TW200916505A

TW200916505A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device

Info

Publication number: TW200916505A
Application number: TW97137307A
Authority: TW
Inventors: Toshiyuki Akiike; Michinori Nishikawa
Original assignee: Jsr Corp
Priority date: 2007-09-26
Filing date: 2008-09-26
Publication date: 2009-04-16
Also published as: JP5105108B2; JPWO2009041708A1; KR20100053648A; WO2009041708A1; KR101092397B1; CN101802692A; CN101802692B; TWI445735B

Abstract

Disclosed is a liquid crystal aligning agent containing (A) a specific compound typified by a compound represented by the formula (1-1) below, (B) a compound having two or more epoxy groups in a molecule, and (C) polymer(s) including at least one polymer selected from the group consisting of polyamic acids and polyimides. (In the formula (1-1), R1 represents a hydrogen atom, an alkyl group having 1-20 carbon atoms or an alicyclic group having 5-50 carbon atoms, and some or all of the hydrogen atoms in the alkyl group or the alicyclic group may be substituted by fluorine atoms, cyano groups or aryl groups.)

Description

200916505 九、發明說明【發明所屬之技術領域】本發明係關於液晶配向劑、液晶配向膜及液晶顯件。更詳言之，係關於適用於在未進行摩擦處理而藉射偏光或非偏光之輻射線形成液晶配向膜時之曝光量液晶配向劑、顯示均勻液晶配向能及優異電特性之液向膜及顯示高品質顯示性能之信賴性優異之液晶顯件。【先前技術】過去，具有正介電各向異性向列型液晶係在附有液晶配向膜之透明電極之基板夾層構造中，因應必要液晶分子之長軸在基板間以0〜3 60度連續扭轉而形成知有具有 TN (扭轉型向歹U，Twisted Nematic )型、 (超扭轉型向列，Super Twisted Nematic)型、IPS ( 內切換，In Plane Switching)型等液晶單元之液晶顯件（參照特開昭5 6-9 1 277號公報及特開平1 - 1 205 28 報）。該等液晶單元中，爲了使液晶分子以相對於基板一定方向配向，因此有必要在基板表面上設置液晶膜。該液晶配向膜通常係藉由以縲縈等布材以一定方基板表面上形成之有機膜表面往復摩擦之方法（摩擦形成。但，若以摩擦處理進行液晶配向膜之形成，由易在製程內產生塵埃及靜電，故有於配向膜表面附著示元由照少之晶配示元具有而使，已 STN 平面示元號公面於配向向對法）於容麈埃 -4- 200916505 而成爲顯示不良發生原因之問題。尤其是具有TFT (薄膜電晶體Thin Film Transistor)元件之基板之情況’因產生之靜電造成TFT元件之電路受損，亦爲成品率下降之原因而造成問題。而且，對於爾後逐漸高精密化之液晶顯示元件，由於伴隨著像素之高密度化而不可避免的在基板表面上產生凹凸，故進行均勻摩擦處理變得有困難。作爲於液晶單元中使液晶配向之其他方法，已知有藉由使在基板表面上形成之由聚乙烯月桂酸酯、聚醯亞胺、偶氮苯衍生物等之敏輻射線性薄膜照射偏光或非偏光輻射線，藉此賦予液晶配向能之光配向法。依據此方法，不會發生靜電或塵埃，而可實現均一液晶配向（參照特開平6 - 2 8 745 3號公報、特開平1 0-25 1 646號公報、特開平11-2815號公報、特開平 1 1 - 1 5247 5號公報、特開 2000-1 44 1 36號公報、特開 2000-3 1 95 1 0號公報、特開 2000-28 1 724號公報、特開平 9-2973 1 3號公報、特開 2003- 3 0773 6號公報、特開2004- 1 63 646號公報以及特開2002-250924號公報）。不過，TN (扭轉型向列）型、STN (超扭轉向列）型等之液晶單元中，液晶配向膜有必要具有使液晶分子相對於基板面以既定角度成傾斜配向之預傾角特性。藉由光配向法形成液晶配向膜時，預傾角特性通常係藉由使照射之輻射線朝基板面之入射方向自基板法線傾斜而賦予。已知上述光配向法作爲垂直配向模式之液晶單元中控制液晶分子傾斜方向之方法亦有用。亦即已知藉由使用以 -5- 200916505 光配向法賦予配向控制力及預傾角特性之垂直配向均一地控制施加電壓時之液晶分子傾斜方向（參 2003-307736號公報、特開2〇〇4_163646號公報 2〇04_83810號公報、特開平9-211468號公報及特圍 1 1 443 7號公報）。以光配向法製造之液晶配向膜爲可有效適用於晶顯示元件者。然而’過去已知之作爲適用於光配液晶配向劑之問題爲若要獲得大的預傾角必需照射射線。例如已報導有以光配向法賦予含有偶氮苯衍光配向膜液晶配向能時，爲了獲得充分之預傾角不射1 0,000J/m2以上之其光軸自基板法線傾斜之輻射照特開2002-250924號公報、特開2004-83810號公 of the SID 11/3, 2003, p.579)。【發明內容】本發明之目的係提供一種於不進行摩擦處理而: 射偏光或非偏光之輻射線形成液晶配向膜時曝光量適用之液晶配向劑 '顯示均一液晶配向能及優異電! 液晶配向膜、以及顯示高品質顯示性能之信賴性優晶顯不兀件。本發明又其他目的及優點由下列說明可更加明目| 依據本發明’本發明之上述目的及優點，係藉發明而達成’即一種液晶配向劑，其含有下列成分： (A )以下式（1 )表示之化合物：膜，可照特開、特開 I 2003- 各種液向法之大量轄生物之得不照線（參報及J. 由照少時亦特性之異之液由第一 -6 - 200916505 R1—R2-^R3—R4'200916505 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display. More specifically, it relates to a liquid crystal alignment agent suitable for forming a liquid crystal alignment film by irradiating a polarized or non-polarized radiation without performing rubbing treatment, a liquid crystal film exhibiting uniform liquid crystal alignment energy and excellent electrical characteristics, and A liquid crystal display that exhibits high-quality display performance and excellent reliability. [Prior Art] In the past, in a substrate sandwich structure having a positive dielectric anisotropic nematic liquid crystal in a transparent electrode with a liquid crystal alignment film, the long axis of the liquid crystal molecules is required to be continuously between 0 and 3 60 degrees between the substrates. By twisting, a liquid crystal display having a liquid crystal cell such as a TN (Twisted Nematic) type, a Super Twisted Nematic type, or an IPS (In Plane Switching type) is known ( Reference is made to JP-A-Open 5-6-9 1 277 and JP-A-Open 1 - 1 205 28). In these liquid crystal cells, in order to align liquid crystal molecules in a certain direction with respect to the substrate, it is necessary to provide a liquid crystal film on the surface of the substrate. The liquid crystal alignment film is usually formed by rubbing and rubbing the surface of the organic film formed on the surface of a certain substrate with a cloth such as ruthenium (friction formation. However, if the liquid crystal alignment film is formed by rubbing treatment, it is easy to process The dust is electrostatically generated in the interior of Egypt. Therefore, the surface of the alignment film is attached to the surface of the alignment film. The STN plane is shown in the alignment direction. 容麈 -4- 200916505 It becomes a problem of the cause of the display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, the circuit of the TFT element is damaged by the generated static electricity, which also causes a problem of a decrease in yield. Further, in the liquid crystal display device which is gradually higher in precision, unevenness is generated on the surface of the substrate inevitably due to the increase in density of the pixels, so that it is difficult to perform uniform rubbing treatment. As another method of aligning liquid crystals in a liquid crystal cell, it is known to irradiate polarized light by a linear film of a sensitive radiation such as polyethylene laurate, polyamidiamine or azobenzene derivative formed on the surface of a substrate. Non-polarizing radiation, thereby imparting a light alignment method to the alignment energy of the liquid crystal. According to this method, static electricity or dust does not occur, and a uniform liquid crystal alignment can be realized (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping 1 1 - 1 5247 5, JP-A-2000-1 44 1 36, JP-A-2000-3 1 95 1 0, JP-A-2000-28 1 724, and JP-A 9-2973 1 3 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. However, in a liquid crystal cell such as a TN (torsional nematic) type or an STN (super twisted nematic) type, it is necessary for the liquid crystal alignment film to have a pretilt characteristic in which liquid crystal molecules are obliquely aligned at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle characteristic is usually imparted by inclining the incident radiation from the substrate normal to the incident direction of the substrate surface. It is also known that the above-described photoalignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. That is, it is known that the tilt direction of the liquid crystal molecules when the applied voltage is uniformly controlled by using the vertical alignment imparting the alignment control force and the pretilt angle characteristic by the -5 - 200916505 optical alignment method (refer to Japanese Laid-Open Patent Publication No. 2003-307736, No. 2003-307736 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The liquid crystal alignment film produced by the photo-alignment method is effective for a crystal display element. However, the problem known in the past as being suitable for a photo-aligned liquid crystal alignment agent is that it is necessary to irradiate rays in order to obtain a large pretilt angle. For example, when a liquid crystal alignment energy containing an azobenzene-derived alignment film is imparted by a photo-alignment method, in order to obtain a sufficient pretilt angle, the optical axis of the optical axis from the substrate normal is not more than 10,000 J/m2 or more. Publication No. 2002-250924, JP-A-2004-83810, publicly on the SID 11/3, 2003, p. 579). SUMMARY OF THE INVENTION The object of the present invention is to provide a liquid crystal alignment agent that exhibits an exposure amount when a polarized light or a non-polarized radiation is formed to form a liquid crystal alignment film, which exhibits uniform liquid crystal alignment energy and excellent electric power. The film and the reliability of the display of high-quality display performance are outstanding. The other objects and advantages of the present invention will become more apparent from the following description. The above objects and advantages of the present invention are achieved by the invention, that is, a liquid crystal alignment agent containing the following components: (A) 1) Compounds indicated: Membrane, can be opened according to special opening, special opening I 2003 - various liquids to the law of a large number of ruling organisms are not according to the line (reported and J. from the time of the small is also the characteristics of the different liquid by the first -6 - 200916505 R1—R2-^R3—R4'

XyXy

CH=CH—CCH=CH—C

R5-(CH2)b-)—Z / c oR5-(CH2)b-)-Z / c o

(式（1)中，R1爲氫原子、碳數1〜20之烷基或碳數 5〜50之脂環式基，該等烷基或脂環式基之氫原子之—部份或全部亦可經氟原子、氰基或芳基取代；R2及R4各獨立爲單鍵、-〇-、-S-、-COO-、-OCO-、-CONH-、-NHC〇-、 -COS-、-SCO-、-0-C0-0-、-NH-COO-、-O-CO-NH-或 -CO-; R3爲碳數6〜20之2價芳香族基、碳數5〜30之2價脂環式基、具有碳數6〜30之縮合環之2價基或5~30員之 2價雜環基；R3中之2價芳香族基、2價脂環式基、具有縮合環之2價基或2價雜環基之氫原子之一部份或全部亦可經氟原子、甲基或氰基取代；R5爲單鍵、-〇_、-S_、 -COO-、-OCO-、-NR7-(其中R7爲氫原子、碳數^2 0之烷基或碳數6〜2 0之芳基）或下式（2)所表示之2價基：(In the formula (1), R1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms, and some or all of the hydrogen atoms of the alkyl group or the alicyclic group. It may also be substituted by a fluorine atom, a cyano group or an aryl group; R2 and R4 are each independently a single bond, -〇-, -S-, -COO-, -OCO-, -CONH-, -NHC〇-, -COS- , -SCO-, -0-C0-0-, -NH-COO-, -O-CO-NH- or -CO-; R3 is a divalent aromatic group having a carbon number of 6 to 20, carbon number 5 to 30 a divalent alicyclic group, a divalent group having a condensed ring having 6 to 30 carbon atoms or a divalent heterocyclic group having 5 to 30 members; a divalent aromatic group in R3; a divalent alicyclic group; Part or all of one or all of the hydrogen atoms of the divalent or divalent heterocyclic group of the fused ring may be substituted by a fluorine atom, a methyl group or a cyano group; R5 is a single bond, -〇_, -S_, -COO-, -OCO-, -NR7- (wherein R7 is a hydrogen atom, an alkyl group having a carbon number of 2,000 or an aryl group having a carbon number of 6 to 20) or a divalent group represented by the following formula (2):

