crystal molecules are substantially in the film surface by the liquid crystal alignment film. f line alignment 'is the cause of the irregularities caused by the liquid crystal alignment 暝 forming surface The meaning of the slight tilt of the liquid crystal molecules is not limited. The pretilt angle is preferably 0.1. The following is more preferably 0.05. Below, preferably 0^ This liquid crystal alignment film exhibiting a low pretilt angle can be, for example, by poly 201243461 At least one organic polymer selected from the group consisting of a ruthenium-based polymer of a proline, a polyacrylic acid, an acrylic resin, and a polyorganosiloxane is used as the liquid crystal alignment film in the present invention. Preferably, the group consisting of: a polyaminic acid and a polyamidouric acid-imidized polymer is selected to be a liquid helium-aligning film formed by an organic polymer. It can be formed by a step of forming a liquid crystal alignment agent containing the above-mentioned preferred organic molecules on a substrate. - Heating the coating film to perform the preferred pan phthalocyanine alignment agent for forming the present invention Description: The liquid of the day-to-day alignment film can be obtained by making tetrazoic acid. The polymer is aminated by dehydrating the polyamic acid and reacting with a diamine.羝舱_ Hard 驮一Examples of the acid di-needle, the alicyclic tetracarboxylic dianhydride, and the aromatic: aliphatic tetracarboxylic acid are specific examples of these, and are, for example, an aliphatic bismuth needle, etc. Acid dianhydride, etc.; and tetracarboxylic dianhydride, as the alicyclic tetraphthalic acid dianhydride, may be exemplified by the serotonic acid, 2,3,5-trisylcyclopentanthene such as 1,2, 3,4-ring l,3,3a,4,5,9b-hexahydrotetrahydro-2,5_two-side gas=diacetate' [1,2-cKm steel, i,3,3a,4, 5,9b4 夫基基)-蔡和d!]辛·2,4.二嗣_6_ snail_3, (four 氲^,3-two copper, 3-), 5_(2,5-two sides Oxytetrahydro _3_fur. South base (a) methyl-2',5-monoketone dicarboxylic anhydride, 3,5,6-two-sweeping 9 铋田甘々土, 3~cyclohexene-1,2- Carboxy-2-carboxymethylnorbornane-St ' 201243461 2,4,6,8-tetracarboxybicyclo[3·3'〇]octane_2:4,6:8-dianhydride, 4,9 - Dioxetane [5.3.1.〇2,6]undecane_3,5,8,1〇-tetraketone, etc.; as the aromatic tetracarboxylic dianhydride, for example, pyromellitic acid Anhydride, etc. As the tetracarboxylic dianhydride for synthesizing the above polyamic acid, a tetracarboxylic dianhydride containing an alicyclic tetraphthalic dianhydride is preferably used in the case of 5 kel, etc., and preferably comprises 2 , 3,5_tridecylcyclopentyl acetic acid dianhydride and i 2 3 4 production: at least one selected from the group consisting of acid-lowering di-hepatic is used for the combination & 4 w tetracarboxylic acid The dicarboxylic acid is intoxicated into the above-mentioned polyamic acid tetracarboxylic dianhydride, and it is preferably contained in an amount of more than 10%, more preferably more than 1% by mole, more preferably more than 2% by mole, more preferably containing cyclobutanetetracarboxylic acid. , bis-carboxycyclopentyl acetic acid dianhydride and 1,2,3,4- are at least one selected from the group consisting of 2,3,5-three: into: group; optimal carboxylic dianhydride structure The Cyclopentylacetic acid dianhydride and the 1,2,3,4-cyclobutane are formed as at least one selected from the above group. -----amine, -p, , having 9,1 〇_二备W, for example, a diamine, an aromatic diamine having a fluorene structure, a diamine, an aliphatic diamine, an alicyclic ring Formula 2 is, for example, A~amino-based organooxane and the like. For example, a diamine having a 2,7-diamino group having a first structure may be exemplified as a compound having the formula (1) and having the following formula (1); The diamine of the structure may, for example, be a compound or the like. -10- 201243461
