TW201012801A

TW201012801A - Diamine, liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display device

Info

Publication number: TW201012801A
Application number: TW98127877A
Authority: TW
Inventors: Norio Tamura; Takahiro Mori; Daisuke Touma
Original assignee: Chisso Corp; Chisso Petrochemical Corp
Priority date: 2008-08-20
Filing date: 2009-08-19
Publication date: 2010-04-01
Also published as: JP2010070537A; TWI391375B; JP5359643B2

Abstract

The present invention is provided to develop a polyamic acid capable of achieving many characteristics (high voltage holding capacity, little remained DC (direct current), high liquid crystal alignability, high rubbing resistance, etc.) required by a liquid crystal (LC) alignment layer. The invention is achieved through a diamine shown by formula (1). In formula (1), Y represents a single bond or a 1-9 C linear alkylene group, and any -CH2- in the alkylene group may be replaced by -O-, -N(CH3)-, 1,4-phenylene, 1,4-cyclohexylene or piperazine-1,4-diyl; n is 0 or 1; and one hydrogen of a benzene ring that the amino group is bonded to may be replaced by -OH. However, when Y is an alkylene and n is 0, -CH2- that the amino group is bonded to is not replaced by -O- or -N(CH3)-.

Description

201012801 jzuo^pu 六、發明說明：【發明所屬之技術領域】本發明是關於一種新穎的二胺（diamine)及使用該二胺而獲得的聚酿胺酸（polyamic acid)，進一步關於該聚酿胺酸的用途。另外，本發明中的用語「液晶配向劑（liquid crystal aligning agent )」意指為了形成液晶配向膜而使用的含聚合物之組成物。【先前技術】液晶顯示元件多用於行動電話的顯示部、筆記型電腦 (notebook personal computer )或桌上型電腦（desktop personal computer)的螢幕，還有用於攝影機（video camera) 的取景器（view finder )、投影顯示器（projection display ) 等各種顯示裝置中’最近也開始用於電視（television)中。而且，液晶顯示元件亦用作光學印字頭（optical printer head)、光學傅立葉變換（optical Fourier transform)元件、光閥（light valve )等的光電子（optoelectronic )相關元件。先前的液晶顯示元件，其主流是使用向列液晶（nematic liquid crystal)的顯示元件，實用化的有1)扭轉9〇度的扭轉向列（Twisted Nematic ’ TN)型液晶顯示元件、2) 通常扭轉180度或180度以上的超扭轉向列（sUper Twisted Nematic，STN)型液晶顯示元件、3)使用薄膜電晶體的所謂薄膜電晶體（Thin Film Transistor，TFT )型液晶顯示元件等。然而’這些液晶顯示元件具有如下缺點：可適當視認 201012801 圖像的視角狹小，自斜向觀看時會產生亮度或對比度的下降以及半色調的亮度反轉。近年來，視角的問題利用以下技術而得到進一步改良：丨）使用光學補償薄膜的型液晶顯示元件、2)使用垂直配向與光學補償薄膜的垂直配向（Vertical Alignment，VA )型液晶顯示元件、3 )將垂直配向與突起結構物的技術併用的多象限垂直配向（Multi Domain Vertical Alignment，MVA )型液晶顯示元件、或 4 ) 橫向電場方式的共平面切換（In-Plane Switching，IPS)型液日日顯示元件、5)電控雙折射（Electrically Controlled Birefringence，ECB)型液晶顯示元件、6)光學補償彎曲 (Optically Compensated Bend、或〇ptically self-Compensated Birefringence，〇CB)型液晶顯示元件等’如此可使這些元件實用化。液晶顯示元件技術的發展不僅可藉由改良該些液晶顯示元件的驅動方式或元件結構’亦可藉由改良顯示元件中所使用之構成成分(constructional element)而達成。顯示參元件中所使用之構成成分之中’尤其液晶配向膜是與^晶顯示元件的顯示品質有關的重要因素之一，隨著顯示元件的南品質化，液晶配向膜的作用日益變得重要。液晶配向膜是由液晶配向劑製備。當前，所謂主要使用的液晶配向劑’是指使聚醯胺酸或可溶性聚醯亞胺溶解於有機溶劑中而成的溶液。將此種溶液塗佈於基板上後，利用加熱等方法進行成膜而形成聚醯亞胺系配向膜。亦對聚醯胺酸以外的各種液晶配向劑進行研究，但就耐熱性、 201012801 耐化學品性（耐液晶性）、塗佈性、液晶配向性、電特性、光學特性、顯示特性等方面而言，幾乎未達實用化。為了提高液晶顯示元件（LCD，liquid CryStai display ) 的顯示品質而對液晶配向膜所要求的特性，必須為電壓保持率（VHR，voltage holding rati〇 )高。於主動矩陣（active matrix)型LCD中，例如若電壓保持率低，則於訊框(frame) 期間中與液晶相關的電壓下降，結果導致亮度變化，未形成正常諧調。尤其最近LCD開始用於電視用途，VHR的隨時間劣化小亦變得重要。為了製作大畫面且顯示清晰的 ❿ LCD，而尋求背光的亮度變高，且VHR不會由於光或熱而劣化的配向膜。其次，對配向膜中所要求的重要特性，可列舉殘留電荷（DC (direct current，直流））小。所謂殘留DC，是指隨著LCD的驅動而積存於電極間的電荷，由於該現象會將多餘的電壓施加至電極，例如在切斷電壓後產生顯示圖像未消失而殘留的所謂「殘像」。最近報告有可藉由使用具有氮原子的二胺而製作殘留DC小的液晶配向膜（專利文獻 ❹ 卜2、3) ’來作為減小殘留DC的方法之一。 [先前技術文獻] [專利文獻1]國際公開2004-053583號手冊 [專利文獻2]國際公開2004-021076號手冊 [專利文獻3]曰本專利特開平i〇_1〇4633號公報然而’隨著液晶顯示元件的高性能化發展，需要可進一步降低殘留DC的配向膜，僅以先前提出的技術，難以 6 201012801 完全滿足所要求的特性。【發明内容】本發明的目的在於開發一種可達所要求的报多特性（電壓保持率高、=晶配向膜中向性擦(rubbing)性高等)的聚酿胺i、液“ 發月者們為了解決上述課題而進行可藉由向作為聚酿胺酸的原料的二胺中導發現 e :合物構成的配向膜的‘:丨= 面保持回電壓保持率一面使殘留Dc下降。進而發現本發明的二胺以及使用本發明的二胺的聚醯胺酿亞胺對於通常使用的㈣具有高溶解性，從而完成本發本發明的二胺是由以下第[η項所表示。 [1]一種二胺，其由式（1)所表示：201012801 jzuo^pu VI. Description of the Invention: [Technical Field] The present invention relates to a novel diamine and a polyamic acid obtained by using the same, and further relates to the polysaccharide The use of aminic acid. Further, the term "liquid crystal aligning agent" as used in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film. [Prior Art] Liquid crystal display elements are mostly used for the display portion of a mobile phone, a notebook personal computer or a desktop personal computer, and a viewfinder for a video camera (view finder) In various display devices such as projection displays, 'it has recently been used in television. Further, the liquid crystal display element is also used as an optoelectronic related element such as an optical printer head, an optical Fourier transform element, a light valve, or the like. The liquid crystal display element of the prior art is a display element using a nematic liquid crystal, and is practically used: 1) a twisted nematic (TN) type liquid crystal display element having a twist of 9 degrees, 2) A sUper Twisted Nematic (STN) type liquid crystal display element which is twisted by 180 degrees or more, 3) a thin film transistor (TFT) type liquid crystal display element which uses a thin film transistor, or the like. However, these liquid crystal display elements have a drawback in that the angle of view of the image of 201012801 can be appropriately recognized, and the brightness or contrast is lowered and the halftone brightness is reversed when viewed obliquely. In recent years, the problem of the viewing angle has been further improved by the following techniques: 丨) a liquid crystal display element using an optical compensation film, 2) a vertical alignment (VA) type liquid crystal display element using a vertical alignment and an optical compensation film, 3 ) Multi-Vertical Vertical Alignment (MVA) type liquid crystal display element for vertical alignment and protrusion structure technology, or 4) In-Plane Switching (IPS) type liquid day Japanese display elements, 5) Electronically Controlled Birefringence (ECB) type liquid crystal display elements, 6) Optically Compensated Bend (or ptentially self-Compensated Birefringence, 〇CB) type liquid crystal display elements, etc. These components can be put to practical use. The development of the liquid crystal display element technology can be achieved not only by improving the driving method or the element structure of the liquid crystal display elements, but also by improving the constituent elements used in the display elements. Among the constituent components used in the display unit, the liquid crystal alignment film is one of the important factors related to the display quality of the crystal display element. With the south quality of the display element, the role of the liquid crystal alignment film becomes increasingly important. . The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, the term "liquid crystal alignment agent mainly used" means a solution obtained by dissolving polylysine or soluble polyimine in an organic solvent. After applying such a solution onto a substrate, a film is formed by heating or the like to form a polyimide film. Various liquid crystal alignment agents other than polyglycolic acid have also been studied, but in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, and display properties, 201012801 Words are almost not practical. In order to improve the display quality of a liquid crystal display element (LCD), the characteristics required for the liquid crystal alignment film must be high (VHR, voltage holding rati). In an active matrix type LCD, for example, if the voltage holding ratio is low, the voltage associated with the liquid crystal during the frame period is lowered, resulting in a change in luminance, and a normal harmonic is not formed. Especially recently, LCDs have been used for television applications, and the VHR's degradation over time has become important. In order to produce a large screen and display a clear ❿ LCD, an aligning film in which the brightness of the backlight becomes high and the VHR does not deteriorate due to light or heat is sought. Next, the important characteristics required for the alignment film are as small as possible (DC (direct current)). The residual DC refers to the electric charge accumulated between the electrodes as the LCD is driven. This phenomenon applies an excessive voltage to the electrode. For example, after the voltage is cut off, the so-called "afterimage" remains after the display image does not disappear. "." Recently, it has been reported that a liquid crystal alignment film having a small residual DC (Patent Documents 2, 3) can be produced by using a diamine having a nitrogen atom as one of methods for reducing residual DC. [Prior Art Document] [Patent Document 1] International Publication No. 2004-053583 Handbook [Patent Document 2] International Publication No. 2004-021076 Manual [Patent Document 3] Japanese Patent Laid-Open No. Hei. No. 4633 No. With the development of high performance of liquid crystal display elements, there is a need for an alignment film which can further reduce residual DC, and it is difficult to fully satisfy the required characteristics by the previously proposed technique only by 6 201012801. SUMMARY OF THE INVENTION An object of the present invention is to develop a polyamine II, a liquid "moon-returner" that can achieve the required multi-reporting characteristics (high voltage holding ratio, high crystal-graining, etc.) In order to solve the above-mentioned problem, the alignment film formed of the e: compound in the diamine which is a raw material of the poly-branched acid can be used to reduce the residual Dc while maintaining the return voltage holding ratio. It has been found that the diamine of the present invention and the polyamine amine-containing amine using the diamine of the present invention have high solubility for the commonly used (IV), and thus the diamine of the present invention is completed by the following [n]. 1] A diamine represented by the formula (1):

其中，υ為單鍵或碳數為1〜9的直鏈伸烷基；該伸烧基的任意-CH2·可由-0-、-N(CH3)-、1，4-伸笨基、ι，4_伸環己基或哌嗪-1，4-二基取代；η為0或1 ;並且，鍵結有胺基的苯環的一個氫可由-OH取代。其中，當Y為伸烷基且 n為〇時，並無鍵結有胺基的-CH2-由-〇-或-N(CH3)-取代的情況。 201012801 ^^uozpu [發明之效果] 、本發明的二胺不須使用特殊的反應裝置就可容易地合成，而且本發明的液晶配向劑可溶於該技術中通常使用的溶劑中’保存時不會產生沉澱。並且，利用本發明，可提供一種電壓保持率高、殘留DC小驗晶顯示元件。為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。【實施方式】首先，_對本發明中使用的用語進行說明。有時將由式 ⑴所表示的二胺稱為二胺⑴。有時由其他式所表示的 -胺亦彻相同簡寫方絲示。對於二胺以外的化合物，例如有時將由式（A)所表示的四竣酸二奸簡寫成酸軒 (A)。對化學式進行說明時所使用僅位置可自由選擇，數量亦可自由選擇」可由:B、C、D或E取代」的表述不僅具有—個A可由B、 C、D或E取代的含義，及多個A的任—者均可*B、c、 DAE的任—者取代的含義，亦具有由B取代的A、由c 取代的A、由D取代的A、以及由E取代的A的至少混合存在的含義。任意偶·可㈣♦代時，*包括結果產生鍵結基團的取代。環的碳的鍵結位置不明確的取代基意指結位置於無化學性問題的範_是自由的1多個3 用相同記號的情況意指該基團具有相同定義㈣，= 表示於所有式中必綱時為相團。於多個式_^ 201012801 izuozpir 同基團，亦可於不同式中為不同基困。本發明是由上述第[1]項與以下第構成。 P]如第[1]項所述之二胺，其中鍵結有胺基的笨環為不具有-OH作為取代基的苯環。 [3] 如第[1]項所述之二胺，其中鍵結有胺基的苯環為於相對於胺基的其中一鄰位(01^0 p0siti〇n)具有取代基_〇H 的苯環。 [4] 如第⑴項所述之二胺，其中Y為單鍵或1，4-伸苯擊基，並且η為0。 [5] 如第[1]項所述之二胺，其中γ為單鍵、或任意_€112_ 可由-0-或-N(CH3)-取代的碳數為i〜9的直鏈伸烷基；並且η為1。 [6] —種聚醯胺酸，是使至少一種如第[丨]項所述之二胺、或者至少一種由如第[1]項所述之二胺與至少一種其他二胺所構成的二胺混合物，與至少一種四叛酸肝進行反應而獲得。 # [7]如第[6]項所述之聚醯胺酸，其中至少一種四羧酸酐為選自由式（A1)〜式（A63)所表示的化合物中的四叛酸酐。 201012801 όζυοζριιWherein, υ is a single bond or a linear alkyl group having a carbon number of 1 to 9; any -CH 2 · of the stretching group may be -0-, -N(CH3)-, 1,4-extension, ι , 4_cyclohexylene or piperazine-1,4-diyl substituted; η is 0 or 1; and, a hydrogen of a benzene ring to which an amine group is bonded may be substituted by -OH. Wherein, when Y is an alkylene group and n is hydrazine, there is no case where -CH2 having an amine group bonded thereto is substituted by -〇- or -N(CH3)-. 201012801 ^^uozpu [Effects of the Invention] The diamine of the present invention can be easily synthesized without using a special reaction device, and the liquid crystal alignment agent of the present invention can be dissolved in a solvent generally used in the art. Will produce a precipitate. Further, according to the present invention, it is possible to provide a residual DC small crystal display element having a high voltage holding ratio. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] First, the terms used in the present invention will be described. The diamine represented by the formula (1) is sometimes referred to as a diamine (1). Sometimes the amines represented by other formulas are also abbreviated in the same square. For the compound other than the diamine, for example, the tetradecanoic acid represented by the formula (A) is sometimes abbreviated as the acid (A). For the description of the chemical formula, the position can be freely selected, and the quantity can be freely selected. The expression "may be replaced by: B, C, D or E" has not only the meaning that A can be replaced by B, C, D or E, and Any of a plurality of A's can be substituted by any of *B, c, and DAE, and also has A substituted by B, A substituted by C, A substituted by D, and A substituted by E. At least mix the meaning of existence. Any even · (4) ♦ generation, * including the result of the substitution of the bonding group. The ambiguous substituent of the carbon bond position of the ring means that the position of the knot is in the absence of a chemical problem. _ is free. More than 3. The same mark means that the group has the same definition (four), and = is expressed at all. In the formula, it must be a group. In the same formula _^ 201012801 izuozpir same group, can also be different in different formulas. The present invention is constituted by the above item [1] and the following. P] The diamine according to [1], wherein the stupid ring to which an amine group is bonded is a benzene ring having no -OH as a substituent. [3] The diamine according to [1], wherein the benzene ring to which the amine group is bonded has a substituent _〇H with respect to one of the ortho positions (01^0 p0siti〇n) of the amine group. Benzene ring. [4] The diamine according to item (1), wherein Y is a single bond or a 1,4-benzazole group, and η is 0. [5] The diamine according to [1], wherein γ is a single bond, or any _€112_ linear alkylene having a carbon number of i~9 which may be substituted by -0- or -N(CH3)- Base; and η is 1. [6] A poly-proline, which comprises at least one diamine as described in the item [丨], or at least one of the diamine as described in the item [1] and at least one other diamine. A diamine mixture is obtained by reacting with at least one of four resorcinating livers. The poly-proline acid according to the item [6], wherein at least one of the tetracarboxylic anhydrides is a tetra-anhydrous anhydride selected from the compounds represented by the formulae (A1) to (A63). 201012801 όζυοζριι

10 201012801 Μ Μ Ο Ο 0· Ο (Α14) (Α15) (Α16) (Α17)10 201012801 Μ Μ Ο Ο 0· Ο (Α14) (Α15) (Α16) (Α17)

(Α19) (Α20) (Α21) Ο(Α19) (Α20) (Α21) Ο

贼 Ο (Α23)Thief Ο (Α23)

(Α25)(Α25)

❹❹

ο ο (Α31)ο ο (Α31)

ΟΟ

11 20101280111 201012801

(A37) (A38) 〇4 (A39) (A40) (A41)(A37) (A38) 〇 4 (A39) (A40) (A41)

(A45)(A45)

(A53)(A53)

12 201012801 0,12 201012801 0,

QQ

Ο (A54)Ο (A54)

&0 (Α59) (Α59) ❹ Ο&0 (Α59) (Α59) ❹ Ο

(Α58)(Α58)

(Α62) (Α63) [8] —種聚醯亞胺’是將如第[6]項所述之聚醯胺酸脫水開環而獲得。 [9] 一種溶液，包括選自由如第[6]項所述之聚醯胺酸以及如第[8]項所述之聚醯亞胺所組成的組群中的至少一種聚合物。 [10] —種液晶配向劑，由如第[9]項所述之聚合物溶液構成。 [11] 一種液晶顯示元件’包括由如第[1〇]項所述之液晶配向劑而獲得的液晶配向膜。本發明的二胺是由式（1)所表示。 13 201012801(Α62) (Α63) [8] A polyimine is obtained by dehydrating and dehydrating a polylysine as described in the item [6]. [9] A solution comprising at least one polymer selected from the group consisting of polylysine as described in the item [6] and polyamidene according to item [8]. [10] A liquid crystal alignment agent comprising the polymer solution according to [9]. [11] A liquid crystal display element ' comprises a liquid crystal alignment film obtained by the liquid crystal alignment agent according to item [1]. The diamine of the present invention is represented by the formula (1). 13 201012801

於式（1)中，Y為單鍵或碳數為1〜9的直鏈伸烧基 (linear alkylene group)。並且，該伸烷基的任意_Ch2_可由 -Ο-、·Ν(0Ή3)-、1，4-伸苯基(i，4-phenylene)、1，4-伸環己基 (1，4-cy clohexylene)或哌嗪 _ 1，4_ 二基(piperazine_ j，4_diy ^ 取代。Y的較好例子為單鍵、M_伸苯基、哌嗪·Μ_二基以及任意-CH2·可由办或叫^士取代的碳數為卜9的直鏈伸烷基。Υ的更好例子為i，4_伸苯基以及任意_Ch2_可由_〇_ 或-N(CH3)-取代的碳數為丨〜9的直鏈伸烷基。n為〇或j。然而’當Y為上述伸絲時，並無鍵結有胺基的 :CH2-由-0-f-N(CH3)-取代的情況。並且，鍵結有胺基的苯環的-個氫可由_〇h取代。鮮環具有—個取代基项時’其位置相對於胺基的鍵結位置為鄰位或間位㈣也 position)，較佳是鄰位。藉由使二胺⑴與四叛酸二肝反應而獲得的聚釀胺酸對溶劑的轉性高，可防止保存於冰箱+等時聚合物析出根據—胺⑴以外的原料組成，如預期會變成溶解性較差的ί醯胺酸時’較佳歧用η為G的非對稱二胺⑴，因可提解性。而且，在將溶解性低於輯胺酸的聚醯亞胺用於配向射的情況下，使用式（1)中的η為0的二胺（1)也較好。此外’為了獲得具有較大配向限制力的配向膜，Υ較 201012801 32062pit 佳是碳數為1〜9的直鏈伸垸基，更佳是碳數為2〜9的直鏈伸燒基。該情況下的伸烷基是-CH2_未由其他基團取代的伸烷基。由以本發明的二胺為原料的聚醯胺酸獲得的配向膜降低殘留DC的效果明顯大。因此，藉由將下述所示的配向限制力特別大的公知的其他二胺與二胺（丨）加以組合來使用’亦可獲得對液晶的配向限制力大、殘留DC低的配向膜。為了將配向膜的電特性製備成所需的值，γ的直鏈伸烷基中的任意-CHr可由_〇_或N(CH3)-取代。此時，自原料獲取的容易度考慮，較佳是與吲哚環鄰接的-(：：112_由_〇>_或 • N(CH3)_取代，自化合物的穩定性考慮，較佳是_〇_與 N(CH3)-不相鄰。 ' 以下表不一胺（1)的具體例。 ❹ 15 201012801 32062pitIn the formula (1), Y is a single bond or a linear alkylene group having a carbon number of 1 to 9. Further, any _Ch2_ of the alkylene group may be -Ο-, Ν(0Ή3)-, 1,4-phenylene (i,4-phenylene), 1,4-cyclohexylene (1,4- Cy clohexylene) or piperazine _ 1,4_ diyl (piperazine_ j, 4_diy ^ substituted. A preferred example of Y is a single bond, M_phenylene, piperazine·Μ_diyl, and any -CH2· can be or A linear alkyl group substituted with a carbon number of 9 is a straight chain alkyl group. A better example of hydrazine is i, 4_phenylene and any _Ch2_ carbon number which may be substituted by _〇_ or -N(CH3)- Is a linear alkyl group of 丨~9. n is 〇 or j. However, when Y is the above-mentioned wire, there is no amine group bonded to it: CH2- is replaced by -0-fN(CH3)- Moreover, the hydrogen of the benzene ring to which the amine group is bonded may be substituted by _〇h. When the fresh ring has a substituent, the position of the bond with respect to the amine group is ortho or meta (four) also positions. ), preferably adjacent. The polystyryl obtained by reacting the diamine (1) with the tetra-rebel di-hepatic acid has high conversion to the solvent, and prevents the precipitation of the polymer stored in the refrigerator + isochronous according to the composition of the raw material other than the amine (1), as expected When it becomes a poorly soluble lysine, it is preferable to use an asymmetric diamine (1) in which η is G, because it is resolvable. Further, in the case where a polyimine having a solubility lower than that of arginine is used for the alignment, it is also preferred to use a diamine (1) wherein η is 0 in the formula (1). Further, in order to obtain an alignment film having a large alignment regulating force, Υ is preferably a linear stretching group having a carbon number of 1 to 9 as compared with 201012801 32062pit, and more preferably a linear stretching group having a carbon number of 2 to 9. The alkylene group in this case is an alkylene group in which -CH2_ is not substituted by another group. The effect of reducing the residual DC by the alignment film obtained from the polyamine which is a raw material of the diamine of the present invention is remarkably large. Therefore, by using a combination of a known other diamine having a particularly large alignment resistance as shown below and a diamine, it is also possible to obtain an alignment film having a large alignment resistance to liquid crystal and a low residual DC. In order to prepare the electrical properties of the alignment film to a desired value, any -CHr in the linear alkyl group of γ may be substituted by _〇_ or N(CH3)-. At this time, from the viewpoint of easiness of obtaining the raw material, it is preferred to substitute -(::112_by _〇>_ or N(CH3)_ adjacent to the anthracene ring, from the viewpoint of stability of the compound, preferably. Yes _〇_ and N(CH3)- are not adjacent. 'The following table is not a specific example of the amine (1). ❹ 15 201012801 32062pit

CCnOO Φ ^ H2N (1.3) nh2CCnOO Φ ^ H2N (1.3) nh2

h2N (1.7) nh2 ODUhJDoh2N (1.7) nh2 ODUhJDo

HzN (1-8) NHzHzN (1-8) NHz

16 20101280116 201012801

CCr(CH2,5T〇0 φ ^ H2N (1-13, NH2 〇〇r(CH2,6TD〇 H2N (1-1S, NH2CCr(CH2,5T〇0 φ ^ H2N (1-13, NH2 〇〇r(CH2,6TD〇 H2N (1-1S, NH2)

〇Dr(CH2,7iQO 0 h2n (1-17) nh2 cc ^J-(CH2)8 tDO 0 h2n (1-19} nh2 CCr，9 IDO V h2n (1-21)〇Dr(CH2,7iQO 0 h2n (1-17) nh2 cc ^J-(CH2)8 tDO 0 h2n (1-19} nh2 CCr,9 IDO V h2n (1-21)

17 201012801 32U02pit17 201012801 32U02pit

18 20101280118 201012801

Y為單鍵且η為0的二胺（1)可利用以下所示的途徑來合成。The diamine (1) wherein Y is a single bond and η is 0 can be synthesized by the route shown below.

於流程1中，於氫化鈉等鹼存在下，使由所表示的市售的5-胺基吲哚或6-胺基吲哚與4-氟硝基苯進行反應，獲得由（S1-2)所表示的化合物。繼而，對由（§1_2) 所表示的化合物，以氫催化還原而將瑞基還原，藉此可合成由式（1)所表示的二胺。當Y是碳數為1〜9的直鏈伸烧基且η為1的化合物 © 時，可利用以下所示的途徑來合成。 (CH2CH^OH)3N-HCI RuCij*nH2〇, PPh)1In Scheme 1, a commercially available 5-amino hydrazine or 6-amino hydrazine is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain (S1-2). ) the compound represented. Then, the compound represented by (§1_2) is reduced by hydrogen catalytic reduction to reduce the thio group, whereby the diamine represented by the formula (1) can be synthesized. When Y is a compound of a linear stretching group having a carbon number of 1 to 9 and η is 1, it can be synthesized by the route shown below. (CH2CH^OH)3N-HCI RuCij*nH2〇, PPh)1

流程2 於上述流程 2 中，依據 Tetrahedron Letters 41(11)， 1811-1814(2000)中記載的方法，使由（S2-1)所表示的二 201012801 ，巧中Y為單鍵或碳數為丨〜9的直鍵狀基）與氣化三乙醇鍵進行反應’獲得由（S2_2)所絲的化合物。繼而，於氫化鈉等鹼存在下，使上述由（S2_2)所表示的化合物與4·_基苯進行反應，獲得由（S2_3)所表示的化合物。繼而，對由（S2-3)所表示的化合物以氫催化還原而將硝基還原，藉此可合成由式（1)所表示的二胺。當Y是碳數為2〜9的直鏈伸絲且n為G的化合物時，可利用以下所示的途徑來合成。 Η2Ν-γIn the above Scheme 2, according to the method described in Tetrahedron Letters 41 (11), 1811-1814 (2000), the two 201012801 represented by (S2-1), Y is a single bond or the carbon number is The direct bond-like group of 丨~9 is reacted with a vaporized triethanol bond to obtain a compound which is obtained from (S2_2). Then, the compound represented by the above (S2_2) is reacted with 4·_ylbenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S2_3). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S2-3), whereby the diamine represented by the formula (1) can be synthesized. When Y is a compound having a linear stretch of 2 to 9 carbon atoms and n is G, it can be synthesized by the route shown below. Η2Ν-γ

βγ€〇 (S3-1)HΓγ€〇 (S3-1)H

HjN-v-S Pd(PPh3)4 r 胺HjN-v-S Pd(PPh3)4 r amine

(S3-2) H(S3-2) H

❹ 於上述流程 3 中’依據 Tetrahedron Letters 34(40) 6403-6406 (1993)中記載的方法，使由所表示的化合物與胺基炔化物（其中Y，為單鍵或碳數為i〜7的直鏈伸烷基）進行反應，獲得由（S3_2)所表示的化合物。繼而，於氫化鈉等鹼存在下，使上述由（S3_2)所表示的化合物與4-氟硝基苯進行反應，獲得由（S3_3)所表示的化合物。繼而，對由（S3-3)所表示的化合物以氫催化還原而將硝基還原，藉此可合成由式（丨）所表示的二胺。當Y是碳數為1的亞甲基且n為〇的化合物可利用以下所示的途徑來合成。 20 201012801 H/〇c> H 鹼 (S4-1)于In the above Scheme 3, the compound represented by the compound and the amino acetylide (where Y is a single bond or a carbon number of i~7) according to the method described in Tetrahedron Letters 34 (40) 6403-6406 (1993) The linear alkyl group is reacted to obtain a compound represented by (S3_2). Then, the compound represented by the above (S3_2) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S3_3). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S3-3), whereby the diamine represented by the formula (?) can be synthesized. A compound in which Y is a methylene group having a carbon number of 1 and n is ruthenium can be synthesized by the route shown below. 20 201012801 H/〇c> H base (S4-1)

在上述流程4中，於氫化納等驗存在下，使由（S4_i ) 所表示的市售的5-(胺基甲基)吲哚或6_(胺基曱基)吲哚盘 4·氟硝基笨進行反應，獲得由（S4_2)所表示的化合物了繼而，對由（S4-2)所表示的化合物以氫催化還原而將硝基還原，藉此可合成由式（1)所表示的二胺。 § Y為1,4-伸本基且η為0的化合物時，可利用以下所示的途徑來合成。 OH)j (S5-1)In the above Scheme 4, commercially available 5-(aminomethyl)phosphonium or 6-(aminosulfonyl)pyrene 4·fluorine nitrate represented by (S4_i ) is present in the presence of hydrogenation. The reaction is carried out to obtain a compound represented by (S4_2), and then the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S4-2), whereby the compound represented by the formula (1) can be synthesized. Diamine. When Y is a compound having a 1,4-extension base and η is 0, it can be synthesized by the route shown below. OH)j (S5-1)

(S5-2)(S5-2)

於上述流程5中，使由（m-D所表示的市售的孓溴吲哚或6-溴吲哚與市售的4-胺基苯基硼酸，藉由使用鈀觸媒進行偶合反應崎得由（S5_2)所表示的化合物。繼而，於氫化鱗时在下，使±述由（S5_2)所表示的化合物與4-氟硝基苯進行反應，獲得由（S5_3 )所表示的化合物。繼而’對由（S5_3)所表示的化合物以氫催化還原而將靖基還原，藉此可合成由式⑴所表示的二胺。 21 201012801 其次，對本發明的聚醯胺酸進行具體說明。藉由使二胺（1)於溶劑中與四羧酸二酐進行反應，而獲得含有聚醯胺酸、經部分醯亞胺化的聚醯胺酸、或該些的混合物的溶液。於以下說明中有時將該些的溶液稱為清漆(varnish)。進而，藉由利用脫水反應使該些清漆中所含的聚醯胺酸、經部分醯亞胺化的聚醯胺酸或該些的混合物開環，而獲得含有聚醯亞胺的清漆。於本發明中，二胺（1)可單獨使用，亦可將兩種或兩種以上的二胺（1)加以組合。而且，亦可將由式（1)所表示的二胺與其他已知的二胺併用。於以下 ❹ 說明中’將聚醯胺酸、或經部分醯亞胺化的聚醯胺酸、或該些的混合物等聚醯胺酸類，以及使聚醯胺酸、或經部分醯亞胺化的聚醯胺酸、或該些的混合物脫水開環而獲得的聚醯亞胺類總稱為聚合物。本發明的聚合物的分子量是以利用凝膠滲透層析 (Gel Permeation Chromatography，GPC)法所測定的重量平均分子量計’較佳是1，000〜500,000，更佳是1〇,〇〇〇〜 250,〇〇〇。其原因在於，若重量平均分子量大於等於 ❹ 10,000 ’則於形成配向膜時的基板煆燒步驟中，抑制聚合物的昇華’若重量平均分子量小於等於250,000，則可防止對溶劑的溶解性下降，將配向劑塗佈於基板時的聚合物部分析出等得到抑制。本發明中’並無特別限定四羧酸二酐的理由，以下表不適合使用的較好四羧酸二酐的具體例。 22 201012801 ^zuozpuIn the above Scheme 5, a commercially available ruthenium bromide or 6-bromofluorene represented by mD and a commercially available 4-aminophenylboronic acid are subjected to a coupling reaction by using a palladium catalyst. (S5-2) The compound represented by (S5_3) is obtained by reacting the compound represented by (S5_2) with 4-fluoronitrobenzene under the hydrogenation scale, and then obtaining the compound represented by (S5_3). The diamine represented by the formula (1) can be synthesized by hydrogen-catalyzed reduction of the compound represented by (S5_3), whereby the polyamine represented by the formula (1) can be synthesized. 21 201012801 Next, the polyamine of the present invention will be specifically described. (1) reacting with a tetracarboxylic dianhydride in a solvent to obtain a solution containing polyglycine, partially ruthenized polylysine, or a mixture thereof, which will sometimes be described in the following description. These solutions are referred to as varnish. Further, by using a dehydration reaction, the polylysine contained in the varnish, the partially ruthenized polylysine or a mixture thereof is opened, And obtaining a varnish containing polyimine. In the present invention, the diamine (1) can be Alternatively, two or more kinds of diamines (1) may be combined. Further, the diamine represented by the formula (1) may be used in combination with other known diamines. Polylysine, or partially ruthenized polylysine, or a mixture thereof, and polylysine, or polylysine, or partially ruminated imine, Or the polyethylenimine obtained by dehydration and ring-opening of the mixture is collectively referred to as a polymer. The molecular weight of the polymer of the present invention is a weight average molecular weight measured by a gel permeation chromatography (GPC) method. Preferably, it is 1,000 to 500,000, more preferably 1 〇, 〇〇〇〜 250, 〇〇〇. The reason is that if the weight average molecular weight is ❹ 10,000 Å, the substrate is sintered when the alignment film is formed. In the step, the sublimation of the polymer is suppressed. When the weight average molecular weight is 250,000 or less, the solubility in a solvent can be prevented from being lowered, and the analysis of the polymer portion when the alignment agent is applied to the substrate can be suppressed. No special limited tetracarboxylic acid The reason for the acid dianhydride is a specific example of a preferred tetracarboxylic dianhydride which is not suitable for use in the following table. 22 201012801 ^zuozpu

23 201012801 Μ Μ Μ Ο Ο Ο Ο Ο (Α14) (Α15) (Α16) (Α17)23 201012801 Μ Μ Μ Ο Ο Ο Ο Ο (Α14) (Α15) (Α16) (Α17)

(Α19)(Α19)

Ο Ο Ο Μ (Α21)Ο Ο Ο Μ (Α21)

㈣ (Α23)(4) (Α23)

οο

ΟΟ

❿ 24 201012801❿ 24 201012801

。^〇4 (A39) (A40). ^〇4 (A39) (A40)

(A41)(A41)

(A45)(A45)

(A47)(A47)

(A53) 25 201012801 ^zuozpu(A53) 25 201012801 ^zuozpu

(A63) 該些讀酸二酐可單獨使用，亦可將兩種或兩種以上 t使用。這些四魏二軒之中，尤其好的例子是 iA1)、酸酐（A2)以及酸酐⑽），藉由使用這些赠 =軒中的至少-種’可提供電壓保持率更高的液晶顯示 ❿ 内，聚所合表物時’在不損及本發明效果的範圍的效果，將二胺的總量設為10〇m^n發明式⑴所表示的〇莫耳百刀比_祝)時，由莫耳百分比，二/二tt例為〇·5料百分比〜％公知-盼=是莫耳百分比〜9〇莫耳百分比。好例子為選自下述所示的由式（II)〜 26 201012801 式（VIII)所表示的化合物組群中的二胺。可將該些二胺的至少-種與二胺⑴併用。另外，亦可併用並非由式⑻ 〜式（VIII)所表示的二胺。 η2ν—(〇η2^一νη2 ⑻(A63) These acid dianhydrides may be used singly or in combination of two or more kinds. Among these four Wei Erxuan, particularly good examples are iA1), anhydride (A2) and anhydride (10)), and by using at least one of these gifts, a liquid crystal display having a higher voltage retention ratio can be provided. When the surface is combined, the effect of the range of the effect of the present invention is set to 10 〇m^n, which is expressed by the invention formula (1). Percentage of ear, two / two tt cases are 〇·5 material percentage ~% known - hope = is the percentage of moles ~ 9 〇 mole percentage. A good example is a diamine selected from the group consisting of compounds represented by the formula (II) to 26 201012801 (VIII) shown below. At least one of these diamines may be used in combination with the diamine (1). Further, a diamine not represented by the formula (8) to the formula (VIII) may be used in combination. Η2ν—(〇η2^一νη2 (8)

於式（II)〜式（VIII)中，m為1〜12的整數，G1 獨立為單鍵、-〇-、_S-、-S-S-、-S〇2·、-CO-、-CONTi-、 -NHCO,、-C(CH3)2-、_C(CF3)2-、-(CH2)k-、-〇-(CH2)k_〇·、或-S-(CH2)k-S_、-N(CH3)-(CH2)k-N(CH3)-，且 k 為！〜12 的整數；G2 獨立為單鍵、-〇-、-S-、-CO-、_C(CH3)2-、-C(CF3)2-或碳數為1〜3的伸烷基；而環己烷環以及苯環的任意氫可由氟或-CH3取代。於式（III)中，較佳是兩個胺基不鍵結於相同碳原子上。式（IV)中的胺基較佳是不鍵結於鍵結有G1的碳原子上。 27 201012801 jzuozpu 以下表示二胺（II)〜二胺（IV)的具體例。 ,nh2 H2N<^^NHz H2N^^NH2 Η〆 (11-1) (ΙΙ-2) η2ν—^ ^-νη2 (111-1) η2ν (ΙΙΙ-2) (ΙΙ-3) (H-4)hzn-(Z)sn^C^-n Ηζ (ΙΙΙ-3)In the formulae (II) to (VIII), m is an integer of 1 to 12, and G1 is independently a single bond, -〇-, _S-, -SS-, -S〇2·, -CO-, -CONTi- , -NHCO,, -C(CH3)2-, _C(CF3)2-, -(CH2)k-, -〇-(CH2)k_〇·, or -S-(CH2)k-S_,- N(CH3)-(CH2)kN(CH3)-, and k is! An integer of ～12; G2 is independently a single bond, -〇-, -S-, -CO-, _C(CH3)2-, -C(CF3)2- or an alkylene group having a carbon number of 1 to 3; Any hydrogen of the cyclohexane ring and the benzene ring may be substituted by fluorine or -CH3. In the formula (III), it is preferred that the two amine groups are not bonded to the same carbon atom. The amine group in the formula (IV) is preferably not bonded to a carbon atom to which G1 is bonded. 27 201012801 jzuozpu Specific examples of the diamine (II) to diamine (IV) are shown below. ,nh2 H2N<^^NHz H2N^^NH2 Η〆(11-1) (ΙΙ-2) η2ν—^ ^-νη2 (111-1) η2ν (ΙΙΙ-2) (ΙΙ-3) (H-4) Hzn-(Z)sn^C^-n Ηζ (ΙΙΙ-3)

Η2Ν—^ ΝΗ2 (IV-2) 以下表示二胺（V)的具體例。 HzN-^^-NHj C^~NHz H2N-^VnH2 W HjN 尸 (V-1) 以下表示二胺（VI)的具體例Η2Ν—^ ΝΗ2 (IV-2) Specific examples of the diamine (V) are shown below. HzN-^^-NHj C^~NHz H2N-^VnH2 W HjN Corpse (V-1) Specific examples of the diamine (VI) are shown below.