(式（2)中，R爲献原子、氰基、碳數1〜2〇之院基或碳數 6〜20 之芳基；R9 爲單鍵、_◦_、_s_、_c〇〇_、·〇(：〇_、 -NHCO-、-COS-、-SCO-、 -O-CO-O-、_NH- 200916505 COO-、-O-CO-NH-或-CO- ; e爲0〜4之整數；其中式 (2 )之附有「*」之鍵結鍵係與CH2 ) b_鍵結）·’ R6係選自氟原子、甲基或氰基；Z爲經基或殘基·’ a爲0~3之整數；於R5爲以上述式（2)表示之2價基時，b爲0〜20 之整數；於 R5 爲單鍵、-〇_、_S_、_C00_、_0C0_ 或 _nr7_ (其中R7爲氫原子、碳數1~2〇之烷基或碳數6〜20之芳基）時，b爲1〜20之整數；c爲0〜4之整數；d爲〇〜4之整數）； (B) —分子中具有2個以上環氧基之化合物；及 (C) 選自聚醯胺酸及聚醯亞胺所成群組之至少一種聚合物。本發明之上述目的可藉第二之在基板上塗佈上述液晶配向劑形成塗膜’且對該塗膜照射輻射線而形成液晶配向膜之方法而達成。又本發明之上述目的可藉第三之自上述液晶配向劑形成之液晶配向膜，第四之具備該液晶配向膜之液晶顯示元件而達成。【實施方式】 [液晶配向劑] 本發明之液晶配向劑含有下列： (A )以上述式（1 )表示之化合物（以下稱爲「化合物（A )」）， (B) —分子中具有兩個以上環氧基之化合物（以下 -8- 200916505 稱爲「（ B )環氧化合物」），及 (C)含有選自聚醯胺酸及聚醯亞胺組成之群之至少一種之聚合物（以下稱爲「聚合物（C )」）。以下針對本發明之液晶配向劑所含各成分詳細的說明。 [化合物（A )] 本發明中所用化合物（A )爲以上述式（1 )表示之化合物。上述式（1)中之R1較好爲氫原子、碳數1〜8之烷基、碳數1〜6之氟烷基或碳數17〜30之脂環式基。至於該等之具體例，碳數1〜8之烷基可舉例爲例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等；碳數1〜6之氟烷基可舉例爲例如4,4,4-三氟丁基、 3,3,4,4,4-五氟丁基、4,4,5,5,5-五氟戊基、4,4,5,5,6,6,6-七氟己基等；碳數1 7〜3 0之脂環式基可分別舉例爲例如膽巢烯基、膽巢院基等。 R2及R4較好各獨立爲單鍵、-0-、-COO-或-OCO-。 R3之具體例可舉例爲例如1,4-伸苯基、1,3-伸苯基、 1，4 -伸環己基、1 , 3 -伸環己基、吡啶-2,5 -二基、嘧啶-2，5 -二基、2,5 -噻吩二基、2,5 -伸呋喃基或CH基亦可經氮原子取代之1，4 -伸萘基或2,6 -伸萘基。其中以1，4 -伸苯基較佳。 R5爲以上述式（2)表示之2價基時之e較好爲〇或 1。至於R5爲單鍵或-0-或以上述式（2)表示之2價基中 -9 - 200916505 之1，4-伸苯基，較好爲以下述式（2-1) 、（2-2)或（2- 3 )表示之2價基： /\(In the formula (2), R is an atom, a cyano group, a phenyl group having a carbon number of 1 to 2 Å or an aryl group having a carbon number of 6 to 20; R9 is a single bond, _◦_, _s_, _c〇〇_, ·〇(:〇_, -NHCO-, -COS-, -SCO-, -O-CO-O-, _NH- 200916505 COO-, -O-CO-NH- or -CO-; e is 0~4 An integer of the formula (2) with a "*" bond and a CH2) b_ bond) · R6 is selected from a fluorine atom, a methyl group or a cyano group; Z is a radical or a residue. ' a is an integer from 0 to 3; when R5 is a divalent group represented by the above formula (2), b is an integer of 0 to 20; and R5 is a single bond, -〇_, _S_, _C00_, _0C0_ or _ Nr7_ (wherein R7 is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or an aryl group having 6 to 20 carbon atoms), b is an integer of 1 to 20; c is an integer of 0 to 4; d is 〇~4 (B) - a compound having two or more epoxy groups in the molecule; and (C) at least one polymer selected from the group consisting of polylysine and polyimine. The above object of the present invention can be attained by a method of applying a liquid crystal alignment agent to form a coating film on a substrate, and irradiating the coating film with radiation to form a liquid crystal alignment film. Further, the above object of the present invention can be attained by the third liquid crystal alignment film formed from the above liquid crystal alignment agent and the fourth liquid crystal display element having the liquid crystal alignment film. [Embodiment] [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention contains the following: (A) a compound represented by the above formula (1) (hereinafter referred to as "compound (A)"), (B) - two in a molecule a compound having more than one epoxy group (hereinafter referred to as "(B) epoxy compound" in -8-200916505), and (C) a polymer containing at least one selected from the group consisting of polylysine and polyamidiamine (hereinafter referred to as "polymer (C)"). The respective components contained in the liquid crystal alignment agent of the present invention will be described in detail below. [Compound (A)] The compound (A) used in the present invention is a compound represented by the above formula (1). R1 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms or an alicyclic group having 17 to 30 carbon atoms. As such specific examples, the alkyl group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group or the like; The fluoroalkyl group of 1 to 6 can be exemplified by, for example, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 4,4,5,5,5-pentafluoro. Amyl, 4,4,5,5,6,6,6-heptafluorohexyl, etc.; an alicyclic group having a carbon number of 17 to 30 can be exemplified by, for example, cholestyl group, cholestyramine group and the like. R2 and R4 are each independently a single bond, -0-, -COO- or -OCO-. Specific examples of R3 may, for example, be 1,4-phenylene, 1,3-phenylene, 1,4-cyclohexylene, 1,3-cyclohexylene, pyridine-2,5-diyl, pyrimidine. -2,5-diyl, 2,5-thiophenediyl, 2,5-furanyl or CH group may also be substituted with a nitrogen atom to a 1,4-anthranyl group or a 2,6-naphthyl group. Among them, 1,4 -phenylene is preferred. When R5 is a divalent group represented by the above formula (2), e is preferably 〇 or 1. R4 is a single bond or -0- or a 1,4-phenylene group of -9 - 200916505 in the divalent group represented by the above formula (2), preferably having the following formula (2-1), (2- 2) or (2- 3) indicates the 2 valence group: /\

oyc 本 2Oyc this 2

ο 氺 2 2- oyc ο (上述式中，附加「*」之鍵結位置係與-(ch2 ) b-基鍵結）。 R6較好爲氟原子。 a較好爲〇或1。於R5爲單鍵或以上述式（2)表示之2價基時之b較好爲0〜10之整數，於R5爲- 0-、-S-、-COO-、-OC◦-或 -NR7-(其中R7爲氫原子、碳數1〜20之烷基或碳數6〜20 之芳基）時之b較好爲1〜10之整數。 c較好爲〇或1。 d較好爲0或1。上述之Z爲羥基或羧基，但在c爲0時之Z較好爲羥基。本發明中所用之化合物（A )之較佳實例可舉例爲例 -10- 200916505 如分別以下述式（1-1 )至（1-26 )表示之化合物：ο 氺 2 2- oyc ο (In the above formula, the key position of the "*" is attached to the -(ch2) b-base key). R6 is preferably a fluorine atom. a is preferably 〇 or 1. b when R5 is a single bond or a divalent group represented by the above formula (2) is preferably an integer of 0 to 10, and R5 is -0-, -S-, -COO-, -OC◦- or - NR7- (wherein R7 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms) is preferably an integer of 1 to 10. c is preferably 〇 or 1. d is preferably 0 or 1. The above Z is a hydroxyl group or a carboxyl group, but when c is 0, Z is preferably a hydroxyl group. Preferred examples of the compound (A) used in the present invention are exemplified by the examples of the compounds represented by the following formulas (1-1) to (1-26):

R1—<( CH=CH-COOH λ一/ (1-1)R1—<( CH=CH-COOH λ一 / (1-1)

R10—^ CH=CH-COOH '~^ (1-2) R1 ^〇"~coohC^~ CH=CH-COOH (1-3) R10 hQ^-coo-<Q- CH=CH-COOH (1-4)R10—^ CH=CH-COOH '~^ (1-2) R1 ^〇"~coohC^~ CH=CH-COOH (1-3) R10 hQ^-coo-<Q- CH=CH-COOH (1-4)

R1COO -Or coo <y CH=CH-COOH (1—5)R1COO -Or coo <y CH=CH-COOH (1-5)

CH=CH—COOH (1—6)CH=CH—COOH (1–6)

r1〇^〇-〇hO~ CH=CH—COOH (1-7)R1〇^〇-〇hO~ CH=CH—COOH (1-7)

r1coohQkohQh CH=CH-COOH (1-8) -11 - 200916505r1coohQkohQh CH=CH-COOH (1-8) -11 - 200916505

R1COO CH=CH-COOH (1-9)R1COO CH=CH-COOH (1-9)

r1~0~ CH=CH-COO-(CH2)-OH (1-10)R1~0~ CH=CH-COO-(CH2)-OH (1-10)

R10—^~^-CH=CH—C0Q-(CH2)-0H (1-11)R10—^~^-CH=CH—C0Q-(CH2)-0H (1-11)

R1COOR1COO

OrOr

CH=CH-COO-(CH2)-OH (1-12) CH=CH·CH=CH-COO-(CH2)-OH (1-12) CH=CH·

•C00-(CH2)「C00H (1-13)•C00-(CH2)"C00H (1-13)

R1Q—CH=CH-COO-(CH2)g-C〇〇H (1 -14) r1coo—^~^-ch=ch-coo-(ch2)-cooh (1-15)R1Q—CH=CH-COO-(CH2)g-C〇〇H (1 -14) r1coo—^~^-ch=ch-coo-(ch2)-cooh (1-15)

r1~〇- COO~^ CH=CH-COO-(CH2) _OH (1 -16) -12- 200916505R1~〇- COO~^ CH=CH-COO-(CH2) _OH (1 -16) -12- 200916505

COQ-^~^—CH=CH-C00-(CH2)-0H (1-17)COQ-^~^—CH=CH-C00-(CH2)-0H (1-17)

R1COO—COO-^~^—CH=CH-C00-(CH2)-0H (1-18)R1COO—COO-^~^—CH=CH-C00-(CH2)-0H (1-18)

故Or COQ-^~^—CH=CH-COO-(CH2)-COOH (1-19)Therefore, Or COQ-^~^—CH=CH-COO-(CH2)-COOH (1-19)

r1〇~0^ COO-^~^—CH=CH-COO-(CH2)-COOH (1--20)R1〇~0^ COO-^~^—CH=CH-COO-(CH2)-COOH (1--20)

R1COO <y COQ-^~~^—CH=CH-CQ〇-(CH2)-COOH (1-21) l_〇O" i?R1COO <y COQ-^~~^-CH=CH-CQ〇-(CH2)-COOH (1-21) l_〇O" i?

_ u R1—COO~^ ^~CH=CH~C-(CH；2)「OH CH=CH—C-(CH2)—OH b (1-22) (1-23) o_ u R1—COO~^ ^~CH=CH~C-(CH;2)“OH CH=CH—C—(CH2)—OH b (1-22) (1-23) o

COOH (1-24) OHCOOH (1-24) OH

CH=CH-C oCH=CH-C o

CH=CH-C (1-25) — 0 一CH=CH-C (1-25) — 0 one

r1〇_0^ CH=CH-C—OOC-(CH2)2-C〇〇H (1-26) -13- 200916505 (式（1-1 )至（1-26 )中，R1及b分別意指與上述式 (1 )中相同之意）。以上述式（1 )表不之化合物之合成方法並無特別限制，可以有機化學慣用之方法適當進行。以下針對以上述式（1 )表示之化合物中之數種化合物說明其合成方法之例，但合成方法並不受限於該等。例如以上述式（1 - 2 )表示之化合物可例如藉由使羥基桂皮酸與化合物RlX(其中，R1與上述式（1)中相同之意，X爲鹵素原子）在鹼（例如碳酸鉀等）存在下反應後，接著在鹼金屬化合物（例如，氫氧化鈉等）存在下水解而合成。至於X之鹵素原子較好爲碘原子、溴原子或氯原子。上述式（1_4)表不之化合物可藉由例如下述之反應路徑合成。亦即，首先藉由使羥基苯甲酸甲酯與化合物 I^XCR1及X與上述相同之意）在鹼（例如碳酸鉀等）存在下反應後’接著在鹼金屬化合物（例如氫氧化鈉等）存在下水解，獲得以下述式（1 _ 4 - a )表示之中間物：R1〇_0^ CH=CH-C—OOC-(CH2)2-C〇〇H (1-26) -13- 200916505 (in equations (1-1) to (1-26), R1 and b respectively It means the same as in the above formula (1)). The method for synthesizing the compound represented by the above formula (1) is not particularly limited, and can be suitably carried out by a method conventionally used in organic chemistry. Hereinafter, an example of the synthesis method of the compound represented by the above formula (1) will be described, but the synthesis method is not limited thereto. For example, the compound represented by the above formula (1-2) can be, for example, by reacting hydroxycinnamic acid with the compound R1X (wherein R1 is the same as in the above formula (1), X is a halogen atom) in a base (for example, potassium carbonate or the like). After the reaction is carried out, it is then hydrolyzed in the presence of an alkali metal compound (for example, sodium hydroxide or the like) to synthesize. The halogen atom of X is preferably an iodine atom, a bromine atom or a chlorine atom. The compound represented by the above formula (1_4) can be synthesized by, for example, the following reaction route. That is, first, by reacting methyl hydroxybenzoate with the compounds I^XCR1 and X in the same manner as described above) in the presence of a base (for example, potassium carbonate or the like), followed by an alkali metal compound (for example, sodium hydroxide or the like). In the presence of hydrolysis, an intermediate represented by the following formula (1 _ 4 - a ) is obtained:

R1-0—COOH (1-4-a) (式（l-4-a)中’ R1係與上述式（；ι_4 )中相同之意）。接著使其成爲醯氯後在鹼（例如碳酸鉀等）存在下與羧基桂皮酸反應’可獲得以式（4 )表示之化合物。 -14 - 200916505 以上述式（1 -24 )表示之化合物可藉由例如甲醛與化合物I^XCR1及X與上述相同之意）在碳酸鉀等）存在下反應，接著使該反應產物在鹼物（例如氫氧化鈉等）存在下與乙醯基苯甲酸進合、脫水而合成。以上述式（1-25)表示之化合物可在上述式表示之化合物之合成中，經由使用乙醯基酚替代甲酸而合成。而且，以上述式（1-26)表示之化合物可藉鹼（例如三乙胺等）存在下使以上述式（1 -25 ) 合物與琥珀酸酐反應而合成。 [(B )環氧化合物] 本發明中所用之（B)環氧化合物爲一分子個以上環氧基之化合物，具有藉加熱進行交聯, 能。 (B )環氧化合物可舉例爲例如雙酚A型環酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂環族環氧樹脂、縮水甘油酯系環氧樹脂、縮水系環氧樹脂、雜環式環氧樹脂、具有環氧基之丙等。該等之市售品可舉例爲例如 EPOLITE EPOLITE3 002 (共榮社化學（股）製造）， 828、EPICOTE 152、環氧酚醛清漆180S (日本 (股）製造）等。使羥基苯鹼（例如金屬化合行醛醇縮 (1-24 ) 乙醯基苯由在有機表示之化中具有兩反應之功氧樹脂、脂、環狀甘油二胺燃酸樹脂 400E、 EPICOTE 環氧樹脂 -15- 200916505 該等中’以縮水甘油二胺系環氧樹脂較佳，更好爲以下述式（3)表示之化合物：R1-0—COOH (1-4-a) (In the formula (l-4-a), the 'R1 is the same as in the above formula (; ι_4)). Then, it is made to react with carboxycinnamic acid in the presence of a base (e.g., potassium carbonate or the like) to obtain a compound represented by the formula (4). -14 - 200916505 The compound represented by the above formula (1-24) can be reacted in the presence of, for example, potassium carbonate or the like by, for example, formaldehyde and the compound I^XCR1 and X, and then the reaction product is in the alkali In the presence of (for example, sodium hydroxide or the like), it is synthesized by combining with acetonitrile benzoic acid and dehydrating. The compound represented by the above formula (1-25) can be synthesized by using ethyl decyl phenol instead of formic acid in the synthesis of the compound represented by the above formula. Further, the compound represented by the above formula (1-26) can be synthesized by reacting the above formula (1 - 25) with succinic anhydride in the presence of a base (e.g., triethylamine or the like). [(B) Epoxy compound] The (B) epoxy compound used in the present invention is a compound having one or more epoxy groups, and has a crosslinking property by heating. (B) The epoxy compound can be exemplified by, for example, a bisphenol A type cyclic phenol novolak type epoxy resin, a cresol novolac type epoxy resin ring epoxy resin, a glycidyl ester type epoxy resin, a shrinkage type epoxy resin. , a heterocyclic epoxy resin, a C with an epoxy group, and the like. Such commercially available products can be exemplified by, for example, EPOLITE EPOLITE 3 002 (manufactured by Kyoeisha Chemical Co., Ltd.), 828, EPICOTE 152, epoxy novolac varnish 180S (manufactured by Japan). A hydroxyphenyl base (for example, a metallized aldol alcohol (1-24) ethenyl benzene having two reactions in the organic representation, an oxygen resin, a fat, a cyclic glycerin diamine flammable resin 400E, an EPICOTE ring Oxygen resin-15- 200916505 These are preferably a glycidyl diamine-based epoxy resin, more preferably a compound represented by the following formula (3):

⑶ (式（3)中，r爲具有芳香環或環己烷環之碳數6〜4 0之 2價有機基，其中r基中亦可含有氧原子或硫原子）。以上述式（3 )表示之化合物之具體例可舉例爲例如分別以下述式（3 _ ；!)至（3 -1 4 )表示之化合物： 200916505(3) (In the formula (3), r is a divalent organic group having 6 to 40 carbon atoms having an aromatic ring or a cyclohexane ring, wherein the r group may further contain an oxygen atom or a sulfur atom). Specific examples of the compound represented by the above formula (3) can be exemplified by, for example, compounds represented by the following formulas (3 _ ;!) to (3 -1 4 ): 200916505

(3-7) -17- 200916505(3-7) -17- 200916505

(B )環氧化合物，爲有效地引起交聯反應之目的，亦可與鹼觸媒倂用。該鹼觸媒hJ舉例爲例如1 -苄基-2 -甲基咪唑等。 [聚合物（C )] 及酸胺醯聚由白選含包 I )8 c-1 Γν 物合聚之用所中明發本 200916505 聚醯亞胺組成之群之至少一種者。 [聚醯胺酸] 聚醯胺酸可藉由使四羧酸二酐與二胺化合物，較好在有機溶劑中反應而合成。聚醯胺酸之合成中所用之四羧酸二酐可舉例爲例如下列之芳香族四羧酸二酐等：2，3,5 -三羧基環戊基乙酸二酐、丁烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、3,5,6-三羧基降冰片烯-2-乙酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、1 ,3,3 a, 4，5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基）-萘并[l，2-c]-呋喃-1,3-二酮、l，3,3a,4,5,9b-六氫-5(四氫-2,5-二氧代-3-呋喃基）-8-甲基-萘并[1，2-£；]-呋喃-1，3-二酮、5- (2,5-二氧代四氫呋喃基）-3-甲基-3-環己烯-1,2-二羧酸二酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、分別以下述式（T-1 )至（T- 1 4 )表示之四羧酸二酐等脂防族或脂環族四羧酸二酐： -19- 200916505(B) The epoxy compound may be used in combination with a base catalyst for the purpose of effectively causing a crosslinking reaction. The base catalyst hJ is exemplified by, for example, 1-benzyl-2-methylimidazole. [Polymer (C)] and acid amine 聚 Polymerization is selected from the group consisting of I) 8 c-1 Γ ν 聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚[Polyuric acid] Polylysine can be synthesized by reacting a tetracarboxylic dianhydride with a diamine compound, preferably in an organic solvent. The tetracarboxylic dianhydride used in the synthesis of polyamic acid can be exemplified by, for example, the following aromatic tetracarboxylic dianhydrides: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic acid Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornene-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3 a , 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[1,2-£;]-furan -1,3-diketone, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2]- An anti-family or alicyclic ring such as tetracarboxylic acid dianhydride represented by the following formulas (T-1) to (T-14), respectively, of oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Group of tetracarboxylic dianhydrides: -19- 200916505

(Τ-2) (T-l)(Τ-2) (T-l)

(Τ-8) (Τ-9)(Τ-8) (Τ-9)

Ό (Τ^3) (Τ-4)Ό (Τ^3) (Τ-4)

(ΤΜΟ)(ΤΜΟ)

(Τ-δ)(Τ-δ)

(Τ-12)(Τ-12)

(Τ-6)(Τ-6)

(Τ-13)(Τ-13)

(Τ·7)(Τ·7)

(Τ-14) 20- 200916505 均苯四酸二酐、3,3’，4,4’-聯苯颯四羧酸二酐、 1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3’，4,4’-聯苯醚四羧酸二酐、3,3’，4,4’-二甲基二苯基矽烷四羧酸二酐、3,3’，4,4’-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙（3,4-二羧基苯氧基）二苯基硫醚二酐、 4,4’ -雙（3,4 -二羧基苯氧基）二苯基砸二酐、4,4’-雙 (3,4-二羧基苯氧基）二苯基丙烷二酐、3,3’，4,4’-全氟異亞丙基二酞酸二酐、3,3’，4，4’-聯苯四羧酸二酐、雙（酞酸）苯基膦氧化物二酐、對-伸苯基-雙（三苯基酞酸）二酐、間-伸苯基-雙（三苯基酞酸）二酐、雙（三苯基酞酸）-4,4’-二苯基醚二酐、雙（三苯基酞酸）-4,4’-二苯基甲烷二酐、分別以下述式（T-15 )至（T-18 )表示之四羧酸二酐等： -21 - 200916505(Τ-14) 20- 200916505 Pyromellitic dianhydride, 3,3',4,4'-biphenyl fluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyl decane Tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis (3, 4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylate Acid dianhydride, bis(decanoic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphosphonate) dianhydride, m-phenylene-bis(triphenylphosphonate) dianhydride , bis(triphenylphosphonic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphosphonic acid)-4,4'-diphenylmethane dianhydride, respectively, according to the following formula (T- 15) to (T-18), such as tetracarboxylic dianhydride, etc.: -21 - 200916505

該等中較佳者可舉例爲1，3,33,4,5,913_六氫-5-(四氫- 2,5-二氧代-3-呋喃基）-萘并[1,24]-呋喃-1,3-二酮、 1.3.3a.4,5.9b-六氫-5 (四氫- 2,5-二氧代-3-呋喃基）-8-甲基-萘并[l，2-c]-呋喃-1,3-二酮、2,3,5-三羧基環戊基乙酸二酐、丁烷四羧酸二酐、1，3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、均苯四酸二酐、 3,3’，4,4’-聯苯颯四羧酸二酐、1,4,5,8-萘四羧酸二酐、 -22- 200916505 2,3,6,7-萘四羧酸二酐、3,3’，4,4’-聯苯醚四羧酸二酐及以上述式（T-l) 、（T-2)及（T-15)至（T-18)分別表示之四羧酸二酐。該等四羧酸二酐可單獨或組合2種以上使用。至於上述聚醯胺酸合成中所用之二胺化合物可舉例爲例如對-苯二胺、間-苯二胺、4,4 ’ -二胺基二苯基甲烷、 4,4’-二胺基二苯基乙烷、4,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基颯、3,3’-二甲基-4,4’-二胺基聯苯、4,4、二胺基苯甲醯苯胺、4,4’-二胺基二苯基醚、1，5-二胺基萘、 3 , 3 ’ -二甲基-4，4 ’ -二胺基聯苯、5 -胺基-1 - ( 4 ’ -胺基苯基）-1,3,3 -三甲基茚滿、6 -胺基-1-( 4’ -胺基苯基）-1,3,3-三甲基茚滿、3,4’-二胺基二苯基醚、2,2-雙（4-胺基苯氧基）丙烷、2,2-雙[4- ( 4-胺基苯氧基）苯基]丙烷、 2,2-雙[4- (4-胺基苯氧基）苯基]六氟丙烷、2,2-雙（4-胺基苯基）六氟丙烷、2,2-雙[4- (4-胺基苯氧基）苯基]颯、 1,4-雙（4-胺基苯氧基）苯、1，3 _雙（4-胺基苯氧基）苯、 1,3 -雙（3 -胺基苯氧基）苯、9,9 -雙（4 -胺基苯基）-10 -氫蒽、2,7 -二胺基芴、9,9 -雙（4 -胺基苯基）芴、4,4’-亞甲基-雙（2-氯苯胺）、2,2’，5,5’-四氯-4,4’-二胺基聯苯、 2,2’-二氯-4,4’-二胺基-5,5’-二甲氧基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、4,4’-(對-伸苯基異丙叉）雙苯胺、 4,4’-(間-伸苯基異丙叉）雙苯胺、2,2-雙[4- ( 4-胺基-2-三氟甲基苯氧基）苯基]六氟丙烷、4,4’-二胺基-2，2’-雙 (三氟甲基）聯苯、4,4’-雙[(4-胺基-2_三氟甲基）苯氧 -23- 200916505 基]-八氟聯苯、6-(4-苯丙烯醯苯基（（；11&1(；〇11>^1)氧基）己基氧基（2,4-二胺基苯）、6- (4’-氟-4-苯丙烯醯苯基氧基）己基氧基（2,4-二胺基苯）、8- (4-苯丙烯醯苯基氧基）辛基氧基（2,4-二胺基苯）、8- (4’-氟-4-苯丙烯醯苯基氧基）羊基氧基（2,4 - 一胺基苯）、1-十一院氧基-2,4_ 二胺基苯、1-十四烷氧基-2,4 -二胺基苯、1-十五烷氧基-2,4-二胺基苯、1-十六烷氧基-2,4-二胺基苯、1-十八烷氧基-2,4 - 一胺基本、1-膽巢燒基氣基-2,4 - _胺基苯、1-膽巢烷基烷氧基-2,4 -二胺基苯、十二烷氧基（3,5 -二胺基苯甲醯基）、十四烷氧基（3,5 -二胺基苯甲醯基）、十五烷氧基（3,5 -二胺基苯甲醯基）、十六烷氧基（3, 5_二胺基苯甲醯基）、十八烷氧基（3,5 -二胺基苯甲醯基）、膽巢烯基氧基（3,5 -二胺基苯甲醯基）、膽巢烷基氧基（3 ,5 -二胺基苯甲醯基）、（2,4-二胺基苯氧基）棕櫚酸酯、 (2,4-二胺基苯氧基）硬脂酸酯、（2,4-二胺基苯氧基）-4-三氟甲基苯甲酸酯、分別以下述式（D-1 )至D-5 )表示之二胺化合物等芳香族二胺；Preferred among these are, for example, 1,3,33,4,5,913-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,24]- Furan-1,3-dione, 1.3.3a.4,5.9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[1, 2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl fluorene Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, -22- 200916505 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-linked A phenyl ether tetracarboxylic dianhydride and a tetracarboxylic dianhydride represented by the above formulas (T1), (T-2) and (T-15) to (T-18), respectively. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types. As the diamine compound used in the above polyamic acid synthesis, for example, p-phenylenediamine, m-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4'-diamino group can be exemplified. Diphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4'-diamino Biphenyl, 4,4, diaminobenzimidanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4' -diaminobiphenyl, 5-amino-1 -( 4 '-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-( 4'-aminobenzene 1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane, 2,2-double [ 4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-amino group Phenyl) hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3 _ double (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7- Diamine guanidine, 9,9-double 4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2-bis[4-(4-amino- 2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4 -amino-2_trifluoromethyl)phenoxy-23- 200916505 base]-octafluorobiphenyl, 6-(4-phenylpropenylphenyl) ((;11&1(;〇11>^1) oxygen Hexyloxy (2,4-diaminobenzene), 6-(4'-fluoro-4-phenylpropenylphenyloxy)hexyloxy (2,4-diaminobenzene), 8- (4-Benzene fluorenyl phenyloxy) octyloxy (2,4-diaminobenzene), 8-(4'-fluoro-4-phenylpropenylphenyloxy) sorbyloxy (2 , 4-aminoaminobenzene), 1-Eleventhyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy- 2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene 1-octadecyloxy-2,4-diamine basic, 1-cholesteryl-based gas-2,4-aminobenzene, 1-cholestylalkylalkoxy-2,4-diamine Benzobenzene, dodecyloxy (3,5-diaminobenzimidyl), tetradecyloxy (3,5-diaminobenzimidyl), pentadecyloxy (3,5) -diaminobenzimidyl),hexadecanyloxy (3,5-diaminobenzimidyl), octadecyloxy (3,5-diaminobenzylidene), biliary Alkenyloxy (3,5-diaminobenzimidyl), cholestyloxy (3,5-diaminobenzylidene), (2,4-diaminophenoxy) Palmitate, (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy)-4-trifluoromethylbenzoate, respectively, according to the following formula ( An aromatic diamine such as a diamine compound represented by D-1) to D-5);