(式（1)和（2)中的R1分別是單鍵、伸苯基、基-Ph-Ο(其中 ，Ph是伸苯基，連接的方向不限。） R2分別是碳原子數為1〜6的烷基、碳原子數為1〜6的烷氧 基或鹵原子； a分別是0〜4的整數；而且 複數個a和複數個R1以及存在時的多個R2可以分別為相 同，也可以為不同。） 分別是，作為上述式（1)所示的化合物，可以列舉出 例如下述式（1-1)〜（1-3)分別表示的化合物等； -11 - 201243461 作為上述式（2)所示的化合物，可以列舉出例如下述 式（2-1)〜（2-3)分別表示的化合物等。(R1 in the formulae (1) and (2) are a single bond, a phenyl group, and a phenyl-Ph-fluorene, respectively (wherein Ph is a phenyl group, and the direction of attachment is not limited.) R2 is 1 carbon atom, respectively. An alkyl group of 1-6, an alkoxy group having 1 to 6 carbon atoms or a halogen atom; a each being an integer of 0 to 4; and a plurality of a and a plurality of R1 and a plurality of R2 in existence may be the same, In addition, as the compound represented by the above formula (1), for example, a compound represented by the following formulas (1-1) to (1-3), etc.; -11 - 201243461 The compound represented by the formula (2), for example, a compound represented by the following formulas (2-1) to (2-3), and the like.
H2 NH2 N
NH2 (1-1)NH2 (1-1)
(1-2)(1-2)
(2-1) -12- 201243461(2-1) -12- 201243461
(2-3) 作為上述以外的二胺，分別是作為脂肪族二胺，可 以列舉出例如間苯二曱胺、1，3-丙二胺、1，4-丁二胺、1，5-戊二胺、1,6-己二胺等； 作為脂環式二胺，可以列舉出例如1,4-二胺基環己 烷、4,4’-亞曱基二（環己基胺）、1，3-二（胺基甲基）環己烷 等； 作為芳香族二胺，可以列舉出例如對苯二胺、4,4 ’ -二胺基二苯基曱烷、4,4’-二胺基二苯基硫醚、1，5 -二胺 基萘、2,2’-二曱基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-二（三氟曱基）聯苯、4,4’-二胺基二苯基醚、2，2-二[4-(4-胺基苯氧基）苯基]丙烷、4,4’-(對伸苯基二伸異丙基）二（ -13- 201243461 苯胺广七^⑽伸苯基二伸異丙基以苯胺广七^二。 胺基苯氧基）聯苯、2,6_二胺基吼咬、3,4_二胺基定、 2,4-二胺基。密D定、3,6_二胺基。丫咬、3,6_二胺基#唾、Ν· 甲基-3,6-二胺基味唾、N_乙基_3,6_二胺基味嗤、&苯基 -3，^二胺基咔唑、M•二_(4胺基苯基）-哌啩、3,5_二胺 基本甲酸、1’1_二（4-((胺基苯基）甲基）苯基）4 丁基環己 烷、l’l-二（4-((胺基苯基）f基）苯基）4·庚基環己烷、丨卜 二（4_((胺基苯氧基）甲基）苯基）4庚基環己烷、丨，丨’二 (4 ((胺基苯基）甲基）苯基庚基環己基）環己烷，以 及具有g結構的二胺和具有9, ！ Q•二氫蒽結構的二胺等； 作為一胺基有機矽氧烷，可以列舉出例如1，3-二（3· 胺基丙基）-四甲基二矽氧烷等。 作為上述二胺較佳為包含由具有第結構的二胺和具 —9，1〇·二氫蒽結構的二胺所構成的群組中選出之至少 _ 作為上述一胺中由具有苐結構的二胺和具有9, ι〇_ 氫蒽結構的二胺所構成的群組中選出之至少一種的比 ’相對於全部二胺，較佳為5〇m〇i%以上更佳為7—。 ’特佳為90m〇1%以上。最佳為作為二胺只使用由具 另弗結構的二胺和具有9 1 〇 _ $ # Τ八有I10· 一虱恩結構的二胺所構成 的群虹中選出之至少一種。 另外’作為聚醯胺酸及其醯亞胺化聚合物之原料的 :酸二肝和二胺分別較佳為具有留族骨架的基團、（ 二環己基、（烧基）聯苯基、（烧基）環己基苯基、碳 基和^為A以上的烧基、碳原子數為2以上的敦院基、氰 ^說原子之任意情形的基團。 -14- 201243461 合成聚醯胺酴n生 双k時，四羧酸二酐和二胺的 相對於1當量二胗认M w 巾比例， 艰^的胺基，四羧酸二酐的酸酐基軔 0 · 2〜2當量的比仓| 圭為 例’更佳為0.3〜1.2當量的比例。 聚醯胺酸的人士 σ成反應較佳為在有機溶劑中進杆 佳在-2CTC〜150V * u 。 較 ’更佳在0 C〜1 0 0 °C下’較佳為進 0.1〜24小時，# Q硬仃 ^ 更佳為進行0.5〜12小時。 此處’作為有機溶劑，可以列舉出例如非質 性溶劑、苯酚及复舛+ 4 極 一何生物、醇、酮、酯、喊、鹵化煙、 烴等。作為有機溶劑的具體例子，可以列舉出例如 基吡咯啶酮、γ_丁内酯、丁基溶纖劑、N，N-二甲基乙醯 胺、N，N-二曱基曱醯胺、N，N-二曱基咪唑啶酮、二甲基 亞砜、四甲基脲、六曱基磷酸三醯胺等，較佳為使用： 自δ亥專之中的一種以上。 藉由將如上得到的聚醯胺酸脫水閉環醯亞胺化，可 以得到聚醯胺酸的醯亞胺化聚合物。 聚醯胺酸的脫水閉環較佳以藉由加熱聚醯胺酸的方 法，或者將聚醯胺酸溶解在有機溶劑中，在該溶液中添 加脫水劑和脫水閉環催化劑、根據需要加熱的方法進行 。其中，較佳為以後者方法進行。 在上述聚醯胺酸溶液中添加脫水劑和脫水閉環催化 劑的方法中，作為脫水劑，可以列舉出例如乙酸酐、丙 酸酐、三氟乙酸酐等酸酐。脫水劑的使用比例，相對於 lmol聚醯胺酸的醯胺酸結構，較佳為〇 〇l〜2〇m〇^作為 脫水閉環催化劑，可以列舉出例如吡咬、三甲基吡〇定、 二曱基吡啶、三乙胺等三級胺。脫水閉環催化劑的使用 201243461 比例’相對於lmol使用的脫水劑，較佳為o.oi〜i〇mol。 作為脫水閉環反應中使用的有機溶劑，可以列舉出 作為合成聚醯胺酸使用的溶劑例示的有機溶劑。 脫水閉環反應的反應溫度較佳為〇〜1 8 〇 °c，更佳為 10〜150C。反應時間較佳為1·0〜120小時，更佳為2.0〜30 小時。 又，上述聚醯胺酸、聚醯胺酸的醯亞胺化聚合物基 於凝膠滲透色譜（GPC)測定所得的聚苯乙烯換算重量平 均分子量（Mw)較佳為1〇00〜500000，特佳為2〇〇〇〜3〇〇〇〇〇 。且，Mw與基於凝膠滲透色譜（GPC)測定所得的聚苯乙 烯換算數量平均分子量（Mn)的比（Mw/Mn)較佳為15以下 ，特佳為1 0以下。因處於如此的分子量範圍申，可確保 液晶顯示元件的良好的配向性以及穩定性。 本發明中的液晶配向劑較佳為包含有機高分子，嗦 有機高分子包含由上述這種聚醯胺酸和聚醯胺酸的醯： 胺化聚合物所構成的群組中選出之至少一種； 更佳為包含一種有機高 .....乃例1肉分子包合占 聚醯胺酸和前述聚醯胗舻&航π p h w 3田 J述眾醞胺酉夂的醯亞胺化聚合物所構成的教 組中選出之至少-種(以下，稱作「特定聚合物成)的群 Q聚醯胺酸是四缓酸二軒和由具有第結構的二胺」二該 9,10-二氫蒽結構的_ 芽具有 僻π —胺所構成的群組中 種的二胺反應得到的。 至少一 有機聚合物在含有特 ’作為其它聚合物較佳為 胺酸、該聚醯胺酸的醯亞 -16 - 種。 有機高分子的總量，作為本 定聚合物的含有比例，較佳 里〇/°以上，進一步更佳為1 0 0 較佳為將如上有機高分子溶 液而製備。作為上述溶劑， 性溶劑、苯酚及其衍生物、 煙等中選出之至少一種，特 、丁基溶纖劑、γ _ 丁内醋、 曱基甲酿胺、Ν，Ν -二曱基〇米 基腺和六曱基磷酸三醯胺等 以上。 機高分子的含有比例，较佳 重量％。 顯示元件中的液晶配向膜， 法進行，該步驟是：在依次 號電極的基板的信號電極上 配向劑，形成塗膜，接著加 述的在基板的「信號電極上 不一定要解釋為該字的字面 極是具有多個梳齒的梳狀電 它梳齒的間隙露出絕緣層， 具有通常知識者應當瞭解不 包含下述情形：由在信號電 201243461 構成的群組中選出之至少— 相對於液晶配向劑中的 發明中的液晶配向劑中的特 為5 0重量％以上，更佳為8 〇重 重量％。 本發明中的液晶配向劑 解到適當的溶劑中，作為溶 可以使用例如由非質子性極 醇、酮、g旨、醚、鹵化烴、 佳為使用由N-甲基吡咯啶酮 Ν,Ν-二甲基乙醞胺、N，N-二 唑啶酮、二曱基亞砜、四曱 所構成的群組中選出的一種 作為液晶配向劑中的有 為1〜10重量％，更佳為1.5〜9 為了形成本發明的液晶 可以藉由經過下述步驟的方 形成共用電極、絕緣層和仏 ，塗布包含如上所述的液晶 熱該塗膜的步騍。這裡’所 」形成液晶配向劑的塗膜’ 含義。例如，在上述信號電 極時，由於梳齒和鄰接的其 所以本發明所屬技術領域中 僅是上述文字所述’而且還 -17- 201243461 區域和在絕緣層上形成液晶配向 極上形成液晶配向膜的 膜的區域所構成。 極上塗布液晶配向劑的方法， 旋塗法、印刷法、喷墨法等適 作為在基板的信號電 可以列舉出例如輥塗法、 當的塗布方法。 形成的塗膜較佳兔益+ ^ 与藉由預加熱（預烘烤），然後燒製（ 後烘焙）形成有機膜。預 （ _ 頌烤條件例如是在4 0〜1 2 0 °C下進 行0.1〜5分鐘，後批缺政& + 八烤條件較佳為在120〜300。(：、更佳爲 在150〜250。(：下，較伟主'e a 佳為進仃5〜200分鐘，更佳為進杆 10〜100分鐘。 、後供烤後的有機膜的膜厚較佳為為0.001〜Ιμηι，更佳 為 0.005〜〇·5μπι。 、塗布液Ba S己向劑時，為了使信號電極或絕緣層與形 成的液晶配向膜的點合性更好，可以在信號電極和絕緣 層上預先塗布官能枓HP 1 月b f生矽烷化合物、鈦酸鹽化合物等，加 熱，進行前處理。 在這樣形成的液晶配向膜中可以藉由周知方法進行 摩擦處理，為了最大限度地發揮出本發明的效果，較佳 為不進行摩擦處理。 本發明的液晶顯示元件如下構成：使用如上依次形 成/、用電極、絕緣層、信號電極和液晶配向膜的基板與 沒有這些電極的基板（對向電極）作為一對，在該一對基 板間夾住液晶層所構成。於此，形成共用電極等的基板 以形成該等的面側朝向液晶層而使用。 對向電極可以具有液晶配向膜，也可以沒有。為了 -18- 201243461 在對向基板上形成配向膜，降7 * 认直4 a * β 力了使用不形成共用電極箄 的基板作為基板以外，可以知L、、 .t . 上述同樣地進行0對向其 板較佳為具有液晶配向膜。 土 本發明的液晶顯示元件的 &心』、 夜晶層較佳為由正型液晶 所形成。作為該正型液晶，較 又住為棒狀的正型液晶。 液晶層的厚度（信號電極釦 #對向基板的距離）較佳為 3〜ΙΟμιη。 