TW200906914A

TW200906914A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display

Info

Publication number: TW200906914A
Application number: TW097129711A
Authority: TW
Inventors: Takahiro Mori; Daisuke Touma
Original assignee: Chisso Corp; Chisso Petrochemical Corp
Priority date: 2007-08-08
Filing date: 2008-08-05
Publication date: 2009-02-16
Also published as: JP5130907B2; CN101364009A; JP2009058928A; CN101364009B; TWI421280B; KR20090015829A; KR101489716B1

Abstract

A liquid crystal alignment layer with high voltage holding ratio, low residual DC and greater retardation is provided, and a liquid crystal display (LCD) having the liquid crystal alignment layer and excellent contrast without inducing persistence is further provided. A liquid crystal aligning agent of the present invention includes polyamic acid or derivatives thereof which is a reaction product of tetracarboxylic acid dianhydride and diamines, wherein the diamines is a kind of diamine having a specific radical consisting of imino group and alkylene group that may have a substituent.

Description

200906914 ZO1OJpn 九、發明說明：【發明所屬之技術領域】本發明涉及種聚合物、使用此聚合物而形成的液晶配向劑、利用此液晶配向劑獲得的液晶配向膜及具有此液晶配向膜的液晶顯示元件，所述聚合物含有以主鏈上具有三級胺與亞烷基的二胺作為主成分的聚醢胺酸或其衍生物、即聚醯胺酸及聚醯亞胺。【先前技術】液晶顯示元件用在以筆記本電腦（notebook)或桌上電腦（desktop C〇mputer)的顯示器（m〇nit〇r)為代表的攝像機（video camera)的取景器（view fmder)、投影式 (projection)顯不器（display)等各種液晶顯示裝置中，最近也用作電視的顯示元件。此外，也用作光學打印頭 (optical printer head)、光學傅立葉變換（〇pticai tmnsf〇rm )元件、光閥（light valve )等光電子學 (op^leCtronics)相關元件。作為先前的液晶顯示元件，主流是使用向列魏晶（nematie liquid町咖）的顯示元件，正在實用化的是扭轉90度的扭轉向列（Twisted Nematic ’ TN)型液晶顯示元件、通常扭轉18〇度或18〇度以上的超扭轉向列（Super Twisted Nematic，STN)型液晶顯示元件、使用薄膜電晶體的所謂TFT (Thin film transistor ’薄膜電晶體）型液晶顯示元件。然而，這些液晶顯示元件存在以下缺點：能夠比較好地觀察圖像的視錄為狹窄，斜向觀看時，亮度及對比度 200906914 (contrast)會降低，並且產生半色調的亮度反轉。近年來，針對所述視角問題，利用使用光學補償膜的TN型液晶顯示元件、並用垂直配向與突起構造物的技術的多區域垂直排列（Multi domain Vertical Alignment，MVA )型液晶顯示元件 '或者橫向電場方式的平面轉換（In pi叻e Switching，IPS)型液晶顯示元件等技術進行改良，並將此改良技術實用化（例如，參照日本專利特公昭63_219的號公報、日本專利特開平6_16〇878號公報及日本平9-15650號公報）。」％開液晶顯示元件的技術發展不僅僅是通過這些200906914 ZO1OJpn IX. The invention relates to a seed polymer, a liquid crystal alignment agent formed using the polymer, a liquid crystal alignment film obtained by using the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film. A display element comprising a polyaminic acid or a derivative thereof having a diamine having a tertiary amine and an alkylene group as a main component in the main chain, that is, polylysine and polyimine. [Prior Art] A liquid crystal display element is used in a viewfinder (view fmder) of a video camera typified by a display of a notebook or a desktop computer (m〇nit〇r). Various liquid crystal display devices such as a projection display have recently been used as display elements for televisions. In addition, it is also used as an opto-electronics (optical printer head), optical Fourier transform (〇pticai tmnsf〇rm) element, light valve (optical valve) and other optoelectronic (op^leCtronics) related components. As a liquid crystal display element of the prior art, a display element using a nematic liquid crystal is used, and a Twisted Nematic 'TN type liquid crystal display element which is twisted by 90 degrees and is usually twisted 18 is being put into practical use. A super Twisted Nematic (STN) type liquid crystal display element having a twist or 18 degrees or more, or a so-called TFT (Thin film transistor) type liquid crystal display element using a thin film transistor. However, these liquid crystal display elements have the following drawbacks: the viewability of the image which can be observed relatively well is narrow, and when viewed obliquely, the brightness and contrast 200906914 (contrast) is lowered, and halftone brightness inversion is generated. In recent years, in view of the viewing angle problem, a multi-domain vertical alignment (MVA) type liquid crystal display element' or a lateral direction using a TN type liquid crystal display element using an optical compensation film and a technique of using a vertical alignment and a protrusion structure is used. Techniques such as an electric field type in-plane switching (IPS) type liquid crystal display element are improved, and the improved technique is put into practical use (for example, refer to Japanese Patent Publication No. Sho 63-219, Japanese Patent Laid-Open No. Hei 6_16 878 Bulletin No. 9-15650). "% open LCD technology development is not just through these

Li::·良來實現’也可以通過用於液晶顯示元ί :構現。用於液晶顯示元件的構成構: 中，尤其疋液日曰配向膜’它是與液晶顯示元件的顯示相關的重要要素之-，縣液㈣，化1 晶配向膜的作用逐年重要。仟的问扣貝化，夜Li::·good to achieve' can also be used for liquid crystal display element ί: construction. For the constitution of the liquid crystal display element: in particular, the sputum corrugated alignment film ’ is an important element related to the display of the liquid crystal display element, and the role of the prefecture liquid (4) and the crystal 1 alignment film is important year by year.问的问扣贝化,夜

為了提高液晶顯示元件的顯示品質 =所要求的重要特性’可舉出電壓保及留己間二—t施加至液=二=在：免度降低，有時會對正常的諸調顯示造成障礙降另其; 如果殘留DC較大，那麼在施加礙另一方面，的“殘像(PerSiStenCe)”，即儘管將電壓气置殘留應消失的圖像。 a h置為QFF ’但仍另外，作為其他表示液晶顯示元件的性能的指標之 200906914 序可使=顯示㈣度相·黑顯示的亮度的比率即對 =二：般來說，白顯示的亮度不會產生很大變化，所以上是ΐ黑顯示的亮度的影響。因此，為乂同對比度，重要的疋降低黑顯示的亮度。單麵為了提高液晶顯示元件的對比度，而使用 =酉己向性心的液晶配向膜，使液晶顯示元件中的液晶配向’提高黑顯示特性，由此可解决所述參照日本專利特開細掘397號公報）。也晶配向膜的單軸配向性，增大液晶配向膜的延遲（retardation)即可。需要根Ϊ =情況’為了提高液晶顯示元件的顯示品質，需要I種電壓保持率高、殘留Dc小、且延遲㈣㈣料。 =S面’作為液晶配向劑的材料，已知有具本，二氨基的二價有絲的雜胺 :.的==_83號小冊子研^的表現及其進-步提關觀點來說，f要進一步進行【發明内容】本發明的課題在於提供一種可形成電壓俘，低、此外具有較大延遲的液晶配向膜=二殘 ^生物即聚醯胺酸及聚醒亞胺系聚合物，^ 3及 ::的液晶配向膜，及具有此液晶配向二：對比度、不會引起引起殘像的液晶顯示元件。有1'的本發明者等人為了解决所述課題而進行積極研究，發 200906914 現通過對聚合物原料即二胺導入亞烷基結構，由聚合物所構成的液晶配向膜可使液晶顯示元件中的液晶分子更加均勻地配向’其結果’使用此液晶配向膜的液晶顯示元件具有較大的延遲。並且發現，通過對所述二胺導入三級胺，並使用組入所述二胺的聚合物，可使液晶配向膜在用於液晶顯示元件時具有高電壓保持率與低殘留DC。本發明由下述内容構成。 [1] 一種液晶配向劑，其含有四叛酸二針 (tetracarboxylic acid dianhydride)與二胺的反應產物、即聚酿胺酸或其衍生物，其特徵在於’所述二胺包含以下述通式（1)表示的二胺。 [化1]In order to improve the display quality of the liquid crystal display element = the important characteristics required, it can be mentioned that the voltage is maintained and the second is applied to the liquid = two = in: the degree of reduction is reduced, which may cause obstacles to the normal display. If the residual DC is large, the "PerSiStenCe", which is on the other hand, is an image that should disappear despite the residual voltage. Ah is set to QFF 'but still in addition, as another indicator of the performance of the liquid crystal display element, the 200906914 order can be used to display the ratio of the brightness of the (four) degree phase and the black display, that is, the ratio = two: generally, the brightness of the white display is not There will be a big change, so the effect is the brightness of the black display. Therefore, for the same contrast, the important 疋 reduces the brightness of the black display. In order to improve the contrast of the liquid crystal display element, the liquid crystal alignment film of the ambiguity is used to improve the black display characteristics of the liquid crystal alignment in the liquid crystal display element, thereby solving the problem of the reference Japanese patent Bulletin No. 397). It is also possible to increase the uniaxial alignment of the crystal alignment film and increase the retardation of the liquid crystal alignment film. In order to improve the display quality of the liquid crystal display device, it is necessary to have a high voltage holding ratio, a small residual Dc, and a delay (four) (four). =S surface' as the material of the liquid crystal alignment agent, it is known that there is a diamined diamine having a diamino group: the performance of the booklet of the ==_83 booklet and its step-by-step approach f. Further to the present invention, an object of the present invention is to provide a liquid crystal alignment film which is capable of forming a voltage trap, which has a low retardation, and which has a large retardation, a poly-proline and a polyamidite-based polymer. ^ 3 and :: liquid crystal alignment film, and liquid crystal display element having the liquid crystal alignment 2: contrast, which does not cause an afterimage. The inventors of the present invention have actively studied in order to solve the problem, and issued 200906914. The liquid crystal display element can be obtained by introducing an alkylene structure into a polymer raw material, that is, a diamine. The liquid crystal molecules in the alignment are more uniformly aligned. As a result, the liquid crystal display element using the liquid crystal alignment film has a large retardation. Further, it has been found that by introducing a tertiary amine into the diamine and using a polymer incorporated in the diamine, the liquid crystal alignment film can have a high voltage holding ratio and a low residual DC when used for a liquid crystal display element. The present invention consists of the following contents. [1] A liquid crystal alignment agent comprising a reaction product of tetracarboxylic acid dianhydride and a diamine, i.e., polyacrylic acid or a derivative thereof, characterized in that the diamine comprises the following formula (1) A diamine represented. [Chemical 1]

通式（1)中’ R1獨立地表示一價有機基，R2獨立地表示一價基，Z表示包含碳數i〜5的亞烷基的二價基。 [2] 如[1]所述的液晶配向劑，其特徵在於，Ri獨立為碳數1〜3的烷基’ R2獨立為氫、碳數〗〜3之烷基、氟、氯或漠·。 [3] 如[1]或[2]所述的液晶配向劑，其特徵在於，以通式（1)表示的二胺，在兩端的笨基上，在對應於Ν·Ζ_Ν 主鏈的各個對位上具有氨基。 [4] 如[3]所述的液晶配向劑，其特徵在於，以通式（1) 200906914 J ριι 表示的二胺是從下述結構式239〜253及258〜262所組成的族群中選擇的一個或一個以上。[化2] 239 H2N 241 h2n 243 H2N 245 H2N 247 H2N 249 H2N 251 H2N 253[化3]In the formula (1), R1 independently represents a monovalent organic group, R2 independently represents a monovalent group, and Z represents a divalent group of an alkylene group having a carbon number of i to 5. [2] The liquid crystal alignment agent according to [1], wherein Ri is independently a C 1 to 3 alkyl group, R 2 is independently hydrogen, a carbon number of 〜 3 alkyl, fluorine, chlorine or desert . [3] The liquid crystal alignment agent according to [1] or [2], wherein the diamine represented by the formula (1) is on the stupid base at both ends, and corresponds to each of the main chains of the Ν·Ζ_Ν There is an amino group in the para position. [4] The liquid crystal alignment agent according to [3], wherein the diamine represented by the formula (1) 200906914 J ριι is selected from the group consisting of the following structural formulas 239 to 253 and 258 to 262; One or more of them. 239 H2N 241 h2n 243 H2N 245 H2N 247 H2N 249 H2N 251 H2N 253 [Chemical 3]

N---N CH3 ch3 ch3 ch3 (CH2)3-NN---N CH3 ch3 ch3 ch3 (CH2)3-N

nh2Nh2

nh2 CH^ CH3 (ch2)5-nNh2 CH^ CH3 (ch2)5-n

nh2Nh2

?2H5 C2H N-(CH2)2-N?2H5 C2H N-(CH2)2-N

〒2H5 ?2H今 (ch2)4-n〒2H5 ?2H today (ch2)4-n

c3h7 C3H7 Ν'^-NC3h7 C3H7 Ν'^-N

〒3H7 〇3H^ N"(CH2)3-N〒3H7 〇3H^ N"(CH2)3-N

C3H7 C3H7/ N-(CH2)5-N 240 h2nC3H7 C3H7/ N-(CH2)5-N 240 h2n

242 H2N242 H2N

CH3 CH3i N-(CH2)2-N _ pL!CH3 CH3i N-(CH2)2-N _ pL!

244 H2N 246 NH2 h2n 248 NH2 h2n244 H2N 246 NH2 h2n 248 NH2 h2n

nh2 ch3 ch (ch2)4-nNh2 ch3 ch (ch2)4-n

nh2 N-^-N c2h5 〇2h5Nh2 N-^-N c2h5 〇2h5

c2h5 C2H N-(CH2)3-NC2h5 C2H N-(CH2)3-N

nh2Nh2

〒2H5 ?2H 令 N-(CH2)5-N -a〒2H5 ?2H Let N-(CH2)5-N -a

nh2Nh2

250 /==rv C3H7 〇3H^ NH2 H2N —/ N~(CH2)2'N 252/=\ ?sH? NH2 (s|，(CH2)4-N250 /==rv C3H7 〇3H^ NH2 H2N —/ N~(CH2)2'N 252/=\ ?sH? NH2 (s|,(CH2)4-N

nh2Nh2

NH 2NH 2

9 200906914 2609 200906914 260

[5]如[1]至[4]中任一項所述的液晶配向劑，其特徵在於，所述四羧酸二酐是從下述結構式500、505〜508、511、 515及517中選擇的一個或一個以上。 [化4][5] The liquid crystal alignment agent according to any one of [1] to [4] wherein the tetracarboxylic dianhydride is from the following structural formulas 500, 505 to 508, 511, 515 and 517. One or more of the choices. [Chemical 4]

[6]如[5]所述的液晶配向劑，其特徵在於，所述四叛酸 10 200906914 J O^pil 二酐是所述結構式5〇〇及511的一者或兩者。 [7]如[1]至[6]中#一項所述的液晶配向劑，其特徵在於，所述二胺進—少包含以下述通式（2)表示的二胺。 [化5] H2N-R3-NH2 通式（2)中，K3表示具有取代基及不包含兩個或兩個以上的亞氨基的二償有機基。 ' [8]如[7]所述的浪晶配向劑，其特徵在於，以通式（2) 表示的二胺包含以下述通式（3)〜（5)表示的二胺。 [化6][6] The liquid crystal alignment agent according to [5], wherein the tetrazoic acid 10 200906914 J O^pil dianhydride is one or both of the structural formulae 5 and 511. [7] The liquid crystal alignment agent according to the above [1], wherein the diamine further contains a diamine represented by the following formula (2). H2N-R3-NH2 In the formula (2), K3 represents a divalent organic group having a substituent and not containing two or more imino groups. [8] The smectite agent according to the above [7], wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5). [Chemical 6]

通式（3)中，γ表示包含碳數1〜5的亞烷基、氧及硫的一種或一種以上的二價基。 [化ηIn the formula (3), γ represents one or more divalent groups containing an alkylene group having 1 to 5 carbon atoms, oxygen and sulfur. [化η

通式（4)中，χ!獨立地表示亞甲基或氧，$表示可具有曱基或〇^3作騎代基的碳數丨〜。 [化8] 11 (5) 200906914 R4In the formula (4), χ! independently represents a methylene group or oxygen, and $ represents a carbon number 丨~ which may have a mercapto group or a ruthenium group. [化8] 11 (5) 200906914 R4

ff

通式（5)中’x獨立地表不碳數i〜6的亞院基或氧， X表不單鍵或碳數1〜3的亞烷基，環τ表示1，4-亞苯基或1，4-亞環己基，R4表示氫或碳數丨〜3〇的烷基（其中，所述院基中’碳數2〜30的烷基中的任意的亞甲基可獨立地被氧' -CH=CH-或-CeC-取代，所述烷基中，氧並不相鄰）’h表示〇或1。 [9] 如[8]所述的液晶配向劑，其特徵在於，通式（3) 〜（5)中，兩個氨基的位置相對於γ或χΐ是對位。 [10] 如[9]所述的液晶配向劑，其特徵在於，以通式（3) 表示的二胺是從下述結構式3〇1〜304、3〇6、3〇7及313 所組成的族群中選擇的一個或一個以上，以通式（4)表示的二胺是從下述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式（5)表示的二胺是從下述結構式381、384、390及398所組成的族群中選擇的個或一個以上[化9] 301 302In the general formula (5), 'x independently represents a sub-group or oxygen having a carbon number of i to 6, X represents a single bond or an alkylene group having 1 to 3 carbon atoms, and ring τ represents a 1,4-phenylene group or 1 , 4-cyclohexylene, R 4 represents hydrogen or an alkyl group having a carbon number of 丨〇 3 ( (wherein any methylene group in the alkyl group having 2 to 30 carbon atoms may be independently oxygenated in the hospital group) -CH=CH- or -CeC-substitution in which oxygen is not adjacent) 'h' represents hydrazine or 1. [9] The liquid crystal alignment agent according to [8], wherein, in the general formulae (3) to (5), the positions of the two amino groups are aligned with respect to γ or χΐ. [10] The liquid crystal alignment agent according to [9], wherein the diamine represented by the formula (3) is from the following structural formulas 3〇1 to 304, 3〇6, 3〇7, and 313. One or more selected from the group consisting of the diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367, and 372. The diamine represented by the formula (5) is one or more selected from the group consisting of the following structural formulas 381, 384, 390 and 398. [Chem. 9] 301 302

Η2Ν (CH2)2 Or nh2 12 304 200906914 303 H2N o (CH2)3 〇 nh2 h2n o (CH2)4 Or nh2Η2Ν (CH2)2 Or nh2 12 304 200906914 303 H2N o (CH2)3 〇 nh2 h2n o (CH2)4 Or nh2

306 H2N 307 nh2 nh2 h2n306 H2N 307 nh2 nh2 h2n

313 H2N s-(CH2)4-s 2 [化 10] 360 H2N o·。分，313 H2N s-(CH2)4-s 2 [Chemical 10] 360 H2N o·. Minute,

nh2Nh2

372 H2N372 H2N

[化n] (CH2)3-[化n] (CH2)3-

nh2 1 N 38H2Nh2 1 N 38H2

H2 N 13 200906914H2 N 13 200906914

[11] 如[8]至[10]中任一項所述的液晶配向劑，其特徵在於，所述二胺中，以通式（1)表示的二胺的含有率為 20〜99莫耳％，以通式（2)表示的二胺的含有率為1〜80 莫耳％。 [12] —種液晶配向劑，其含有：四羧酸二酐A與二胺 A的反應產物即聚醯胺酸或其衍生物A、以及四羧酸二酐 B與二胺B的反應產物即聚醯胺酸或其衍生物B的液晶配向劑，其特徵在於，所述二胺A包含以上述通式（1)表示的二胺， 14 200906914 所述二胺B不包含以上述通式（1 )表示的二胺。 [13] 如[12]所述的液晶配向劑’其特徵在於，通式d ) 中，R1獨立為碳數1〜3的烷基，R2獨立為氫、碳數1〜3 的烧基、氟、氯或溴。 [14] 如[12]或[13]所述的液晶配向劑，其特徵在於，以通式（1)表示的二胺，在兩端的苯基上，在對應於N-Z-N 主鏈的各個對位上具有氨基。 [15] 如[14]所述的液晶配向劑，其特徵在於，以通式（！）表示的二胺是從上述結構式239〜253及258〜262所組成的族群中選擇的一個或一個以上。 [16] 如[12]至[15]中任一項所述的液晶配向劑，其特徵在於’所述一胺B包含以上述通式（2)表示的二胺。 [17] 如[16]所述的液晶配向劑，其特徵在於，以通式（2) 表示的二胺包含以上述通式（3)〜（5)表示的二胺。 [18] 如[17]所述的液晶配向劑，其特徵在於，通式（3) 〜（5)中’兩個氨基的位置相對於丫或义是對位。 [19] 如[18]所述的液晶配向劑，其特徵在於，以通式（3 ) 表示的二胺是從上述結構式301〜304、3〇6、3〇7及313 所組成的族群中選擇的一個或一個以上，以通式（4)表示的二胺是從上述結構式360、364、365、367及372所組成，族群中選擇的一個或一個以上，以通式（5)表示的二胺是從上述結構式38卜384、39〇及398所組成的族群中擇的一個或一個以上。、 [2〇]如[12]至[19]中任一項所述的液晶配向劑，其特徵 200906914 在於，所述四羧酸二酐A及四羧酸二酐B是從上述結搆式 500、505〜508、511、515及517中選擇的一個或〆僩以上0 [21]如[20]所述的液晶配向劑，其特徵在於，所述四羧酸二酐A及四羧酸二酐B是上述結構式5〇〇及511的〆者或兩者〇[11] The liquid crystal alignment agent according to any one of [8], wherein the content of the diamine represented by the formula (1) in the diamine is 20 to 99. The content of the diamine, the content of the diamine represented by the general formula (2) is 1 to 80 mol%. [12] A liquid crystal alignment agent comprising: a reaction product of a tetracarboxylic dianhydride A and a diamine A, that is, a polyamic acid or a derivative thereof A, and a reaction product of a tetracarboxylic dianhydride B and a diamine B. A liquid crystal alignment agent of poly-proline or a derivative B thereof, wherein the diamine A contains a diamine represented by the above formula (1), and 14 200906914, the diamine B does not contain the above formula. (1) The diamine represented. [13] The liquid crystal alignment agent according to [12], wherein, in the formula d), R1 is independently an alkyl group having 1 to 3 carbon atoms, and R2 is independently hydrogen and a carbon number of 1 to 3; Fluorine, chlorine or bromine. [14] The liquid crystal alignment agent according to [12] or [13] characterized in that the diamine represented by the formula (1) is on the phenyl groups at both ends, and corresponds to each alignment of the NZN main chain. It has an amino group. [15] The liquid crystal alignment agent according to [14], wherein the diamine represented by the formula (!) is one or a group selected from the group consisting of the above structural formulas 239 to 253 and 258 to 262. the above. [16] The liquid crystal alignment agent according to any one of [12] to [15] wherein the monoamine B comprises a diamine represented by the above formula (2). [17] The liquid crystal alignment agent according to [16], wherein the diamine represented by the formula (2) contains a diamine represented by the above formulas (3) to (5). [18] The liquid crystal alignment agent according to [17], wherein the positions of the two amino groups in the general formulae (3) to (5) are aligned with respect to 丫 or 义. [19] The liquid crystal alignment agent according to [18], wherein the diamine represented by the formula (3) is a group consisting of the above structural formulas 301 to 304, 3〇6, 3〇7, and 313. One or more selected ones or more, the diamine represented by the general formula (4) is one or more selected from the above structural formulas 360, 364, 365, 367 and 372, and the general formula (5) The diamine represented is one or more selected from the group consisting of the above structural formulas 38, 384, 39, and 398. The liquid crystal alignment agent according to any one of [12] to [19], characterized in that the tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are from the above structural formula 500. The liquid crystal alignment agent according to [20], wherein the tetracarboxylic dianhydride A and the tetracarboxylic acid II are selected from the group consisting of 505 to 508, 511, 515, and 517. Anhydride B is the latter or both of the above structural formulas 5 and 511

在於環任氧:項合:述的液晶配向劑’其特徵 [23]如[22]所述的液晶配向劑，其特徵在於，化合物是從下述結構式（E1 )〜（£3 )、（£5 )及 v畏氣 (E4)所組成的族群中選擇的一個或一個以上。下迷通式 [化 12]The liquid crystal alignment agent according to the above [22], wherein the compound is from the following structural formula (E1) to (£3), One or more selected from the group consisting of (£5) and v-frustration (E4). Under the general formula [Chemistry 12]

0-CH2 0 P、〇-CH2"CH-CH20-CH2 0 P, 〇-CH2"CH-CH2

H2 (E1)H2 (E1)

(Ε3)(Ε3)

ΟΟ

16 200906914 1〇Jpu16 200906914 1〇Jpu

通式（E4)中，n表示0〜10的整數。 fIn the formula (E4), n represents an integer of 0 to 10. f

[24]如[22]或[23]所述的液晶配向劑，其特徵在於，相對於所述聚醯胺酸或其衍生物的總量而包含〇1〜4〇 wt% 的所述環氧化合物。 ° [25]—種液晶配向膜’其是由[1]至[24]中任一項的液晶配向劑而獲得的。對基板；含有液 [26]—種液晶顯示元件，其具有： =子’⑽成於所述—聽板之間的液晶層；對液晶層壓的電極；使所述液晶分子於特定方向上配向的液 =向膜；其特徵在於，所舰晶配向膜是间的液晶配【27]如[26]所述的液晶顯示元件，述電極在相對於所述基板的表面水平的述電極在相對於徵在於，其是所層施加電壓的用於縱向電場：方间上對所返液晶 [2 9 ] -種聚合物，其是酸_ ^^不兀件。胺與以上料< 狀⑴表示的二 200906914 [30] 如[29]所述的聚合物’其特徵在於，通式⑴中， R1獨立為碳數1〜3的錄，R2獨立為氫、碳數卜3的院基、氣、氯或溴。 [31] 如[29]或[3〇]戶斤述的聚合物，其特徵在於，以通式 (1)表不的二胺，在兩端的笨基上，在對應於N_z_N主鏈的各個對位上具有氨基。一 [32]如[32]所述的聚合物，其特徵在於，以通式（1) 表不的一胺是從上述結構式239〜253及258〜262所組成的族群中選擇的一個或一個以上。一 [33]如[32]所述的聚合物，其特徵在於，以通式（】）表示的二胺是上述結構式24〇。 [34] 如[29]至[33]中任一項所述的聚合物，其特徵在於：以通式⑵表示的二胺包含以上述通式⑴〜⑸ 表示的二胺。 [35] 如[34]所述的聚合物，其特徵在於，通式（3)〜 (5)中，兩個氨基的位置相對於γ或χΙ是對位。一[36]如[35]所述的聚合物，其特徵在於，以通式表示的二胺是從上述結構式301〜304、306、307及313 所組成的族群中選擇的一個或一個以上，以通式（4)表示的二胺是從上述結構式360、364、365、367及372所組成，族群中選擇的-個或一個以±，以通式⑸表示的二胺是從上述結構式381、384、390及398所组成的族群; 擇的一個或一個以上。、 [37]如[36]所述的的聚合物，其特徵在於，以通式（3) 18 200906914[24] The liquid crystal alignment agent according to [22] or [23], wherein the ring is contained in an amount of from 1 to 4% by weight based on the total amount of the polyaminic acid or a derivative thereof. Oxygen compound. [25] A liquid crystal alignment film which is obtained by the liquid crystal alignment agent of any one of [1] to [24]. a liquid crystal display element having: a liquid crystal display element having: = sub-(10) formed in the liquid crystal layer between the listening plates; an electrode laminated on the liquid crystal; the liquid crystal molecules being oriented in a specific direction Aligned liquid = a film; characterized in that the ship crystal alignment film is a liquid crystal display. [27] The liquid crystal display element according to [26], wherein the electrode is at a level relative to a surface of the substrate Relative to the sign, it is the applied electric field of the layer for the longitudinal electric field: the square liquid is returned to the liquid crystal [2 9 ] - the polymer, which is an acid _ ^ ^. Amine and the above-mentioned material <2,069,014, [1] The polymer according to [29] is characterized in that, in the formula (1), R1 is independently a carbon number of 1 to 3, and R2 is independently hydrogen. The base, gas, chlorine or bromine of carbon number 3. [31] A polymer as described in [29] or [3〇], characterized in that the diamine represented by the formula (1) is on the stupid base at both ends, and corresponds to each of the N_z_N main chains. There is an amino group in the para position. [32] The polymer according to [32], wherein the amine represented by the formula (1) is one selected from the group consisting of the above structural formulas 239 to 253 and 258 to 262 or More than one. [33] The polymer according to [32], wherein the diamine represented by the formula (]) is the above formula 24. [14] The polymer according to any one of [29] to [33], wherein the diamine represented by the formula (2) contains a diamine represented by the above formulas (1) to (5). [35] The polymer according to [34], wherein, in the general formulae (3) to (5), the positions of the two amino groups are para-position with respect to γ or χΙ. [36] The polymer according to [35], wherein the diamine represented by the formula is one or more selected from the group consisting of the structural formulae 301 to 304, 306, 307, and 313. The diamine represented by the formula (4) is composed of the above structural formulas 360, 364, 365, 367 and 372, and one or one selected from the group is ±, and the diamine represented by the formula (5) is from the above a group consisting of structural formulas 381, 384, 390, and 398; one or more selected. [37] The polymer according to [36], which is characterized by the formula (3) 18 200906914

表示的二胺是所述結構式301及3〇6的一者或兩者，以通式（4)表不的二胺是上述結構式364，以通式（5)表示的二胺是上述結構式381。 [38] 如[29]至[37]中任一項所述的聚合物，其特徵在於，所述四叛酸二酐是從上述結構式5〇〇、5〇5〜5〇8、511、 515及517中選擇的—個或一個以上。The diamine represented by the above formulae 301 and 3〇6, the diamine represented by the formula (4) is the above structural formula 364, and the diamine represented by the formula (5) is the above Structural formula 381. [38] The polymer according to any one of [29] to [37] wherein the tetra-retensive dianhydride is from the above structural formula 5, 5〇5 to 5〇8, 511 One or more selected from 515 and 517.

