TW201226473A

TW201226473A - Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device including the liquid crystal alignment film

Info

Publication number: TW201226473A
Application number: TW100130079A
Authority: TW
Inventors: Jae-Deuk Yang; Eum-Ha Kim; Myoung-Youp Shin; Yong-Sik Yoo; Guk-Pyo Jo; Jung-Gon Choi
Original assignee: Cheil Ind Inc
Priority date: 2010-12-29
Filing date: 2011-08-23
Publication date: 2012-07-01
Also published as: TWI453254B; KR101387736B1; KR20120076288A

Abstract

Disclosed is a liquid crystal alignment agent that includes a polymer selected from polyamic acid including a repeating unit represented by the following Chemical Formula 1, polyimide including a repeating unit represented by the following Chemical Formula 2, and a combination thereof. In Chemical Formulae 1 and 2, X1, X2, Y1 and Y2 are the same as defined in the detailed description.

Description

201226473 Λ. 六、發明說明：【發明所屬之技術領域】本發明有關於一種液晶配向劑、使用其製造的液晶配向膜和包括該液晶配向膜的液晶顯示器。【先前技術】液晶顯示器（LCD)包括液晶配向膜，且液晶配向膜主要由聚合物材料製成。該液晶配向膜在液晶分子配向中起到導向器的作用。當液晶分子在電場的影響下移動來顯示圖像時’液晶配向膜使液晶分子按照預定方向配向。通常，為了對LCD提供均勻亮度和高對比度，需要使液晶分子均勻配向。然而，隨著LCD市場的日益擴大，越來越需要高品質的LCD。此外，因為LCD正在迅速變大，越來越需要高生産性的液晶配向膜。因此，一直需要具有在]LCD生産過程中低次比、優異光電特性、高可靠性和廣泛滿足各種開發中LCD不同特性的局性能的液晶配向膜。【發明内容】本發明的一個實施方式提供了一種液晶配向劑，其通過提高光響應速率並最小化殘留雙鍵的影響來提高配向層穩定性。本發明的另一實施方式提供了使用所述液晶配向劑製造的液晶配向膜。本發明的又一實施方式提供了包括所述液晶配向膜的液晶顯示器。 4 201226473 根據本發明的一個實施方式，提供了一種液晶配向劑，所述液晶配向劑包括聚合物，所述聚合物選自包括以下化學式1所示的重複單元的聚醯胺酸、包括以下化學式 2所示的重複單元的聚醯亞胺和它們的組合中。 [化學式1]201226473 发明. Description of the Invention: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film produced using the same, and a liquid crystal display including the liquid crystal alignment film. [Prior Art] A liquid crystal display (LCD) includes a liquid crystal alignment film, and the liquid crystal alignment film is mainly made of a polymer material. The liquid crystal alignment film functions as a guide in alignment of liquid crystal molecules. When the liquid crystal molecules move under the influence of an electric field to display an image, the liquid crystal alignment film aligns the liquid crystal molecules in a predetermined direction. In general, in order to provide uniform brightness and high contrast to the LCD, it is necessary to uniformly align the liquid crystal molecules. However, as the LCD market continues to expand, there is a growing need for high quality LCDs. In addition, as LCDs are rapidly becoming larger, there is an increasing demand for highly productive liquid crystal alignment films. Therefore, there has been a demand for a liquid crystal alignment film having a low order ratio, excellent photoelectric characteristics, high reliability, and a local performance which satisfies various characteristics of various LCDs in various developments in the LCD production process. SUMMARY OF THE INVENTION One embodiment of the present invention provides a liquid crystal alignment agent which improves the stability of an alignment layer by increasing the photoresponse rate and minimizing the influence of residual double bonds. Another embodiment of the present invention provides a liquid crystal alignment film produced using the liquid crystal alignment agent. Yet another embodiment of the present invention provides a liquid crystal display including the liquid crystal alignment film. 4 201226473 According to an embodiment of the present invention, there is provided a liquid crystal alignment agent comprising a polymer selected from the group consisting of polyamines including a repeating unit represented by the following Chemical Formula 1, including the following chemical formula 2 repeating units of polyimine and combinations thereof. [Chemical Formula 1]

〇〇 [化學式2]〇〇 [Chemical Formula 2]

Ο 〇在化學式1和化學式2中， X1和X2為相同或不同，且各自獨立地為由脂環酸二酐或芳族酸二酐衍生的四價有機基團；且 Y1和Y2為相同或不同，且各自獨立地為由二胺衍生的二價有機基團，且所述二胺包括以下化學式3所示的一種。 [化學式3] ΟΟ 〇 In Chemical Formula 1 and Chemical Formula 2, X1 and X2 are the same or different, and each independently is a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride; and Y1 and Y2 are the same or Different, and each independently is a divalent organic group derived from a diamine, and the diamine includes one represented by the following Chemical Formula 3. [Chemical Formula 3] Ο