7 在製造這種液晶顯示元件拉 凡件時’可以列舉出例如下述 兩種方法。 第一種方法是首先透過間隙,人 υ处、间隙（盒間隙），將一對基板 對向配置，使用密封劑將兩塊基 瓜丞板的周圍部貼合。此時 ’是在基板上形成液晶配向膜辇 1 J眠寺的基板時，該面朝向對 向配置的内側。然後’在藉由基板表面和密封劑區分的 盒間隙内注入填充正型液晶後，密封注入孔，藉由該方 法，可以製造液晶顯示元件。 第二種方法是，在一對基板中的一個基板上（在基板 上形成液晶配向膜等的基板的情況下所對應的面）的規 定位置’例如塗布紫外光固化性密封材料，然後在基板 面（或者液晶配向膜的面）上的規定幾個位置滴加正型液 晶後’貼合和另一個基板（是在基板上形成液晶配向膜等 的基板的情況下，是該面的下方），同時將正型液晶在基 板整面鋪開，然後，對透明基板的整面照射紫外光，將 密封劑固化，可以製造液晶顯示元件。 然後，在上述一對基板的各外側表面較佳為貼合偏 光片。 -19- 201243461 作為上述密封劑，可以你田/丨，A ^ w J以使用例如含有作為隔片的氧 化紹球和固化劑的環氧樹脂等。 作為貼合到—對基板的各外側表面的偏u，可以 列舉出邊將聚乙浠醇延展配向，邊用醋酸纖維素保護膜 夾住已吸收碘的稱作「Η膜的 狀」w侷光膜形成的偏光片或由 Η膜本身所形成的偏光片等。 本發明的液晶顯示元件中，對於上述說明以外的事 項可以是和現有技術文獻中記載的相同的方案，或者加 入了本發明所屬技術領域中具有通常知識者周知的或發 揮出一般的想像力引起之變化的方案。 [實施例] 合成例1 將44.83g(0.20mol)的2,3,5_三羧基環戊基乙酸二酐 和69.69g(0.2〇m〇l)上述式（1])所示的化合物溶解到565g 的γ-丁内酯中’在60ec下反應6小時。 將得到的反應溶液注入大量過量的甲醇中，使反應 產物沉澱後回收沉澱物，用甲醇洗滌、減壓、4〇它下乾 燥1 5小時，得到U 2.3 g聚醯胺酸。該聚醯胺酸的對數黏 度（Ή1 η)是 1.22dl/g。 將上述得到的聚醯胺酸中的4 〇 〇 g溶解到8 〇 〇 g的丫 · 丁 内酯中，在該溶液中添加35 2g吡啶和27 6g乙酸酐，在i 1〇 C下進行4小時脫水閉環反應（醯亞胺化反應）。接著，和 上述聚醯胺酸的情形同樣地進行反應產物的沉澱、分離 、洗滌、乾燥，得到3 8 · 5 g醯亞胺化聚合物（PI_丨）。該醯 亞胺化聚合物（PI-1)的對數黏度（?11[1)是丨23dl/g。 -20- 201243461 合成例2 除了在上述合成例1中’使用75.29g(〇.20mol)上述式 (1 -2)所示的化合物代替上述式（1 -1)所示的化合物以外 ’和合成例1同樣地得到1〇7.88對數黏度（11111)為1.08(11/§ 的聚酿胺酸。 接著’除了使用上述聚醯胺酸中的40.0g以外，和合 成例1同樣地進行脫水閉環反應’得到3 7.5 g醯亞胺化聚 合物（PI-2)。該醯亞胺化聚合物（PI-2)的對數黏度（η1η)是 1.13dl/g。 合成例3 除了在上述合成例1中’使用60.23g(0.16mol)上述式 (1-2)所示的化合物和4.32g(0.04mol)對苯二胺代替上述 式（1 -1)所示的化合物以外，和合成例1同樣地，得到 107.2g對數黏度為1.15dl/g的聚醯胺酸。 接著，除了使用上述聚醯胺酸中的40.Og以外，和合 成例1同樣地進行脫水閉環反應，得到38.Og醯亞胺化聚 合物（PI-3)。該醯亞胺化聚合物（PI-3)的對數黏度是 1 · 1 7dl/g。 比較合成例1 除了在上述合成例1中，使用l〇.8g(〇.l〇mol)對苯二 胺和52_38(0.1〇111〇1)的3,5-二胺基苯曱酸3-膽甾烷基酯代 替上述式（1-1)所示的化合物以外’和合成例1同樣地，得 到105.7g對數黏度（η1η)為1.23dl/g的聚醯胺酸。 接著，除了使用上述聚醯胺酸中的40. Og以外，和合 成例1同樣地進行脫水閉環反應，得-到38.Og醯亞胺化聚 -21 - 201243461 合物（pi-1)。該酿亞胺化聚合物（rpi_l)的對數黏度（η|η)是 1.34dl/g。 比較合成例2 除了在上述合成例1中，使用2〇.16g(〇.20mol)對苯二 胺代替上述式（1-1)所示的化合物以外，和合成例1同樣地 得到63.7g對數黏度為l.25dl/g的聚醯胺酸。 接著’除了使用上述聚醯胺酸中的40.0g以外，和合 成例1同樣地進行脫水閉環反應，得到3 7.8 g醯亞胺化聚 合物（rpi-2)。該醯亞胺化聚合物（rpi_2)的對數黏度是 1.28dl/g。 實施例 在以下的實施例中，製造本發明的液晶顯示元件， 進行其運行確認。 圖3中表示用於說明實施例和比較例製造的液晶顯 示元件100的結構的剖視圖。該液晶顯示元件100在基板 101和對向基板102中夾住液晶層1〇3形成，其中基板101 是依次形成玻璃基板l〇la、ITO (In203-Sn02)膜的共用電 極101b、氮化矽的絕緣層101c、IT〇膜的信號電極101d 和液晶配向膜10 le的基板，對向基板1〇2是只在玻璃基板 102a上形成液晶配向膜1〇2b的基板。 該液晶顯示元件1〇〇的信號電極101d是具有直線狀 梳齒的梳狀電極。共用電極是沒有圖案的「β膜」。 該液晶顯示元件1 00分別在基板丨〇 1、對抗基板1 〇2 的外侧兩面配置偏光片（未圖示），在圖3的下側的基板 1 0 1下方配置背光（未圖示），和該元件組合使用。 -22- 201243461 實施例1 <液晶配向劑的製備> 將作為有ϋκ ·*、 機阿分子的上述合成例1所得到的醯亞胺 化本δ物（ΡΙ·1)溶解到由50重量份Ν-甲基吡咯啶酮和5〇 重畺伤之丁基,谷纖劑形成的混合溶劑中’形成聚合物濃 度3重$ %的溶液。該溶液使用孔徑0.2μιη的過滤器過據 ’製備液晶配向劑。 <液晶配向膜的形成> 在依次形成共用電極、絕緣層和信號電極的基板的 電極等形成面、以及沒有形成它們的對向基板的一面上 ，分別使用旋塗器塗布上述液晶配向劑，形成塗膜，將 該塗膜在8CTC下預烘烤1分鐘，然後，在2〇(rc下後烘烤1 小時’形成平均膜厚600 A的液晶配向膜。 <液晶顯示元件的製造> 將如上分別形成液晶配向膜的一對基板的液晶配向 膜面相對地通過厚度1 〇 μπι的隔片對向配置後，留出液晶 注入口 ’密封側面。從液晶注入口注入棒狀的正型液晶 後，密封液晶注入口。 接著，藉由在兩基板的外側面分別貼合偏光片，製 造FFS模式的液晶顯示元件。於此，兩塊偏光片是其偏光 方向相互正交’而且和信號電極所具有的梳齒的方向平 行或垂直地貼合。 〈液晶顯示元件之操作確認> 對上述製造的液晶顯示元件測定未施加電壓時的可 見光透射率、以及在共用電極和信號電極間施加5 V交流 -23- 201243461 電壓時的可見光透射率 結果如表1所示。 然後， 線漏過時， 傾斜不良。 目視研究驅動時信號電極的梳齒附近有無光 沒有觀察到光線漏過，推測沒有產生相反預 實施例2和3以及比較例丨和2 除了在上述實施例丨的 <液晶配向劑的製備 > 中，分別 使用表1所5己載的有機高分子作為有機高分子以外，和實 ，例1同樣地製備液晶配向劑，使用該液晶配向劑製造液 晶顯示元件，進行操作確認。 結果如表1所示 [表1] 液晶配向劑 液晶顯示元件 有機高分子 種類 預傾角 (度） 可見光透射率(％) 運行時 光線漏過 未施加電壓時 施加電壓時 實施例1 PI-1 0.0 0.1 95 無 實施例2 PI-2 0.0 0.3 93 無 實施例3 PI-3 0.2 0.3 90 無 比較例1 rpi-1 3.0 0.3 84 有 比較例2 rpi-2 1.5 0.3 85 有 【圖式簡單說明】 圖1疋用於說明本發明的液晶顯示元件的信號電極 的一個例子的概況圖。 圖2疋用於說明本發明的液晶顯示元件的信號電極 的另一個例子的概況圖。 圖3是表示實施例和比較例製造的液晶顯示元件的 結構的剖視圖。 -24- 201243461 【主要元件符號說明】 1 背 部 2 梳 齒 100 液 晶 顯 示 元件 101 基 板 101a 玻 璃 基 板 101b 共 用 電 極 101c 絕 緣 層 101d 信 號 電 極 lOle 液 晶 配 向 膜 102 對 向 基 板 102a 玻 璃 基 板 102b 液 晶 配 向 膜 a 寬 度 b 距 離 L 長 度 ω 角 度 δ 角 度 θ 角 度 -25-(2-3) The diamines other than the above are each an aliphatic diamine, and examples thereof include isophthalamide, 1,3-propanediamine, 1,4-butanediamine, and 1,5-. Pentaamine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-arylene di(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane; etc.; as the aromatic diamine, for example, p-phenylenediamine, 4,4 '-diaminodiphenylnonane, 4,4'- Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimercapto-4,4'-diaminobiphenyl, 4,4'-diamino-2,2 '-Di(trifluoromethyl)biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4 '-(p-phenylene di-extension isopropyl) bis( -13- 201243461 aniline guangqi^(10) phenyl di-extension isopropyl to aniline guangqi^^. Aminophenoxy)biphenyl, 2, 