H2N—/>~NH2 HjN—/>—nh2 h2n- nh, (V-2) (V-3) (V-4) (V-5) (VI-1) ΗζΝ·Λ\ //% // (Vl-2) NH,H2N—/>~NH2 HjN—/>—nh2 h2n- nh, (V-2) (V-3) (V-4) (V-5) (VI-1) ΗζΝ·Λ\ //% // (Vl-2) NH,

(VI-3) NH, -^^xVsC^~nh2 h2n-C^s^^'nh2 h* ⑩ H2N—^ iT //-NH2 (VI-4) h2n-Q^V〇-NH2 (VI-7)(VI-3) NH, -^^xVsC^~nh2 h2n-C^s^^'nh2 h* 10 H2N—^ iT //-NH2 (VI-4) h2n-Q^V〇-NH2 (VI- 7)

(VI-5) h2n(VI-5) h2n

nh2 (VI-8) H2N-^Vp^N^ (VI-8)Nh2 (VI-8) H2N-^Vp^N^ (VI-8)

h ^-NH2 (VI-11) H2N-0^^0~NH2 η,ν-^ (VI-10) 28 201012801h ^-NH2 (VI-11) H2N-0^^0~NH2 η,ν-^ (VI-10) 28 201012801

(VM2)(VM2)

>-ΝΗ2 (VI-13)>-ΝΗ2 (VI-13)

(VI-16) (VI-14) (VI-15) ΝΗ2 Φ Η2Ν-〇"〇νχ〇ν〇-ΝΗ^ Η2Ν-^^°^〇Ό~' (VI-17) (VI-18) η2ν—s·*·*σ-·^^"~ΝΗ2 Η:(VI-16) (VI-14) (VI-15) ΝΗ2 Φ Η2Ν-〇"〇νχ〇ν〇-ΝΗ^ Η2Ν-^^°^〇Ό~' (VI-17) (VI-18) Η2ν—s·*·*σ-·^^"~ΝΗ2 Η:

，〇ν〇-ΝΗ^ (VI-19) (VI-20) h2n^O^NvO~nH2 η2ν-〇"ν^"^~ΝΗ2 (VI-21) (VI-22) H2N"O^SV^^~NHz H2N-^^SvSX0_NH2 H2N~^^SV^SVC^_NH2 (VI-23) (VI-24),〇ν〇-ΝΗ^ (VI-19) (VI-20) h2n^O^NvO~nH2 η2ν-〇"ν^"^~ΝΗ2 (VI-21) (VI-22) H2N"O^ SV^^~NHz H2N-^^SvSX0_NH2 H2N~^^SV^SVC^_NH2 (VI-23) (VI-24)

(VI-25) NHZ (VI-26) (VI-27)(VI-25) NHZ (VI-26) (VI-27)

H2NH2N

>-〇-nh2 (VI-28) (VI-29)>-〇-nh2 (VI-28) (VI-29)

nh2 h2n -ζ^~-^~ΗΗί HzN-C^>^C^_i (VI-30) (VI-31) (VI-32) Q Η2Ν-θ~Ό^Nh2 h2n -ζ^~-^~ΗΗί HzN-C^>^C^_i (VI-30) (VI-31) (VI-32) Q Η2Ν-θ~Ό^

NHS Η2ΝβΟ^Ό"ΝΗ2 η2ν-Ο^Ό"νη2 h2n~〇^vO_nh2 (VI-33) (VI-34) (VI-35) 29 201012801 ^zuozpu 以下表示二胺（VII)的具體例NHS Η2ΝβΟ^Ό"ΝΗ2 η2ν-Ο^Ό"νη2 h2n~〇^vO_nh2 (VI-33) (VI-34) (VI-35) 29 201012801 ^zuozpu The following shows a specific example of the diamine (VII)

吵^〇^〇^0^〇-叫 Η2Ν-〇-〇"〇·〇Ό·ΝΗί (VII-4)Noisy ^〇^〇^0^〇-叫 Η2Ν-〇-〇"〇·〇Ό·ΝΗί (VII-4)

(VII-3) (VII-5)(VII-3) (VII-5)

Q 以下表示二胺（VIII)的具體例。Q Specific examples of the diamine (VIII) are shown below.

(VHI-5)(VHI-5)

30 201012801 32ϋ62ρΐί (VIII-8) (VIII-9) (VIII-10) (VIIM1) (VIII-12) 二胺（II)〜二胺（VIII)由於可藉由將這些二胺中的至少一種與本發明的二胺（1)合併使用，而將液晶分子的預傾角調整為0°〜3°，故適合作為IPS用配向膜原料。為了獲得電壓保持率更高的IPS用配向膜，較佳是將二胺（VI-1)或二胺（VI-2)合併使用。 % 為了獲得殘留DC更低的配向膜，較佳是將二胺 (VI-14)、二胺（VI-15)或二胺（VI-22)合併使用，尤其好的是將二胺（VI-22)合併使用。為了獲得提高液晶顯示元件的黑顯示特性的配向膜，較佳是將由二胺（VI-10)或二胺（VIII-3)所表示的二胺合併使用。作為其他公知的二胺，可列舉具有侧鏈結構的二胺。具有側鏈結構的公知二胺的例子是下述二胺（IX)〜二胺 31 201012801 jzuozpu (XII)。可將這些二胺中的至少一種與二胺（1)合併使用。可將二胺（II)〜二胺（VIII)中的至少一種及二胺（IX) 〜二胺（XII)中的至少一種與二胺（1)合併使用。另外，於本發明中，除了二胺（Π)〜二胺（XII)，亦可使用這些二胺以外的二胺。 R130 201012801 32ϋ62ρΐί (VIII-8) (VIII-9) (VIII-10) (VIIM1) (VIII-12) Diamines (II) to diamines (VIII) can be obtained by at least one of these diamines The diamine (1) of the present invention is used in combination, and the pretilt angle of the liquid crystal molecules is adjusted to 0 to 3°, which is suitable as an alignment film raw material for IPS. In order to obtain an alignment film for IPS having a higher voltage holding ratio, it is preferred to use a diamine (VI-1) or a diamine (VI-2) in combination. % In order to obtain a lower alignment film of residual DC, it is preferred to use a diamine (VI-14), a diamine (VI-15) or a diamine (VI-22) in combination, and particularly preferably a diamine (VI). -22) Combined use. In order to obtain an alignment film which enhances the black display property of the liquid crystal display element, it is preferred to use a diamine represented by a diamine (VI-10) or a diamine (VIII-3) in combination. As another well-known diamine, a diamine which has a side chain structure is mentioned. An example of a known diamine having a side chain structure is the following diamine (IX) to diamine 31 201012801 jzuozpu (XII). At least one of these diamines may be used in combination with the diamine (1). At least one of the diamines (II) to diamines (VIII) and at least one of the diamines (IX) to diamines (XII) may be used in combination with the diamine (1). Further, in the present invention, in addition to the diamine (oxime) to the diamine (XII), a diamine other than these diamines may be used. R1

32 201012801 j^uozpu 式（IX)中，G3 為單鍵、-0、-COO-、-OCO-、-CO-、 -CONH-或-(CH2)k-，且k為1〜12的整數。R1是碳數為3 〜20的烧基、苯基、具有類固醇（steroid)骨架的基團、或由下述式（IX_S)所表示的基團。於該烷基中，任意氫可由氟取代’並且任意-CH2-可由-0-、-CH=CH-或-C = C-取代。該苯基的氫可由-F、-CH3、-OCH3、-OCH2F、-〇CHF2 或-OCF3取代。胺基對苯環的鍵結位置為任意，但較佳是兩個胺基的鍵結位置關係為間位或對位。即，基團「rLg3-, 」的鍵結位置為1位時，較佳是兩個胺基分別鍵結於3位與 5位、或2位與5位。 (IX-S) 式（IX-S)中，R5為氫、氟、碳數為1〜2〇的烷基、碳數為1〜20的經氟取代的烷基、碳數為丨〜如的烷氧基、 -CN、-〇CH2F、-〇CHF2 或-〇CF3，G7、G8 以及 G9 為鍵結基團’且該些獨立為單鍵、〇_、_c〇〇、_〇c〇_、c〇nh、 33 201012801 G4獨立為單鍵、_(：〇_或-〇12·。< (XII)中的苯環的一個氫可由碳數為1〜20的烷基或苯基取代。式（X)中，較佳是兩個基團「NH2-伸笨基-G4-〇· 的其：-個，、__醇核的3位’另醇核的6位。式㈤中兩個基團「固^ 為苯===類_的鍵結位置而;: © 的鍵結位置_是相料(ΧΠ)巾’胺基對笨環式（XII)中’R4為^的鍵結位置而為間位或對位。烷基中碳數為2〜20 碳數為1〜20的烧基’且該 -CH=CH-或-CeC-取代。)基中的任意_CH2_可由、基。A1為1，4-伸苯基或i為七-或碳數為1〜ό的伸烷 1〜3的伸燒基，並且a‘伸環己基’G6為單鍵或碳數為較佳是相對於G5的鍵結j 〇或1。胺基對苯環的鍵結位置以下表示二胺d而為間位或對位。的具想例。 nh2 0½ OX-2)32 201012801 j^uozpu In the formula (IX), G3 is a single bond, -0, -COO-, -OCO-, -CO-, -CONH- or -(CH2)k-, and k is an integer from 1 to 12. . R1 is a group having a carbon number of 3 to 20, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (IX_S). In the alkyl group, any hydrogen may be substituted by fluorine ' and any -CH2- may be substituted by -0-, -CH=CH- or -C=C-. The hydrogen of the phenyl group may be substituted by -F, -CH3, -OCH3, -OCH2F, -〇CHF2 or -OCF3. The bonding position of the amine group to the benzene ring is arbitrary, but it is preferred that the bonding position relationship of the two amine groups is meta or para. That is, when the bonding position of the group "rLg3-," is 1 position, it is preferred that the two amine groups are bonded to the 3 position and the 5 position, or the 2 position and the 5 position, respectively. (IX-S) In the formula (IX-S), R5 is hydrogen, fluorine, an alkyl group having 1 to 2 carbon atoms, a fluorine-substituted alkyl group having 1 to 20 carbon atoms, and a carbon number of 丨~ Alkoxy, -CN, -〇CH2F, -〇CHF2 or -〇CF3, G7, G8 and G9 are bonding groups' and these are independently a single bond, 〇_, _c〇〇, _〇c〇 _, c〇nh, 33 201012801 G4 is independently a single bond, _(: 〇_ or -〇12·. < (XII) a hydrogen of the benzene ring may be an alkyl group or a phenyl group having a carbon number of 1 to 20 In the formula (X), it is preferred that the two groups "NH2-extension base-G4-〇· have: -, __ the 3 position of the alcohol nucleus" 6 positions of the alcohol nucleus. The two groups "solid" are the bonding positions of benzene === class _;; the bonding position of © is the phase material (ΧΠ) towel 'amine group' to the stupid ring type (XII) 'R4 is ^ The bonding position is meta or para. The carbon number in the alkyl group is 2 to 20, and the carbon number is 1 to 20, and any of the -CH=CH- or -CeC-substitution. CH2_ can be, a group. A1 is a 1,4-phenylene group or i is a seven- or an alkylene group having a carbon number of 1 to 伸, and the a'-cyclohexyl group 'G6 is a single bond or The carbon number is preferably relative to G5 Bond j amine square or 1. d represents a diamine of the bonding position of the phenyl ring and the meta- or para-position. Example WITH like. Nh2 0½ OX-2)

HaN (IX-3) NH2 nCsHii H2N _ (IX 句 (1X4} nh2 OX-6) 34 201012801 32ϋ62ρΐί _ 參HaN (IX-3) NH2 nCsHii H2N _ (IX sentence (1X4} nh2 OX-6) 34 201012801 32ϋ62ρΐί _

Π〇ΐβΗ33Π〇ΐβΗ33

π〇5Η*μ〇5〇*μ

nC7H15nC7H15

H2NH2N

> η〇8Η17 (IX-17)> η〇8Η17 (IX-17)

^5H11 {IX-19}^5H11 {IX-19}

λ—nC16H33λ-nC16H33

ιτΟςΗ”ιτΟςΗ"

nC16H33 h2n (IX-18)nC16H33 h2n (IX-18)

UC5H” (IX-20)UC5H” (IX-20)

H2N h2n h2n 0^°^Ο"π〇5Ηι1 h2n (IX-22) (IX-21) 35 201012801 ^zuozpu (IX-23) H2N ^-nC12H25H2N h2n h2n 0^°^Ο"π〇5Ηι1 h2n (IX-22) (IX-21) 35 201012801 ^zuozpu (IX-23) H2N ^-nC12H25

11C3H711C3H7

H2NH2N

36 201012801 32062pit 以下表示二胺（X)的具體例。36 201012801 32062pit Specific examples of the diamine (X) are shown below.

以下表示二胺（XI)的具體例。Specific examples of the diamine (XI) are shown below.

37 201012801 32062pif37 201012801 32062pif

以下表示二胺（XII)的具體例。Specific examples of the diamine (XII) are shown below.

(XII-Q 201012801 ο(XII-Q 201012801 ο

nh2Nh2

nh9Nh9

nh2 Φ 二胺（IX-1)〜二胺（IX_4)、二胺（IX-25)〜二胺 (IX-28)、以及二胺（XII-1)〜二胺（ΧΠ-6)，可藉由將該些二胺中的至少一種與本發明的二胺（1)合併使用，而將液晶分子的預傾角調整為3°〜15°，因此適合作為TN、 STN、OCB用配向膜原料。電壓保持率更高、可將殘留DC抑制為較低、且無論 39 201012801 配向膜形成步驟的條件如何均可穩定地對液晶分子賦予一定的所需預傾角的TN、STN、OCB用配向膜的原料，較佳是將二胺（ΙΧ·2)、二胺（χπ^)、二胺（χιι_4)以及二胺（ΧΙΙ-6)中的至少一種與二胺（i)合併使用。二胺（ΙΧ-7)、二胺（ιχ_8)、二胺（Ιχ·13)〜二胺 (ΙΧ-16)、二胺（ΙΧ-29)〜二胺（ΙΧ_33)、二胺（χ4) 〜二胺（Χ-4)、二胺（xw)〜二胺（χι_4)、以及二胺 (ΧΙΙ-7)〜一胺（ΧΠ-11 )，可藉由將該些二胺中的至少一種與二胺（1)合併使用而將液晶分子的預傾角調整為 90°，因此適合作為VA用配向膜原料。如要電壓保持率更高、可將殘留DC抑制為較低、且無論配向膜形成步驟的條件如何均可穩定地對液晶分子職予一定的所需預傾角之VA用配向膜原料，較佳是將二胺 (IX-7)、一胺（IX-8)、二胺（IX-13)、以及二胺（ιχ_ΐ4) 中的至少一種與二胺（1)合併使用。此外，可與本發明的二胺合併使用的二胺，可列舉包含矽氧烷鍵的矽氧烷系二胺。該矽氧烷系二胺並無特別限定，較佳是使用由式（S1)所表示的二胺。 R7 R7 Η2Ν—R6—^-Si—0-] Si—R6-NH2 (Si) R8 f R8 其中，R6獨立為碳數為1〜6的伸燒基、伸苯基或經烧基取代的伸苯基。R7以及R8獨立為碳數為1〜3的燒基或苯基。並且f為1〜10的整數。該些矽氧烷系二胺的使用量备為不損及本發明效果的範圍，則無特別限定。 201012801 對本發明的液晶配向劑進行說明。本發明的液晶配向劑是含有選自本發明的聚合物中的一種或一種以上的聚合物溶液。本發明的液晶配向劑的具體例為藉由使二胺（1) 與酸二酐進行反應而獲得的本發明的聚醯胺酸溶液、使自該聚醯胺酸溶液中除去溶劑而獲得的聚醯胺酸的聚合物溶解於溶劑令所獲得的聚醯胺酸溶液以及該些的混合物等。本發明的液晶配向劑可為製備本發明的聚合物時所使用的馨反應溶液本身，亦可為使自反應溶液中餾去溶劑而獲得的聚合物溶解於與該反應所使用的溶劑不同的溶劑中而成的溶液。本發明的液晶配向劑中所使用的溶劑並無特別限定’例如可列舉：N-曱基-2-吡咯啶酮 (N-methyl-2-pyrrolidone ’ NMP )、二曱基曱醯胺（dimethyl formamide，DMF )、二曱基乙醯胺（dimethyl acetamide， DMAc)、二甲基亞硬（dimethyl sulfoxide，DMSO)、乙二醇單丁醚（ethylene glycol monobutylether，BC)、乙二醇 ❹單乙_、h丁内醋（γ-butyrolactone)等。於本發明中，可將選自上述溶劑中的兩種或兩種以上混合使用。而且，若本發明的聚合物可溶，則可使用上述以外的溶劑。本發明的液晶配向劑中，為了表現出作為配向膜的更好的特性，可進-步添加選自公知的所有聚合物中的一種上。此時’為了表現出本發明的效果’本發明聚。物在總聚合物中所佔的較佳比例為5G重量百分比〜ι〇〇重量百分比’更佳比例是70重量百分比〜1〇〇重量百分 41 201012801 ^/υοζριι 比。此種聚合物的例子可列舉：⑽胺、聚胺基甲駿輯、聚腺聚Sa、聚環氧化物、聚g旨多^醇、石夕改質聚胺酸酯、矽改質聚酯等。甲〜本發明的液晶配向劑中所含的聚合物比例並無特限定，可根據製作液晶顯示元件時的步驟來選擇最合適值。通常，為了抑制對玻璃基板塗佈時的不均或針孔 (pinhole)等，上述聚合物比例相對於液晶配向劑總量，較佳是0.1重量百分比〜30重量百分比，更佳是^ 量百分比〜10重量百分比。 Ο 若於本發明的液晶配向劑中添加有機矽化合物，則可調節配向膜對玻璃基板的附著性及硬度，可改善由於藉由 f擦等而削去聚醯亞胺所導致的顯示不良。於本發明的液 :曰配向劑中添加的有機矽化合物並無特別限定，例如較佳是添加：胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、N-(2-胺基乙基)_3·胺基丙基甲基二甲氧基矽烧、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽院、3-縮水甘油氧基丙基三曱氧基矽烷、3_縮水甘油氧基丙基甲基二曱氧基矽烷、2-(3,4-環氧環己基）乙基三曱氧基石夕燒等矽烷偶合劑’二曱基聚矽氧烷、聚二曱基矽氧烷、聚二苯基矽氧烷等矽油；尤其好的是添加胺基丙基三乙氧基發烷、3-縮水甘油氧基丙基曱基二曱氧基矽烷、2_(3,4_ 環氧環己基）乙基三曱氧基矽烷。這種有機矽化合物於液晶配向劑中的添加比例，若是 42 201012801 能在不損輯上述配向麟要求騎性而改善顯示不良的範圍内，則無特別限制。然而，若添加大量的這些有機石夕化合物，則製成配向臈時會產生液晶的配向不良。因此，相對於液晶配向劑中所含有的聚合物的總重量，該些矽化合物的濃度較佳是0.01重量百分比〜5〇重/^百分比，更佳是0·1重量百分比〜20重量百分比。刀 ο 藉由混合使用不同種類的聚合物，亦可製備可賦予需預傾角的液晶配向劑。這是利用如下情況：若將表面铲量不同的多種聚合物混合，則該些聚合物形成薄膜時，= 面能量小的聚合物易於向表面偏析。藉由摻合此種聚人物，可於配向膜的表面對液晶分子賦予預傾角，且形二示出良好液晶配向性的成分（稱為聚合物Α)的層，V並且於塗佈基板侧形成表現出良好電特性的成分（聚的層。即，可獲得該些兩種特性優異的配二法，揭示於日本專利特開平8-43831號公報中。本發明的液晶配向劑中亦可摻合聚合物。本發明合物形成電特性優異_向膜’因此適合作為聚合物成分。而且，如上文所述，本發明的聚合物藉由將由' 所表示的本發明的二胺與其他二胺加以、板合，而4二J 聚合物A的成分。Nh2 Φ diamine (IX-1) to diamine (IX_4), diamine (IX-25) to diamine (IX-28), and diamine (XII-1) to diamine (ΧΠ-6), By using at least one of these diamines in combination with the diamine (1) of the present invention, the pretilt angle of the liquid crystal molecules is adjusted to 3 to 15°, and thus it is suitable as an alignment film raw material for TN, STN, and OCB. . The alignment film of TN, STN, and OCB which has a higher voltage holding ratio and can suppress residual DC to a lower TN, STN, and OCB which can stably impart a desired pretilt angle to liquid crystal molecules regardless of the conditions of the alignment film forming step of 39 201012801. As the raw material, at least one of diamine (ΙΧ·2), diamine (χπ^), diamine (χιι_4), and diamine (ΧΙΙ-6) is preferably used in combination with the diamine (i). Diamine (ΙΧ-7), diamine (ιχ_8), diamine (Ιχ·13)~diamine (ΙΧ-16), diamine (ΙΧ-29)~diamine (ΙΧ_33), diamine (χ4)~ Diamine (Χ-4), diamine (xw)~diamine (χι_4), and diamine (ΧΙΙ-7)~monoamine (ΧΠ-11) by using at least one of these diamines The diamine (1) is used in combination to adjust the pretilt angle of the liquid crystal molecules to 90°, and thus is suitable as an alignment film raw material for VA. If the voltage retention ratio is higher, the residual DC can be suppressed to a lower level, and the alignment film raw material of the VA for which the liquid crystal molecule is stably required to have a desired pretilt angle can be stably obtained regardless of the conditions of the alignment film formation step. At least one of the diamine (IX-7), the monoamine (IX-8), the diamine (IX-13), and the diamine (ιχ_ΐ4) is used in combination with the diamine (1). Further, examples of the diamine which can be used in combination with the diamine of the present invention include a decane-based diamine containing a siloxane chain. The dioxane-based diamine is not particularly limited, and a diamine represented by the formula (S1) is preferably used. R7 R7 Η2Ν—R6—^—Si—0—] Si—R6—NH 2 (Si) R 8 f R8 wherein R 6 is independently a stretching group having a carbon number of 1 to 6, a stretching phenyl group or a substituted alkyl group. Phenyl. R7 and R8 are independently a decyl group or a phenyl group having a carbon number of 1 to 3. And f is an integer of 1 to 10. The amount of the oxirane-based diamine to be used is not particularly limited as long as it does not impair the effects of the present invention. 201012801 A liquid crystal alignment agent of the present invention will be described. The liquid crystal alignment agent of the present invention is one or more polymer solutions containing a polymer selected from the present invention. Specific examples of the liquid crystal alignment agent of the present invention are obtained by reacting a diamine (1) with an acid dianhydride to obtain a polyaminic acid solution of the present invention, and removing a solvent from the polyamic acid solution. The polymer of poly-proline is dissolved in a solvent to obtain a poly-proline solution, a mixture of these, and the like. The liquid crystal alignment agent of the present invention may be the sensible reaction solution itself used in the preparation of the polymer of the present invention, or may be a polymer obtained by distilling off the solvent from the reaction solution, which is different from the solvent used in the reaction. A solution made from a solvent. The solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone 'NMP and dimethyl hydrazine. Formamide, DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol monobutylether (BC), ethylene glycol monoethyl ether _, h butyl vinegar (γ-butyrolactone) and the like. In the present invention, two or more kinds selected from the above solvents may be used in combination. Further, if the polymer of the present invention is soluble, a solvent other than the above may be used. In the liquid crystal alignment agent of the present invention, in order to exhibit better characteristics as an alignment film, one selected from all of the well-known polymers may be further added. At this time, in order to exhibit the effects of the present invention, the present invention is concentrated. A preferred ratio of the material in the total polymer is 5 G weight percent to 1 〇〇重量%. A more preferred ratio is 70 weight percent to 1 weight percent 41 201012801 ^/υοζριι ratio. Examples of such a polymer include (10) an amine, a polyaminocarbazide, a poly agglomerated Sa, a polyepoxide, a polyglycol, a polyglycol, a ruthenium modified polyester, and a ruthenium modified polyester. Wait. The proportion of the polymer contained in the liquid crystal alignment agent of the present invention is not particularly limited, and the optimum value can be selected in accordance with the procedure for producing a liquid crystal display element. In general, in order to suppress unevenness or pinholes or the like at the time of coating the glass substrate, the ratio of the above polymer is preferably from 0.1% by weight to 30% by weight, more preferably from the total amount of the liquid crystal alignment agent. ~10 weight percent. When the organic ruthenium compound is added to the liquid crystal alignment agent of the present invention, the adhesion and hardness of the alignment film to the glass substrate can be adjusted, and the display failure caused by the removal of the polyimide by the rubbing or the like can be improved. The organic hydrazine compound to be added to the liquid: hydrazine alignment agent of the present invention is not particularly limited, and for example, it is preferably added: aminopropyltrimethoxydecane, aminopropyltriethoxydecane, vinyltrimethoxy矽, N-(2-Aminoethyl)_3·aminopropylmethyldimethoxy oxime, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, ethylene Triethoxy decane, 3-methylpropenyloxypropyltrimethoxy fluorene, 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropylmethyl dioxin a decane coupling agent such as decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy oxetane, 'dimercaptopolyoxyalkylene, polydidecyloxynonane, polydiphenylphosphonium oxide An oil such as an alkane; particularly preferred is the addition of aminopropyltriethoxycarbonyl, 3-glycidoxypropylmercaptodimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriazine Oxydecane. The ratio of the addition of such an organic cerium compound to the liquid crystal alignment agent is not particularly limited as long as it can improve the display failure without impairing the riding property of the above-mentioned alignment. However, when a large amount of these organic cerium compounds are added, alignment failure of the liquid crystal occurs when the alignment enthalpy is formed. Therefore, the concentration of the cerium compound is preferably 0.01% by weight to 5% by weight, more preferably from 0.1% by weight to 20% by weight, based on the total mass of the polymer contained in the liquid crystal alignment agent. Knife ο A liquid crystal alignment agent which imparts a pretilt angle can be prepared by mixing different kinds of polymers. This is the case where, when a plurality of polymers having different surface sizing amounts are mixed, when the polymers form a film, the polymer having a small surface energy tends to segregate toward the surface. By blending such a poly person, a pretilt angle can be imparted to the liquid crystal molecules on the surface of the alignment film, and a layer showing a composition of good liquid crystal alignment (referred to as a polymer crucible), V and on the side of the coated substrate can be given. A component which exhibits a good electrical property (a polylayer), that is, a method of obtaining the two properties which are excellent in the two properties, is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-43831. The liquid crystal alignment agent of the present invention may also be used. The polymer of the present invention is excellent in electrical properties. The film is thus suitable as a polymer component. Moreover, as described above, the polymer of the present invention is represented by the diamine of the present invention represented by ' The diamine is added, plated, and the composition of the 4 J J polymer A.