在化學式3中， 201226473 A1為經取代或未經取代的Cl至C20伸烷基； A 為單鍵、〇、S〇2 或 C(Ri〇3)(R1〇4)，其中 R1〇3 和 Rl〇4 為相同或不同，且獨立地為氫、或經取代或未經取代的Cl 至C6伸燒基； A3 為-〇·、_〇c〇-、-COO-、-CONH-或-NHCO-; 各R1為經取代或未經取代的C1至C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至 C30雜芳基； R2為經取代或未經取代的C1-C30伸烷基、至少一個 -CH2-基團獨立地被-CO-、-CO-0-、-NZ-、-NZ-CO-、-CO-NZ-或-CH=CH-取代的C1-C30伸燒基，其中z為氫或C1-C10 烷基，條件是氧原子彼此不直接鍵合；各R3相同或不同，且獨立地為經取代或未經取代的 C1至C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至C30雜芳基； Q!、Q2和Q3獨立地為氫或鹵素； η為〇至3的整數； ml為〇至3的整數；且 m2為〇至4的整數。所述二胺可進一步包括選自以下化學式4所示的二胺和以下化學式5所示的二胺中的至少一種。 6 201226473t [化學式4]In Chemical Formula 3, 201226473 A1 is a substituted or unsubstituted Cl to C20 alkyl group; A is a single bond, hydrazine, S〇2 or C(Ri〇3)(R1〇4), wherein R1〇3 and Rl〇4 are the same or different and are independently hydrogen, or a substituted or unsubstituted Cl to C6 alkylene group; A3 is -〇·, _〇c〇-, -COO-, -CONH- or - NHCO-; each R1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group; R2 is substituted Or unsubstituted C1-C30 alkylene, at least one -CH2- group independently of -CO-, -CO-0-, -NZ-, -NZ-CO-, -CO-NZ- or -CH a CH-substituted C1-C30 alkylene group wherein z is hydrogen or a C1-C10 alkyl group, provided that the oxygen atoms are not directly bonded to each other; each R3 is the same or different and independently substituted or unsubstituted a C1 to C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group; Q!, Q2 and Q3 are independently hydrogen or halogen; An integer of 3; ml is an integer from 〇 to 3; and m2 is an integer from 〇 to 4. The diamine may further include at least one selected from the group consisting of a diamine represented by the following Chemical Formula 4 and a diamine represented by the following Chemical Formula 5. 6 201226473t [Chemical Formula 4]

在化學式4中， R4為經取代或未經取代的C1-C30伸烷基、至少一個 -CH2-基團獨立地被-CO-、-C0-0-、-NZ-、-NZ-CO-、-CO-NZ-或-CH=CH-取代的C1-C30伸烷基，其中Z為氫或C1-C10 炫基’條件是氧原子彼此不直接鍵合；且 Q4 ' Q5、Q6、Q7、Q8和Q9獨立地為氫或鹵素。 [化學式5] nh2In Chemical Formula 4, R4 is a substituted or unsubstituted C1-C30 alkylene group, and at least one -CH2- group is independently -CO-, -C0-0-, -NZ-, -NZ-CO- , -CO-NZ- or -CH=CH-substituted C1-C30 alkylene, wherein Z is hydrogen or C1-C10 leuco', the condition is that the oxygen atoms are not directly bonded to each other; and Q4 'Q5, Q6, Q7 Q8 and Q9 are independently hydrogen or halogen. [chemical formula 5] nh2

在化學式5中， R為氫、經取代或未經取代的C1-C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2-C30 雜芳基； Κ為經取代或未經取代的C1-C30烷基、經取代或未經取代的C6_C3G芳基紐取代或未經取代的C2_C3〇雜芳 201226473 基；且 n6為0至3的整數。以二胺的總量計，所述二胺可包括30莫耳％至90莫耳％的由以上化學式3表系的一私、5莫耳％至20莫耳〇/0 的由以上化學式4表示的二胺、和5莫耳％至50莫耳％的由以上化學式5表示的二胺° 以上化學式3所示的>胺可為例如以下化學式6所示的二胺。 [化學式6]In Chemical Formula 5, R is hydrogen, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C6-C30 aryl group or substituted or unsubstituted C2-C30 heteroaryl group; Is a substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6_C3G aryl neon substituted or unsubstituted C2_C3 oxa aryl 201226473; and n6 is an integer from 0 to 3. The diamine may include 30 mol% to 90 mol% of a private, 5 mol% to 20 mTorr/0 of the above formula 3, based on the total amount of the diamine. The diamine represented by the above Chemical Formula 5 and the amine represented by the above Chemical Formula 3 may be, for example, a diamine represented by the following Chemical Formula 6 as the diamine represented by the above formula (5). [Chemical Formula 6]