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二胺基四苯基噻吩等之具有雜原子之芳香族二胺；二甲苯二胺、1,3-丙烷二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、七亞甲基二胺、八亞甲基二胺、九亞甲基二胺、1,4-二胺基環己烷、異冰片基二胺、四氫二環戊二烯二胺、六氫-4,7-甲橋伸茆滿二亞甲基二胺、三環 [6.2_1.02’7]-伸十一烷基二甲基二胺、4,4’-亞甲基雙（環己基胺）等之脂肪族及脂環式二胺；二胺基六甲基二矽氧烷等之二胺基有機矽氧烷等。該等中，較佳者可舉例爲對-苯二胺、4,4 ’ -二胺基二苯基甲烷、1，5-二胺基萘、2,7-二胺基芴、4,4’-二胺基二苯基醚、4,4’-(對-伸苯基二異亞丙基）雙苯胺、2,2-雙 [4-( 4-胺基苯氧基）苯基]六氟丙烷、2,2-雙（4-胺基苯基）六氟丙烷、2,2 -雙[4- (4-胺基-2-三氟甲基苯氧基）苯 -25- 200916505 基]六氟丙垸、4,4，-二胺基·2,2，-雙（三氟甲基）聯苯、 4,4’-雙[(4_胺基_2·三氟甲基）苯氧基]•八氟聯苯、卜十六烷氧基-2,4-二胺基苯、丨-十八烷氧基_2,4_二胺基苯、卜膽巢烯基氧基-2,4 -二胺基苯、1-膽巢烷基氧基_2,4_二胺基苯、十六烷氧基（3,5-二胺基苯甲醯基）、十八烷氧基 (3,5 -一 §女基本甲醯基）、膽巢嫌基氧基（3二胺基苯甲醯基）、膽巢烷基氧基（3,5 -二胺基苯甲酿基）及分別以上述式（D-1)至（D-5)表示之二胺。該等二胺可單獨使用或組合兩種以上使用。供給至聚醯胺酸合成反應中之四羧酸二酐與二胺化合物之使用比例’相對於1當量之二胺化合物中所含胺基，四羧酸二酐之酸酐基比例較好爲0.2~2當量，更好爲〇·3〜1.2當量之比例。聚醯胺酸之合成反應較好在有機溶劑中，且較好在 _2G°C〜150°C，更好在0〜100°C之溫度條件下，且較好進行 0_5〜24小時，更好進行2〜10小時。其中，有機溶劑並無特別限制，只要可使合成之聚醯胺酸溶解即可，可舉例爲例如N_甲基-2-吡略啶酮、Ν,Ν-二甲基乙醯胺、Ν,Ν-二甲基甲醯胺、Ν,Ν·二甲基咪唑啶酮、二甲基亞碾、γ -丁內酯、四甲基尿素、六甲基磷三醯胺等非質子系極性溶劑：間-甲酚、二甲酚、酚、鹵化酚等酚系溶劑等。有機溶劑之使用量（a :其中，有機溶劑與後述之弱溶劑倂用時，指該等之合計使用量）較好爲使四羧酸二酐與二胺化合物之總量（b )，相對於反應溶液之總量（a + b )爲0.1〜5 0 -26- 200916505 重量％之量，更好爲5~30重量％之量。又，於上述有機溶劑中，可在不使生成之聚醯胺酸析出之範圍內倂用爲聚醯胺酸之弱溶劑之醇類、酮類、酯類、醚類、鹵化烴、烴等。至於該等弱溶劑之具體例列舉有例如甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、 1,4-丁二醇、三乙二醇、乙二醇單甲基醚、乳酸乙酯、乳酸丁酯、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、草酸二乙酯、丙二酸二乙酯、二***、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、四氫呋喃、二氯甲烷、 1，2_二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰·二氯苯、己烷、庚烷、辛烷、苯、甲苯、二甲苯等。聚醯胺酸製造時在有機溶劑中倂用如上述之弱溶劑之情況，其使用比例可在不使生成之聚醯胺酸析出之範圍內適當設定，但較好爲全部溶劑之5 0重量％以下。如上述獲得使聚醯胺酸溶解之反應溶液。該反應溶液可供給至液晶配向劑之調製，使反應溶液中所含之聚醯胺酸單離後供給至液晶配向劑之調製，或者將經單離之聚醯胺酸純化後供給至液晶配向劑之調製。聚醯胺酸之單離可將上述反應溶液注入大量之弱溶劑中而獲得析出物’並使 -27- 200916505 該析出物於減壓下乾燥之方法，或者，可藉由以蒸發器減壓餾除反應溶液之方法進行。又，可使該聚醯胺酸再度溶解於有機溶劑中，接著以弱溶劑析出之方法，或者可以蒸發器減壓餾除之步驟進行一次或數次之方法，使聚醯胺酸純化。 [聚醯亞胺] 本發明之聚醯亞胺可藉由使如上述般獲得之聚醯胺酸所具有之醯胺酸構造脫水閉環而製造。此時，可使醯胺酸構造之全部經脫水閉環完全醯亞胺化，或者亦可僅使醯胺酸構造之一部分脫水閉環成爲醯胺酸構造與醯亞胺構造倂存之部分醯亞胺化物。聚醯胺酸之脫水閉環爲（i )藉由將聚醯胺酸加熱之方法，或（Π )藉由將聚醯胺酸溶解於有機溶劑中，於該溶液中添加脫水劑及脫水閉環觸媒，並視情況加熱之方法而進行。上述（i)之使聚醯胺酸加熱之方法中之反應溫度較好爲50〜200t：，更好爲60〜170°C。反應溫度未達5(TC則難以充分進行脫水閉環反應，反應溫度超過200°C則有使所得醯亞胺化聚合物之分子量降低之情況。將聚醯胺酸加熱之方法屮之反應時間較好爲0.5〜4 8小時，更好爲2〜2 0 小時。另一方面，上述（ii )之於聚醯胺酸溶液中添加脫水劑及脫水閉環觸媒之方法中，脫水劑可使用例如乙酸酐、 -28- 200916505 丙酸酐、三氟乙酸酐等酸酐。脫水劑之用量，相對於聚醯胺酸構造單位1莫耳’較好爲0.01〜20莫耳。脫水閉環觸媒可使用例如吡啶、三甲基吡啶、二甲基吡啶、三乙基胺等三級胺。但，並不限於該等。脫水閉環觸媒之使用量，相對於1莫耳所用之脫水劑，較好爲〇 · 〇 1〜1 〇莫耳。脫水閉環反應中所用之有機溶劑可舉例爲於聚醯胺酸合成中所用者例示之有機溶劑。脫水閉環反應之反應溫度較好爲 0〜18 0°c，更好爲l〇~15〇°C。反應時間較好爲0.5〜20小時，更好爲1〜8小時。上述方法（i )中獲得之聚醯亞胺可直接供給至液晶配向劑之調製，或者亦可將所得聚醯亞胺純化後供給至液晶配向劑之調製。另一方面，依據上述方法（i i )可獲得含有聚醯亞胺之反應溶液。該反應溶液可直接供給至液晶配向劑之調製，亦可自反應溶液去除脫水劑及脫水閉環觸媒後供給至液晶配向劑之調製，亦可使聚醯亞胺單離後供給至液晶配向劑之調製，或者亦可將經單離之聚醯亞胺純化後供給至液晶配向劑之調製中。自反應溶液去除脫水劑及脫水閉環觸媒可適當的使用例如溶劑置換等方法。聚醯亞胺之單離、純化可藉由與上述聚醯胺酸之單離、純化方法同樣進行操作而進行。 [其他聚合物] 本發明中之聚合物（C)可僅包含選自由如上述聚醯胺酸及聚醯亞胺組成之群之至少一種’亦可包含除選自由 -29 - 200916505 聚醯胺酸及聚醯亞胺組成之群之至少一種以外之其他聚合物。其他聚合物可用於改善溶液特性及電特性，其實例可舉例爲例如聚醯胺酸酯、聚酯、聚醯胺、聚矽氧烷、織維素衍生物、聚乙縮醛、聚苯乙烯衍生物、聚（苯乙烯-苯基馬來醯亞胺）衍生物、聚（甲基）丙烯酸酯等。本發明之聚合物（C)爲含有其他聚合物者之情況，其含有比例相對於聚合物（c )之總量’較好爲5 0重量％以下。本發明之聚合物（C)最好爲不含其他聚合物者。 [液晶配向劑] 本發明之液晶配向劑，含有如上述之化合物（A )、 (B )環氧化合物以及聚合物（C )作爲必要成分且較好調製爲溶液。本發明之液晶配向劑除上述（A )〜（c )成分以外，可視情況含有其他成分。該等其他成分可舉例爲例如敏輻射線***聯劑、感應性矽烷化合物等。上述敏輻射線***聯劑可舉例爲例如以上述式（1 ) 表示之化合物與上述縮水甘油二胺系環氧樹脂之反應產物等。以上述式（1 )表示之化合物與縮水甘油二胺系環氧樹脂之反應時所用二者之比例’相對於1當量之縮水甘油二胺系環氧樹脂，以上述式（1)表示之化合物之量較好爲0.01〜10當量，較好爲〇.2 ~2當量。反應溫度較好爲 2〇〜2 5(TC，更好爲50~18 0°C，反應時間較好爲〇·5〜200小 -30- 200916505 時，更好爲1〜1 0小時。反應時亦可視情況添加適當之鹼觸媒以促進反應。反應較好在有機溶劑中進行。此處可使用之有機溶劑以非質子性有機溶劑較佳，具體之實例可舉例爲例如1 -甲基-2-吡咯啶酮等。在有機溶劑中進行反應時，相對於反應溶液之總量，以上述式（1 )表示之化合物與上述縮水甘油二胺系環氧樹脂之總重量之比例（固體成分濃度）較好爲1重量％以上，更好爲5〜50重量％。上述官能性矽烷化合物係爲了提升所得液晶配性膜與基板之接著性之目的而使用。官能性矽烷化合物可列舉爲例如3 -胺基丙基三甲氧基矽烷、3 -胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、Ν-(2-胺基乙基）-3-胺基丙基三甲氧基矽烷、ν-(2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、3_脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、Ν-乙氧基羰基-3-胺基丙基三甲氧基矽烷、Ν-乙氧基羰基-3-胺基丙基三乙氧基矽烷、Ν-三乙氧基矽烷基丙基三伸乙基三胺、Ν_三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基― 1，4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3，6-二氮雜壬基乙酸酯、Ν-苄基-3-胺基丙基三甲氧基矽烷、Ν-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、Ν-苯基-3-胺基丙基三乙氧基矽烷、Ν-雙（環氧乙烷）-3-胺基丙基三甲氧基矽烷、Ν-雙 -31 - 200916505 (環氧乙烷）-3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、2-(3,4-環氧基環己基）乙基三甲氧基矽烷等，另外可舉例爲特開昭63 -29 1 922號公報中所述之四羧酸二酐與具有胺基之矽烷化合物之反應物等。本發明之液晶配向劑所含各成分之使用比例如下：化合物（A )之使用比例，相對於100重量份之聚合物合計（聚合物（C )之合計，亦即聚醯胺酸、聚醯亞胺及其他聚合物之合計。以下同），較好爲1〜100重量份，更好爲10~50重量份。 (B )環氧化合物之使用比例，相對於1 〇〇重量份之聚合物之合計，較好爲1〜100重量份，更好爲10〜50重量份。與（B)環氧化合物一起使用鹼觸媒時，鹼觸媒之使用比例相對於1 00重量份之環氧化合物較好爲50重量份以下，更好爲2 0重量份以下。本發明之液晶配向劑含有感熱***聯劑時，其使用比例，相對於聚合物合計1 〇〇重量份，較好爲5 0重量份以下，更好爲2 0重量份以下。本發明之液晶配向劑含有敏輻射線***聯劑時’其使用比例，相對於聚合物合計1 〇〇重量份，較好爲50重量份以下，更好爲20重量份以下。本發明之液晶配向劑含有感應性矽烷化合物時’其使用比例，相對於聚合物合計100重量份’較好爲50重量份以下’更好爲2 0重量份以下。本發明之液晶配向劑調配成溶液狀態時使用之溶劑只 -32- 200916505 要爲可使上述（A) ~(C)之各成分及任意含有之其他成分溶解，但不與該等反應之有機溶劑即可，而無特別限制。該等溶劑可舉例爲例如聚醯胺酸之合成中使用者所例示之有機溶劑。此時，亦可合倂使用聚醯胺酸之合成中所用者例示之弱溶劑。該等有機溶劑可單獨使用，或者組合兩種以上使用。本發明之液晶配向劑調製中所用之較佳溶劑爲上述有機溶劑中之一種或組合兩種以上而獲得者，爲於下述較佳之固體成分濃度中不使液晶配向劑中所含各成分析出，且液晶配向劑之表面張力在25〜40mN/m之範圍者。本發明之液晶配向劑之固體成分濃度，亦即液晶配向劑中溶劑以外之全部成分之重量佔液晶配向劑總重量之比例係考量黏性、揮發性等加以選擇，但較好爲1〜1 〇重量％之範圍。本發明之液晶配向劑係塗佈在基板表面上，形成液晶配向膜之塗膜，但當固體成分未達1重量％時，該塗膜之膜厚過小而有難以獲得良好液晶配向膜之情況。另一方面，當固體成分濃度超過10重量％時，塗膜之膜厚過大而難以獲得良好的液晶配向膜，又，液晶配向劑之黏性增大會有塗佈特性不足之情況。特別好之固體成分濃度範圍係隨液晶配向劑塗佈於基板上時採用之方法而不同。例如採用旋塗法時以〗_5〜4.5重量％之範圍最佳。採用印刷法時之固體成分濃度爲3〜9重量％之範圍，藉此溶液黏度以 12〜5 OmPa . S之範圍爲最佳。採用噴墨法時，固體成分濃度爲1〜5重量％之範圍，藉此溶液黏度以3〜15mPa· S之 -33 - 200916505 範圍爲最佳。調製本發明之液晶配向劑時之溫度較好 °C，更好爲 20°C ~60°C。 [液晶配向膜之形成方法] 本發明之液晶配向劑可適當使用於形成液至於形成液晶配向膜之方法，可舉例有例如在本發明之液晶配向劑形成塗膜，接著藉由對該射線賦予液晶配向能之方法。首先，於設有圖案狀透明導電膜之基板的側，藉由例如輥塗佈法、旋塗法、印刷法、噴塗佈方法，塗佈本發明之液晶配向劑。塗佈後塗佈之液晶配向劑液垂之目的，較好實施預烤）。預供烤溫度較好爲3 0〜2 0 0 °C，更好爲且最好爲40〜100°C。預烘烤時間較好爲〇.1 好爲0.5 ~5分鐘。隨後，爲了將溶劑完全去除施燒成（後烘烤）步驟。該後烘烤溫度較好爲更好爲120〜25〇°C。後烘烤時間較好爲1〜300 爲2〜120分鐘。此處形成之塗膜膜厚，爲去除厚，較好爲0.001〜l//m，更好爲0.005~0.5yn 作爲上述基板，可使用例如浮法玻璃、鈉玻璃；聚對苯二甲酸乙二醇酯、聚對苯二甲酸聚醚楓、聚碳酸酯等之塑膠所構成之透明基板上述透明導電膜可使用由Sn〇2所構成之爲0。(：〜200 晶配向膜。基板上塗佈塗膜照射輻透明導電膜墨法等適宜，爲了防止加熱（預烘 4 0 ~ 1 5 0 〇C ’ ί 0分鐘，更之目的而實 8 0 〜3 0 0 〇C ’ 分鐘，更好溶劑後之膜 1 ° 鈣玻璃等之丁二醇酯、〇 NESA 膜' -34- 200916505 由In203-Sn02所構成之ITO膜等。該等透明導電膜之圖案化可藉由係使用光·蝕刻法或於形成透明導電膜之際使用光罩之方法。液晶配向劑塗佈時，爲了使基板或透明導電膜與塗膜之接著性更加良好，亦可於基板及透明導電膜上，預先塗佈官能性矽烷化合物、鈦酸酯等。接著，藉由於上述塗膜上，照射直線偏光或部分偏光之輻射線或無偏光之輻射線，視情況進而在1 5 0〜2 5 0 °C之溫度下較好進行1~120分鐘之加熱處理，而賦予液晶配向能。此處，作爲輻射線，例如可使用包含150〜8 OOnm波長之光之紫外線以及可見光線，但較好爲包含3 00〜400nm波長之光之紫外線。使用之輻射線爲直線偏光或部分偏光時’照射可對基板面垂直之方向進行，亦可自用以賦予預傾角之傾斜方向進行，又，亦可結合該等而進行。於照射無偏光輻射線時，照射方向有必要爲傾斜方向。至於所使用之光源，可使用例如低壓水銀燈、高壓水銀燈 '氘燈、金屬鹵素燈、氬共振燈、氙氣燈、準分子雷射等。上述之較佳波長領域之紫外光，可藉由同時利用上述光源及例如濾光片、繞射光柵等手段而獲得。至於輻射線照射量，較好爲U/m2以上、未達10,000 J/m2，更好爲10〜3,000J/m2。又，於藉以往已知之液晶配向劑形成之塗膜上藉由光配向法賦予液晶配向能時，輻射線照射量有必要爲1 〇，〇〇〇 j / m 2以上。然而，若使用本發明之液晶配向劑’於光配向法時之輻射線照射量未達〗〇，〇〇〇 -35- 200916505 J/m2，進而在3，000 J/m2以下，特別^ 其中即使是在8 00J/m2以下亦可賦予可减低液晶顯示元件之製造成本。又’本說明書中所謂之「預傾角與基板面形成之方向傾斜之角度。 [液晶顯示元件之製造方法] 使用本發明之液晶配向劑形成液如如下列般製造。準備一對（2片）形成有如上述板，使其所具有之液晶配向膜相對向輻射線之偏光方向成爲特定角度，以圍部分密封，注入、充塡液晶，且封液晶單元。接著，較好將液晶單元加向同性之溫度後，冷去至室溫，去除接著，在其兩面上，藉由以使偏晶配向膜之配向容易軸成特定角度之成液晶顯示元件。於液晶配向膜爲水有液晶配向膜之2片基板上，藉由調輻射線之偏光方向所成之角度以及各度，而可獲得具有TN型或STN型液件。另一方面，於液晶配向膜爲垂直成有液晶配向膜之2片基板以使配向形之方式構成單元，於其中，藉由使在 1，000J/m2 以下，良好之液晶配向性，」，表不液晶分子自晶液晶顯示元件可例般之液晶配向膜之基以與所照射直線偏光密封劑將基板間之周住液晶注入口而構成熱至使所用液晶成各注入時之流動配向。光方向與各基板之液方式貼合偏光板，形平配向性時，於形成 I整所照射之直線偏光基板及與偏光板之角 :晶卓兀之液晶顯不兀配向性之情況，使形容易軸之方向成爲平偏光板之偏光方向與 -36- 200916505 配向容易軸成45度之角度貼合，可成爲具有垂直配向型液晶單元之液晶顯示元件。作爲上述密封劑，可使用例如含有作爲間隔物之氧化鋁球及硬化劑之環氧樹脂等。至於上述液晶，可使用例如向列型液晶、層列型液晶等。於TN型液晶單元或S TN型液晶單元時，較好具有形成向列型液晶之正的介電各向異性者，例如可使用聯苯系液晶、苯基環己烷系液晶、酯系液晶、三聯苯系液晶、聯苯環己烷系液晶、嘧啶系液晶、二噁烷系液晶、雙環辛烷系液晶、方院（Cubane)系液晶等。另外上述液晶中，亦可進而添加使用例如膽醯氯、膽醯基壬酸酯、膽醯基碳酸酯等膽固醇型液晶；以商品名「C- 1 5」、「CB- 1 5」 (Merck公司製）販售之對掌性劑；對-去甲矽氧烷苄叉-對-胺基-2-甲基丁基月桂酸酯等強介電性液晶。另一方面，於垂直配向型液晶單元時，較好具有形成層列型液晶之負的介電各向異性者，例如可使用二氰基苯系液晶、嗒嗪系液晶、薛福（Schiff )鹼系液晶、偶氮氧 (azoxy )系液晶、聯苯系液晶、苯基環己烷系液晶等。至於在液晶單元外側上所使用之偏光板，可舉例有使聚乙烯醇進行延伸配向同時吸收碘之稱爲「Η膜」之偏光膜以乙酸纖維素保護膜挾持之偏光板或以Η膜本身構成之偏光板等。實施例 -37- 200916505 以下藉由實施例更具體說明本發明，但本發明並不受該等實施例之限制。 <化合物（A )之合成> 合成例1 於1升琉型反應瓶中饋入82克對-經基桂皮酸、304 克之碳酸鉀及400毫升之N -甲基-2-吡咯啶酮，在室溫下進行攪拌1小時後，添加166克之1-溴戊烷，且在100。(：下攪拌5小時。隨後，減壓餾除溶劑。接著，於其中添加 4 8克之氫氧化鈉及4 0 0毫升水，且回流3小時進行水解反應。反應結束後，以鹽酸中和反應系統，回收產生之沉澱物，且以乙醇再結晶，獲得8 0克以下式（1 - 2 - 1 )表示之化合物（以下稱爲「化合物（1 -2- 1 )」）之白色結晶：An aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; xylene diamine, 1,3-propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene di Amine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isobornyldiamine, tetrahydrodicyclopentadienediamine, Hexahydro-4,7-methyl bridge diazide dimethylene diamine, tricyclo[6.2_1.02'7]-edecyldimethyldiamine, 4,4'-methylene double An aliphatic or alicyclic diamine such as (cyclohexylamine); a diamine organooxane such as diamine hexamethyldioxane; and the like. Among these, preferred are p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diamino fluorene, 4, 4 '-Diaminodiphenyl ether, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)benzene-25- 200916505 Hexafluoropyrene, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2·trifluoromethyl) Phenoxy]•octafluorobiphenyl, hexadecaneoxy-2,4-diaminobenzene, fluorenyl-octadecyloxy-2,4-diaminobenzene, b-choline alkenyl oxygen Base-2,4-diaminobenzene, 1-cholestyloxy 2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzylidene), 18 Alkoxy (3,5-a § female basic carbaryl), cholestyryloxy (3 diaminobenzhydryl), cholestyloxy (3,5-diaminobenzoic) The base is represented by a diamine represented by the above formulas (D-1) to (D-5). These diamines may be used singly or in combination of two or more. The ratio of use of the tetracarboxylic dianhydride to the diamine compound to be supplied to the polyaminic acid synthesis reaction is '0.2 based on the amine group contained in the equivalent amount of the diamine compound, and the tetracarboxylic dianhydride is preferably 0.2. ~2 equivalents, more preferably 〇·3~1.2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent, and preferably at _2 G ° C to 150 ° C, more preferably at a temperature of 0 to 100 ° C, and preferably for 0 to 5 to 24 hours, more preferably Good to carry out 2 to 10 hours. The organic solvent is not particularly limited as long as the synthetic polyaminic acid can be dissolved, and examples thereof include N-methyl-2-pyrrolidone, anthracene, fluorene-dimethylacetamide, and hydrazine. , aprotic polarity such as Ν-dimethylformamide, hydrazine, hydrazine dimethylimidazolidinone, dimethyl arylene, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide Solvent: a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent used (a: wherein the organic solvent and the weak solvent to be described later are used in a total amount) is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is relatively The total amount (a + b ) of the reaction solution is 0.1 to 5 0 -26 to 200916505% by weight, more preferably 5 to 30% by weight. Further, in the above organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like which is a weak solvent of polylysine may be used in a range in which the produced polyamine acid is not precipitated. . Specific examples of such weak solvents include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, Ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl Ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether , ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane , 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. In the case where polyacrylic acid is produced by using a weak solvent as described above in an organic solvent, the ratio of use thereof can be appropriately set within a range in which the produced polyamic acid is not precipitated, but preferably 50% of the total solvent. %the following. A reaction solution for dissolving polylysine was obtained as described above. The reaction solution can be supplied to a liquid crystal alignment agent, and the polylysine contained in the reaction solution can be supplied to the liquid crystal alignment agent after being separated, or the separated polyamic acid can be purified and supplied to the liquid crystal alignment. Modulation of the agent. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a weak solvent to obtain a precipitate, and drying the precipitate of -27-200916505 under reduced pressure, or by decompressing with an evaporator. The method of distilling off the reaction solution is carried out. Further, the polylysine may be further dissolved in an organic solvent, followed by precipitation by a weak solvent, or may be carried out one or several times by a step of distilling off under reduced pressure in an evaporator to purify the polyamic acid. [Polyimide] The polyimine of the present invention can be produced by dehydration ring closure of a proline structure having a polyamic acid obtained as described above. At this time, all of the proline structure can be completely deuterated by dehydration, or only a part of the proline structure can be dehydrated and closed to form a part of the quinone imine structure and the quinone imine structure. Compound. The dehydration ring of polylysine is (i) by heating poly-proline, or (Π) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and dehydrating ring-contact in the solution. The medium is carried out according to the method of heating. The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 t: more preferably from 60 to 170 °C. When the reaction temperature is less than 5 (TC is difficult to sufficiently carry out the dehydration ring-closure reaction, and when the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may be lowered. Preferably, it is 0.5 to 4 8 hours, more preferably 2 to 2 0 hours. On the other hand, in the method of (ii) adding a dehydrating agent and a dehydration ring-closing catalyst to the poly-proline solution, the dehydrating agent can be used, for example. Acetic anhydride, -28-200916505 Anhydride anhydride such as propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the structural unit of polyglycine. The dehydration ring-closing catalyst can be used, for example. a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst used is preferably relative to the dehydrating agent used for 1 mol. 〇· 〇1~1 〇莫耳. The organic solvent used in the dehydration ring closure reaction can be exemplified by the organic solvent exemplified in the synthesis of polylysine. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 18 0 °c. More preferably l〇~15〇°C. Reaction time Preferably, it is 0.5 to 20 hours, more preferably 1 to 8 hours. The polyimine obtained in the above method (i) can be directly supplied to the liquid crystal alignment agent, or the obtained polyimine can be purified and supplied to The preparation of the liquid crystal alignment agent. On the other hand, according to the above method (ii), a reaction solution containing polyimine can be obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, and the dehydrating agent can be removed from the reaction solution and dehydrated. After the closed-loop catalyst is supplied to the liquid crystal alignment agent, the polyimine may be supplied to the liquid crystal alignment agent after being separated, or the mono-sized polyimine may be purified and supplied to the liquid crystal alignment agent. In the preparation, the dehydrating agent and the dehydration ring-closure catalyst can be appropriately removed from the reaction solution, for example, by solvent replacement, etc. The separation and purification of the polyimine can be carried out by the same method as the separation and purification of the above polyamic acid. [Other polymers] The polymer (C) in the present invention may comprise only at least one selected from the group consisting of polylysine and polyimine as described above.200916505 Other polymers than at least one of the group consisting of polyaminic acid and polyamidiamine. Other polymers may be used to improve solution properties and electrical properties, and examples thereof may be, for example, polyglycolate, polyester, poly Guanidine, polyoxyalkylene, vesin derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. The polymer (C) of the present invention is in the case of containing another polymer, and the content thereof is preferably 50% by weight or less based on the total amount of the polymer (c). The polymer (C) of the present invention is preferably. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention contains the above-mentioned compound (A), (B) epoxy compound and polymer (C) as essential components and is preferably prepared into a solution. . The liquid crystal alignment agent of the present invention may contain other components as the case may be, in addition to the above components (A) to (c). These other components may, for example, be, for example, a sensitive radiation crosslinking agent, an inductive decane compound or the like. The above-mentioned radiation-sensitive linear crosslinking agent can be, for example, a reaction product of the compound represented by the above formula (1) and the above-mentioned glycidyl diamine-based epoxy resin. The ratio of the two compounds used in the reaction of the compound represented by the above formula (1) to the glycidyl diamine epoxy resin is a compound represented by the above formula (1) with respect to 1 equivalent of the glycidoxydiamine epoxy resin. The amount is preferably from 0.01 to 10 equivalents, preferably from 0.2 to 2 equivalents. The reaction temperature is preferably from 2 〇 to 2 5 (TC, more preferably from 50 to 180 ° C, and the reaction time is preferably from 〇·5 to 200 -30 to 200916505, more preferably from 1 to 10 hours. An appropriate base catalyst may be added as needed to promote the reaction. The reaction is preferably carried out in an organic solvent. The organic solvent usable herein is preferably an aprotic organic solvent, and specific examples thereof are, for example, 1-methyl group. -2-pyrrolidone or the like. When the reaction is carried out in an organic solvent, the ratio of the compound represented by the above formula (1) to the total weight of the above-mentioned glycidated diamine-based epoxy resin is relative to the total amount of the reaction solution (solid The component concentration is preferably 1% by weight or more, more preferably 5 to 50% by weight. The functional decane compound is used for the purpose of improving the adhesion between the obtained liquid crystal matching film and the substrate. The functional decane compound is exemplified as For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, oxime-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, ν-(2-Amino B 3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, oxime-ethoxycarbonyl-3-amine Propyltrimethoxydecane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylidenetriamine, Ν_trimethoxydecane Propyl triethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane , 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, Ν-benzyl-3 -Aminopropyltrimethoxydecane, Ν-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, fluorene-phenyl-3- Aminopropyltriethoxydecane, fluorene-bis(ethylene oxide)-3-aminopropyltrimethoxydecane, hydrazine-bis-31 - 200916505 (ethylene oxide)-3-aminopropyl Triethoxy decane, 3-glycidoxy propyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, etc., and another example is JP-A 63 -29. The reaction product of the tetracarboxylic dianhydride and the decane compound having an amine group, etc., is used in the liquid crystal alignment agent of the present invention, and the ratio of use of the compound (A) is as follows: With respect to 100 parts by weight of the total of the polymers (the total of the polymer (C), that is, the total of the polyamic acid, the polyimine, and the other polymers, the same applies hereinafter, preferably from 1 to 100 parts by weight, more The ratio of the epoxy compound to be used is preferably from 1 to 100 parts by weight, more preferably from 10 to 50 parts by weight, based on the total of the polymer of the 10,000 parts by weight. When an alkali catalyst is used together with the (B) epoxy compound, the base catalyst is preferably used in an amount of 50 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the epoxy compound. When the liquid crystal alignment agent of the present invention contains a heat-sensitive crosslinking agent, the use ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on 1 part by weight of the total of the polymer. When the liquid crystal alignment agent of the present invention contains a radiation-sensitive linear crosslinking agent, the ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on 1 part by weight of the total of the polymer. When the liquid crystal alignment agent of the present invention contains an inductive decane compound, the ratio thereof is preferably 50 parts by weight or less per 100 parts by weight or less, more preferably 20 parts by weight or less. The solvent used in the liquid phase alignment agent of the present invention in a solution state is only -32-200916505. It is an organic solution which can dissolve the components (A) to (C) and any other components contained therein. The solvent can be used without particular limitation. These solvents can be exemplified by, for example, an organic solvent exemplified by a user in the synthesis of polylysine. In this case, a weak solvent exemplified by those used in the synthesis of polylysine may also be used in combination. These organic solvents may be used singly or in combination of two or more. The preferred solvent to be used in the preparation of the liquid crystal alignment agent of the present invention is one or a combination of two or more of the above organic solvents, and the composition of the liquid crystal alignment agent is not analyzed in the preferred solid concentration of the following. The surface tension of the liquid crystal alignment agent is in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the ratio of the weight of all the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent is selected as the viscosity, the volatility, etc., but preferably 1 to 1 〇 The range of weight %. The liquid crystal alignment agent of the present invention is coated on the surface of the substrate to form a coating film of the liquid crystal alignment film. However, when the solid content is less than 1% by weight, the film thickness of the coating film is too small and it is difficult to obtain a good liquid crystal alignment film. . On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to have insufficient coating properties. A particularly preferable solid content concentration range differs depending on the method employed when the liquid crystal alignment agent is applied to the substrate. For example, the spin coating method is preferably in the range of _5 to 4.5% by weight. The solid content concentration in the printing method is in the range of 3 to 9 wt%, whereby the solution viscosity is preferably in the range of 12 to 5 OmPa.s. In the case of the ink jet method, the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity is preferably in the range of 3 to 15 mPa·s -33 to 200916505. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably ° C, more preferably 20 ° C to 60 ° C. [Method of Forming Liquid Crystal Alignment Film] The liquid crystal alignment agent of the present invention can be suitably used for forming a liquid to form a liquid crystal alignment film, and for example, a liquid crystal alignment agent of the present invention can be used to form a coating film, and then the radiation can be imparted thereto. The method of liquid crystal alignment. First, the liquid crystal alignment agent of the present invention is applied to the side of the substrate provided with the patterned transparent conductive film by, for example, a roll coating method, a spin coating method, a printing method, or a spray coating method. It is preferred to carry out prebaking after the application of the liquid crystal alignment agent applied after coating. The pre-bake temperature is preferably from 3 to 200 ° C, more preferably from 40 to 100 ° C. The prebaking time is preferably 〇.1, preferably 0.5 to 5 minutes. Subsequently, in order to completely remove the solvent, a firing (post-baking) step is performed. The post-baking temperature is preferably from 120 to 25 ° C. The post-baking time is preferably from 1 to 300 for 2 to 120 minutes. The thickness of the coating film formed here is preferably 0.001 to 1/m, more preferably 0.005 to 0.5 yn as the substrate, and for example, float glass, soda glass, or polyethylene terephthalate can be used. A transparent substrate made of a plastic such as a glycol ester, a polybutylene terephthalate or a polycarbonate. The transparent conductive film can be made of Sn 2 and has a thickness of 0. (: ~200 crystal alignment film. The coating film on the substrate is irradiated with a transparent transparent conductive film, etc., in order to prevent heating (pre-bake 4 0 ~ 150 〇 C ' ί 0 minutes, more purpose and real 80 ~3 0 0 〇C 'minutes, film after better solvent 1 ° Butylene glycol ester such as calcium glass, 〇NESA film '-34- 200916505 ITO film composed of In203-Sn02, etc. These transparent conductive films The patterning can be performed by using a light etching method or a method of forming a transparent conductive film when forming a transparent conductive film. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, A functional decane compound, titanate, or the like may be applied to the substrate and the transparent conductive film in advance. Then, by irradiating the linear or partially polarized radiation or the unpolarized radiation on the coating film, the case may be further It is preferable to carry out heat treatment for 1 to 120 minutes at a temperature of 150 to 250 ° C to impart liquid crystal alignment energy. Here, as the radiation, for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm can be used. And visible light, but better package Ultraviolet rays of light of a wavelength of 00 to 400 nm. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the surface of the substrate, or may be performed in an oblique direction for imparting a pretilt angle, or may be combined When the non-polarizing radiation is irradiated, the irradiation direction is necessary to be an oblique direction. As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or a quasi-electrode can be used. Molecular laser, etc. The ultraviolet light of the preferred wavelength range described above can be obtained by simultaneously using the above-mentioned light source and such as a filter, a diffraction grating, etc. As for the radiation dose, it is preferably U/m2 or more. It is less than 10,000 J/m2, more preferably 10 to 3,000 J/m2. Further, when the liquid crystal alignment energy is imparted by the photo-alignment method on a coating film formed by a conventional liquid crystal alignment agent, it is necessary to irradiate the radiation. 1 〇, 〇〇〇j / m 2 or more. However, if the liquid crystal alignment agent of the present invention is used in the photo-alignment method, the radiation dose is less than 〇, 〇〇〇-35- 200916505 J/m2, In the case of 3,000 J/m2 or less, the manufacturing cost of the liquid crystal display element can be reduced even if it is less than 800 J/m2. Further, the "pretilt angle and the direction in which the substrate surface is formed are inclined" in the present specification. [Manufacturing Method of Liquid Crystal Display Element] The liquid crystal alignment agent forming liquid of the present invention is produced as follows. A pair of (two sheets) is formed to form a liquid crystal alignment film having a relative radiation to the liquid crystal alignment film. The polarizing direction becomes a specific angle, and the surrounding portion is sealed, injected, filled with liquid crystal, and the liquid crystal cell is sealed. Next, the liquid crystal cell is preferably subjected to a temperature of the same polarity, and then cooled to room temperature, and then removed, and then, on both surfaces thereof, a liquid crystal display element is easily formed at a specific angle by aligning the alignment film. On a two-layer substrate in which the liquid crystal alignment film is a liquid crystal alignment film, a liquid having a TN type or an STN type can be obtained by adjusting the angle and degree of the polarization direction of the radiation. On the other hand, in the liquid crystal alignment film, two substrates perpendicular to the liquid crystal alignment film are formed so as to form an alignment film, and a liquid crystal alignment property of 1,000 J/m 2 or less is obtained. The liquid crystal molecular self-crystal liquid crystal display element can be used as a liquid crystal alignment film, and the liquid crystal injection port is formed between the substrate and the irradiated linear polarizing sealant to form a heat to the liquid crystal when the liquid crystal used is injected. The light direction is attached to the polarizing plate in the liquid mode of each substrate, and when the alignment is uniform, the linear polarizing substrate which is irradiated with I and the angle of the polarizing plate are formed: the liquid crystal of the crystal is not suitable for alignment. The shape of the easy axis becomes the polarizing direction of the flat polarizing plate and the angle of the -36-200916505 alignment is easy to form an angle of 45 degrees, and can be a liquid crystal display element having a vertical alignment type liquid crystal cell. As the sealing agent, for example, an epoxy resin containing an alumina sphere as a spacer and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal or the like can be used. In the case of a TN type liquid crystal cell or a S TN type liquid crystal cell, it is preferred to have a positive dielectric anisotropy for forming a nematic liquid crystal. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal can be used. A terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a Cubane liquid crystal, or the like. Further, in the above liquid crystal, a cholesteric liquid crystal such as cholesteric chlorine, cholesteryl phthalate or cholesteryl carbonate may be further added; and under the trade names "C-15" and "CB-1" (Merck) Co., Ltd. is a commercially available pair of palmitic agents; a strong dielectric liquid crystal such as p-norbymethoxybenzylidene-p-amino-2-methylbutyl laurate. On the other hand, in the case of a vertical alignment type liquid crystal cell, it is preferred to have a negative dielectric anisotropy for forming a smectic liquid crystal. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, or a Schiff can be used. An alkali liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. As the polarizing plate to be used on the outer side of the liquid crystal cell, a polarizing film called a "ruthenium film" which is obtained by stretching and aligning polyvinyl alcohol while absorbing iodine may be exemplified by a polarizing plate held by a cellulose acetate protective film or by a ruthenium film itself. A polarizing plate or the like is formed. EXAMPLES -37-200916505 The present invention is more specifically illustrated by the following examples, but the invention is not limited by the examples. <Synthesis of Compound (A)> Synthesis Example 1 82 g of p-cyanoic acid, 304 g of potassium carbonate and 400 ml of N-methyl-2-pyrrolidone were fed into a 1 liter sputum type reaction flask. After stirring at room temperature for 1 hour, 166 g of 1-bromopentane was added at 100. (: stirring for 5 hours. Then, the solvent was distilled off under reduced pressure. Then, 4 8 g of sodium hydroxide and 200 ml of water were added thereto, and refluxing was carried out for 3 hours to carry out a hydrolysis reaction. After the reaction, the reaction was neutralized with hydrochloric acid. In the system, the resulting precipitate is recovered and recrystallized from ethanol to obtain a white crystal of 80 g of a compound represented by the following formula (1 - 2 - 1 ) (hereinafter referred to as "compound (1 -2- 1 )"):