聚合物A與聚合物B的混合比分別可於〗重量百八〜99重量百分比之間任意選擇。然而，為了表現液晶配向特性以及保持著預傾角的良好電特性，聚人叩的比例以聚合物總重量為基準，較佳是i重量百八^ A 43 201012801 重量百分比，更佳是5重將與聚酿紐的〜3G重量百分比。明的液晶配向劑中，亦對基反應的交聯劑添加於本發因環境而劣化而言較為用以防止特性隨時間而劣化或利第3049699號公報、日本裒去此種交聯劍，可列舉日本專日本專利㈣平1Q_2l24t41=薦_27536(>號公報、氧、異氰酸輯材料等。而且交::報^中記載的多官能環 0 ^ A 4,1 „ 相同的目的。此種交聯劑，可列舉：日本專利特開平1()·31_8 : 酿亞脸f 等中載的多官能乙_、順丁烯二衍生物^ 、或雙柄基魏亞胺（bisallyl nadiimide ) 另外’本發明中使用的交聯劑可為這些以外的 ^ :使用交聯劑時，為了呈現本發明的效果，交聯劑例以相對於本發明的聚合物的重量比計較佳是〇〇5 〜〇·5 ’更佳是0.1〜〇.3。 · 本發明的液晶配向劑的黏度是根據塗佈的方法、聚合物的種類或濃度、溶劑的種類等’較佳是5 mPa · s〜1〇〇 mPa S ’更佳是丨〇 mPa · s〜80mPa · s。為了獲得充分的膜厚，較理想的是大於5 mPa· s的黏度，為了不產生印刷不均’較理想的是小於100 mPa · s的黏度。其中，於利用喷墨法進行印刷的情況，黏度小於等於5 mPa.s的液晶配向劑亦可使用。其·•欠’對本發明的液晶顯示元件進行說明。本發明的 _ Ο 201012801 32062pif 液晶顯示元件包括：對向配置的一對基板；（2)形成於上述一對基板之分別對向的面上的液晶配向膜；以及（3) 夾持於上述一對基板間的液晶層。於此一對基板的兩者上可配置有電極，但於IPS型液晶顯示元件的情況，是於一，，板的其t之-上配置電極（可為梳狀或鑛齒結構的電上述液晶配向膜是藉由將本發明的液晶配向劑塗佈於上述基板上’進行加熱而形成的液晶配向膜。此處，液晶配向膜的膜厚較佳是10 nm〜3〇〇 nm，更佳是3〇 nm〜 100nm。此外，液晶配向膜較佳是經摩擦處理。上述對向配置的-對附有電極之基板，較佳是透明基板（例如玻璃基板）。夾持於上述-對基板間的液晶層包含液晶組成物。此處，液晶組成物並無特別限制，根據驅動模式，可使用介，常數各向異性為正的液晶組成物以及介電常數各向異性 ^負的液晶組成物中的任一種組成物。介電常數各向異性缺2較佳液晶組成物的例子揭示於日本專利第娜挪號么報、日本專利第2635435號公報、日本專利特 5-501735號公報、日本專利特開平8七號公報、、 =利特開平8_231_號公報、日本專利號公報⑽觀舰）、日本專利特開平9_3〇2346號公報 (EP8〇6466A1 )、曰本專利特開平8·199168號八報 jEP722998Al )、日本專利特開平沾加號公報^本專利特開平9·255956號公報、日本專利制平&遍43 45 201012801The mixing ratio of the polymer A to the polymer B can be arbitrarily selected from about 8% to 99% by weight, respectively. However, in order to express the liquid crystal alignment characteristics and the good electrical characteristics of maintaining the pretilt angle, the ratio of the polybenzazole is based on the total weight of the polymer, preferably i weight 8%, A, 4, 2010, 12,801,801, and more preferably 5 weights. ~3G weight percent with poly-branches. In the liquid crystal alignment agent of the prior art, the crosslinking agent for the base reaction is also used to prevent deterioration of the characteristics with time due to deterioration of the environment due to the environment, or the cross-linking sword is removed from Japan in Japanese Patent No. 3049699. Japanese special Japanese patent (4) flat 1Q_2l24t41=recommended _27536 (>, bullet, oxygen, isocyanate material, etc., and the following: the polyfunctional ring described in the report ^ 0, A 4, 1 „ the same purpose Such a crosslinking agent can be exemplified by: Japanese Patent Laid-Open No. 1 () 31_8: Polyfunctional B-, maleic derivative, or bisallyl Nadiimide) Further, the crosslinking agent used in the present invention may be other than these. When a crosslinking agent is used, in order to exhibit the effects of the present invention, the crosslinking agent is preferably a weight ratio with respect to the polymer of the present invention. 〇〇5 〇5·5 is more preferably 0.1 〇.3. The viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa depending on the method of application, the type or concentration of the polymer, the type of the solvent, and the like. · s~1〇〇mPa S 'better is 丨〇mPa · s~80mPa · s. In order to get full Thick, more preferably a viscosity of more than 5 mPa·s, in order not to cause uneven printing, it is preferably a viscosity of less than 100 mPa·s. Among them, in the case of printing by the inkjet method, the viscosity is 5 mPa or less. The liquid crystal display element of the present invention can also be used. The liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention includes: a pair of substrates arranged in opposite directions; (2) formed on the above a liquid crystal alignment film on a surface of the pair of substrates facing each other; and (3) a liquid crystal layer sandwiched between the pair of substrates. An electrode may be disposed on both of the pair of substrates, but the IPS liquid crystal is provided. In the case of the display element, the electrode is disposed on the t-top of the plate (the comb-like or mineral-tooth structure is electrically applied to the liquid crystal alignment film by applying the liquid crystal alignment agent of the present invention to the substrate 'The liquid crystal alignment film formed by heating. Here, the film thickness of the liquid crystal alignment film is preferably 10 nm to 3 Å, more preferably 3 Å to 100 nm. Further, the liquid crystal alignment film is preferably subjected to rubbing treatment. The above opposite configuration - a substrate to which an electrode is attached, preferably a transparent substrate (for example, a glass substrate). The liquid crystal layer sandwiched between the above-mentioned pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and depending on the driving mode, Any one of a liquid crystal composition having a positive anisotropy and a liquid crystal composition having a positive dielectric anisotropy can be used. A dielectric constant anisotropy is preferable. Japanese Patent No. 1 Nagano, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. 8-7, No. 5, No. 8-231_, Japanese Patent No. (10) [Patent Ship], Japanese Patent Laid-Open No. 9_3〇2346 (EP8〇6466A1), 曰本专利特开平8·199168号八报jEP722998Al), Japanese Patent Unexamined Gazette Plus Gazette ^This Patent Special Kaiping 9·255956 Bulletin, Japanese Patent System Flat & All 43 45 201012801

3ZU0ZPU 報（EP885271A1)、日本專利特開平1G_2G4㈣號公 a本^4^9^)^本專利特開平1G_2_號公報、日本專利特開千侧1482號 2;關7°4°號公報、日本專利特開2—^^ 數各Γ異元件中使用的液晶組成物可為介電常朗昭57_114532號公報、日本專利特 Θ 日本專利特ίΛ 日本專利特開平4-224885號公報、 953號公報、日本專利特開平本專利、日本專_開平i(M68G76號公報、日本專利特開平咖=tti0-236990號公教、曰 __3號公報、曰太報、曰本專利特開平本專利特η ^本專特開平10-236994號公報、日 ❹ =!二。曰2^ ； 1〇 Itot It10'237024 ' 3 10-237075辨Γ相號公報、日本專利特開平本專利如^報、日本專利制平1G·237076號公報、日利特、1G_237448號公報（EP967261A1)、日本專號公:、日ΓΓ874號公報、日本專利特開平10-287875 開平11 02958^特開平10-291945號公報、日本專利特報日本專二、日本專利特開平U·080049號公報日本專利特開2_-256307號公報、 463ZU0ZPU newspaper (EP885271A1), Japanese patent special Kaiping 1G_2G4 (four) No. a ^ ^ ^ ^ ^ ^ ^ This patent special open flat 1G_2_ bulletin, Japanese patent special open thousand side 1482 2; Guan 7 ° 4 ° bulletin, Japan The liquid crystal composition used in each of the various elements of the invention is disclosed in Japanese Laid-Open Patent Publication No. Hei 57-114532, Japanese Patent Laid-Open Publication No. Hei No. Hei-4-224885, No. 953 Japanese patent special patent, Japanese special _ Kaiping i (M68G76 bulletin, Japanese patent special open flat coffee = tti0-236990, public education, 曰__3 bulletin, 曰太报, 曰本 patent special open patent η ^ This special Kaiping No. 10-236994, Japanese ❹ =! II. 曰 2^ ; 1〇 Itot It10'237024 ' 3 10-237075 Γ Γ phase bulletin, Japanese patent special open flat patent such as ^ newspaper, Japanese patent system Japanese Patent Publication No. 1G-237076, Japanese Patent No. 1G_237448 (EP967261A1), Japanese Patent No.: Japanese Patent No. 874, Japanese Patent Laid-Open No. Hei 10-287875, Kaiping 11 02958, Japanese Patent Laid-Open No. Hei 10-291945, Japanese Patent Special Report Japanese Specialist, Japanese Patent Special Open U.080049 Japanese Patent Laid-Open Publication No. 2_ -256307, 46

參 201012801 ^^UDZpil 號公報、日本專彳_測刚626號公報、曰本專利特開2001-192657號公報等中。對=述介電常數各向異性為正或㈣液晶組成物來說丄也可以添加-種或―種以上的光學活性化合物。本發明的液晶顯示元件可具有其他構件。例如，使用薄膜電晶體的彩色顯示TFT型液晶元种，於第—透明基板上形成薄膜電晶體、絕緣膜、保護膜、信號電極、晝素電極等’且於第二透明基板上具有輯畫素區域以外之光的黑色矩陣（black matrix )、彩色濾光片（e〇1〇r _γ ) 坦化膜以及晝素電極等。 VA型液晶顯示元件尤其是MVA型液晶顯示元件中，於第透％基板上形成稱為域（dGmain)的微小突起物。而且，亦可為了於基板間形成單元間隙而形成間隔片 (spacer)。本發明的液晶顯示元件是利用任意方法製作，例如利用包含如下步驟的方法來製作：（1)於上述兩片透明基板上進行的液晶配向劑塗佈步驟；（2)對所塗佈的液晶配向劑進行的乾燥步驟；（3)用以使經乾燥的液晶配向劑進行脫水·開環反應的加熱處理步驟；（4)對所得配向膜進行的配向處理步驟；（5)在將兩片基板貼合後於基板間封入液晶的液晶封入步驟，或者使液晶滴在其甲一片基板上後使另一片基板貼合的步驟。上述塗佈液晶配向劑的步驟中的塗佈方法，通常已知有旋轉器（spinner)法、印刷法、浸潰（ipping)法、滴 47 201012801 加法=nkjet)法等。該些方法亦可助於本發明中。理步驟的方法，诵赍士从l “丁π乂高的加熱處理、於有於洪箱中或紅外爐中的加熱處明中；史、^上的加熱處理等。該些方法亦可應用於本發 (5〇t l^較佳是於溶射蒸發的朗⑽較低溫度二:=二熱處卿通常較佳是於⑼Japanese Patent Publication No. 2010-12801 ^^UDZpil, Japanese Patent Publication No. 626, and Japanese Patent Laid-Open No. 2001-192657. For the case where the dielectric anisotropy is positive or the (iv) liquid crystal composition, an optically active compound of the above species or a plurality of kinds may be added. The liquid crystal display element of the present invention may have other members. For example, a color display TFT type liquid crystal cell using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a halogen electrode, etc. are formed on the first transparent substrate and has a picture on the second transparent substrate A black matrix (light matrix), a color filter (e〇1〇r _γ ), a dendrite film, and the like, which are light outside the prime region. In the VA type liquid crystal display element, in particular, the MVA type liquid crystal display element, minute projections called domains (dGmain) are formed on the first%% substrate. Further, a spacer may be formed in order to form a cell gap between the substrates. The liquid crystal display element of the present invention is produced by any method, and is produced, for example, by a method comprising the steps of: (1) a liquid crystal alignment agent coating step on the two transparent substrates; and (2) coating the liquid crystal. a drying step of the alignment agent; (3) a heat treatment step for subjecting the dried liquid crystal alignment agent to a dehydration/ring-opening reaction; (4) an alignment treatment step for the obtained alignment film; and (5) two sheets at the same A step of sealing a liquid crystal in which a liquid crystal is sealed between substrates, or a step of bonding liquid crystals onto one of the substrates to bond the other substrate. The coating method in the step of applying the liquid crystal alignment agent is generally known as a spinner method, a printing method, a dicing method, a dropping method, and a NKjet method. These methods are also useful in the present invention. The method of the step, the gentleman from the "Ding π 乂 high heat treatment, in the heating box in the flood box or in the infrared furnace; history, heat treatment on the ^, etc.. These methods can also be applied In this hair (5 〇 tl ^ is preferably in the evaporation of the lang (10) lower temperature two: = two heat clerk is usually better at (9)

型液S/純科件、咖生履晶顯不兀件，所述配向處理通仃摩擦處理。對於VA型液晶顯示元件，則不進行摩擦處理的情況較多，但亦可進行雜處理。，著’於其中—片基板上塗佈黏著舰貼合再於減液晶。於滴加注人法的情況下，則是於貼合前將 ^加至基板上’然後貼合另—絲板。制於貼合的黏=劑以熱或紫外線來硬化，從而製作本發明的液晶顯示 7G件。The type liquid S/pure parts and the gritty crystals are displayed, and the alignment treatment is performed by rubbing treatment. In the case of the VA liquid crystal display element, the rubbing treatment is not performed, but the miscellaneous treatment can be performed. Applying adhesive tape to the substrate to remove the liquid crystal. In the case of the drop-filling method, it is added to the substrate before the bonding, and then the other wire plate is attached. The adhesive agent to be bonded is hardened by heat or ultraviolet rays to produce a liquid crystal display 7G member of the present invention.

、本發明的液晶肺元件中可安裝偏紐（偏光膜）、波長板、光散射膜、驅動電路等。本發明的液晶顯示元件具有電壓保持率高、且殘 DC低的特徵。其原因在於，本發明的液晶顯示元件的晶配向膜;^包括使用由二胺⑴所表示的化合物而的聚醜胺酸或者該聚醯胺酸的衍生物的液晶配向劑所形成。對此於下述實施例中進行說明。【實施例】 48 201012801 由以下實施例，對本發明的二胺、藉由使用該二胺而獲得的液晶配向劑以及液晶顯示元件進行詳細說明，但發明並不限定於這些實施例。實施例中，是於氘化二甲基亞颯(deuterateddimethyl sulf〇xide)中進行。^ 子量的測定是使肖GPC，以聚苯乙歸為標準溶液，溶析^ 是使用DMF。另外，於以下實施例中，容積的單位升是以 L表示。因此，mL意指毫升。首先，對實施例中使用的液晶顯示元件的評價方法進響行說明。In the liquid crystal lung element of the present invention, a polarizing film (polarizing film), a wavelength plate, a light scattering film, a driving circuit, and the like can be mounted. The liquid crystal display device of the present invention has a feature that the voltage holding ratio is high and the residual DC is low. The reason for this is that the crystal alignment film of the liquid crystal display element of the present invention comprises a liquid crystal alignment agent using a poly leuco acid which is a compound represented by the diamine (1) or a derivative of the polyaminic acid. This is illustrated in the following examples. [Examples] 48 201012801 The diamine of the present invention, the liquid crystal alignment agent obtained by using the diamine, and the liquid crystal display element will be described in detail in the following examples, but the invention is not limited to these examples. In the examples, it was carried out in deuterated dimethyl sulfoxixide. The sub-quantity is determined by using Xiao GPC, which is classified as polystyrene and standard solution, and using DMF. Further, in the following examples, the unit liter of the volume is represented by L. Therefore, mL means milliliters. First, the evaluation method of the liquid crystal display element used in the embodiment will be described.

(1) 殘留DC 對30 Hz、3 V的矩形波重疊1 V的直流電壓30分鐘 ' 後，測定10分鐘後的閃爍（flicker)消除電壓，將該值的絕對值作為殘留DC。殘留DC越小，則留痕越少，可謂良好。 (2) 電壓保持率依據「水嶋他，第14次液晶討論會預稿集P78」中 ® 6己載的方法。測定是將閘極寬度（gate width)為)59 ps、頻率（frequency)為 0.3 Hz、脈高（pulse height)為±5.0 V 的矩形波施加至單元而進行。測定溫度為6(TC。 (3) 預傾角預傾角的測定是利用晶體旋轉法（crystal rotation method)進行。測定所使用的光的波長為589 nm。 [實施例1] <二胺（M)的合成> 49 201012801 32062pit 向安裝有撥拌機、溫度計以及氮氣導人口的iL三口燒瓶中加入11.4g(〇.46m〇l)的60%氫化納，添加1〇〇mL 的DMF。使溶液冷卻至5艺，然後於其中滴加使 mol)的市售的5-胺基吲哚溶解於2〇〇 mL的DMF中而成的;谷液。然後使溶液升溫至室溫，於氮氣環境下攪拌i小時。再次使溶液冷卻至5°c，再於其中滴加使39 g (〇 28 mol)的4-氟硝基苯溶解於2〇〇mL的DMF中而成的溶液。接著使溶液升溫至室溫，於氮氣環境下攪拌12小時。之後，將反應溶液放至500 mL乙酸乙酯以及5〇〇 mL純水的 ⑩ 混合溶劑中進行萃取，將有機層以500 mL純水清洗3次。使有機層以無水硫酸鈉乾燥後，將無水硫酸鈉除去，將溶劑減壓館去，獲得粗結晶。然後利用管柱層析法（曱笨：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，獲得n_(4_ ' 硝基苯基)-5-胺基吲哚（產量為35.0 g，產率為60%)。 · 於咼壓蒸氣滅菌處理（autoclave)用反應管中加入35 〇 g (0.14 mol)所獲得的N-(4-确基苯基)-5-胺基吲哚、3 5g 的鈀碳粉末，添加350 mL的乙醇以及35 mL的乙酸乙輯。使系統内成為氳氣環境下，於氫壓0.49 MPa、室溫下授掉懸 12小時。接著將把碳粉末除去，將所獲得的溶液濃縮，獲得粗結晶。然後利用管柱層析法（曱苯：乙酸乙酯=3 : i (v/v))將粗結晶分離純化，獲得二胺（ι_4) (N_(4_胺基苯基)-5-胺基吲哚）（產量為28.8 g，產率為92%)。 'H-NMR (ppm): 3.53 (-NH2, br. s, 2H), 3.74 (-NH2, br. s, 2H)，6·43·7·25 (arm· H，m，9H)· 50 201012801 [實施例2] <二胺（1-2)的合成> 除將5-硝基吲哚替代為6_硝基吲哚以外，依據實施例 1中記載的方法，獲得二胺（1-2)(义(4_胺基苯基)_6_胺基 °弓ί哚）。 ^-NMR (ppm)； 3.52 (-NH2, br. s, 2H), 3.75 (-NH2, br. s, 2H), 5.85-8.18 (arm. H, m, 9H).(1) Residual DC After a DC voltage of 1 V is superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes ', the flicker elimination voltage after 10 minutes is measured, and the absolute value of this value is taken as residual DC. The smaller the residual DC, the less the trace is, which is good. (2) Voltage holding ratio According to the method of "6 己, he is the 14th liquid crystal seminar prep draft P78". The measurement was performed by applying a rectangular wave having a gate width of 59 ps, a frequency of 0.3 Hz, and a pulse height of ±5.0 V to the cell. The measurement temperature was 6 (TC. (3) The pretilt angle pretilt angle was measured by a crystal rotation method. The wavelength of light used for the measurement was 589 nm. [Example 1] <Diamine (M Synthesis of > 49 201012801 32062pit To a iL three-necked flask equipped with a mixer, a thermometer, and a nitrogen-conducting population, 11.4 g (〇.46 m〇l) of 60% sodium hydride was added, and 1 mL of DMF was added. The solution was cooled to 5 liters, and then a commercially available 5-amino hydrazine of mol) was dissolved in 2 liters of DMF; The solution was then allowed to warm to room temperature and stirred for 1 hour under a nitrogen atmosphere. The solution was again cooled to 5 ° C, and a solution obtained by dissolving 39 g (〇 28 mol) of 4-fluoronitrobenzene in 2 mL of DMF was added dropwise thereto. The solution was then warmed to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was subjected to extraction in a mixed solvent of 500 mL of ethyl acetate and 5 mL of pure water, and the organic layer was washed 3 times with 500 mL of pure water. After the organic layer was dried over anhydrous sodium sulfate, anhydrous sodium sulfate was removed, and the solvent was evaporated to give a crude crystal. Then, the crude crystals were separated and purified by column chromatography (acetonitrile: ethyl acetate = 5:1 (v/v)) to obtain n-(4_' nitrophenyl)-5-amino hydrazine (yield was 35.0 g, yield 60%). · N-(4-decylphenyl)-5-amino hydrazine, 35 g of palladium carbon powder obtained by adding 35 〇g (0.14 mol) to a reaction tube for autoclave autoclave Add 350 mL of ethanol and 35 mL of Acetate. The system was allowed to be suspended in a helium atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (phenylbenzene: ethyl acetate = 3: i (v/v)) to obtain diamine (1) (N-(4-aminophenyl)-5-amine. Base) (yield 28.8 g, yield 92%). 'H-NMR (ppm): 3.53 (-NH2, br. s, 2H), 3.74 (-NH2, br. s, 2H), 6·43·7·25 (arm· H, m, 9H)· 50 201012801 [Example 2] <Synthesis of diamine (1-2)> In addition to 5-nitroguanidine instead of 6-nitroguanidine, a diamine was obtained according to the method described in Example 1 ( 1-2) (I(4_Aminophenyl)_6-amino group ° bow 哚). ^-NMR (ppm); 3.52 (-NH2, br. s, 2H), 3.75 (-NH2, br. s, 2H), 5.85-8.18 (arm. H, m, 9H).

[實施例3] <二胺（1-5)的合成> 依據 Tetrahedron Letters 41，1815-1818 (2000)中記載的方法，向安裝有攪拌機、溫度計、冷卻器以及氮氣導入口的1 L三口燒瓶中加入5〇 g (〇25 m〇1)的4,4，_二胺基一苯基甲烷、18.6 g (〇.1〇 mol)的三乙醇胺鹽酸鹽、u 3 g (〇.〇5mol)的氯化錫（II)二水合物、i 〇g (〇〇〇5m〇1) 的氣化釕（III) n水合物以及3.9g (0.015m〇1)的三苯基膦，添加500 mL的二噁烷以及5〇 mL的純水。使系統内成為氮氣環境下。於18〇。(：下攪拌20小時。放置冷卻後，將反應溶液放入至500 mL的5〇/〇鹽酸中，以5〇〇 mL的氣仿進行萃取。將有機層以500 mL的純水中清洗3次，然後使有機層以無水硫酸錤乾燥後，將無水硫酸鎂除去，再將溶_壓館去’獲得粗結晶。織_管柱層析法（乙，乙酯：己烷ί (v/v))進行分離純化，獲得雙(5_〇弓丨哚基)曱烷（產量為7.3g，產率為59%)。向安裝有攪拌機、溫度計以及氮氣導入口的i L三口 51 201012801 32062pif 燒瓶中加入1.3 g (0.056 mol)的60%氫化鈉，添加10 mL 的DMF。使溶液冷卻至5¾，向其中滴加使7g(0.028mol) 的雙(5-吲哚基）甲烷溶解於2〇 mL的DMF中而成的溶液。然後使溶液升溫至室溫，於氮氣環境下攪拌1小時。再次使；谷液冷卻至5。〇 ’向其中滴加使4.7 g (0.034)的4-氣硝基苯溶解於2〇mL的DMF中而成的溶液。接著使溶液升溫至室溫’於氮氣環境下攪拌12小時。之後，將反應溶液放至100 mL乙酸乙酯以及1〇〇 mL純水的混合溶劑中進行萃取，將有機層以100 mL的純水清洗3次。使有機層以無 ⑩ 水硫酸鈉乾燥後，將無水硫酸鈉除去，將溶劑減壓餾去，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，獲得雙基苯基丨哚基）甲烷（產量為9.3g，產率為68%)。向高壓蒸氣滅菌處理用反應管中加入9〇 g (〇〇18 * mo1)所獲得的雙〇Ν-(4·確基苯基)0引哚基）甲烧、〇 9 g的鈀碳粉末，添加1〇〇 mL的乙醇以及1〇 mL的乙酸乙酯。使系統内成為氫氣環境下，於氫壓〇49 Mpa、室溫下攪拌 =小時。接著將鈀碳粉末除去，將所獲得的溶液濃縮獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=3 : i (v/v))將粗結晶分離純化，獲得二胺（U)(雙(5_n_(4_ 胺基，基基)曱烧）（產量為7] g，產率為91%)。 'H-NMR (ppm): 3.86 (-CH2-, s, 2H), 4.1 (-NH2, br. s, 4H), 6.52-8.72 (arm. H, m, 18H).[Example 3] <Synthesis of diamine (1-5)> According to the method described in Tetrahedron Letters 41, 1815-1818 (2000), 1 L was attached to a mixer, a thermometer, a cooler, and a nitrogen introduction port. 5 〇g (〇25 m〇1) of 4,4,-diamino-monophenylmethane, 18.6 g (〇.1〇mol) of triethanolamine hydrochloride, u 3 g (〇. 〇5 mol) of tin (II) chloride dihydrate, i 〇g (〇〇〇5m〇1) of vaporized cerium (III) n hydrate and 3.9 g (0.015 m 〇 1) of triphenylphosphine, Add 500 mL of dioxane and 5 mL of pure water. Make the system inside the nitrogen atmosphere. At 18 baht. (: stirring for 20 hours. After standing to cool, the reaction solution was placed in 500 mL of 5 〇 / 〇 hydrochloric acid, and extracted with 5 〇〇 mL of gas. The organic layer was washed with 500 mL of pure water 3 Then, after drying the organic layer with anhydrous barium sulfate, the anhydrous magnesium sulfate was removed, and then the solution was taken to obtain crude crystals. Weaving_column chromatography (B, ethyl ester: hexane ί (v/) v)) Separation and purification to obtain bis(5-fluorenyl) decane (yield 7.3 g, yield 59%). i L three port 51 equipped with a mixer, thermometer and nitrogen inlet port 201012801 32062pif 1.3 g (0.056 mol) of 60% sodium hydride was added to the flask, and 10 mL of DMF was added. The solution was cooled to 53⁄4, and 7 g (0.028 mol) of bis(5-fluorenyl)methane was dissolved in 2 A solution of 〇mL of DMF. The solution was then allowed to warm to room temperature and stirred under nitrogen for 1 hour. Again, the solution was cooled to 5. 〇' was added dropwise to make 4.7 g (0.034) of 4- A solution of gaseous nitrobenzene dissolved in 2 mL of DMF. The solution was then allowed to warm to room temperature and stirred under nitrogen for 12 hours. The reaction solution was extracted into a mixed solvent of 100 mL of ethyl acetate and 1 mL of pure water, and the organic layer was washed three times with 100 mL of pure water. The organic layer was dried over sodium sulfate without water. The anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to give crude crystals. The crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 5:1 (v/v)) to obtain diphenylbenzene. Methane (methane) (yield 9.3 g, yield 68%). To the reaction tube for autoclaving, 9 〇g (〇〇18 * mo1) obtained by adding bismuth-(4·decylphenyl)0 fluorenyl)methane, 〇9 g of palladium carbon powder Finally, 1 mL of ethanol and 1 mL of ethyl acetate were added. The system was placed under a hydrogen atmosphere at a hydrogen pressure of 49 Mpa and stirred at room temperature for an hour. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3: i (v/v)) to obtain a diamine (U) (bis(5_n_(4_amino, yl))) (yield is 7 g), yield is 91%). 'H-NMR (ppm): 3.86 (-CH2-, s, 2H), 4.1 (-NH2, br. s, 4H), 6.52-8.72 (arm H, m, 18H).

[實施例4] 52 201012801 νυοζριι <二胺（1-9)的合成> 除將4,4'-二胺基二苯基曱烷替代為1，3-雙(4-胺基苯基) 丙烷以外，依據實施例3中記載的方法，獲得二胺（1-9) (1，3-雙(5-Ν_(4-胺基苯基)巧哚基)丙烷）。 !H-NMR (ppm): 1.95 (-CH2-, q, 2H), 2.62 (-CH2-, t, 4H), 3.72 (-NH2, br. s, 4H), 6.51-8.78 (arm. H, m, 18H).[Example 4] 52 201012801 νυοζριι <Synthesis of diamine (1-9)> In addition to replacing 4,4'-diaminodiphenyl decane with 1,3-bis(4-aminophenyl group) In addition to propane, according to the method described in Example 3, a diamine (1-9) (1,3-bis(5-fluorene-(4-aminophenyl)carboxanyl)propane) was obtained. !H-NMR (ppm): 1.95 (-CH2-, q, 2H), 2.62 (-CH2-, t, 4H), 3.72 (-NH2, br. s, 4H), 6.51-8.78 (arm. H, m, 18H).

[實施例5] <二胺（1-28)的合成> ® 除將4,4’-二胺基二苯基曱烷替代為4,4'-二胺基二苯基醚以外，依據實施例3中記載的方法，獲得二胺（1-28) (雙(5-N-(4-胺基苯基户引哚基)醚）。 !H-NMR (ppm): 3.79 (-NH2, br. s, 4H), 6.52-8.04 (arm.[Example 5] <Synthesis of diamine (1-28)> ® In addition to 4,4'-diaminodiphenyl decane instead of 4,4'-diaminodiphenyl ether, According to the method described in Example 3, a diamine (1-28) (bis(5-N-(4-aminophenyl fluorenyl) ether) was obtained. !H-NMR (ppm): 3.79 (- NH2, br. s, 4H), 6.52-8.04 (arm.

[實施例6] <二胺（1-31)的合成> 除將4,4’-二胺基二苯基曱烷替代為N，N’-二甲基-N，N’-_ 雙(4·胺基苯基）乙二胺以外，依據實施例3中記載的方法，獲得二胺（1-31) (Ν，：ΝΓ-二曱基-N，N'·雙(5-N-(4-胺基苯基）吲哚基）乙二胺）。 ^-NMR (ppm): 2.75 (>NCH3, s, 4H), 3.58 (-CH2-, s, 4H), 3.69 (-NH2, br. s, 4H), 6.52-7.76 (arm. H, m, 18H).[Example 6] <Synthesis of diamine (1-31)> In addition to replacing 4,4'-diaminodiphenyl decane with N,N'-dimethyl-N,N'-_ In addition to bis(4-aminophenyl)ethylenediamine, according to the method described in Example 3, a diamine (1-31) was obtained (Ν, :ΝΓ-dimercapto-N,N'·double (5- N-(4-Aminophenyl)indenyl)ethylenediamine). ^-NMR (ppm): 2.75 (>NCH3, s, 4H), 3.58 (-CH2-, s, 4H), 3.69 (-NH2, br. s, 4H), 6.52-7.76 (arm. H, m , 18H).

[實施例7] <二胺（1-35)的合成> 向安裝有攪拌機、溫度計、冷卻器以及氮氣導入口的 53 201012801 jzuozpu 1 L三口燒瓶中加入20g(〇.l〇mol)市售的5_漠n引π系、;[5 i g(0.11 mol)市售的 4-胺基苯基硼酸、0.35 g(0.0005 m〇i) 的雙(三苯基膦)二氣化鈀（II)、20.7 g (0.15 mol)的碳酸卸以及8.1 g ( 0.025 mol)的漠化四丁基銨，添加150 mL 的乙醇、75 mL的曱苯以及100 mL的純水。於氮氣環境下加熱回流3小時。放置冷卻後，將反應溶液放入至水中，以200 mL的曱苯進行萃取，將有機層以200 mL的純水清洗3次。接著使有機層以無水硫酸鈉乾燥後，將無水硫酸鈉除去’將溶劑減壓餾去，獲得粗結晶。然後利用管柱層 ❹ 析法（甲苯：乙酸乙酯=5 : 1 ( v/v))將粗結晶分離純化，獲得5-(4-胺基苯基户引哚（產量為17.9 g，產率為86%)。向安裝有攪拌機、溫度計以及氮氣導入口的1L三口燒瓶中加入3.8 g (0.16 mol)的60%氫化鈉，添加40 mL 的DMF。使溶液冷卻至5。(：，向其中滴加使16 7 g (〇〇8 ^ mol)的5-(4-胺基苯基)吲哚溶解於200 mL的DMF中而成的溶液。然後使溶液升溫至室溫，於氮氣環境下攪拌1小時。再次使溶液冷卻至5。〇向其中滴加使14.1 g(〇.l〇m〇i) 的氟石肖基苯溶解於150 mL的DMF中而成的溶液。接著使溶液升溫至室溫，於氮氣環境下攪拌12小時。之後’將反應溶液放至500 mL乙酸乙酯以及500 mL純水的混合溶劑中進行萃取，將有機層以500 mL的純水清洗3次。使有機層以無水硫酸鈉乾燥後，將無水硫酸納除去，將溶劑減壓餾去，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，N_(4_硝基苯 54 201012801 基)-5-(4:胺基^基Η卜朵（產量為166g，產率為63%)。向尚壓蒸氣滅菌處理用反應管中加入16〇 g (〇〇49 m〇1)的Ν-(4·硝基笨基)_5_(4_胺基笨基)辦、u g的把碳粉末y添加200 mL乙醇以及2〇 mL乙酸乙醋。使系統内成為氫氣環境下，於錢〇.49MPa、室溫下獅12小時。接著驗碳粉末除去，將所獲得的溶液濃縮，獲得粗結晶。然後利用管柱層析法（甲笨：乙酸乙§旨=3:丨（★))將 Φ e 離T ’獲得二胺（⑻）（Ν·(4·胺基笨基)邻_ 胺基，基)°㈣）（產量為l33g，產率為91%)。 H-NMR (ppm): 3.53 (-KH2, br. S} 2H), 3.74 (-NH2, br. s, 2H), 6.42-8.18 (arm. H，m，13H) ’ ， [實施例8] * <聚醯胺酸的製備> -ί女f有孤度°十、攪拌機以及氮氣導入口的200 mL 三口燒瓶中加人2.59 g的二胺（w )，使其溶解於6〇 g的脫水猜中。—面將溶液保持為5t：，—面添加1 14 g 的化合物⑷4)以及U7 g的化合物（A1)。_吏溶液升溫至室溫’於氮氣環境下反應12小時後，添加10 g的 γ 丁内^日以及25 g的BC，進—步搜拌3小時。為了使所獲得的溶液的黏度下降，而將溶液於6〇Ό下加熱搜掉直至溶液的黏度達到35 mPa · s，獲得聚醯胺酸濃度為5重量百分比的溶液。將娜航作清漆A。贿漆胺酸的重量平均分子量為64,〇〇〇。聚 [實施例9〜25、比較例1〜2、以及參考例1] 55 201012801 32062pif 將二胺以及四羧酸二酐以如表1所示的方式使用，以和實施例8相同的方式製造聚醯胺酸，製備清漆B〜U。 <表1> 實施例No. 清漆名稱二胺四羧酸二酐 Mw No. mole% No. mole% 8 清漆A (1-0 50 (Al) (A14) 25 25 64,000 9 清漆B (1-1) (VI-1) 25 25 (Al) (A14) 25 25 72,000 10 清漆C (Μ) (VI-1) 25 25 (A20) 50 48,000 11 清漆D (1-1) (VI-7) 40 10 (Al) (A14) 25 25 38,000 12 清漆E (Μ) (IX-13) 40 10 (Al) (A14) 25 25 45,000 13 清漆F (1-1) (XII-1) 40 10 (Al) (A14) 25 25 50,000 14 清漆G (1-5) 50 (Al) (A14) 25 25 58,000 15 清漆Η (1-5) (VI-1) 25 25 (Al) (A14) 25 25 66,000 16 清漆I (1-5) (VI-1) 25 25 (A20) 50 39,000 17 清漆J (1-5) (VI-7) 40 10 (Al) (A14) 25 25 41,000 18 清漆Κ (1-5) (IX-13) 40 10 (Al) (A14) 25 25 42,000 19 清漆L (1-5) (XII-1) 40 10 (Al) (A14) 25 25 37,000 20 清漆Μ (1-35) 50 (Al) (A14) 25 25 54,000 21 清漆Ν (1-35) (VI-1) 25 25 (Al) (A14) 25 25 69,000 22 清漆〇 (1-35) 25 25 (A20) 50 40,000 56 201012801 jzuozpu 23[Example 7] <Synthesis of diamine (1-35)> 20 g (〇.l〇mol) was added to a 53 201012801 jzuozpu 1 L three-necked flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet. 5 漠 n π 、 ; ;; [5 ig (0.11 mol) commercially available 4-aminophenylboronic acid, 0.35 g (0.0005 m〇i) of bis(triphenylphosphine) dipalladium ( II), 20.7 g (0.15 mol) of carbonic acid unloading and 8.1 g (0.025 mol) of desertified tetrabutylammonium, adding 150 mL of ethanol, 75 mL of toluene and 100 mL of pure water. The mixture was heated to reflux for 3 hours under a nitrogen atmosphere. After standing to cool, the reaction solution was placed in water, extracted with 200 mL of toluene, and the organic layer was washed three times with 200 mL of pure water. Then, the organic layer was dried over anhydrous sodium sulfate, and then anhydrous sodium sulfate was removed. The solvent was evaporated under reduced pressure to give crude crystals. Then, the crude crystals were separated and purified by a column chromatography method (toluene: ethyl acetate = 5:1 (v/v)) to obtain 5-(4-aminophenylphenyl hydrazine (yield: 17.9 g, yield). The rate was 86%. To a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 3.8 g (0.16 mol) of 60% sodium hydride was added, and 40 mL of DMF was added to cool the solution to 5. (:, A solution of 16 7 g (〇〇8 ^ mol) of 5-(4-aminophenyl)phosphonium dissolved in 200 mL of DMF was added dropwise, and then the solution was allowed to warm to room temperature under a nitrogen atmosphere. The mixture was stirred for 1 hour, and the solution was again cooled to 5. A solution obtained by dissolving 14.1 g (〇.l〇m〇i) of fluorescein thiobenzene in 150 mL of DMF was added dropwise thereto. Stir at room temperature for 12 hours under nitrogen. Then, the reaction solution was extracted into a mixed solvent of 500 mL of ethyl acetate and 500 mL of pure water, and the organic layer was washed 3 times with 500 mL of pure water. After the layer was dried over anhydrous sodium sulfate, anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to give crude crystals. Benzene: ethyl acetate = 5: 1 (v/v)) The crude crystals were separated and purified, N_(4_nitrobenzene 54 201012801 base)-5-(4:amino group Η 朵朵 (yield 166 g, The yield was 63%.) To the reaction tube for steam sterilization, 16 〇g (〇〇49 m〇1) of Ν-(4·nitrophenyl)_5_(4-amino stupyl) was added. Ug add carbon dioxide y to 200 mL of ethanol and 2 〇mL of ethyl acetate. Make the system into a hydrogen atmosphere, and lion for 12 hours at 49 MPa and room temperature. Then remove the carbon powder and remove it. The obtained solution is concentrated to obtain a crude crystal. Then, by column chromatography (A stupid: acetic acid B = 3: 丨 (★)), Φ e is obtained from T ' to obtain a diamine ((8)) (Ν·(4· Amino-based, ortho-amino, yl) (4)) (yield: l33g, yield 91%) H-NMR (ppm): 3.53 (-KH2, br. S} 2H), 3.74 (-NH2 , br. s, 2H), 6.42-8.18 (arm. H, m, 13H) ' , [Example 8] * <Preparation of polyglycine> - ί female f has a degree of separation °, a blender and Add 2.59 g of diamine (w) to a 200 mL three-necked flask at the nitrogen inlet to dissolve it in a 6 〇g dehydration guess. 5t:, add - 1 14 g of compound (4) 4) and U7 g of compound (A1). _ 吏 solution is warmed to room temperature 'after 12 hours of reaction under nitrogen atmosphere, add 10 g of γ 内 ^ ^ day and 25 BC of g, step by step and mix for 3 hours. In order to lower the viscosity of the obtained solution, the solution was heated and found at 6 Torr until the viscosity of the solution reached 35 mPa·s, and a solution having a polyglycine concentration of 5 wt% was obtained. Na Na is used as varnish A. The weight average molecular weight of the amine acid is 64, 〇〇〇. Poly [Examples 9 to 25, Comparative Examples 1 to 2, and Reference Example 1] 55 201012801 32062 pif A diamine and a tetracarboxylic dianhydride were used in the same manner as in Example 8 in the same manner as in Example 8. Polylysine, preparation of varnish B~U. <Table 1> Example No. Varnish name Diamine tetracarboxylic acid dianhydride Mw No. mole% No. mole% 8 Varnish A (1-0 50 (Al) (A14) 25 25 64,000 9 Varnish B (1- 1) (VI-1) 25 25 (Al) (A14) 25 25 72,000 10 Varnish C (Μ) (VI-1) 25 25 (A20) 50 48,000 11 Varnish D (1-1) (VI-7) 40 10 (Al) (A14) 25 25 38,000 12 Varnish E (Μ) (IX-13) 40 10 (Al) (A14) 25 25 45,000 13 Varnish F (1-1) (XII-1) 40 10 (Al) (A14) 25 25 50,000 14 Varnish G (1-5) 50 (Al) (A14) 25 25 58,000 15 Varnish Η (1-5) (VI-1) 25 25 (Al) (A14) 25 25 66,000 16 Varnish I (1-5) (VI-1) 25 25 (A20) 50 39,000 17 Clear lacquer J (1-5) (VI-7) 40 10 (Al) (A14) 25 25 41,000 18 Varnish Κ (1-5) (IX-13) 40 10 (Al) (A14) 25 25 42,000 19 Clear lacquer L (1-5) (XII-1) 40 10 (Al) (A14) 25 25 37,000 20 Varnish Μ (1-35) 50 ( Al) (A14) 25 25 54,000 21 Varnish Ν (1-35) (VI-1) 25 25 (Al) (A14) 25 25 69,000 22 Varnish 〇 (1-35) 25 25 (A20) 50 40,000 56 201012801 jzuozpu twenty three

清漆P 24 25Varnish P 24 25

清漆 ------- 清漆R (VI-1)〇5?τίν^Τ)O^sT lIX-13) ~TU35Ti2sy_) dda 40JO 40jO 40 10Varnish ------- Varnish R (VI-1)〇5?τίν^Τ)O^sT lIX-13) ~TU35Ti2sy_) dda 40JO 40jO 40 10

比較例1 清漆SComparative Example 1 Varnish S

[實施例261 50 25 25 40 10 (Al) (A14) (Al)" (A14) (AlY (A14)(AlT (A14) (AlT (A14) (AlT (A14) 25 25 25 25 25 25 25 25 25 25 25 25 41,000 43,000 51,000 57,000 71,000 38,000 〈電特性用调定單元的製作> 將實施例8中製備的清漆A以NMP/BC = 6/4 (Wv) 的混合_加以稀釋’將聚醯胺比’將其製佈崎漆。[Example 261 50 25 25 40 10 (Al) (A14) (Al) " (A14) (AlY (A14) (AlT (A14) (AlT (A14) (AlT (A14) 25 25 25 25 25 25 25 25 25 25 25 25 41,000 43,000 51,000 57,000 71,000 38,000 <Preparation of setting unit for electric characteristics> The varnish A prepared in Example 8 was diluted with a mixture of NMP/BC = 6/4 (Wv) The guanamine is made of smear.