[39] 如[38]所述的聚合物，其特徵在於，所述四羧酸二酐是上述結構式500及511的一者或兩者。、通過士發明，可提供一種具有特別優異的對比度、電 2持率高、殘留DC下降、不會引起所謂的殘像的蓄積，荷減少的液晶顯示元件，用以形成此液緣枝件的液 :配向膜以及可形成此液晶配向膜的聚合物及液晶劑。【實施方式】本發明的液晶配向劑含有四缓酸二酐與二胺的反應產 ^即聚醯胺酸或其衍生物。所謂所述聚醯胺酸的衍生物， =旨在製成含有溶_後述液晶配向劑時溶解於溶劑的成 :，疋指在將此液晶配向劑製成後述液晶配向膜時，可形作為主成分的液晶配向膜的成分。作為這種㈣射物，例如可舉出：可溶 _及聚醯胺酸酸胺等缝匕, 胺酴站觫古勻甘-, 了又八篮木说，可舉出.1)聚醯 ^ 基/、羧基進行脫水閉環反應而獲得的|醯亞恥、2)聚醯胺酸的—邱八与甘& ^ 叙伃妁汆醞亞酯的聚獲得的部/减與縣進行财_反應而刀X -亞胺、3)將聚醯胺酸的羧基轉換為 19 200906914 分替換I、4)將四羧酸二酐化合物所包含的酸二酐的一部胺共妒^有機二羧酸且使其反應而獲得的聚醯胺酸-聚醯或^二勿，、此外5)使此聚醯胺酸_聚醯胺共聚物的一部分卩進行脫水閉環反應而獲得的聚醢胺醯亞胺。所述聚酿胺酸或其衍生物既可以是-種化合物，也可以是兩種或兩種以上的化合物。所述二胺包含以下述通式（1)表示的二胺。以通式（1) 表示的二胺可以是一種化合物，也可以是兩種或兩種以上的化合物。 [化 13][39] The polymer according to [38], wherein the tetracarboxylic dianhydride is one or both of the structural formulae 500 and 511. According to the invention, it is possible to provide a liquid crystal display element having a particularly excellent contrast ratio, a high electric holding ratio, a residual DC drop, and a so-called accumulation of residual images, and a reduced load, for forming the liquid edge branch. Liquid: an alignment film and a polymer and a liquid crystal agent capable of forming the liquid crystal alignment film. [Embodiment] The liquid crystal alignment agent of the present invention contains a reaction product of a tetrabasic acid dianhydride and a diamine, i.e., polylysine or a derivative thereof. The derivative of the poly-proline acid is intended to be dissolved in a solvent when the liquid crystal alignment agent described later is contained, and the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later. The composition of the liquid crystal alignment film of the main component. Examples of such (four) projectiles include: soluble sputum and poly-proline amide amine, and the like, and the amine 酴觫觫匀 - , , , , , , , , , , 八八八八八八八八八八八八八八八八八八八八八^ base /, carboxyl group obtained by dehydration ring-closing reaction | 醯耻 shame, 2) poly-proline acid - Qiu Ba and Gan & ^ 伃妁汆酝伃妁汆酝的的获得减减减_Reacting with knife X-imine, 3) Converting the carboxyl group of polyproline to 19 200906914 Substituting I, 4) An amine of the acid dianhydride contained in the tetracarboxylic dianhydride compound Polyammonium acid obtained by reacting a carboxylic acid and reacting it, and further, 5) a polydecylamine obtained by subjecting a part of the polyamic acid polyamide copolymer to dehydration ring closure reaction Yttrium. The polyamic acid or a derivative thereof may be either a compound or two or more compounds. The diamine contains a diamine represented by the following formula (1). The diamine represented by the formula (1) may be one kind of compound or two or more types of compounds. [Chem. 13]

所述通式（1)中’ R1獨立地表示一價有機基，R2獨立地表示一價基，Z表示包含碳數1〜5的亞烷基的二價基。所述R〗可以使用各種一價有機基’優選R1獨立為碳數1〜3的烷基。所述r2可以使用各種一價基’ R2較好的是獨立為氫、碳數1〜3的烷基、氟、氯或溴。所述z可以使用包含碳數1〜5的亞烧基的各種結構的二價基。Z既可以是碳數1〜5的亞院基’也可以是具有碳數1〜5的亞烷基與其他二價基的基團。所述亞烧基既可以是一種，也可以是雨種或兩種以上（其中’不相連）。這種Z例如可舉出以下述通式（8)表示的二價基。 [化H] 20 (8) 200906914 Ζδίδ^ρΐΐIn the formula (1), R1 independently represents a monovalent organic group, R2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms. As the R, various monovalent organic groups can be used, and it is preferred that R1 is independently an alkyl group having 1 to 3 carbon atoms. The r2 may use various monovalent groups. R2 is preferably an alkyl group independently derived from hydrogen or a carbon number of 1 to 3, fluorine, chlorine or bromine. As the z, a divalent group of various structures containing a mercapto group having 1 to 5 carbon atoms can be used. Z may be a sub-group having a carbon number of 1 to 5 or a group having an alkylene group having 1 to 5 carbon atoms and another divalent group. The sub-alkyl group may be either one type or a rain type or two or more types (where 'unconnected'). Such a Z is, for example, a divalent group represented by the following formula (8). [化H] 20 (8) 200906914 Ζδίδ^ρΐΐ

通式（8)中，R8獨立地表示氫或碳數1〜3的烷基， η表示1〜5的整數。所述亞烷基較好的是碳數2〜5的亞烧基。In the formula (8), R8 independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and η represents an integer of 1 to 5. The alkylene group is preferably a calcined group having 2 to 5 carbon atoms.

以通式（1)表示的二胺在兩端的苯基上分別具有氨基。這些氨基的位置相對於Ν-Ζ-Ν主鏈，可以是鄰位 (ortho )、間位（meta)、對位（para )的任一位置，但就提高液晶顯示元件的施加電壓時的黑顯示特性的觀點而言，優選均為對位。本發明中，作為以通式（1)表示的二胺，例如可舉出以下化合物。 h2nThe diamine represented by the formula (1) has an amino group at each of the phenyl groups at both ends. The position of these amino groups may be any position of ortho, meta, or para with respect to the Ν-Ζ-Ν main chain, but the black of the liquid crystal display element is increased. From the viewpoint of display characteristics, it is preferable to be both para-positions. In the present invention, examples of the diamine represented by the formula (1) include the following compounds. H2n

[化 15] X[化15] X

ch3 ch I N-CH 3Ch3 ch I N-CH 3

A C3H7 C3H7 \_^nh2A C3H7 C3H7 \_^nh2

h2n 4 h2n nh2 6H2n 4 h2n nh2 6

C3H7 C3H7 N-(CH2)2-N y C2H5 〇2^5 N-(CH2)2-N y nh2C3H7 C3H7 N-(CH2)2-N y C2H5 〇2^5 N-(CH2)2-N y nh2

h2n 8 h2nt 10H2n 8 h2nt 10

nh2 〒2H5 〒2H5 -N-(CH2)3~N—《^ nh2 ch3 ch3 (CH2)4-N 、 ^Nh2 〒2H5 〒2H5 -N-(CH2)3~N—“^ nh2 ch3 ch3 (CH2)4-N, ^

nh2 21 12200906914 11Nh2 21 12200906914 11

C3H7 〒3H7C3H7 〒3H7

C3H7 〇3H7 N-(CH2)4-N h2n 14 〇-： h2n^^ c2h5 n-(〇h2)5-C3H7 〇3H7 N-(CH2)4-N h2n 14 〇-: h2n^^ c2h5 n-(〇h2)5-

-N-(CH2)5*-N—\ < h2n^^ ^ nh2 17-N-(CH2)5*-N-\ < h2n^^ ^ nh2 17

JfeH5 ch3 ch3/=i^5 λ ^N'CH2_N_A_/nh2 h2n [化 16]JfeH5 ch3 ch3/=i^5 λ ^N'CH2_N_A_/nh2 h2n [化16]

h2n 21 19 CH3H2n 21 19 CH3

CH3 ch3 /4= N-(CH2)2-N-CH3 ch3 /4= N-(CH2)2-N-

CH 20 nh5 h2nCH 20 nh5 h2n

H^5 ch3 ch3 -N—(CH2)2_NH^5 ch3 ch3 -N—(CH2)2_N

h2n 23 黑7 ?H3 ch3 ^ -N-(CH2)2-N—( ^H2n 23 black 7 ?H3 ch3 ^ -N-(CH2)2-N-( ^

nh2 =K： ?H3 ?H3/=K5 H>^~N_(CH2)3_N^iNH2 25 CH3 o h2n 27 . . OH3 〒H3 -n-(ch2)4-n-^ ^ 22 CH3 rR rH =|=\ yH3 yH3 -N-(CH2)3-N- h2n 24 h2n 26 ίΗ3 ?H3 }~N-(CH2〉3-N~<Nh2 = K: ?H3 ?H3/=K5 H>^~N_(CH2)3_N^iNH2 25 CH3 o h2n 27 . . OH3 〒H3 -n-(ch2)4-n-^ ^ 22 CH3 rR rH =| =\ yH3 yH3 -N-(CH2)3-N- h2n 24 h2n 26 ίΗ3 ?H3 }~N-(CH2>3-N~<

CH3 c«. -N-(CH2)4-N h2n h2n 29 C2H5CH3 c«. -N-(CH2)4-N h2n h2n 29 C2H5

ch3 i 於nh2 CH3/Jf4H5 NH2Ch3 i in nh2 CH3/Jf4H5 NH2

H2hT 28 /Η=^γ?Η3 ? ^ /-n-(ch2)5-n H2N 30 C3H7〇 1 ch3.0 31 CH3 h2nt 宁2H5 C2H5 -N—CH2-N—《^H2hT 28 /Η=^γ?Η3 ? ^ /-n-(ch2)5-n H2N 30 C3H7〇 1 ch3.0 31 CH3 h2nt Ning 2H5 C2H5 -N—CH2-N—“^

CH3 C N-(CH2)5-N h2n，3V气，Hs ?H2NQ~n，2-N 200906914 l ο_>ριι 33 H2N 35 Η==\7 (f2hl5 〒此广?々 -N—CH2~~N—^ ^ NH2CH3 C N-(CH2)5-N h2n, 3V gas, Hs ?H2NQ~n,2-N 200906914 l ο_>ριι 33 H2N 35 Η==\7 (f2hl5 〒此广?々-N-CH2~~ N—^ ^ NH2

CH3.D /H^5 ?2H5 c2Hr^7i>N - (CH2)2-NONH2 34 CH^ CHq c2h5 〒2H”丫 =3 -N-(CH2)2-N—^ h2n〜 ' Y 36 nh2 h2n 37 CH3 ^ LJ ^ lt CH3 λ=(===\ ?2Η^/=|=λ -n-(ch2)3-n- h2n 38 /¾7 ?2H5 C2Hr^7ϋΝ-{°Η2)2，Λ_Α NH2CH3.D /H^5 ?2H5 c2Hr^7i>N - (CH2)2-NONH2 34 CH^ CHq c2h5 〒2H"丫=3 -N-(CH2)2-N-^ h2n~ ' Y 36 nh2 h2n 37 CH3 ^ LJ ^ lt CH3 λ=(===\ ?2Η^/=|=λ -n-(ch2)3-n- h2n 38 /3⁄47 ?2H5 C2Hr^7ϋΝ-{°Η2)2,Λ_Α NH2

H2IsTH2IsT

nh2Nh2

c2h5 -N-(CH2)3-N H〆 [化 17] h2n 41 Ά 严 c2nr^〇~n—(ch2)3-nHh2 /¾5 ?2H5 43 CH3 Γ丨' h2N\_/ u'mh2,?气7 〒2H5 pH”?气7 h2N>^n'(CH2)5~n \_yr C2H5 C2H5/if=S •N-(CH2)5-N—^ > 40 /?\ ?2Hs ?2HrR >^Ν·{〇Η2)4_ΝΛ_/νη2 /¾7 ?2H5 c2h^ν>Ν-(ϋΗ2)4~ΝΛ_/ΝΗ2 /¾5 ^h5 c2Hjpr5 〇~N_(CH2)5"NA_/nh, h2n 42 h2n 44C2h5 -N-(CH2)3-NH〆[化17] h2n 41 Ά 严 c2nr^〇~n—(ch2)3-nHh2 /3⁄45 ?2H5 43 CH3 Γ丨' h2N\_/ u'mh2, qi 7 〒2H5 pH"? gas 7 h2N>^n'(CH2)5~n \_yr C2H5 C2H5/if=S •N-(CH2)5-N-^ > 40 /?\ ?2Hs ?2HrR > ^Ν·{〇Η2)4_ΝΛ_/νη2 /3⁄47 ?2H5 c2h^ν>Ν-(ϋΗ2)4~ΝΛ_/ΝΗ2 /3⁄45 ^h5 c2Hjpr5 〇~N_(CH2)5"NA_/nh, h2n 42 h2n 44

46 Chh CHo "C3H7 C3H7/=| 3 -N—CH2_N—L 47 h2n 48 h2n 49 CH3 h2n 51 H2NT 53 /=l=\ ?3H7 \_/~N_(CH2)2-N\_/f H气7 〒3H7 CsHy^Jj^.-， -N-(CH2)2-N-^ ^ H2N 5046 Chh CHo "C3H7 C3H7/=| 3 -N-CH2_N-L 47 h2n 48 h2n 49 CH3 h2n 51 H2NT 53 /=l=\ ?3H7 \_/~N_(CH2)2-N\_/f H Gas 7 〒3H7 CsHy^Jj^.-, -N-(CH2)2-N-^ ^ H2N 50

H2hTH2hT

Vn3 o ii7 c3h7 c3h7 ^ 货n~O_ \_γ·νη?Vn3 o ii7 c3h7 c3h7 ^ Goods n~O_ \_γ·νη?

/=^5 C3H7 C3Hv -N-(CH2)2-N 52 CH3 〜，〜.CH3 H=\ i3H7 〒3HJH=\ n-(ch2)3-n^ ^ 巧？3h7 c3h^5 w h2n 54 於NH, r , r 7-1—\ n-(ch2)3-n—J \-^NH2/=^5 C3H7 C3Hv -N-(CH2)2-N 52 CH3 ~, ~.CH3 H=\ i3H7 〒3HJH=\ n-(ch2)3-n^ ^ Qiao? 3h7 c3h^5 w h2n 54 at NH, r , r 7-1—n-(ch2)3-n—J \-^NH2

H2hT Η=ί7 C3H7 〒3Η^=〒々 ^-N-(CH2)3-N-^NH2 23 200906914 h2n [化 18] 57 55 CH3H2hT Η=ί7 C3H7 〒3Η^=〒々 ^-N-(CH2)3-N-^NH2 23 200906914 h2n [Chem. 18] 57 55 CH3

H2N 59 C3H7 〇3Η^=|=^ n-(ch2)4-n^Jnh2 ?3ηΓ!^7 N vJnh,H2N 59 C3H7 〇3Η^=|=^ n-(ch2)4-n^Jnh2 ?3ηΓ!^7 N vJnh,

=¾7 c3h7 N-(CH2)4-N 56 C2He Q H2N^-^ ch3.0 C3H7 〒3H广丨气5 -N-(CH2)4-N- nh2 /¾5 C3H7 CshJ^5 ί >N-(CH2)5-N~\Jnh,=3⁄47 c3h7 N-(CH2)4-N 56 C2He Q H2N^-^ ch3.0 C3H7 〒3H Guangqi gas 5 -N-(CH2)4-N- nh2 /3⁄45 C3H7 CshJ^5 ί >N- (CH2)5-N~\Jnh,

h2n 85 FH2n 85 F

H2N 87 H2N 90 广丨' ?H3 YH3/=K 4_/"n-CH2_nO丨 6 CH3 CH3 /=j=^ -N-(CH2)3"N-H2N 87 H2N 90 广丨' ?H3 YH3/=K 4_/"n-CH2_nO丨 6 CH3 CH3 /=j=^ -N-(CH2)3"N-

nh2 58 CH^ c3H7 c3h7^_ 〜到 _5_ΝΚη230 ^3Η? c3h7 ^ N-(CH2)5., ^ 86 F F 1 〒H3 CHy=K h2NV>N-(CH2)2_N^ /=i=\ ?H3 CH3 ν^ΝΗ：Nh2 58 CH^ c3H7 c3h7^_ ~ to _5_ΝΚη230 ^3Η? c3h7 ^ N-(CH2)5., ^ 86 FF 1 〒H3 CHy=K h2NV>N-(CH2)2_N^ /=i=\ ?H3 CH3 ν^ΝΗ:

nh2 h2n 91 nh2Nh2 h2n 91 nh2

h2n 93 F /=l=\ 于 2比〇2^5/=|=\ X >-n-ch2-n-^ nh2H2n 93 F /=l=\ at 2 ratio 〇2^5/=|=\ X >-n-ch2-n-^ nh2

h2n^ 95 H2M义 97 FH2n^ 95 H2M meaning 97 F

C2H5 N-(CH2)3-N 2^5^=|=\\x nh2C2H5 N-(CH2)3-N 2^5^=|=\\x nh2

〒2H5 C2^5 n-(ch2)5-n〒2H5 C2^5 n-(ch2)5-n

nh2 /=丨==\ 〒3H7 C3Hy=L·H2Ni>_2)2_NH2Nh2 /=丨==\ 〒3H7 C3Hy=L·H2Ni>_2)2_NH2

[化 19] 99 tf /=l=\ ?3H7 C3Ht^UH2N0(CH2)4_d2[Chem. 19] 99 tf /=l=\ ?3H7 C3Ht^UH2N0(CH2)4_d2

24 200906914 2δ1«3ρΐί 101 Cl ί Η2Ν^ν 103 Cl24 200906914 2δ1«3ρΐί 101 Cl ί Η2Ν^ν 103 Cl

ClCl

〒Η3 CH3 /=ΐ=\ N-CH2-hJ-^ ^ NH, η2ν〆' 105 Cl〒Η3 CH3 /=ΐ=\ N-CH2-hJ-^ ^ NH, η2ν〆' 105 Cl

Cl 〒Η3 CH3 /=|==\ N-(CH2)3-N-Cl 〒Η3 CH3 /=|==\ N-(CH2)3-N-

nh2 102 Cl Cl rK fHs ?V'I=\ Η2Ν〇-ν_™ΌΝΗ2 104 Cl Cl rK ?Hs ?V|=\»，η2)4_ν_(^ y^=l=\ 丫丨丨 3 CH3 /=|=\Nh2 102 Cl Cl rK fHs ?V'I=\ Η2Ν〇-ν_TMΌΝΗ2 104 Cl Cl rK ?Hs ?V|=\»,η2)4_ν_(^ y^=l=\ 丫丨丨3 CH3 /=| =\

h2n' 106 CIH2n' 106 CI

Cl f \ h2n 107 Cl Cl 〒2H5 〒2H5,|= -N-(CH2)2-N- 7Cl f \ h2n 107 Cl Cl 〒2H5 〒2H5,|= -N-(CH2)2-N- 7

(p2H5 C2H5 n-ch2-n—( ^(p2H5 C2H5 n-ch2-n-( ^

H2lA 108 GI nh2 109 Cl Cl /=l=\ 92H5 C2H5/=K H2N〇-(cH2)4-NdH2 111 Cl ci /=K 〒3H7 ^h7/=k H2»n-CH2-n~Q 113 /=1=^ 93H7 〒3H7,|=y^_N.(CH2)3_N^> 、nh2 nh2H2lA 108 GI nh2 109 Cl Cl /=l=\ 92H5 C2H5/=K H2N〇-(cH2)4-NdH2 111 Cl ci /=K 〒3H7 ^h7/=k H2»n-CH2-n~Q 113 / =1=^ 93H7 〒3H7,|=y^_N.(CH2)3_N^> , nh2 nh2

h2nA 110 Cl (p2H5 〇2H5/=|=\ N-(CH2)3-N—( nh2 h2n 115 9 nh2h2nA 110 Cl (p2H5 〇2H5/=|=\ N-(CH2)3-N-( nh2 h2n 115 9 nh2

ClCl

C3H7 〇3Η7 N-(CH2)5-N h2n〆、 117 ψ 、nh2 h2nC3H7 〇3Η7 N-(CH2)5-N h2n〆, 117 ψ, nh2 h2n

〒h3 ch3 iL N-(CH2)2-N-^ J〒h3 ch3 iL N-(CH2)2-N-^ J

Cl Cl /=l=\ 丨、 H2N0—dH2 112 Cl Cl /=l=\ p3H7 93H7/=|====\ C J^-N-(CH2)2-N—y ) h2n"^~^ i^nh2 Λ ΛΑ CI Cl /=K c3h7 〇3Η7/=κ h2»爾NdH2 116 'Γ ch3 CH3JL CH2—N—\ /) ^^nh2 118 Br Br 1 CH3 ch3 'Cl Cl /=l=\ 丨, H2N0-dH2 112 Cl Cl /=l=\ p3H7 93H7/=|====\ CJ^-N-(CH2)2-N-y ) h2n"^~^ i ^nh2 Λ ΛΑ CI Cl /=K c3h7 〇3Η7/=κ h2»尔NdH2 116 'Γ ch3 CH3JL CH2—N—\ /) ^^nh2 118 Br Br 1 CH3 ch3 '

nh2 h2n ΛNh2 h2n Λ

(CH2)3-N(CH2)3-N

nh2 [化 20] 119 BrNh2 [化 20] 119 Br

Br 丨〒h3 H2n^L_/ V_>Nh2 121 Br Br C2H5 C2H5^/=[=\ N—CH2-N—^ ^Br 丨〒h3 H2n^L_/ V_>Nh2 121 Br Br C2H5 C2H5^/=[=\ N—CH2-N—^ ^

H2NH2N

nh2 120 Br Br/=k 〇h3 c^, i, /-n-(ch2)5-n^1 J H2N^~/ V_>Nh2 122 i c2h6 C2HaH\H2N0-(cH2)2ONH2 25 200906914 123 Br Br /=|=v c2h5 c2h5^=\=.\ ^n-(ch2)3-n—\ J h2n^~^ ^^nh2 125 Br Br ?2H5 〒2H^=|=\^ -N-(CH2)5-N—4 J H2N,^~^ \_>Nh2 124 Br BrC2H5 〇2Η^=|=-n-(〇h2)4-n-\ J h2n, 'i~,J ^~~^nh2Nh2 120 Br Br/=k 〇h3 c^, i, /-n-(ch2)5-n^1 J H2N^~/ V_>Nh2 122 i c2h6 C2HaH\H2N0-(cH2)2ONH2 25 200906914 123 Br Br /=|=v c2h5 c2h5^=\=.\ ^n-(ch2)3-n—\ J h2n^~^ ^^nh2 125 Br Br 2H5 〒2H^=|=\^ -N-(CH2 )5-N—4 J H2N,^~^ \_>Nh2 124 Br BrC2H5 〇2Η^=|=-n-(〇h2)4-n-\ J h2n, 'i~,J ^~~^nh2

126 Br Br 广丨'〒 3H7 C3HyJL>^J^N~CH2_N vJ 127 Br126 Br Br 广丨'〒 3H7 C3HyJL>^J^N~CH2_N vJ 127 Br

Br Br /=K ?3H7 ?3H7/=K〇~N_(CH2)rN{>>NH2 h2n 128 BrBr Br /=K ?3H7 ?3H7/=K〇~N_(CH2)rN{>>NH2 h2n 128 Br

Br h2n 129 Br BrC3H7 〇3H7/=1==^ -N-(CH2)4-N-^ ) H2N^~~u ^NH2Br h2n 129 Br BrC3H7 〇3H7/=1==^ -N-(CH2)4-N-^ ) H2N^~~u ^NH2

131 CH3 CH3131 CH3 CH3

H2NH2N

C3H7 C3H7^=1==^ n-(ch2)3-n- / 、nh2 NH2 h2n 130 Br Br C3H7 〇3η7/=|==\ -N-(CH2)5-N—L H2N, ^~^ ^-^NH2 132 CH3 CH3 [0^^H0"(CH2)2"0^^~OnC3H7 C3H7^=1==^ n-(ch2)3-n- / , nh2 NH2 h2n 130 Br Br C3H7 〇3η7/=|==\ -N-(CH2)5-N-L H2N, ^~^ ^-^NH2 132 CH3 CH3 [0^^H0"(CH2)2"0^^~On

133 CH3 CH3 H2N^〇(CH2)3〇-^-〇r nh2 135 CH3 CH3 H2N^0(CH2)5^^f nh2 134 CH3 CH3 h2nQ^〇(〇h2)^-G 136 C2H5 C2H5 H2N〇^o^^NH2 [化 21] 137133 CH3 CH3 H2N^〇(CH2)3〇-^-〇r nh2 135 CH3 CH3 H2N^0(CH2)5^^f nh2 134 CH3 CH3 h2nQ^〇(〇h2)^-G 136 C2H5 C2H5 H2N〇^ o^^NH2 [化21] 137

—〒2H^_ — 〇2^5_ 138 C2H5 C2H5 h2nQ^h2)2〇-^nh2 H2NQ^〇(ch2)3〇-^ 139_ C2H5_ _ C2Ha 140 __ ?2Hi_ _ C2Ha H2nC^N0-(CH2)4-^^n0NH2 H2nON〇-<CH2)5〇-N^ …二 ^ C3H7 142 _ C3H7. C3H7 I0^N_0/X3^N^}Nh2 H2N〇N^)H(CH2)2^/^N^}r 144 C3H7 C3H7 ΟΌ叫 H2NQ^(CH2k^Q 2 2—〒2H^_ — 〇2^5_ 138 C2H5 C2H5 h2nQ^h2)2〇-^nh2 H2NQ^〇(ch2)3〇-^ 139_ C2H5_ _ C2Ha 140 __ ?2Hi_ _ C2Ha H2nC^N0-(CH2)4 -^^n0NH2 H2nON〇-<CH2)5〇-N^ ... 2^ C3H7 142 _ C3H7. C3H7 I0^N_0/X3^N^}Nh2 H2N〇N^)H(CH2)2^/^N^ }r 144 C3H7 C3H7 Howling H2NQ^(CH2k^Q 2 2

h2n 143_ C3H7 H2nQ-^〇(CH2)3\ 145 C3H7 C3H7 H2nOHN^J^(CH2)5-〇^^G 2 nh2 26 200906914 158 H2N\ CH3CH3 CH3 CH3 159 CH3CH3 〇-〇^心2 A心…〜…叫 CH3_CH3 161 CH3CH3 ch3 ch3 160 CH3CH3lO_NhO^<CH2)3· h2n 'NH2 H2N， 162 CH3CH3 CH3 CH3 163 ^〇-(ch2)5〇-^ -(CH2)2·2 143 〇 CH CH CH CH CH ...called CH3_CH3 161 CH3CH3 ch3 ch3 160 CH3CH3lO_NhO^<CH2)3· h2n 'NH2 H2N, 162 CH3CH3 CH3 CH3 163 ^〇-(ch2)5〇-^ -(CH2)2·

nh2 CH3 C2H5 C2H5CH3 i0^n_0^C^n~0n ^C^CH3 165 CH3O2H5 ^CH： l4^K^(CH2)2(^N-〇 Η2Ν〇·1〇·(〇η2)3·^^ι^^丨 h2n 164 CH H2N: 、NH2 H2lNh [化 22] 166 9¾ H2N: 168 5C H3\、 I CH3C2H5 C2H5Cl· CH3 ?3H7 C3H7CH, 170 CH3C3H7 C3H7CH3h2nO~nO_(ch2)3~C^n~Oi ! MX 嘴 185 CoHsCHs CH3 C2l· 172 CH3 」一 ^ h2n:Nh2 CH3 C2H5 C2H5CH3 i0^n_0^C^n~0n ^C^CH3 165 CH3O2H5 ^CH: l4^K^(CH2)2(^N-〇Η2Ν〇·1〇·(〇η2)3·^^ι ^^丨h2n 164 CH H2N: , NH2 H2lNh [化22] 166 93⁄4 H2N: 168 5C H3\, I CH3C2H5 C2H5Cl· CH3 ?3H7 C3H7CH, 170 CH3C3H7 C3H7CH3h2nO~nO_(ch2)3~C^n~Oi ! MX Mouth 185 CoHsCHs CH3 C2l· 172 CH3 ” one ^ h2n:

187 C h2n 167 CH3 h2n\ 169 nh2 h2n\ 171 CH r nh2 H2N\ 2 CH3C2H5 C2H5CH： ^0(CH2)5〇-^-〇 9Η3?3Η7 C3H7 CH; 〇^(CH2)2^-^ CH393H7 93H7CH3 C2H5 186 C2H5CH3 nh2 h2n^_ nh2 nh2 C2H5CH3 ch3 c2h [0~r^〇(CH2)2〇-N^^|s C2H5CH3_ CH3 C2H5 188 C2H5CH3 CH3 C2H i€^_N0'(CH2)3^}-N_0NH2 H2n0~^0H(CH2)4^^^I^5|v nh2 189 C2H5CH3 Η2Ν〇~^Όί°Η2 191/^f5J^S f2H5&H5 192 C2H5C2H5187 C h2n 167 CH3 h2n\ 169 nh2 h2n\ 171 CH r nh2 H2N\ 2 CH3C2H5 C2H5CH: ^0(CH2)5〇-^-〇9Η3?3Η7 C3H7 CH; 〇^(CH2)2^-^ CH393H7 93H7CH3 C2H5 186 C2H5CH3 nh2 h2n^_ nh2 nh2 C2H5CH3 ch3 c2h [0~r^〇(CH2)2〇-N^^|s C2H5CH3_ CH3 C2H5 188 C2H5CH3 CH3 C2H i€^N0'(CH2)3^}-N_0NH2 H2n0~ ^0H(CH2)4^^^I^5|v nh2 189 C2H5CH3 Η2Ν〇~^Όί°Η2 191/^f5J^S f2H5&H5 192 C2H5C2H5

90 C2H5C2H5 C2H5C2H5h2^-〇^^NH2 193 ^H5C2H5_ Η2νΟ^ΝΗ^^CH2)4 C2H5 C2H5.〇^iNH2 h2 C2H5C2H5 n^〇(ch2),90 C2H5C2H5 C2H5C2H5h2^-〇^^NH2 193 ^H5C2H5_ Η2νΟ^ΝΗ^^CH2)4 C2H5 C2H5.〇^iNH2 h2 C2H5C2H5 n^〇(ch2),

27 200906914 195 η2ν· C2H5C3H7 CzH7 C2H5 19627 200906914 195 η2ν· C2H5C3H7 CzH7 C2H5 196

(CH2)2(CH2)2

[化 23] 197 197 C2H5〇3H7 C3H7C2HH2nC^N^^(CH2)3'0-N~0i[Chem. 23] 197 197 C2H5〇3H7 C3H7C2HH2nC^N^^(CH2)3'0-N~0i

CsHtCjHs 198 C2H5C3H7CsHtCjHs 198 C2H5C3H7

NH2H2N\厂丨、飞/厂㈣‘NH2H2N\Factory, Fly/Factory (4) ‘

199 C2H5C3H7 h2n^〇-(ch2)5- C3H7 c2h >12 C3H7CH3 CH3 C3H7 H 214 C3H7CH3H2N€^O(CH2)3. nh2 213199 C2H5C3H7 h2n^〇-(ch2)5- C3H7 c2h >12 C3H7CH3 CH3 C3H7 H 214 C3H7CH3H2N€^O(CH2)3. nh2 213

C3H7CH3,〇^h2)4- (CH2)2-C3H7CH3, 〇^h2)4- (CH2)2-

h2n\ 、NH2 〇2Η5〇3Η7 221ι· ，2嗔 rKv^, 93H792H5 92闩5_93 卜 ^〇(CH2)5Q-^ (CH2)3- 222 1 C3H7C2H5 93^7 C3H7 93^793*^7 223 C3H7C3H7 C3H7 〇3^7 i{^-N-〇^xC^N-〇NH, h2nC^'n〇(ch2)2〇n^^N]H2n\, NH2 〇2Η5〇3Η7 221ι· , 2嗔rKv^, 93H792H5 92Latch 5_93 卜^〇(CH2)5Q-^ (CH2)3- 222 1 C3H7C2H5 93^7 C3H7 93^793*^7 223 C3H7C3H7 C3H7 〇3^7 i{^-N-〇^xC^N-〇NH, h2nC^'n〇(ch2)2〇n^^N]

h2n 224 C3H7C3H7 H2N nh2 93H7 C3H7 作為更優選的以通式（1)表示的二胺，可舉出以下化合物。 [化 24] 28 240200906914 ΔΟ 1 Ο jpii 239 Η2Ν 241 η2ν 243 Η2Ν 245H2n 224 C3H7C3H7 H2N nh2 93H7 C3H7 The diamine represented by the formula (1) is more preferable, and the following compounds are exemplified. 28 24200906914 ΔΟ 1 Ο jpii 239 Η2Ν 241 η2ν 243 Η2Ν 245

CH3 ch3 ch3 ch3/ -(CH2)3-CH3 ch3 ch3 ch3/ -(CH2)3-

NH2 h2nNH2 h2n

242242

nh2 h2n ch3 ill—(ch2)5- ch3Nh2 h2n ch3 ill—(ch2)5- ch3

仆 ch3 ch3 '-(CH2)2H CH3 CHa 山—(CH2)4-Servant ch3 ch3 '-(CH2)2H CH3 CHa Mountain—(CH2)4-

nh2Nh2

nh2 244 nh2 h2nNh2 244 nh2 h2n

c2h5 c2h5C2h5 c2h5

nh2 f 245 246 …· /=\ C2H5 C2H5 /=. ?2Ηβ C2H5 H2N—^ J—N—(CH2)2~~N—^ V-NH2 H2N—^ \—N-(CH2)3-N—NH2 247 H2'Nh2 f 245 246 ...· /=\ C2H5 C2H5 /=. 2Ηβ C2H5 H2N—^ J—N—(CH2)2~~N—^ V-NH2 H2N—^ \—N-(CH2)3-N— NH2 247 H2'

248 N-(CH2)4-N-^ ^^nh2 h2nh^ \—N-(ch2〉5-n—^》—nh2 250 249248 N-(CH2)4-N-^ ^^nh2 h2nh^ \—N-(ch2>5-n-^)—nh2 250 249

nh2 h2n- 丨 251 253 /=\ C3H7 ?3h7^= h2n—yV-n-(ch2)5-n^ -nh2 252 NH2 h2nNh2 h2n- 丨 251 253 /=\ C3H7 ?3h7^= h2n-yV-n-(ch2)5-n^ -nh2 252 NH2 h2n

C3H7 山-(CH2)4- CH2)2.C3H7 Mountain-(CH2)4-CH2)2.

[化 25] 258 CH3 CH3 259 CH3 _ CH3 260 ch3[Chem. 25] 258 CH3 CH3 259 CH3 _ CH3 260 ch3

ch3 I 261 ch3 H2N^=yt!l-(=y(CH2)3-{=yt!j〇-NH2 Η2Ν-(=)-Λ-〇-(ΟΗ2)4〇^Ν^^ΝΗ2 262 CH3 CH3 267 _ C2H5_ _ 〇2Ηδ_ 268 _ 02^_ _ 〇2Ηδ_ H2^y-n-^y^yy~H-^y-m2 η2ν<^ν~^··((3η2)2<]}-νη^·νη2 29 200906914 269 —〒2H土 —〒2Η[ 270 _ C2H5_ _ 〇2Ηδ_ H2N'hv]/^N^C^^CH2^4K3KN_<(Z)>_NH2 272 C2H5 C2H5 H2N-^-i-^(CH2)5-^li-^-NH2 277 _ C3Ht_ 一 C3H7_ 278 _ C3h7_ _ 〇3Η^ H2N-ζ^l·t^y^ζy-l·i-ζ^-m2 H2N-^^N-{^(CH2)2-{^-N-^}-NH2 279 _ C3Ht_ _ C3Ht_ 280 _ C3Ht_ _ C3Ht_ h2nO-n^-(ch2)3O-Ki-^^nh2 h2n^h!j^*(ch2)4OhIi*^nh2 282 —〒3H: _ C3Ht_ H2N-^N^^(CH2)5^^N-〇-NH2 f 此外，作為進一步優選的以通式（1)表示的二胺，可舉出所述結構式239〜253及258〜262的化合物，作為進一步更優選的以通式（1)表示的二胺，可舉出所述結構式 240〜243及259〜262的化合物。所述二胺既可以僅包含以所述通式（1)表示的二胺，也可以進一步包含以下述通式（2)表示的其他二胺。以通式（2)表示的二胺既可以是一種化合物，也可以是兩種或兩種以上的化合物。 [化 26] H2N-R3-NH2 (2) 通式（2)中，R3表示具有取代基及不包含兩個或兩個以上的亞氨基的二價有機基。以通式（2)表示的二胺中包含各種二胺，優選舉出以下述通式（3)〜（6)表示的二胺。 [化 27] 30 200906914Ch3 I 261 ch3 H2N^=yt!l-(=y(CH2)3-{=yt!j〇-NH2 Η2Ν-(=)-Λ-〇-(ΟΗ2)4〇^Ν^^ΝΗ2 262 CH3 CH3 267 _ C2H5_ _ 〇2Ηδ_ 268 _ 02^_ _ 〇2Ηδ_ H2^yn-^y^yy~H-^y-m2 η2ν<^ν~^··((3η2)2<]}-νη^·νη2 29 200906914 269 —〒2H土—〒2Η[ 270 _ C2H5_ _ 〇2Ηδ_ H2N'hv]/^N^C^^CH2^4K3KN_<(Z)>_NH2 272 C2H5 C2H5 H2N-^-i-^(CH2 )5-^li-^-NH2 277 _ C3Ht_ A C3H7_ 278 _ C3h7_ _ 〇3Η^ H2N-ζ^l·t^y^ζy-l·i-ζ^-m2 H2N-^^N-{^( CH2)2-{^-N-^}-NH2 279 _ C3Ht_ _ C3Ht_ 280 _ C3Ht_ _ C3Ht_ h2nO-n^-(ch2)3O-Ki-^^nh2 h2n^h!j^*(ch2)4OhIi* ^nh2 282 - 〒3H: _ C3Ht_ H2N-^N^^(CH2)5^^N-〇-NH2 f Further, as a further preferred diamine represented by the formula (1), the structure is exemplified The compound of the formulae 239 to 253 and 258 to 262, and the diamine represented by the formula (1) are more preferably a compound of the above formulas 240 to 243 and 259 to 262. The diamine represented by the above formula (1) may be further contained, and may further contain another diamine represented by the following formula (2). The diamine represented may be either a compound or two or more compounds. In the formula (2), R3 represents a substituent and does not contain two. The divalent organic group of two or more imino groups. The diamine represented by the formula (2) contains various diamines, and preferably a diamine represented by the following general formulae (3) to (6). 27] 30 200906914

H2N V—^ NH^ 通式（3)中，Y表示包含碳數1〜5的亞烷基、氧及硫的一種或一種以上的二價基。 [化 28]H2N V - ^ NH^ In the formula (3), Y represents one or more divalent groups containing an alkylene group having 1 to 5 carbon atoms, oxygen and sulfur. [化 28]

通式（4)中，X1獨立地表示亞甲基或氧，X2表示可具有甲基或CF3作為取代基的碳數1〜8的亞烷基。 [化 29]In the formula (4), X1 independently represents a methylene group or oxygen, and X2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF3 as a substituent. [化29]

通式（5)中，X1獨立地表示碳數1〜6的亞烷基或氧， X3表示單鍵或碳數1〜3的亞烷基，環T表示1,4-亞苯基或1,4-亞環己基，R4表示氫或碳數1〜30的烷基，h表示 0或1。其中，R4中的所述烷基中，碳數2〜30的烷基中的任意的亞曱基可獨立地被氧、-CH=CH-或-C三C-取代，所述烷基中，氧並不相鄰。 [化 30]In the formula (5), X1 independently represents an alkylene group having 1 to 6 carbon atoms or oxygen, X3 represents a single bond or an alkylene group having 1 to 3 carbon atoms, and a ring T represents a 1,4-phenylene group or 1 , 4-cyclohexylene, R 4 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and h represents 0 or 1. Wherein, in the alkyl group in R4, any of the alkylidene groups in the alkyl group having 2 to 30 carbon atoms may be independently substituted by oxygen, -CH=CH- or -C tri C- in the alkyl group. The oxygen is not adjacent. [化30]

31 200906914 通式（6)中，R5表示氫或一價基。所述一價基可以使用各種有機基，優選碳數1〜30的烴基。此烴基優選為具有亞烷基、環亞烷基、亞芳基等二價烴基與烷基的基圑。所述通式（3)〜（5)中，鍵結於兩端的苯基上的兩個氨基的位置相對於Y或X1可以是鄰位、間位及對位的任一位置，但就提高液晶顯示元件的施加電壓時的黑顯示特性的觀點而言，優選相對於Y或X1為對位。31 200906914 In the formula (6), R5 represents hydrogen or a monovalent group. The monovalent group may use various organic groups, preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group is preferably a hydrazine having a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group or an arylene group and an alkyl group. In the general formulae (3) to (5), the positions of the two amino groups bonded to the phenyl groups at both ends may be any position of the ortho, meta and para positions with respect to Y or X1, but are improved. From the viewpoint of black display characteristics when a voltage is applied to the liquid crystal display element, it is preferable to be aligned with respect to Y or X1.

另外，所述通式（6)中，鍵結於末端的苯基上的兩個氨基的位置相互之間可以是鄰位、間位及對位的任一位置，但就使液晶顯示元件中表現出較大的預傾角的觀點而言，優選相互之間為間位。作為以通式（3)表示的二胺，例如可舉出以下化合物。 [化 31] 283Further, in the above formula (6), the positions of the two amino groups bonded to the phenyl group at the terminal may be any position of the ortho, meta and para positions, but in the liquid crystal display element From the viewpoint of exhibiting a large pretilt angle, it is preferable to be meta-position with each other. The diamine represented by the formula (3) is exemplified by the following compounds. [化31] 283

284284

h2nO"S~CH2'SOnh2 32 294 200906914 292-2 H2N[化 32] 293 H2N 295h2nO"S~CH2'SOnh2 32 294 200906914 292-2 H2N[化32] 293 H2N 295

S_(CH2)2_SS_(CH2)2_S

nh2 S-(CH2)3-S·Nh2 S-(CH2)3-S·

nh2Nh2

h2n 297 H2N 299 H2NH2n 297 H2N 299 H2N

S-(CH2)5-SS-(CH2)5-S

(ch2)2-o(ch2)2-o

Or nh2 nh2 〇-(CH2)4-〇Or nh2 nh2 〇-(CH2)4-〇

NH 2 H2N 296 H2N 298NH 2 H2N 296 H2N 298

OrOr

S-(CH2)4-SS-(CH2)4-S

nh2 h2n 300 η2Ν^' O—CH2_〇.Nh2 h2n 300 η2Ν^' O—CH2_〇.

NH o-(CH2)3-〇NH o-(CH2)3-〇

2 nh2 o-(CH2)5-〇2 nh2 o-(CH2)5-〇

nh2 作為更優選的以通式（3)表示的二胺，可舉出以下化合物 [化 33]Nh2 is a more preferable diamine represented by the formula (3), and the following compounds are exemplified.

302h2^-^ ^-(ch2)2-^ - 303 H2N 305 (CH2)3 ο- nh2 h2n 304 h2n- 306 nh2 -(CH2)4·302h2^-^ ^-(ch2)2-^ - 303 H2N 305 (CH2)3 ο- nh2 h2n 304 h2n- 306 nh2 -(CH2)4·

nh2Nh2

307 H2N307 H2N

H2N~、,(CH2)5、)—nh2 ~<\ ^~~S~~~NH2 H2N—^ y—〇—^ jj—nh2 308 H2N- 33 310200906914H2N~,,(CH2)5,)-nh2 ~<\ ^~~S~~~NH2 H2N—^ y—〇—^ jj—nh2 308 H2N- 33 310200906914

309 H2N309 H2N

S〇2 s-ch2-s Ό^νη2 [化 34] 311S〇2 s-ch2-s Ό^νη2 [化 34] 311

η2ν· 313 H2N. 315 H2N 317 H2N 319 h2n h2n 312 nh2 h2n. 314 —^ ^-NH2 h2n——S-(CH2)5-S——卜 316 -^〇-CH2-〇-^NH2 h2N-Q-〇-(CH2)2-〇-^-I 318 〇-(CH2)3-〇 nh2 h2n ~^]γ o_(ch2)4-o <y'Η2ν· 313 H2N. 315 H2N 317 H2N 319 h2n h2n 312 nh2 h2n. 314 —^ ^-NH2 h2n——S-(CH2)5-S——Bu 316 -^〇-CH2-〇-^NH2 h2N-Q -〇-(CH2)2-〇-^-I 318 〇-(CH2)3-〇nh2 h2n ~^]γ o_(ch2)4-o <y'

S-(CH2)2-SS-(CH2)2-S

S-(CH2)4-S- 〇-(CH2)5-〇S-(CH2)4-S-〇-(CH2)5-〇

s-(ch2)3-s 2S-(ch2)3-s 2

作為進一步優選的以通式（3)表示的二胺，可舉出所述結構式301〜307及311〜319的化合物，作為進一步更優選的以通式（3)表示的二胺，可舉出所述結構式301〜 304、306、307及313的化合物。作為以通式（4)表示的二胺，例如可舉出以下化合物。 321 cf3 [化 35] 320 CH3The diamine represented by the formula (3) is further preferably a compound of the above structural formulas 301 to 307 and 311 to 319, and more preferably a diamine represented by the formula (3). The compounds of the structural formulas 301 to 304, 306, 307 and 313 are mentioned. The diamine represented by the formula (4) is exemplified by the following compounds. 321 cf3 [化35] 320 CH3

323 ΝΗ2 η2ν 325 〇·°~〇ΝΗ2 Η2Ν〇·°^^°·〇ΝΗ323 ΝΗ2 η2ν 325 〇·°~〇ΝΗ2 Η2Ν〇·°^^°·〇ΝΗ

7~(CH2)3·-(〇η2)5〇^νΗ2 νη2 η2ν 3277~(CH2)3·-(〇η2)5〇^νΗ2 νη2 η2ν 327

34 329 200906914 ZOJ Ojpil34 329 200906914 ZOJ Ojpil

NH2 h2n 331 333 nh2 nh2 H2N0^仆㈣ H2N^ ^ U V_^-nh2 H2N^ ^ \_2^NH2 334 335 2 H2N〇"°^(CH2)50,〇'^NH2 Η2Ν〇^〇"〇·{〇Η2)6·〇^〇νΟ*| 336 337 h2n〇^〇^(CH2)7-〇^Onh2 h2n〇^〇^(CH2)8〇^〇v〇nh2 作為更優選的以通式（4)表示的二胺，可舉出以下化合物。 [化 36] 360 CH3 361 CF3 Η2νΌ~0_Ο--〇·°~0~ΝΗ2 ~^Ι}_0~Ο_ΝΗ2 ch3 cf3 362 363 H2N_0^X3_CH2_0/N0~NH2 H2N-〇/N〇k(ch2)2O/S〇-NH2 364 365 η2νΌ^Οη(〇η2)3〇/ν〇-νη2 H2N-Q/^Q-(CH2)4-Q^Q-NH2 366 367 h2n^/n〇"(ch2)5〇/n〇-nh2 H2N-Q/nQ^(CH2)6^Q^Q^NH2 368 369 H2N^〇/X3-(CH2)7HCXS<C}-NH2 H2N-0/N^^(CH2)8-(^//N0-NH2 370 371 H2nO^〇O-ch2-^°O-nh2 H2N-QA^(CH2〉2hQ^〇hNH2 372 373 H2N^〇〇-(CH2)3〇°O-NH2 H2N^0^-(CH2)4-Q^〇O-NH2 374 375 H2N-Q^°'<〇^(CH2)5^0'^NH2 H2N^^°-^〇h(CH2)6^〇O^NH2 376 377 H2nO〇^(ch2)7^°^Qknh2 h2nhQ〇O^(ch2)s^°O-nh2 35 200906914 作為進一步優選的以通式（4)表示的二胺，可舉出所述結構式360、364〜367及372的化合物，作為進一步更優選的以通式（4)表示的二胺，可舉出所述結構式360、 364、365、367及372的化合物。作為以通式（5)表示的二胺，例如可舉出以下化合物。NH2 h2n 331 333 nh2 nh2 H2N0^servant (4) H2N^ ^ U V_^-nh2 H2N^ ^ \_2^NH2 334 335 2 H2N〇"°^(CH2)50,〇'^NH2 Η2Ν〇^〇"〇 ·{〇Η2)6·〇^〇νΟ*| 336 337 h2n〇^〇^(CH2)7-〇^Onh2 h2n〇^〇^(CH2)8〇^〇v〇nh2 as a more preferred formula The diamine represented by (4) includes the following compounds. [化36] 360 CH3 361 CF3 Η2νΌ~0_Ο--〇·°~0~ΝΗ2 ~^Ι}_0~Ο_ΝΗ2 ch3 cf3 362 363 H2N_0^X3_CH2_0/N0~NH2 H2N-〇/N〇k(ch2)2O/ S〇-NH2 364 365 η2νΌ^Οη(〇η2)3〇/ν〇-νη2 H2N-Q/^Q-(CH2)4-Q^Q-NH2 366 367 h2n^/n〇"(ch2)5 〇/n〇-nh2 H2N-Q/nQ^(CH2)6^Q^Q^NH2 368 369 H2N^〇/X3-(CH2)7HCXS<C}-NH2 H2N-0/N^^(CH2)8 -(^//N0-NH2 370 371 H2nO^〇O-ch2-^°O-nh2 H2N-QA^(CH2>2hQ^〇hNH2 372 373 H2N^〇〇-(CH2)3〇°O-NH2 H2N ^0^-(CH2)4-Q^〇O-NH2 374 375 H2N-Q^°'<〇^(CH2)5^0'^NH2 H2N^^°-^〇h(CH2)6^〇 O^NH2 376 377 H2nO〇^(ch2)7^°^Qknh2 h2nhQ〇O^(ch2)s^°O-nh2 35 200906914 Further preferred examples of the diamine represented by the formula (4) include The compound of the structural formulas 360, 364 to 367, and 372, and the diamine represented by the formula (4) are more preferable, and the compounds of the structural formulas 360, 364, 365, 367, and 372 are exemplified. The diamine represented by the formula (5) is exemplified by the following compounds.

[化 37][化37]

36 200906914 J.O 1 O Jpu36 200906914 J.O 1 O Jpu

349 明 NH2349 Ming NH2

[化 39][化39]

355355

ch3(CH2)3 357Ch3(CH2)3 357

37 200906914 CH337 200906914 CH3

9Η39Η3

作為更優選的以通式（5)表示的二胺，可舉出以下化合物。 κ [化 40]The diamine represented by the formula (5) is more preferable, and the following compounds are exemplified. κ [化40]

νη2Ηη2

38 200906914 ZOlOJpil38 200906914 ZOlOJpil

[化 41][化41]

39 20090691439 200906914

作為進一步優選的以通式（5)表示的二胺，可舉出所述結構式38卜382、384、390及398的化合物，作為進一步更優選的以通式（5)表示的二胺，可舉出所述結構式 38卜384、390及398的化合物。作為以通式（6)表示的二胺，例如可舉出以下化合物。 [化 42] 400 401 402 CH3 h2n5^-^nh2 H2n\-^NH2 h2n\-^nh2 h2n\-/nh； 404 405 (CH2)3-CH3Further, the diamine represented by the formula (5) is exemplified by the compound of the formula 38, 382, 384, 390 and 398, and the diamine represented by the formula (5) is further more preferable. The compounds of the formula 38, 384, 390 and 398 can be mentioned. The diamine represented by the formula (6) is exemplified by the following compounds. 400 401 402 CH3 h2n5^-^nh2 H2n\-^NH2 h2n\-^nh2 h2n\-/nh; 404 405 (CH2)3-CH3

^2Η5 403^2Η5 403

η2ν^^ήη2 407Η2ν^^ήη2 407

h2n^-/nh2 408 406H2n^-/nh2 408 406

/(CH2)6-CH3 410 411 ^ (CH2)9-CH3/(CH2)6-CH3 410 411 ^ (CH2)9-CH3

H2N；^NH2 413H2N;^NH2 413

h2n^-/nh2 414 (CH2)4-CH3 /~~^_y-(CH2)5~CH3 h2n^4jh2 409 (CH2)7-CH3 /~^~^-(CH2)8-CH3 η2ιΑ~Λιη2 412 (CH2)i〇-CH3 /-<(—^-(CH2)i fCH32 - 412 412 412 412 412 412 412 (CH2)i〇-CH3 /-<(—^-(CH2)i fCH3

^^^ ~(CH2)i2"CH3 H2N31-/nH2 h2n^-/nh； η2ν^-Λιη2 415 (CH2)i3-CH3 ^/-^~~)K(CH2)i4-CH3 h2n^^nh2 40 418200906914 [〇->μιι 416 417 ^ -(ch2)15-ch3^^^ ~(CH2)i2"CH3 H2N31-/nH2 h2n^-/nh; η2ν^-Λιη2 415 (CH2)i3-CH3 ^/-^~~)K(CH2)i4-CH3 h2n^^nh2 40 418200906914 [〇->μιι 416 417 ^ -(ch2)15-ch3

η2ν;^νη；Η2ν;^νη;

(CH2)l6'CH3 ^ ^~(CH2)l7'^^*3 2 Η2ν\-^ΝΗ2 η2ν^-^νη2 419 420 421-1 /r \ / ^CH2)l8~CH3 /\ ^(CH2)19-CH3 j-< H2N；1-/NH2 H2N^-^NH2 H2N^—/nH: 421-2 厂 -Λ. cj<yi _)-c2h5 rT^ h2n^^nh2 h2n^^nh2 [化 43] 423 /==\ / ~\ 424 一/^V_z rT^ ^~~(CH2)3’CH3 rT^ h2n^^nh2 η2ν(·^νη2 426 Ό3Η7 -(ch2)4-ch3 425(CH2)l6'CH3 ^ ^~(CH2)l7'^^*3 2 Η2ν\-^ΝΗ2 η2ν^-^νη2 419 420 421-1 /r \ / ^CH2)l8~CH3 /\ ^(CH2) 19-CH3 j-<H2N; 1-/NH2 H2N^-^NH2 H2N^-/nH: 421-2 Factory-Λ. cj<yi _)-c2h5 rT^ h2n^^nh2 h2n^^nh2 43] 423 /==\ / ~\ 424 A/^V_z rT^ ^~~(CH2)3'CH3 rT^ h2n^^nh2 η2ν(·^νη2 426 Ό3Η7 -(ch2)4-ch3 425

C2H5 Η2Ν^-^ΝΗ2 427C2H5 Η2Ν^-^ΝΗ2 427

_c3h7 η2ν(^νη2 428_c3h7 η2ν(^νη2 428

C4H9 Η2Ν^^ΝΗ2 429C4H9 Η2Ν^^ΝΗ2 429

Η2Ν^^ΝΗ2 431Η2Ν^^ΝΗ2 431

h2n^LJ^nh: 432 C5H” η2ν^-/νη；c2H4-^_y-c2H5 433 Η2Ν；1~^ΝΗ2 430H2n^LJ^nh: 432 C5H" η2ν^-/νη;c2H4-^_y-c2H5 433 Η2Ν;1~^ΝΗ2 430

C2H4-( /-CH3C2H4-( /-CH3

η2ν·^νη2 434 C2H4〇KCH2)2-CH3 ^~^~(^。2〜〇^2)3-彳 h2n^—πμη2 ch3 435Η2ν·^νη2 434 C2H4〇KCH2)2-CH3 ^~^~(^.2~〇^2)3-彳 h2n^-πμη2 ch3 435