在化學式6中， 1為0至10的整數；且 m為0至3的整數。所述聚醯胺酸和所述聚醯亞胺可具有1〇,〇〇〇至 300,000的重量平均分子量。所述液晶配向劑可包括重量比為1:99至5〇·5〇的所述聚醯胺酸和所述聚醯亞胺。所述液晶配向劑可包括1 wt%至3〇 wt%的固體。所述液晶配向劑可具有3 cps至30 cps的黏度。根據本發明的另一個實施方式，提供了一種通過在基板上塗布所述液晶配向劑所製備的液晶配向膜。 201226473，根據本發明的又-個實施方式，提供了包括所述液晶配向膜的液晶顯示器。所述液晶配向劑增加配向層的穩定性並最小化雙鍵導致的影響。【實施方式】以下將更詳細地描述本發明的示例性實施方式。麸而，這些實施方式僅是示例性的，且本發明不限於此。…、如本文所用，當未提供具體定義時，術語“經取代，，可指被選自由齒素（F、Br、cl5iu)，&H、^、氨基（NH2、NH(R100)或，其中 Rl00、Rl01 或 R1G2為相同或不同，且各自獨立地為cl〜cl〇烷基）、脒基、肼基、腙基、羧基、經取代或未經取代的烷基、經取代或未經取代的！i代烷基、經取代或未經取代的烷氧基、，取代或未經取代的脂環有機基團、經取代或未經取代的芳基、經取代或未經取代的烯基、經取代或未經取代的炔基、經取代或未經取代的雜芳基和經取代或未經取代的雜環烧基組成的組中的取代基取代官能團中至少一個氫。如本文所用，當未提供具體定義時，術語“烷基，，可指 C1至C30的烷基’具體為C1至C20的烷基；術語“環烷基”可指C3至C30的環烷基’具體為C3至C20的環烷基；術語“雜環烷基’，可指C2至C30的雜環烷基，具體為C2至 C2〇的雜環烷基；術語“伸烷基，，可指C1至C30的伸烷基，具體為C1至C20的伸烧基；術語“院氧基，，可指C1至C30 的燒氧基，具體為C1至C20的烷氧基；術語“環伸烷基，， 201226473 繼，具體為C3至⑽的環伸烧 :二？C=/，，可指C2至C3。的雜環繼，具 ··，、至C20的雜環伸烷基；術語“芳基” 的芳基’具體為C6至C2〇的芳美心C6至C30 至C30 _ -1 打浯雜芳基，，可指。2 t可於^ 具縣C2至08的雜故術語“伸芳基了扎C6至C30的伸芳基，具體為c 術語“雜伸芳基，，伽至C30的雜伸芳基 C18的雜伸芳基；術語“烧芳基，，可指〇至⑶的烧 C7至C20的烧芳基；且術語“幽素，，可指二〇、 13r 或 I 〇如本文所用，當未提供具體定義時，雜環燒基伸烧基、雜芳基和雜伸芳基可分別指在—個環巾包括選自 ί Γ=、s和p原子組成的組中的1至3個雜原子和剩餘的碳原子的環烷基、環伸烷基、芳基和伸芳基。如本文所用，當未提供具體定義時，術語“脂族（的），，可指C1至C30的烧基、C2至C3〇的稀基、C2至⑶的炔基、C1至C30的伸烧基、C2至C3〇的伸烯基或c2至 C3〇的伸块基，且具體為C1至C20的烧基、C2至⑶的烯基、C2至C20的块基、C1至C20的伸烷基、C2至C2〇的伸烯基或C2至C20的伸炔基；術語“脂環（的），，可指 C3至C30的環烷基、C3至C30的環烯基、C3至⑶^ 環炔基、C3至C30的環伸烷基、C3至C30的環伸烯基或 C3至C30的環伸炔基，且具體為C3至C2〇的環烷基、 C3至C20的環烯基、C3至C20的環炔基、C3至C2〇的 201226473 環伸烷基、C3至C20 且術語“芳族（的），，雜芳基、C6至C30 ί 的王裒伸烯基或C3至C20 “芳族（的）’’可指C6至C30的芳基、、C6至C30的伸芳基或C2至C30的的環伸炔基; C2至C30的具體為C6至C16的芳基、C2至C16的雜芳基的伸芳基或C2至C16的雜伸芳基。的雜伸芳基，且芳基、C6至C16 如本文所用，當未提供具體定義時，術語“組合，，可指混合或共聚，或者在脂環有機基團和芳族有機基團"中，^ 指兩個或更多個環、或者通過單鍵、 s(=〇)、S(=0)2、Si(CH3)2、（CH2)p (其中 1SPS2)、（CF2)q (其In Chemical Formula 6, 1 is an integer of 0 to 10; and m is an integer of 0 to 3. The polyamic acid and the polyimine may have a weight average molecular weight of from 1 Torr to 300300,000. The liquid crystal alignment agent may include the polyamic acid and the polyimine in a weight ratio of 1:99 to 5 Å·5 Torr. The liquid crystal alignment agent may include 1 wt% to 3 wt% solids. The liquid crystal alignment agent may have a viscosity of 3 cps to 30 cps. According to another embodiment of the present invention, there is provided a liquid crystal alignment film prepared by coating the liquid crystal alignment agent on a substrate. 201226473, in accordance with yet another embodiment of the present invention, a liquid crystal display including the liquid crystal alignment film is provided. The liquid crystal alignment agent increases the stability of the alignment layer and minimizes the effects caused by double bonds. [Embodiment] Hereinafter, an exemplary embodiment of the present invention will be described in more detail. The embodiments are merely exemplary, and the invention is not limited thereto. As used herein, when a specific definition is not provided, the term "substituted" may be taken to be selected from the group consisting of dentate (F, Br, cl5iu), & H, ^, amino (NH2, NH(R100) or, Wherein Rl00, Rl01 or R1G2 are the same or different and are each independently cl~cl〇alkyl), fluorenyl, fluorenyl, fluorenyl, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted Substituted: i-alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl, substituted or unsubstituted alkene Substituents in the group consisting of a substituted, unsubstituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group are substituted for at least one hydrogen in the functional group. As used herein, when a specific definition is not provided, the term "alkyl, may refer to an alkyl group of C1 to C30" is specifically a C1 to C20 alkyl group; the term "cycloalkyl" may mean a C3 to C30 cycloalkyl group specific a cycloalkyl group of C3 to C20; the term "heterocycloalkyl" may mean a heterocycloalkyl group of C2 to C30, specifically C2 to a heterocycloalkyl group of C2〇; the term "alkylene group", which may refer to a C1 to C30 alkylene group, specifically a C1 to C20 alkylene group; the term "household oxygen," may refer to a C1 to C30 burning oxygen. a group, specifically an alkoxy group of C1 to C20; the term "cycloalkylene," 201226473, specifically a C3 to (10) ring-extension: two? C=/,, can refer to C2 to C3. a heterocyclic ring followed by a heterocycloalkyl group having a C20; the aryl group of the term "aryl" is specifically a C6 to C2 oxime aromatic C6 to C30 to C30 _ -1 samarium heteroaryl , can refer. 2 t can be used in the term "C2 to 08" of the county, "the aryl group has a C6 to C30 extended aryl group, specifically the c term "hetero-extension aryl, gamma to C30 hetero-aryl aryl C18 miscellaneous An aromatic group; the term "aromatic aryl," may refer to a burnt aryl group of C7 to C20 which is enthalpy to (3); and the term "leucoin, may refer to diterpene, 13r or I" as used herein, when no specific When defined, a heterocycloalkylene group, a heteroaryl group, and a heteroaryl group can mean 1 to 3 heteroatoms and the remainder, respectively, in a ring comprising a group consisting of ί 、, s, and p atoms. A cycloalkyl group, a cycloalkyl group, an aryl group and an extended aryl group of a carbon atom. As used herein, the term "aliphatic", when not specifically defined, may refer to a C1 to C30 alkyl group, a C2 to C3 oxime group, a C2 to (3) alkynyl group, and a C1 to C30 extension. a base group, an extended alkenyl group of C2 to C3〇 or a stretching group of c2 to C3〇, and specifically a C1 to C20 alkyl group, a C2 to (3) alkenyl group, a C2 to C20 block group, and a C1 to C20 alkylene group. Or an alkenyl group of C2 to C2〇 or an alkynyl group of C2 to C20; the term "alicyclic", which may refer to a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to (3)^ a cycloalkynyl group, a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group or a C3 to C30 cycloalkynyl group, and specifically a C3 to C2 fluorene cycloalkyl group, a C3 to C20 cycloalkenyl group , C3 to C20 cycloalkynyl, C3 to C2 oxime 201226473 cycloalkylene, C3 to C20 and the terms "aromatic, heteroaryl, C6 to C30 ί 裒裒 alkenyl or C3 to C20" The term "aromatic" may mean a C6 to C30 aryl group, a C6 to C30 extended aryl group or a C2 to C30 cycloalkenyl alkynyl group; a C2 to C30 specific C6 to C16 aryl group, C2 to An extended aryl group of a heteroaryl group of C16 or a heteroaryl group of C2 to C16. Heteroaryl, and aryl, C6 to C16, as used herein, when a specific definition is not provided, the term "combination, may mean mixing or copolymerization, or in an alicyclic organic group and an aromatic organic group". Where ^ refers to two or more rings, or by a single bond, s(=〇), S(=0)2, Si(CH3)2, (CH2)p (where 1SPS2), (CF2)q ( its