利用旋轉器法將該塗佈用清漆塗佈於附IT0電極的玻璃基板上。塗佈條件是以2,000rpm、15秒進行。塗佈後，將基板加熱至80 C而預備煆燒5分鐘後，於21〇°c下進行 20分鐘加熱處理，形成膜厚約為8〇nm的液晶配向膜。然後對所獲得的配向膜實施摩擦處理。摩擦處理是使用毛長度為1.9mm的嫘縈製摩擦布，以毛壓入量為〇 4〇111111、平台移動速度為60mm/sec、輥轉速為ΐ，〇〇〇ιριη的條件實施。將摩擦處理後的玻璃基板於超純水中進行5分鐘的超音波清洗後，再於烘箱中120°C下乾燥30分鐘。於一片基板上散布7 μιη的間隙劑（gap agent)，將另一片基板以失 57 201012801 著間隙劑的方式重疊，並以環氧硬化劑密封，來製作間隙為7 μιη的反平行單元（antiparallel cell)。然後在該單元中注入下述液晶組成物A作為液晶材料，將注入口以光硬化樹脂密封。繼而，將單元於ll〇°C下進行30分鐘加熱處理，獲得電壓保持率、殘留DC以及預傾角測定用單元。This coating varnish was applied onto a glass substrate with an IT0 electrode by a spinner method. The coating conditions were carried out at 2,000 rpm for 15 seconds. After coating, the substrate was heated to 80 C and preliminarily calcined for 5 minutes, and then heat-treated at 21 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 8 Å. The obtained alignment film is then subjected to a rubbing treatment. The rubbing treatment was carried out using a rubbing rubbing cloth having a hair length of 1.9 mm, and the conditions of the embossing amount of 〇 4〇111111, the moving speed of the table of 60 mm/sec, and the rotation speed of the rolls were ΐ, 〇〇〇ιριη. The rubbed glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. A 7 μm gap agent is spread on one substrate, and the other substrate is overlapped by a gap agent, and sealed with an epoxy hardener to form an antiparallel unit having a gap of 7 μm. Cell). Then, the liquid crystal composition A described below was injected into the unit as a liquid crystal material, and the injection port was sealed with a photocurable resin. Then, the unit was subjected to heat treatment at ll 〇 ° C for 30 minutes to obtain a voltage holding ratio, residual DC, and pretilt angle measuring unit.

c2h5C2h5

17wt%17wt%

17wt% 16wt% 10wt%17wt% 16wt% 10wt%

5 wt%5 wt%

η-〇3Η7η-〇3Η7

10wt%10wt%

6wt% 58 201012801 iZObipa 6wt°/〇 13wt% 使用所製作的單元，利用上述方法來測定電壓保持率、殘留DC以及預傾角，結果分別為96.2%、1.8 mV以及 1.7° 。6wt% 58 201012801 iZObipa 6wt°/〇 13wt% Using the fabricated unit, the voltage retention, residual DC, and pretilt angle were measured by the above methods, and the results were 96.2%, 1.8 mV, and 1.7°, respectively.

[實施例27〜43、以及比較例3〜4] 使用清漆B〜清漆T，依據實施例26中記載的方法製作單元，測定電壓保持率、殘留DC以及預傾角。將測定結果示於表2中（實施例26亦再次揭示）。其中，對於使用清漆E、清漆K以及清漆Q而形成的配向膜不進行摩擦處理，且，所注入的液晶材料是使用液晶組成物B來代替液晶組成物A。 <液晶組成物B >[Examples 27 to 43 and Comparative Examples 3 to 4] Using a varnish B to varnish T, a cell was produced in accordance with the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured. The measurement results are shown in Table 2 (Example 26 is also disclosed again). Here, the alignment film formed using the varnish E, the varnish K, and the varnish Q was not subjected to rubbing treatment, and the liquid crystal material to be injected was replaced with the liquid crystal composition A by using the liquid crystal composition B. <Liquid crystal composition B >

η-〇3^7' _c2h5Η-〇3^7' _c2h5

12 w% 11 w% 15 w% 15 w% 59 201012801 szmzpn12 w% 11 w% 15 w% 15 w% 59 201012801 szmzpn

n-C^Hg η-〇3Η7'n-C^Hg η-〇3Η7'

η-〇3Η7η-〇3Η7

n-CsHfi n-CgHyn-CsHfi n-CgHy

O-CH3 η-〇3Η7O-CH3 η-〇3Η7

O—IVC3H7O-IVC3H7

^θ^〇2Η5n-CaHyV^V/^X 5w% 6w% 6w% 5w% 5w% 6w% 6w% 4 w% 4w%^θ^〇2Η5n-CaHyV^V/^X 5w% 6w% 6w% 5w% 5w% 6w% 6w% 4 w% 4w%

[實施例44以及45] <掺合配向劑的電特性評價> 製備將清漆A與清漆U以重量比8 : 2混合而成的清漆AU。使用該清漆AU，依據實施例26中記載的方法製作單元。製備將清漆B與清漆U以重量比8 : 2混合而成的清漆BU，使用該清漆BU，以與清漆AU相同的方式製作單元。將對該些單元測定電壓保持率、殘留DC以及預傾角所得的結果示於表2。 60 201012801 ^ζυοζριι 〈表2> ❹[Examples 44 and 45] <Evaluation of electric characteristics of blended alignment agent> A varnish AU obtained by mixing varnish A and varnish U at a weight ratio of 8:2 was prepared. Using this varnish AU, a unit was produced in accordance with the method described in Example 26. A varnish BU obtained by mixing varnish B and varnish U at a weight ratio of 8 : 2 was prepared, and the varnish BU was used to prepare a unit in the same manner as varnish AU. The results obtained by measuring the voltage holding ratio, residual DC, and pretilt angle for these units are shown in Table 2. 60 201012801 ^ζυοζριι 〈表2> ❹

實施例 No. 清漆名稱電壓保持率（％) 殘留DC (mV) 預傾角（°) 26 清漆A -_____lEnid 1.8 1.7 — 27 清漆 96.6 10 1.3 28 清漆C 95.9 1 ο 1.4 — 29 清漆D 95.4 一 17 0.9 30 清漆E 94.9 21 90 ~~ 31 清漆 _ 95.0 19 5.0 ~~ 32 清漆 96.1 1.4 33 清漆 _ 96.4 11 1.4 — 34 清漆Γ~ 95.3 一 15 1.5 ~ 35 清漆J~~ 95.7 16 0 8 36 清漆Κ 94.6 22 V/· 〇 90 37 清漆L 94.9 17 5.1 ~ 38 清漆 96.0 2.2 1.5 39 清漆N 96.7 9.3 1.3 40 清漆0 Γ 95.4 ' — - .. 94.9 10 —------- 21 1.8 09 41 清漆 42 清漆 94.4 26 90 43 '-sic 7% /貧漆R 95.7 18 Γ 5.1 44 清漆AU 95.6 11 5.3 ~~ 45 清漆BU 96.6 10 5.4 比較例3 清漆S 90.8 2.7 1.6 比較例4 清漆τ 95.3 1.9 「2.2 [實施例46〜50、以及比較例5〜6] <保存穩定性的確認> 製備清漆Α、清漆Β、清漆F、清漆j、清漆Au、清漆S以及清漆T後，於-20°C下保存60天，使用該保存^ 漆，依據實施例26中記載的方法製作單元，測定電塵保持率、殘留DC以及預傾角。測定結果示於表3。 μ、 61 201012801 02Wlpit 〈表3> 實施例 No, 清漆名稱電壓保持率（％) 殘留DC (mV) 預傾角（。） 46 清漆A 95.9 3.6 ------ 1.6 47 清漆B 96.0 18 1.3 48 清漆F 94.5 27 5.0 49 清漆J 95.0 23 0.8 50 清漆AU 96.0 18 5.4 比較例5 清漆S 由於聚合物析出而無法盤# F單元比較例6 清漆T 91.9 39 ~~ΰ~~ --- [實施例51] <聚醯亞胺的製備> 於200mL圓底燒瓶中稱取100&的清漆A，向其中添加 9.5 g (0.09 mol)的乙酸酐、4.4 g (〇.〇6 mol)的吡啶，於120eC下攪拌3小時。然後將溶液放入至1〇〇〇虹的純水中，獲得4.5 g的聚醯亞胺。該聚醯亞胺的重量平均分子量為49,000，藉由1H-NMR測定，該聚醯亞胺的醯亞二化率為94%。使4 g所獲得的聚醯亞胺溶解於％邑的 NMP-GBL-BC混合溶劑（體積比為！： i : υ中，獲得聚醯亞胺濃度為5%的清漆V。 [實施例52] 使用清漆V’依據實施例26中記載的方法製作單元，測定電壓保持率、殘留DC、以及預傾角，結果分別為 95.9%、4.2 mV、以及 1.6。。 # [比較例7] 除將二胺（M)替代為曰本專利特開平1〇-1〇4633號 62 201012801 32062pit 公報中記載的N,N，-雙(4-胺基苯基)-l，4-哌嗪以外，依據實施例8中記載的方法獲得清漆W。於200 mL圓底燒瓶中稱取g的清漆W，向其中添加 8.2g(0.08mol)的乙酸酐、3.8g(〇.〇5mol)的吡啶’ 加熱至120°C，結果於加熱開始1小時後沉澱析出，即便將溶液的溫度升溫至180°C，該沉澱亦未溶解。 [實施例53]Example No. Varnish name Voltage retention ratio (%) Residual DC (mV) Pretilt angle (°) 26 Varnish A -_____lEnid 1.8 1.7 — 27 Varnish 96.6 10 1.3 28 Varnish C 95.9 1 ο 1.4 — 29 Varnish D 95.4 A 17 0.9 30 Varnish E 94.9 21 90 ~~ 31 Varnish _ 95.0 19 5.0 ~~ 32 Varnish 96.1 1.4 33 Varnish _ 96.4 11 1.4 — 34 Varnish Γ~ 95.3 A 15 1.5 ~ 35 Varnish J~~ 95.7 16 0 8 36 Varnish Κ 94.6 22 V/· 〇90 37 Varnish L 94.9 17 5.1 ~ 38 Varnish 96.0 2.2 1.5 39 Varnish N 96.7 9.3 1.3 40 Varnish 0 Γ 95.4 ' — - .. 94.9 10 —------- 21 1.8 09 41 Varnish 42 Varnish 94.4 26 90 43 '-sic 7% / poor paint R 95.7 18 Γ 5.1 44 Varnish AU 95.6 11 5.3 ~~ 45 Varnish BU 96.6 10 5.4 Comparative Example 3 Varnish S 90.8 2.7 1.6 Comparative Example 4 Varnish τ 95.3 1.9 "2.2 [Implementation Examples 46 to 50 and Comparative Examples 5 to 6] <Confirmation of storage stability> After preparation of varnish enamel, varnish enamel, varnish F, varnish j, varnish Au, varnish S, and varnish T, at -20 ° C After 60 days of storage, using the preservation paint, a single sheet was prepared according to the method described in Example 26. The electric dust retention rate, residual DC, and pretilt angle were measured. The measurement results are shown in Table 3. μ, 61 201012801 02Wlpit <Table 3> Example No. Varnish name voltage retention ratio (%) Residual DC (mV) Pretilt angle ( 46) Varnish A 95.9 3.6 ------ 1.6 47 Varnish B 96.0 18 1.3 48 Varnish F 94.5 27 5.0 49 Varnish J 95.0 23 0.8 50 Varnish AU 96.0 18 5.4 Comparative Example 5 Varnish S Unable to disc due to polymer precipitation #Funit Comparative Example 6 Varnish T 91.9 39 ~~ΰ~~ --- [Example 51] <Preparation of Polyimine>100& Varnish A was weighed in a 200 mL round bottom flask, and added thereto 9.5 g (0.09 mol) of acetic anhydride and 4.4 g of pyridine (6 mol) were stirred at 120 ° C for 3 hours. The solution was then placed in pure water of 1 〇〇〇 rainbow to obtain 4.5 g of polyimine. The polyamidimide had a weight average molecular weight of 49,000, and the polyamidimide had a sulfonium dimerization rate of 94% as determined by 1H-NMR. 4 g of the obtained polyimine was dissolved in a N邑-NMP-GBL-BC mixed solvent of %邑 (volume ratio: : i : υ, a varnish V having a polyamidene concentration of 5% was obtained. [Example 52 Using a varnish V', a cell was produced according to the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured and found to be 95.9%, 4.2 mV, and 1.6, respectively. # [Comparative Example 7] The amine (M) is replaced by the N,N,-bis(4-aminophenyl)-l,4-piperazine described in the Japanese Patent Publication No. Hei 1〇-1〇4633 62 201012801 32062pit. The varnish W was obtained by the method described in Example 8. The varnish W of g was weighed in a 200 mL round bottom flask, and 8.2 g (0.08 mol) of acetic anhydride and 3.8 g of pyridine (5 mol) of pyridine were added thereto to heat. At 120 ° C, the precipitate was precipitated one hour after the start of heating, and the precipitate was not dissolved even when the temperature of the solution was raised to 180 ° C. [Example 53]

<二胺（Ml)的合成> 向安裝有攪拌機、溫度計以及氮氣導入口的500 mL 三口燒瓶中加入29.0 g ( 102 mmol)市售的5-蛾吲哚以及 17.0 g ( 122 mmol)的碳酸鉀，添加200 mL的DMF。向其中添加使17.3 g (122 mmol)市售的4-氟硝基苯溶解於<Synthesis of Diamine (Ml)> To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 29.0 g (102 mmol) of commercially available 5-mothone and 17.0 g (122 mmol) were added. Potassium carbonate, add 200 mL of DMF. To this was added 17.3 g (122 mmol) of commercially available 4-fluoronitrobenzene was dissolved in

100mL的DMF中而成的溶液，於氮氣環境下、14〇。匸下攪拌2小時。然後將反應液放至5〇〇 mL乙酸乙酯以及5〇〇 mL 純水的混合溶劑中進行萃取，使有機層以無水硫酸鎂乾燥。將硫酸鎂過濾分離，將溶劑減壓餾去，獲得粗結晶。將所獲得的粗結晶自甲苯中再結晶，獲得N_(4_硝基苯基)-5-碘吲哚（產量為33g，產率為83%)。 —向安裝有搜拌機、溫度計以及氮氣導入口的5〇〇mL :燒瓶中添加33 g (91 mm〇i)所獲得的N_(4_續基苯 3·2^ (4,6mm〇1)的雙(三苯基膦)二氣化鈀A solution of 100 mL of DMF was placed under a nitrogen atmosphere at 14 Torr. Stir in the underarm for 2 hours. Then, the reaction mixture was poured into a mixed solvent of 5 mL of ethyl acetate and 5 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was separated by filtration, and the solvent was evaporated under reduced pressure to give crude crystals. The obtained crude crystals were recrystallized from toluene to obtain N-(4-nitrophenyl)-5-iodonium (yield: 33 g, yield: 83%). - N_(4_ contiguous benzene 3·2^ (4,6mm〇1) obtained by adding 33 g (91 mm〇i) to a 5 mL: flask equipped with a mixer, thermometer and nitrogen inlet. Bis(triphenylphosphine) di-palladium palladium

t L\(46mmQl)的碟化銅⑴，添加3〇〇mL 向其中添加10·7 g (109 mmol)市售的 h、’於氮氣環境下加熱回流 6小時。接著 63 201012801 ^zuozpu 將反應液放入至500 mL乙酸乙酿以及500 mT,純水的混合溶劑中進行萃取’使有機層以無水硫酸鎂乾燥。將硫酸錢過濾分離，將溶劑減壓餾去，獲得N-(4-确基苯基)_5_((三曱基矽烷基)乙炔基)-吲哚的粗結晶（產量為27 g，產率為 88%) 〇向安裝有攪拌機、溫度計以及氮氣導入口的500 mL 三口燒瓶中加入27 g (81 mmol)所獲得的N-(4-硝基苯基)-5-((三甲基矽烧基）乙炔基)·η弓丨哚，使其溶解於2〇〇 mL 的四氫吱味中。於氮氣環境下，將溶液於乾冰·丙酮浴（dry _ ice-acetone bath)中冷卻至-78°C，一面將液溫保持為-78 °C，一面向其中滴加85 mL市售的氟化四丁基銨1 m〇i/L 溶液。將溶液保持為-78°C ’攪拌2小時後，將反應液放入至500 mL乙酸乙酯以及500 mL純水的混合溶劑中進行萃取，使有機層以無水硫酸鎂乾燥。將溶劑減壓餾去，獲得 N-(4-硝基笨基)-5-乙炔基吲哚（產量為17g，產率為79%)。向安裝有攪拌機、溫度計以及空氣導入口的500 mL 三口燒瓶中加入17 g (65 mmol)所獲得的Ν-(4·>ε肖基苯 ❿ 基)-5-乙炔基吲嗓、1.3 g (13 mmol)的氣化銅（I)以及 2.5 g (21 mmol)的Ν，Ν·-四甲基乙二胺’添加100 mL乙二醇二甲醚。一面使用水槽用空氣泵向系統内送入空氣，一面於室溫下攪拌24小時。將反應液過濾，將所獲得的反應產物以300 mL的氨水中清洗1次，以300 mL的純水清洗2次，獲得1,4-雙(5-(Ν-(4·破基苯基)-吲哚基))-1，3-丁二炔（產量為14 g，產率為82%) 64 201012801 j^uozpu =高壓蒸氣滅菌處理用反應管中To L\(46mmQl), copper (1) was added, and 3 〇〇mL was added thereto, and 10·7 g (109 mmol) of commercially available h, ' was heated under reflux for 6 hours under a nitrogen atmosphere. Next, 63 201012801 ^zuozpu The reaction solution was placed in a mixture of 500 mL of acetic acid and 500 mT of pure water for extraction. The organic layer was dried over anhydrous magnesium sulfate. The sulfuric acid was separated by filtration, and the solvent was evaporated under reduced pressure to give crude crystals of N-(4-decylphenyl)-5-((tridecylidene)ethynyl)-indole (yield: 27 g, yield (88%) 〇 Adding 27 g (81 mmol) of N-(4-nitrophenyl)-5-((trimethylhydrazine) obtained to a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet The alkyl group acetylene) was dissolved in 2 mL of tetrahydroanthracene. Under a nitrogen atmosphere, the solution was cooled to -78 ° C in a dry ice-acetone bath while maintaining the liquid temperature at -78 ° C, and 85 mL of commercially available fluorine was added dropwise thereto. Tetrabutylammonium 1 m〇i/L solution. After the solution was stirred at -78 ° C for 2 hours, the reaction mixture was poured into a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give N-(4-nitrophenyl)-5-ethynylhydrazine (yield: 17 g, yield: 79%). To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and an air introduction port, 17 g (65 mmol) of yttrium-(4·> ε-succinylphenyl)-5-ethynyl fluorene, 1.3 g was added. (13 mmol) of copper (I) and 2.5 g (21 mmol) of hydrazine, Ν·-tetramethylethylenediamine' was added with 100 mL of ethylene glycol dimethyl ether. While using an air pump to feed air into the system, the air was stirred at room temperature for 24 hours. The reaction solution was filtered, and the obtained reaction product was washed once with 300 mL of aqueous ammonia, and washed twice with 300 mL of pure water to obtain 1,4-bis(5-(Ν-(4·基基基) )-mercapto))-1,3-butadiyne (yield 14 g, yield 82%) 64 201012801 j^uozpu = in the reaction tube for autoclaving

Γ ί末，添加l5〇mL乙醇以及ΐ5— 使' ^Γ為氫氣環境下’於氫壓G.49MPa、 12小時。接著將纪碳粉末除去，將所獲得的溶 ^縮’獲得粗結晶。然後管柱層析法（二氯甲烧： Z=1G: Uv/v))將粗結晶分離純化，自乙醇中再結晶，獲得1，4_雙(5-(N♦胺基苯基)_啊基))丁⑨（產量為12 g，產率為91%)。 1H-NMR (ppm): 1.74-1.76 (-CH2-, m, 4H) 2.74-2.76 KH2_，t，J = 6.4 Hz，4H)，3.76 (·ΝΗ2, br. s，4H)，6.52-7.45 (arm. H，18H) [實施例54] <二胺（1-37)的合成> 向安裝有攪拌機、溫度計以及氮氣導入口的500 mL 二口燒瓶中加入26.0 g ( 161 mmol)市售的5-硝基吲哚以及27.0 g ( 194 mmol)的碳酸鉀，添加2〇〇 mL的DMF。向其中添加使38.0g (242 mmol)市售的5-氟-2-硝基苯酚溶解於100 mL的DMF中而成的溶液，於氮氣環境下、14〇 °C下攪拌2小時。然後將反應液放入至1 L純水中，將所獲得的結晶以500 mL的純水清洗2次，以500 mL的乙醇清洗2次，使其乾燥，獲得N-(3-羥基-4-硝基苯基)-5-确基吲哚（產量為45 g，產率為94%)。於高壓蒸氣滅菌處理用反應管中加入45.0 g (150 65 201012801 3^ϋ62ρΐί mmol)的Ν-(3-經基-4-墙基苯基)-5-硝基°引嗓、4.5 g的把碳粉末，添加500 mL的乙醇。使系統内成為氫氣環境下，於氫壓0.49 MPa、室溫下攪拌12小時。接著將把碳粉末除去’將所獲得的溶液濃縮’獲得粗結晶。將粗結晶自乙醇/純水=1 : 1 (v/v)中再結晶，獲得Ν·(4-胺基_3·羥基苯基)·5-胺基吲哚（產量為30g，產率為83%)。Γ ί, adding l5〇mL of ethanol and ΐ5—so that '^Γ is under hydrogen atmosphere' at a hydrogen pressure of G.49MPa for 12 hours. Next, the carbon powder was removed, and the obtained melted to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (dichloromethane: Z = 1G: Uv/v), and recrystallized from ethanol to obtain 1,4-bis(5-(N♦aminophenyl). _ ah base) butyl 9 (yield 12 g, yield 91%). 1H-NMR (ppm): 1.74-1.76 (-CH2-, m, 4H) 2.74-2.76 KH2_, t, J = 6.4 Hz, 4H), 3.76 (·ΝΗ2, br. s, 4H), 6.52-7.45 ( Arm. H, 18H) [Example 54] <Synthesis of diamine (1-37)> To a 500 mL two-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 26.0 g (161 mmol) was commercially available. 5-nitroguanidine and 27.0 g (194 mmol) of potassium carbonate were added to 2 mL of DMF. A solution obtained by dissolving 38.0 g (242 mmol) of commercially available 5-fluoro-2-nitrophenol in 100 mL of DMF was added thereto, and the mixture was stirred at 14 ° C for 2 hours under a nitrogen atmosphere. Then, the reaction solution was placed in 1 L of pure water, and the obtained crystal was washed twice with 500 mL of pure water, twice with 500 mL of ethanol, and dried to obtain N-(3-hydroxy-4). -Nitrophenyl)-5-decyl hydrazine (yield 45 g, yield 94%). 45.0 g (150 65 201012801 3^ϋ62ρΐί mmol) of Ν-(3-pyrimidin-4-wallylphenyl)-5-nitro ° 嗓, 4.5 g of the reaction tube was added to the reaction tube for autoclaving Carbon powder, add 500 mL of ethanol. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the carbon powder is removed, and the obtained solution is concentrated to obtain a crude crystal. The crude crystals were recrystallized from ethanol/pure water = 1: 1 (v/v) to give Ν·(4-amino-3·hydroxyphenyl)·5-aminoindole (yield 30 g, yield 83%).

1H-NMR (ppm): 4.59 (-NH2, br. s, 2H), 4.66 (-NH2, br. s, 2H), 6.29-6.30 (=CH-, d, J = 3.0 Hz, 1H), 6.53-7.13 (Irm. H, m, 6H), 7.24-7.25 (=CH-, d, J = 3.0 Hz, 1H) 使用本發明液晶配向劑的液晶顯示元件如上所述，與先前的液晶顯示元件相比，表現出電壓保持率高、殘留Dc 小等良好的特性《而且，可知本發明的液晶配向劑的保存穩定性優異，且對於通常所使用的溶劑亦具有較高溶解性。雖然本發明已以實施例揭露如上’然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範_，當可作些許之更動與_，故本1H-NMR (ppm): 4.59 (-NH2, br. s, 2H), 4.66 (-NH2, br. s, 2H), 6.29-6.30 (=CH-, d, J = 3.0 Hz, 1H), 6.53 -7.13 (Irm. H, m, 6H), 7.24-7.25 (=CH-, d, J = 3.0 Hz, 1H) The liquid crystal display element using the liquid crystal alignment agent of the present invention is as described above, and the liquid crystal display element is In addition, the liquid crystal alignment agent of the present invention is excellent in storage stability and has high solubility in a solvent which is usually used. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make a few changes and _ without departing from the spirit and scope of the present invention.

發明之保護範圍當視後附之申請專利範圍所界定者為【圖式簡單說明】無【主要元件符號說明】無 66The scope of protection of the invention is defined by the scope of the appended patent application. [Simple description of the diagram] None [Key component symbol description] None 66

Claims

201012801 32062pit 不七、申請專利範圍： 1. 一種二胺，其由式（1)所表201012801 32062pit No. 7. Patent application scope: 1. A diamine, which is represented by formula (1)

(1) ❹ 其中，Y為單鍵或碳數為1〜9的直鏈伸烷基；該基的任意偶_可由_〇_、娜叫、认伸苯基、己基或哌嗪-1，4-二基取代；η為〇或丨；並且，鍵結义的苯環的-個氫可由·〇Η取代；其中，當γ為伸烧基且1 時，並無鍵結有胺基的_CH2_*_〇_或取代的 2.如申請專利範圍第1項所述有胺f的，為不具有侦作為取代基的^ 有胺基H專利範圍第1項所述之二胺，其中所述鍵結基-OH的苯環:於相對於所職絲其卜雜具有取代鍵：二申^乂項所述之二2中Y為單的直鍵伸烧基；並且η由為0i•或娜Η3)-取代的碳數為卜9 6.種聚酿胺酸’是使至少-種如申請專利範圍第1 67 201012801 32062pif 項所述之二胺、或者由至少一種如申請專利範圍第1項所述之二胺與至少一種其他二胺所構成的二胺混合物，與至少一種四羧酸酐進行反應而獲得。 7.如申請專利範圍第6項所述之聚醯胺酸，其中所述至少一種四羧酸酐為選自由式（A1)〜式（A63)所表示的化合物中的四羧酸酐：(1) ❹ wherein Y is a single bond or a linear alkyl group having a carbon number of 1 to 9; any of the groups may be _〇_, Na, phenyl, hexyl or piperazine-1, 4-diyl substituted; η is ruthenium or osmium; and, the hydrogen of the bonded benzene ring may be substituted by 〇Η; wherein, when γ is a stretching group and 1 is, no amine group is bonded _CH2_*_〇_ or substituted 2. The amine having the amine f as described in claim 1 of the patent application, is a diamine having the amine group H of the above-mentioned patent range No. 1, wherein The benzene ring of the bonding group -OH: has a substitution bond with respect to the ruthenium of the ruthenium: Y is a single straight bond extension base; and η is 0i • or Nathan 3)-substituted carbon number is s9. 6. Polylactam' is such that at least one of the diamines as described in the patent application No. 1 67 201012801 32062pif, or at least one such as the scope of patent application The diamine mixture of the above-mentioned diamine and at least one other diamine is obtained by reacting with at least one tetracarboxylic anhydride. 7. The polyaminic acid according to claim 6, wherein the at least one tetracarboxylic anhydride is a tetracarboxylic anhydride selected from the compounds represented by the formulae (A1) to (A63):

68 201012801 32062pit Μ Η Μ (Α14) (Α15) (Α16> ο ο ο. (Α17) ρ68 201012801 32062pit Μ Η Μ (Α14) (Α15) (Α16> ο ο ο. (Α17) ρ

Ο (Α18)Ο (Α18)

r\r\

Μ (Α21) ❹Μ (Α21) ❹

ΟΟ

69 201012801 izwzpn69 201012801 izwzpn

(A39) (A40)(A39) (A40)

(A48)(A48)

(A53)(A53)

70 201012801 i^uwpit ❿ d70 201012801 i^uwpit ❿ d

(A54)(A54)

oo

(A55)(A55)

_0_0

(Αβ2) (A63, 〇 O(Αβ2) (A63, 〇 O

6項所述之 8. 一種聚醯亞胺’是將如申請專利範圍第聚醯胺酸脫水開環而獲得。The above-mentioned item 8. A polyimine is obtained by dehydrating and opening a polyglycine as claimed in the patent application.

9. 一種溶液’包括選自由如申請專利範圍第6項所述之聚醯胺酸以及如申請專利範圍第8項所述之聚醯亞胺所組成的組群中的至少一種聚合物。 10· —種液晶配向劑，由如申請專利範圍第9項所述之聚合物溶液構成。 —種液晶顯示元件’包括由如申請專利範圍第10 項所述之液晶配向劑所獲得的液晶配向膜。 71 201012801 jzuozpu 四、指定代表圖： (一）本案之指定代表圖：無 (二）本代表圖之元件符號簡單說明：無五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：A solution 'includes at least one polymer selected from the group consisting of polylysine as described in claim 6 and polyamidiamine as described in claim 8 of the patent application. A liquid crystal alignment agent comprising a polymer solution as described in claim 9 of the patent application. A liquid crystal display element 'includes a liquid crystal alignment film obtained by the liquid crystal alignment agent as described in claim 10 of the patent application. 71 201012801 jzuozpu IV. Designated representative map: (1) The designated representative figure of the case: None (2) The symbol of the symbol of the representative figure is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

Η〆 NH2 〇 (1)Η〆 NH2 〇 (1)

3 201012801 # k ' : iSi_9*^7877號中文說明書無劃線修正本修正日期:卯-1 Ll 27、曰發明專利說明書 (本說明書格式、順序，請勿任意更動，※記號部分請勿填寫） ※申請案號： 6AD 1⑽06.01> ※申請日： ' ※”(：分類：% ί2〇〇6*〇η 一、發明名稱：知 ί2006·01Ι 二胺、液晶配向劑、液晶配向膜、以及液晶顯示元件 DIAMINE, LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER, AND • LIQUID CRYSTAL DISPLAY DEVICE 二、中文發明摘要：本發明的課題在於開發一種可達成對液晶配向膜中所 * 要求的很多特性（電壓保持率高、殘留DC小、液晶配向 . 性高、耐摩擦性高等）的聚醯胺酸。該課題是由式（1)所表示的二胺來解決。於式（1)中’ γ為單鍵或碳數為1〜 9的直鏈伸烷基；該伸烷基的任意-CH2-可由-〇_、 -N(CH；3)-、1，4-伸苯基、l，4-伸環己基或°辰嗪-l，4-二基取代； ❹ η為0或1 ;並且，鍵結有胺基的苯環的一個氫可由_〇H 取代。其中’當γ為伸烷基且η為〇時，並無鍵結有胺基的-CH2-由-0-或-N(CH3)-取代的情況。3 201012801 # k ' : iSi_9*^7877 Chinese manual without slash correction This correction date: 卯-1 Ll 27, 曰 invention patent specification (this specification format, order, please do not change, please do not fill in the ※ part) ※Application number: 6AD 1(10)06.01> ※Application date: '※" (: Classification: % ί2〇〇6*〇η I. Name of the invention: 知ί2006·01Ι Diamine, liquid crystal alignment agent, liquid crystal alignment film, and Liquid crystal display element DIAMINE, LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER, AND • LIQUID CRYSTAL DISPLAY DEVICE 2. SUMMARY OF THE INVENTION The object of the present invention is to develop a property (voltage retention) that can be achieved in a liquid crystal alignment film* Poly-proline which has a high rate, small residual DC, high liquid crystal alignment, high friction resistance, etc. This problem is solved by the diamine represented by the formula (1). In the formula (1), 'γ is a single a bond or a linear alkyl group having a carbon number of 1 to 9; any -CH 2 of the alkyl group may be -〇_, -N(CH;3)-, 1,4-phenylene, 1,4- Cyclohexylene or phenazine-l,4-diyl substitution; ❹ η is 0 or 1; and a hydrogen of a benzene ring to which an amine group is bonded may be substituted by _〇H. wherein 'when γ is an alkyl group and η is 〇, there is no -CH 2 bonded with an amine group. - the case of being replaced by -0- or -N(CH3)-.