Η2Ν^->ΝΗ2 C2H4~{^HCH2)4-CH3 f^H^~<^C2H4DHCH2)5-CH3 h2nt^〉nh2 41 200906914Η2Ν^->ΝΗ2 C2H4~{^HCH2)4-CH3 f^H^~<^C2H4DHCH2)5-CH3 h2nt^>nh2 41 200906914

作為更優選的以通式（6)表示的二胺，可舉出以下化 k. 合物| [化 44] 438More preferably, the diamine represented by the formula (6) is exemplified by the following k. compound | [44] 438

442 439442 439

H2NH2N

(CH2)10-CH3 NH^(CH2)10-CH3 NH^

443 h2n443 h2n

(CH2)irCH3 NH2 (ch2)13-ch3 444 H2N 446 h2n-(CH2)irCH3 NH2 (ch2)13-ch3 444 H2N 446 h2n-

(CH2)12-CH3 NH2 445(CH2)12-CH3 NH2 445

H2NH2N

nh2Nh2

(CH2)14-CH3 nh2 447(CH2)14-CH3 nh2 447

(ch2)15-ch3 448(ch2)15-ch3 448

449449

450450

42 20090691442 200906914

作為進一步優選的以通式（6)表示的二胺，可舉出所述結構式438、443、447及449〜451的化合物。本發明中，作為所述二胺，可進一步使用以通式（1 ) 及（2)表示的二胺以外的其他二胺。作為這種其他二胺，可舉出以下述通式（9a)或（9b)表示的二胺及具有石夕氧烷鍵的矽氧烷系二胺。 [化 45]Further, the diamine represented by the formula (6) is exemplified by the compounds of the structural formulae 438, 443, 447 and 449 to 451. In the present invention, as the diamine, other diamines other than the diamines represented by the general formulae (1) and (2) can be further used. Examples of such other diamines include a diamine represented by the following formula (9a) or (9b) and a decane oxide-based diamine having a oxacyclooxygen bond. [化45]

通式（9a)及（％)中，Q表示氧、硫、磺醯基、可具有取代基的碳數6〜20的亞芳基、可具有取代基的碳數 3〜20的環亞烷基、或可具有取代基的亞氨基。所述亞芳基、環亞絲及亞氨基可具㈣取代基可舉蝴立為碳數 1〜3的烷基、氟、氯及溴等一價有機基。所述亞芳基可舉出1，4-亞苯基，所述環亞烷基可舉出丨，4•亞環己基。通式 (9a)及（9b)中的Ri、R2&R8與所述通式及相同。作為以通式（9a)或（％)表示的二胺，例如可舉 43 nh2In the general formulae (9a) and (%), Q represents an oxygen, sulfur, sulfonyl group, a hexylene group having 6 to 20 carbon atoms which may have a substituent, and a cycloalkylene having 3 to 20 carbon atoms which may have a substituent. A group or an imino group which may have a substituent. The arylene group, the cyclofilament and the imino group may have a (IV) substituent group which may be a monovalent organic group such as an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine or bromine. The arylene group may, for example, be a 1,4-phenylene group, and the cycloalkylene group may be an anthracene or a cyclohexylene group. Ri, R2 & R8 in the formulae (9a) and (9b) are the same as the above formula. As the diamine represented by the formula (9a) or (%), for example, 43 nh2

200906914 出以下化合物 [化 46] 61 ._ CH,200906914 The following compounds were produced [Chem. 46] 61 ._ CH,

^r^CH3/=x CH3/=^ Η2νΛ / η»ΝΛ_>Ν~〇ΝΗ2 V^H5iH3^ ?Η3/^5 Η2νΛ [化 47] 93^7^r^CH3/=x CH3/=^ Η2νΛ / η»ΝΛ_>Ν~〇ΝΗ2 V^H5iH3^ ?Η3/^5 Η2νΛ [化 47] 93^7

44 200906914 ΖόΙΟ^ρΐΤ 83 f 84 Jf^7 C3H7 — C3H7i^7 h2n^_fj ^~/ '~^'nh2 H2N 146 CH3 CH3 147 h2n〇-^,^^-〇O_^~Onh, h2n( 148 \_/NH2H2N\ 150 C，H«； ΟρΗς 151 r C2H5 C2H544 200906914 ΖόΙΟ^ρΐΤ 83 f 84 Jf^7 C3H7 — C3H7i^7 h2n^_fj ^~/ '~^'nh2 H2N 146 CH3 CH3 147 h2n〇-^,^^-〇O_^~Onh, h2n( 148 \ _/NH2H2N\ 150 C,H«; ΟρΗς 151 r C2H5 C2H5

h2n\ 152 h2n\ 154 h2n\ ' C2H5 C2H5 151 _ c3h7_ _ c3h7_ 〇-^~O~s_0_^-0NH2h2n0_n_O~s_0~n_0i CH3 9H3 153 C2H5 92*^5 〇-^^}_s〇2〇-NhONH2H2N〇_N_0~s〇2^^N^0, C3H7 93*^7G^n^C^s〇2^^n^C^, nh2 155 CH3 ^h2h2n〇 nh2H2n\ 152 h2n\ 154 h2n\ ' C2H5 C2H5 151 _ c3h7_ _ c3h7_ 〇-^~O~s_0_^-0NH2h2n0_n_O~s_0~n_0i CH3 9H3 153 C2H5 92*^5 〇-^^}_s〇2〇-NhONH2H2N〇 _N_0~s〇2^^N^0, C3H7 93*^7G^n^C^s〇2^^n^C^, nh2 155 CH3 ^h2h2n〇nh2

i C2H5 C2H5 157 C3H7 ?3H7 ch3 CH3 CH3 174 CH J, h2n\ H2N〇-N-〇~，f-〇-N_0NH2 CH3 ch3 ^ CH3 C2H5 C2H5CH3i C2H5 C2H5 157 C3H7 ?3H7 ch3 CH3 CH3 174 CH J, h2n\ H2N〇-N-〇~,f-〇-N_0NH2 CH3 ch3 ^ CH3 C2H5 C2H5CH3

^-〇-〇-〇-i-〇NH2 h2n u, CH3 C2H5 C2H5CH3 178 CH3 C3H7 93Η7〇Η： h2n〇-^~0~s^^_n^^NH2h2n〇-n^O~s_0~n^O, 177 nh2 179 CH3CH3 ch3 ch3 180 ch3 c2h5 C2H5CH3 h2n€5_n'~Os〇20~n^5>Nh2H2nC^n~0"s〇2^^n^^nh2 〇3Hr C3H7CH3 ^ch3CH3 _ fsCHs H2N〇~N~0_S〇20_NH0Nh2 H2N〇_N^^_ffO"N^NH2 ch3 45 200906914 ch3 ch3 nh2 200 〇2Η5〇Η3 h2n h2n\ 206 92H5CH3 h2n: [化 49] nh2 h2n 203 h2n: nh2 9H3 c2h5 nh2 〕9?h5?h3 ch3 c2h5 202 C2H5C3H7 C3H7 c2h5 η2Ν〇^〇·0^·ΑΗ2 9gH5 92h5 o2h5 c2h5 C2H5CH3 CH3 C2H5 ^-〇so2^^ C2H5 〇2H5 92Hs p2H5 c2h59h3 9Hs ^ 0_N_0^sKI^_Or 205 C2H5C3H7 C3H7C2H5^-〇-〇-〇-i-〇NH2 h2n u, CH3 C2H5 C2H5CH3 178 CH3 C3H7 93Η7〇Η: h2n〇-^~0~s^^__^^^NH2h2n〇-n^O~s_0~n^O , 177 nh2 179 CH3CH3 ch3 ch3 180 ch3 c2h5 C2H5CH3 h2n€5_n'~Os〇20~n^5>Nh2H2nC^n~0"s〇2^^n^^nh2 〇3Hr C3H7CH3 ^ch3CH3 _ fsCHs H2N〇~N ~0_S〇20_NH0Nh2 H2N〇_N^^_ffO"N^NH2 ch3 45 200906914 ch3 ch3 nh2 200 〇2Η5〇Η3 h2n h2n\ 206 92H5CH3 h2n: [化49] nh2 h2n 203 h2n: nh2 9H3 c2h5 nh2 〕9?h5 ?h3 ch3 c2h5 202 C2H5C3H7 C3H7 c2h5 η2Ν〇^〇·0^·ΑΗ2 9gH5 92h5 o2h5 c2h5 C2H5CH3 CH3 C2H5 ^-〇so2^^ C2H5 〇2H5 92Hs p2H5 c2h59h3 9Hs ^ 0_N_0^sKI^_Or 205 C2H5C3H7 C3H7C2H5

h2N€>^-~G"KXh2N€>^-~G"KX

207 C2H5C2H5 C2H5C2H H2nO~N~0^S°2〇^N_Ok207 C2H5C2H5 C2H5C2H H2nO~N~0^S°2〇^N_Ok

H2nC 209 C2H5CH3H2nC 209 C2H5CH3

1 92H5p3H7 9sH? 92H5 i€^N~〇's〇2〇-N-〇NH2 ^ 92^592^5 92^*592^5 211 ^2^5〇3(47 C3H7C2H5 2 N〇-N-〇-,f-〇-N-〇NH2 H2N〇^N^^~f~^^N_0Ni 227 〇. H2N; 229 c： H2N: 231 C3H793H7 93H? i〇^N~0~oO~N_Ot 〇3η7 92*^5 92% 93H7 0^n~0^s_h^n^^m, c3h7 ch3 ch3 C3h ^〇s〇2〇-i-〇f 235 C3H7C3H7 93^7 h2n€>-^o2^-〇( h2n 233 H2N\ nh2 C3H7 nh2 228 C3H792H5 92H5 〇3卜 η2νΟ~νΌ~°-〇~ν-〇ι 230 C3H7 P^3 9^3 93^ H2N〇"N"{^s^J^N^5r 2 nh2 p3H7 nh2 h7 NH H71 92H5p3H7 9sH? 92H5 i€^N~〇's〇2〇-N-〇NH2 ^ 92^592^5 92^*592^5 211 ^2^5〇3(47 C3H7C2H5 2 N〇-N-〇- , f-〇-N-〇NH2 H2N〇^N^^~f~^^N_0Ni 227 〇. H2N; 229 c: H2N: 231 C3H793H7 93H? i〇^N~0~oO~N_Ot 〇3η7 92*^ 5 92% 93H7 0^n~0^s_h^n^^m, c3h7 ch3 ch3 C3h ^〇s〇2〇-i-〇f 235 C3H7C3H7 93^7 h2n€>-^o2^-〇( h2n 233 H2N\ nh2 C3H7 nh2 228 C3H792H5 92H5 〇3 η2νΟ~νΌ~°-〇~ν-〇ι 230 C3H7 P^3 9^3 93^ H2N〇"N"{^s^J^N^5r 2 nh2 p3H7 nh2 h7 NH H7

9—3H7〒2H5 _ c2H5〇3h7 ,〇->ίι-〇-3〇2〇-ίΙ-〇ΝΗ ，7γ3「〇 h2n\ 236 NH2 5p3H7 C3H7CH3 CH3 C3H7 ch3 237 93Η792Η5 C2H5C3H7 238 93H7(p3H7 C3H7C3H7h2N€>-^^-〇NH2㈠办仆⑼众 ch3 ch3 46 200906914 Z.O J Ο J jJIl9—3H7〒2H5 _ c2H5〇3h7 ,〇->ίι-〇-3〇2〇-ίΙ-〇ΝΗ ,7γ3“ 〇h2n\ 236 NH2 5p3H7 C3H7CH3 CH3 C3H7 ch3 237 93Η792Η5 C2H5C3H7 238 93H7(p3H7 C3H7C3H7h2N€&gt ;-^^-〇NH2(一)办仆(9)众ch3 ch3 46 200906914 ZO J Ο J jJIl

461 ch3461 ch3

463 C3H7 C3H7^-〇-R^-〇NH2 h2n [化 50] 465 CH3C2H5,：I=V J·广 h2n 467 H2N 469 462 464 ch3 9h3463 C3H7 C3H7^-〇-R^-〇NH2 h2n [化50] 465 CH3C2H5,:I=V J·广 h2n 467 H2N 469 462 464 ch3 9h3

P2H5CH3WNH c2H5yM3_ _ ch3c2h5i〇^N^I^NO^N_Of C2H5Cp3H7 C3H7C2H5 〒3H7?2H5 92Ηδ<?3ΗP2H5CH3WNH c2H5yM3_ _ ch3c2h5i〇^N^I^NO^N_Of C2H5Cp3H7 C3H7C2H5 〒3H7?2H5 92Ηδ<?3Η

H2N 471 C3H nh2 H5 nh2 h7 466 CH3 〒3H7 468 470 472 h2n CH3 ?3H7 93H7CH3 C2H5C2H5 c2h5c2h C3H7?H3 w ?H3C3H7 C3H7C3H7 C3H7C3H7 NH2 nh2 以通式（9a)或（9b)表示的二胺在兩端的苯基上分別具有氨基。這些氨基的位置相對於所述二價有機基，可以是鄰位、間位、對位的任一位置，但就提高液晶顯示元件的施加電壓時的黑顯示特性的觀點而言，優選均為對位。作為優選的以通式（9a)或（9b)表示的二胺，可舉出以下化合物。 254 [化 51] CH3 ch3 255 CH3 ch3 H2N-{3_N-^^-〇-^^-N-^^-NH2 H2N^Q^N^^S02{3_N_O^NH2 256 CH3 CH3 257 CH3 CH3 ch3H2N 471 C3H nh2 H5 nh2 h7 466 CH3 〒3H7 468 470 472 h2n CH3 ?3H7 93H7CH3 C2H5C2H5 c2h5c2h C3H7?H3 w ?H3C3H7 C3H7C3H7 C3H7C3H7 NH2 nh2 Phenyl group of diamine represented by formula (9a) or (9b) Each has an amino group. The position of the amino group may be any position of the ortho, meta or para position with respect to the divalent organic group, but it is preferably from the viewpoint of improving the black display property when the voltage is applied to the liquid crystal display element. Counterpoint. Preferred examples of the diamine represented by the formula (9a) or (9b) include the following compounds. 254 [化 51] CH3 ch3 255 CH3 ch3 H2N-{3_N-^^-〇-^^-N-^^-NH2 H2N^Q^N^^S02{3_N_O^NH2 256 CH3 CH3 257 CH3 CH3 ch3

263 H2N 1 _ C2H^ _ 〇2H5_ 264 G2H5 C2H5 47 200906914 丨2263 H2N 1 _ C2H^ _ 〇2H5_ 264 G2H5 C2H5 47 200906914 丨2

35 02Ηδ C2H5 n-〇-n-〇_s'〇-^-〇-n!35 02Ηδ C2H5 n-〇-n-〇_s'〇-^-〇-n!

273 H2N 275 H2N p3^7 C3H7 C3H7 c3h7 i-〇-^-〇-s-〇^-〇-NH2 可以在本聲273 H2N 275 H2N p3^7 C3H7 C3H7 c3h7 i-〇-^-〇-s-〇^-〇-NH2 can be in this sound

對於所述石夕氧烧系二胺並沒有特別明中比較好地使用以通式（7)表示的二 [化 52] R22 R22 R23 H2N^R21^a-〇)y-Si-(R2VNH2 {7) 通式〔7)中 ,21 獨立地表示碳數1〜3 基H立Γ表Γ亞ψ基、絲基或被'絲取代白= 本基，X㈣立地表不1〜6的整數，y表示卜1()的亞本發明中，所使用的所述二胺的種類可以根據示元件的電場方式進行確定。已知液示元件曰= 式有橫向電場方式無向電場方式，在橫向電場方式= 晶顯不兀件中，必須表現出較小的預傾角，也就是所$ = 低預傾角，所以如果是以通式（2)表示的二胺，那麼】I 使用以通式（3)或（4)表示的二胺。 Α 本發明中，由使用1〇〇莫耳％的以通式（1)表示的二胺作為所述二胺的液晶配向劑而獲得的液晶顯示元件同時具有較大的對比度、低殘留Dc、及低預傾角的特性。因此，有效作為橫向電場方式的液晶配向膜。關於需要較大 48 200906914 ZOlOjpu 現出較大的預顯示元件，必須與表具有支鏈的二胺，如二具有支鏈的二胺细。作為所述以舉出以通式⑸ Μ通式⑵表示的二胺，那麼可必須是使用具有支=6) f示的f胺，作為並用的形態，盥直他（:例^的一胺所獲得的聚醯胺酸或其衍生物或者==傾角)聚酿胺酸或其衍生物的混合物此外2胺與低預傾角的二胺的共聚物。胺與以通式（2)矣-从_ 、式（1)表不的二使液晶顯示元件中制—觀—種以上。此時，就選所述二财DC明顯轉低的觀點而言，優耳％或20草耳。/、、式（1)表不的二胺的含有率為20莫有率^♦ 如果以通式⑴表示的二胺的含 f 莫耳那麼有時殘旨DC的降低效果會較小，而=會表現出針對殘像的效果。 4 動士^向電場方式的液晶顯示元件中，就提高不施加電 4 特性的觀點而言，優選在以通式⑴表示的二㈣基礎上進—步並用以通式⑶及⑷表示的二胺 ^-種或-種以上。進—步使用這些二胺，會成為低預傾角’所崎橫向電場方式非常有效。所述二胺中的以通式及（4)表示的二胺越多則越是提高液晶顯示元件的電壓保持率，但是考慮到殘留DC的降低，那麼所述含有率較好的是在1莫耳％〜80莫耳％的範圍内。另外，在縱向電場方式即TN方式、光學補償彎曲 (Optically Compensated Bend，OCB )方式、垂直排列 49 200906914 (Vertical Alignment，VA )方式中，必須表現出較大的預傾角。此時，必須將帶有支鏈的以通式（5)及（6)表示的二胺的一種或一種以上與以通式（1)表示的一胺並用。通過控制這些二胺的種類及比例，能夠表現出預定的預傾角’但考慮到降低殘留DC，那麽優選戶斤述含有率在1莫耳°/。〜80莫耳％的範圍内。應用通過並用以通式（5)及（6) 表示的二胺而獲得的聚合物的液晶顯示元件可成為進一步提高電壓保持率的縱向電場方式的液晶顯示元件。一另外，在進一步含有所述通式（1)〜（6)以外的其他二胺時’在應用所獲得的聚合物的液晶顯示元件中，就充刀表見出殘留DC的降低或黑顯示特性的提高點而言，其他-脸沾人士方π从木曰]觀 30莫耳％；^的含有率優選二胺整體的3G莫耳％或作為所述四竣酸二酐，名下，可使用苦知及本發明的效果的情況 J便用方香無糸四羧酸 |月况肪族四綾酸二酐等各衣式四竣酸二酐及脂以上。、種或者兩種或兩種合物〇，例如可舉出以下化 [化 53] 500It is not particularly preferable to use the above-mentioned oxime-oxygen-based diamine as the ruthenium represented by the formula (7): R22 R22 R23 H2N^R21^a-〇)y-Si-(R2VNH2 { 7) In the formula [7), 21 independently represents a carbon number of 1 to 3, a group of H, an anthracene group, a silk group or an integer substituted by a silk substitution white = a base, and an X (four) standing surface of not 1 to 6 y represents the sub-invention of the invention. The type of the diamine used can be determined according to the electric field mode of the device. It is known that the liquid display element 曰 = has a transverse electric field mode non-directional electric field mode, and in the transverse electric field mode = crystal display element, it must exhibit a small pretilt angle, that is, $ = low pretilt angle, so if it is The diamine represented by the formula (2), then I uses the diamine represented by the formula (3) or (4). In the present invention, a liquid crystal display element obtained by using a diamine represented by the general formula (1) as a liquid crystal alignment agent of the diamine has a large contrast ratio and a low residual Dc. And low pretilt characteristics. Therefore, it is effective as a liquid crystal alignment film of a transverse electric field type. About the need for larger 48 200906914 ZOlOjpu A large pre-display element is present, which must be fine with a diamine having a branch, such as a branched diamine. As the diamine represented by the general formula (5) and the general formula (2), it is necessary to use a f-amine having a branch = 6) f as a combined form, and it is an amine of the formula The obtained polyaminic acid or a derivative thereof or a mixture of == dip) poly-aracine or a derivative thereof is furthermore a copolymer of 2 amine and a low pretilt diamine. The amine is one or more kinds of the liquid crystal display element which is represented by the formula (2) 矣-from _ and the formula (1). At this time, in terms of choosing the second financial DC to be significantly lower, the ear is 20% or 20 ears. The content of the diamine represented by the formula (1) is 20%. If the f-mol of the diamine represented by the formula (1) is used, the effect of reducing the DC may be small, and = will show the effect on the afterimage. In the liquid crystal display element of the electric field type, in order to improve the characteristics of the non-applied electric power 4, it is preferable to further advance on the basis of the two (four) represented by the general formula (1) and to use the two formulas (3) and (4). Amines - or more than -. It is very effective to use these diamines in a stepwise manner to become a low pretilt angle. The more the diamine represented by the formula and (4) in the diamine, the more the voltage holding ratio of the liquid crystal display element is increased, but in view of the decrease in residual DC, the content ratio is preferably 1 Mole% ~ 80% of the range of moles. In addition, in the vertical electric field mode, that is, the TN mode, the optically compensated bend (OCB) mode, and the vertical alignment 49 200906914 (Vertical Alignment, VA), it is necessary to exhibit a large pretilt angle. In this case, one or more kinds of the diamines represented by the general formulae (5) and (6) having a branched chain must be used in combination with the monoamine represented by the general formula (1). By controlling the type and ratio of these diamines, a predetermined pretilt angle can be exhibited. However, in view of reducing residual DC, it is preferable to have a content ratio of 1 mol/. ~80% of the range of moles. A liquid crystal display element using a polymer obtained by using the diamines represented by the general formulae (5) and (6) can be a liquid crystal display element of a longitudinal electric field type which further increases the voltage holding ratio. In addition, when further containing other diamines other than the above formulas (1) to (6), 'in the liquid crystal display element of the polymer obtained by application, a reduction in residual DC or a black display is seen in the filling table. In terms of improvement of the characteristics, the other-face-to-face π is from the hibiscus] 30% by mole; the content of ^ is preferably 3 Gole % of the entire diamine or as the tetraphthalic acid dianhydride, In the case where the effects of the present invention and the effects of the present invention can be used, it is possible to use the above-mentioned various types of tetrahydrophthalic acid dianhydrides such as scented sulphuric acid and succinic acid. , species or two or two compounds 〇, for example, the following formula [Chem. 53] 500

50 200906914 ί 50350 200906914 ί 503

506506

508-1508-1

508 507508 507

509509

[化 54] 511 〇 512 Ο 513 〇〇〇 514 0 Κ 0 515 〇 oh 0 Λ 516 ^ Υ\ 0 Υ 0 517 〇 0 518 519 Ο I f 0 V Λ-χ )ί Ο 〇 τ ο ο^Λ_> 520 521 523511 〇 512 Ο 513 〇〇〇 514 0 Κ 0 515 〇 oh 0 Λ 516 ^ Υ \ 0 Υ 0 517 〇 0 518 519 Ο I f 0 V Λ-χ ) Ο 〇 τ ο ο ^ Λ _ gt ; 520 521 523

〇^ 0 524 Q〇^ 0 524 Q

200906914 (200906914 (

[化 55][化55]

所述四羧酸二酐優選所述結構式500、505〜508、 52 200906914 zoio^pu 511、515及517的化合物，更優選所述結構式500及Sll 的化合物。所述聚醯胺酸或其衍生物的分子量，例如為利用凝膠滲透色譜法（Gel Permeation Chromatography，GPC)的所獲得的聚苯乙烯換算的重量平均分子量（Mw)，優選1〇,〇〇〇〜500,000 ’更優選 20,000〜200,000。所述聚醢胺酸或其衍生物，除了使用所述四羧酸二酐與二胺以外，也可以與聚醯亞胺膜的形成中所使用的公知的聚醯胺酸或其衍生物同樣進行製造。例如，向具備原料投入口、氮氣導入口、溫度計、攪拌機及冷凝器的反應容器中投入以通式（1)及（2)〜（6)表示的二胺的一種或者兩種或兩種以上、以及根據情況從其他二胺中選擇的一種或者兩種或兩種以上的二胺，此外根據需要投入所需量的單胺。接著’投入溶劑（例如，醯胺系極性溶劑即曱基_2_ 吡咯炫酮或一甲基甲醯胺等）及四羧酸二酐的—種或者兩種或雨種以上，此外根據需要投入羧酸酐。此時，四羧酸二酐的總投入量優選與二胺的總莫耳數大致相等的莫耳數 (莫耳比0.9〜U左右）。、所述聚醯胺酸或其衍生物包含以通式〇)表示的二胺與四羧酸二酐反應而生成的結構，此外可包含以通式（2) 表示的二胺與讀I酐反應而生成的結構。作=以通式 ⑴表不的—胺與四_二酐反應而生成的結構，例如可舉出以下述通式（10)及（11)表示的結構，作為以通式 53 200906914 (2)表示的二胺與四羧酸二酐的反應而生成的結構，例如可舉出以下述通式（12)及（13)表示的結構。另外，通式（10)〜（13)中’ 表示來源於四叛酸二酐的四價有機基，R1及R2與通式（1)相同，R3與通式（2)相同。 [化 56]The tetracarboxylic dianhydride is preferably a compound of the structural formulas 500, 505 to 508, 52 200906914 zoio^pu 511, 515 and 517, more preferably a compound of the structural formulas 500 and S11. The molecular weight of the poly-proline or a derivative thereof is, for example, a polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC), preferably 1 Torr, 〇〇〇~500,000' is more preferably 20,000 to 200,000. The polyamic acid or a derivative thereof may be the same as the known poly-proline or the derivative thereof used in the formation of the polyimide film, in addition to the tetracarboxylic dianhydride and the diamine. Made for manufacturing. For example, one or two or more kinds of diamines represented by the general formulae (1) and (2) to (6) are introduced into a reaction container having a raw material inlet, a nitrogen gas inlet, a thermometer, a stirrer, and a condenser. And one or two or more kinds of diamines selected from other diamines as the case may be, and further, a desired amount of the monoamine is supplied as needed. Then, 'input solvent (for example, guanamine-based polar solvent, ie, thiol-2-pyrrolidone or monomethylguanidamine) and tetracarboxylic dianhydride, or two or more types of rain, or more, Carboxylic anhydride. In this case, the total amount of the tetracarboxylic dianhydride to be charged is preferably approximately the same number of moles as the total number of moles of the diamine (the molar ratio is about 0.9 to U). The polyaminic acid or a derivative thereof comprises a structure formed by reacting a diamine represented by the formula (〇) with a tetracarboxylic dianhydride, and further comprises a diamine represented by the formula (2) and a read I anhydride. The structure formed by the reaction. The structure which is produced by reacting an amine represented by the formula (1) with tetra-dianhydride, for example, has a structure represented by the following general formulae (10) and (11), and is a general formula 53 200906914 (2) Examples of the structure formed by the reaction of the diamine and the tetracarboxylic dianhydride shown by the following formulas (12) and (13) are mentioned. Further, in the general formulae (10) to (13), 'is a tetravalent organic group derived from tetrarebaric acid dianhydride, R1 and R2 are the same as those of the general formula (1), and R3 is the same as the general formula (2). [化56]

ψ R1 f :… w/ (10)ψ R1 f :... w/ (10)

XCOOHXCOOH

(11) (12) (13) 所述聚酸胺酸或其衍生物中的以通式⑽）〜（⑴ 結^通過較聚合物的結構時的通常技術來加以 f疋’更I體來說’可通過紅外光譜（M—d Spectroscopy，IR )或核磁 . '丁' 、丄，、振(nuclear magnetic resonance，NMR)來確定。 =細，:對於本發明中的聚《酸或其衍生物，以大篁的孩㈣使其獄，_财等㈣劑完全分離，並以IR、NMR _分析，㈣可加以敎t 此外， KOH或NaQH等㈣切液㈣體成 54 200906914 醯胺酸或其衍生物分解後，以有機溶劑進行萃取，並以氣相色譜（Gas Chromatography，GC )、高效液相色譜法（High performance Liquid Chromatography，HPLC)或氣相色譜/ 質譜分析法（Gas Chromatography-Mass Spectr〇metIy， GC-MS)進行分析，由此可鑒定所使用的單體。、本發明的液晶配向劑也可以進-步含有所述聚醯胺酸(11) (12) (13) In the polyamic acid or a derivative thereof, the general formula (10)) to ((1) is obtained by a general technique in the case of a polymer structure. Said ' can be determined by infrared spectroscopy (IR) or nuclear magnetic. 'Ding', 丄, 振 (nuclear magnetic resonance (NMR)) = fine, for the polyacid or its derivatives in the present invention Objects, with the big children (four) to make their prison, _ Cai et al (4) agent completely separated, and analyzed by IR, NMR _, (4) can be 敎 t In addition, KOH or NaQH, etc. (four) cut liquid (four) body formation 54 200906914 proline After decomposing or derivatizing the derivative thereof, extraction is carried out in an organic solvent, and gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography/mass spectrometry (Gas Chromatography- Mass Spectr〇metIy, GC-MS) is analyzed to thereby identify the monomer used. The liquid crystal alignment agent of the present invention may further contain the polyamic acid.