中 l$q$2)、C(CH3)2、C(CF3)2、C(CH3)(CF3)或 c(=〇)NH 連接的兩個或更多個環形成的稠環。在本文中，術語“共聚，，可指嵌段共聚至無規共聚，且術語“共聚物，，可指嵌段共聚物至無規共聚物。是指與相同或不同的原子或化學式連接的位置。根據本發明的一個實施方式的液晶配向劑包括聚合物’所述聚合物選自包括由以下化學式1所示的重複單元的聚醯胺酸、包括由以下化學式2所示的重複單元的聚醯亞胺和它們的組合中。 [化學式1]A fused ring formed by two or more rings of l$q$2), C(CH3)2, C(CF3)2, C(CH3)(CF3) or c(=〇)NH. As used herein, the term "copolymerization" may refer to block copolymerization to random copolymerization, and the term "copolymer" may refer to a block copolymer to a random copolymer. Refers to a location that is connected to the same or a different atom or chemical formula. The liquid crystal alignment agent according to one embodiment of the present invention includes a polymer selected from the group consisting of polylysine including a repeating unit represented by the following Chemical Formula 1, a polyfluorene including a repeating unit represented by the following Chemical Formula 2 Imines and combinations thereof. [Chemical Formula 1]

[化學式2] 11 201226473[Chemical Formula 2] 11 201226473

在化學式1和2中， ^和X2為相同或不同，且各自獨立地為由脂環酸二肝或务族酸二gf衍生的四價有機基團4在各重複單元可相同1或不：’且X在各重複單元内可相同或不同。 Y1和Y2為相同或不同，且各自獨立地為由二胺衍生的-價 1有絲團，且上述二胺包括以下化學式3所示的一 =41在各重複單it内可為相同或不同，且¥2在各重複單元内可為相同或不同。 [化學式3]In Chemical Formulas 1 and 2, ^ and X2 are the same or different, and each independently is a tetravalent organic group derived from dihepatic acid diacid or tritic acid gf in the same unit 1 or no: 'And X may be the same or different in each repeating unit. Y1 and Y2 are the same or different, and each independently is a valence 1 filament group derived from a diamine, and the above diamine includes a =41 shown in the following Chemical Formula 3, which may be the same or different in each repeating single it And ¥2 may be the same or different in each repeating unit. [Chemical Formula 3]

在化學式3中， A1為經取代或未經取代的C1至C20伸烷基； A2為單鍵、0、S〇24C(Ri〇3)(Ri〇4)，其中尺1〇3和厌叫為相同或不同，且獨立地為氫、或經取代或未經取代的^ 至C6伸烷基； A3 為-0- ' -OCO-、_c〇0---CONH-或-NHCO-; 各R1為經取代或未經取代的C1至C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至 C30雜芳基； 12 201226473t R2為經取代或未經取代的C1-C30伸烷基、至少一個 -CH2-基團獨立地被-CO-、-C0-0-、-NZ-、-NZ-CO-、-CO-NZ-或-CH=CH-取代的C1-C30伸烷基，其中z為氫或C1-C10 烷基，條件是氧原子彼此不直接鍵合；各R3為相同或不同，且各自獨立地為經取代或未經取代的C1至C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至C30雜芳基；In Chemical Formula 3, A1 is a substituted or unsubstituted C1 to C20 alkyl group; A2 is a single bond, 0, S〇24C(Ri〇3)(Ri〇4), wherein the ruler 1〇3 and the squeaky Alternate or different, and independently hydrogen, or substituted or unsubstituted alkyl to alkyl; A3 is -0-'-OCO-, _c〇0---CONH- or -NHCO-; R1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group; 12 201226473t R2 is substituted or not Substituted C1-C30 alkylene, at least one -CH2- group independently of -CO-, -C0-0-, -NZ-, -NZ-CO-, -CO-NZ- or -CH=CH a substituted C1-C30 alkylene group wherein z is hydrogen or a C1-C10 alkyl group, provided that the oxygen atoms are not directly bonded to each other; each R3 is the same or different and each independently is substituted or unsubstituted a C1 to C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group;

Ql、Q2和Q3獨立地為氫或鹵素； η為0至3的整數； ml為0至3的整數；且 m2為0至4的整數。化學式3所示的二胺通過使用單肉桂酸酯結構可降低單體量。也可通過將兩個或更多個雙鍵量引入單肉桂酸酉旨以增加反應位點來提局光反應性，並讀保配向穩定性和加工性。以上化學式3所示的二胺可為例如以下化學式6所示的二胺，但不限於此。 ' [化學式6]Ql, Q2 and Q3 are independently hydrogen or halogen; η is an integer from 0 to 3; ml is an integer from 0 to 3; and m2 is an integer from 0 to 4. The diamine represented by Chemical Formula 3 can reduce the amount of the monomer by using a monocinnamate structure. It is also possible to improve the photoreactivity by introducing two or more double bond amounts into the monocinnamic acid to increase the reaction site, and to read the alignment stability and the workability. The diamine represented by the above Chemical Formula 3 may be, for example, a diamine represented by the following Chemical Formula 6, but is not limited thereto. '[Chemical Formula 6]