(1) 1 201012801 ^zuozpui 六、發明說明：【發明所屬之技術領域】本發明是關於一種新穎的二胺（diamine)及使用該二胺而獲得的聚醯胺酸（polyamicacid)，進一步關於該聚醯胺酸的用途。另外，本發明中的用語「液晶配向劑（liquid crystal aligning agent )」意指為了形成液晶配向膜而使用的含聚合物之組成物。【先前技術】液晶顯示元件多用於行動電話的顯示部、筆記型電腦 (notebook personal computer )或桌上型電腦（desktop personal computer)的螢幕’還有用於攝影機（video camera) 的取景器（view finder)、投影顯示器（projecti〇I1 display ) 等各種顯不裝置中’最近也開始用於電視（television)中。而且’液晶顯示元件亦用作光學印字頭（0pticai printer head)、光學傅立葉變換（optical Fourier transform)元件、光閥（light valve)等的光電子（optoelectr〇nic )相關元件。先前的液晶顯示元件’其主流是使用向列液晶（nematic liquid crystal)的顯示元件，實用化的有^扭轉9〇度的扭轉向列（Twisted Nematic，ΤΝ)型液晶顯示元件、2) 通常扭轉180度或180度以上的超扭轉向列（SuperTwisted Nenmtic，STN)型液晶顯示元件、3)使用薄膜電晶體的所明薄膜電晶體（Thin Film Transistor，TFT )型液晶顯示元件等。日日’、然而，這些液晶顯示元件具有如下缺點：可適當視認 201012801 ^zuozpui 圖像的視角狭小’自斜向觀看時會產生亮度或對比度的下降以及半色調的亮度反轉。近年來，視角的問題利用以下技術而得到進一步改良：1)使用光學補償薄膜的TN_TFT 型液晶顯示元件、2)使用垂直配向與光學補償薄膜的垂直配向（VerticalAlignment，VA)型液晶顯示元件、3)將垂直配向與突起結構物的技術併用的多象限垂直配向（Multi Domain Vertical Alignment，MVA )型液晶顯示元件、或 4 ) 橫向電場方式的共平面切換（In-Plane Switching，IPS )型參液晶顯示元件、5)電控雙折射（Electrically Controlled Birefringence，ECB)型液晶顯示元件、6)光學補償彎曲 (Optically Compensated Bend 、或 Optically * self-Compensated Birefringence，OCB )型液晶顯示元件 - 等，如此可使這些元件實用化。液晶顯示元件技術的發展不僅可藉由改良該些液晶顯示元件的驅動方式或元件結構，亦可藉由改良顯示元件中所使用之構成成分(constructional element)而達成。顯示 • 元件中所使用之構成成分之中’尤其液晶配向膜是與液晶顯示元件的顯示品質有關的重要因素之一，隨著顯示元件的高品質化，液晶配向膜的作用日益變得重要。液晶配向膜是由液晶配向劑製備。當前，所謂主要使用的液晶配向劑，是指使聚醯胺酸或可溶性聚醯亞胺溶解於有機溶劑中而成的溶液。將此種溶液塗佈於基板上後，利用加熱等方法進行成膜而形成聚醯亞胺系配向膜。亦對聚醯胺酸以外的各種液晶配向劑進行研究，但就_熱性、 5 201012801 szwzpm * 对化學品性（财液晶性）、塗佈性、液晶配向性、電特性、光學特性、顯示特性等方面而言，幾乎未達實用化。為了扼尚液晶顯不元件（LCD，liquid crystal display) 的顯示品質而對液晶配向膜所要求的特性，必須為電壓保持率（VHR，voltage holding ratio )高。於主動矩陣（active matrix )型LCD中’例如若電壓保持率低，則於訊框(frame) 期間中與液晶相關的電壓下降，結果導致亮度變化，未形成正常階調。尤其最近LCD開始用於電視用途，VHR的隨時間劣化小亦變得重要。為了製作大晝面且顧示清晰的 LCD，而尋求背光的亮度變高，且不會由於光或熱而劣化的配向膜。其次’對配向膜中所要求的重要特性，可列舉殘留電荷（DC (direct current，直流））小。所謂殘留dc，是指隨著LCD的驅動而積存於電極間的電荷，由於該現象會將多餘的電壓施加至電極’例如在切斷電壓後產生顯示圖像未消失而殘留的所謂「殘像」。最近報告有可藉由使用具有氮原子的二胺而製作殘留DC小的液晶配向膜（專利文獻卜2、3)，來作為減小殘留DC的方法之一。 [先前技術文獻] [專利文獻1]國際公開2004-053583號手冊 [專利文獻2]國際公開2004-021076號手冊 [專利文獻3]日本專利特開平UM04633號公報然而’隨著液晶顯示元件的南性能化發展，需要可進一步降低殘留DC的配向膜’僅以先前提出的技術，難以 201012801 32062pifl 完全滿足所要求的特性。【發明内容】本發明的目的在於開發一種可達所要求的很多特性（電壓保持率高A f 中向I*生同、耐摩擦（rubbing)性高等）的聚酿胺酸。構中(1) 1 201012801 ^zuozpui VI. Description of the Invention: [Technical Field] The present invention relates to a novel diamine and a polyamic acid obtained by using the same, further The use of polylysine. Further, the term "liquid crystal aligning agent" as used in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film. [Prior Art] Liquid crystal display elements are mostly used for the display portion of a mobile phone, a notebook personal computer or a desktop personal computer screen, and a viewfinder for a video camera (view finder) In various display devices such as projection display (projecti〇I1 display), 'it has recently been used in television. Further, the liquid crystal display element is also used as a photoelectron (optoelectr〇nic) related element such as an optical print head (optical fourier transform element), an optical valve (light valve), or the like. The liquid crystal display element of the prior art is mainly a display element using a nematic liquid crystal, and has a twisted nematic (Twisted Nematic) type liquid crystal display element which is practically twisted by 9 degrees, 2) usually twisted SuperTwisted Nenmtic (STN) type liquid crystal display element of 180 degrees or more, 3) Thin film transistor (TFT) type liquid crystal display element using a thin film transistor, or the like. However, these liquid crystal display elements have the following disadvantages: 201012801 ^zuozpui image has a narrow viewing angle. When viewed from an oblique direction, brightness or contrast is lowered and halftone brightness is reversed. In recent years, the problem of the viewing angle has been further improved by the following techniques: 1) a TN_TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment (VA) type liquid crystal display element using a vertical alignment and an optical compensation film, 3 ) Multi-Vertical Vertical Alignment (MVA) type liquid crystal display element for vertical alignment and protrusion structure technology, or 4) In-Plane Switching (IPS) type reference liquid crystal in transverse electric field mode Display element, 5) Electrically Controlled Birefringence (ECB) type liquid crystal display element, 6) Optically Compensated Bend, or Optically * self-Compensated Birefringence (OCB) type liquid crystal display element - etc. Make these components practical. The development of the liquid crystal display device technology can be achieved not only by improving the driving method or the element structure of the liquid crystal display elements, but also by improving the constituent elements used in the display elements. Display • Among the constituent components used in the element, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and as the display element is made higher in quality, the role of the liquid crystal alignment film is becoming more and more important. The liquid crystal alignment film is prepared from a liquid crystal alignment agent. Currently, the liquid crystal alignment agent mainly used is a solution obtained by dissolving polylysine or soluble polyimine in an organic solvent. After applying such a solution onto a substrate, a film is formed by heating or the like to form a polyimide film. Various liquid crystal alignment agents other than polyglycolic acid have also been studied, but in terms of heat, 5 201012801 szwzpm * chemical properties (liquid crystallinity), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties In other respects, it has hardly been put into practical use. In order to control the display quality of the liquid crystal display (LCD), the characteristics required for the liquid crystal alignment film must be high (VHR, voltage holding ratio). In an active matrix type LCD, for example, if the voltage holding ratio is low, the voltage associated with the liquid crystal during the frame period is lowered, resulting in a change in luminance, and a normal tone is not formed. Especially recently, LCDs have been used for television applications, and the VHR's degradation over time has become important. In order to produce a large-faced and clear-cut LCD, an alignment film which is high in brightness of the backlight and which is not deteriorated by light or heat is sought. Next, the important characteristics required for the alignment film include a small residual current (DC (direct current)). The term "residual dc" refers to the charge accumulated between the electrodes as the LCD is driven. This phenomenon causes an excessive voltage to be applied to the electrode. For example, after the voltage is turned off, the so-called "afterimage" remains after the display image does not disappear. "." Recently, it has been reported that a liquid crystal alignment film having a small residual DC can be produced by using a diamine having a nitrogen atom (Patent Documents 2 and 3) as one of methods for reducing residual DC. [Prior Art Document] [Patent Document 1] International Publication No. 2004-053583 (Patent Document 2) International Publication No. 2004-021076 (Patent Document 3) Japanese Patent Laid-Open Publication No. UM04633 With the development of performance, there is a need for an alignment film that can further reduce residual DC. Only with the previously proposed technology, it is difficult for 201012801 32062pifl to fully satisfy the required characteristics. DISCLOSURE OF THE INVENTION An object of the present invention is to develop a poly-brenic acid which has many characteristics (high voltage holding ratio A f , high I*, high rubbing resistance, etc.). Structure

ί們為了解決上述課題輯行努力研究，發現 11作為聚醯胺酸的原料的二胺中導入1苯基，噪結構而於具有由該聚合物構成的配向膜的液晶顯示元件，一面保持尚電壓保持率一面使殘留DC下降。進而，發現本發明的二胺以及使用本發明的二胺的聚醯胺酸或聚醯亞胺對於通常使用的溶劑具有高溶解性，從而完成本發明。本發明的二胺是由以下第[1]項所表示。 [1]一種二胺，其由式（1)所表示：In order to solve the above problems, we have worked hard to find that a liquid crystal display element having an aligning film composed of the polymer is introduced as a diamine which is a raw material of poly-proline. The voltage holding rate lowers the residual DC. Further, it has been found that the diamine of the present invention and the polyamic acid or polyimine using the diamine of the present invention have high solubility with respect to a solvent which is usually used, thereby completing the present invention. The diamine of the present invention is represented by the following item [1]. [1] A diamine represented by the formula (1):

其中，Y為單鍵或碳數為1〜9的直鏈伸烷基；該伸烷基的任意-CH2-可由-0-、-N(CH3)-、1，4-伸苯基、1，4-伸環己基或哌嗪·1，4-二基取代；η為0或1 ;並且，鍵結有胺基的苯環的一個氫可由-ΟΗ取代。其中，當Υ為伸烷基且 η為0時，並無鍵結有胺基的-CH2i_0-或-N(CH3)-取代的情況。 7 201012801 32062piil . [發明之效果] 人本發明的二胺不須使用特殊的反應裝置就可容易地〇成，而且本發明的液晶配向劑可溶於該技術中通常使用的溶劑中，保存時不會產生沉殿。並且’利用本發明，可提供一種電壓保持率高、殘留DC小的液晶顯示元件。為讓本發明之上述特徵和優點能更明顯易僅，下文特舉實施例，並配合所附圖式作詳細說明如下。【實施方式】首先，對本發明中使用的用語進行說明。有時將由式 ❿ U)所表示的二胺稱為二胺（υ。有時由其他式所表示的一胺亦利用相同簡寫方式表示。對於二胺以外的化合物，例如有時將由式（A)所表示的四羧酸二酐簡寫成酸酐 _ (A)。對化學式進行說明時所使用的用語「任意」意指「不僅位置可自由選擇，數量亦可自由選擇」。例如，「任意A 可由B、C、D或E取代」的表述不僅具有一個A可由B、 C、D或E取代的含義’及多個a的任一者均可由b、c、 D及E的任一者取代的含義，亦具有由B取代的A、由匚 ❹ 取代的A、由D取代的A、以及由E取代的A的至少兩者混合存在的含義。任意-CH2·可由-〇_取代時，不包括結果產生鍵結基團-0-0-的取代。與構成環的碳的鍵結位置不明確的取代基意指其鍵結位置於無化學性問題的範圍内是自由的。於多個式中使用相同記號的情況意指該基團具有相同定義範圍，但並不表示於所有式中必須同時為相同基團。於多個式中可為相 8 201012801 32UWplti 同基團’亦可於不同式巾為不同基團。本發明是由上述第[1]項與以下第[2]〜[11]項構成。 [2] 如第[1]項所述之二胺，其中鍵結有胺基的苯環為不具有-OH作為取代基的苯環。 [3] 如第[1]項所述之二胺’其中鍵結有胺基的苯環為於相對於胺基的其中一鄰位(0池〇 position)具有取代基-oh 的苯環。 [4] 如第[1]項所述之二胺，其中Y為單鍵或μ-伸苯 •基，並且η為0。 [5] 如第[1]項所述之二胺’其中Υ為單鍵、或任意/!^-可由-0-或-N(CH3)-取代的碳數為1〜9的直鏈伸烧基；並 - 且η為1。 . [6]—種聚醯胺酸，是使至少一種如第[1]項所述之二胺、或者至少一種由如第[1]項所述之二胺與至少一種其他二胺所構成的二胺混合物’與至少一種四致酸酐進行反應而獲得。 • [7]如第[6]項所述之聚醯胺酸’其中至少一種四羧酸酐為選自由式（Α1)〜式（Α63)所表示的化合物中的四羧酸酐。 9 201012801 32062pitlWherein Y is a single bond or a linear alkylene group having a carbon number of 1 to 9; any -CH2- of the alkylene group may be -0-, -N(CH3)-, 1,4-phenylene, 1 , 4-cyclohexylene or piperazine·1,4-diyl substituted; η is 0 or 1; and, a hydrogen of a benzene ring to which an amine group is bonded may be substituted by -ΟΗ. Wherein, when hydrazine is an alkylene group and η is 0, there is no case of -CH2i_0- or -N(CH3)- substitution in which an amine group is bonded. 7 201012801 32062piil . [Effects of the Invention] The diamine of the present invention can be easily formed without using a special reaction device, and the liquid crystal alignment agent of the present invention is soluble in a solvent commonly used in the art, and is preserved. There will be no sinking. Further, by the present invention, it is possible to provide a liquid crystal display element having a high voltage holding ratio and a small residual DC. The above described features and advantages of the present invention will become more apparent and obvious. [Embodiment] First, the terms used in the present invention will be described. The diamine represented by the formula ) U) is sometimes referred to as a diamine (υ. Sometimes, the amine represented by the other formula is also represented by the same abbreviated form. For compounds other than the diamine, for example, sometimes the formula (A) The tetracarboxylic dianhydride represented by the formula is abbreviated as an acid anhydride _ (A). The term "arbitrary" used in the description of the chemical formula means "not only the position can be freely selected, but also the number can be freely selected." For example, "Any The expression "may be substituted by B, C, D or E" has not only a meaning that A can be replaced by B, C, D or E, and any of a plurality of a can be replaced by any of b, c, D and E. The meaning also has the meaning of a mixture of A substituted by B, A substituted by 、, A substituted by D, and A substituted by E. When any -CH2· can be substituted by -〇_, The substitution which results in the formation of the bonding group -0-0- is not included. The substituent having an unclear bonding position with the carbon constituting the ring means that the bonding position is free in the range of no chemical problem. The use of the same token in the formula means that the group has the same definition range, but not It is indicated that all of the formulae must be the same group at the same time. In many formulas, it may be phase 8 201012801 32UWplti The same group 'may be different groups in different types of towels. The present invention is the above item [1] and below [2] The diamine according to [1], wherein the benzene ring to which the amine group is bonded is a benzene ring having no -OH as a substituent. [3] The diamine described in the item [1] wherein the benzene ring to which an amine group is bonded is a benzene ring having a substituent -oh relative to one of the ortho positions of the amine group. The diamine according to the item [1], wherein Y is a single bond or a μ-phenylene group, and η is 0. [5] The diamine of the item [1] wherein Υ is a single bond Or any /!^- a linear stretch group having a carbon number of 1 to 9 which may be substituted by -0- or -N(CH3)-; and - and η is 1. [6]-polyproline Is a mixture of at least one diamine as described in the item [1], or at least one diamine composed of the diamine as described in the item [1] and at least one other diamine The anhydride is obtained by a reaction. [7] The polyamine described in the item [6] 'Wherein at least one tetracarboxylic acid anhydride is selected from Formula (alpha] l) ~ tetracarboxylic acid anhydride compound of formula (Α63) are represented. 9 201012801 32062pitl

10 201012801 32062pifl10 201012801 32062pifl

(A14) (A15) (A16) (A17)(A14) (A15) (A16) (A17)

WWWWWW

(A29) (A26) (A27) (A28)(A29) (A26) (A27) (A28)

11 201012801 32062pitl oAx^o O11 201012801 32062pitl oAx^o O

(A37) O O(A37) O O

O O (A38) (A36) (A39)O O (A38) (A36) (A39)

(A42) (MO) (A41)(A42) (MO) (A41)

(A44) O G (A43) ,0(A44) O G (A43) , 0

(A45) Μ M (A46) (A47) O °pxix0 °pm^〇 °pmd,0 (A48) O(A45) Μ M (A46) (A47) O °pxix0 °pm^〇 °pmd,0 (A48) O

(A51) (A49)(A51) (A49)

(A52) (A50) Q (A53) 12 201012801 32062pitl(A52) (A50) Q (A53) 12 201012801 32062pitl

(A61)(A61)

(A55)(A55)

:时卜4 (Αβ2) (A63):时卜4 (Αβ2) (A63)

(A60) [8] —種聚酿亞胺’是將如第[6]項所述之聚醯胺酸脫水開環而獲得。 [9] 一種溶液，包括選自由如第[6]項所述之聚醯胺酸以 • 及如第[8]項所述之聚醯亞胺所組成的組群中的至少一種聚合物。 [10] —種液晶配向劑，由如第[9]項所述之聚合物溶液構成。 [11] 一種液晶顯示元件，包括由如第[10]項所述之液晶配向劑而獲得的液晶配向膜。本發明的二胺是由式（1)所表示。 13 201012801 32ϋ62ρΐίΊ(A60) [8] A kind of polyienimine' is obtained by dehydrating and opening a polyamic acid as described in the item [6]. [9] A solution comprising at least one polymer selected from the group consisting of polylysine as described in the item [6] and the polyamidene according to item [8]. [10] A liquid crystal alignment agent comprising the polymer solution according to [9]. [11] A liquid crystal display element comprising the liquid crystal alignment film obtained by the liquid crystal alignment agent according to [10]. The diamine of the present invention is represented by the formula (1). 13 201012801 32ϋ62ρΐίΊ

(linear alkylene group)。並且，該伸烷基的任意_Ch2_可由 -0-、-N(CH3)-、1，4-伸苯基(l，4-phenylene)、1，4-伸環己基 (l，4-cyclohexylene)或哌嗪-1,4-二基（piperazine_ 14_diyl)取代。Y的較好例子為單鍵、1，4-伸苯基、哌嗪二基以及任意-CH2·可由·0-或-N(CH3)-取代的碳數為1〜9的直鏈伸烷基。Y的更好例子為1，4-伸苯基以及任意-CH2_可由或-N(CH3)-取代的碳數為1〜9的直鏈伸烧基。^為〇或！。然而，當Y為上述伸烷基且！！為〇時，並無鍵結有胺基的 -CH2·由-Ο·或-N(CH3)·取代的情況。並且，鍵結有胺基的苯環的一個氫可由-OH取代。該苯環具有一個取代基_〇H 時，其位置相對於胺基的鍵結位置為鄰位或間位(meta position)，較佳是鄰位。藉由使二胺（1 )與四羧酸二酐反應而獲得的聚酿胺酸對溶劑的溶解性高，可防止保存於冰箱中等時聚合物析出。根據二胺（1 )以外的原料組成，如預期會變成溶解性較差的聚醯胺酸時’較佳是使用n為〇的非對稱二胺（i )，因可提咼溶解性。而且，在將溶解性低於聚醯胺酸的聚醯亞胺用於配向劑中的情況下，使用式（1)中的η為〇的二胺（1)也較好。此外’為了獲得具有較大配向限制力的配向膜，γ較 201012801 32U62piil 佳是碳數為1〜9的直鏈伸烷基，更佳是碳數為2〜9的直鏈伸烷基。該情況下的伸烷基是·αι2-未由其他基團取代的伸烷基。由以本發明的二胺為原料的聚醯胺酸獲得的配向膜降低殘留DC的效果明顯大。因此，藉由將下述所示的配向限制力特別大的公知的其他二胺與二胺（1)加以組合來使用’亦可獲得對液晶的配向限制力大、殘留DC低的配向膜。為了將配向膜的電特性製備成所需的值’ Y的直鍵伸烷基中的任意-CH2-可由-〇-或n(ch3)-取代。此時，自原料獲取的容易度考慮，較佳是與n弓丨嗓環鄰接的-CH2-由-0-或 N(CH3)-取代，自化合物的穩定性考慮，較佳是-0-與 N(CH3)-不相鄰。以下表示二胺（1)的具體例。籲 15 201012801 32062pitl(linear alkylene group). Moreover, any _Ch2_ of the alkylene group may be -0-, -N(CH3)-, 1,4-phenylene (1,4-phenylene), 1,4-cyclohexylene (l,4- Cyclohexylene) or piperazine-1,4-diyl (piperazine_ 14_diyl). Preferred examples of Y are a single bond, a 1,4-phenylene group, a piperazine diyl group, and any -CH2. a linear alkylene group having a carbon number of 1 to 9 which may be substituted by ·0- or -N(CH3)-. base. A more preferred example of Y is a 1,4-phenylene group and any -CH2_ straight-chain alkylene group having a carbon number of 1 to 9 which may be substituted by -N(CH3)-. ^为〇 or! . However, when Y is the above alkyl group and! ! In the case of hydrazine, there is no case where -CH2· having an amine group bonded thereto is substituted by -Ο· or -N(CH3)·. Further, a hydrogen of a benzene ring to which an amine group is bonded may be substituted by -OH. When the benzene ring has a substituent _〇H, its position relative to the bond position of the amine group is an ortho position, preferably an ortho position. The polystyroic acid obtained by reacting the diamine (1) with the tetracarboxylic dianhydride has high solubility in a solvent, and prevents precipitation of the polymer when it is stored in a refrigerator or the like. When the composition of the raw material other than the diamine (1) is expected to become a poorly soluble polyamic acid, it is preferred to use an asymmetric diamine (i) wherein n is ruthenium, since the solubility can be improved. Further, in the case where a polyimine having a solubility lower than polyglycolic acid is used in the alignment agent, it is also preferred to use a diamine (1) wherein η is an anthracene in the formula (1). Further, in order to obtain an alignment film having a larger alignment restricting force, γ is preferably a linear alkylene group having a carbon number of 1 to 9 and more preferably a linear alkylene group having a carbon number of 2 to 9 as compared with 201012801 32U62piil. The alkylene group in this case is an alkyl group which is not substituted by another group. The effect of reducing the residual DC by the alignment film obtained from the polyamine which is a raw material of the diamine of the present invention is remarkably large. Therefore, by using a known other diamine having a particularly large alignment resistance as shown below and a diamine (1), it is also possible to obtain an alignment film having a large alignment resistance to liquid crystal and a low residual DC. In order to prepare the electrical properties of the alignment film to a desired value, Y - any of the -CH 2 - may be substituted by -〇- or n(ch3)-. At this time, from the viewpoint of easiness of obtaining the raw material, it is preferred that -CH2- adjacent to the n-ring ring is substituted by -0- or N(CH3)-, and from the viewpoint of stability of the compound, preferably -0- Not adjacent to N(CH3)-. Specific examples of the diamine (1) are shown below.申 15 201012801 32062pitl

CCn〇〇 H2N (1.3) nh2CCn〇〇 H2N (1.3) nh2

16 201012801 32ϋ62ριί116 201012801 32ϋ62ριί1

η2ν ΝΗ2Η2ν ΝΗ2

(1-17)(1-17)

17 201012801 32062pitl17 201012801 32062pitl

18 201012801 32062pifl18 201012801 32062pifl

nh2 h2n (1-37) Y為單鍵且n為0的二胺（1)可利用以下所示的途徑來合成。Nh2 h2n (1-37) The diamine (1) wherein Y is a single bond and n is 0 can be synthesized by the route shown below.

於流程1 _，於氫化鈉等鹼存在下，使由（S1-1)所表示的市售的5-胺基吲哚或6-胺基吲哚與4·氟硝基苯進行反應，獲得由（S1-2)所表示的化合物。繼而，對由（si-2) 所表示的化合物，以氫催化還原而將硝基還原，藉此可合成由式（1)所表示的二胺。In the first step, in the presence of a base such as sodium hydride, a commercially available 5-amino hydrazine or 6-amino hydrazine represented by (S1-1) is reacted with 4· fluoronitrobenzene to obtain A compound represented by (S1-2). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (si-2), whereby the diamine represented by the formula (1) can be synthesized.

當Y是碳數為1〜9的直鏈伸烷基且η為1的化合物時，可利用以下所示的途徑來合成。When Y is a compound having a linear alkyl group having 1 to 9 carbon atoms and η is 1, it can be synthesized by the route shown below.

於上述流程 2 中，依據 Tetrahedron Letters 41(11)， 1811—1814(2_)中記載的方法，使由（S24)所表示的二 19 201012801 32062pitl 胺（其中Y為單鍵或碳數為i〜9的直鏈伸垸基）與氣化三乙醇銨進行反應，獲得由（S2_2)所表示的化合物。繼而，於氫化__在下，使上述由（S2_2)所表示的化合物與4-氟硝基苯進行反應，獲得由（S2_3) 合物。繼而，對由㈣所表示的化合物以=丁：而將硝基還原，藉此可合成由式（1)所表示的二胺。當Y是碳數為2〜9的直鏈伸烷基且n為〇的化合物時’可利用以下所示的途徑來合成。In the above Scheme 2, according to the method described in Tetrahedron Letters 41 (11), 1811-1814 (2_), the two 19 201012801 32062 pitl amine represented by (S24) (where Y is a single bond or the carbon number is i~) The linear chain of 9 is reacted with vaporized triethanolammonium to obtain a compound represented by (S2_2). Then, the above-mentioned compound represented by (S2_2) is reacted with 4-fluoronitrobenzene under hydrogenation to obtain (S2_3). Then, the compound represented by the formula (IV) is reduced by reducing the nitro group with the compound represented by the formula (4), whereby the diamine represented by the formula (1) can be synthesized. When Y is a compound having a linear alkyl group having 2 to 9 carbon atoms and n is ruthenium, ' can be synthesized by the route shown below.

6403-6406 (1993)中記載的方法，使由（83_υ所表示的化合物與胺基炔化物（其中Υ，為單鍵或碳數為i〜7的直鏈伸燒基）進行反應，獲得由（S3-2)所表示的化合物。繼而，於氳化鈉等鹼存在下，使上述由（S3_2)所表示的化合物與4-氟硝基苯進行反應，獲得由（S3_3)所表示的化合物。繼而’對由（S3_3)所表示的化合物以氫催化還原而將硝基還原’藉此可合成由式（1)所表示的二胺。當Y是碳數為1的亞甲基且η為〇的化合物可利用以下所示的途徑來合成。 20 201012801 32062ρίΠ6403-6406 (1993) a method of reacting a compound represented by (83_υ with an amino acetylide (wherein, a single bond or a linear stretch group having a carbon number of i to 7) is obtained by (S3-2) The compound represented by (S3-2) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S3_3). Then, 'the compound represented by (S3_3) is reduced by hydrogen-catalyzed reduction to reduce the nitro group', whereby the diamine represented by the formula (1) can be synthesized. When Y is a methylene group having a carbon number of 1, and η The compounds which are oxime can be synthesized by the route shown below. 20 201012801 32062ρίΠ

在上述流程4中，於氫化納等驗存在下，使由（) 所表示的市售的5-(胺基甲基)η引哚或6_(胺基甲基户引嗓與 4-氟硝基苯進行反應，獲得由（S4-2)所表示的化合物。繼而’對由（S4-2)所表示的化合物以氫催化還原而將硝基還原’藉此可合成由式（1)所表示的二胺。當Υ為1，4-伸苯基且η為0的化合物時，可利用以下所示的途徑來合成。 (S5-2) μ〇ηη〇2 釦一 h 參 (S5-3) N〇2 (1) NH2 流程5 凡於上述流程5中，使由（Μ。）所表示的市售的5溴吲哚或6-溴吲哚與市售的4_胺基苯基硼酸，藉由使用鈀觸媒進行偶合反應而獲得由（S5_2)所表示的化合物。繼而， :氫化鈉等驗存在下，使上述由（S5_2)所表示的化合物，、4-氟碗基苯進行反應，獲得由（S5_3)所表示的化合物。 f而’對纟（S5-3)所表示的化合物以氫催化還原而將硝基還原’藉此可合成由式⑴所表示的二胺。 201012801 32062pifl 其次，對本發明的聚醯胺酸進行具體說明。藉由使二胺（1)於溶劑中與四羧酸二酐進行反應，而獲得含有聚醯胺酸、經部分醯亞胺化的聚醢胺酸、或該些的混合物的溶液。於以下說明中有時將該些的溶液稱為清漆(vamish)。進而，藉由利用脫水反應使該些清漆中所含的聚醯胺酸、經部分醯亞胺化的聚醯胺酸或該些的混合物開環，而獲得含有聚醯亞胺的清漆。於本發明中，二胺（1)可單獨使用，亦可將兩種或兩種以上的二胺（1)加以組合。而且，亦可將由式（1)所表示的二胺與其他已知的二胺併用。於以下說明中，將聚醯胺酸、或經部分醯亞胺化的聚醯胺酸、或該些的混合物等聚醯胺酸類，以及使聚醯胺酸、或經部分醯亞胺化的聚醯胺酸、或該些的混合物脫水開環而獲得的聚醯亞胺類總稱為聚合物。本發明的聚合物的分子量是以利用凝膠滲透層析 (Gel Permeation Chromatography，GPC )法所測定的重量平均分子量計，較佳是1，000〜500 〇〇〇，更佳是1〇〇〇〇〜 250,000。其原因在於，若重量平均分子量大於等於 10,000，則於形成配向膜時的基板煆燒步驟中，抑制聚合物的昇華，若重量平均分子量小於等於25〇〇〇〇，則可防止對溶劑的溶解性下降，將配向劑塗佈於基板時的聚合物部分析出等得到抑制。 _本發明中，並無特別限定四羧酸二酐的理由，以下表示適合使用的較好四羧酸二酐的具體例。 22 201012801 32U62pitlIn the above Scheme 4, the commercially available 5-(aminomethyl)η 哚 or 6_(aminomethyl hydrazine and 4-fluorene nitrate) represented by () is present in the presence of hydrogenation. The benzene is reacted to obtain a compound represented by (S4-2). Then, the compound represented by (S4-2) is hydrogen-catalyzed to reduce the nitro group, thereby synthesizing the formula (1) The diamine represented by the formula. When the fluorene is a compound having a 1,4-phenylene group and η is 0, it can be synthesized by the following route. (S5-2) μ〇ηη〇2 扣一h 参(S5- 3) N〇2 (1) NH2 Scheme 5 In the above Scheme 5, commercially available 5 bromoindole or 6-bromoindole represented by (Μ.) and commercially available 4-aminophenyl group Boric acid, a compound represented by (S5_2) is obtained by a coupling reaction using a palladium catalyst. Then, in the presence of sodium hydride or the like, the compound represented by the above (S5_2), 4-fluorophenanthrene is obtained. The reaction is carried out to obtain a compound represented by the formula (1), and the compound represented by the formula (1) can be synthesized by hydrogen-catalyzed reduction of the compound represented by the oxime (S5-3).201012801 32062pifl Next, the poly-proline acid of the present invention will be specifically described. By reacting the diamine (1) with a tetracarboxylic dianhydride in a solvent, a polyammonium-containing product and a partial ruthenium imidization are obtained. Polyacetic acid, or a solution of a mixture of these. In the following description, these solutions are sometimes referred to as varnish. Further, the poly-proline contained in the varnish is obtained by utilizing a dehydration reaction. And the partially ruthenized polyamic acid or a mixture of the rings is opened to obtain a varnish containing a polyimine. In the present invention, the diamine (1) may be used alone or two or Two or more kinds of diamines (1) may be combined. Further, the diamine represented by the formula (1) may be used in combination with other known diamines. In the following description, polyglycine or partial hydrazine may be used. An imidized polylysine, or a polyamic acid such as a mixture thereof, and a polylysine, or a partially arniminated poly-proline, or a mixture of the same, obtained by dehydration and ring opening Polyimines are collectively referred to as polymers. The molecular weight of the polymers of the present invention is The weight average molecular weight measured by a gel permeation chromatography (GPC) method is preferably 1,000 to 500 Å, more preferably 1 Å to 250,000. When the weight average molecular weight is 10,000 or more, the sublimation of the polymer is suppressed in the substrate calcination step in forming the alignment film, and if the weight average molecular weight is 25 Å or less, the solubility in the solvent can be prevented from decreasing, and the alignment is prevented. The analysis of the polymer portion when the agent is applied to the substrate is suppressed. In the present invention, the reason for the tetracarboxylic dianhydride is not particularly limited, and specific examples of the preferred tetracarboxylic dianhydride which are suitably used are shown below. 22 201012801 32U62pitl

23 201012801 32062pifl23 201012801 32062pifl

(A14) (A15) (A16) (A17) W妓执Μ (A18) (A19) (A20) (A21)(A14) (A15) (A16) (A17) W妓 Μ (A18) (A19) (A20) (A21)

M ^ (Α22) (Α23) (Α24) (Α25) °ϊ^〇。两 (Α26) (Α27) (Α28) (Α29)M ^ (Α22) (Α23) (Α24) (Α25) °ϊ^〇. Two (Α26) (Α27) (Α28) (Α29)

(Α30) (Α31) (Α32)(Α30) (Α31) (Α32)

(Α33)(Α33)

24 201012801 32062pifl G24 201012801 32062pifl G

O (A36)O (A36)

(A37) O O(A37) O O

(A40) 參 (A39)(A40) Reference (A39)

0 o o o (A43)0 o o o (A43)

(A44) (A46)(A44) (A46)

Ό ㈣ (A47)Ό (4) (A47)

ΌΌ

(A49)(A49)

O (A53) 25 201012801 32U62pillO (A53) 25 201012801 32U62pill

M :时Μ (Αβ1) (Α62) (Α63)M : hour Α (Αβ1) (Α62) (Α63)

(Α57)(Α57)

(ΑβΟ) ❿ 該些四羧酸二酐可單獨使用，亦可將兩種或兩種以上混合使用。這些四羧酸二酐之中，尤其好的例子是酸酐 (Α1)、酸酐（Α2)以及酸酐（Α20)，藉由使用這些四羧酸二酐中的至少一種，可提供電壓保持率更高的液晶顯示元件。内(ΑβΟ) ❿ These tetracarboxylic dianhydrides may be used singly or in combination of two or more. Among these tetracarboxylic dianhydrides, particularly preferred examples are an acid anhydride (Α1), an acid anhydride (Α2), and an acid anhydride (Α20), which can provide a higher voltage holding ratio by using at least one of these tetracarboxylic dianhydrides. Liquid crystal display element. Inside

衣谓个货π列本瓦奶町，牡个損及本發明效果的 m，可將由式（1)所表示的二胺與並非由式（1)所的公知二胺合併使用。此時，為了最大限度地發揮本的效果，將二胺的總量設為刚莫耳百分比(m。式⑴所衫的二賴含有_為G5 、莫耳百分比，較佳是5莫耳¥分比〜9()莫耳百分^ 公知二胺的較好例子為選自下述所示的由 26 201012801 32062ρίΠ 式（VIII)所表示的化合物組群中的二胺。可將該些二胺的至少一種與二胺（1)併用。另外，亦可併用並非由式（π) 〜式（VIII)所表示的二胺。 H2N—(CHz)m—nh2 (II) h2n-^^-nh2 (III) \->νη2 (IV) h2n~〇~nh2 (V) η2Ν0^1"0ΝΗ2 (VI) Η2Ν〇^〇2^〇ΝΗ2 (VII) L2 _) 於式（II)〜式（VIII)中，m為1〜12的整數，G1 鲁獨立為单鍵、-0，、-S-、-S-S-、-S〇2-、-CO·、-CONH-、 -NHCO-、-C(CH3)2-、-C(CF3)2-、-(CH2)k-、-〇_(CH2)k-0-、或-S-(CH2)k-S-、-N(CH3)-(CH2)k-N(CH3)·，且 k 為 i〜12 的整數；G2 獨立為單鍵、-O-、-S-、-CO·、-C(CH3)2-、-C(CF3)2· 或碳數為1〜3的伸烷基；而環己烷環以及苯環的任意氫可由氟或-CH3取代。於式（III)中，較佳是兩個胺基不鍵結於相同碳原子上。式（IV)中的胺基較佳是不鍵結於鍵結有G1的碳原子上。 27 201012801 όζ\)〇ζριη 以下表示二胺（II)〜二胺（IV)的具體例。 Η〆 ,ΝΗ, η2ν，ν 'νη2 η2ν- (H-2) (ΙΙ-3) ,ΝΗ, Η〆 ,ΝΗ, (H-4) Η2ΝThe clothes are referred to as individual goods, and the diamines represented by the formula (1) can be used in combination with the known diamines not represented by the formula (1). In this case, in order to maximize the effect of the present invention, the total amount of the diamine is set to the percentage of the molars (m. The second meaning of the shirt of the formula (1) is _ is G5, the percentage of moles, preferably 5 moles. A typical example of a known diamine is a diamine selected from the group consisting of compounds represented by the formula (VIII) shown in the following paragraphs: </ RTI> </ RTI> </ RTI> At least one of the amines may be used in combination with the diamine (1). Alternatively, a diamine not represented by the formula (π) to the formula (VIII) may be used in combination. H2N-(CHz)m-nh2 (II) h2n-^^- Nh2 (III) \->νη2 (IV) h2n~〇~nh2 (V) η2Ν0^1"0ΝΗ2 (VI) Η2Ν〇^〇2^〇ΝΗ2 (VII) L2 _) in formula (II)~ In VIII), m is an integer of 1 to 12, and G1 is independently a single bond, -0, -S-, -SS-, -S〇2-, -CO·, -CONH-, -NHCO-, - C(CH3)2-, -C(CF3)2-, -(CH2)k-, -〇_(CH2)k-0-, or -S-(CH2)kS-, -N(CH3)-( CH2)kN(CH3)·, and k is an integer of i~12; G2 is independently a single bond, -O-, -S-, -CO·, -C(CH3)2-, -C(CF3)2· Or an alkylene group having a carbon number of 1 to 3; and a cyclohexane ring Arbitrary hydrogen substituted with fluorine may be a benzene ring or -CH3. In the formula (III), it is preferred that the two amine groups are not bonded to the same carbon atom. The amine group in the formula (IV) is preferably not bonded to a carbon atom to which G1 is bonded. 27 201012801 όζ\)〇ζριη Specific examples of the diamine (II) to the diamine (IV) are shown below. Η〆 ,ΝΗ, η2ν,ν 'νη2 η2ν- (H-2) (ΙΙ-3) ,ΝΗ, Η〆 ,ΝΗ, (H-4) Η2Ν

^^-νη2 η2ν^^-νη2 η2ν

νη2 (ΙΙΙ-2) (HI-3) (ΙΙΜ)Ηη2 (ΙΙΙ-2) (HI-3) (ΙΙΜ)

Η2Η2

Η2 以下表示二胺（V)的具體例 Η2Ν-^^-νη2 η2ν-^^-νη2 Ηζν-^^~νη2 η2ν-^^-νη2 (V-1) (V-2) (V^) (V-4) (V-5) 以下表示二胺（VI)的具體例。Η2 The following is a specific example of the diamine (V) Η2Ν-^^-νη2 η2ν-^^-νη2 Ηζν-^^~νη2 η2ν-^^-νη2 (V-1) (V-2) (V^) ( V-4) (V-5) Specific examples of the diamine (VI) are shown below.