或，衍生物以外的其他成分。其他成分可以是一種，也可以是兩種或兩種以上。例如就提高液晶配向膜的耐久性的觀點而言，例如所^的液晶配向劑也可以進—步含有環氧化合物。如果合物具有環氧基，那麼並沒有特觀制，但優 ;物可以是-種化合物，也可__種“ 3 不發明中沒有特別_ ㈣述環氧化合物的含量並就優化不易因摩擦處理而使膜磨向膜中’ 而言，優選所述環氧化合_含量相H㈣久性的觀點〜40職，更優選0·2〜30 wt%。對於液晶配向劑為0」作為所述環氧化合物，例如 ^二縮水甘油®旨型環氧化合物二氧化有¥乳乙燒基的單體㈣ 3 ☆私祕合物、具與其他單體的共聚物m‘”環氣乙絲的單體 ^ ^αΤ«Γ(Β；) Τ-} ^ (Ε3)'(Ε5) 表不的化合物等。 200906914Or, other ingredients than derivatives. The other ingredients may be one type or two or more types. For example, from the viewpoint of improving the durability of the liquid crystal alignment film, for example, the liquid crystal alignment agent may further contain an epoxy compound. If the compound has an epoxy group, then there is no special system, but it is excellent; the material may be a compound or a compound of the formula: "3" is not in the invention, and the content of the epoxy compound is not easily optimized. The rubbing treatment to make the film rub into the film' is preferably from the viewpoint of the epoxidation-content phase H (four) longness to 40, more preferably 0·2 to 30 wt%. For the liquid crystal alignment agent, it is 0" as the The epoxy compound, for example, a diglycidyl®-based epoxy compound, has a monomer of a emulsified ethyl group (IV) 3 ☆ a private compound, and a copolymer with other monomers m'" Monomer ^ ^αΤ«Γ(Β;) Τ-} ^ (Ε3)'(Ε5) Table of compounds, etc. 200906914

.κ [化 57].κ [化57]

(Ε4) 通式（Ε4)中，η表示0〜10的整數。更具體來說，作為所述環氧化合物，可舉出：商品名 “Epikote 807” 、“Epikote 815” 、“Epikote 825” 、 “Epikote 827” 。作為以通式（E4)表示的化合物，可舉出：商品名 56 200906914 O^pil(Ε4) In the formula (Ε4), η represents an integer of 0 to 10. More specifically, examples of the epoxy compound include the trade names "Epikote 807", "Epikote 815", "Epikote 825", and "Epikote 827". The compound represented by the formula (E4): trade name 56 200906914 O^pil

“Epikote 828”、“Epikotel90P”、“Epikotel91P”（以上為YUKA SHELL EPOXY股份有限公司製造）、商品名 “Epikote 1004” 、“Epikote 1256” （以上為 JAPAN EPOXY RESINS股份有限公司製造）、商品名“Araidite CY177” 。作為以結構式（E1)表示的化合物，可舉出商品名 “Araldite CY184” （日本CIBA-GEIGY股份有限公司製造）。作為以結構式（E2 )表示的化合物，可舉出商品名 “Celloxide 2021P”、“EHPE-3150”（DAICEL 化學工業股份有限公司製造）。作為以結構式（E3)表示的化合物，可舉出商品名 “TECMOA VG3101L” （三井化學股份有限公司製造）。作為以結構式（E5)表示的化合物，可舉出“4,4，-亞曱基雙(N，N-二縮水甘油基苯胺)” （sigma_ALdRICH公司製造）。就優化液晶配向膜的透明性與平坦性的觀點而言，這些化合物中，所述環氧化合物優選包含：以通式（E4)表示的化合物（n = 〇〜4的化合物的混合物）即“Epik〇te 828 、以結構式（El )表示的化合物即“Araidite CY184” (日本CffiA-GEIGY股份有限公司製造）、以結構式（E2) 表示的化合物即商品名“Celloxide 2021P” （DAICEL化學工業鼓伤有限公司製造）、以結構式（)表示的化合物即商品名“TECMOAVG3101L”（三井化學股份有限公 57 200906914 二N 構式（E5)表示的化合物“4,4,_亞甲基雙 ‘水甘油基苯胺）”（SIGMa_al腦⑶公司製鍵、^甘環氧化合物’例如可舉出··縮水甘油月旨、縮水甘“二環氧基的丙稀酸系樹化合物是=脂肪族型環氧化合物。而且，環氣基的樹脂倾基的化合物，環氧樹脂是指具有環氣合物作ί St’例如可舉出··雙紛A型環氧化又-里環氧化合物、雙紛S型環氧化人物、雔^ 型環氧化合物、氨化雔 =^化口物雙驗型環氧化Μ ^ 型减合物、氫化雙_ 轰作人你 '、氣化雙齡-S型環氧化合物、氫化雙盼型環化人^、笨^雙Μ型環氧化合物、漠化雙驗·F型環氣化口物轉_清漆（phen〇In_ 氣型環氧化合物、漠化曱龄_清漆__、紛 _清漆型環氧化合物、含有萘骨架丄化合物、二… 曰衣式—縮水甘油醚化合物、脂肪族 (polysulfide) 物及聯本酚（biphenol)型環氧化合物。口作為所述縮水甘油醋，例如可舉出二縮物及縮水甘油酯環氧化合物。 / ·曰化口 58 200906914 物。作為所述縮水甘油胺，例如可舉出聚縮水甘油胺化合及共聚物胺，例如可舉出縮水甘油基醯作為所述縮水甘油基醯胺型環氧化合物。"Epikote 828", "Epikotel90P", "Epikotel91P" (above, manufactured by YUKA SHELL EPOXY Co., Ltd.), trade name "Epikote 1004", "Epikote 1256" (above, manufactured by JAPAN EPOXY RESINS Co., Ltd.), trade name " Araidite CY177”. The compound represented by the structural formula (E1) is exemplified by the trade name "Araldite CY184" (manufactured by CIBA-GEIGY Co., Ltd., Japan). The compound represented by the structural formula (E2) is exemplified by the trade name "Celloxide 2021P" and "EHPE-3150" (manufactured by DAICEL Chemical Industry Co., Ltd.). The compound represented by the structural formula (E3) is exemplified by the trade name "TECMOA VG3101L" (manufactured by Mitsui Chemicals, Inc.). The compound represented by the formula (E5) is "4,4,-indenyl bis(N,N-diglycidylaniline)" (manufactured by Sigma-Aldrich Co., Ltd.). In view of optimizing the transparency and flatness of the liquid crystal alignment film, in the compound, the epoxy compound preferably contains a compound represented by the formula (E4) (a mixture of compounds of n = 〇〜 4), that is, " Epik〇te 828, a compound represented by the structural formula (El), namely "Araidite CY184" (manufactured by CffiA-GEIGY Co., Ltd., Japan), and a compound represented by the structural formula (E2), trade name "Celloxide 2021P" (DAICEL Chemical Industry) The compound represented by the formula (), the compound represented by the structural formula (), the trade name "TECMOAVG3101L" (Mitsui Chemical Co., Ltd. 57 200906914, two N configuration (E5), the compound "4,4,_methylene double" "Glycidyl aniline" (" SIGMa_al brain (3) company bond, glycerol epoxide compound", for example, glycidyl sulphate, glycosylation "dihydroxy acyl acid tree compound = aliphatic type Epoxy compound. Moreover, a ring-based resin-based compound, epoxy resin means having a ring gas compound as ί St', for example, a double-type A-epoxidation--epoxy compound, double S Epoxidized character, 雔^ type epoxy compound, ammoniated hydrazine = ^ chemistry, double-spectrum type epoxidized Μ ^ type compound, hydrogenated double _ bombardment of you', gasification double age - S type epoxy compound Hydrogenated double-prospective cyclized human ^, stupid double oxime epoxy compound, desertified double test · F type ring gasification mouth material _ varnish (phen〇In_ gas type epoxy compound, desertification age _ varnish __, _ varnish type epoxy compound, containing naphthalene skeleton 丄 compound, two... 曰-type glycidyl ether compound, aliphatic (polysulfide) and biphenol type epoxy compound. Examples of the glycidol vinegar include a dicondensate and a glycidyl ester epoxy compound. / · 曰化口58 200906914. Examples of the glycidylamine include polyglycidylamine compound and copolymer amine, for example. A glycidyl hydrazine is exemplified as the glycidyl guanamine type epoxy compound.

一作為所述鏈狀脂肪族型環氧化合物，例如可舉出使烯烴化合物的碳-碳雙鍵氧化而獲得的含有環氧基的化合物。作為所述環狀脂肪族型環氧化合物，例如可舉出使環烯烴化合物的碳_碳雙鍵氧化而獲得的含有環氧基的化合物。作為所述雙酸A型環氧化合物，例如可舉出：828、As the chain aliphatic epoxy compound, for example, an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound can be mentioned. The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound. As the diacid type A epoxy compound, for example, 828,

1001、1002、1〇〇3、1004、1〇〇7、1010 (均為 japan EPOXY RESINS製造）、Epotohto YD-128 (東都化成公司製造）、 DER-331、DER-332、DER-324 (均為 DOW CHEMICAL 公司製造）、Epikuron 840、Epikuron 850、Epikuron 1050 (均為大曰本油墨公司製造）、Epomic R-140、Epomic R-301及Epomic R-304 (均為三井化學公司製造）。作為所述雙酚F型環氧化合物，例如可舉出806、807、 4004P (均為 JAPAN EPOXY RESINS 製造）、Epotohto YDF-170、Epotohto YDF-175S、Epotohto YDF-2001 (均為東都化成公司製造）、DER-354 (DOW CHEMICAL公司製造）、Epikuron 830及Epikuron 835 (均為大曰本油墨公司 59 200906914 製造）。作為所述雙酚型環氧化合物，例如可舉出：2,2_雙(4_ 羥基笨基)-1，1，1，3,3,3-六氟丙烷的環氧化物。作為所述氫化雙酚-A型環氧化合物，例如可舉出： Suntohto ST-3000(東都化成公司製造）、RicaresinHBE_i〇〇 (新日本理化公司製造）及Denacol EX-252 (NAGASE CHEMTEX公司製造）。作為所述氩化雙驗型環氧化合物，例如可舉出氮化 2,2-雙(4_經基本基)-1，1，1，3,3,3-六氟丙烧的環氧化物。作為所述溴化雙酚-A型環氧化合物，例如可舉出： 5050、5051 (均為 JAPAN EPOXY RESINS 製造）、Epotohto YDB-360、Epotohto YDB-400 (均為東都化成公司製造）、 DER-530、DER-538 (均為 DOW CHEMICAL 公司製造）、 Epikuron 152及Epikuron 153(均為大曰本油墨公司製造> 作為所述苯酚酚醛清漆型環氧化合物，例如可舉出： 152、154 (均為 JAPAN EPOXY RESINS 製造）、YDPN-638 (東都化成公司製造）、DEN431、DEN438 (均為DOW CHEMICAL公司製造）、Epikuron N-770 (大曰本油墨化學工業股份有限公司製造）、EPPN-201及EPPN-202 (均為日本化藥股份有限公司製造）。作為所述甲酚酚醛清漆型環氧化合物’例如可舉出： 180S75 (JAPAN EPOXY RESINS 製造）、YDCN-701、 YDCN-702 (均為東都化成公司製造）、Epikuron N-665、 Epikuron N-695 (均為大曰本油墨化學工業股份有限公司 60 200906914 28J83pli 製造）、EOCN-102S、EOCN-103S、EOCN-104S、 EOCN-1020、EOCN-1025 及 EOCN-1027 (均為日本化藥股份有限公司製造）。 ^ 作為所述雙紛A盼备清漆型環氧化合物，例如可舉出：157S70 (JAPAN EPOXY RESINS股份有限公司製造）及Epikuron N-880 (大曰本油墨化學工業股份有限公司製造）。 r 作為所述含有萘骨架的環氧化合物，例如可舉出： 1 Epikuron HP-4032 ' Epikuron HP-4700 > Epikuron HP-4770 (均為大日本油墨化學工業股份有限公司製造）及 NC-7000 (日本化藥公司製造）。作為所述芳香族聚縮水甘油鍵化合物，例如可舉出：對苯二酚二縮水甘油醚（下述結構式E101)、鄰苯二酚二縮水甘油醚（下述結構式E102)、間苯二酚二縮水甘油醚 (下述結構式E103)、三(4-縮水甘油氧基苯基）曱烷（下述結構式 E105)、1031S、1032H60 (均為 JAPAN EPOXY C RESINS 製造）、TACTIX-742 (DOW CHEMICAL 公司製造）、Denacol EX-201 (NAGASE CHEMTEX 公司製造）、 DPPN-503、DPPN-502H、DPPN-501H、NC6000 (均為曰本化藥股份有限公司製造）、TECMOA VG3101L (三井化學公司製造）、以下述結構式E106表示的化合物及以卞述結構式E107表示的化合物。 [化 58] 61 2009069141001, 1002, 1〇〇3, 1004, 1〇〇7, 1010 (all manufactured by Japan EPOXY RESINS), Epotohto YD-128 (made by Dongdu Chemical Co., Ltd.), DER-331, DER-332, DER-324 (both It is manufactured by Mitsubishi Chemical Co., Ltd., Epikuron 840, Epikuron 850, Epikuron 1050 (all manufactured by Otsuka Ink Co., Ltd.), Epomic R-140, Epomic R-301, and Epomic R-304 (all manufactured by Mitsui Chemicals, Inc.). Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by JAPAN EPOXY RESINS), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). ), DER-354 (manufactured by DOW CHEMICAL), Epikuron 830, and Epikuron 835 (all manufactured by Otsuka Ink Co., Ltd. 59 200906914). Examples of the bisphenol type epoxy compound include an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. Examples of the hydrogenated bisphenol-A type epoxy compound include Suntohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Ricaresin HBE_i (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (manufactured by NAGASE CHEMTEX Co., Ltd.). . As the argon double-type epoxy compound, for example, an epoxy 2,2-bis(4-based)-1,1,1,3,3,3-hexafluoropropane oxide can be exemplified. Compound. Examples of the brominated bisphenol-A type epoxy compound include 5050 and 5051 (all manufactured by JAPAN EPOXY RESINS), Epotohto YDB-360, and Epotohto YDB-400 (all manufactured by Tohto Kasei Co., Ltd.), and DER. - 530, DER-538 (all manufactured by Dow Chemical Co., Ltd.), Epikuron 152, and Epikuron 153 (all manufactured by Otsuka Ink Co., Ltd.) As the phenol novolak type epoxy compound, for example, 152, 154 (all manufactured by JAPAN EPOXY RESINS), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (both manufactured by DOW CHEMICAL), Epikuron N-770 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.), EPPN- 201 and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy compound are: 180S75 (manufactured by JAPAN EPOXY RESINS), YDCN-701, YDCN-702 ( Edukuron N-665, Epikuron N-695 (both manufactured by Otsuka Ink Chemical Industry Co., Ltd. 60 200906914 28J83pli), EOCN-102S, EOCN-103S, EOCN-104S, EOCN -1020, EOCN-1025 and EOCN-1027 (both manufactured by Nippon Kayaku Co., Ltd.) ^ As the bismuth-like epoxy compound, for example, 157S70 (JAPAN EPOXY RESINS Co., Ltd.) Manufacturing) and Epikuron N-880 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) r As the epoxy compound containing a naphthalene skeleton, for example, 1 Epikuron HP-4032 ' Epikuron HP-4700 > Epikuron HP-4770 (both manufactured by Dainippon Ink and Chemicals Co., Ltd.) and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the aromatic polyglycidyl bond compound include hydroquinone condensate. Glycerol ether (structure E101 below), catechol diglycidyl ether (structure E102 below), resorcinol diglycidyl ether (structure E103 below), tris(4-glycidyloxy) Phenyl) decane (structure E105 below), 1031S, 1032H60 (all manufactured by JAPAN EPOXY C RESINS), TACTIX-742 (manufactured by DOW CHEMICAL), Denacol EX-201 (manufactured by NAGASE CHEMTEX), DPPN-503 , DPPN-502H DPPN-501H, NC6000 (both said present Kayaku Co. manufactured), TECMOA VG3101L (manufactured by Mitsui Chemical Co.), a compound represented by the following structural formula and a compound E106 to E107 Bian represented by the following structural formula. [化58] 61 200906914

(E1〇1) (E1〇2) (E103)(E1〇1) (E1〇2) (E103)

作為所述二環戊二烯苯酚型環氧化合物’例如可舉出：TACTlX-556(DOW CHEMICAL 公司製造）及 Epikuron HP_72〇〇 (大曰本油墨化學工業股份有限公司製造）。作為所述脂環式二縮水甘油醚化合物，例如可舉出：環己烷二甲醇二縮水甘油醚化合物及Ricaresin DME-100 (新日本理化公司製造）。作為所述脂肪族聚縮水甘油醚化合物，例如可舉出： 62 200906914 乙二醇二縮水甘油醚（下述結構式E108)、二乙二醇二、縮水甘油醚（下述結構式E109)、聚乙二醇二縮水甘油謎、丙二醇二縮水甘油醚（下述結構式E110)、三丙二醇二、縮水甘油醚（下述結構式E111)、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚（下述結構式E112)、1,4-丁二醇二縮水甘油醚（下述結構式E113)、1,6_己二醇二縮水甘油趟 (下述結構式E114)、二溴新戊二醇二縮水甘油醚（下述結構式 El 15 )、Denacol EX-810、Denacol EX-851、Denacol EX-8301 ' Denacol EX-911 ' Denacol EX-920 > Denacol EX-931 > Denacol EX-211 > Denacol EX-212' Denacol EX-313 (均為NAGASE CHEMTEX公司製造）、DD-503 (旭電化公司製造）、Ricaresin W-100 (新日本理化公司製造）、 1，3,5,6-四縮水甘油基-2,4-己二醇（下述結構式E116)、甘油聚縮水甘油醚、山梨醇聚縮水甘油醚、三經曱基丙烧聚縮水甘油醚、季戊四醇聚縮水甘油鰱、Denaco1 EX-313、 Denacol ΕΧ-6Π、Denacol EX-321 及 Denaco1 EX_411 (均 i 為 NAGASE CHEMTEX 公司製造）。 [化 59]As the dicyclopentadiene phenol type epoxy compound, for example, TACT1X-556 (manufactured by DOW CHEMICAL Co., Ltd.) and Epikuron HP_72 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) can be mentioned. Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Ricaresin DME-100 (manufactured by Shin-Nippon Chemical Co., Ltd.). Examples of the aliphatic polyglycidyl ether compound include: 62 200906914 ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol dihydrate, glycidyl ether (the following structural formula E109), Polyethylene glycol diglycidyl mystery, propylene glycol diglycidyl ether (structure E110 below), tripropylene glycol dihydrate, glycidyl ether (structure E111 below), polypropylene glycol diglycidyl ether, neopentyl glycol condensate Glycerol ether (structure E112 below), 1,4-butanediol diglycidyl ether (structure E113 below), 1,6-hexanediol diglycidylhydrazine (structure E114 below), dibromo Neopentyl glycol diglycidyl ether (the following structural formula El 15), Denacol EX-810, Denacol EX-851, Denacol EX-8301 'Denacol EX-911 ' Denacol EX-920 > Denacol EX-931 > Denacol EX-211 > Denacol EX-212' Denacol EX-313 (all manufactured by NAGASE CHEMTEX), DD-503 (made by Asahi Kasei Co., Ltd.), Ricaresin W-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5 , 6-tetraglycidyl-2,4-hexanediol (structure E116 below), glycerol polyglycidyl ether, mountain Polyglycidyl ether, triethylene by Yue-yl propan-burning polyglycidyl ether, pentaerythritol polyglycidol silver carp, Denaco1 EX-313, Denacol ΕΧ-6Π, Denacol EX-321 and Denaco1 EX_411 (both manufactured NAGASE CHEMTEX company i). [化59]

(£109)(£109)

63 20090691463 200906914

(Ε115) (Ε116) 作為所述多硫化物型二縮水甘油醚化合物，例如可舉出：FLDP-50 及 FLDP-60 (均為 Toray Thiokol 製造）。作為所述聯苯酚型環氧化合物，例如可舉出： YX-4000、YL-6121H (均為 JAPAN EPOXY RESINS 製造）、NC-3〇0〇P及NC-3000S (均為日本化藥股份有限公司製造）。 κ 免作^所述二縮水甘油酯化合物，例如可舉出：對苯二甲酉欠一縮水甘油酯（下述結構式117)、鄰苯二曱酸二縮水甘^函_曰（下述結構式E118)、雙(2-甲基環氧乙烷基曱基) 鄰苯二曱酸g旨（下述結構式E119)、以下述結構式E121 表不的化合物、以下述結構式E122表示的化合物及以下述=tE123表示的化合物。 64 200906914 ^.O i O J pi(Ε115) (Ε116) Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol). Examples of the biphenol-type epoxy compound include YX-4000 and YL-6121H (all manufactured by JAPAN EPOXY RESINS), NC-3〇0〇P, and NC-3000S (all of which are limited by Nippon Chemical Co., Ltd.). Made by the company). κ is not used as the diglycidyl ester compound, and examples thereof include: p-xylylene oxime-glycidyl ester (the following structural formula 117), and phthalic acid digoxime _ 曰 (described below) Structural formula E118), bis(2-methyloxiranyl fluorenyl) phthalic acid g (the following structural formula E119), a compound represented by the following structural formula E121, represented by the following structural formula E122 The compound and the compound represented by the following = tE123. 64 200906914 ^.O i O J pi

(E122)(E122)

(E123) 作為所述縮水甘油酉旨環氧化合物，例如可舉出：87i、奶（均為 JAPAN Ερ〇χγ 咖⑽製造）、Epik· 2〇〇、(E123) Examples of the glycidyl epoxy compound include 87i, milk (all manufactured by JAPAN Ερ〇χγ coffee (10)), and Epik·2〇〇.

Epikuron働（均為大日本油墨化學工業股份有限公司製Epikuron働 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.)

造）、Denacol EX-711 及 Denacol EX-721 (均為 NAGASE CHEMTEX公司製造）。作為所述I縮水甘油胺化合物，例如可舉出：NN-二縮水甘油基笨胺（下述結構式Ε124)、Ν，Κμ二縮水甘油基-鄰曱笨胺（卞述結構式£125) ' Ν，Ν_二縮水甘油基-間曱苯胺（下述結媾式£126)、风>^二縮水甘油基-2,4,6-三溴苯胺（下述結媾武Ε127)、3-(Ν，Ν_二縮水甘油基)氨基丙基三曱氧基雜（卞述結構式別28)、灿，〇_三縮水甘油基- 65 200906914 對氨基笨酚（下述結構式Bl29)、N，N,0-三縮水甘油泰一間氨基笨酴C下述、、、。構式E130 )、ν,Ν,Ν',Ν1-四縮水甘油基 -間苯二甲胺（TETRAD-X (三菱瓦斯化學）、下述結構式 Ε132 )、1,3-雙（Ν，Ν二縮水甘油基氨基曱基）環已蝝 (TETRAD，（三菱瓦斯化學）、下述結構式Ε133)、I，4"" 雙(Ν，Ν-二縮水甘油基氨基甲基）環己烷（下述結構式 Ε134)、1,3-雙(Ν，Ν_二縮水甘油基氨基)環己烷（下述結才冓式Ε135)、I,4-雙(Ν，Ν二縮水甘油基氨基)環己烷（下述結構式Ε136)、丨，3-雙(Ν，Ν-二縮水甘油基氨基)苯（下述結構式Ε137)、丨十雙(Ν，Ν_二縮水甘油基氨基)笨（下述結構武 Ε138 )、2,6-雙(Ν，Ν-二縮水甘油基氨基甲基）雙環[H1] 庚烷（下述姨構式£139)、凡凡：^'，：^’-四縮水甘油基-4,4'一二氨基二環己基曱烷（下述結構式Ε140)、2,2’-二甲基 -(Ν" Ν' Ν"1 四縮水甘油基一氨基聯苯（下述結構式 E141 )、四縮水甘油基-4,4’_二氨基二苯趟（下述会士構式Ε142)、1，3,5-三(4·(Ν，Ν-〆細水甘油基)氨基苯氧基) ^ ^述録構式Ε143 )、2,4,於三(Ν，Ν-二縮水甘油基氨基) :苯醚（下述結構式Ε144)、彡(4-(Ν，Ν_二縮水甘油基)氨 ^亡基}甲烷（下述結構式El45)、3,4,3’，4’-四(Ν，Ν_二縮水二、tijL基)聯笨（下述結構式 Ε146)、3,4,3'，4，·四(Ν，Ν•二、以下述結構 )表示的化合物。 [化 61] 66 200906914Made), Denacol EX-711 and Denacol EX-721 (both manufactured by NAGASE CHEMTEX). Examples of the I glycidylamine compound include NN-diglycidyl succinimide (the following structural formula Ε124), hydrazine, Κμ diglycidyl-o-indoleamine (detailed structural formula: £125). 'Ν,Ν_ diglycidyl-m-anilide (the following formula: £126), wind>^ diglycidyl-2,4,6-tribromoaniline (the following knot 媾 Ε 127), 3-(Ν,Ν_ diglycidyl)aminopropyltrimethoxylate (detailed structural formula 28), can, 〇_triglycidyl-65 200906914 p-amino phenol (the following structural formula Bl29) ), N, N, 0-triglycidyl, an amino alum, C, the following,,,. Configuration E130), ν, Ν, Ν', Ν1-tetraglycidyl-m-xylylenediamine (TETRAD-X (Mitsubishi Gas Chemical), the following structural formula Ε132), 1,3-double (Ν, Ν Diglycidylaminoindenyl)cyclopentane (TETRAD, (Mitsubishi Gas Chemical), the following structural formula Ε133), I, 4"" Bis(Ν,Ν-diglycidylaminomethyl)cyclohexane (Structural formula 134 below), 1,3-bis(indole, Ν_diglycidylamino)cyclohexane (hereinafter referred to as Ε135), I,4-bis(indole, fluorene diglycidyl) Amino)cyclohexane (the following structural formula Ε136), hydrazine, 3-bis(indole, fluorene-diglycidylamino)benzene (the following structural formula Ε137), 丨10 bis(Ν,Ν_diglycidyl) Amino) stupid (the following structure Ε138), 2,6-bis(Ν, Ν-diglycidylaminomethyl)bicyclo[H1]heptane (the following 姨 configuration £139), Fan: ^', :^'-tetraglycidyl-4,4'-diaminodicyclohexyldecane (the following structural formula Ε140), 2,2'-dimethyl-(Ν" Ν' Ν"1 tetraglycidyl Monoaminobiphenyl (Structure E141 below), tetraglycidyl-4,4'-diaminodiphenylhydrazine (The following stipulations Ε 142), 1,3,5-three (4·(Ν,Ν-〆水水 ) 氨基)aminophenoxy) ^ ^ 构构 Ε Ε 143 ), 2, 4, Tris(Ν,Ν-diglycidylamino): phenyl ether (structure Ε 144 below), 彡 (4-(Ν, Ν_ diglycidyl) ammonia) methane (structure El45 below) , 3,4,3',4'-four (Ν,Ν_二水二,tijL base) Lian (the following structural formula Ε146), 3,4,3',4,·four (Ν,Ν• 2. A compound represented by the following structure. [Chem. 61] 66 200906914

(E125) (E126) (E124)(E125) (E126) (E124)

,Ν, Ν

QQ

-Ο (Ε128) (Ε129)-Ο (Ε128) (Ε129)

(Ε130)(Ε130)

(Ε136) [化 62](Ε136) [Chem. 62]

(Ε138)(Ε138)

67 20090691467 200906914

(E146)(E146)

68 20090691468 200906914

(E148) η(E148) η

(Ε149) 作為所述具有環氧乙烷基的單體的均聚物，例如可舉出：聚甲基丙烯酸縮水甘油酯。作為所述具有環氧乙炫基的單體的共聚物，例如可舉出：笨基順丁烯二醯亞胺_(Ε149) The homopolymer of the monomer having an oxiranyl group may, for example, be polyglycidyl methacrylate. As the copolymer of the monomer having an ethylene oxide group, for example, a strepyl-butyleneimine