6-diamine-based bites, 3,4-diaminolated, 2,4-diamino. D, 3,6-diamine. Bite, 3,6-diamino-based saliva, oxime-methyl-3,6-diamine-based saliva, N-ethyl-3,6-diamine-based miso, &phenyl-3, ^Diaminocarbazole, M•di-(4-aminophenyl)-piperazine, 3,5-diamine basic formic acid, 1'1_bis(4-((aminophenyl)methyl)benzene 4) butylcyclohexane, l'l-bis(4-((aminophenyl)fyl)phenyl)4.heptylcyclohexane, bismuth (4_((aminophenoxy) a methyl)phenyl)4heptylcyclohexane, anthracene, fluorene bis(4((aminophenyl)methyl)phenylheptylcyclohexyl)cyclohexane, and a diamine having a g structure With 9,! The diamine or the like of the Q-indoline structure; and the monoaminoorganooxane may, for example, be 1,3-bis(3·aminopropyl)-tetramethyldioxane. The diamine preferably contains at least one selected from the group consisting of a diamine having a first structure and a diamine having a structure of -9,1 indenyl dihydroanthracene. The ratio of at least one selected from the group consisting of a diamine and a diamine having a 9, oxime hydroquinone structure is preferably 5 〇m〇i% or more and more preferably 7 to all diamines. 'Specially good is 90m 〇 1% or more. It is preferable to use at least one selected from the group consisting of diamines having a different structure and diamines having a structure of 9 1 〇 _ $ # Τ8 having an I10· 虱 虱 structure as a diamine. Further, 'as a raw material of polylysine and its quinone imidized polymer: diuret and diamine are preferably a group having a leaving skeleton, (dicyclohexyl, (alkyl) biphenyl, a group in which a cyclohexylphenyl group, a carbon group, and a group having a carbon atom number of A or more, a group having a carbon number of 2 or more, and a cyano group atom may be used. -14- 201243461 Synthetic polyamine When 双n produces double k, the ratio of tetracarboxylic dianhydride and diamine relative to 1 equivalent of dioxime Mw towel, the amine group, the acid anhydride group of tetracarboxylic dianhydride 轫 0 · 2~2 equivalent BIT | For example, the ratio is preferably 0.3 to 1.2 equivalents. The sigma reaction of polylysine is preferably in the organic solvent at -2 CTC ~ 150 V * u. More than 'better in 0 It is preferable to carry out from 0.1 to 24 hours, and it is preferable to carry out from 0.5 to 12 hours at C to 1 0 0 ° C. Here, as the organic solvent, for example, an amorphous solvent, phenol, and the like are mentioned.舛 舛 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Lactone, butyl cellosolve, N,N-dimethylacetamide, N,N-didecylguanamine, N,N-dimercaptoididinone, dimethyl sulfoxide, tetramethylurea And tridecylamine hexamethylphosphoric acid, etc., preferably used: one or more selected from the group consisting of δ hai special. The ruthenium of polyglycine can be obtained by the imidization of the polylysine obtained by dehydration The imidization polymer. The dehydration ring closure of the poly-proline is preferably carried out by heating the poly-proline, or dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. In the method of adding the dehydrating agent and the dehydration ring-closure catalyst, the dehydrating agent may, for example, be acetic anhydride or propionic anhydride. An acid anhydride such as trifluoroacetic acid anhydride. The use ratio of the dehydrating agent is preferably 〇〇1 to 2〇m〇^ as a dehydration ring-closure catalyst with respect to the structure of the proline acid of 1 mol of polyamic acid, and examples thereof include a pyridation. Trimethylpyridinidine, dimercaptopyridine, triethylamine, etc. The amine is used. The use of the dehydration ring-closing catalyst is 201243461. The ratio 'is relative to 1 mol of the dehydrating agent used, preferably o. oi to i 〇 mol. As the organic solvent used in the dehydration ring-closure reaction, it can be exemplified as the synthetic polylysine. The solvent is exemplified as the organic solvent. The reaction temperature of the dehydration ring closure reaction is preferably 〇~1 8 〇°c, more preferably 10 to 150 C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours. Moreover, the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement of the polyaminic acid or polyaminic acid quinone imidized polymer is preferably from 1 to 00 to 500,000. Very good for 2〇〇〇~3〇〇〇〇〇. Further, the ratio (Mw/Mn) of the Mw to the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 