在化學式6中， 1為0至10的整數，且 13 201226473 m為〇至3的整數。二胺可單獨進一步包括以上化學式3所示的二胺，或包括以上化學式3所示的二胺與以下化學式4所示的二胺和/或以下化學式5所示的二胺的混合物。 [化學式4]In Chemical Formula 6, 1 is an integer of 0 to 10, and 13 201226473 m is an integer of 〇 to 3. The diamine may further include a diamine represented by the above Chemical Formula 3 alone, or a mixture of the diamine represented by the above Chemical Formula 3 and the diamine represented by the following Chemical Formula 4 and/or the diamine represented by the following Chemical Formula 5. [Chemical Formula 4]

在化學式4中， R4為經取代或未經取代的C1-C30伸烷基、至少一個 -CH2-基團獨立地被-CO-、-C0-0·、-ΝΖ-、-NZ-CO-、-CO-NZ-或-CH=CH-取代的C1-C30伸烷基，其中Z為氫或C1-C10 烷基，條件是氧原子彼此不直接鍵合；且 Q4、Q5、Q6、Q7、Q8和Q9獨立地為氫或i素。 [化學式5]In Chemical Formula 4, R4 is a substituted or unsubstituted C1-C30 alkylene group, and at least one -CH2- group is independently -CO-, -C0-0., -ΝΖ-, -NZ-CO- , -CO-NZ- or -CH=CH-substituted C1-C30 alkylene, wherein Z is hydrogen or C1-C10 alkyl, provided that the oxygen atoms are not directly bonded to each other; and Q4, Q5, Q6, Q7 Q8 and Q9 are independently hydrogen or i. [Chemical Formula 5]