甲基丙烯酸縮水甘油酯共聚物、Ν-環己基順丁烯二醯亞胺 -曱基丙烯酸縮水甘油酯共聚物、曱基丙烯酸苄酯_甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸丁酯-曱基丙烯酸縮水甘油醋共聚物、曱I丙烯冑2老基乙__甲基丙稀酸縮水甘油醋共聚物、甲基丙烯酸(3-乙基-3-氧雜環丁基）甲醋-甲美丙烯酸縮水甘油，共聚物及苯乙烯岬土: 酯共聚物。例如可舉出：（曱基) 作為所述具有環氧乙烷基的單體， 69 200906914 環己i旨及（甲丙烯酸縮水甘油酯、（甲基）丙烯酸3,4_環氧基基）丙烯酸甲基縮水甘油醋。作為所述具有環氧乙烧基的單體的共聚物有環氧乙烷基的單體以外的其他單體，例如可舉出^其、丙烯酸、(甲基)丙烯醆甲酯、(甲基)丙烯酸乙酯土)Glycidyl methacrylate copolymer, fluorene-cyclohexyl maleimide-glycidyl methacrylate copolymer, benzyl methacrylate _ glycidyl methacrylate copolymer, butyl methacrylate - mercaptoacrylic acid glycidinated vinegar copolymer, 曱I propylene 胄 2 old base _ _ methyl methacrylate glycidol vinegar copolymer, methacrylic acid (3-ethyl-3-oxetanyl) methyl vinegar - Amethacrylic acid glycidol, copolymer and styrene alumina: ester copolymer. For example, (mercapto) is used as the monomer having an oxirane group, and 69 200906914 is intended to be a glycidyl methacrylate or a (meth)acrylic acid 3,4-epoxy group. Acrylic methyl glycoacetic acid vinegar. Examples of the monomer other than the monomer having an oxirane group as the copolymer of the epoxy group-containing monomer include, for example, acrylic acid, (meth) acryl methyl ester, and (a) Ethyl acrylate

烯酸異㈣、（甲基)内烯酸丁醋、（甲基)丙晞酸異T酷t (甲丙烯酸叔丁酯、（甲基）丙烯酸環己酯、（曱基）丙烯酸苄，、（曱基）丙烯酸2-羥基乙酯、（曱基)丙烯酸2_羥基丙酯、苯乙歸、甲基笨乙烯、氯甲基苯乙烯、（曱基)丙晞酸(^乙基3氧雜環丁基）曱醋、環己基順丁稀二醯亞胺及笨基順丁烯二醢亞胺。作為所述縮水甘油基異氰尿酸酯，例如可舉出：1，3,5_ 二縮水甘油基-1,3,5-三嗪-2,4,6-(111,311，511)-三酮（下述結構式E150)、1，3_二縮水甘油基·5_烯丙基―丨二5·三嗪 -2，^，6-(1氏311，5办三酮（下述結構式£151)及縮水甘油基異氰尿酸酯型環氧樹脂。 [化 64]Isoenoic acid (tetra), (meth) enoic acid butyl vinegar, (methyl) acrylic acid ketone T (t-butyl methacrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (mercapto) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, phenylethyl, methyl streptoethylene, chloromethyl styrene, (mercapto) propionate (^ethyl 3 oxygen) Heterocyclic butyl) hydrazine vinegar, cyclohexyl cis-butyl bis-imide imidate, and stilbene maleimide. Examples of the glycidyl isocyanurate include 1,3,5_ Diglycidyl-1,3,5-triazine-2,4,6-(111,311,511)-trione (structure E150 below), 1,3-glycidyl 5-I-allyl ―丨二5·Triazine-2,^,6-(1 311,5 tridecyl (the following structural formula: £151) and glycidyl isocyanurate type epoxy resin. [Chem. 64]

(E150) (E151) 作為所述鏈狀脂肪族型環氧化合物，例如可舉出：環氧化聚丁二烯及Epolead PB3600 (DAICEL化學工業股份有限公司製造）。作為所述環狀脂肪族型環氧化合物，例如可舉出：2- 70 200906914 ZOi ό^ρΐΐ 甲基I環氧環己基曱基1甲基_3’，4’_環氧環己基魏醋 (下述結構式則）、2,3-環氧環戊基_2，，3，、環氧環細（下述結構式E154)、ε-己内醋改質3,4_環氧環己基甲基-3,4,_ 環氧環己烧紐自旨、u紗二環氧檸檬烯（⑽〇xide3_ (DAICEL化學工業股份有限公司製造）、τ述結構式 E155)、以下述結構式E156表示的化合物、CY_175、 CY-177、CY-H9 (均為 CIBA-GEIGY 公司製造）、(E150) (E151) Examples of the chain-like aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by DAICEL Chemical Industry Co., Ltd.). Examples of the cyclic aliphatic epoxy compound include 2-70 200906914 ZOi ό^ρΐΐ methyl I epoxycyclohexyl fluorenyl 1 methyl _3', 4'-epoxycyclohexyl vinegar (The following structural formula), 2,3-epoxycyclopentyl 2,, 3, epoxy ring fine (the following structural formula E154), ε-hexane vinegar modified 3,4_epoxy ring Hexylmethyl-3,4,_epoxycyclohexene carbazide, u-yarn epoxide limonene ((10) 〇xide3_ (manufactured by DAICEL Chemical Industry Co., Ltd.), τ, structural formula E155), and the following structural formula E156 Compounds indicated, CY_175, CY-177, CY-H9 (both manufactured by CIBA-GEIGY),

EHPD-315〇 (DAICEL化學工業股份有限公司製造）及環狀脂肪族型環氧樹脂。 [化 65]EHPD-315(R) (manufactured by DAICEL Chemical Industry Co., Ltd.) and a cyclic aliphatic epoxy resin. [Chem. 65]

(E153)(E153)

(E155) (E154)(E155) (E154)

另外，例如，就提高對基板的密接性的觀點而言，本發明的,晶配*劑也可以進—步含有魏偶合劑、欽系偶 5 d及氨基々化合物等偶合劑。所述偶合劑可以是—種化合物，也可以是兩種或兩種以上的化合物。作為所述氨基石夕化合物，可舉出：對氨基苯基三曱氧土石夕烧、，氨基苯基三乙氧基魏、間氨絲基三曱氧基广烧間氨基苯基二乙氧基石規、氨基丙基三甲氧基石夕烧、氨基丙基三乙氧基矽烷等。斤I偶5 Μ的含有率，在液晶配向劑中優選〇·〇 1〜3 71 200906914Further, for example, from the viewpoint of improving the adhesion to the substrate, the crystal matching agent of the present invention may further contain a coupling agent such as a Wei coupling agent, an indole 5 d or an aminoguanidine compound. The coupling agent may be a compound or two or more compounds. Examples of the amino-based compound include p-aminophenyl trioxonite, aminophenyltriethoxyween, m-aminotrimoxy-terminated polyaminophenyldiethoxylate. Base stone, aminopropyltrimethoxy sulphur, aminopropyltriethoxy decane, and the like. The content of jin I even 5 Μ is preferable in the liquid crystal alignment agent 〇·〇 1~3 71 200906914

Wt% 0 如’在不損及本發明的特性的範圍（優選所二 u其衍生物的20 wt%以内）0，本發明的液晶配向巧可以進—步含有聚®旨、丙稀酸聚合物、丙烯酸醋聚合物專聚合物成分。並且，例如，在不損及本發明目的的範圍内，本發明的液晶配向劑也可以進—步含有二魏或其衍生物與二胺的反應產物即聚醯胺，或四羧酸二酐、二羧酸或其衍生物與二胺的反應產物即聚醯胺醯亞胺等其他聚合物成分。另外，例如，就實現液晶配向劑的塗佈性的提高的觀點而言，本發明的液晶配向劑也可以進一步含有用以實現此目的的表面活性劑，就提高液晶配向劑的抗靜電性的觀點而言，本發明的液晶配向劑也可以進一步含有抗靜電劑。另外，例如，就液晶配向劑的塗佈性及所述聚醯胺酸或其衍生物的濃度的調整的觀點而言，本發明的液晶配向劑也可以進一步含有溶劑。所述溶劑如果是具有可溶解高分子成分的能力的溶劑，那麽並沒有特別限制，可以應用。所述溶劑廣泛包含在聚酸胺酸、可溶性聚酿亞胺等高分子成分的製造步驟及用途方面通常所使用的溶劑，根據使用目的可適當選擇。所述溶劑玎以是一種，也可以是兩種或兩種以上的混合溶劑。作為所述溶劑，可舉出所述聚醯胺酸或其衍生物的良》谷劑(good solvent)、或以改善盡佈性為目的的其他溶劑。作為對於所述聚醯胺酸或其衍生物而言為良溶劑的非 200906914Wt% 0 such as 'within the range that does not impair the characteristics of the present invention (preferably within 20% by weight of its derivative) 0, the liquid crystal alignment of the present invention can be further integrated with poly(acrylic acid) polymerization. Material, acrylic acid vinegar polymer polymer component. Further, for example, the liquid crystal alignment agent of the present invention may further contain a reaction product of diwei or a derivative thereof and a diamine, that is, polydecylamine or tetracarboxylic dianhydride, within a range not impairing the object of the present invention. The reaction product of a dicarboxylic acid or a derivative thereof and a diamine is another polymer component such as polyamidoximine. Further, for example, from the viewpoint of improving the coatability of the liquid crystal alignment agent, the liquid crystal alignment agent of the present invention may further contain a surfactant for achieving the object, thereby improving the antistatic property of the liquid crystal alignment agent. In view of the above, the liquid crystal alignment agent of the present invention may further contain an antistatic agent. Further, for example, the liquid crystal alignment agent of the present invention may further contain a solvent from the viewpoint of the applicability of the liquid crystal alignment agent and the adjustment of the concentration of the polyaminic acid or its derivative. The solvent is not particularly limited and can be used if it is a solvent having an ability to dissolve a high molecular component. The solvent is widely used in a production step and a use of a polymer component such as a polyamic acid or a soluble polyamidiamine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types. The solvent may, for example, be a good solvent of the polyaminic acid or a derivative thereof, or another solvent for the purpose of improving the uniformity. As a good solvent for the poly-proline or its derivative, 200906914

ΔΟ 1 OJpiI 質子欧極&有機溶劑，可舉出：、二曱基"米”同、队甲基己内醯胺、N-曱基丙醯胺、N，N-二曱基乙醯胺、二甲基亞颯、N,N-二曱基曱醯胺、n，N-二乙基甲醯胺、、二乙基乙醯胺、r-丁内醋等内醋。作為以所述改善塗佈性等為目的的其他溶劑例，可舉出：乳酸烷基酯、3_甲基_3_曱氧基丁醇、萘滿（tetralin)、異佛、乙二醇單丁鱗等乙二醇單規基趟、二乙二醇單 ( ***等二乙二醇單烷基醚、乙二醇單烷基醚或乙酸笨酯、三乙二醇單烷基醚、丙二醇單丁醚等丙二醇單烷基醚、丙二酸二乙酯等丙二酸二烷基酯、二丙二醇單甲醚等二丙二醇單烷基醚、這些乙酸酯類等的酯化合物。這些溶劑中，所述溶劑尤其優選使用曱基吡嘻燒酮、二曱基咪唑啉酮、r-丁内酯、乙二醇單丁醚、二乙二醇單乙鱗、丙二醇單丁醚及二丙二醇單甲峻等。本發明中，液晶配向劑中的包含所述聚醯胺酸或其衍生物的高分子成分的濃度並沒有特別限制，優選Ο.〗〜4〇 ί wt%。將此液晶配向劑塗佈在基板上時，為了調整膜厚，有時必須事先進行利用溶劑稀釋所含有的高分子成分的操作。為了調整膜厚而必須稀釋液晶配向劑時，就調整液晶配向劑的黏度以使其成為適於容易地混合溶劑的黏度的觀點而言’所述高分子成分的濃度優選40 wt%或40 wt%以下。另外，液晶配向劑中的所述高分子成分的濃度有時也根據液晶配向劑的塗佈方法來進行調整。液晶配向劑的塗 200906914 佈方法為旋塗法（spinner)或印刷法時，為了良好地保持膜厚’通常多數情況是將所述高分子成分的濃度調整為1〇ΔΟ 1 OJpiI Proton Ouji & organic solvent, which can be exemplified by: dimercapto "rice", methylprednisolone, N-mercaptopropylamine, N,N-didecylacetamidine An internal vinegar such as an amine, dimethyl hydrazine, N,N-didecyl decylamine, n,N-diethylformamide, diethylacetamide, r-butane vinegar, etc. Examples of other solvents for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophor, and ethylene glycol monobutyl scale. Ethylene glycol monobasic hydrazine, diethylene glycol mono (diethylene glycol monoalkyl ether such as diethyl ether, ethylene glycol monoalkyl ether or stearic acid ester, triethylene glycol monoalkyl ether, propylene glycol monobutyl a dipropylene glycol monoalkyl ether such as propylene glycol monoalkyl ether such as ether or diethyl malonate; dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether; or an ester compound such as these acetates. The solvent is particularly preferably decyl pyridone, dinonyl imidazolidinone, r-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl sulphate, propylene glycol monobutyl ether and dipropylene glycol monomethyl sulphate. Etc. In the present invention, The concentration of the polymer component containing the polyaminic acid or a derivative thereof in the liquid crystal alignment agent is not particularly limited, and is preferably Ο. 4 〇 wt wt%. When the liquid crystal alignment agent is coated on a substrate, In order to adjust the film thickness, it is necessary to perform an operation of diluting the polymer component contained in the solvent in advance. When it is necessary to dilute the liquid crystal alignment agent in order to adjust the film thickness, the viscosity of the liquid crystal alignment agent is adjusted so as to be suitable for easy mixing. From the viewpoint of the viscosity of the solvent, the concentration of the polymer component is preferably 40% by weight or less, and the concentration of the polymer component in the liquid crystal alignment agent may be according to the method of applying the liquid crystal alignment agent. For the adjustment of the liquid crystal alignment agent, the 200906914 cloth method is a spinner method or a printing method, in order to maintain the film thickness well'. In most cases, the concentration of the polymer component is adjusted to 1〇.

Wt /°以下。在其他塗佈方法、例如浸塗法（dipping )或噴墨法（inkjet)的情況下，有時也可以調整為更低的濃度。另方面’如果所述两分子成分的濃度為0.1 wt%以上，那麼容易將所獲得的液晶配向膜的膜厚調整為最佳厚度。所以’在通常的旋轉塗佈法或印刷法等的情況下，所述高分子成分的濃度為0.1 wt%以上，優選〇.5〜1〇wt%。然而，根據液晶配向劑的塗佈方法，也可以在更加稀薄的濃度下使用。而且’在用於製作液晶配向膜時，本發明的液晶配向劑的點度可根據形成此液晶配向劑的膜的手段及方法而確定。例如’在使用印刷機來形成液晶配向劑的膜時，就獲知充刀的膜厚的觀點而言，優選5 mPa.s或5 mPa.s以上，另外’就抑制印刷不均的觀點而言，優選1〇〇 mPa.s以下，更優選10〜80 mPa.s。利用旋塗法塗佈液晶配向劑而形成液晶配向劑的膜時’就同樣的觀點而言，優選5〜2〇()rnpa. S ’更優選10〜l〇〇mPa.s。液晶配向劑的黏度，可通過以溶劑進行稀釋或通過伴隨攪拌的熟化來降低。Wt / ° or less. In the case of other coating methods, such as dipping or inkjet, it may be adjusted to a lower concentration. On the other hand, if the concentration of the two molecular components is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film is easily adjusted to an optimum thickness. Therefore, in the case of a usual spin coating method, printing method, or the like, the concentration of the high molecular component is 0.1 wt% or more, preferably 〇5 to 1 〇 wt%. However, it can also be used at a more dilute concentration depending on the method of applying the liquid crystal alignment agent. Further, when used for producing a liquid crystal alignment film, the degree of the liquid crystal alignment agent of the present invention can be determined according to the means and method for forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed by using a printing machine, it is preferably 5 mPa·s or 5 mPa·s or more from the viewpoint of the film thickness of the filling blade, and 'in terms of suppressing printing unevenness Preferably, it is 1 〇〇mPa.s or less, more preferably 10 to 80 mPa.s. When the liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, from the same viewpoint, it is preferably 5 to 2 Å () rnpa. S Å is more preferably 10 to 10 Å mPa.s. The viscosity of the liquid crystal alignment agent can be lowered by dilution with a solvent or by aging with stirring.

本發明的液晶配向劑也可以是所謂的聚合物摻合的形恶。這種形態的液晶配向劑是含有四羧酸二酐A與二胺A 的反應產物即聚酿胺酸或其衍生物A、與四羧酸二酐b與二胺B的反應生成物即聚醯胺酸或其衍生物b的液晶配向劑，可舉出二胺A包含以通式（1)表示的二胺、二胺B 74 200906914 不包通式⑴表示的二胺的液晶配向劑。立一，ϋ職或其魅物A與所述的本發明的聚醯胺酸或 lj、物相同。聚醯胺酸或其衍生物B除了所述二胺中不二==通式（1)表示的二胺以外、即所述二胺使用所述其胺以外’與所述的本發明的聚醯胺酸或其衍生物相同。 A及B可使麟述的讀酸。所述二胺A ^ 3以通式（1)表示的二胺即可，也可以進一步包含The liquid crystal alignment agent of the present invention may also be a so-called polymer blended form. The liquid crystal alignment agent of this form is a reaction product containing a reaction product of tetracarboxylic dianhydride A and diamine A, i.e., polyacrylic acid or a derivative thereof, and a reaction product of tetracarboxylic dianhydride b and diamine B. The liquid crystal alignment agent of the phthalic acid or the derivative b thereof is a liquid crystal alignment agent containing the diamine represented by the formula (1) and the diamine represented by the formula (1). Li Yi, dereliction of duty or its charm A is the same as the poly-proline or lj of the present invention. The polyaminic acid or its derivative B is other than the diamine in the diamine == the diamine represented by the formula (1), that is, the diamine is used in addition to the amine thereof The proline or its derivative is the same. A and B can read the acid of Lin Shu. The diamine A ^ 3 may be a diamine represented by the formula (1), and may further comprise

二二胺。所述二胺B可使用以通式（1)表示的二胺以外的所述其他二胺。的含ί發明的所述液晶配向劑中的聚醯胺酸或其衍生物B PP制1 =果是可表現出本發明效果的量，那麼並沒有特別、fc就同時具有表現本發明的效果與調整配向性兩方面 △ ^而s ’聚酿胺酸或其衍生物B的含量相對於液晶配向背中的聚合物總量優選1〜50 wt%，更優選2〜30 wt%。 / β =發明的液晶配向膜可由所述本發明的液晶配向劑獲侍+發明的液晶配向膜可通過利用液晶配向劑製作液晶 :己向”的通常的方法而獲得，例如，本發明的液晶配向膜可t過开y成本發明的液晶配向劑的塗膜的步驟與對其加熱並鏵又燒的步驟而獲得。對於本發明的液晶配向膜，根據需要也可以對所述鍛燒步驟中所獲得的膜進行摩擦處理。、、所，塗膜，與通常製作液晶配向膜的情況相同，可通過於液日日顯、不疋件中的基板上塗佈本發明的液晶配向劑而形成。所述基板可舉出：可設置氧化銦錫Undium Tin 〇Xlde’IT〇)電極等電極或彩色濾光片（color filter)等的 75 200906914 以玻璃製造的基板。作為將液晶配向劑塗佈於基板上的方法，—般已知有旋塗法、印刷法、浸塗法、滴下法、喷墨法等。這些方法在本發明中也可以同樣應用。所^膜的锻燒可在所述聚醯胺酸或其衍生物進行脫釦右閉二反f所而的條件下進行。所述塗膜的鍛燒-般已 f i t a 或紅外線爐中進行加熱處理的方法、也^加熱處理的方法等。這些方法在本發明中行！分鐘i、時':般優選在15G〜赋左右的溫度下進的摩與用於液晶配向膜的配向處理的延遲的條件下即可晶配向膜可獲得充分〜一载物台(sta==件是毛墨入量。.2 子（roller)旋轉球声動速度5〜250 mm/sec、輥配向處理方法，除^摩擦作為液晶配向膜的轉印法等。在可择彳θ : 卜，一般已知有光配向法或摩擦處理中並用^其二内，也可以在所述獲得本發明的外的方法可比較好地使所述塗膜乾燥的步他步驟，可舉出：膜的步驟等。 q洗液清洗摩擦處理前後的 1:斤燥步驟與所述鍛燒步驟同# _紅外_中進行加熱處理的方已知有在烘在加熱板上進行加 200906914 Ζ,Ο I OJpn 熱處理的方法等。這些方法士中。乾择+驟蜃撰為f 也叫可應用於戶斤述乾燥步驟 :乾知步驟優透在可〉谷劑蒸發的範圍内的溫施，】優選在㈣於所述錢㈣的溫度吨低^溫度下實法Γ清洗液清洗液晶配向膜的方、喷霧(〜y)、蒸氣清洗或超聲U等。這些方法既可以單獨進行，也可以並Didiamine. As the diamine B, the other diamines other than the diamine represented by the formula (1) can be used. The poly-proline or the derivative thereof in the liquid crystal alignment agent of the invention contains B PP = 1 is an amount which can exhibit the effects of the present invention, and then there is no particular, fc has the effect of expressing the present invention. The content of Δ' and the content of the polyacrylic acid or its derivative B is preferably from 1 to 50% by weight, more preferably from 2 to 30% by weight, based on the total amount of the polymer in the liquid crystal alignment back. /β = Invented liquid crystal alignment film can be obtained by the liquid crystal alignment agent of the present invention + the liquid crystal alignment film of the invention can be obtained by a usual method of producing a liquid crystal by using a liquid crystal alignment agent, for example, the liquid crystal of the present invention The alignment film can be obtained by the step of heating the coating film of the liquid crystal alignment agent of the invention and the step of heating and calcining it. For the liquid crystal alignment film of the present invention, the calcination step can also be performed as needed. The obtained film is subjected to a rubbing treatment, and the coating film is formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid-free day or the like, as in the case of generally producing a liquid crystal alignment film. The substrate may be an electrode such as an indium tin oxide (Undium Tin 〇Xlde'IT〇) electrode, or a color filter or the like. 75 200906914 A substrate made of glass. As a liquid crystal alignment agent As the method on the substrate, spin coating, printing, dip coating, dropping, ink jet, etc. are generally known. These methods can also be applied in the same manner in the present invention. Description The valeric acid or a derivative thereof is subjected to a condition in which the right side is closed and the second is reversed. The method of calcining the coating film, the method of heat treatment in a fita or infrared furnace, and the method of heat treatment, etc. These methods are in the present invention! The minute i, the time ': generally preferably at a temperature of 15 G to the left and right and the retardation of the alignment treatment for the liquid crystal alignment film, the crystal alignment can be obtained sufficiently. A stage (sta==piece is the amount of ink input. .2 roller (roller) rotating ball sound velocity 5~250 mm/sec, roller alignment treatment method, except rubbing as a liquid crystal alignment film transfer method, etc. In the alternative θ: 卜, generally known in the photo-alignment method or the rubbing treatment, and in the second method, the method of obtaining the method of the present invention can better dry the coating film. The steps of the film may be as follows: a step of a film, etc. q: a washing liquid before and after the rubbing treatment: a jinning step and the calcining step are the same as the heat treatment in the #_infrared_ Adding 200906914 Ζ, Ο I OJpn heat treatment method, etc. These methods Dry selection + 蜃蜃蜃 f 也也也也也也也也也也也也也也也也也也也也也也 : : : : : : : : : : : : : : : : : : : : : : : : : : The method of cleaning the liquid crystal alignment film, the spray (~y), the steam cleaning or the ultrasonic U, etc. at a low temperature, the method can be carried out separately or in combination.

i. 用。作為清洗液，可使用純水，或甲醇、乙醇、異丙醇等 j醇類’苯、曱苯、—曱苯等芳香族烴類，二氣甲烧等㈣系溶劑，賴、曱基乙基_鴨，但並不限定於這些。當然’這些清洗液是制充分純化_質較少的清洗液。這種清洗絲也可以應詩形成本發_液晶配向膜的所述清洗步驟中。本發明的液晶配向膜的膜厚並沒有特別限制，優選10 〜300 nm’更優選30〜150 nm。本發明的液晶配向膜的膜厚可通過輪廓儀（pr〇rn〇meter)或橢圓計（eUips〇meter) 等公知的膜厚測定裝置進行測定。本發明的液晶顯示元件包括：一對基板；含有液晶分子，且形成於所述一對基板之間的液晶層；對液晶層施加電壓的電極；及使所述液晶分子於特定方向上配向的液晶配向膜。所述液晶配向膜使用所述的本發明的液晶配向膜。對於所述基板，在本發明的液晶配向膜的情況下，可使用所述玻璃制的基板；對於所述電極，在本發明的液晶配向膜的情況下，如上所述’可使用形成於玻璃制基板上 77 200906914 的ITO電極。所述液晶層由密封在下述相對向的一對基板之間的缝隙中的液晶組合物所形成，所述一對基板的對向方式是所述一對基板中的一塊基板的形成有液晶配向膜的面朝向另一塊基板。i. Use. As the cleaning liquid, pure water or an aromatic hydrocarbon such as methanol, ethanol or isopropanol, such as benzene, toluene or fluorene, or a gas such as dimethyl benzene or the like, may be used. Base _ duck, but not limited to these. Of course, these cleaning solutions are prepared to be fully purified. Such a cleaning wire can also be used in the cleaning step of forming a liquid crystal alignment film. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, and is preferably 10 to 300 nm', more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer. A liquid crystal display device of the present invention includes: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and an alignment of the liquid crystal molecules in a specific direction Liquid crystal alignment film. The liquid crystal alignment film described above uses the liquid crystal alignment film of the present invention. For the substrate, in the case of the liquid crystal alignment film of the present invention, the substrate made of the glass can be used; and in the case of the liquid crystal alignment film of the present invention, the electrode can be used to form the glass as described above. ITO electrode of 77 200906914 on the substrate. The liquid crystal layer is formed by a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein a pair of substrates is formed by liquid crystal alignment of one of the pair of substrates The face of the film faces the other substrate.