(VI-10) (VI-11) 28 201012801 32U62pitl(VI-10) (VI-11) 28 201012801 32U62pitl

H2N-〇^〇V^〇V〇-nh2 h2n-^^°^^o^〇_NH2 (VI-17) (VI-18) ® h2n-^^°v^^〇^〇-4JH2 h2n-^^°^V^^°v^_Nh2 (VI-19) (VI-20) H2N-^^N>^^-NH2 «2N-^^NV^NXC^_NH2 (VI-21) (VI-22) h2n-^-s's^〇-nh^ h2nO"SvxSv〇-nh2 (Vl>23) (VI-24) (Vk25) H2N_^^s>w^SvO^H2H2N-〇^〇V^〇V〇-nh2 h2n-^^°^^o^〇_NH2 (VI-17) (VI-18) ® h2n-^^°v^^〇^〇-4JH2 h2n- ^^°^V^^°v^_Nh2 (VI-19) (VI-20) H2N-^^N>^^-NH2 «2N-^^NV^NXC^_NH2 (VI-21) (VI-22 H2n-^-s's^〇-nh^ h2nO"SvxSv〇-nh2 (Vl>23) (VI-24) (Vk25) H2N_^^s>w^SvO^H2

(VI-26) (Vk27) Η2Ν-^^ν,^-^δ^〇-ΝΗ2 (VI-28) (VI-29)(VI-26) (Vk27) Η2Ν-^^ν,^-^δ^〇-ΝΗ2 (VI-28) (VI-29)

(VI-33) (νμ35) (VI-34) 29 以下表示二胺（VII)的具體例(VI-33) (νμ35) (VI-34) 29 Specific examples of the diamine (VII) are shown below.

(Vi-5)(Vi-5)

201012801 32062pifl 吵"0^^0^乂）-^2 HzN~G 以下表示二胺（VIII)的具體例。 Ο201012801 32062pifl Noisy "0^^0^乂)-^2 HzN~G The following shows a specific example of the diamine (VIII). Ο

(VIIH)(VIIH)

\ /7-ΝΗ^ 〇 (νιιμδ)\ /7-ΝΗ^ 〇 (νιιμδ)

30 201012801 32062ρίΠ Η2Ν 令。^〇^〇^叫 (νΐΐμ8)30 201012801 32062ρίΠ Η2Ν Order. ^〇^〇^叫 (νΐΐμ8)

(VBM1) w (VB|.12) w 二胺（II)〜_ 的至少ml二胺（VIII)由於可藉由將這些二胺中的預傾角調整為〇Ha)合併使用’而將液晶分子 υ〜3 ’故適合作為IPS用配向膜原料。 -吐krr 、得電壓保持率更高的IPS用配向膜’較佳是將一胺二胺㈣合併使用。 (vi-ij獲得殘留DC更低的配向膜，較佳是將二胺、一胺（VI-15)或二胺（VI-22)合併使用，尤 Π%22)合併使用。了獲知"提高液晶顯示元件的黑顯示特性的配向 ’較佳是將由二胺（VI-10)或二胺（VIII-3)所表示的一胺合併使用。作為其他公知的二胺’可列舉具有側鏈結構的二胺。具有侧鏈結構的公知二胺的例子是下述二胺（IX)〜二胺 31 201012801 (XII)。可將這些二胺中的至少—種盥二 :將二胺⑻〜二胺(VIII)中的至7—== 用X; 一胺（XII)中的至少一種與二胺（1)合併使用。另外，於本發明中，除了二胺（II)〜二胺（XII)，亦可使用這些二胺以外的二胺。 (IX)(VBM1) w (VB|.12) w at least ml diamine (VIII) of diamine (II)~_ because liquid crystal molecules can be combined by adjusting the pretilt angle in these diamines to 〇Ha) υ~3' is suitable as a raw material for alignment film for IPS. - The aligning film for IPS having a higher voltage holding ratio is preferably used for combining the amine diamine (IV). (vi-ij obtains a lower alignment film of residual DC, preferably a combination of diamine, monoamine (VI-15) or diamine (VI-22), especially 22%). It is known that the alignment of the black display characteristics of the liquid crystal display element is improved. Preferably, a monoamine represented by a diamine (VI-10) or a diamine (VIII-3) is used in combination. As another well-known diamine, a diamine which has a side chain structure is mentioned. An example of a known diamine having a side chain structure is the following diamine (IX) to diamine 31 201012801 (XII). At least one of these diamines may be used: a combination of at least one of the diamines (8) to diamines (VIII) to 7-== with X; one of the amines (XII) and the diamine (1) . Further, in the present invention, in addition to the diamine (II) to the diamine (XII), diamines other than these diamines may be used. (IX)

h2n〇tc R2 R3H2n〇tc R2 R3

O-G4 (X) 、==^nh5 R3 h2n€^~' G4-。O-G4 (X), ==^nh5 R3 h2n€^~' G4-.

(XI)(XI)

(XII) 32 201012801 J 厶 V/U 厶 plil 式（IX)中 ’G3 為單鍵、-o-、-coo-、_oco-、-co-、 -CONH-或-(CH2)k-，且k為1〜12的整數。R1是碳數為3 〜20的烧基、苯基、具有類固醇（steroid)骨架的基團、或由下述式（IX-S)所表示的基團。於該烷基中，任意氫可由氟取代’並且任意-CH2-可由-〇-、-CH=CH-或-CeC-取代。該苯基的氳可由-F、-CH3、-OCH3、-〇CH2F、-OCHF2 或-OCF3取代。胺基對苯環的鍵結位置為任意，但較佳是兩個胺基的鍵結位置關係為間位或對位。即，基團「rLG3-」 ® 的鍵結位置為1位時，較佳是兩個胺基分別鍵結於3位與 5位、或2位與5位° 一^^4<37-A2^(g8-A3-J-(g9-a4-^-Rs (IX-S) • 武（IX_S)中，R5為氫、氟、碳數為1〜20的烷基、碳數為1〜20的經氟取代的烷基、碳數為1〜20的烷氡基、 •CN、-〇CH2F、〇CHF2 或-OCF3，G7、G8 以及 G9 為鍵結基團’且該些獨立為單鍵、-0-、-€00-'-0(：0-、-(：01<[11-、 -CH=CH-或碳數為1〜12的伸烷基，A2、A3以及A4為環， Φ J•該些獨立為1，4-伸苯基、1，4-伸環己基、1，3-二喔烧-2,5- 二基、，咬>2,5-二基、π比嘴;_2,5_二基、萘-u-二基、萘_2,7-二基或葱-9，10-二基，於所有環中，任意氫可由氟或-CH3 取代；b、C以及d獨立為0〜2的整數，且該些的合計為1 〜5’b、c或a為2時，兩個鍵結基團可相同亦可不同，並且兩個環可相同亦可不同。式（X)以及式（XI)中，R2獨立為氫或曱基。R3 獨立為氫、碳數為1〜20的烷基、或碳數為2〜20的烯基》 33 201012801 G4獨立為單鍵、-CO-或-CHr。式（ΧΠ)中的苯環的一個氫可由碳數為1〜20的烷基或苯基取代。式（X)中，較佳是兩個基團「ΝΗ2-伸苯基-G4-0-」的其中一個鍵結於類固醇核的3位，另一個鍵結於類固酵，的6位。式（XI)巾兩個基is「νη2·伸苯基·σ4_α·」對置=二於類固醇核的鍵結位置而分別的鍵結位置較佳是=Gr及式(χπ)中’胺基對笨環式（ΧΙΙ)中的鍵結位置_位或對仇。 o 炫基中碳數為2〜2G狀基，且該 -CH=CH-^-CsC^^ 〇 ' 基。A1為认伸苯基幻為·0·或碳^為1〜6的伸燒 1〜3的伸烷基，並且a為dG巧鍵或碳數為較佳是相對於G5的鍵⑽/。减對4環的鍵結位置 m : 置而為間位或對位。 NH2 H2N ΟΧ-2) η。下表不二胺（IX)的具體例。 0^0 αχ-ΐ) ❹ NH2 (IX-3) !0^〇- η〇τΗ15 (IX-5) (IX-4) NH2 H2N ox^) 34 201012801(XII) 32 201012801 J 厶V/U 厶plil In the formula (IX), 'G3 is a single bond, -o-, -coo-, _oco-, -co-, -CONH- or -(CH2)k-, and k is an integer of 1 to 12. R1 is a group having a carbon number of 3 to 20, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (IX-S). In the alkyl group, any hydrogen may be substituted by fluorine ' and any -CH2 may be substituted by -〇-, -CH=CH- or -CeC-. The hydrazine of the phenyl group may be substituted by -F, -CH3, -OCH3, -〇CH2F, -OCHF2 or -OCF3. The bonding position of the amine group to the benzene ring is arbitrary, but it is preferred that the bonding position relationship of the two amine groups is meta or para. That is, when the bonding position of the group "rLG3-" ® is 1 position, it is preferred that the two amine groups are respectively bonded to the 3 and 5 positions, or the 2 and 5 positions, respectively, a ^^4 < 37-A2 ^(g8-A3-J-(g9-a4-^-Rs (IX-S) • 武 (IX_S), R5 is hydrogen, fluorine, an alkyl group having a carbon number of 1 to 20, and a carbon number of 1 to 20 Fluorine-substituted alkyl group, alkyl group having 1 to 20 carbon atoms, •CN, -〇CH2F, 〇CHF2 or -OCF3, G7, G8 and G9 are bonding groups' and these are independently single bonds , -0-, -€00-'-0 (:0-, -(:01<[11-, -CH=CH- or an alkyl group having a carbon number of 1 to 12, A2, A3 and A4 are rings) , Φ J• These are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxin-2,5-diyl, biting > 2,5-diyl, π than the mouth; _2,5-diyl, naphthalene-u-diyl, naphthalene-2,7-diyl or onion-9,10-diyl, in any ring, any hydrogen may be substituted by fluorine or -CH3; b, C and d are independently an integer of 0 to 2, and when the total of these is 1 to 5'b, c or a is 2, the two bonding groups may be the same or different, and the two rings may be the same In the formula (X) and formula (XI), R2 is independently hydrogen or fluorenyl. R3 is independent. Hydrogen, an alkyl group having a carbon number of 1 to 20, or an alkenyl group having a carbon number of 2 to 20" 33 201012801 G4 is independently a single bond, -CO- or -CHr. A hydrogen of the benzene ring in the formula (ΧΠ) may be The alkyl group or the phenyl group having a carbon number of 1 to 20 is substituted. In the formula (X), preferably one of the two groups "ΝΗ2-phenylene-G4-0-" is bonded to the 3 position of the steroid nucleus. The other is bonded to the 6-position of the type of solidification. The two bases of the formula (XI) are "νη2·extended phenyl·σ4_α·" and the opposite position is the bonding position of the steroid nucleus. Preferably, it is =Gr and in the formula (χπ), the position of the bond in the amino group to the stupid ring (ΧΙΙ) is _ bit or venge. o The carbon number in the dazzle is 2~2G, and the -CH= CH-^-CsC^^ 〇' base. A1 is an alkylene group having a stretching phenyl phantom of 0 or carbon of 1 to 6 and a a dG bond or a carbon number of It is preferably a bond (10) / with respect to G5. The bond position m of the minus 4 ring is set to a meta or para position. NH2 H2N ΟΧ - 2) η. The following is a specific example of the non-diamine (IX). 0^0 αχ-ΐ) ❹ NH2 (IX-3) !0^〇- η〇τΗ15 (IX-5) (IX-4) NH2 H2N ox^) 34 201012801

h2n (IX-21)H2n (IX-21)

h2n (1X-18)H2n (1X-18)

H2N (IX-22) 35 201012801 η05Η” (DC-23) Η2Ν ^b-nC12H25 Η2Ν (IX-25)H2N (IX-22) 35 201012801 η05Η” (DC-23) Η2Ν ^b-nC12H25 Η2Ν (IX-25)

(ΙΧ-28)(ΙΧ-28)

nC12H25 Η2ΝnC12H25 Η2Ν

(ΙΧ-27)(ΙΧ-27)

36 201012801 以下表示二胺（X)的具體例。36 201012801 Specific examples of the diamine (X) are shown below.

37 201012801 32062ρϋΊ37 201012801 32062ρϋΊ

38 201012801 ❹38 201012801 ❹

NH2 H2NNH2 H2N

(XH-7)(XH-7)

NH〇NH〇

nh2 參二胺（IX-1)〜二胺（IX-4)、二胺（IX-25)〜二胺 (IX-28)、以及二胺（XII-1)〜二胺（XII-6)，可藉由將該些二胺中的至少一種與本發明的二胺（1)合併使用，而將液晶分子的預傾角調整為3°〜15°，因此適合作為TN、 STN、0CB用配向膜原料。電壓保持率更高、可將殘留DC抑制為較低、且無論 39 201012801 配向膜形成步驟的條件如何均可穩定地對液晶分子賦予一疋的所需預傾角的TN、STN、OCB用配向膜的原料，較佳是將二胺（IX-2)、二胺（χιυ)、二胺（xjjy)以及二胺（XII-6)中的至少一種與二胺〇)合併使用。二胺（IX-7)、二胺（IX_8；)、二胺（ιχ·13)〜二胺 (ΙΧ-16)、二胺（ΐχ_29)〜二胺（ΙΧ_33)、二胺（X]) 〜二胺（X-4)、二胺（xw)〜二胺（χΜ)、以及二胺 (XII-7)〜二胺（χπ-Η)，可藉由將該些二胺中的至少一種/、一胺（1)合併使用而將液晶分子的預傾角調整為 90° ’因此適合作為VA用配向膜原料。如要電壓保持率更高、可將殘留DC抑制為較低、且無論配向膜形成步驟的條件如何均可穩定地對液晶分子賦予一定的所需預傾角之VA用配向膜原料，較佳是將一浪-7)、二胺 σχ_8)、二胺（IX_13)、以及中的至少一種與二胺（丨）合併使用。此外，可與本發明的二胺合併使用的二胺，可列舉包 ^石夕氧院_魏料、二胺。該魏H胺並無特別限疋’較佳疋使用由式（Si)所表示的二胺。 R7 R7 H2N-R6-^si-〇-)_^_R6_Nh2 (S1) R8 f r8 其中Nh2 ginodiamine (IX-1)~diamine (IX-4), diamine (IX-25)~diamine (IX-28), and diamine (XII-1)~diamine (XII-6) By using at least one of these diamines in combination with the diamine (1) of the present invention, the pretilt angle of the liquid crystal molecules is adjusted to 3 to 15°, and thus it is suitable as a alignment for TN, STN, and 0CB. Membrane raw material. The aligning film for TN, STN, and OCB which has a higher voltage holding ratio and can suppress residual DC to a lower TN, STN, and OCB which can stably impart a desired pretilt angle to liquid crystal molecules regardless of the conditions of the alignment film forming step of 39 201012801. As the raw material, it is preferred to use at least one of diamine (IX-2), diamine (χιυ), diamine (xjjy), and diamine (XII-6) in combination with diamine oxime. Diamine (IX-7), diamine (IX_8;), diamine (ιχ13)~diamine (ΙΧ-16), diamine (ΐχ_29)~diamine (ΙΧ_33), diamine (X))~ Diamine (X-4), diamine (xw) to diamine (oxime), and diamine (XII-7) to diamine (χπ-Η), by at least one of these diamines/ The monoamine (1) is used in combination to adjust the pretilt angle of the liquid crystal molecules to 90°. Therefore, it is suitable as an alignment film raw material for VA. If the voltage retention ratio is higher, the residual DC can be suppressed to a lower level, and the alignment film material for the VA can be stably imparted to the liquid crystal molecules with a desired pretilt angle regardless of the conditions of the alignment film formation step. At least one of a wave-7), a diamine σχ_8), a diamine (IX_13), and a diamine (丨) is used in combination. Further, a diamine which can be used in combination with the diamine of the present invention may be a package of a diamine or a diamine. The Wei H amine is not particularly limited. Preferably, a diamine represented by the formula (Si) is used. R7 R7 H2N-R6-^si-〇-)_^_R6_Nh2 (S1) R8 f r8

R獨立為破數為1〜6的伸烷基、伸苯基或烧基取代_苯基。R7以及R8獨立為碳數為卜3的烧或苯基。並且f為丨〜⑺的整數。該些矽用量若為不損及本發明效果的範圍，則無特別 40 201012801 32062pitl 對本發明的液晶配向劑進行說明。本發明的液晶配向劑是含有選自本發明的聚合物中的—種或—種以上的聚合物溶液。本發明的液晶配向劑的具體例為藉由使二胺（1) 與酸二酐進行反應而獲得的本發明的聚醯胺酸溶液、使自該聚醯胺酸溶液中除去溶劑而獲得的聚醯胺酸的聚合物溶解於溶劑中所獲得的聚醯胺酸溶液以及該些的混合物等。本發明的液晶配向劑可為製備本發明的聚合物時所使用的 0 反應溶液本身，亦可為使自反應溶液中餾去溶劑而獲得的聚合物溶解於與該反應所使用的溶劑不同的溶劑中而成的溶液。本發明的液晶配向劑中所使用的溶劑並無特別限 ' 定，例如可列舉：N-甲基-2-吡咯啶酮 (N-methyl-2-pyrrolidone，NMP )、二甲基甲醯胺（dimethyl formamide，DMF)、一甲基乙釀胺（dimethyl acetamide， DMAc)、二曱基亞瑕（dimethyl sulfoxide，DMSO )、乙二醇單丁醚（ethylene glycol monobutylether，BC)、乙二醇 ft 單乙鍵、γ-丁内酯（Y_butyr〇iact〇ne)等。於本發明中，可將選自上述溶劑中的兩種或兩種以上混合使用。而且，若本發明的聚合物可溶，則可使用上述以外的溶劑。本發明的液晶配向劑中，為了表現出作為配向膜的更好的特性，可進一步添加選自公知的所有聚合物中的一種或一種以上。此時，為了表現出本發明的效果，本發明聚合物在總聚合物中所佔的較佳比例為5〇重量百分比〜1〇〇重量百分比’更佳比例是70重量百分比〜1〇〇重量百分 201012801 32062pifl 比。此種聚合物的例子可列舉：聚醯胺、聚胺基曱酸酯、聚脲、聚酯、聚環氧化物、聚酯多元醇、矽改質聚胺基甲酸酯、矽改質聚酯等。本發明的液晶配向劑中所含的聚合物比例並無特別限定，可根據製作液晶顯示元件時的步驟來選擇最合適的值。通常’為了抑制對玻璃基板塗佈時的不均或針孔 (pinhole)等’上述聚合物比例相對於液晶配向劑總重量，較佳是0.1重量百分比〜3〇重量百分比，更佳是i重量百分比〜10重量百分比。若於本發明的液晶配向劑中添加有機矽化合物，則可調節配向膜對玻璃基板的附著性及硬度，可改善由於藉由摩擦等而削去聚醢亞胺所導致的顯示不良。於本發明的液晶配向劑中添加的有機矽化合物並無特別限定，例如較佳是添加：胺基丙基三曱氧基矽烷、胺基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、N-(2-胺基乙基)·3-胺基丙基甲基二甲氧基矽烷、Ν-(2-胺基乙基)·3-胺基丙基三曱氧基矽烷、乙烯基三乙氧基矽烷、曱基丙烯醢氧基丙基三曱氧基矽烧、3-縮水甘油氧基丙基三曱氧基矽烷、3_縮水甘油氧基丙基曱基二曱氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等矽烷偶合劑，二甲基聚矽氧烷、聚二甲基矽氧烷、聚二苯基矽氧烷等矽油；尤其好的是添加胺基丙基三乙氧基石夕燒、3-縮水甘油氧基丙基甲基二曱氧基矽烷、2-(3,4-環氧環己基）乙基三甲氧基梦烧。這種有機矽化合物於液晶配向劑中的添加比例，若是 42 201012801 szwj.pm 能在不損及對上述配向膜所要求的特性而改善範圍内，則無特別限制。然而，若添加大量的這些^石夕化合物，則製成配向膜時會產生液晶的配向不良了因此，相對於液晶配向劑中所含有的聚合物的總重量广矽化合物的濃度較佳是0.01重量百分比〜s〇比，更佳是0.1重量百分比〜20重量百分比。刀藉由混合使用不同種類的聚合物，亦可製 f賴角的液晶配向劑。這是湘如下情況：若將表面能量不同的多種聚合物混合，則該些聚合物形成薄膜時，^ 面能量小的聚合物易於向表面偏析。藉由推合此種聚合物’可於配賴的表面對液晶分子賦予預傾角，且形成二示出良好液晶配向性的成分（稱為聚合物A)的層，並且於塗佈基板侧形成表現出良好電特性的成分（聚合物B) 的層。即’可獲得該些兩種特性優異的配向膜於該方法，揭示於曰本專利特開平8-43831號公報中。本發明的液晶配向劑中亦可摻合聚合物。本發明的聚 • 合物形成電特性優異的配向膜，因此適合作為聚合物㈣成分。而且，如上文所述，本發明的聚合物藉由將由式（1) 所表示的本發明的二胺與其他二胺加以組合，而亦可用作聚合物A的成分。聚合物A與聚合物B的混合比分別可於1重量百分比〜99重量百分比之間任意選擇。然而，為了表現出良好的液晶配向特性以及保持著預傾角的良好電特性，聚合物A 的比例以聚合物總重量為基準，較佳是1重量百分比〜 43 201012801 重量百分比，更佳是5番县將與聚醢胺酸的比〜3〇t量百分比。明的液晶配向劑中，亦對 ' 應的父聯劑添加於本發因環境而劣麵言較為仏Μ防止雜隨相而劣化或利第3G49699號公報Γ日本4 ^交聯劑’可列舉日本專姻84中糊多官能環聯劑本身進行反應而：上=?:或聚_琪強度的材日本專利㈣平⑽咖號公報、日本專利 2硫004-34刪號公報等中記載的多官能乙_、順丁稀I 生物、或雙烯丙基耐地醯亞胺(bisaiiy 1 nadiimide) 何生物等。另外，本發明中使用的交聯劑可為這些以外的父聯劑。使用交聯劑時，為了呈現本發明的效果，交聯劑的比例以相對於本發明的聚合物的重量比計較佳是⑽5 〜0.5，更佳是0.1〜0.3。本發明的液晶配向劑的黏度是根據塗佈的方法、聚合物的種類或濃度、溶劑的種類等，較佳是5 mPa · s〜100 mPa · s ’更佳是10 mPa · s〜80mPa · S。為了獲得充分的膜厚’較理想的是大於5 mPa· s的黏度，為了不產生印刷不均’較理想的是小於1〇〇 mpa· s的黏度。其中，於利用喷墨法進行印刷的情況，黏度小於等於5 mPa· s的液晶配向劑亦可使用。其次’對本發明的液晶顯示元件進行說明。本發明的 201012801 液晶顯示元件包括：（1)對向配置的一對基板；（2)形成於上述一對基板之分別對向的面上的液晶配向膜；以及（3) 夹持於上述一對基板間的液晶層。於此一對基板的兩者上可配置有電極，但於IPS型液晶顯示元件的情況，是於一對基板的其中之一上配置電極（可為梳狀或鋸齒結構的電極）。上述液晶配向膜是藉由將本發明的液晶配向劑塗佈於上述基板上，進行加熱而形成的液晶配向膜。此處，液晶配向膜的膜厚較佳是nm〜300 nm，更佳是30 nm〜 100 nm。此外，液晶配向膜較佳是經摩擦處理。上述對向配置的一對附有電極之基板，較佳是透明基 ‘ 板（例如玻璃基板）。夾持於上述一對基板間的液晶層包含液晶組成物。此處，液晶組成物並無特別限制，根據驅動模式，可使用介電常數各向異性為正的液晶組成物以及介電常數各向異性為負的液晶組成物中的任-種組成物。介電常數各向異性 • 為正的較佳液晶組成物的例子揭示於日本專利第3086228 號公報、曰本專利第2635435號公報、曰本專利特表平 5-501735號公報、日本專利特開平8_157826號公報、曰本專利特開平8·23·號公報、日本專利_平㈣祕號公報（ΕΡ885272Α1 )、日本專利特開平w〇2346號公 (EP806466A1 )、日本專利特開平8199168號°公 (EP722998A1)、日本專利特開平9_235552號公專利特開平9_255956號公報、日本專利特開平&遍^ 45 201012801 ^^^^^广專利特開平Μ，號公報（E^844229A1)、日本專利特開平1〇·2〇44 2專利特開平__號公報、日本專= 2000-087040. g 2〇〇1.4882^^ VA型液晶顯示元件中使用的液晶組數各向異性為負的各種液晶組n 子揭示於曰本專利特開昭57_114532 === 參 =;?;ra本專利特開平曰本專利特開平8_40953 讯：1：= 本專利特開平公報'a本專利特開平I 〇本專利特開平二專利特開平10_237024號公報、曰 10-237075號公報、日號公報、曰本專利特開平本專利平1G.2374t8 ^=修雇6號公報、日利特開平1(»_287874 ss4Lm=2=、日本專號公報、日太直4,^ 曰本專利特開平10-287875 報、日本專利特本專利特開平號公 _ 56307號公報、日本專利特開 46 201012801 32〇t2pm 號公報、日本專利特開2GG1-G72626號公報、曰本專利特開2001-192657號公耜笙由對，上述介電常數各向異性為正或負的液晶組成物來說，也可以添加-種或―_上的絲活性化合物。R is independently an alkylene group having a number of 1 to 6 and a phenyl group or a decyl group. R7 and R8 are independently a calcined or phenyl group having a carbon number of 3 . And f is an integer of 丨~(7). The amount of the ruthenium used is not particularly limited to the extent of the effect of the present invention. The liquid crystal alignment agent of the present invention will be described. The liquid crystal alignment agent of the present invention is a polymer solution containing one or more kinds selected from the polymers of the present invention. Specific examples of the liquid crystal alignment agent of the present invention are obtained by reacting a diamine (1) with an acid dianhydride to obtain a polyaminic acid solution of the present invention, and removing a solvent from the polyamic acid solution. A polyphthalic acid solution obtained by dissolving a polymer of polylysine in a solvent, a mixture of these, and the like. The liquid crystal alignment agent of the present invention may be the 0 reaction solution itself used in the preparation of the polymer of the present invention, or the polymer obtained by distilling off the solvent from the reaction solution may be dissolved in a solvent different from the solvent used in the reaction. A solution made from a solvent. The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP) and dimethylformamide. (dimethyl formamide, DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol monobutylether (BC), ethylene glycol ft Single-ethyl bond, γ-butyrolactone (Y_butyr〇iact〇ne), and the like. In the present invention, two or more kinds selected from the above solvents may be used in combination. Further, if the polymer of the present invention is soluble, a solvent other than the above may be used. In the liquid crystal alignment agent of the present invention, in order to exhibit better characteristics as an alignment film, one or more selected from all of the well-known polymers may be further added. At this time, in order to exhibit the effects of the present invention, a preferred ratio of the polymer of the present invention to the total polymer is 5 〇 by weight to 1 〇〇 by weight, and a more preferred ratio is 70% by weight to 1 〇〇 by weight. Percentage of 201012801 32062pifl. Examples of such a polymer include polyamine, polyamino phthalate, polyurea, polyester, polyepoxide, polyester polyol, hydrazine modified polyurethane, hydrazine polycondensation Ester and the like. The proportion of the polymer contained in the liquid crystal alignment agent of the present invention is not particularly limited, and the most suitable value can be selected in accordance with the procedure in the production of the liquid crystal display element. Usually, 'in order to suppress unevenness or pinholes or the like at the time of coating a glass substrate, the above polymer ratio is preferably 0.1% by weight to 3% by weight, more preferably i by weight, based on the total weight of the liquid crystal alignment agent. Percentage ~ 10 weight percent. When an organic ruthenium compound is added to the liquid crystal alignment agent of the present invention, the adhesion and hardness of the alignment film to the glass substrate can be adjusted, and display defects due to the removal of the polyimide by rubbing or the like can be improved. The organic ruthenium compound to be added to the liquid crystal alignment agent of the present invention is not particularly limited, and for example, it is preferably added: aminopropyltrimethoxy decane, aminopropyltriethoxysilane, vinyltrimethoxydecane , N-(2-Aminoethyl)·3-aminopropylmethyldimethoxydecane, Ν-(2-aminoethyl)·3-aminopropyltrimethoxy decane, ethylene Triethoxy decane, decyl propylene methoxy propyl trimethoxy oxime, 3-glycidoxy propyl trimethoxy decane, 3-glycidoxypropyl decyl decyloxy a decane coupling agent such as decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, an oxime oil such as dimethyl polyoxane, polydimethyl siloxane or polydiphenyl fluorene oxide. Particularly preferred is the addition of aminopropyltriethoxylate, 3-glycidoxypropylmethyldimethoxyoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Dream burns. The proportion of such an organic cerium compound to be added to the liquid crystal alignment agent is not particularly limited as long as it can be improved without impairing the properties required for the above alignment film, 42 201012801 szwj. However, when a large amount of these compounds are added, the alignment of the liquid crystal occurs when the alignment film is formed. Therefore, the concentration of the compound is preferably 0.01 with respect to the total weight of the polymer contained in the liquid crystal alignment agent. The weight percentage is s to 〇, more preferably 0.1% by weight to 20% by weight. The knife can also be used as a liquid crystal alignment agent by mixing different types of polymers. This is the case where, when a plurality of polymers having different surface energies are mixed, when the polymers form a film, the polymer having a small surface energy tends to segregate toward the surface. By advancing such a polymer', a pretilt angle can be imparted to the liquid crystal molecules on the surface to be matched, and a layer of a component showing a good liquid crystal alignment (referred to as polymer A) can be formed, and formed on the coated substrate side. A layer of a component (Polymer B) that exhibits good electrical properties. That is, an aligning film which is excellent in the two kinds of characteristics can be obtained by the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-43831. The polymer may also be blended in the liquid crystal alignment agent of the present invention. Since the polymer of the present invention forms an alignment film having excellent electrical properties, it is suitable as a component of the polymer (IV). Further, as described above, the polymer of the present invention can also be used as a component of the polymer A by combining the diamine of the present invention represented by the formula (1) with other diamines. The mixing ratio of the polymer A to the polymer B can be arbitrarily selected from 1% by weight to 99% by weight, respectively. However, in order to exhibit good liquid crystal alignment characteristics and good electrical characteristics maintaining the pretilt angle, the ratio of the polymer A is based on the total weight of the polymer, preferably 1% by weight to 43 201012801% by weight, more preferably 5 parts by weight. The county will be compared with the poly-proline to a percentage of ~3〇t. In the liquid crystal alignment agent of the bright liquid, the addition of the parental agent to the present invention is inferior to the environment, and it is more difficult to prevent the deterioration of the phase with the phase or the third party. In Japan, the paste-type polyfunctional ring-linking agent itself is reacted by: the above-mentioned:?: or the material of the poly-p-intensity of the Japanese patent (4) Ping (10), the Japanese version of the Japanese Patent No. 2, 004-34, and the like. Polyfunctional B-, cis-butyl I, or bisaiiy 1 nadiimide. Further, the crosslinking agent used in the present invention may be a parent crosslinking agent other than these. In the case of using the crosslinking agent, in order to exhibit the effects of the present invention, the ratio of the crosslinking agent is preferably from (10) 5 to 0.5, more preferably from 0.1 to 0.3 by weight based on the weight of the polymer of the present invention. The viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa · s to 100 mPa · s ', more preferably 10 mPa · s to 80 mPa, depending on the method of coating, the kind or concentration of the polymer, the kind of the solvent, and the like. S. In order to obtain a sufficient film thickness 'preferably, a viscosity of more than 5 mPa·s is preferable, and in order not to cause printing unevenness, it is preferable that the viscosity is less than 1 〇〇 mpa·s. Among them, in the case of printing by the ink jet method, a liquid crystal alignment agent having a viscosity of 5 mPa·s or less can also be used. Next, the liquid crystal display element of the present invention will be described. The 201012801 liquid crystal display device of the present invention comprises: (1) a pair of substrates disposed oppositely; (2) a liquid crystal alignment film formed on opposite faces of the pair of substrates; and (3) sandwiching the one A liquid crystal layer between the substrates. An electrode may be disposed on both of the pair of substrates, but in the case of the IPS type liquid crystal display device, an electrode (which may be a comb-shaped or sawtooth electrode) is disposed on one of the pair of substrates. The liquid crystal alignment film is a liquid crystal alignment film formed by applying the liquid crystal alignment agent of the present invention onto the substrate and heating it. Here, the film thickness of the liquid crystal alignment film is preferably from nm to 300 nm, more preferably from 30 nm to 100 nm. Further, the liquid crystal alignment film is preferably subjected to rubbing treatment. The pair of electrode-attached substrates disposed in the opposite direction are preferably transparent base plates (e.g., glass substrates). The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and any liquid crystal composition having a positive dielectric anisotropy and a liquid crystal composition having a negative dielectric anisotropy can be used depending on the driving mode. Examples of a preferred liquid crystal composition having a positive dielectric anisotropy and being positive are disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. 8-157826, Japanese Patent Laid-Open No. 8/23., Japanese Patent_Ping (4) Secret No. (ΕΡ885272Α1), Japanese Patent Special Kaiping No. 2346 (EP806466A1), Japanese Patent Special Open No. 8199168 Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open &pp; 45 201012801 ^^^^^Guangzhou Patent Special Kaiping, No. (E^844229A1), Japanese Patent Special Kaiping 1〇·2〇44 2 Patent special open __ bulletin, Japanese special = 2000-087040. g 2〇〇1.4882^^ Various liquid crystal groups n with negative liquid crystal number anisotropy used in VA liquid crystal display elements The disclosure of this patent is disclosed in Japanese Patent Laid-Open No. 57_114532 === 参=;?;ra This patent is open to the public. This patent is open to the public. 8_40953 News: 1:= This patent is open to the public. Kaiping II patent Kaiping No. 10_237024, 曰10-237075, Japanese Bulletin, 曰本专利专开平本专利平1G.2374t8 ^=Repair No. 6 Bulletin, Rilit Kaiping 1 (»_287874 ss4Lm=2=, Japan Special Number Bulletin, Japanese version 4, ^ 曰专利专利 10 10 10 10 10 10 10 10 10 10 10 10 10 - - - 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 In the liquid crystal composition in which the above dielectric anisotropy is positive or negative, it is also possible to add a silk active compound of the above-mentioned type or "-" to the liquid crystal composition of the above-mentioned dielectric constant anisotropy No. 2001-192657. .