在化學式5中， R5為氫、經取代或未經取代的C1-C30烷基、經取代 201226473 =代的⑽〇芳基或經取代或未經取代的c2_c3〇㈣ϋ練代或未經取代的C1_C3G絲、經取代或未 =·代的C6.C3G芳基或經取代或未經取代的c2 C3〇雜芳基，且為0至3的整數。 -田一胺包括以上化學式4所示的二胺、以上化學式5 所示的一胺以及以上化學式3所示的二胺時，所述二胺可〇括30莫耳4至9〇莫耳。/〇的以上化學式3所示的二胺、5 〇莫耳％至2〇莫耳％的以上化學式4所示的二胺、和5莫耳 /〇至50莫耳％的以上化學式5所示的二胺，以二胺的總量叶。當每種二胺在此範圍内時，可通過控制預傾角改進透光率，且可有效地改進液晶配向性能、耐化學品性、光電特性、熱穩定性和機械特性。聚醯胺酸和聚醯亞胺可具有1〇,〇〇〇至3〇〇〇〇〇的重量平均分子量。當聚醯胺酸和聚醯亞胺具有此範圍内的重量平均分子量時’可有效地改進可靠性和光電特性，且可具有優異的耐化學品性，並且即使在驅動液晶顯示器後穩定地保持預傾角。液晶配向劑可包括重量比為1:99至50..50的聚醯胺酸和聚醯亞胺。當聚醯胺酸和聚醯亞胺在此範圍内時，可改進配向穩定性。例如，可包括10:99至50:50重量比的聚酿胺酸和聚醯亞胺。液晶配向劑可包括lwt%至25 wt%的上述聚合物。當 15 201226473 上述聚合物在此範圍内時，可改進可印性和液晶配向性能。例如’可包括3wt%至20wt%的上述聚合物。根據本發明一個實施方式的液晶配向劑包括適合的溶劑以溶解聚合物。用於溶解聚合物的適合溶劑可包括甲基-2-吡咯烷酮、N，N-一曱基乙酿胺、N，N-二曱基甲酿胺、二曱亞石風、 γ-丁内酯、四氫呋喃（THF)和酚類溶劑(如間曱酚、苯酚、鹵代苯酚等），但不限於此。溶劑可進一步包括2-丁基溶纖劑（2-BC)，因此，可改進可印性。基於包含2-丁基溶纖劑的溶劑總量，可包含 lwt%至60wt%的2-丁基溶纖劑。當2-丁基溶纖劑包含在上述範圍内時，能够容易地改善可印性。例如，基於包含 2-丁基溶纖劑的溶劑總量，可包含1〇^^%至6〇%1%的2•丁基溶纖劑。此外’只要可溶性聚醯亞胺聚合物不沉澱，溶劑就可進一步包括不良溶劑，例如醇類、酮類、酯類、醚類、烴類或函代煙類。在塗布製程期間，不良溶劑降低了液晶配向劑的表面能，以改善伸展性和平整度。基於包含不良溶劑的溶劑總量，可包含1 wt%至90 wt% ’如1加％至7〇 wt%的不良溶劑。不良溶劑可包括甲醇、乙醇、異丙醇、環己醇、乙二醇、丙一醇、1，4_ 丁二醇、三甘醇、丙酮、甲乙酮、環己綱乙酉夂曱酿、乙酸乙酉旨、乙酸丁醋、二乙基草酸醋、丙一酸醋、二乙驗、乙二醇單甲醚、乙二醇二甲醚、乙二醇 201226473t 單乙峻、乙二醇苯醚、乙二醇笨基甲基醚、乙二醇苯基乙基醚、二甘醇二曱醚、二甘醇二甲醚、二甘醇醚、二甘醇單曱喊、二甘醇單***、二甘醇單甲醚乙酸酯、二甘醇單乙謎乙酸g旨、乙二醇甲醚乙酸酯、乙二醇乙趟乙酸g旨、4_ 經基-4-曱基-2-戊酮、2-經基乙基丙酸g旨、2-經基-2-曱基乙基丙酸酯、乙氧基乙基乙酸酯、乙酸經乙酯、2-經基_3_甲基丁酸曱酯、3-甲氧基丙酸曱酯、3_曱氧基丙酸乙醋、3_ 乙氧基丙酸乙酯、3-乙氧基丙酸曱酯、曱基甲氧基丁醇、乙基甲氧基丁醇、曱基乙氧基丁醇、乙基乙氧基丁醇、四氫呋喃、二氯曱烷、1，2-二氣乙烷、1，4_二氯丁烷、三氣乙烧、氣苯、鄰二氣笨、己院、庚院、辛烧、笨、曱笨、二甲苯、或一種或多種的混合物。在液晶配向劑中未限制溶劑量’但液晶配向劑的固含量可在1至30wt%，如3至20wt°/〇的範圍内。當固含量在此範圍内時，在印刷過程中可降低受基板表面雜質的影響並保持適當黏度。因此，可防止在印刷過程中由於高黏声而使塗層的均勻性變差，並提供適當的透射率。、。-又所述液晶配向劑可具有3 cps至30 cps的黏度。當晶配向劑具有此範圍内的黏度時，其可改進塗層均勻二塗層性能。例如，液晶配向劑可具有3啊至25啊的點液晶配向劑可進一步包括其它添加劑。，它，加劑可包括環氧化合物。環氧化合物用於了罪性和光電躲，且環氧化合物可包括具有2至8個進 17 201226473 如2至4個環氧基的至少一種環氧化合物。基於100 4量份的聚合物，可包括〇1重量份至量份的環氧化合物。當包含此範_的環氧化合物時，$ 塗布基板期間可提供合適的可印性和平整度，而且可容 ^文善可靠性和光電特性。例如，基於刚重量份的聚合物’可包括1重讀至3G重量份的環氧化合物。環氧化合物的實例可包括以下化學式23所示的化合物，但不限於此。 [化學式23]In Chemical Formula 5, R5 is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted (10) anthracene group substituted by 201226473 = or a substituted or unsubstituted c2_c3〇(tetra)anthracene or unsubstituted C1_C3G filament, substituted or unsubstituted C6.C3G aryl or substituted or unsubstituted c2 C3 doped aryl, and is an integer from 0 to 3. When the monoamine includes the diamine represented by the above Chemical Formula 4, the monoamine represented by the above Chemical Formula 5, and the diamine represented by the above Chemical Formula 3, the diamine may include 30 moles of 4 to 9 moles. a diamine represented by the above Chemical Formula 3, a diamine represented by the above Chemical Formula 4 of 5 % by mole to 2 % by mole, and a chemical formula of 5 mol / 〇 to 50 mol % shown in the above Chemical Formula 5 The diamine, with the total amount of diamine leaves. When each of the diamines is within this range, the light transmittance can be improved by controlling the pretilt angle, and the liquid crystal alignment property, chemical resistance, photoelectric properties, thermal stability, and mechanical properties can be effectively improved. The polyglycolic acid and the polyimine may have a weight average molecular weight of from 1 Torr to 3 Torr. When polyamic acid and polyimine have a weight average molecular weight within this range, 'the reliability and photoelectric characteristics can be effectively improved, and excellent chemical resistance can be obtained, and stably maintained even after driving the liquid crystal display. Pretilt angle. The liquid crystal aligning agent may include polyamic acid and polyimine in a weight ratio of 1:99 to 50..50. When the polyamic acid and the polyimine are in this range, the alignment stability can be improved. For example, polyamic acid and polyamidiamine in a weight ratio of 10:99 to 50:50 may be included. The liquid crystal alignment agent may include 1 wt% to 25 wt% of the above polymer. When 15 201226473 above the polymer is within this range, printability and liquid crystal alignment properties can be improved. For example, '3 wt% to 20 wt% of the above polymer may be included. The liquid crystal alignment agent according to one embodiment of the present invention includes a suitable solvent to dissolve the polymer. Suitable solvents for dissolving the polymer may include methyl-2-pyrrolidone, N,N-monodecylamine, N,N-dimercaptoamine, diterpene, gamma-butyrolactone , tetrahydrofuran (THF) and phenolic solvents (such as m-phenol, phenol, halogenated phenol, etc.), but are not limited thereto. The solvent may further include 2-butyl cellosolve (2-BC), and therefore, printability can be improved. Depending on the total amount of solvent comprising 2-butyl cellosolve, from 1% to 60% by weight of 2-butyl cellosolve may be included. When the 2-butyl cellosolve is contained in the above range, the printability can be easily improved. For example, based on the total amount of the solvent comprising 2-butyl cellosolve, it may comprise from 1% to 6% by weight of 2% butyl cellosolve. Further, as long as the soluble polyimine polymer does not precipitate, the solvent may further include a poor solvent such as an alcohol, a ketone, an ester, an ether, a hydrocarbon or a halogen. The poor solvent reduces the surface energy of the liquid crystal alignment agent during the coating process to improve stretch and flatness. A poor solvent such as 1% by weight to 90% by weight, such as 1% by weight to 7% by weight, may be contained based on the total amount of the solvent containing the poor solvent. The poor solvent may include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propanol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cycloheximide, acetic acid , butyl vinegar acetate, diethyl oxalic acid vinegar, vinegar vinegar, diacetate, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol 201226473t single sulphur, ethylene glycol phenyl ether, ethylene Alcohol base methyl ether, ethylene glycol phenyl ethyl ether, diethylene glycol dioxime ether, diglyme, diethylene glycol ether, diethylene glycol monoterpene, diethylene glycol monoethyl ether, digan Alcohol monomethyl ether acetate, diethylene glycol monoacetic acid acetic acid, ethylene glycol methyl ether acetate, ethylene glycol acetonitrile acetic acid, 4_ mercapto-4-mercapto-2-pentanone, 2-glyethylpropionic acid g, 2-carbyl-2-mercaptoethylpropionate, ethoxyethyl acetate, acetic acid, ethyl acetate, 2-amino-3-methylbutyrate Hydrate ester, decyl 3-methoxypropionate, ethyl acetoacetate, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, decyl methoxybutanol , Ethyl methoxybutanol, Mercaptoethoxybutanol, Ethylethoxybutanol, Tetrahydrofuran , Dichlorodecane, 1,2-dioxaethane, 1,4-dichlorobutane, tri-hexane, gas, benzene, neighboring gas, hexa, gengyuan, Xinzhuo, stupid, stupid , xylene, or a mixture of one or more. The amount of solvent is not limited in the liquid crystal alignment agent', but the solid content of the liquid crystal alignment agent may be in the range of 1 to 30% by weight, such as 3 to 20% by weight. When the solid content is within this range, the influence of impurities on the surface of the substrate can be reduced and the proper viscosity can be maintained during the printing process. Therefore, it is possible to prevent the uniformity of the coating from being deteriorated due to high viscous sound during printing, and to provide an appropriate transmittance. ,. Further, the liquid crystal alignment agent may have a viscosity of 3 cps to 30 cps. When the crystallizing agent has a viscosity within this range, it improves the uniform coating performance of the coating. For example, the liquid crystal alignment agent may have a point of from 3 to 25 Å. The liquid crystal alignment agent may further include other additives. It may include an epoxy compound. The epoxy compound is used for sin and photo-occlusion, and the epoxy compound may include at least one epoxy compound having 2 to 8 into 17 201226473 such as 2 to 4 epoxy groups. The epoxy compound may be included in an amount of from 1 part by weight to 1 part by weight based on 100 parts by weight of the polymer. When the epoxy compound is included, the substrate can provide suitable printability and flatness during coating of the substrate, and can satisfy the reliability and photoelectric characteristics. For example, the polymer based on the part by weight may include 1 to 3 parts by weight of the epoxy compound. Examples of the epoxy compound may include the compound represented by the following Chemical Formula 23, but are not limited thereto. [Chemical Formula 23]