對於所述液晶組合物並沒有特別限制，可使用介電各向異性為正或負的各種液晶組合物。介電各向昱性為正的優選液晶組合物可舉出下述文獻中記載的液晶組合物：曰本專利第3086228號公報、日本專利第263Μ35號公報、曰本專利特表平5_5G1735號公報、日本專利特開平 8-157826號公報、日本專利制平8·231號公報、日本專利特開平9_241644號公報（ΕΡ885272Α1說明書）、日本專利特開平9.302346號公報（EP8G6466A〗說明^ )、日本 f利特開平8-199!68號公報（EP722998A1說明書）、開平9·2迎2號公報、日本專利特開平9_255956 tU、日本專利特開平9韻⑷號公報（Ερ88527ΐΑΐ 二二、日本專利制平1()·2_6號公報（ΕΡ844229Αί :書)、日本專利特開平iG•綱436號公報、日本專利特 :太直:23】482號公報、日本專利特開2__G87_公報、曰本專利特開2001-48822公報等。中所S = 的出下述文獻報、日本專㈣料冰i^tT/24532號公 4-22488^ ^ )諕公報、曰本專利特開平 ^公報、日本專利特開平請扮號公報、日本 200906914 專利特開平8-104869號公報、The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. The liquid crystal composition described in the following documents is exemplified by the following Japanese Patent Publication No. 3086228, Japanese Patent No. 263Μ35, and Japanese Patent Laid-Open No. Hei 5_5G1735 Japanese Patent Laid-Open No. Hei 8-157826, Japanese Patent Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 9-241644. Japanese Patent Laid-Open No. Hei 8-199! No. 68 (EP722998A1), Kaiping 9·2 No. 2, Japanese Patent Laid-Open No. 9_255956 tU, Japanese Patent Laid-Open No. 9 (4) (Ερ88527ΐΑΐ22, Japanese Patent No. 1) ) · 2_6 bulletin (ΕΡ 844229Αί : book), Japanese Patent Special Kaiping iG • Gang 436 bulletin, Japanese patent special: too straight: 23] 482 bulletin, Japanese Patent Special Open 2__G87_ bulletin, 曰本专利特开2001- 48822 Gazette, etc. The following documents are published in the S=, Japanese special (4) material ice i^tT/24532 No. 4-22488^^) 諕 Gazette, 曰本专利特开平^ bulletin, Japanese patent special Kaiping number News, Japanese Unexamined Patent Publication No. 8-104869 200,906,914 Gazette,

κ 號公報、日本專利特開平1〇日本專利特開平10-168076 開平10-236989號公報、日^8453號公報、日本專利特報、日本專利特開平1〇_23物利特開平10_23699〇號公 10-236993號公報、太 2號公報、日本專利特開平本專利特開平1ΰ23^Γ平1G·236994號公報、日 10-237004號公報、日太 ^公報、日本專利特開平本專利特開平1〇_237〇35 =開平1〇J37024號公報、曰 10-237075號公齟、n 士 $唬公報、日本專利特開平本專利撕日本專利特開平im鶴i A1說明書）、 10-287875號公報 ;：報、曰本專利特開平本專利特開平η侧⑽1945號公報、日 __號公報、日本二=曰^專利特開平專利特開现_5 ^開2隊2_公報、日本公報、日本—_1_日5=#特開厕德26 f加也所述介電各向異性為正或㈣液晶組合物中添加Γ種或上的光學錄化合物岐用。㈣晶顯示元件可通過τ述方式獲得：在-對 i向膜朝二:塊基板上形成本發明的液晶配向膜，以液晶對^料、方式介關隔物（spaeer)而使所獲得的— :基=向，在形成於基板之間的間隙中封裝入液晶組合成液晶層。在製造本發_液晶齡元件時，根據而’也可以包含於基板上貼附偏光膜等的其他步驟。 79 200906914 巧明的液晶顯示元件可形成用於各種電場方式的液晶顯示元件。這種用於電場方式的液_示元件可舉出：在相對於所述基板的表面水平的方向上，所述電極對所述液曰B層施加電壓的用於橫向電場方式的浪晶顯示元件，或在相對於所絲板的表㈣直的方向上，所述電極對所述液晶層施加於縱向電場方式的浪晶顯示元件。用於橫向電場方式的液晶顯示元件也可以不表現出比較大的預，所以可以比較好地使Μ訂述本發明的液晶配向劑所獲得的液晶配向膜，此本發明的液晶配向劑由不包含具有支鏈的二胺的二胺而獲得。用於縱向電場方式的液晶顯示元件需要表現出比較大的預傾角，所以可以比較好地使用利用下述本發明的液晶配向劑所獲得的液晶配向膜，此本發明的液晶配向劑是由除了以通式（1)表示的二胺以外、也包含具有支鏈的二胺的一胺所獲得的液晶配向劑，或者所述二胺Β中包含具有支鏈的二胺的液晶配向劑。這樣，將本發明的液晶配向劑作為原料而製作的液晶配向膜，通過適當選擇其原料即聚合物，可應用在各種顯示驅動方式的液晶顯示元件中。 [實施例] 以下，根據實施例詳細說明通過使用本發明的聚合物而獲得的液晶配向劑及液晶顯示元件，但本發明並不限定於這些貫施例。貫知例中，分子量的測定使用Gpc ,將繫苯乙婦作為標準溶液，洗提液使用！用甲基C甲= 200906914 Ζ61δ_)ρΐΓ (Dimethylformamide，DMF )。另外，以下的實施例中，容積的單位升以L表示。所以，mL表示毫升。以下記載實施例中使用的液晶顯示元件的評價方法。Kappa Gazette, Japanese Patent Laid-Open Patent Publication No. 10-168076, Kaiping 10-236989, Japanese Patent No. 8453, Japanese Patent Special Report, Japanese Patent Special Open 1〇_23 Japanese Patent Laid-Open No. 10-236993, Japanese Patent Publication No. 2, Japanese Patent Laid-Open Publication No. Hei No. 1 ΰ Γ Γ Γ Γ Γ Γ Γ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 10 10 10 10 10 10 10 10 10 10 10 10 1 〇_237〇35 = Kaiping 1〇J37024, 曰10-237075, n n 唬唬、、、、、、、、、、、、、、、、、、日本日本日本日本日本日本日本 287 287 287 287 287 287 287 287 287 287 287 287 287 287 287 287 287 ;: 报曰曰专利专利专利专利专利 η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η 专利专利专利专利专利专利专利专利专利专利专利专利专利Japan—_1_日5=#Special open toilets 26 f plus the dielectric anisotropy is also positive or (iv) the liquid crystal composition is added with or on the optical recording compound. (4) The crystal display element can be obtained by the method of τ: forming the liquid crystal alignment film of the present invention on the i-direction film toward the two: bulk substrate, and obtaining the liquid crystal by means of a liquid crystal material and a viae spacer. — : Base = direction, in which a liquid crystal is encapsulated into a liquid crystal layer in a gap formed between the substrates. In the case of producing the present invention, the liquid crystal age element may be further included in the step of attaching a polarizing film or the like to the substrate. 79 200906914 A clever liquid crystal display element can form a liquid crystal display element for various electric field modes. Such a liquid-indicating element for an electric field method may be a wave crystal display for a transverse electric field mode in which a voltage is applied to the liquid layer B layer in a direction horizontal to a surface of the substrate. The element, or in a direction perpendicular to the table (four) of the filament plate, applies the liquid crystal layer to the longitudinal electric field mode of the wave crystal display element. The liquid crystal display element used in the transverse electric field mode may not exhibit a relatively large pre-precision, so that the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be better described, and the liquid crystal alignment agent of the present invention is not Obtained from a diamine containing a branched diamine. The liquid crystal display element for the longitudinal electric field mode needs to exhibit a relatively large pretilt angle, so that the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention described below can be used relatively well, and the liquid crystal alignment agent of the present invention is composed of A liquid crystal alignment agent obtained by using a monoamine having a branched diamine in addition to the diamine represented by the formula (1), or a liquid crystal alignment agent having a branched diamine in the diamine oxime. In this way, the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material. [Examples] Hereinafter, a liquid crystal alignment agent and a liquid crystal display element obtained by using the polymer of the present invention will be described in detail based on examples, but the present invention is not limited to these examples. In the example, the molecular weight is measured using Gpc, and the styrene is used as a standard solution, and the eluent is used! Methyl C A = 200906914 Ζ 61δ_) ρ ΐΓ (Dimethylformamide, DMF). In addition, in the following examples, the unit of volume is expressed by L. Therefore, mL means milliliters. The evaluation method of the liquid crystal display element used in the examples is described below.

(1 )殘留DC 對30 Hz、3 V的矩形波重叠3 V的直流電壓30分鐘後，測定5分鐘後的閃爍消失電壓，將此值的絕對值作為殘留DC。殘留DC越小’殘像越少，可以說良好。 (2) 電壓保持率（VHR，Voltage Holding Ratio) 使用“水島等人，第14次液晶討論會會議錄p78 (1988 ) ”中記載的方法。測定是對單元（ceii)施加柵極 (gate)寬度69 ps、頻率60 Hz、波高±5 V的矩形波。在測定溫度為60°C。 (3) 延遲（R)測定使用分光橢圓計 M-2000U ( J.A.Woollam Co.Inc.製造）’求得配向膜的延遲（R)。R的值越大，配向膜越向摩擦方向延伸，而具有較高的單軸配向性。結果可以說專顯示良好。 (4) 預傾角（Pt角）以中央精機股份有限公司製造的液晶評價裝置 (OMS-CA3)，在室溫下進行測定。實施例及比較例中所使用的四羧酸二酐、二胺及溶劑的名稱以縮寫表示。以下的記述中有時使用這些縮寫。四羧酸二酐(1) Residual DC After a DC voltage of 3 V was superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes, the flickering disappearance voltage after 5 minutes was measured, and the absolute value of this value was taken as residual DC. The smaller the residual DC, the less the residual image, the better. (2) Voltage holding ratio (VHR, Voltage Holding Ratio) The method described in "Water Island et al., 14th Liquid Crystal Symposium Proceedings p78 (1988)" was used. The measurement was performed by applying a rectangular wave having a gate width of 69 ps, a frequency of 60 Hz, and a wave height of ±5 V to the cell (ceii). The measurement temperature was 60 °C. (3) Delay (R) measurement The retardation (R) of the alignment film was determined using a spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.). The larger the value of R, the more the alignment film extends toward the rubbing direction and the higher the uniaxial alignment. The result can be said to show good. (4) Pretilt angle (Pt angle) The liquid crystal evaluation apparatus (OMS-CA3) manufactured by Central Seiki Co., Ltd. was measured at room temperature. The names of the tetracarboxylic dianhydride, the diamine and the solvent used in the examples and the comparative examples are abbreviated. These abbreviations are sometimes used in the following descriptions. Tetracarboxylic dianhydride

1,2,3,4-環丁烷四曱酸二酐：CBDA 200906914 均苯四曱酸二酐：PMDA 二胺1,2,3,4-cyclobutane tetraphthalic acid dianhydride: CBDA 200906914 pyromellitic acid dianhydride: PMDA diamine

4,4'-二氨基二苯基甲烷：DDM 1,3-雙(4-(4·氨基节基)笨基)丙烷：BZ3 4,4’-二氨基二苯醚：APE U-雙[4-[(4-氨基苯基）曱基]苯基]-4-正丁基環己烷：PMBCh f Ν,Ν’-雙（4-氨基苯基）_N,N，_二曱基乙二 % 胺:NN2D AMe4,4'-diaminodiphenylmethane: DDM 1,3-bis(4-(4.amino)phenyl)propane: BZ3 4,4'-diaminodiphenyl ether: APE U-double [ 4-[(4-Aminophenyl)indenyl]phenyl]-4-n-butylcyclohexane: PMBCh f Ν, Ν'-bis(4-aminophenyl)_N,N,_didecyl Diamine Amine: NN2D AMe

2,6-二氨基吡啶:DAPY 4,4'-二氨基二苯基胺：DADPA 溶劑成分 N-曱基-2-吡咯烷酮：NMP 丁内酯：GBL 丁基溶纖劑· ： BC 合成例1 ( 液晶配向膜用組合物A1 (清漆A1)的製備2,6-diaminopyridine: DAPY 4,4'-diaminodiphenylamine: DADPA Solvent component N-mercapto-2-pyrrolidone: NMP butyrolactone: GBL butyl cellosolve · : BC Synthesis Example 1 (Liquid crystal Preparation of composition film A1 (varnish A1) for alignment film

向具備溫度計、攪拌機、原料投入口及氮氣導入口的 100 mL的四口燒瓶中投入2·83 g的、53.4 mL 的脫水NMP，在乾燥氮氣流下授拌溶解。一邊將反應系統的溫度保持在5°C，一邊添加1.03 g的CBDA、l l4 g的 PMDA’使其反應30小時後，添加27.7址的BC、13.3 mL =GBL ’製備高分子成分的濃度為$对%的聚醯胺酸的清漆。在原料的反應中，利用反應熱使反應溫度上升時，將 82 200906914 ζοιο^ριι 反應溫度控制在約70°C或70°C以下而使其反應。而且’在本發明的實施例中，一邊確認反應中的黏度一邊進行反應’在添加BC後的清漆的黏度達到30〜35 mPa，s (使用E型黏度計，25t：)的時間點結束反應，在低溫下保存。所獲得的聚醯胺酸的重量平均分子量為 62,320。另外，重量平均分子量是使用WATERS製造的2,83 g of 53.4 mL of dehydrated NMP was placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and the mixture was dissolved under a dry nitrogen stream. While maintaining the temperature of the reaction system at 5 ° C, 1.03 g of CBDA and 1 l 4 g of PMDA' were added and allowed to react for 30 hours, and then the concentration of the polymer component was determined by adding 27.7 BC and 13.3 mL = GBL. $% viscle of polyamic acid. In the reaction of the raw material, when the reaction temperature is raised by the heat of reaction, the reaction temperature of 82 200906914 ζοιο^ριι is controlled to be about 70 ° C or lower to react. Further, in the embodiment of the present invention, the reaction was carried out while confirming the viscosity in the reaction. The viscosity of the varnish after the addition of BC reached 30 to 35 mPa, and the reaction was terminated at the time point of using s-type viscosity meter (25t:). , stored at low temperatures. The polyamic acid obtained had a weight average molecular weight of 62,320. In addition, the weight average molecular weight is manufactured using WATERS.

GPC測定裝置（軟件]£1111)(^¥£1>)且在管柱溫度5〇〇°c下進行測定。以NMP/BC/GBL (=60/25/15，重量比）的混合溶劑 2釋如上所述獲得的清漆，進行調整以使總高分子成分的 >辰度達到3 wt%，從而製備用於塗佈的清漆A1。合成例2〜8 各種清漆的製備除了以下；4表1的莫耳比使帛表丨的原料以外，以盘 j A!相同的方法，製備並獲得清漆a2〜a8。清漆μThe GPC measuring device (software) £1111) (^¥£1>) was measured at a column temperature of 5 °C. The varnish obtained as described above was discharged in a mixed solvent 2 of NMP/BC/GBL (=60/25/15, weight ratio), and adjusted so as to have a total polymer component of 3 wt%, thereby preparing for use. Coating varnish A1. Synthesis Examples 2 to 8 Preparation of various varnishes A varnish a2 to a8 were prepared and obtained in the same manner as in the tray j A! except that the molar ratio of Table 1 was used to make the enamel of Table 丨. Varnish μ

的八料種類、其莫耳^及顧㈣魏麟的重量平均分子量示於表1中。 T 200906914 表1 清漆莫耳比重量平均分子量四羧® 1二酐二胺 PMDA CBDA NN2DAMe DDM APE BZ3 PMBCh 合成例 A1 50 50 100 ----— 62,320 合成例 2 A2 50 50 50 50 63,0〇〇合成例 3 A3 50 50 50 50 61,050 合成例 4 A4 50 50 50 50 67,5〇〇合成例 5 A5 50 50 50 25 25 62,170 合成例 6 A6 50 50 80 20 73,860 合成例 7 A7 50 50 50 40 10 49,0〇〇合成例 8 A8 50 50 50 50 45,〇〇〇實施例1 r % 用於測定預傾角、電壓保持率及殘留DC的單元汪的製作所述用於測定的單元a的基板使用帶有IT〇電極的玻璃基板。 κ 以旋轉器將合成例1中所獲得的清漆Α1塗佈於所述帶有ιτο電極的玻璃基板上。塗佈條件為口⑻_、15 秒鐘。塗膜後，在80。〇下預锻燒約3分鐘後，在咖。^ =熱處理’形成膜厚大約為70腿的液晶齡 A理带t 乂 GAUGE製作所股份有限公司製造的摩擦擦布(毛長人造纖維㈤—) 子旋轉速Ϊ ^ 麵、载物台移動速度為mm/sec、粮膜進行^二r的條件下，對所獲得的瓣胺丁厚擦處理，獲得液晶夹持用基板。 84 200906914 在超純水中對所獲得的液晶失持用基板進行5分鐘超聲波清洗後，在烘箱中在120V下乾燥30分鐘。在其中一塊帶有ιτο電極的玻璃基板上散布7 μιη的間隙劑，以環氧硬化劑密封另-塊帶有ΙΤ〇電極的玻璃基板，製作間= 為7 μΠ1的逆平行單元（antipamlld cell)。向所述單元、入液晶材料’以光硬化劑密封注入口。接著，在^ 加熱處理30分鐘，冑成祕峡綱肖留DC的單元a。田从v a U ,, 主丨木诗丰及殘The weight average molecular weights of the eight types of materials, their Mohs and Gu (4) Wei Lin are shown in Table 1. T 200906914 Table 1 Varnish Mohr Ratio Weight Average Molecular Weight Tetracarboxy® 1 dianhydride Diamine PMDA CBDA NN2DAMe DDM APE BZ3 PMBCh Synthesis Example A1 50 50 100 ----- 62,320 Synthesis Example 2 A2 50 50 50 50 63,0〇〇 Synthesis Example 3 A3 50 50 50 50 61,050 Synthesis Example 4 A4 50 50 50 50 67, 5 〇〇 Synthesis Example 5 A5 50 50 50 25 25 62, 170 Synthesis Example 6 A6 50 50 80 20 73, 860 Synthesis Example 7 A7 50 50 50 40 10 49,0〇〇Synthesis Example 8 A8 50 50 50 50 45, 〇〇〇Example 1 r % For the measurement of the pretilt angle, the voltage holding ratio, and the residual DC unit, the unit a for the measurement was prepared. A glass substrate with an IT crucible electrode was used for the substrate. κ The varnish Α1 obtained in Synthesis Example 1 was applied onto the glass substrate with the ιτο electrode as a spinner. The coating conditions were mouth (8) _, 15 seconds. After coating, at 80. After the calaming is pre-calcined for about 3 minutes, it is in the coffee. ^ = heat treatment 'forms a liquid crystal age of about 70 legs. A tape t 乂GAUGE Co., Ltd. made a friction wipe (hair length rayon (5) -) sub-rotation speed ^ surface, stage movement speed is Under the conditions of mm/sec and grain filming, the obtained valeridine was subjected to thick rubbing treatment to obtain a substrate for liquid crystal clamping. 84 200906914 The obtained substrate for liquid crystal loss held in ultrapure water was subjected to ultrasonic cleaning for 5 minutes, and then dried in an oven at 120 V for 30 minutes. A 7 μm interstitial agent was spread on one of the glass substrates with the electrodes of the ιτο electrode, and the other glass substrate with the ruthenium electrode was sealed with an epoxy hardener to prepare an antiparallel cell with a ratio of 7 μΠ1. . The injection port is sealed with a light hardener to the unit, into the liquid crystal material. Next, after heat treatment for 30 minutes, the unit a of the DC is left. Tian from v a U , the main 丨木诗丰和残

用作液日日材料的液晶組合物A 於下文。此組合物的NI點為〗、、成不 [化66] 為雙折射為0.093。Liquid crystal composition A used as a liquid day material is hereinafter. The NI point of this composition is 〗〖, and the ratio is not [Chem. 66] and the birefringence is 0.093.

液晶组合物ALiquid crystal composition A

C3H7-<^C2H4_Q^_fC3H7-<^C2H4_Q^_f

ο5Ηιι-η〇-ο2Η4η〇-^-ρΗ5Ηιι-η〇-ο2Η4η〇-^-ρ

17wt.% 17wt.% 16wt.% 10wt.°/〇 5wt.% 10wt% 6wt.% 6wt.% 13wt.% 85 200906914 預傾角、電壓保持率及殘留DC的測定使用所述用於測定的單元a，以所述記載的方法測定預傾角、電M保持率及殘留DC，結果預傾角為2.3。，電壓保持率為99.0°/〇 ’殘留DC為2mV。用於剛定延遲的基板b的製作的基板使用透明玻璃基板。17wt.% 17wt.% 16wt.% 10wt.°/〇5wt.% 10wt% 6wt.% 6wt.% 13wt.% 85 200906914 Pretilt angle, voltage retention and residual DC determination using the unit a for measurement The pretilt angle, the electric M retention ratio, and the residual DC were measured by the method described above, and as a result, the pretilt angle was 2.3. The voltage holding ratio was 99.0 ° / 〇 ' residual DC was 2 mV. A substrate for the production of the substrate b which is just retarded is a transparent glass substrate.

透明玻璃基板上Γ ‘ :所€_清漆Αϊ塗佈於所述。。下預鍛燒約3分:後為J，700 ―1、15秒鐘。在8〇理，形成膜厚大約為後7f23〇C下進行20分鐘的加熱處 GAUGE製作所股份 nm白勺液晶配向膜。使用飯沼擦布（毛長】8mm ΑΓ司製造的摩擦處理裝置，在摩載物台移動速度為^=纖維）的錢入量為〇屬咖、的條件下，對所猙/θ、 sec、輥子旋轉速度為〗，〇〇〇 rpm 於測定的基板b^ ^亞胺膜進行摩擦處理，獲得用 κ: 延遲测定利用分光橢圓計求使用所獲得_於測定的基板b，得延遲。所獲得的R為_nm。實施例2〜7 使用合成例2〜7中所媒.主、水 ^同樣製作用於測定的單^^^漆^〜^’與實施例例工同樣測定預傾角'及用於測定的基板b，與實施肖電堡保持率（VHR)、殘留DC及延 86 200906914 ZOl 〇J>pil 遲（R)。測定結果示於表2中。表2 清漆預傾角[Ί VHRr〇/〇i 殘留DC [mV] R[nml 員存!I 1 A1 2.3 99.0 2 0.65 ~ 貫施例2 A2 1.5 99.4 3 0·44 〜實施例3 A3 1.7 99.1 3 0.45 ~~~' 實施例4 1 A4 2.3 99.4 5 ** <»« 0.62 實施例5 A5 1.6 99.3 3 0.45 '''' 貫施例6 A6 7.0 99.1 3 0.22 〜貫施例7 A7 4.5 99.3 5On the transparent glass substrate, ‘: _ _ varnish Αϊ is applied to the above. . The pre-calcining is about 3 minutes: after J, 700 - 1, 15 seconds. At 8 o'clock, a film thickness of about 7f23 〇C was developed for 20 minutes. GAUGE produced a liquid crystal alignment film of nm. Using a rice-rice cloth (hair length) 8mm 摩擦制造 friction processing device, when the movement speed of the friction stage is ^=fiber), the amount of money is 〇/θ, sec, The rotation speed of the roll was 〇〇〇, and 〇〇〇 rpm was subjected to rubbing treatment on the measured substrate b-imide film to obtain a retardation by using κ: retardation measurement using the spectroscopic ellipsometer to obtain the obtained substrate b. The obtained R is _nm. Examples 2 to 7 Using the materials of Synthesis Examples 2 to 7, the main and water were prepared in the same manner as in the case of the measurement, and the pretilt angle and the substrate for measurement were measured in the same manner as in the example. b, and the implementation of the Xiaodianbao retention rate (VHR), residual DC and extension 86 200906914 ZOl 〇 J > pil late (R). The measurement results are shown in Table 2. Table 2 Pre-tilt angle of varnish [Ί VHRr〇/〇i Residual DC [mV] R [nml staff! I 1 A1 2.3 99.0 2 0.65 ~ Example 2 A2 1.5 99.4 3 0·44 ~ Example 3 A3 1.7 99.1 3 0.45 ~~~' Example 4 1 A4 2.3 99.4 5 ** <»« 0.62 Example 5 A5 1.6 99.3 3 0.45 '''' Example 6 A6 7.0 99.1 3 0.22 ~ Example 7 A7 4.5 99.3 5

另外，本發明的實施例的試驗方法中，如果電壓保持率為99.0%以上的值，那麼算是良好，如果殘留Dc為忉 mV以下的值，那麼算是良好，如果延遲為〇.2 nm以上的，，那麼算是良好。如果延遲的值為Q 2 以下，那麼算疋配向力較弱’流動配向或不施光。尤其是在橫向電埸太士丁晃％方式下’延遲的值是重要的灸數 (parameter)。關於預傾条、町，數要的值也不同，因此無法省各驅動方式不同，所需好，但在IPS等橫向電γ斤獲得的數值具體判斷好或不下），在ΤΝ為代表的縱向式下，優選較小的值（3.0。以。以上）。 ° %；l昜方式下，優選比較大的值（4·〇實施例8及9 分別以後述的表3中戶〜製備清漆Α卜八2及八8,不的聚合物組成（重量比）來進行預傾角、電壓保持率使用這些清漆，與實施例1同樣結果示於表3中。、…、殘留DC及延遲的測定。測定 87 200906914 表3 清漆預傾角 VHR[%] 殘留 R[nm] 重量比 Γ] DC[mV] 實施例 8 A1 A8 Al/A8 = 9/1 10.3 99.2 5 0.25 實施例 9 A2 A8 A2/A8 = 9/l 10.4 99.3 7 0.25 實施例10 向20 g (固體成分濃度5 wt%)合成例1中所獲得的清漆A1中混合0.1 g (相對於清漆A1的聚合物為10 wt%) 環氧化合物即4,4'-亞曱基雙(N，N-二縮水甘油基苯胺） (SIGMA-ALDRICH公司製造），製備清漆B1，使用此清漆B1，與實施例1同樣進行預傾角、電壓保持率、殘留 DC及延遲的測定。表4 清漆預傾角 [Ί VHR[%] 殘留DC [mV] R[nm] 實施例10 B1 2.3 99.4 2 0.60 合成例10〜14 各種清漆的製備除了以下述表5的莫耳比使用下述表5的原料以外，利用與清漆A1相同的方法，製備並獲得清漆C1〜C5。清漆C1〜C5的原料種類、其莫耳比及所獲得的聚醯胺酸的重量平均分子量示於表5中。 88 200906914 i 5^pil 表5 清漆莫耳比重量平均分子量四羧酸二酐二月安 PMDA CBDA DDM APE BZ3 DAPY DADPA 合成例10 C1 50 50 100 64,070 合成例11 C2 50 50 100 62,120 合成例12 C3 50 50 100 68,950 合成例13 C4 50 50 100 2,560 合成例14 C5 50 50 100 63,660 比較例1〜5 使用合成例10〜14中所獲得的清漆Cl〜C5來替代清漆A1，與實施例1同樣製作用於測定的單元a及用於測定的基板b，與實施例1同樣測定預傾角、電壓保持率、殘留DC及延遲。測定結果示於表6中。表6 清漆預傾角[Ί VHR[°/〇] 殘留 DC「mVl R[nm] 比較例1 C1 1.0 99.5 40 0.19 比較例2 C2 1.4 98.5 30 0.18 比較例3 C3 2.0 99.5 55 0.60 比較例4 C4 分子量並未提高，產生摩擦磨損。無法評價。比較例5 C5 1.5 99.2 3 0.12 根據實施例1〜10及比較例1〜5的結果可知，通過使用本發明的具有包含三級胺的二胺的聚醯胺酸，可製作能夠同時滿足殘留DC降低與較大延遲的液晶顯示元件。 89 200906914 【圖式簡單說明】無。【主要元件符號說明】無0Further, in the test method of the embodiment of the present invention, if the voltage holding ratio is a value of 99.0% or more, it is considered to be good, and if the residual Dc is a value of 忉mV or less, it is considered to be good, and if the retardation is 〇.2 nm or more. , then it is good. If the value of the delay is below Q 2 , then the 疋 alignment force is weaker 'flow alignment or no light. Especially in the case of the horizontal electric 埸士晃晃 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Regarding the pre-dipping, the town, the value of the number is also different, so it is impossible to save the different driving methods, and the need is good, but the value obtained by the horizontal electric γ jin such as IPS is judged well or not), and the portrait represented by ΤΝ In the formula, a smaller value (3.0 or more) is preferred. ° %; l昜 mode, preferably a relatively large value (4 · 〇 Examples 8 and 9 respectively later in the table 3 to prepare varnish Α 八八 8 and 8 8 , no polymer composition (weight ratio) These varnishes were used for the pretilt angle and the voltage holding ratio, and the results are shown in Table 3 in the same manner as in Example 1. Measurement of residual DC and retardation. Measurement 87 200906914 Table 3 Pre-tilt angle of varnish VHR [%] Residual R [nm ] Weight ratio Γ] DC [mV] Example 8 A1 A8 Al/A8 = 9/1 10.3 99.2 5 0.25 Example 9 A2 A8 A2/A8 = 9/l 10.4 99.3 7 0.25 Example 10 to 20 g (solid content) 5 wt%) The varnish A1 obtained in Synthesis Example 1 was mixed with 0.1 g (10 wt% based on the polymer of varnish A1). The epoxy compound was 4,4'-arylene di(N,N-di Glycidyl aniline (manufactured by SIGMA-ALDRICH), varnish B1 was prepared, and the pre-tilt angle, voltage holding ratio, residual DC, and retardation were measured in the same manner as in Example 1 using this varnish B1. Table 4 Pre-tilt angle of varnish [Ί VHR [%] Residual DC [mV] R [nm] Example 10 B1 2.3 99.4 2 0.60 Synthesis Example 10 to 14 Preparation of various varnishes except the following Table 5 The varnishes C1 to C5 were prepared and obtained in the same manner as in the varnish A1 except for using the raw materials of the following Table 5. The raw material types of the varnishes C1 to C5, the molar ratio thereof, and the weight average of the obtained polyamic acid. The molecular weights are shown in Table 5. 88 200906914 i 5^pil Table 5 Varnish Mohr Ratio Weight average molecular weight Tetracarboxylic dianhydride Ernst PMDA CBDA DDM APE BZ3 DAPY DADPA Synthesis Example 10 C1 50 50 100 64,070 Synthesis Example 11 C2 50 50 100 62,120 Synthesis Example 12 C3 50 50 100 68,950 Synthesis Example 13 C4 50 50 100 2,560 Synthesis Example 14 C5 50 50 100 63,660 Comparative Examples 1 to 5 Using the varnishes C1 to C5 obtained in Synthesis Examples 10 to 14 instead of the varnish A1 The unit a for measurement and the substrate b for measurement were prepared in the same manner as in Example 1. The pretilt angle, the voltage holding ratio, the residual DC, and the retardation were measured in the same manner as in Example 1. The measurement results are shown in Table 6. Table 6 Varnish Pretilt angle [Ί VHR[°/〇] Residual DC "mVl R[nm] Comparative Example 1 C1 1.0 99.5 40 0.19 Comparative Example 2 C2 1.4 98.5 30 0.18 Comparative Example 3 C3 2.0 99.5 55 0.60 Comparative Example 4 C4 Molecular weight is not improved Friction wear. Unable to evaluate. Comparative Example 5 C5 1.5 99.2 3 0.12 According to the results of Examples 1 to 10 and Comparative Examples 1 to 5, it was found that by using the polyamine having a diamine containing a tertiary amine of the present invention, it was possible to simultaneously satisfy the residual DC. Lowering the liquid crystal display element with a larger delay. 89 200906914 [Simple description of the schema] None. [Main component symbol description] No 0

Claims

200906914 ΔΟίOjpu 十、申請專利範圍： μ 】.一種液晶配向劑，其含有四羧酸二酐與>腠的f = 產物、即聚醯胺酸或其衍生物，其特徵在於，所述>胺^ 含以下述通式（1)表示的；胺， [化】]200906914 ΔΟίOjpu X. Patent Application Range: μ 】 A liquid crystal alignment agent containing tetracarboxylic dianhydride and > oxime f = product, ie poly-proline or its derivative, characterized in that said > The amine ^ is represented by the following formula (1); an amine, [Chemical]

通式（1)中’ R1獨立地表示一價有機基，;R2獨立地表示一價基，Z表示包含破數1〜5的亞院基的二價基。 2.如申請專利範圍第1項所述的液晶配向劑，其中R 獨立為兔數1〜3的燒基，R_2獨立為氫、碳數1〜3之炫基氟、氯或溴。 3. 如申請專利範圍第1頊所述的液晶配向劑，其中以 I式（1)表示的二胺，在雨端的苯基上，在對應於N-Z_N L鏈的各個騎上具有氨基。 UIn the formula (1), R1 independently represents a monovalent organic group; R2 independently represents a monovalent group, and Z represents a divalent group containing a subunit having a number of 1-5. 2. The liquid crystal alignment agent according to claim 1, wherein R is independently a calcining group of 1 to 3 rabbits, and R 2 is independently hydrogen, fluoro, chlorine or bromine having a carbon number of 1 to 3. 3. The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine represented by the formula (1) has an amino group on each of the phenyl groups corresponding to the N-Z_N L chain on the phenyl group at the rain end. U

4. 如申請專利範㈣3 一述雜晶配向劑，其中以固弟3 缺構式239〜253及258〜 I式（1)表示的二胺是從卞述知掛、、 62所組成的族群中選擇的〆裀成〆個以上， ί匕2] 3 /^Χ 2414. For example, the application of the patent (4) 3 describes the heterogeneous alignment agent, wherein the diamine represented by the formula of 239~253 and 258~I (1) is selected from the group consisting of 卞知、, and 62 More than one, 匕2] 3 /^Χ 241

ΝΗ2ΝΗ2

CH3 CHy N-(CH2)2-N-{ >—nh2 CH3 N_(CH2)4_NCH3 CHy N-(CH2)2-N-{ >-nh2 CH3 N_(CH2)4_N

CHCH

nh2 244200906914 243 H2N 245 H2N ch3 ch3 n-(ch2)5-nNh2 244200906914 243 H2N 245 H2N ch3 ch3 n-(ch2)5-n

NH C2H5 C2H N-(CH2)2-NNH C2H5 C2H N-(CH2)2-N

nh2 丨2Nh2 丨2

nh2 nh2 248 247Nh2 nh2 248 247

250250

?2H5 C2H^ N-(CH2)5-N C3H7 N-(CH2)2-N 251 H2N 253?2H5 C2H^ N-(CH2)5-N C3H7 N-(CH2)2-N 251 H2N 253

==y C3H7 (CH2)5-N==y C3H7 (CH2)5-N

C3H7 C3H^ n-(ch2)3-n _/=\ t3' H2N—^ [化3] 252 /=\ C3H7 ?3H) nh2 h2n-^ ^-n，(ch2)4-nC3H7 C3H^ n-(ch2)3-n _/=\ t3' H2N—^ [Chemical 3] 252 /=\ C3H7 ?3H) nh2 h2n-^ ^-n,(ch2)4-n

(ch2)4.(ch2)4.