合成例2 依據合成例1，除使用262克1-碘-4,4,4-三氟丁烷替代1 -溴戊烷外' 其餘與合成例1相同，獲得9 0克以下述式（1 - 2 - 2 )表不之化合物（以下稱爲「化合物（1 _ 2 · 2 )」）之白色結晶’· -38- 200916505Synthesis Example 2 According to Synthesis Example 1, except that 262 g of 1-iodo-4,4,4-trifluorobutane was used instead of 1-bromopentane, the rest was the same as in Synthesis Example 1, and 90 g was obtained by the following formula (1). - 2 - 2 ) White crystals of the compound (hereinafter referred to as "compound (1 _ 2 · 2 )") -· -38- 200916505

cf3—C3H6-〇〇cf3—C3H6-〇〇

IIII

CH=CH-C—OH (1-2-2) 合成例3 於1升茄型反應瓶中饋入91.3克4-羥基苯甲酸甲酯、182.4克碳酸鉀及320毫升之N -甲基-2-吡咯啶酮，在室溫下進行攪拌1小時後，添加9 9.7克卜溴戊烷，且在 1 00 °C下攪拌5小時。反應結束後，以水進行再沉澱。接著，將48克氫氧化鈉及400毫升水添加於該沉澱中且回流3小時進行水解反應。反應結束後，以鹽酸中和，回收產生之沉澱物且以乙醇再結晶，獲得1 02克以下述式（ΙΑ - 1 - a ) 表示之化合物之白色結晶：CH=CH-C-OH (1-2-2) Synthesis Example 3 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 ml of N-methyl group were fed into a 1 liter eggplant type reaction flask. 2-Pyrrolidone, after stirring at room temperature for 1 hour, 99.7 g of bromopentane was added, and stirred at 100 ° C for 5 hours. After the reaction was completed, reprecipitation was carried out with water. Next, 48 g of sodium hydroxide and 400 ml of water were added to the precipitate and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the mixture was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain 10 2 g of white crystals of the compound represented by the formula ( ΙΑ - 1 - a ):