H2C—~CH*—CH Η2〇— -CH 一CHj 在化學式23中， A14為經取代或未經取代的C6至α2芳族有機基團、或經取代絲經取代的C6至C12二伽環有機基團、或經取代或未經取代的C6至C12二價職有機基團，且特別為經取代或未經取代的C1至C6伸燒基。環氧化合物可包括N，N，N，，N，-四縮水甘油基·44，-二氨基苯基甲烷(TGDDM)、Ν，Ν，Ν，，Ν，-四縮水甘油基_4’4，_二氨基苯基乙燒、职叩，-四縮水甘油基.4,4，_二氨基苯基丙烷、Ν，Ν，Ν，，Ν，-四縮水甘油基-4,4，-二氨基苯基丁烷、 Ν，Ν，Ν，，Ν，·四縮水甘油基_4,4，_二氨基$、乙二醇二縮水甘油I聚乙二醇二縮水甘油騎、丙二醇二縮水甘油謎、三丙二醇二縮水甘賴、聚丙二醇二縮水甘_、新戊二醇 201226473t 二縮水甘賴、i，6_己二醇二縮水甘油㈣、丙三醇二縮水 IS 二溴新戊二醇二縮水甘油醚、如，6-四縮水甘油基·2,4-己二醇、Ν，Ν，Ν，，Ν，_四縮水甘油基_丨4· 四縮水甘油㈣二？苯：胺、N，Nw_四縮水甘油基-2,2 -二曱基_4,4，_二氨基聯苯、2,2·雙 & ::由二，氧基)苯基]丙院，㈣美、广'^本基甲烧、以雙_·二縮水甘油基氨基曱基)％己烷、1，3-雙(即-二縮水甘油基氨基甲基) 但不限於此。 $矣印性’可進—步包括如合適的石夕烧偶聯劑或表面活性劑作為添加劑。，據另-個實施方式的液晶配向輯過使用液晶配向劑來提供。 …液晶配向膜可通過在基板上塗布液晶配向劑來獲付。將液晶配向劑塗布在基板上的方法可包括旋塗柔性 P刷喷墨印刷等。通常使用柔性印刷，因為其提供優里的塗布均勻性且容易提供大面積。八基板只要是透明的，則沒有具體限制，但可包括玻璃基板、或諸如丙烯酸基板或聚碳酸酯板等塑料基板。此外，當使用用於驅動液晶的氧化銦錫（ΠΌ)電極等形成的基板時，可簡化製造製程。為了改善膜的均勻性，將液晶配向劑均勻地塗布在基板亡並在室溫至20(Tc、例如如艽至说艺、或4〇。。至 120C的溫度下預乾燥〗分鐘至1〇〇分鐘。通過預乾燥過 201226473 A Λ ▲ 程’可控制液晶配向獅各組分的揮發性，從度偏差的均勻膜。 Μ 然後，在80C至300。(：，如120¾至280°C的溫度下燒製5分鐘至3GG分鐘以完全蒸發溶劑，從而製得液晶配向膜。根據本發明的又-個實施方式，提供了包括液晶配向膜的液晶顯示器。以下實施例更詳細地說明本公開。然而，它們是本公開的示例性實施方式且不限制本公開。 (實施例）對比例1:聚醯胺酸的製備在通入氮氣的同時，在暗室中將〇 5m〇1的由以下化學，la—所不的 4-(4,4,4-三氟丁氧基)_苯甲酸(Ε)_4_(3_(2,4·二氨基苯乙縫)_3_氧代丙絲基)苯帥Nm鱗烧酮（NMP)加人裝有祕器、溫度控制器、氣氣注射器和冷却器的四口燒瓶中，以提供混合溶液。將⑼福的固態 4’H)·二氧雜·三環[⑴.⑻]十二烧^灿·四綱加入到此混合溶液中並劇烈_。隨後，將G5mc>1的由化學式u 所示的4-(仏4_三氟丁氧基)·苯甲酸⑹-4-(3-(2,4-二氨基苯乙氧基)。3氧代，基苯基)苯g旨力。人其中並反應。將溫度保持在30C至6GC下反應24小時，以提供包括聚醯胺酸的液晶配向劑（ΡΑΑ·39)。提供的液晶配向劑具有3〇wt%的固含量和209 cps的黏度。 [化學式la] 201226473H2C—~CH*—CH Η2〇——CH—CHj In Chemical Formula 23, A14 is a substituted or unsubstituted C6 to α2 aromatic organic group, or a substituted silk substituted C6 to C12 digamma ring. An organic group, or a substituted or unsubstituted C6 to C12 divalent organic group, and particularly a substituted or unsubstituted C1 to C6 alkylene group. The epoxy compound may include N,N,N,,N,-tetraglycidyl-44,-diaminophenylmethane (TGDDM), hydrazine, hydrazine, hydrazine, hydrazine, tetraglycidyl _4'4 , _diaminophenyl bromide, 叩, -tetraglycidyl. 4,4,-diaminophenylpropane, hydrazine, hydrazine, hydrazine, hydrazine, -tetraglycidyl-4,4,-two Aminophenylbutane, hydrazine, hydrazine, hydrazine, hydrazine, tetraglycidyl _4,4, _diamino$, ethylene glycol diglycidyl I polyethylene glycol diglycidol, propylene glycol diglycidyl Mystery, tripropylene glycol dihydrate, propylene glycol digoxime, neopentyl glycol 201226473t dihydrated lysine, i,6-hexanediol diglycidyl (tetra), glycerol dihydrate IS dibromo neopentyl glycol Diglycidyl ether, for example, 6-tetraglycidyl 2,4-hexanediol, hydrazine, hydrazine, hydrazine, hydrazine, _tetraglycidyl _ 丨 4 · tetraglycidyl (tetra) 2? Benzene: amine, N, Nw_tetraglycidyl-2,2-dimercapto-4,4,-diaminobiphenyl, 2,2·bis &::di-oxy)phenyl]-propyl The hospital, (4) Mei, Guang '^ 本基甲烧, 双 _ diglycidylamino fluorenyl)% hexane, 1,3-bis (ie, diglycidylaminomethyl) is not limited thereto. The "printing" step can include, for example, a suitable Shihua burning coupling agent or a surfactant as an additive. According to another embodiment, the liquid crystal alignment is provided by using a liquid crystal alignment agent. The liquid crystal alignment film can be obtained by coating a liquid crystal alignment agent on a substrate. The method of coating the liquid crystal alignment agent on the substrate may include spin-coating flexible P-brush inkjet printing or the like. Flexographic printing is generally used because it provides uniform coating uniformity and is easy to provide a large area. The eighth substrate is not particularly limited as long as it is transparent, but may include a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate plate. Further, when a substrate formed by using an indium tin oxide (ITO) electrode for driving a liquid crystal or the like is used, the manufacturing process can be simplified. In order to improve the uniformity of the film, the liquid crystal alignment agent is uniformly coated on the substrate and allowed to stand at room temperature to 20 (Tc, for example, to 说说说, or 4 〇. to pre-drying at a temperature of 120 C) to 1 〇. 〇 min. By pre-drying through 201226473 A Λ ▲ ” ” can control the volatility of the liquid crystal alignment lion components, from the degree of deviation of the uniform film. Μ Then, at 80C to 300. (:, such as 1203⁄4 to 280 ° C The liquid crystal alignment film is prepared by firing at a temperature for 5 minutes to 3 GG minutes to completely evaporate the solvent. According to still another embodiment of the present invention, a liquid crystal display including a liquid crystal alignment film is provided. The following embodiments illustrate the present disclosure in more detail. However, they are exemplary embodiments of the present disclosure and do not limit the disclosure. (Examples) Comparative Example 1: Preparation of polyproline while introducing nitrogen gas, while in the dark room, 〇5m〇1 Chemical, la-all 4-(4,4,4-trifluorobutoxy)-benzoic acid (Ε)_4_(3_(2,4·diaminophenylethylidene)_3_oxopropanyl) Benzene Nm scalar ketone (NMP) plus four equipped with secrets, temperature controller, gas injector and cooler In the flask, a mixed solution is provided. The solid 4'H)·dioxatricyclo[(1).(8)] 12-burning-can-four of the (9) Fu is added to the mixed solution and vigorously _. Subsequently, 4-(仏4_Trifluorobutoxy)benzoic acid (6)-4-(3-(2,4-diaminophenylethoxy).3 oxo, represented by the formula u of G5mc>1 Phenyl) benzene g. The reaction is carried out by a person. The temperature is maintained at 30 C to 6 GC for 24 hours to provide a liquid crystal alignment agent (poly 39) including polylysine. The liquid crystal alignment agent is provided with 3 Å. The solid content of wt% and the viscosity of 209 cps. [Chemical formula la] 201226473