本發明的液晶顯示元件可具有其他構件。例如，使用薄膜電晶體的彩色顯示TFT型液晶元件中，於第一透明基板上形成薄膜f晶體、絕緣膜、保護膜、信號電極、晝素電極等，且於第二透明基板上具有阻斷畫素區域以外之光的黑色矩陣（black matrix )、彩色濾光片“〇1〇麻〇、平坦化膜以及畫素電極等。 VA型液晶顯不讀尤其是MVA型液晶顯示元件中，於第透明基板上形成稱為域（d〇main) #微小突起物。而且’亦可為了於基板間形成單元間隙而形成間隔片 (spacer)。本發明的液晶顯示元件是利用任意方法製作，例如利用包^如下步_方法來製作：⑴於上述兩片透明基板上進行的液晶配_塗佈步驟；⑵對所塗佈的液晶配向劑進行的乾燥步驟；（3)用以使經乾燥的液㈣向劑進行脫水·開環反應的加熱處理步驟；（4)對所得配向膜進行的配向處理步驟；（5)在將兩片基板貼合後於基板間封入液晶的液晶封入步驟，或者使液晶滴在其中一片基板上後使另一片基板貼合的步驟。上述塗佈液晶配向劑的步驟中的塗佈方法，通常已知有旋轉器（spinner)法、印刷法、浸潰（ipping)法、滴 47The liquid crystal display element of the present invention may have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film f crystal, an insulating film, a protective film, a signal electrode, a halogen electrode, or the like is formed on the first transparent substrate, and is blocked on the second transparent substrate. a black matrix (light matrix) of light outside the pixel area, a color filter "〇1〇 paralysis, a flattening film, and a pixel electrode. VA type liquid crystal display is not read, especially in an MVA type liquid crystal display element, On the first transparent substrate, a microprotrusion is formed. Further, a spacer may be formed in order to form a cell gap between the substrates. The liquid crystal display element of the present invention is produced by any method, for example, The following steps are used to prepare: (1) a liquid crystal alignment step on the two transparent substrates; (2) a drying step on the applied liquid crystal alignment agent; and (3) a drying step. Liquid (4) a heat treatment step of dehydrating and ring-opening reaction to the agent; (4) an alignment treatment step of the obtained alignment film; (5) a liquid crystal in which liquid crystal is sealed between the substrates after bonding the two substrates a step of encapsulating, or a step of bonding the liquid crystal onto one of the substrates to bond the other substrate. The coating method in the step of applying the liquid crystal alignment agent is generally known as a spinner method, a printing method, Pour method, drop 47

201012801 加法、喷墨（inkjet)法等。該些方法亦可應用於本發明中。理步Sit步驟以及脫水·開環反應中所必需的加熱處 Ξ ’通常已知有於烘箱#或紅外爐中的加熱處理、於加熱板上的加熱處理等。該些方法亦可乾^較佳是於溶劑可蒸發的範圍内的較低溫度。「下實施。加熱處理步騎常触是於150 C〜300C左右的溫度下進行。201012801 Addition, inkjet (inkjet) method, etc. These methods are also applicable to the present invention. The steps of the step Sit and the heating required in the dehydration/ring-opening reaction are generally known as heating treatment in an oven # or an infrared furnace, heat treatment on a hot plate, and the like. These methods may also be preferably at a lower temperature within the range in which the solvent can evaporate. "Under the implementation. The heat treatment step is usually carried out at a temperature of about 150 C to 300 C.

對於OCB魏晶顯示元件、TN魏晶顯示元件、則型液晶顯示元件、IPS型液晶顯示元件，所述配向處理通常是進行摩擦處理。對於VA型液晶顯示元件，則不進行摩擦處理的情況較多，但亦可進行摩擦處理。接著，於其中一片基板上塗佈黏著劑並貼合，再於減壓下注人液晶。於滴加注人法的情況下，則是於貼合前將液晶滴加至基板上，然後貼合另一片基板。將用於貼合的黏著劑以熱或紫外線來硬化，從而製作本發明的液晶顯示元件。For the OCB Wei-Cry display element, the TN Wei-Cry display element, the T-type liquid crystal display element, and the IPS-type liquid crystal display element, the alignment treatment is usually performed by rubbing treatment. In the case of the VA liquid crystal display element, the rubbing treatment is not performed, but the rubbing treatment may be performed. Next, an adhesive is applied to one of the substrates and bonded, and the liquid crystal is injected under reduced pressure. In the case of the drop-filling method, the liquid crystal is dropped onto the substrate before bonding, and then the other substrate is bonded. The adhesive for bonding is cured by heat or ultraviolet rays to fabricate the liquid crystal display element of the present invention.

本發明的液晶顯示元件中可安裝偏光板（偏光膜）、波長板、光散射膜、驅動電路等。本發明的液晶顯示元件具有電壓保持率高、且殘留 DC低的特徵。其原因在於，本發明的液晶顯示元件的液晶配向膜是由包括使用由二胺（I)所表示的化合物而合成的聚醜胺酸或者該聚醯胺酸的衍生物的液晶配向劑所形成。對此於下述實施例中進行說明。【實施例】 48 201012801 ^zuozpin 由以下實施例，對本發明的二胺、藉由使用該二胺而獲得的液晶配向劑以及液晶顯示元件進行詳細說伸本發明並不限定於這些實施例。實施例中，1H_NMR剩^是於氘化二甲基亞颯(deuterateddimethyl sulfoxide)中進行。八子量的測定是使用GPC，以聚苯乙烯為標準溶液，=析二是使用DMF。另外，於以下實施例中，容積的單位升是以 L表示。因此，mL意指毫升。A polarizing plate (polarizing film), a wavelength plate, a light-scattering film, a driving circuit, and the like can be mounted in the liquid crystal display element of the present invention. The liquid crystal display device of the present invention has a feature that the voltage holding ratio is high and the residual DC is low. The reason for this is that the liquid crystal alignment film of the liquid crystal display element of the present invention is formed of a liquid crystal alignment agent comprising a poly leuco acid synthesized using a compound represented by a diamine (I) or a derivative of the polyaminic acid. . This is illustrated in the following examples. [Examples] 48 201012801 ^zuozpin By the following examples, the diamine of the present invention, the liquid crystal alignment agent obtained by using the diamine, and the liquid crystal display element will be described in detail. The invention is not limited to these examples. In the examples, 1H_NMR residual was carried out in deuterated dimethyl sulfoxide. The eight-quantity is determined by using GPC, using polystyrene as the standard solution, and the second analysis using DMF. Further, in the following examples, the unit liter of the volume is represented by L. Therefore, mL means milliliters.

首先，對實施例中使用的液晶顯示元件的評價方法行說明。 (1) 殘留DC ,對30 Hz、3 V的矩形波重疊1 V的直流電壓3〇分鐘後，測疋10分鐘後的閃爍（f!icker)消除電壓，將該值的絕對值作為殘留DC。殘留DC越小，則留痕越少，可謂良好0 (2) 電壓保持率 >依據「水嶋他，第14次液晶討論會預稿集p78」中 ”己載的方法。測定是將閘極寬度（职把…她）為69 μ3、頻率（frequency )為〇 3 Hz、脈高（pulse height)為土5·〇 V 的矩形波施加至單元而進行。測定溫度為6〇β(：。 (3) 預傾角預傾角的測定是利用晶體旋轉法（crystal rotation 〇d)進行。測定所使用的光的波長為589 nm。 [實施例1] 〈二胺（1-1)的合成> 49 201012801 向安裝有攪拌機、溫度計以及氮氣導入口的丨L三口燒瓶中加入11.4g(〇.46mol)的60%氫化鈉，添加100mL 的DMF。使溶液冷卻至，然後於其中滴加使3〇 g(〇 23 mol)的市售的5-胺基吲哚溶解於2〇〇 mL的DMF中而成的溶液。然後使溶液升溫至室溫，於氮氣環境下攪拌i小時。再次使溶液冷卻至rc ,再於其中滴加使39 g (0 28 mol)的4·氟硝基苯溶解於2〇〇 mL的DMF中而成的溶液。接著使溶液升溫至室溫，於氮氣環境下攪拌12小時。之後，將反應溶液放至500 mL乙酸乙酯以及500 mL純水的 β 混合溶劑中進行萃取，將有機層以5〇〇 mL純水清洗3次。使有機層以無水硫酸鈉乾燥後，將無水硫酸鈉除去，將溶劑減壓餾去，獲得粗結晶^然後利用管柱層析法（曱苯：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，獲得n-(4-硝基苯基)-5-胺基，哚（產量為35.0 g，產率為60%)。於尚壓蒸氣滅菌處理（autoclave)用反應管中加入35.0 g (0.14 mol)所獲得的N-(4-硝基苯基)-5-胺基吲哚、3.5 g 的纪碳粉末，添加350 mL的乙醇以及35 mL的乙酸乙酯。 ❹ 使系統内成為氫氣環境下，於氫壓0.49 MPa、室溫下攪拌 12小時。接著將鈀碳粉末除去，將所獲得的溶液濃縮，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=3 : 1 (Wv))將粗結晶分離純化，獲得二胺(N_(4_胺基苯基)_5_胺基》弓丨哚）（產量為28.8 g，產率為92%)。 ]H-NMR (ppm): 3.53 (-NH2, br. s, 2H), 3.74 (-NH2, br. s, 2H), 6.43-7.25 (arm. H, m, 9H). 50 201012801 [實施例2] <二胺（1-2)的合成> 除將5-胺基吲哚替代為6-胺基吲哚以外，依據實施例 1中記載的方法，獲得二胺（1-2) (N-(4-胺基苯基)-6-胺基吲哚）。 ^-NMR (ppm): 3.52 (-NH2, br. s, 2H), 3.75 (-NH2, br. s, 2H), 5.85-8.18 (arm. H, m, 9H). [實施例3] ❹ 〈二胺（1-5)的合成〉依據 Tetrahedron Letters 41，1815-1818 (2000)中記載的方法，向安裝有攪拌機、温度計、冷卻器以及氮氣導入口的1 L三口燒瓶中加入50 g (0.25 mol)的4,4，-二胺基二苯基甲烷、18.6 g (0.10 mol)的三乙醇胺鹽酸鹽、u.3 g (0.05 mol)的氯化錫（π)二水合物、i.o g (0 005 moi) 的氯化釕（III) n水合物以及3.9g (〇.〇l5m〇l)的三苯基膦，添加500 mL的二噁烷以及50 mL的純水。使系統内 • 成為氮氣環境下。於180t下攪拌20小時。放置冷卻後，將反應溶液放入至5〇〇 mL的5%鹽酸中，以500 mL的氯仿進行萃取。將有機層以500 mL的純水中清洗3次，然後使有機層以無水硫酸鎮乾燥後，將無水硫酸錤除去，再將溶，減壓餘去，獲得粗結晶。然後利用管柱層析法（乙酸^醋.己燒=1 : 1 (v/v))進行分離純化，獲得雙(5-, 哚基)曱烷（產量為7 3g，產率為59%)。向女裝·有授拌機、溫度計以及I氣導入口的1 L三口 51 201012801 燒瓶中加入1.3g(0.056 m〇1)的6〇%氫化納，添加1〇mL 的dmf。使溶液冷卻至rc，向其中滴加使7 g(〇〇28 的雙(5-吲η木基）曱烷溶解於2〇mL的dmf中而成的溶液。然後使溶液升溫至室溫，於氮氣環境下攪拌丨小時。再次使溶液冷部至5。(：，向其中滴加使4.7g(〇〇34)的4_氟硝 m^20mL的DMF中而成的溶液。接著使溶液升溫至室溫，於氮氣環境下攪拌12小時。之後，將反應溶液放至100 mL乙酸乙酯以及1〇〇mL純水的混合溶劑中進行萃取’將有機層以100 mL的純水清洗3次。使有機層以無 _ 水硫酸鈉乾燥後，將無水硫酸鈉除去，將溶劑減壓餾去，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，獲得雙(5_^_(4_硝基苯基)吲嘴基)甲院（產量為9.3 g，產率為68〇/〇)。向高壓蒸氣滅菌處理用反應管中加入9.〇 g (〇.〇18 mol)所獲得的雙(5-N-(4-磺基苯基户引哚基)曱烷、0.9 g的鈀碳粉末’添加100 mL的乙醇以及10 mL的乙酸乙酯。使系統内成為氫氣環境下，於氫壓〇·49 MPa、室溫下攪拌 12小時。接著將鈀碳粉末除去，將所獲得的溶液濃縮，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙酯=3 : i (v/v))將粗結晶分離純化，獲得二胺（ι_5)(雙(5_ν·(4_ 胺基苯基)吲哚基)甲烷）（產量為7丨g，產率為91%)。 !H-NMR (ppm): 3.86 (-CH2-, s, 2H), 4.1 (.NH2, br. s, 4H), 6.52-8.72 (arm. H, m, 18H). [實施例4] 52 201012801 <二胺（1-9)的合成> 除將4,4’-二胺基二苯基曱烷替代為1，3-雙(4-胺基苯基) 丙烷以外，依據實施例3中記載的方法，獲得二胺（1-9) (1,3-雙(5·Ν_(4-胺基苯基户弓卜朵基)丙烷）。 ^-NMR (ppm): 1.95 (-CH2-, q, 2H), 2.62 (-CH2-, t, 4H), 3.72 (-NH2, br. s, 4H), 6.51-8.78 (arm. H, m, 18H). [實施例5] <二胺（1-28)的合成> ® 除將4,4’-二胺基二苯基曱烷替代為4,谷二胺基二苯基醚以外，依據實施例3中記載的方法，獲得二胺（1-28) (雙(5-N-(4-胺基苯基户引哚基)醚）。 . ]H-NMR (ppm): 3.79 (-NH2, br. s, 4H), 6.52-8.04 (arm. H, m, 18H). [實施例6] <二胺（1-31)的合成> 除將4,4’_二胺基二苯基甲烷替代為Ν,Μ-二曱基-Ν，；ΝΓ-φ 雙(4-胺基苯基）乙二胺以外，依據實施例3中記載的方法，獲得二胺（1-31) (N，N’_二曱基-N，N’-雙(5-Ν-(4·胺基苯基）吲哚基）乙二胺）。 ^-NMR (ppm): 2.75 (>NCH3, s, 4H), 3.58 (-CH2-, s, 4H), 3.69 (-NH2, br. s, 4H), 6.52-7.76 (arm. H, m, 18H). [實施例7] <二胺（1-35)的合成> 向安裝有攪拌機、溫度計、冷卻器以及氮氣導入口的 53 201012801 J 厶 VU 厶 pill 1 L三口燒瓶中加入20 g( 0.10 mol)市售的5-淳π弓丨蜂、ϋΐ g (0.11 mol)市售的 4-胺基苯基硼酸、0.35 g (0.0005 m〇l) 的雙(三苯基膦)二氣化把（Π)、20.7 g (0.15 mol)的碳酸鉀以及8.1 g (0.025 mol)的溴化四丁基銨，添加150 mL 的乙醇、75 mL的曱苯以及100 mL的純水。於氮氣環境下加熱回流3小時。放置冷卻後，將反應溶液放入至水中，以200 mL的曱苯進行萃取，將有機層以200 mL的純水清洗3次。接者使有機層以無水硫酸納乾燥後，將無水硫酸鈉除去，將溶劑減壓餾去，獲得粗結晶。然後利用管柱層 ❹ 析法（甲苯：乙酸乙酯=5 : 1 (v/v))將粗結晶分離純化，獲得5-(4-胺基苯基户引哚（產量為17.9 g，產率為86%)。向安裝有攪拌機、溫度計以及氮氣導入口的1L三口燒瓶中加入3.8 g (0.16 mol)的60%氫化鈉’添加4〇的DMF。使溶液冷卻至5。(：，向其中滴加使167 g(〇〇8 mol)的5-(4-胺基苯基)吲哚溶解於2〇〇 mL的DMF中而成的溶液。然後使溶液升溫至室溫，於氮氣環境下攪拌1小時。再次使溶液冷卻至5°C，向其中滴加使14.1 g(〇.i〇 m〇i) 的4-氟硝基苯溶解於15〇11^的DMF中而成的溶液。接著 © 使溶液升溫至室溫，於氮氣環境下攪拌12小時。之後，將反應溶液放至5〇〇 mL乙酸乙酯以及500 mL純水的混合溶劑中進行萃取，將有機層以500 mL的純水清洗3次。使有機層以無水硫酸納乾燥後，將無水硫酸鈉除去，將溶劑減壓餾去，獲得粗結晶。然後利用管柱層析法（甲苯：乙酸乙S曰一5 · 1 (v/v))將粗結晶分離純化，獲得N_(4_硝基 54 201012801 苯基胺基苯基)吲哚（產量為16.6g，產率為63%)。向高壓蒸氣減菌處理用反應管中加入16〇 g (Q()49 的Ν·㈣基苯基)邻.胺基苯基)啊、^的麵碳添加200 mL乙醇以及20 mL乙酸乙醋。使環境下，於氫麼〇.4議、室溫下授拌12小時。將所獲得的溶液濃縮’獲得粗結晶。 …'後則吕柱層析法（甲苯：乙酸 ❹ 絲，基)°㈣）（產量為13.3g，產㈣91%)。 2HX br' S，2H)，174 ^ br· S' [實施例8] <聚醯胺酸的製傷> 三口 ==g:拌=氣導入口一脫水NMP中。一面將溶使其溶解於60 g的的化合物（A14)以及1.27 、、’、、 C，一面添加1·14 g 升溫至室溫，於氮氣環境下物（A1)。然後使溶液 γ-丁内酯以及25 g的BC，進二12小時後，添加10 g的獲得的溶液的黏度下降，而腺二步攪拌3小時。為了使所溶液的黏度達到35 ml>a· s =液於6叱下加熱騎直至百分比的溶液。將該溶液記$聚醯贿漢度為5重量胺酸的重量平均分子量為64:、A。該清漆的聚醯 [實施例9〜25、比較例以以及參考例U 201012801 將二胺以及四羧酸二酐以如表1所示的方式使用，以和實施例8相同的方式製造聚醯胺酸，製備清漆B〜U。 <表1> 實施例No· 清漆名稱二胺四缓酸二Sf Mw No. mole% No. mole% 8 清漆A (Μ) 50 (Al) (A14) 25 25 64,000 9 清漆B (1-1) (VI-D 25 25 (Al) (A14) 25 25 72,000 10 清漆C (1-1) (VI-1) 25 25 (A20) 50 48,000 11 清漆D (1-1) (VI-7) 40 10 (Al) (A14) 25 25 38,000 12 清漆E (1-1) (IX-13) 40 10 (Al) (A14) 25 25 45,000 13 清漆F (1-1) (XII-1) 40 10 (Al) (A14) 25 25 50,000 14 清漆G (1-5) 50 (Al) (A14) 25 25 58,000 15 清漆Η (1-5) (VI-1) 25 25 (Al) (A14) 25 25 66,000 16 清漆I (1-5) (VI-1) 25 25 (A20) 50 39,000 17 清漆J (1-5) (VI-7) 40 10 (Al) (A14) 25 25 41,000 18 清漆Κ (1-5) (IX-13) 40 10 (Al) (A14) 25 25 42,000 19 清漆L (1-5) (XII-1) 40 10 (Al) (A14) 25 25 37,000 20 清漆Μ 0-35) 50 (Al) (A14) 25 25 54,000 21 清漆Ν (1-35) (VT-1) 25 25 (Al) (A14) 25 25 69,000 22 清漆〇 (1-35) 25 25 (A20) 50 40,000 56 201012801First, the evaluation method of the liquid crystal display element used in the examples will be described. (1) Residual DC, after a DC voltage of 1 V is superimposed on a rectangular wave of 30 Hz and 3 V for 3 〇 minutes, the flicker (f!icker) after 10 minutes is measured to eliminate the voltage, and the absolute value of this value is taken as the residual DC. . The smaller the residual DC, the less the trace is, and it is good. (2) Voltage holding rate> According to the "Water Margin, the 14th LCD Symposium Preset p78", the method is carried out. The measurement is the gate. A rectangular wave having a width of 69 μ3, a frequency of 〇3 Hz, and a pulse height of 5 〇V is applied to the cell, and the measurement temperature is 6 〇β (:. (3) The pretilt angle pretilt angle was measured by a crystal rotation method (crystal rotation 〇d). The wavelength of light used for the measurement was 589 nm. [Example 1] <Synthesis of diamine (1-1) > 49 201012801 To a 丨L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 11.4 g (〇.46 mol) of 60% sodium hydride was added, and 100 mL of DMF was added. The solution was cooled until it was added dropwise. g (〇23 mol) of a commercially available 5-amino hydrazine dissolved in 2 〇〇 mL of DMF. The solution was then allowed to warm to room temperature and stirred for 1 hour under nitrogen. The solution was again cooled. To rc, and then add 39 g (0 28 mol) of 4·fluoronitrobenzene to 2 〇〇mL. The solution was formed in DMF. The solution was then warmed to room temperature and stirred under nitrogen for 12 hours. Thereafter, the reaction solution was placed in a mixture of 500 mL of ethyl acetate and 500 mL of pure water in a mixed solvent to extract organic The layer was washed 3 times with 5 mL of pure water. The organic layer was dried over anhydrous sodium sulfate, and then dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give crude crystals. Ethyl acetate = 5 : 1 (v/v)) The crude crystals were separated and purified to give n-(4-nitrophenyl)-5-amine, oxime (yield: 35.0 g, yield 60%). 35.0 g (0.14 mol) of the obtained N-(4-nitrophenyl)-5-amino hydrazine and 3.5 g of carbon powder were added to the reaction tube for autoclave treatment. 350 mL of ethanol and 35 mL of ethyl acetate. ❹ The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. The palladium carbon powder was removed and the obtained solution was concentrated to obtain The crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3:1 (Wv)) to obtain a diamine (N_ (4_Aminophenyl)_5-amino group (a yield of 28.8 g, yield 92%).]H-NMR (ppm): 3.53 (-NH2, br. s, 2H), 3.74 (-NH2, br. s, 2H), 6.43-7.25 (arm. H, m, 9H). 50 201012801 [Example 2] <Synthesis of diamine (1-2) > In addition to 5-amine A diamine (1-2) (N-(4-aminophenyl)-6-aminoindole) was obtained according to the method described in Example 1 except that the base was replaced by 6-aminopurine. ^-NMR (ppm): 3.52 (-NH2, br. s, 2H), 3.75 (-NH2, br. s, 2H), 5.85-8.18 (arm. H, m, 9H). [Example 3] ❹ <Synthesis of Diamine (1-5)> According to the method described in Tetrahedron Letters 41, 1815-1818 (2000), 50 g was added to a 1 L three-necked flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen inlet. (0.25 mol) of 4,4,-diaminodiphenylmethane, 18.6 g (0.10 mol) of triethanolamine hydrochloride, u.3 g (0.05 mol) of tin (π) chloride dihydrate, Io g (0 005 moi) of ruthenium (III) chloride hydrate and 3.9 g of triphenylphosphine of 〇l〇m5m〇l, 500 mL of dioxane and 50 mL of pure water were added. Make the system inside the system to a nitrogen atmosphere. Stir at 180 t for 20 hours. After standing to cool, the reaction solution was placed in 5 mL of 5% hydrochloric acid and extracted with 500 mL of chloroform. The organic layer was washed three times with 500 mL of pure water, and then the organic layer was dried with anhydrous sulfuric acid, and then anhydrous barium sulfate was removed, dissolved, and the residue was evaporated to give crude crystals. Then, it was separated and purified by column chromatography (acetic acid / hexane = 1:1 = 1 (v / v)) to obtain bis(5-, decyl) decane (yield of 7 3 g, yield 59%) ). To the women's wear, a mixer, a thermometer, and a 1 L three port of the I gas inlet 51, a 1.3 g (0.056 m〇1) of 6〇% sodium hydride was added to the flask, and 1 mL of dmf was added. The solution was cooled to rc, and a solution obtained by dissolving 7 g of bis(5-indolyl) decane in 2 mL of dmf was added dropwise thereto, and then the solution was allowed to warm to room temperature. The mixture was stirred for a few hours under a nitrogen atmosphere, and the solution was again cooled to 5. (:, a solution of 4.7 g (〇〇34) of 4_fluoronitrate m^20 mL of DMF was added dropwise thereto. The mixture was heated to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was subjected to extraction in a mixed solvent of 100 mL of ethyl acetate and 1 mL of pure water. The organic layer was washed with 100 mL of pure water. After drying the organic layer with sodium sulfate-free sodium sulfate, anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to give crude crystals, which was then applied to column chromatography (toluene: ethyl acetate = 5:1 (v) /v)) The crude crystals were separated and purified to obtain bis(5_^_(4-nitrophenyl) hydrazino) (yield 9.3 g, yield 68 〇/〇). Adding 100% (5-N-(4-sulfophenyl fluorenyl) decane, 0.9 g of palladium carbon powder obtained by adding 9. 〇g (〇.〇18 mol) to the reaction tube mL of ethanol 10 mL of ethyl acetate was added to the system under a hydrogen atmosphere at a hydrogen pressure of 49 MPa and at room temperature for 12 hours. Then, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3: i (v/v)) to obtain a diamine (m.sup.5) (bis(5_ν·(4_aminophenyl)) fluorenyl group. Methane) (yield 7 丨g, yield 91%). H-NMR (ppm): 3.86 (-CH2-, s, 2H), 4.1 (.NH2, br. s, 4H), 6.52- 8.72 (arm. H, m, 18H). [Example 4] 52 201012801 <Synthesis of diamine (1-9)> In addition to replacing 4,4'-diaminodiphenyl decane with 1, In addition to 3-bis(4-aminophenyl)propane, a diamine (1-9) was obtained according to the method described in Example 3 (1,3-bis(5·Ν_(4-aminophenyl) bow Propyl)propane).--NMR (ppm): 1.95 (-CH2-, q, 2H), 2.62 (-CH2-, t, 4H), 3.72 (-NH2, br. s, 4H), 6.51- 8.78 (arm. H, m, 18H). [Example 5] <Synthesis of diamine (1-28)> ® In addition to 4,4'-diaminodiphenyl decane instead of 4, valley Except for diaminodiphenyl ether, according to the implementation The method described in 3, to obtain the diamine (1-28) (bis (5-N- (4- aminophenyl user indole-yl) ether). H-NMR (ppm): 3.79 (-NH2, br. s, 4H), 6.52-8.04 (arm. H, m, 18H). [Example 6] <Synthesis of diamine (1-31) > In addition to 4,4'-diaminodiphenylmethane instead of hydrazine, fluorenyl-dimercapto-fluorene, ΝΓ-φ bis(4-aminophenyl)ethylenediamine, according to Example 3 In the method described, a diamine (1-31) is obtained (N,N'-dimercapto-N,N'-bis(5-fluorenyl-(4-aminophenyl)indenyl)ethylenediamine) . ^-NMR (ppm): 2.75 (>NCH3, s, 4H), 3.58 (-CH2-, s, 4H), 3.69 (-NH2, br. s, 4H), 6.52-7.76 (arm. H, m 18H). [Example 7] <Synthesis of diamine (1-35)> Adding 20 201012801 J 厶VU 厶pill 1 L three-necked flask to which a stirrer, a thermometer, a cooler, and a nitrogen gas inlet were attached was added. g(0.10 mol) commercially available 5-淳π丨丨, ϋΐ g (0.11 mol) commercially available 4-aminophenylboronic acid, 0.35 g (0.0005 m〇l) of bis(triphenylphosphine) II Gasification (Π), 20.7 g (0.15 mol) of potassium carbonate and 8.1 g (0.025 mol) of tetrabutylammonium bromide were added 150 mL of ethanol, 75 mL of toluene and 100 mL of pure water. The mixture was heated to reflux for 3 hours under a nitrogen atmosphere. After standing to cool, the reaction solution was placed in water, extracted with 200 mL of toluene, and the organic layer was washed three times with 200 mL of pure water. After the organic layer was dried over anhydrous sodium sulfate, anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to give crude crystals. Then, the crude crystals were separated and purified by a column chromatography method (toluene: ethyl acetate = 5:1 (v/v)) to obtain 5-(4-aminophenylphenyl hydrazine (yield: 17.9 g, yield). The rate was 86%.) To a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 3.8 g (0.16 mol) of 60% sodium hydride '4% DMF was added. The solution was cooled to 5. (:, A solution of 167 g (〇〇8 mol) of 5-(4-aminophenyl)phosphonium dissolved in 2 mL of DMF was added dropwise, and then the solution was allowed to warm to room temperature under a nitrogen atmosphere. After stirring for 1 hour, the solution was again cooled to 5 ° C, and a solution obtained by dissolving 14.1 g (〇.i〇m〇i) of 4-fluoronitrobenzene in 15〇11^ of DMF was added dropwise thereto. Then, the solution was allowed to warm to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was placed in a mixed solvent of 5 mL of ethyl acetate and 500 mL of pure water for extraction, and the organic layer was 500 mL. The organic layer was washed three times with anhydrous sodium sulfate, and then anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to give crude crystals. The crude crystals were separated and purified by toluene (toluene: ethyl acetate (5/1 (v/v)) to obtain N_(4_nitro 54 201012801 phenylaminophenyl) hydrazine (yield 16.6 g, yield) The rate is 63%.) Add 16 〇g (Q()49 of Ν·(tetra)phenyl) o-aminophenyl) to the reaction tube for high pressure steam reduction treatment, add 200 mL of ethanol to the surface carbon of ^, ^ And 20 mL of ethyl acetate vinegar. Under the environment, the mixture was stirred for 12 hours at room temperature. The obtained solution was concentrated to obtain a crude crystal. After that, the column was chromatographed (toluene: Acetate acetate, base) ° (iv)) (yield 13.3 g, yield (four) 91%). 2HX br' S, 2H), 174 ^ br · S' [Example 8] <Injury of polylysine> Three mouths == g: Mixing = gas introduction port - Dehydration NMP. The compound (A14) and 1.27, and ', and C were dissolved in 60 g while being dissolved, and the mixture was heated to room temperature under a nitrogen atmosphere (A1). Then, the solution γ-butyrolactone and 25 g of BC were added, and after 12 hours, the viscosity of the obtained solution was decreased by 10 g, and the gland was stirred for 2 hours in two steps. In order to make the viscosity of the solution reach 35 ml>a·s = the liquid is heated to ride at a temperature of 6 直至 until a percentage of the solution. The solution was recorded as a weight of 5 weights. The weight average molecular weight of the amine acid was 64:, A. Polymerization of the varnish [Examples 9 to 25, Comparative Example, and Reference Example U 201012801 A diamine and a tetracarboxylic dianhydride were used in the same manner as in Table 1 to produce a polyfluorene in the same manner as in Example 8. Amine acid, preparation of varnish B~U. <Table 1> Example No. Varnish name Diamine tetrazoic acid Sf Mw No. mole% No. mole% 8 Varnish A (Μ) 50 (Al) (A14) 25 25 64,000 9 Varnish B (1-1 ) (VI-D 25 25 (Al) (A14) 25 25 72,000 10 Varnish C (1-1) (VI-1) 25 25 (A20) 50 48,000 11 Varnish D (1-1) (VI-7) 40 10 (Al) (A14) 25 25 38,000 12 Varnish E (1-1) (IX-13) 40 10 (Al) (A14) 25 25 45,000 13 Varnish F (1-1) (XII-1) 40 10 ( Al) (A14) 25 25 50,000 14 Varnish G (1-5) 50 (Al) (A14) 25 25 58,000 15 Varnish Η (1-5) (VI-1) 25 25 (Al) (A14) 25 25 66,000 16 Varnish I (1-5) (VI-1) 25 25 (A20) 50 39,000 17 Varnish J (1-5) (VI-7) 40 10 (Al) (A14) 25 25 41,000 18 Varnish Κ (1- 5) (IX-13) 40 10 (Al) (A14) 25 25 42,000 19 Clear lacquer L (1-5) (XII-1) 40 10 (Al) (A14) 25 25 37,000 20 Varnish Μ 0-35) 50 (Al) (A14) 25 25 54,000 21 Varnish Ν (1-35) (VT-1) 25 25 (Al) (A14) 25 25 69,000 22 Varnish 〇 (1-35) 25 25 (A20) 50 40,000 56 201012801

[實施例26] <電特性用測定單元的製作> 將實施例8中製備的清漆A以NMp/Bc = 6/4 的混合溶劑加以稀釋，將聚酿胺酸濃度調整為3重量百分比’將其製成塗佈用清漆。[Example 26] <Preparation of measuring unit for electric characteristics> The varnish A prepared in Example 8 was diluted with a mixed solvent of NMp/Bc = 6/4 to adjust the polyaracine concentration to 3 wt%. 'This is made into a varnish for coating.