(1-4-1-a) 將該化合物中之10.41克置於200毫升茄型反應瓶中，於其中加入100毫升亞硫醯氯及77微升N，N-二甲基甲醯胺’且在8 0 °C下攪拌1小時。接著，減壓餾除亞硫醯氯，添加二氯甲烷且以碳酸氫鈉水溶液洗淨，以硫酸鎂乾燥，進行濃縮後，添加2 0 0毫升四氫呋喃。另一方面’於與上述不同之另一 5 00毫升三頸反應瓶中饋入7.39克羥基桂皮酸、13.82克碳酸鉀、0.48克四丁 -39- 200916505 基敍及1 〇〇毫升水。該水溶液以冰冷卻，於其中緩慢滴加上述四氫呋喃溶液，再進行攪拌2小時。反應結束後，添加鹽酸中和，以乙酸乙酯卒取後，以硫酸鎂乾燥，進行濃縮後，以乙醇再結晶，獲得90克以下述式（卜^)表示之化合物（以下稱爲「化合物（1 _ 4 _丨）」）之白色結晶： (1-4-1) 合成例4 依據合成例3，除使用157克1_碘-4,4,4 -三氟丁烷替代1 -溴戊烷外，其餘與合成例3相同，獲得1 〇克以下述式（1-4-2 )表示之化合物（以下稱爲「化合物（卜4-2 )」）之白色結晶：(1-4-1-a) 10.41 g of the compound was placed in a 200 ml eggplant type reaction flask to which 100 ml of sulfoxide and 77 μl of N,N-dimethylformamide were added. It was stirred at 80 ° C for 1 hour. Next, sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the mixture was washed with aqueous sodium hydrogencarbonate, dried over magnesium sulfate, and concentrated, and then, 200 ml of tetrahydrofuran was added. On the other hand, 7.39 g of hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutyl-39-200916505, and 1 ml of water were fed into another 500 ml three-necked reaction flask different from the above. The aqueous solution was cooled with ice, and the above tetrahydrofuran solution was slowly added dropwise thereto, followed by stirring for 2 hours. After completion of the reaction, the mixture was neutralized with hydrochloric acid, and extracted with ethyl acetate. The mixture was dried over magnesium sulfate and concentrated, and then recrystallized from ethanol to obtain 90 g of a compound (hereinafter referred to as "compound") White crystals of (1 _ 4 _丨))): (1-4-1) Synthesis Example 4 According to Synthesis Example 3, 157 g of 1-iodo-4,4,4-trifluorobutane was used instead of 1-bromo In the same manner as in Synthesis Example 3 except for pentane, a white crystal of a compound represented by the following formula (1-4-2) (hereinafter referred to as "compound (B 4-2)") was obtained:

CF3-C3H6-〇-^~~^COO--^~~^^CH=CH-C-OH (1-4-2) <聚醯胺酸及聚醯亞胺之合成> 合成例5 使〇」莫耳（22_42克）2,3,5-三羧基環戊基乙酸二酐及0_1莫耳（14.23克）之1，3-雙（胺基甲基）環己烷溶於146.6克N -甲基-2-卩比咯D定酮中，且在60。<3下反應6小 -40- 200916505 時。接著，將反應混合物注入大爲過量之甲醇中，使反應產物沉澱，回收之沉澱物以甲醇洗淨，且在減壓4 0 °C下乾燥15小時，獲得32克對數黏度0.71 dl/g之聚醯胺酸（以下，稱爲「聚合物la」）。合成例6 上述合成例5中合成之聚合物la中取15克，於其中添加6 0克N -甲基-2 -吡咯啶酮、1 . 8 0克吡啶及2.3 1克乙酸酐，且在1 2 (TC下進行醯亞胺化反應4小時。接著，將該反應混合物注入大爲過量之甲醇中’使反應產物沉澱。隨後以甲醇洗淨該沉澱物，且在減壓乾燥1 5小時，獲得 12克聚醯亞胺（以下，稱爲「聚合物lb」）。聚合物lb 醯亞胺化率爲5 0 %。實施例1 (1 )液晶配向劑之調製將25重量份之作爲化合物（A )之上述合成例1中合成之化合物（1 - 2 -1 )、2 5重量份之作爲（B )環氧化合物之以上述式（3-2)表示之環氧化合物及100重量份之作爲聚合物（C)之上述合成例5中獲得之聚合物1a溶解於 N-甲基-2-吡咯啶酮中’成爲固體成分濃度3·〇重量。/q之溶液，以孔徑1微米之過濾器過濾該溶液’調製液晶配向劑 -41 - 200916505 (2 )液晶顯示元件之製造使用旋轉塗佈機將上述調配之液晶配向劑1塗佈於設有由ITO膜組成之透明電極之玻璃基板之透明電極面上，且在8 0 °c之加熱板上乾燥1分鐘進行預烘烤後，接著在 2 00°C下進行後烘烤1小時，形成膜厚之塗膜。在該塗膜表面上使用Hg-Xe燈及葛蘭-泰勒（Glan_Tayl〇r) 稜鏡，自與塗膜法線成40°傾斜之方向照射l,00(H/m2之含3 1 3 nm輝線之偏光紫外線，形成賦予液晶配向能之液晶配向膜。重複與上述相同之操作，製作成一對（兩片）在透明電極面上具有液晶配向膜之玻璃基板。在該等一對基板之形成各液晶配向膜之面之周圍部分以網版印刷塗佈含有直徑5.5 μιη氧化鋁球之環氧樹脂接著劑後，以與偏光紫外線照射方向成垂直將基板重疊並壓合，在1 50°C下加熱1小時使接著劑熱硬化。接著，自液晶注入口於基板之間隙內充塡正型向列型液晶（Merck公司製造，MLC-622 1，加入對掌性劑）後，以環氧系接著劑將液晶注入口封住。接著，爲了消除液晶注入時之流動配向，因此使之在150°C下加熱10分鐘且緩慢冷卻至室溫。接著，在基板之外側兩面上貼合偏光板以使其偏光方向相互止交且與液晶配向膜之偏光方向成爲7Γ行，藉此製造TN型液晶顯示元件。如下述般進行該液晶顯示元件之評估。結果列於表2 中〇 -42- 200916505 (3 )液晶配向性之評估針對上述製造之液晶顯示元件，以光學顯微 5 V之電壓開.關（施加·解除）時是否有產生之異常區塊，若未觀察到有異常區塊時爲「良好 (4)電壓保持率之評估對上述製造之液晶顯示元件施加5 V電壓歷日之時間’且在施加1 6 7毫秒間隔後，測定自解 167毫秒之電壓維持率。測定裝置使用（{ Technic製造之VHR-1。電壓保持率在90 %以上好」。實施例2〜1 0 依據實施例1，除化合物（A ) 、（ B )環氧聚合物（C )之種類分別如表1所列者以外，其例1相同分別合成液晶配向劑2〜1 0。分別使用該等液晶配向劑且與實施例1相同晶顯示元件並評估。評估結果列於表2。實施例11〜2 0 分別使用上述實施例1〜1 〇中調製之液， 1〜10 ’除偏光紫外線之照射量爲2 00J/m2以外，施例1相同，製造液晶顯示元件並評估。鏡觀察使明暗變化 ί 60微秒除施加後泛）東陽時爲「良化合物及餘與實施般製造液 I配向劑其於與實 -43- 200916505 結果示於表2。表1 化合物(A)名稱 (B)環氧化合物名稱聚合物(C)名稱液晶配性劑名稱實施例1 (1-2-1) (3-2) 聚合物la 液晶配向劑1 實施例2 (1-2-1) (3-8) 聚合物la 液晶配向劑2 實施例3 (1-2-1) (3-14) 聚合物la 液晶配向劑3 實施例4 (1-2-2) (3-14) 聚合物la 液晶配向劑4 實施例5 (1-2-2) (3-14 聚合物lb 液晶配向劑5 實施例6 (1-4-1) (3-2) 聚合物la 液晶配向劑6 實施例7 0-4-1) (3-8) 聚合物la 液晶配向劑7 實施例8 (1-4-1) (3-14) 聚合物la 液晶配向劑8 實施例9 (1-4-2) (3-14) 聚合物la 液晶配向劑9 實施例10 (1-4-2) (3-14) 聚合物lb 液晶配向劑10 表2 液晶配性劑名稱偏光紫外線照射量 (J/m2) 液晶配向性電壓維持率實施例1 液晶配向劑1 1,000 良好良實施例2 液晶配向劑2 1,000 良好良實施例3 液晶配向劑3 1,000 良好良實施例4 液晶配向劑4 1,000 良好良實施例5 液晶配向劑5 1,000 良好良實施例6 液晶配向劑6 1,000 良好良實施例7 液晶配向劑7 1,000 良好良實施例8 液晶配向劑8 1,000 良好良實施例9 液晶配向劑9 1,000 良好良實施例10 液晶配向劑10 1,000 良好良實施例11 液晶配向劑1 200 良好良實施例12 液晶配向劑2 200 良好良實施例13 液晶配向劑3 200 良好良實施例14 液晶配向劑4 200 良好良實施例15 液晶配向劑5 200 良好良實施例16 液晶配向劑6 200 良好良實施例17 液晶配向劑7 200 良好良實施例18 液晶配向劑8 200 良好良實施例19 液晶配向劑9 200 良好良實施例20 液晶配向劑10 200 良好良 -44- 200916505 由以上實施例可明顯看出，本發明之液晶配向劑可採用少輻射線照射量之光配向法形成具有良好液晶配向性及電特性之液晶配向膜，尤其是可適宜使用於TN型液晶顯示元件。另外，由本發明之液晶配向劑形成之液晶配向膜由於其液晶配向性極爲優異，因而可適當地用於液晶塗佈型之相位差薄膜。發明效果本發明之液晶配向劑與以往已知之液晶配向劑相較，可採用少的輻射線照射量之光配向法獲得顯示良好且均一配向性之液晶配向膜。所以，於液晶顯示元件中使用此液晶配向膜時，可以比以往更價廉地製造液晶顯示元件。具備有由本發明液晶配向劑所形成之液晶配向膜之液晶顯示元件可有效使用於各種裝置，例如適用於桌上型電腦、手錶、座鐘、計數顯示板、數字處理機、個人電腦或液晶電視等裝置。本發明之液晶配向劑，尤其是使用於TN型液晶顯示元件中時’可將其有利的效果發揮至最大限度。 -45-CF3-C3H6-〇-^~~^COO--^~~^^CH=CH-C-OH (1-4-2) <Synthesis of polyaminic acid and polyimine> Synthesis Example 5 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 0_1 molar (14.23 g) of 1,3-bis(aminomethyl)cyclohexane were dissolved in 146.6 g. N-methyl-2-indolepyridine D-butanone, and at 60. <3 under the reaction of 6 small -40- 200916505. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product, and the recovered precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain a logarithmic viscosity of 0.31 dl/g. Polylysine (hereinafter referred to as "polymer la"). Synthesis Example 6 15 g of the polymer la synthesized in the above Synthesis Example 5 was added thereto, and 60 g of N-methyl-2-pyrrolidone, 1.80 g of pyridine, and 2.31 g of acetic anhydride were added thereto, and 1 2 (Iridium imidization reaction was carried out for 4 hours at TC. Then, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was subsequently washed with methanol and dried under reduced pressure for 15 hours. 12 g of polyimine (hereinafter referred to as "polymer lb") was obtained. The polymer lb oxime imidization ratio was 50%. Example 1 (1) Preparation of liquid crystal alignment agent 25 parts by weight The compound (1 - 2 -1 ) synthesized in the above Synthesis Example 1 of the compound (A), and 25 parts by weight of the epoxy compound represented by the above formula (3-2) as the (B) epoxy compound and 100 parts by weight The polymer 1a obtained in the above Synthesis Example 5 as the polymer (C) was dissolved in N-methyl-2-pyrrolidone to form a solution having a solid concentration of 3·〇 by weight. Micron filter to filter the solution 'Modified liquid crystal alignment agent-41 - 200916505 (2) Manufacturing of liquid crystal display element using spin coater The liquid crystal alignment agent 1 prepared above is applied onto a transparent electrode surface of a glass substrate provided with a transparent electrode composed of an ITO film, and dried on a hot plate at 80 ° C for 1 minute for prebaking, followed by 2 After baking at 00 ° C for 1 hour, a film thickness film was formed. On the surface of the film, Hg-Xe lamp and Glan_Tayl〇r 稜鏡 were used, and 40 from the film normal. °1,00 (H/m2 polarized ultraviolet light containing 3 1 3 nm glow line is formed in the direction of inclination to form a liquid crystal alignment film which imparts alignment energy to the liquid crystal. Repeat the same operation as above to form a pair (two pieces) on the transparent electrode a glass substrate having a liquid crystal alignment film on a surface thereof. An epoxy resin adhesive containing a 5.5 μm diameter alumina ball is applied by screen printing on a peripheral portion of the surface of each of the pair of substrates on which the liquid crystal alignment film is formed, and The polarized ultraviolet light is irradiated in a vertical direction to overlap and press the substrate, and the adhesive is thermally cured by heating at 150 ° C for 1 hour. Then, the positive nematic liquid crystal is filled in the gap between the substrates from the liquid crystal injection port (Merck Co., Ltd.) Manufacturing, MLC-622 1, join the palm of the hand After the agent, the liquid crystal injection port was sealed with an epoxy-based adhesive. Then, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes and slowly cooled to room temperature. The polarizing plates were bonded to the outer surfaces thereof so that the polarization directions thereof were stopped, and the polarization direction of the liquid crystal alignment film was 7 Å, thereby manufacturing a TN liquid crystal display element. The evaluation of the liquid crystal display elements was carried out as follows. In Table 2, 〇-42- 200916505 (3) Evaluation of liquid crystal alignment property For the liquid crystal display element manufactured above, whether or not an abnormal block is generated when the voltage of the optical microscopy 5 V is turned on and off (applied/released), If no abnormal block is observed, the "good (4) voltage holding rate evaluation is applied to the liquid crystal display element manufactured above for 5 V voltage calendar time" and after the application of the 167 ms interval, the self-solution 167 is measured. The voltage maintenance rate of milliseconds. The measuring apparatus is used ({VHR-1 manufactured by Technic. The voltage holding ratio is preferably 90% or more.) Examples 2 to 1 0 According to Example 1, except for the compound (A), (B) epoxy polymer (C) The liquid crystal alignment agents 2 to 10 were synthesized in the same manner as in Example 1 except that the liquid crystal alignment agents were used in the same manner as in Example 1. The liquid crystal alignment agents were used and the elements were displayed in the same manner as in Example 1. The evaluation results are shown in Table 2. Examples 11 to 2 0 Liquid crystal display elements were produced and evaluated in the same manner as in Example 1 except that the liquid prepared in the above Examples 1 to 1 was used, and the irradiation amount of the polarized ultraviolet rays was 2 00 J/m 2 in the same manner as in Example 1 . Observed to make the light and dark change ί 60 microseconds in addition to the application of the general), Dongyang is "good compound and the same as the implementation of the manufacturing liquid I alignment agent" and the actual -43- 200916505 results are shown in Table 2. Table 1 compound (A) name (B) Epoxy compound name Polymer (C) name Liquid crystal dosing agent name Example 1 (1-2-1) (3-2) Polymer la Liquid crystal alignment agent 1 Example 2 (1-2-1) (3-8) Polymer la Liquid crystal alignment agent 2 Example 3 (1-2-1) (3-14) Polymer la Liquid crystal alignment agent 3 Example 4 (1-2-2) (3-14) Polymer la Liquid crystal alignment agent 4 Example 5 (1-2-2) (3-14 Polymer lb Liquid crystal alignment agent 5 Example 6 (1-4- 1) (3-2) Polymer la Liquid crystal alignment agent 6 Example 7 0-4-1) (3-8) Polymer la Liquid crystal alignment agent 7 Example 8 (1-4-1) (3-14) Polymer la liquid crystal alignment agent 8 Example 9 (1-4-2) (3-14) Polymer la Liquid crystal alignment agent 9 Example 10 (1-4-2) (3-14) Polymer lb Liquid crystal alignment agent 10 Table 2 Liquid crystal dosing agent name Polarized ultraviolet irradiation amount (J/m2) Liquid crystal alignment voltage maintenance rate Example 1 Liquid crystal alignment agent 1 1,000 Good example 2 Liquid crystal alignment agent 2 1,000 Good good example 3 Liquid crystal alignment agent 3 1,000 Good example 4 Liquid crystal alignment agent 4 1,000 Good example 5 Liquid crystal alignment agent 5 1,000 Good example 6 Liquid crystal alignment agent 6 1,000 Good example 7 Liquid crystal alignment agent 7 1,000 Good example 8 Liquid crystal alignment agent 8 1,000 Good Example 9 Liquid Crystal Aligning Agent 9 1,000 Good Example 10 Liquid Crystal Aligning Agent 10 1,000 Good Example 11 Liquid Crystal Aligning Agent 1 200 Good Example 12 Crystalline alignment agent 2 200 Good example 13 Liquid crystal alignment agent 3 200 Good example 14 Liquid crystal alignment agent 4 200 Good example 15 Liquid crystal alignment agent 5 200 Good good example 16 Liquid crystal alignment agent 6 200 Good good example 17 Liquid crystal alignment agent 7 200 Good example 18 Liquid crystal alignment agent 8 200 Good good example 19 Liquid crystal alignment agent 9 200 Good good example 20 Liquid crystal alignment agent 10 200 Good good -44- 200916505 It is apparent from the above examples, The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having good liquid crystal alignment and electrical characteristics by a photo-alignment method with less radiation exposure, and can be suitably used for a TN-type liquid crystal display element. Further, since the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is extremely excellent in liquid crystal alignment, it can be suitably used for a liquid crystal coating type retardation film. EFFECTS OF THE INVENTION The liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment film which exhibits good uniformity and uniform orientation by a light alignment method with a small amount of radiation irradiation as compared with a conventional liquid crystal alignment agent. Therefore, when the liquid crystal alignment film is used for a liquid crystal display device, the liquid crystal display element can be manufactured more inexpensively than ever. A liquid crystal display element having a liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can be effectively used in various devices, for example, for a desktop computer, a watch, a clock, a counter display panel, a digital processor, a personal computer, or a liquid crystal television. Device. The liquid crystal alignment agent of the present invention, particularly when used in a TN type liquid crystal display element, can maximize its advantageous effects. -45-