(CH2)5(CH2)5

92 200906914 Ζ,ΟΙ Ojpil 5.如申請專利範圍第1項所述的液晶配向劑，其中所述四羧酸二酐是從下述結構式500、505〜508、511、515 及517中選擇的一個或一個以上， [化4]The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride is selected from the following structural formulas 500, 505 to 508, 511, 515 and 517. One or more, [Chem. 4]

6. 如申請專利範圍第5項所述的液晶配向劑，其中所述四羧酸二酐是所述結構式500及511的一者或者兩者。 7. 如申請專利範圍第1項所述的液晶配向劑，其中所述二胺進一步包含以下述通式（2)表示的二胺， [化5] H2N-R3—NH2 (2) 通式（2)中，R3表示可具有取代基及不包含兩個或 93 200906914 兩個以上的亞氨基的二價有機基。 δ如中請專利範圍第7項所述的液晶配向劑，其中以 (2)表示的二胺包含以下述通式（3)〜（5)表示的 [化6]6. The liquid crystal alignment agent according to claim 5, wherein the tetracarboxylic dianhydride is one or both of the structural formulas 500 and 511. 7. The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a diamine represented by the following formula (2), [Chem. 5] H2N-R3 - NH2 (2) In 2), R3 represents a divalent organic group which may have a substituent and does not contain two or 93 200906914 two or more imino groups. The liquid crystal alignment agent according to Item 7, wherein the diamine represented by (2) is represented by the following general formulae (3) to (5).

(3) 5的伸烷基、氧及 k式（3)中，γ表示包含碳數硫的—種或一種以上的二價基， [化7](3) 5 alkyl, oxygen, and k (3), γ represents a species or more than a divalent group containing a carbon number of sulfur, [Chem. 7]

(4) 可且ϊίϋ中’x]獨立地表示亞甲基或者氧，χ2表示、土 2 Cp3作為取代基的碳數i〜8的亞烧基， [化 8] ^ R4(4) ’ ϋ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’

94 200906914 中’所述規基中，碳數2〜30的烧基中的任意的亞甲基可獨立地被氧、-CH=CH-或者-CEC-取代，所述烷基中，氧並不相鄰;h表示〇或者1。 9·如申請專利範圍第8項所述的液晶配向劑，其中通式（3)〜（5)中，兩個氨基的位置相對於γ或者χ】是對位。94. In the formula of 200906914, any methylene group in the alkyl group having 2 to 30 carbon atoms may be independently substituted by oxygen, -CH=CH- or -CEC-, in which the oxygen is Not adjacent; h means 〇 or 1. 9. The liquid crystal alignment agent according to claim 8, wherein in the general formulae (3) to (5), the positions of the two amino groups are para-position with respect to γ or χ.

10.如申請專利範圍第9項所述的液晶配向劑，其中以通式（3)表示的二胺是從下述結構式301〜304、306、307 及313所組成的族群中選擇的一個或一個以上，以通式（4)表示的二胺是從下述結構式360、364、 365、367及372所組成的族群中選擇的一個或一個以上，以通式（5)表示的二胺是從下述結構式381、384、 ?0十398馳成的族群中選擇的一個或―個以上，10. The liquid crystal alignment agent according to claim 9, wherein the diamine represented by the general formula (3) is one selected from the group consisting of the following structural formulas 301 to 304, 306, 307 and 313. Or one or more, the diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367 and 372, and the two represented by the formula (5) The amine is one or more selected from the group consisting of the following structural formulas 381, 384 and ?0: 398.

301301

304 307 Η2Ν 313 _ h2n-^^s^(ch2)4.s_^^nh 302 Η2Ν~~-nh2 [化 10] 95304 307 Η2Ν 313 _ h2n-^^s^(ch2)4.s_^^nh 302 Η2Ν~~-nh2 [化 10] 95

H2N~\ / Λ /·{ΟΗ2)3Λ / \ / NH2 200906914 360 H2N 364 /- % 365H2N~\ / Λ /·{ΟΗ2)3Λ / \ / NH2 200906914 360 H2N 364 /- % 365

k [化 11]k [化11]

96 20090691496 200906914

ί \ 11. 如申請專利範圍第8項所述的液晶配向劑，其中所述二胺中，以通式（1)表示的二胺的含有率為20〜99莫耳％，以通式（2)表示的二胺的含有率為1〜80莫耳％。 12. —種液晶配向劑，其含有：四羧酸二酐A與二胺A 的反應產物即聚醯胺酸或其衍生物A、以及四羧酸二酐B 與二胺B的反應產物即聚醯胺酸或其衍生物B，其特徵在於，所述二胺A包含以下述通式（1)表示的二胺，所述二胺B不包含以下述通式（1)表示的二胺， [化 12]The liquid crystal alignment agent according to claim 8, wherein the content of the diamine represented by the general formula (1) in the diamine is 20 to 99 mol%, and the general formula ( 2) The content of the diamine represented is 1 to 80 mol%. 12. A liquid crystal alignment agent comprising: a reaction product of a tetracarboxylic dianhydride A and a diamine A, that is, a reaction product of polyamic acid or a derivative A thereof, and a tetracarboxylic dianhydride B and a diamine B, that is, The polyamine A or a derivative thereof, wherein the diamine A contains a diamine represented by the following formula (1), and the diamine B does not contain a diamine represented by the following formula (1) , [Chemistry 12]

⑴ 通式（1)中，R1獨立地表示一價有機基，R2獨立地表示一價基，Z表示包含碳數1〜5的亞烷基的二價基。 13. 如申請專利範圍第12項所述的液晶配向劑，其中通式（1)中，R1獨立為碳數1〜3的烷基，R2獨立為氫、碳數1〜3的烧基、氧、氣或漠。 14. 如申請專利範圍第12項所述的液晶配向劑，其中 97 200906914 以通式（1)表示的二胺，在兩端的苯基上，在對應於N-Z-N 主鏈的各個對位上具有氧基。 15.如申請專利範圍第14項所述的液晶配向劑，其中以通式（1)表示的二胺是從下述結構式239〜253及258 〜262所組成的族群中選擇的一個或一個以上， [化 13] 239 H2N 241 H2N 243 H2N 245 C2H5 C2H H2N—^ /-N»(CH2)2-N 247 H2N—\ ^"N-(CH2)4~N I Na^N CH3 ch3 ch3 ch3 N-(CH2)3-N ch3 ch3 N-(CH2)5-N(1) In the formula (1), R1 independently represents a monovalent organic group, R2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms. 13. The liquid crystal alignment agent according to claim 12, wherein, in the formula (1), R1 is independently an alkyl group having 1 to 3 carbon atoms, and R2 is independently hydrogen and a carbon number of 1 to 3; Oxygen, gas or desert. 14. The liquid crystal alignment agent according to claim 12, wherein 97 200906914 is a diamine represented by the general formula (1) having oxygen on each of the opposite positions of the NZN main chain on the phenyl groups at both ends base. The liquid crystal alignment agent according to claim 14, wherein the diamine represented by the formula (1) is one or a group selected from the group consisting of the following structural formulas 239 to 253 and 258 to 262; Above, [Chem. 13] 239 H2N 241 H2N 243 H2N 245 C2H5 C2H H2N—^ /-N»(CH2)2-N 247 H2N—\ ^"N-(CH2)4~NI Na^N CH3 ch3 ch3 ch3 N-(CH2)3-N ch3 ch3 N-(CH2)5-N

nh2Nh2

240 h2n +u CH3 CH： N-(CH2)2-N240 h2n +u CH3 CH: N-(CH2)2-N

nh2 242 NH2 h2n CH3 CH； (CH2)4'NNh2 242 NH2 h2n CH3 CH; (CH2)4'N

nh2Nh2

nh2 244 nh2 h2nNh2 244 nh2 h2n

NH2 h2n 斗 _NH2 h2n bucket _

C2H5 246 /=V c2h5 248 N-(CH2)3-N ?2H5 〒: N-(CH2)5-N c2hC2H5 246 /=V c2h5 248 N-(CH2)3-N ?2H5 〒: N-(CH2)5-N c2h

nh2Nh2

nh2 249 250 H2N 〒3H7 (p3H7/=N N^^N-Nh2 249 250 H2N 〒3H7 (p3H7/=N N^^N-

nh2 h2n <y C3H7 C N-(CH2)2-NNh2 h2n <y C3H7 C N-(CH2)2-N

nh2 251 H2N C3H7 c3h7/ N-(CH2)3-NNh2 251 H2N C3H7 c3h7/ N-(CH2)3-N

252/=\ ?3Hy ? nh2 h2n-^ ^-n，(ch2)4-n252/=\ ?3Hy ? nh2 h2n-^ ^-n,(ch2)4-n

nh2 253 Λ=\ ^3Η7 η2Ν_^Γ；οη2)5.ΝNh2 253 Λ=\ ^3Η7 η2Ν_^Γ;οη2)5.Ν

nh5 [化 14] 98 200906914 JLO 1 oopn 258Nh5 [Chem. 14] 98 200906914 JLO 1 oopn 258

16. 如申请專利範圍第12項所述的液晶配向劍，其中所述二胺B包含以下述通式（2)表示的二胺， [化 15] H2N-R3-NH2 (2) 通式（2)中，R3表示具有取代基及不包含兩個或兩個以上的亞氨基的二價有機基。 17. 如申請專利範圍第16項所述的液晶配向劑，其中以通式（2)表示的二胺包含以下述通式（3)〜（5)表示的二胺， [化 16]16. The liquid crystal alignment sword according to claim 12, wherein the diamine B comprises a diamine represented by the following formula (2), [Chem. 15] H2N-R3-NH2 (2) In 2), R3 represents a divalent organic group having a substituent and not containing two or more imino groups. 17. The liquid crystal alignment agent according to claim 16, wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5), [Chem. 16]

通式（3)中，Y表示包含碳數1〜5的亞烷基、氧及 99 200906914 硫的一種或一種以上的二價基 Hb 17]In the formula (3), Y represents an alkylene group having 1 to 5 carbon atoms, oxygen, and one or more divalent groups of 99 200906914 sulfur.

通式（4)中，X1獨立地表示亞甲基或者氧，X2表示可具有甲基或者CF3作為取代基的碳數1〜8的亞烷基， [化 18]In the formula (4), X1 independently represents a methylene group or oxygen, and X2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or a CF3 as a substituent.

通式（5)中，X1獨立地表示碳數1〜6的亞烷基或者氧;X3表示單鍵或者碳數1〜3的亞烷基;環T表示1,4-亞苯基或者1,4-亞環己基;R4表示氳或者碳數1〜30的烷基，其中，所述烷基中，碳數2〜30的烷基中的任意的亞曱基可獨立地被氧、-CH=CH-或者-C三C-取代，所述烷基中，氧並不相鄰）；h表示0或者1。 18. 如申請專利範圍第17項所述的液晶配向劑，其中通式（3)〜（5)中，兩個氨基的位置相對於Y或者X1 是對位。 19. 如申請專利範圍第18項所述的液晶配向劑，其中以通式（3)表示的二胺是從下述結構式301〜304、306、 100 200906914 ΔΟΪ O^pii 307及313所組成的族群中選擇的一個或一個以上，以通式（4)表示的二胺是從下述結構式360、364、 365、367及372所組成的族群中選擇的一個或一個以上，以通式（5)表示的二胺是從下述結構式381、384、 390及398所組成的族群中選擇的一個或一個以上， [化 19] 301 ί 302In the formula (5), X1 independently represents an alkylene group having 1 to 6 carbon atoms or oxygen; X3 represents a single bond or an alkylene group having 1 to 3 carbon atoms; and ring T represents a 1,4-phenylene group or 1 , 4-cyclohexylene; R 4 represents an anthracene or an alkyl group having 1 to 30 carbon atoms, wherein any of the alkylidene groups of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be independently oxygen- CH=CH- or -C triple C-substitution in which oxygen is not adjacent); h represents 0 or 1. 18. The liquid crystal alignment agent according to claim 17, wherein in the general formulae (3) to (5), the positions of the two amino groups are aligned with respect to Y or X1. 19. The liquid crystal alignment agent according to claim 18, wherein the diamine represented by the formula (3) is composed of the following structural formulas 301 to 304, 306, 100 200906914 ΔΟΪ O^pii 307 and 313 One or more selected from the group, the diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367, and 372, The diamine represented by (5) is one or more selected from the group consisting of the following structural formulas 381, 384, 390 and 398, [Chem. 19] 301 ί 302

(ch2)2 Or nh2 h2n ο (CH2)3 Or nh2 h2n (CH2)4 Or nh2 307 nh2 h2n 306 H2N nh2 313 H2N S-(CH2)4-S nh2 [化 20](ch2)2 Or nh2 h2n ο (CH2)3 Or nh2 h2n (CH2)4 Or nh2 307 nh2 h2n 306 H2N nh2 313 H2N S-(CH2)4-S nh2 [Chem. 20]

360 nh2 364360 nh2 364

101 200906914 372 _ _ _ — HsN v^〇x〇k(ch2)3~^^°'X~Vnh2 [化 21]101 200906914 372 _ _ _ — HsN v^〇x〇k(ch2)3~^^°'X~Vnh2 [Chem. 21]

20.如申請專利範圍第12項所述的液晶配向劑，其中所述四羧酸二酐A及四羧酸二酐B是從下述結構式500、 102 200906914 /δ J δ-ίρΐτ 505〜508、511、515及517中選擇的一個或一個以上， [化 22]The liquid crystal alignment agent according to claim 12, wherein the tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are from the following structural formula 500, 102 200906914 / δ J δ - ίρΐτ 505~ One or more selected from 508, 511, 515, and 517, [Chem. 22]

21. 如申請專利範圍第20項所述的液晶配向劑，其中所述四羧酸二酐Α及四羧酸二酐Β是所述結構式500及 511的一者或者兩者。 22. 如申請專利範圍第1項或第12項所述的液晶配向劑，其中還包括環氧化合物。 23. 如申請專利範圍第22項所述的液晶配向劑，其中所述環氧化合物是從下述結構式（E1)〜（E3)、（E5)及下述通式（E4)所組成的族群中選擇的一個或一個以上， [化 23] 103 200906914The liquid crystal alignment agent according to claim 20, wherein the tetracarboxylic dianhydride oxime and the tetracarboxylic dianhydride oxime are one or both of the structural formulae 500 and 511. 22. The liquid crystal alignment agent of claim 1 or 12, which further comprises an epoxy compound. 23. The liquid crystal alignment agent according to claim 22, wherein the epoxy compound is composed of the following structural formulae (E1) to (E3), (E5), and the following general formula (E4); One or more selected among the ethnic groups, [Chem. 23] 103 200906914

通式（E4)中，n表示〇〜ι〇的整數。 24. 如申請專利範圍第22項所述的液晶配向劑，其中相對於所述聚醯胺酸或其衍生物的總量而包含〇.1〜4〇 wt%的所述環氧化合物。 25. —種液晶配向膜，其特徵在於，其是由申請專利範圍第1至24項中任一項的液晶配向劑而獲得的。 104 200906914 2ίίΙ»3ρΐΤ 26. —種液晶顯示元件，包括：一對基板；含有液晶分子’且形成於所述一對基板之間的液晶層；對液晶層施加電壓的電極；使所述液晶分子於特定方向上配向的液晶配向膜；其特徵在於，所述液晶配向膜是申請專利範圍第25 項所述的液晶配向膜。 27. 如申請專利範圍第26項所述的液晶顯示元件，其中所述電極在相對於所述基板的表面水平的方向上，對所述液晶層施加電壓的用於橫向電場方式的液晶顯示元件。 28·如申請專利範圍第26項所述的液晶顯示元件，其中所述電極在相對於所述基板的表面垂直的方向上，對所述液晶層施加電壓的用於縱向電場方式的液晶顯示元件。 29·—種聚合物，其是四羧酸二酐與二胺的反應產物’ 其特徵在於，所述二胺包含以下述通式（1)表不的二胺與以下述通式（2)表示的二胺，In the general formula (E4), n represents an integer of 〇~ι〇. The liquid crystal alignment agent according to claim 22, wherein the epoxy compound is contained in an amount of from 0.1 to 4% by weight based on the total amount of the polyaminic acid or a derivative thereof. A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 24. 104 200906914 2ίίΙ»3ρΐΤ 26. A liquid crystal display element comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; A liquid crystal alignment film which is aligned in a specific direction; and the liquid crystal alignment film is the liquid crystal alignment film according to claim 25 of the patent application. 27. The liquid crystal display element according to claim 26, wherein the electrode is a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction horizontal to a surface of the substrate for a transverse electric field mode . The liquid crystal display element according to claim 26, wherein the electrode is a liquid crystal display element for a vertical electric field mode in which a voltage is applied to the liquid crystal layer in a direction perpendicular to a surface of the substrate. . 29. A polymer which is a reaction product of a tetracarboxylic dianhydride and a diamine, wherein the diamine comprises a diamine represented by the following formula (1) and a formula (2) Derived diamine,

通式（1)中，R1獨立地表示一價有機基，R2獨立地表示一價基，Z表示包含碟數1〜5的亞烷基的二價基， [化 25] H2N-r3—nh2 通式（2)中’ R3表示具有取代基及不包含亞氨基的 105 200906914 二價有機基。 30.如申請專利範圍第29所述的聚合物，其中通式（1) 中，R1獨立為碳數1〜3的烷基，R2獨立為氫、碳數1〜3 的烧基、氣、氯或〉臭。 31. 如申請專利範圍第29項所述的聚合物，其中以通式（1 )表不的 >一胺，在兩端的苯基上，在對應於N-Z-N 主鏈的各個對位上具有氨基。 32. 如申請專利範圍第31項項所述的聚合物，其中以通式（1)表示的二胺是從下述結構式239〜253及258〜 262所組成的族群中選擇的一個或一個以上，In the formula (1), R1 independently represents a monovalent organic group, R2 independently represents a monovalent group, and Z represents a divalent group of an alkylene group having a disk number of 1 to 5, [Chem. 25] H2N-r3-nh2 In the formula (2), 'R3 represents a substituent having a substituent and a group containing no imino group. 2009 200914 14 Divalent organic group. The polymer according to claim 29, wherein, in the formula (1), R1 is independently an alkyl group having 1 to 3 carbon atoms, and R2 is independently hydrogen, a carbon number of 1 to 3, a gas, Chlorine or > odor. The polymer according to claim 29, wherein the amine represented by the formula (1) has an amino group at each of the phenyl groups at the opposite positions of the NZN main chain. . The polymer according to claim 31, wherein the diamine represented by the formula (1) is one or a group selected from the group consisting of the following structural formulas 239 to 253 and 258 to 262; the above,

[化 26] 239[Chem. 26] 239

ch3 ch3 ch3 ch3 N-(CH2)3-N h2n 241 H2N 243 ch3 ch H2N—^ 240 H2N ch3 ch： (CH2)2-NCh3 ch3 ch3 ch3 N-(CH2)3-N h2n 241 H2N 243 ch3 ch H2N—^ 240 H2N ch3 ch: (CH2)2-N

nh2 ~〇TNh2 ~〇T

NH ch3 ch I ^ 丨 N-(CH2)4-NNH ch3 ch I ^ 丨 N-(CH2)4-N

nh2 245 H2N 247 H2N 249 H2N ?2H5 C2H5y N-(CH2)2-N Ο、 C3H7 C3H7 2 242 H2N (CH2)5-N C2H5 N-(CH2)4-NNh2 245 H2N 247 H2N 249 H2N ?2H5 C2H5y N-(CH2)2-N Ο, C3H7 C3H7 2 242 H2N (CH2)5-N C2H5 N-(CH2)4-N

C2H5 C2H5 〒2H5 〇2^γ= N-(CH2)3-NC2H5 C2H5 〒2H5 〇2^γ= N-(CH2)3-N

c2h5 c2h (ch2)5-nC2h5 c2h (ch2)5-n

C3H7 N-(CH2)2-NC3H7 N-(CH2)2-N

106 200906914 ^»Ι^3ριί 251106 200906914 ^»Ι^3ριί 251

?3h7 ?3Η7/==χ \^/^ν~(〇η2)3-ν--^ Vnh2 253 ^~ (CH2}5-?3h7 ?3Η7/==χ \^/^ν~(〇η2)3-ν--^ Vnh2 253 ^~ (CH2}5-

NH2 [化 27] 258NH2 [化27] 258

式 33.如申請專利範 2頊所述的聚合物，其中以通 \ )表示的二胺是所述結構式240。 =4.如申請專利範圍第29項所述的聚合物，其中以通 '表示的二胺包含以下述通式（3)〜（5)表示的二The polymer of claim 2, wherein the diamine represented by the pass-through is the structural formula 240. The polymer according to claim 29, wherein the diamine represented by the general formula contains the two represented by the following general formulae (3) to (5)

(3) 107 200906914 〜5的亞烷基、氧及通式（3)中，γ本-a a w, ,, ^ , 甲γ表不包含碳數硫的一種或一U // X 種以上的二價基，(3) 107 200906914 〜5 alkylene, oxygen and in the general formula (3), γ-aaw, ,, ^, A γ table does not contain one of the carbon number sulfur or a U / X species or more Price base,

[化 29] '[化29] '

(4)(4)

^式(m5)中，χ1獨立地表示碳數1〜6的亞烷基或者 ’、t不早鍵或者碳數1〜3的亞烷基;環τ表示丨，4·亞苯基或者丨，‘亞環己基;R4表示氫或者碳數1〜3〇的烷基，其中所述烷基中，碳數2〜30的烷基中的任意的亞曱基可獨立地被氧、-CH=CH-或者七三。取代，所述烷基中，氧並不相鄰;h表示0或者1。 35.如申請專利範圍第34項所述的聚合物’其中通式 (3)〜（5)中，兩個氨基的位置相對於Y或者χ1是對位。 36.如申請專利範圍第35項所述的聚含物，其中以通 108 200906914 ^ΟΙό^ρΐΊ 式（3)表示的二胺是從下逑妹 3〇1〜3〇4、3〇6、π? 及313所組成的族群中選擇的^ ^威〆個以上，以通式（4)表示的二胺θ…述結構式36〇、364、 365 ^ 367 ^ 以通式⑸表示的二胺是從卞固以上， [化 31] 301 390及398所組成的族群中選擇的/摘成 302In the formula (m5), χ1 independently represents an alkylene group having 1 to 6 carbon atoms or ', t is not an early bond or an alkylene group having 1 to 3 carbon atoms; and ring τ is a fluorene, 4 phenylene group or fluorene. , 'cyclohexylene group; R4 represents hydrogen or an alkyl group having 1 to 3 carbon atoms, wherein any of the alkylidene groups of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be independently oxygen, -CH =CH- or seven or three. Instead, in the alkyl group, oxygen is not adjacent; h represents 0 or 1. 35. The polymer according to claim 34, wherein in the formulae (3) to (5), the positions of the two amino groups are aligned with respect to Y or χ1. 36. The polyamine according to claim 35, wherein the diamine represented by the formula (3) is from the next sister 3〇1~3〇4, 3〇6, More than one selected from the group consisting of π? and 313, the diamine θ represented by the general formula (4), the structural formula 36 〇, 364, 365 ^ 367 ^ The diamine represented by the general formula (5) It is selected from the group consisting of 卞固, [化31] 301 390 and 398.

H2N-<Q^(CH^^〇^(CH2)3"〇^H2 313 _ Η2Ν 303 η2ν 306 NH2 nh2 NH, [化 32] 360H2N-<Q^(CH^^〇^(CH2)3"〇^H2 313 _ Η2Ν 303 η2ν 306 NH2 nh2 NH, [化32] 360

364364

109 200906914 372 [化 33]109 200906914 372 [Chem. 33]

37.如申請專利範圍第36項所述的聚合物，其中以通式（3)表示的二胺是所述結構式301及306的一者或者兩者，以通式（4)表示的二胺是所述結構式364，以通式（5) 110 200906914 ^ O-^pAi 表示的二胺是所述結構式381。四羧利範圍第29項所述的聚合物，其中所述軒是從下述結構式·、5()5〜·、5ιι、$ 517中選擇的一個或一個以上， [化 34]The polymer according to claim 36, wherein the diamine represented by the formula (3) is one or both of the structural formulae 301 and 306, and the two represented by the formula (4) The amine is the structural formula 364, and the diamine represented by the formula (5) 110 200906914 ^ O-^pAi is the structural formula 381. The polymer according to the above item, wherein the oxime is one or more selected from the following structural formulas, 5 () 5 to ·, 5 ι, and 517, [Chem. 34]

39.如申蜻專利範圍第38項所述的聚合物，其中所述四羧酸二酐是所述結構式500及511的一者或者兩者。 111 200906914 七、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。八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： R2 P239. The polymer of claim 38, wherein the tetracarboxylic dianhydride is one or both of the structural formulae 500 and 511. 111 200906914 VII. Designated representative map (1) Representative representative of the case: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: R2 P2

⑴(1)