15 or less, and particularly preferably 10 or less. Due to such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured. The liquid crystal alignment agent in the present invention preferably comprises an organic polymer, and the ruthenium organic polymer comprises at least one selected from the group consisting of ruthenium: aminated polymers of the above polylysine and polyphthalic acid. More preferably, it contains an organic high..... is a case in which the meat molecules are contained in the polyaminic acid and the aforesaid polyazide is a ruthenium imine. The group Q polyproline which is selected from at least one of the groups consisting of polymers (hereinafter referred to as "specific polymer formation" is tetrazoic acid and the diamine having the first structure". The _ bud of the 10-dihydroindole structure is obtained by reacting a diamine of a species consisting of a group of π-amines. At least one of the organic polymers contains a specific polymer as the other polymer, preferably an amine acid, and the polyaminic acid. The total amount of the organic polymer, as the content ratio of the polymer, is preferably 〇/° or more, and more preferably 100%, preferably prepared by dissolving the above organic polymer solution. As the solvent, at least one selected from the group consisting of a solvent, a phenol and a derivative thereof, and a smoke, etc., a special butyl cellosolve, a γ-butyrolactone, a mercaptoamine, an anthraquinone, an anthracene-dimercapto-carbyl gland And tridecylphosphoric acid and the like. The content of the organic polymer is preferably in the weight%. The liquid crystal alignment film in the display element is subjected to a method of forming a coating film on the signal electrode of the substrate of the sequential electrode to form a coating film, which is not necessarily interpreted as a word on the signal electrode of the substrate. The literal pole is a comb-shaped electric motor with a plurality of comb teeth. The gap of the comb teeth exposes the insulating layer. It should be understood by those of ordinary knowledge that the following situation is not included: at least selected from the group consisting of signal power 201243461 - relative to The liquid crystal alignment agent in the liquid crystal alignment agent is particularly preferably 50% by weight or more, more preferably 8% by weight. The liquid crystal alignment agent in the present invention is dissolved in a suitable solvent, and can be used as a solvent, for example, by Aprotic alcohols, ketones, ketones, ethers, halogenated hydrocarbons, preferably used by N-methylpyrrolidone oxime, Ν-dimethylacetamide, N,N-oxazolidinone, dimercapto One selected from the group consisting of sulfoxide and tetrathracene is 1 to 10% by weight, more preferably 1.5 to 9 as the liquid crystal alignment agent. To form the liquid crystal of the present invention, it can be formed by the following steps. Common electrode, insulation layer and仏, a step of coating the coating film containing the liquid crystal as described above is applied. Here, the meaning of the coating film of the liquid crystal alignment agent is formed. For example, in the above-mentioned signal electrode, due to the comb teeth and the adjacent ones, in the technical field of the present invention, only the above-mentioned texts are described, and also the -17-201243461 region and the liquid crystal alignment film are formed on the insulating layer to form a liquid crystal alignment film. The area of the membrane is composed. The method of applying the liquid crystal alignment agent to the electrode, the spin coating method, the printing method, the ink jet method, etc., is suitable as the signal electric power on the substrate, for example, a roll coating method or a coating method. The formed coating film is preferably rabbit-friendly and formed by pre-heating (pre-baking) and then firing (post-baking) to form an organic film. The pre- ( _ 颂 roasting condition is, for example, carried out at 40 to 120 ° C for 0.1 to 5 minutes, the latter batch of vacancy & + eight roasting conditions are preferably in the range of 120 to 300. (:, more preferably at 150 ~250. (: Next, the more beautiful main 'ea good for 5~200 minutes, more preferably 10 to 100 minutes into the rod. The film thickness of the organic film after baking is preferably 0.001~Ιμηι, More preferably, it is 0.005~〇·5μπι. When the coating liquid Ba S is used as a solvent, in order to make the signal electrode or the insulating layer and the formed liquid crystal alignment film have better dot-cohesion, the functional electrode and the insulating layer may be pre-coated with a functional group.