Claims

200916505 十、申請專利範圍 1.一種液晶配向劑，其特徵爲含有下列成分： (A )以下式（丨）表示之化合物：200916505 X. Patent application scope 1. A liquid crystal alignment agent characterized by containing the following components: (A) A compound represented by the following formula (丨):

(式（1)中，R1爲氯原子、碳數1~20之院基或碳數 5〜50之脂環式基，該等烷基或脂環式基之氫原子之一部份或全部亦可經氟原子、氰基或芳基取代；R2及R4各獨立爲單鍵、-0-、-S-、-COO-、-OCO-、-C〇NH-、-NHCO-、 -COS-、-SCO-、-0-C0-0-、-NH-COO-、-0-C0-NH-或 _C0- ; R3爲碳數6〜20之2價芳香族基、碳數5〜30之2價脂環式基、具有碳數6〜30之縮合環之2價基或5〜30員之 2價雜環基；R3中之2價芳香族基、2價脂環式基、具有縮合環之2價基或2價雜環基之氫原子之一部份或全部亦可經氟原子、甲基或氰基取代；R5爲單鍵、-〇-、-S_、 -C〇〇_、_0C0_、-NR7,（其中R7爲氫原子、碳數^2 0之院基或碳數6〜20之芳基）或下式（2)所表示之2價基：(In the formula (1), R1 is a chlorine atom, a hospital group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms, and some or all of the hydrogen atoms of the alkyl group or the alicyclic group It may also be substituted by a fluorine atom, a cyano group or an aryl group; R2 and R4 are each independently a single bond, -0-, -S-, -COO-, -OCO-, -C〇NH-, -NHCO-, -COS -, -SCO-, -0-C0-0-, -NH-COO-, -0-C0-NH- or _C0-; R3 is a divalent aromatic group having a carbon number of 6 to 20, and a carbon number of 5~ a 30-valent alicyclic group, a divalent group having a condensed ring having 6 to 30 carbon atoms or a divalent heterocyclic group having 5 to 30 members; a divalent aromatic group in R3; a divalent alicyclic group; Part or all of a hydrogen atom having a divalent or divalent heterocyclic group of a fused ring may be substituted with a fluorine atom, a methyl group or a cyano group; R5 is a single bond, -〇-, -S_, -C〇〇_, _0C0_, -NR7, (wherein R7 is a hydrogen atom, a carbon number of ^2 0 or an aryl group having a carbon number of 6 to 20) or a divalent group represented by the following formula (2):

46- 200916505 (式（2)中，R8爲氟原子 '氰基、碳數uo之烷基或碳數 6 〜20 之芳基；R9 爲單鍵、-〇-、-s-、-COO-、-0C0-、 -CONH-、-NHCO-、-COS-、-SCO-、-O-CO-O-、-NH-COO-、-O-CO-NH-或-CO- ; e爲〇〜4之整數；其中式 (2)之附有「*」之鍵結鍵係與- (Ch2) b•鍵結）；R6係選自氟原子、甲基或氰基；Z爲羥基或羧基；a爲0〜3之整數；於R5爲以上述式（2)表示之2價基時，b爲0〜20 之整數；於 R5 爲單鍵、-0-、-S-、-COO-、-OCO -或-NR7-(其中R7爲氫原子、碳數1〜20之烷基或碳數6〜2 0之芳基）時，b爲1〜20之整數；c爲0~4之整數；d爲〇~4之整數）； (B) —分子中具有2個以上環氧基之化合物；及 (C )選自聚醯胺酸及聚醯亞胺所成群組之至少一種聚合物。 2 ·如申請專利範圍第1項之液晶配向劑，其中（B ) 化合物爲以下式（3 )表示之化合物：46- 200916505 (In the formula (2), R8 is a fluorine atom 'cyano group, a carbon number uo alkyl group or a carbon number 6 to 20 aryl group; R9 is a single bond, -〇-, -s-, -COO- , -0C0-, -CONH-, -NHCO-, -COS-, -SCO-, -O-CO-O-, -NH-COO-, -O-CO-NH- or -CO-; e is 〇 An integer of ～4; wherein the formula (2) has a "*" bond bond and - (Ch2) b• bond); R6 is selected from a fluorine atom, a methyl group or a cyano group; and Z is a hydroxyl group or a carboxyl group. ; a is an integer of 0 to 3; when R5 is a divalent group represented by the above formula (2), b is an integer of 0 to 20; and R5 is a single bond, -0-, -S-, -COO- , -OCO - or -NR7- (wherein R7 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms), b is an integer of 1 to 20; c is 0 to 4 An integer; d is an integer of 〇~4); (B) a compound having two or more epoxy groups in the molecule; and (C) at least one polymerization selected from the group consisting of polylysine and polyimine Things. 2. The liquid crystal alignment agent of claim 1, wherein the compound (B) is a compound represented by the following formula (3):

(式（3)中，R爲具有芳香環或環己烷環之碳數6〜4 0之 2價有機基，其中R基中亦可含有氧原子或硫原子）。 200916505 3 .如申請專利範圍第1項之液晶配向劑，其中相對於 (C )聚合物1 〇〇重量份，（a )化合物之使用比例爲 1~100重量份，（B)化合物之使用比例爲1〜100重量份。 4 · 一種液晶配向膜之形成方法，其特徵爲塗佈申請專和J範Η第1至3項中任一項之液晶配向劑並形成塗膜，及對該塗膜照射輻射線。 5.如申請專利範圍第4項之液晶配向膜之形成方法，其中輻射線照射量爲U/m2以上、未達i 〇,〇〇〇J/m2。 6 · —種液晶配向膜，係由申請專利範圍第i至3項中任一項之液晶配向劑所形成。 7 ·—種液晶顯示元件，其特徵爲具備申請專利範圍第 6項之液晶配向膜。 -48 - 200916505 七、指定代表圖： (一）、本案指定代表圖為：無 (二）、本代表圖之元件代表符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：式（1_ 1) (1-1) Rl_i /r CH=CH-COOH(In the formula (3), R is a divalent organic group having 6 to 40 carbon atoms of an aromatic ring or a cyclohexane ring, wherein the R group may further contain an oxygen atom or a sulfur atom). 200916505 3. The liquid crystal alignment agent of claim 1, wherein the ratio of the compound (a) is from 1 to 100 parts by weight based on 1 part by weight of the (C) polymer, and (B) the proportion of the compound used It is 1 to 100 parts by weight. 4. A method of forming a liquid crystal alignment film, which comprises coating a liquid crystal alignment agent according to any one of items 1 to 3 of J Fan, and forming a coating film, and irradiating the coating film with radiation. 5. The method for forming a liquid crystal alignment film according to item 4 of the patent application, wherein the radiation exposure amount is U/m2 or more, less than i 〇, 〇〇〇J/m2. A liquid crystal alignment film formed by the liquid crystal alignment agent of any one of the above claims. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 6 of the patent application. -48 - 200916505 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Characteristic chemical formula: formula (1_ 1) (1-1) Rl_i /r CH=CH-COOH