利用旋轉器法將該塗佈用清漆塗佈於附ιτ〇電極的玻璃基板上。塗佈條件是以2,000 rpm、15秒進行。塗佈後，將基板加熱至80 C而預備假燒5分鐘後’於2i〇°c下進行 20分鐘加熱處理，形成膜厚約為8〇 nm的液晶配向膜。然後對所獲得的配向膜實施摩擦處理。摩擦處理是使用毛長度為1.9 mm的嫘縈製摩擦布，以毛壓入量為〇 4〇 mm、平台移動速度為60mm/sec、輥轉速為l，〇〇〇 rpm的條件實施。將摩擦處理後的玻璃基板於超純水中進行5分鐘的超音波清洗後，再於烘箱中120°C下乾燥30分鐘。於一片基板上散布7 μπι的間隙劑（gap agent)，將另一片基板以夹 57 201012801 WO 厶 pill 著間隙劑的方式重疊，並以環氧硬化劑密封，來製作間隙為7 μιη的反平行單元（antiparallel cell)。然後在該單元中注入下述液晶組成物A作為液晶材料，將注入口以光硬化樹脂密封。繼而，將單元於110°C下進行30分鐘加熱處理，獲得電壓保持率、殘留DC以及預傾角測定用單元。 <液晶組成物A> F 17wt% F 17wt% c2h5.This coating varnish was applied onto a glass substrate to which an electrode was attached by a spinner method. The coating conditions were carried out at 2,000 rpm for 15 seconds. After the application, the substrate was heated to 80 C and preliminary calcined for 5 minutes, and then heat-treated at 2 μM for 20 minutes to form a liquid crystal alignment film having a film thickness of about 8 Å. The obtained alignment film is then subjected to a rubbing treatment. The rubbing treatment was carried out using a tanned rubbing cloth having a hair length of 1.9 mm, with a hair pressing amount of 〇 4 〇 mm, a table moving speed of 60 mm/sec, a roll rotation speed of 1, and 〇〇〇 rpm. The rubbed glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. A gap agent of 7 μm is spread on one substrate, and the other substrate is overlapped by a gap between the electrodes 57 201012801 WO 厶pill and sealed with an epoxy hardener to make an anti-parallel with a gap of 7 μm Unit (antiparallel cell). Then, the liquid crystal composition A described below was injected into the unit as a liquid crystal material, and the injection port was sealed with a photocurable resin. Then, the unit was heat-treated at 110 ° C for 30 minutes to obtain a cell for voltage holding ratio, residual DC, and pretilt angle measurement. <Liquid crystal composition A> F 17 wt% F 17 wt% c2h5.

n-C3H7n-C3H7

n-CgHiin-CgHii

16wt% c2h516wt% c2h5

10wt%10wt%

5 wt%5 wt%

ΠΌ3Η7ΠΌ3Η7

10 wt%10 wt%

6wt% 58 201012801 6wt% 13wt°/〇使用所製作的單元，利用上述方法來測定電壓保持率、殘留DC以及預傾角，結果分別為96.2%、1.8 mV以及 1.7°。6wt% 58 201012801 6wt% 13wt°/〇 Using the fabricated unit, the voltage retention, residual DC, and pretilt angle were measured by the above methods, and the results were 96.2%, 1.8 mV, and 1.7°, respectively.

[實施例27〜43、以及比較例3〜4] 使用清漆B〜清漆T，依據實施例26中記載的方法製作單元，測定電壓保持率、殘留DC以及預傾角。將測定結果示於表2中（實施例26亦再次揭示）。其中，對於使用清漆E、清漆K以及清漆Q而形成的配向膜不進行摩擦處理，且，所注入的液晶材料是使用液晶組成物B來代替液晶組成物A。[Examples 27 to 43 and Comparative Examples 3 to 4] Using a varnish B to varnish T, a cell was produced in accordance with the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured. The measurement results are shown in Table 2 (Example 26 is also disclosed again). Here, the alignment film formed using the varnish E, the varnish K, and the varnish Q was not subjected to rubbing treatment, and the liquid crystal material to be injected was replaced with the liquid crystal composition A by using the liquid crystal composition B.

<液晶組成物B〉<Liquid crystal composition B>

12 w%12 w%

11 w% 15 w% 15 w% 59 201012801 ^zuozpin11 w% 15 w% 15 w% 59 201012801 ^zuozpin

n-C3H7—^C2Hs n-C3H7—^y~^~^-0-CH3 5w% 6w% 6w% 5w% 5w% 6w% 6w% 4w% 4w%n-C3H7—^C2Hs n-C3H7—^y~^~^-0-CH3 5w% 6w% 6w% 5w% 5w% 6w% 6w% 4w% 4w%

[實施例44以及45] <摻合配向劑的電特性評價> 製備將清漆A與清漆U以重量比8 : 2混合而成的清漆AU。使用該清漆AU，依據實施例26中記載的方法製作單元。製備將清漆B與清漆U以重量比8: 2混合而成的清漆BU，使用該清漆BU，以與清漆AU相同的方式製作單元。將對該些單元測定電壓保持率、殘留DC以及預[Examples 44 and 45] <Evaluation of electric characteristics of blended alignment agent> A varnish AU obtained by mixing varnish A and varnish U at a weight ratio of 8:2 was prepared. Using this varnish AU, a unit was produced in accordance with the method described in Example 26. A varnish BU obtained by mixing varnish B and varnish U at a weight ratio of 8: 2 was prepared, and the varnish BU was used to prepare a unit in the same manner as varnish AU. The voltage holding ratio, residual DC, and pre-measurement will be measured for these units.

傾角所得的結果示於表2。 60 201012801 〈表2> 實施例 No. 清漆名稱電壓保持率（％) 殘留DC (mV) 預傾角（°) 26 清漆A 96.2 1.8 1.7 27 清漆B 96.6 10 1.3 28 清漆C 95.9 12 1.4 29 清漆D 95.4 17 0.9 30 清漆E 94.9 21 90 31 清漆F 95.0 19 5.0 32 清漆G 96.1 2.5 1.4 33 清漆Η 96.4 11 1.4 34 清漆I 95.3 15 1.5 35 清漆J 95.7 16 0.8 36 清漆Κ 94.6 22 90 37 清漆L 94.9 17 5.1 38 清漆Μ 96.0 2.2 1.5 39 清漆Ν 96.7 9.3 1.3 40 清漆0 95.4 10 1.8 41 清漆Ρ 94.9 21 0.9 42 清漆Q 94.4 26 90 43 清漆R 95.7 18 5.1 44 清漆AU 95.6 11 5.3 45 清漆BU 96.6 10 5.4 比較例3 清漆S 90.8 2.7 1.6 比較例4 清漆Τ 95.3 1.9 2.2 [實施例46〜50、以及比較例5〜6] <保存穩定性的確認> 製備清漆A、清漆B、清漆F、清漆J、清漆AU、清漆S以及清漆T後，於-20°C下保存60天，使用該保存清漆，依據實施例26中記載的方法製作單元，測定電壓保持率、殘留DC以及預傾角。測定結果示於表3。 61 201012801 〈表3> 實施例 No. 清漆名稱電壓保^7^7 Γ—------ 殘留DC (mV) ------- 預傾角（°) 46 清漆A 95.9 ' 47 清漆B 96F—' __3.6 1.6 48 清漆F 94.5 —~~~ ~~~~ 1.3 49 ^清漆J 95.0 ' 5.0 50 清漆AU 96.0 0.8 比較例5 b卜‘妨你1 6 清漆S 由於聚合: ^座而無法製竹 5.4 -〇s — :單7C /貧漆Τ 1.3The results obtained from the dip are shown in Table 2. 60 201012801 <Table 2> Example No. Varnish name Voltage retention (%) Residual DC (mV) Pretilt angle (°) 26 Varnish A 96.2 1.8 1.7 27 Varnish B 96.6 10 1.3 28 Varnish C 95.9 12 1.4 29 Varnish D 95.4 17 0.9 30 Varnish E 94.9 21 90 31 Varnish F 95.0 19 5.0 32 Varnish G 96.1 2.5 1.4 33 Varnish Η 96.4 11 1.4 34 Varnish I 95.3 15 1.5 35 Varnish J 95.7 16 0.8 36 Varnish Κ 94.6 22 90 37 Varnish L 94.9 17 5.1 38 Varnish Μ 96.0 2.2 1.5 39 Varnish Ν 96.7 9.3 1.3 40 Varnish 0 95.4 10 1.8 41 Varnish Ρ 94.9 21 0.9 42 Varnish Q 94.4 26 90 43 Varnish R 95.7 18 5.1 44 Varnish AU 95.6 11 5.3 45 Varnish BU 96.6 10 5.4 Comparative example 3 Varnish S 90.8 2.7 1.6 Comparative Example 4 Varnish Τ 95.3 1.9 2.2 [Examples 46 to 50 and Comparative Examples 5 to 6] <Confirmation of storage stability> Preparation of varnish A, varnish B, varnish F, varnish J, After the varnish AU, the varnish S, and the varnish T were stored at -20 ° C for 60 days, a cell was prepared by the method described in Example 26 using the stored varnish, and the voltage holding ratio, residual DC, and pretilt angle were measured. The measurement results are shown in Table 3. 61 201012801 <Table 3> Example No. Varnish name voltage protection ^7^7 Γ—------ Residual DC (mV) ------- Pretilt angle (°) 46 Varnish A 95.9 ' 47 Varnish B 96F—' __3.6 1.6 48 Varnish F 94.5 —~~~ ~~~~ 1.3 49 ^ Varnish J 95.0 ' 5.0 50 Varnish AU 96.0 0.8 Comparative Example 5 b Bu 'You may 1 6 Varnish S Due to polymerization: ^ Block And can not make bamboo 5.4 - 〇 s - : single 7C / poor paint Τ 1.3

[實施例51] <聚醯亞胺的製備>[Example 51] <Preparation of polyimine>

於200 mL圓底燒瓶中稱取刚g的清漆A，向其中添加 9.5g(〇.〇9mol)的乙酸奸、4.4g(〇〇6m〇1)的吡啶，於not下授拌3小時。然後將溶液放入至1〇〇〇紅的純水中，獲得4.5 g的聚酿亞胺。該聚醯亞胺的重量平均分子量為49,000，藉由m-NMR測定，該聚醯亞胺的醯亞化率為94%。使4 g所獲得的聚醯亞胺溶解於76 g的 NMP-GBL-BC混合溶劑（體積比為！：： υ中，獲得聚醯亞胺濃度為5%的清漆V。 [實施例52] 使用清漆V’依據實施例26中記載的方法製作單元，測定電壓保持率、殘留DC、以及預傾角，結果分別為 95.9%、4.2 mV、以及 1.6。。 [比較例7] 除將二胺（1-1)替代為日本專利特開平10_104633號 62 201012801 ^ζυοζριπ 公報令記載的Ν，Ν，-雙(4_胺基苯基)-:1,4-哌嗪以外，依據實施例8中記載的方法獲得清漆w。於200 mL圓底燒瓶中稱取100 g的清漆W，向其中添加 8.2 g (0.08 mol)的乙酸酐、3.8 g ( 0.05 mol)的吡啶，加熱至120°C，結果於加熱開始1小時後沉澱析出，即便將溶液的溫度升溫至18〇°c，該沉澱亦未溶解。 [實施例53] <二胺（Ml)的合成> ® 向安裝有攪拌機、溫度計以及氮氣導入口的500 mL 二口燒瓶中加入29.0 g ( 102 mmol)市售的5-破0引〇朵以及 17·0 g ( 122 mmol)的碳酸鉀，添加2〇〇 mL的DMF。向 • 其中添加使17.3 g ( 122 mmol)市售的4-氟硝基苯溶解於 100mL的DMF中而成的溶液，於氮氣環境下、14〇。〇下攪拌2小時。然後將反應液放至500 mL乙酸乙酯以及500 mL 純水的混合溶劑中進行萃取，使有機層以無水硫酸錢乾燥。將硫酸鎂過濾分離，將溶劑減壓餾去，獲得粗結晶。 φ 將所獲得的粗結晶自曱苯中再結晶，獲得N_(4-确基苯基)-5-埃'»引鳴（產量為33g，產率為83%)。向安裝有攪拌機、溫度計以及氮氣導入口的500 mL 三口燒瓶中添加33 g (91 mmol)所獲得的N<4_硝基苯基)-5-蛾吲哚、3.2g (4.6mm〇l)的雙(三苯基膦)二氯化鈀 (II)以及 0.87g(4.6mmol)的碘化銅（1)，添加 3〇〇mL 的三乙基胺。然後向其中添加10.7 g (1〇9 mmol)市售的三甲基矽烷基乙炔，於氮氣環境下加熱回流6小時。接著 63 201012801 將反應液放入至500 mL乙酸乙酯以及500 mL純水的混合溶劑中進行萃取’使有機層以無水硫酸鎂乾燥。將硫酸鎮過濾分離’將溶劑減壓餾去’獲得N-(4-硝基苯基)_5_((三甲基石夕院基)乙炔基)-吲°朵的粗結晶（產量為27 g，產率為 88%)。向安裝有攪拌機、溫度計以及It氣導入口的500 mL 三口燒瓶中加入27 g (81 mmol)所獲得的N-(4-硝基苯基)-5-((三曱基石夕烧基）乙炔基)-η弓卜朵，使其溶解於2〇〇 rnT, 的四氫n夫喊中。於氮氣環境下，將溶液於乾冰-丙酮浴（dry _ ice-acetone bath)中冷卻至-78°C ’ 一面將液溫保持為-78 °C，一面向其中滴加85 mL市售的氟化四丁基錢1 m〇i/L 溶液。將溶液保持為-78°C，攪拌2小時後，將反應液放入至500 mL乙酸乙酯以及500 mL純水的混合溶劑中進行萃取，使有機層以無水硫酸鎂乾燥。將溶劑減壓餾去，獲得 N-(4-硝基苯基)-5-乙炔基吲哚（產量為17 g，產率為79%)。向安裝有攪拌機、溫度計以及空氣導入口的500 mL 三口燒瓶中加入17 g (65 mmol)所獲得的Ν-(4-硝基苯 ^ 基)-5-乙炔基吲哚、1.3 g (13 mmol)的氯化銅（I)以及 2.5 g (21 mmol)的N，N'-四曱基乙二胺，添加1〇〇 mL乙二醇二曱喊。一面使用水槽用空氣栗向系統内送入空氣，一面於室溫下攪拌24小時。將反應液過濾，將所獲得的反應產物以300 mL的氨水中清洗1次，以300 mL的純水清洗2次，獲得1，4-雙(5-(N-(4-確基苯基)-吲哚基))-1,3-丁二炔（產量為14 g，產率為82%) 64The varnish A of g immediately after weighing was weighed in a 200 mL round bottom flask, and 9.5 g of acetaminophen, 4.4 g of pyridine (〇〇6m〇1) of pyridine was added thereto, and mixing was carried out for 3 hours under not. The solution was then placed in pure water of 1 blush to obtain 4.5 g of polynymine. The polyamidimide had a weight average molecular weight of 49,000, and the ruthenium imineization rate of the polyimine was 94% as determined by m-NMR. 4 g of the obtained polyimine was dissolved in 76 g of a mixed solvent of NMP-GBL-BC (volume ratio: : : υ, a varnish V having a polyamidene concentration of 5% was obtained. [Example 52] Using a varnish V', a cell was produced according to the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured and found to be 95.9%, 4.2 mV, and 1.6, respectively. [Comparative Example 7] In addition to the diamine ( 1-1) In place of Ν, Ν, - bis(4-aminophenyl)-: 1,4-piperazine described in Japanese Patent Laid-Open No. Hei 10-104633 No. 62 201012801, ζυοζριπ Method to obtain varnish w. Weigh 100 g of varnish W in a 200 mL round bottom flask, add 8.2 g (0.08 mol) of acetic anhydride, 3.8 g (0.05 mol) of pyridine, and heat to 120 ° C. The precipitate was precipitated one hour after the start of heating, and the precipitate was not dissolved even when the temperature of the solution was raised to 18 ° C. [Example 53] <Synthesis of diamine (Ml)> 29.0 g (102 mmol) of commercially available 5-broken 0 was added to a 500 mL two-necked flask with a nitrogen inlet. 〇多 and 17·0 g (122 mmol) of potassium carbonate, adding 2 〇〇mL of DMF. Adding to the solution, 17.3 g (122 mmol) of commercially available 4-fluoronitrobenzene was dissolved in 100 mL of DMF. The resulting solution was stirred under a nitrogen atmosphere for 14 hours under a nitrogen atmosphere, and then the mixture was poured into a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous sulfuric acid. The magnesium sulfate was separated by filtration, and the solvent was evaporated under reduced pressure to give crude crystals. φ The obtained crude crystals were recrystallized from toluene to obtain N-(4-decylphenyl)-5-A'» The yield was 33 g, and the yield was 83%.) To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 33 g (91 mmol) of N<4_nitrophenyl)-5-moth was added.吲哚, 3.2 g (4.6 mm 〇l) of bis(triphenylphosphine)palladium(II) chloride and 0.87 g (4.6 mmol) of copper iodide (1), adding 3 〇〇mL of triethyl amine. Then, 10.7 g (1 〇 9 mmol) of a commercially available trimethyldecyl acetylene was added thereto, and the mixture was heated under reflux for 6 hours under a nitrogen atmosphere. Next, 63 201012801 The reaction solution was placed in a mixed solvent of 500 mL of ethyl acetate and 500 mL of pure water for extraction. The organic layer was dried over anhydrous magnesium sulfate. The sulfuric acid was separated by filtration and the solvent was distilled off under reduced pressure to obtain crude crystals of N-(4-nitrophenyl)-5-((trimethylsulphonyl)ethynyl)-yield (yield 27 g, yield) The rate is 88%). To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and an It gas inlet, 27 g (81 mmol) of N-(4-nitrophenyl)-5-((trimethylsulfanyl) acetylene obtained was added. Base) - η 弓, so that it dissolves in 2 〇〇 rnT, the tetrahydro n scream. Under a nitrogen atmosphere, the solution was cooled to -78 ° C in a dry ice-acetone bath. The liquid temperature was maintained at -78 ° C, and 85 mL of commercially available fluorine was added dropwise thereto. Tetrabutyl monoxide 1 m〇i/L solution. The solution was kept at -78 ° C, and after stirring for 2 hours, the reaction mixture was poured into a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give N-(4-nitrophenyl)-5-ethynylindole (yield: 17 g, yield: 79%). To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and an air inlet, 17 g (65 mmol) of the obtained Ν-(4-nitrophenyl)-5-ethynyl hydrazine, 1.3 g (13 mmol) was added. Copper chloride (I) and 2.5 g (21 mmol) of N,N'-tetradecylethylenediamine were added with 1 mL of ethylene glycol. While using a water tank, air was supplied into the system using an air pump, and the mixture was stirred at room temperature for 24 hours. The reaction solution was filtered, and the obtained reaction product was washed once with 300 mL of aqueous ammonia, and washed twice with 300 mL of pure water to obtain 1,4-bis(5-(N-(4-)phenyl )-mercapto))-1,3-butadiyne (yield 14 g, yield 82%) 64

201012801 ^νοζρπι 二蒸氣滅菌處理甩反 mmol)所獲得的 1>4， τ g 以/ 丁二炔、L4g 嗔⑷硝基苯基Η!絲如，3- r缺，此末’添加MO mL乙醇以及150 mL 液濃％e =將鈀碳粉末除去，將所獲得的溶純=法= 姆叫佩㈣（產量為12 m-NMR (ppm):丨真176 (偶_，％ 4h) 2 74_2 76 (-CH2, t, J = 6.4 Hz, 4H), 3.76 (-NH2, b, s, 4H), 6.52-7.45 (arm. Η, 18H) [實施例54] <二胺（1-37)的合成> _向安裝有擾拌機、溫度計以及氮氣導入口的5〇〇mL 二口燒瓶中加入26.0g (161 mm〇i)市售的5_硝基吲哚以及27.0 g (194 mmol)的碳酸鉀，添加2〇〇 mL的DMF。向其中添加使38.0 g (242 mmol)市售的5-氟-2-硝基苯酚洛解於100mL的DMF中而成的溶液，於氮氣環境下、14〇 C下攪拌2小時。然後將反應液放入至丨L純水中，將所獲得的結晶以500 mL的純水清洗2次，以500 mL的乙醇清洗2次，使其乾燥，獲得N_(3_羥基硝基苯基)_5_破基吲哚（產量為45 g，產率為94%)。於高壓蒸氣滅菌處理用反應管中加入45.0 g (150 65 201012801 :1』的N仰基·4_雜苯基)_5儀啊、4 5 g的叙加500 mL的乙醇。使系統内成為氣氣環境下，二:壓：49 MPa、室溫珊12小時。接著綱粉末獲制雜濃縮，€縣結晶。將粗結晶自乙 Ht1 : 1 (V/V)中再結晶，獲得¥胺基I羥基苯土）- _胺基吲哚（產量為3〇g，產率為83〇/〇)。 1H-NMR (ppm)： 4.59 (-NH2, br. s, 2H), 4.66 (-NH2, br s，2H), 6.29-6.30 (=CH-, d, J = 3.0 Hz, 1H), 6.53-7.13 (arm H, m, 6H), 7.24-7.25 (=CH-, d, J = 3.0 Hz, 1H) 使用本發明液晶配向劑的液晶顯示元件如上所述，與先前的液晶顯示元件相比，表現出電壓保持率高、殘留小等良好的特性。而且，可知本發明的液晶配向劑的保存穩定性優異’且雜通常所使㈣溶翁具有較高溶解性。雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍内，當可作些許之更動與潤飾，故本發明之保護範圍當視後附之申請專利範圍所界定者為準。【圖式簡單說明】〇無【主要元件符號說明】無 66 201012801 # k ' : iSi_9*^7877號中文說明書無劃線修正本修正日期:卯-1 Ll 27、曰發明專利說明書 (本說明書格式、順序，請勿任意更動，※記號部分請勿填寫） ※申請案號： 6AD 1⑽06.01> ※申請日： ' ※”(：分類：% ί2〇〇6*〇η 一、發明名稱：知 ί2006·01Ι 二胺、液晶配向劑、液晶配向膜、以及液晶顯示元件 DIAMINE, LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER, AND • LIQUID CRYSTAL DISPLAY DEVICE 二、中文發明摘要：本發明的課題在於開發一種可達成對液晶配向膜中所 * 要求的很多特性（電壓保持率高、殘留DC小、液晶配向 . 性高、耐摩擦性高等）的聚醯胺酸。該課題是由式（1)所表示的二胺來解決。於式（1)中’ γ為單鍵或碳數為1〜 9的直鏈伸烷基；該伸烷基的任意-CH2-可由-〇_、 -N(CH；3)-、1，4-伸苯基、l，4-伸環己基或°辰嗪-l，4-二基取代； ❹ η為0或1 ;並且，鍵結有胺基的苯環的一個氫可由_〇H 取代。其中’當γ為伸烷基且η為〇時，並無鍵結有胺基的-CH2-由-0-或-N(CH3)-取代的情況。201012801 ^νοζρπι Two steam sterilization treatment 甩 reverse mmol) obtained 1 > 4, τ g to / diacetylene, L4g 嗔 (4) nitrophenyl hydrazine! silk, such as 3- r deficiency, this end 'add MO mL ethanol And 150 mL of liquid concentration %e = removal of palladium carbon powder, the obtained solution purity = method = 姆叫佩 (4) (yield is 12 m-NMR (ppm): 丨真176 (even _,% 4h) 2 74_2 76 (-CH2, t, J = 6.4 Hz, 4H), 3.76 (-NH2, b, s, 4H), 6.52-7.45 (arm. Η, 18H) [Example 54] <Diamine (1- 37) Synthesis> _ Add 26.0 g (161 mm〇i) of commercially available 5-nitroguanidine and 27.0 g to a 5 mL mL two-necked flask equipped with a scrambler, a thermometer, and a nitrogen inlet. 194 mmol) of potassium carbonate, 2 mL of DMF was added thereto, and a solution obtained by dissolving 38.0 g (242 mmol) of commercially available 5-fluoro-2-nitrophenol in 100 mL of DMF was added thereto. Stir under nitrogen atmosphere at 14 ° C for 2 hours. Then, the reaction solution was placed in pure water of 丨L, and the obtained crystal was washed twice with 500 mL of pure water and twice with 500 mL of ethanol. It is dried to obtain N_(3_hydroxynitrophenyl)_5_ broken base ( The amount is 45 g, the yield is 94%. In the reaction tube for autoclaving, 45.0 g (150 65 201012801:1) of N-negative 4-phenylene) 5 5 g, 4 5 g Add 500 mL of ethanol to the system. Make the system into a gas atmosphere, 2: pressure: 49 MPa, room temperature for 12 hours. Then the powder is mixed and concentrated, and the county crystallizes. The crude crystal is from Ht1 : 1 ( Recrystallization in V/V) gave ?Amino hydroxybenzoate)--amino hydrazine (yield 3 〇g, yield 83 〇 / 〇). 1H-NMR (ppm): 4.59 (-NH2, br. s, 2H), 4.66 (-NH2, br s, 2H), 6.29-6.30 (=CH-, d, J = 3.0 Hz, 1H), 6.53- 7.13 (arm H, m, 6H), 7.24-7.25 (=CH-, d, J = 3.0 Hz, 1H) The liquid crystal display element using the liquid crystal alignment agent of the present invention is as described above, compared with the prior liquid crystal display element, It exhibits good characteristics such as high voltage holding ratio and small residual. Further, it is understood that the liquid crystal alignment agent of the present invention has excellent storage stability, and the miscellaneous product generally has a high solubility. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. [Simple description of the diagram] 〇No [Main component symbol description] None 66 201012801 # k ' : iSi_9*^7877 Chinese manual without scribe correction This revision date: 卯-1 Ll 27, 曰 invention patent specification (this manual format In the order, please do not change it. ※Please do not fill in the ※ part. ※Application number: 6AD 1(10)06.01> ※Application date: '※」(:Classification:% 〇〇2〇〇6*〇η I. Name of the invention: Know 20062006·01Ι Diamine, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element DIAMINE, LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER, AND • LIQUID CRYSTAL DISPLAY DEVICE 2. Abstract: The object of the present invention is to develop a A polylysine which achieves many characteristics (high voltage holding ratio, small residual DC, high liquid crystal alignment, high abrasion resistance, etc.) required for the liquid crystal alignment film. This problem is represented by the formula (1). The diamine is solved. In the formula (1), 'γ is a single bond or a linear alkyl group having a carbon number of 1 to 9; any -CH 2 of the alkyl group may be -〇_, -N(CH; 3 )- , 1,4-phenylene, 1,4-cyclohexylene or phenazine-l,4-diyl substituted; ❹ η is 0 or 1; and a hydrogen of a benzene ring bonded to an amine group may be _〇H is substituted, wherein 'when γ is an alkylene group and η is fluorene, there is no case where -CH2- bonded to an amine group is substituted by -0- or -N(CH3)-.

(1) 1 201012801 Λ 三、英文發明摘要： The present invention is provided to develop a polyamic acid capable of achieving many characteristics (high voltage holding capacity, little remained DC (direct current), high liquid crystal alignability, high rubbing resistance, etc.) required by a liquid crystal (LC) alignment layer. The invention is achieved through a diamine shown by formula (1). In formula (1), Y represents a single bond or a 1-9 C linear alkylene group, and any -CH2- in the alkylene group φ may be replaced by —0-，-N(CH3)-, 1,4-phenylene, 1,4-cyclohexylene or piperazine-1,4-diyl; n is 0 or 1; and one hydrogen of a benzene ring that the amino group is bonded to may be replaced by -OH. However, when Y is an alkylene and n is 0, -CH2- that the amino group is bonded to is not replaced by -O- or -N(CH3)-.(1) 1 201012801 Λ 3. English Abstract: The present invention is provided to develop a polyamic acid capable of achieving many characteristics (high voltage holding capacity, little residual DC (direct current), high liquid crystal alignability, high rubbing resistance, The formula is achieved by a liquid crystal (LC) alignment layer. The invention is achieved through a diamine shown by formula (1). In formula (1), Y represents a single bond or a 1-9 C linear alkylene group, and Any -CH2- in the alkylene group φ may be replaced by —0-,-N(CH3)-, 1,4-phenylene, 1,4-cyclohexylene or piperazine-1,4-diyl; n is 0 or 1; And one hydrogen of a benzene ring that the amino group is bonded to may be replaced by -OH. However, when Y is an alkylene and n is 0, -CH2- that the amino group is bonded to is not replaced by -O- Or -N(CH3)-.

2 201012801 szwzpm 七、申請專利範圍： 1. 一種二胺，其由式（1)所表示··2 201012801 szwzpm VII. Patent application scope: 1. A diamine represented by formula (1)··

—so 夂(1, 、NH2 ® 其中’ Y為單鍵或碳數為1〜9的直鏈伸烷基；該伸烷基的任意-CH2·可由_〇_、_N(CH3)-、l，4-伸苯基、1，4-伸環己基或哌嗪-1，4-二基取代；n為〇或丨；並且，鍵結有胺基 • 的苯環的一個氫可由-0H取代；其中，當γ為伸烷基且n 為0 並無鍵結有胺基的-CH2·由-〇-或_n(CH3)-取代的情況。 2. 如申請專利範圍第1項所述之二胺，其中所述鍵結有胺基的笨環為不具有_0H作為取代基的苯環。參 3·如申請專利範圍第1項所述之二胺，其中所述鍵結有胺基的笨環為於相對於所述胺基的其中一鄰位具有取代基-0H的苯環。 4. 如申請專利範圍第1項所述之二胺，其中γ為單鍵或1，4-伸苯基，並且η為〇。 5. 如申請專利範圍第1項所述之二胺，其中γ為單鍵、或者任意-CH2·可由-〇^_N(CH3)-取代的碳數為卜9 的直鏈伸烷基；並且η為1。 6· —種聚醯胺酸，是使至少一種如申請專利範圍第^ 67 201012801 項所述之二胺、或者由至少一種如申請專利範圍第1項所述之二胺與至少一種其他二胺所構成的二胺混合物，與至少一種四羧酸酐進行反應而獲得。 7.如申請專利範圍第6項所述之聚醯胺酸，其中所述至少一種四羧酸酐為選自由式（A1)〜式（A63)所表示的化合物中的四羧酸酐：—so 夂(1, ,NH2 ® wherein 'Y is a single bond or a linear alkyl group having a carbon number of 1 to 9; any -CH2· of the alkyl group may be _〇_, _N(CH3)-, l , 4-phenylene, 1,4-cyclohexylene or piperazine-1,4-diyl substituted; n is ruthenium or osmium; and a hydrogen bonded to the benzene ring of the amine group can be replaced by -OH Wherein, when γ is an alkylene group and n is 0, and -CH2· having an amine group bonded thereto is substituted by -〇- or _n(CH3)-. 2. As described in claim 1 a diamine in which the acyclic ring to which an amine group is bonded is a benzene ring having no _0H as a substituent. The diamine according to claim 1, wherein the bond is an amine The stupid ring of the group is a benzene ring having a substituent -0H with respect to one of the ortho positions of the amine group. 4. The diamine of claim 1, wherein γ is a single bond or 1,4 - phenyl is extended, and η is 〇. 5. The diamine according to claim 1, wherein γ is a single bond, or any -CH2 can be substituted by -〇^_N(CH3)- a straight chain alkyl group of 9; and η is 1. 6 · a poly-proline, Having at least one diamine as described in the scope of the patent application No. 67 201012801, or a mixture of at least one diamine composed of at least one diamine as described in claim 1 and at least one other diamine, and at least one The polycarboxylic acid as described in claim 6, wherein the at least one tetracarboxylic anhydride is selected from the compounds represented by the formula (A1) to the formula (A63). Tetracarboxylic anhydride:

Ο 0 (A1)Ο 0 (A1)

68 201012801 。么uozpu丄 Η ¥k Μ Ο Ο 0‘ Ο (A14) (Α15) (Α16) (Α17)68 201012801. Uuozpu丄 Η ¥k Μ Ο Ο 0‘ Ο (A14) (Α15) (Α16) (Α17)

(A18) Ο(A18) Ο

(Α19)(Α19)

Ο Ο Ο (Α21) ❹Ο Ο Ο (Α21) ❹

(Α22)(Α22)

ΟΟ

❹❹

(Α35) 69 201012801 jxuozpui(Α35) 69 201012801 jxuozpui

ΟΟ

(Α38) 。^〇4(Α38). ^〇4

(Α41) (Α39)(Α41) (Α39)

(Α44)(Α44)

(Α47) (Α45)(Α47) (Α45)

(Α50)(Α50)

(Α53) Ο 70 201012801(Α53) Ο 70 201012801

❿ ㈣私胺’是將如申請專圍第6項所述之聚酿胺酸脫水開環而獲得。 # 9. 一種溶液’包括選自由如申請專利範圍第6項所述之聚酿胺酸以及如㈣專利紐第8項所述之聚酿亞胺所組成的組群中的至少一種聚合物。 10. —種液晶配向劑，由如申請專利範圍第9項所述之溶液構成。 11. 一種液晶顯示元件，包括由如申請專利範圍第10 項所述之液晶配向劑所獲得的液晶配向膜。 71 201012801 jzuozpm 四、指定代表圈： (一）本案之指定代表圖：無 (二）本代表圖之元件符號簡單說明：無❿ (4) The private amine is obtained by dehydrating and opening the polyamic acid as described in Section 6. # 9. A solution' comprises at least one polymer selected from the group consisting of poly-aracine as described in claim 6 and the poly-imine as described in (4) Patent No. 8. A liquid crystal alignment agent comprising a solution as described in claim 9 of the patent application. A liquid crystal display element comprising the liquid crystal alignment film obtained by the liquid crystal alignment agent according to claim 10 of the patent application. 71 201012801 jzuozpm IV. Designated representative circle: (1) The designated representative of the case: None (2) The symbol of the representative figure is simple: None

五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

33