枓HP January bf decane compound, titanate compound, etc., heated and pretreated. The liquid crystal alignment film thus formed can be subjected to a rubbing treatment by a known method, in order to maximize the effect of the present invention, The liquid crystal display element of the present invention is configured to use a substrate in which an electrode, an insulating layer, a signal electrode, and a liquid crystal alignment film are sequentially formed as described above, and a substrate (opposing electrode) having no such electrode as a pair. Between the pair of substrates The liquid crystal layer is formed by forming a substrate such as a common electrode, and the surface side is formed to face the liquid crystal layer. The counter electrode may or may not have a liquid crystal alignment film. For the -18-201243461 on the opposite substrate The alignment film is formed on the surface, and the thickness of the film is reduced by 4*. 4: * * * The substrate is not used as the substrate, and it is known that the substrate is not formed with the common electrode 箄. The alignment film is preferably formed of a positive liquid crystal of the liquid crystal display element of the present invention. As the positive liquid crystal, a positive liquid crystal which lives in a rod shape is further used. (Signal electrode button #distance to the substrate) is preferably 3 to ΙΟμιη. 7 In the manufacture of such a liquid crystal display element, the following two methods can be cited. The first method is to first pass through the gap. A pair of substrates are arranged opposite to each other, and a pair of substrates are disposed opposite to each other, and a sealing agent is used to bond the peripheral portions of the two base plates. At this time, a liquid crystal alignment film is formed on the substrate. When the substrate The surface faces the inner side of the opposite arrangement. Then, after the positive liquid crystal is filled in the cell gap separated by the substrate surface and the sealant, the injection hole is sealed, and by this method, the liquid crystal display element can be manufactured. a predetermined position on a substrate of a pair of substrates (a surface corresponding to a substrate in which a liquid crystal alignment film or the like is formed on a substrate) is applied, for example, to a UV curable sealing material, and then to a substrate surface (or liquid crystal alignment) A positive liquid crystal is dropped at a predetermined position on the surface of the film, and then the other substrate (when a substrate such as a liquid crystal alignment film is formed on the substrate, the lower surface of the surface is formed), and the positive type is simultaneously The liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the transparent substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal display element can be manufactured. Then, it is preferable to apply a polarizer to each outer surface of the pair of substrates. -19- 201243461 As the above-mentioned sealant, it is possible to use, for example, an epoxy resin containing an oxidized glass as a separator and a curing agent, and the like. The offset u to the outer surface of the substrate is exemplified by the fact that the polyethylene oxide is stretched and aligned, and the cellulose acetate protective film is sandwiched between the iodine-absorbing film. A polarizer formed of a light film or a polarizer formed of a ruthenium film itself. In the liquid crystal display device of the present invention, matters other than those described above may be the same as those described in the prior art documents, or may be caused by a person having ordinary knowledge in the technical field to which the present invention pertains or exerting a general imagination. The program of change. [Examples] Synthesis Example 1 44.83 g (0.20 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 69.69 g (0.2 mmol) of the compound represented by the above formula (1)) were dissolved. It was reacted to 565 g of γ-butyrolactone at 60 ec for 6 hours. The obtained reaction solution was poured into a large excess amount of methanol, and the precipitated product was precipitated after the reaction product was precipitated, washed with methanol, decompressed, and dried for 4 hours, to give U 2.3 g of polyamine. The logarithmic viscosity (Ή1 η) of the polyamic acid was 1.22 dl/g. 4 〇〇g of the polylysine obtained above was dissolved in 8 〇〇g of 丫·butyrolactone, and 35 2 g of pyridine and 27 6 g of acetic anhydride were added to the solution, and 4 at i 1 〇C. Hour dehydration ring closure reaction (醯imination reaction). Next, in the same manner as in the case of the above polylysine, precipitation, separation, washing, and drying of the reaction product were carried out to obtain 3 8 · 5 g of ruthenium iodide polymer (PI_丨). The logarithmic viscosity of the ruthenium iodide polymer (PI-1) (?11[1) is 丨23 dl/g. -20-201243461 Synthesis Example 2 In addition to the use of 75.29 g (〇.20 mol) of the compound represented by the above formula (1-2) in the above Synthesis Example 1, in place of the compound represented by the above formula (1-1), and synthesis In the same manner as in Synthesis Example 1, a dehydration ring-closure reaction was carried out in the same manner as in Synthesis Example 1, except that the poly(amino acid) of 1/7.88 was used. '3 7.5 g of ruthenium iodide polymer (PI-2) was obtained. The logarithmic viscosity (η1η) of the ruthenium iodide polymer (PI-2) was 1.13 dl/g. Synthesis Example 3 In addition to the above Synthesis Example 1 In the same manner as in Synthesis Example 1, except that 60.23 g (0.16 mol) of the compound represented by the above formula (1-2) and 4.32 g (0.04 mol) of p-phenylenediamine were used instead of the compound represented by the above formula (1-1). 107.2 g of a poly-proline acid having a logarithmic viscosity of 1.15 dl/g was obtained. Next, a dehydration ring-closure reaction was carried out in the same manner as in Synthesis Example 1 except that 40.Og of the above polyamic acid was used, to obtain 30.8 g. The imidized polymer (PI-3). The logarithmic viscosity of the ruthenium iodide polymer (PI-3) was 1.7 dl/g. Comparative Synthesis Example 1 In addition to the above Synthesis Example 1 In the above formula, 1 g.8g (〇.l〇mol) of p-phenylenediamine and 52_38 (0.1〇111〇1) of 3,5-diaminobenzoic acid 3-cholesteryl ester was used instead of the above formula (1) -1) In addition to the compound shown in the above, 105.7 g of a poly-proline acid having a logarithmic viscosity (η1η) of 1.23 dl/g was obtained in the same manner as in Synthesis Example 1. Next, except for using 40. Og in the above polylysine In the same manner as in Synthesis Example 1, a dehydration ring-closure reaction was carried out to obtain a logarithmic viscosity (η-1) of the yttrium iodide polymer (rpi_l). |η) is 1.34 dl/g. Comparative Synthesis Example 2 In addition to the above-mentioned Synthesis Example 1, 2 〇.16 g (〇.20 mol) of p-phenylenediamine was used instead of the compound represented by the above formula (1-1), and In the same manner as in Synthesis Example 1, a polyacetin having a logarithmic viscosity of 1.25 dl/g was obtained in the same manner as in Synthesis Example 1. Then, a dehydration ring-closure reaction was carried out in the same manner as in Synthesis Example 1 except that 40.0 g of the above polyamic acid was used. 7.8 g 醯 imidized polymer (rpi-2). The logarithmic viscosity of the ruthenium iodide polymer (rpi_2) was 1.28 dl/g. EXAMPLES In the following examples, the liquid crystal display element of the present invention was produced, Fig. 3 is a cross-sectional view showing the structure of the liquid crystal display element 100 manufactured by the embodiment and the comparative example. The liquid crystal display element 100 is formed by sandwiching the liquid crystal layer 1〇3 in the substrate 101 and the opposite substrate 102. The substrate 101 is a substrate in which a glass substrate 10a, a common electrode 101b of an ITO (In203-Sn02) film, an insulating layer 101c of tantalum nitride, a signal electrode 101d of an IT film, and a liquid crystal alignment film 10 le are sequentially formed. The substrate 1 〇 2 is a substrate on which the liquid crystal alignment film 1 〇 2b is formed only on the glass substrate 102a. The signal electrode 101d of the liquid crystal display element 1 is a comb electrode having linear comb teeth. The common electrode is a "beta film" having no pattern. The liquid crystal display element 100 is provided with a polarizer (not shown) on both sides of the substrate 丨〇1 and the counter substrate 1 〇2, and a backlight (not shown) is disposed under the substrate 010 of the lower side of FIG. Used in combination with this component. -22-201243461 Example 1 <Preparation of Liquid Crystal Aligning Agent> The yttrium imidized δ substance (ΡΙ·1) obtained as the above Synthesis Example 1 having ϋκ·* and meyer molecules was dissolved to 50%. A solution of 聚合物-methylpyrrolidone and 5 〇 heavy butyl, a mixed solvent formed by a cereal agent, was formed to form a solution having a polymer concentration of 3 wt%. This solution was prepared by using a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent. <Formation of Liquid Crystal Alignment Film> The surface of the substrate on which the common electrode, the insulating layer, and the signal electrode are sequentially formed, and the surface on which the counter substrate is not formed, and the liquid crystal alignment agent are coated by a spin coater A coating film was formed, and the coating film was prebaked at 8 CTC for 1 minute, and then baked at 2 Torr (1 hour after rc) to form a liquid crystal alignment film having an average film thickness of 600 A. <Manufacture of liquid crystal display element > The liquid crystal alignment film faces of the pair of substrates on which the liquid crystal alignment films are formed as described above are opposed to each other by the spacers having a thickness of 1 μm, and the liquid crystal injection port 'sealing side faces are left. The rods are injected from the liquid crystal injection port. After the positive liquid crystal, the liquid crystal injection port is sealed. Then, the polarizer is bonded to the outer surfaces of the two substrates to fabricate the FFS mode liquid crystal display element. Here, the two polarizers have their polarization directions orthogonal to each other. It is bonded to the direction of the comb teeth of the signal electrode in parallel or perpendicularly. <Operation check of liquid crystal display element> When the voltage is not applied to the liquid crystal display element manufactured as described above The visible light transmittance and the visible light transmittance when applying a voltage of 5 V -23 - 201243461 between the common electrode and the signal electrode are shown in Table 1. Then, when the line leaked, the tilt was poor. Visually study the comb of the signal electrode during driving. There was no light in the vicinity of the teeth, no light leakage was observed, and it was speculated that the opposite Examples 2 and 3 and Comparative Examples 丨 and 2 were used, except for the <Preparation of Liquid Crystal Aligning Agent> in the above Example ,, respectively, using Table 1 A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the organic polymer contained in the organic polymer was used, and a liquid crystal display device was produced using the liquid crystal alignment agent, and the operation was confirmed. The results are shown in Table 1. [Table 1] Liquid crystal Excipient liquid crystal display element Organic polymer type pretilt angle (degrees) Visible light transmittance (%) Light leakage during operation when voltage is applied when no voltage is applied Example 1 PI-1 0.0 0.1 95 No example 2 PI-2 0.0 0.3 93 No Example 3 PI-3 0.2 0.3 90 No comparison example 1 rpi-1 3.0 0.3 84 There is a comparison example 2 rpi-2 1.5 0.3 85 [Simplified description of the diagram] Figure 1疋 is used to say Fig. 2A is a schematic view showing another example of the signal electrode of the liquid crystal display element of the present invention. Fig. 3 is a view showing the manufacture of the examples and the comparative examples. -24- 201243461 [Description of main components] 1 Back 2 comb 100 Liquid crystal display element 101 Substrate 101a Glass substrate 101b Common electrode 101c Insulation layer 101d Signal electrode 10Le Liquid crystal alignment film 102 Glass substrate 102b liquid crystal alignment film a width b distance L length ω angle δ angle θ angle-25-