對比例2:聚醯亞胺的製備將3.0莫耳乙酸軒和5 〇酸溶液中，並在啊下環化6小時。隨7 =所得聚醯胺去除催化劑和溶劑，以提供聚醯亞胺樹脂Λ過真空蒸館劑加入到=的有機溶 =:所得_配實施例1 :聚醯胺酸（PSA_1：)的製備 ^通人氮氣的同時，在暗室中將r 所不的4佩4_三氟丁氧基、=化子式3a 基苯乙氧基” 二 t (，E)_5-(2,1-二氨溫度控制if、氮氣讀旨加人財撥拌器、 -甲基—明’並加入 NMP。 W將化學式3a化合物溶解於 21 1 (約15〇eps)。 1反叙k供適合的黏度所得溶液具有3G wt%_含量。通替溫度在下維持24小時絲啸供_胺酸溶液。 201226473 [化學式3a]Comparative Example 2: Preparation of polyimine A solution of 3.0 moles of acetic acid and 5 decanoic acid was cyclized for 6 hours. With 7 = obtained polyamine removal catalyst and solvent to provide polyimine resin Λ vacuum distillation agent added to = organic solution =: obtained _ with the example 1: preparation of poly-proline (PSA_1:) ^ While passing nitrogen, in the dark room, the 4th 4_trifluorobutoxy group of the r, the 3a phenylethoxy group of the formula 2t (,E)_5-(2,1-two Ammonia temperature control if, nitrogen read add people, -methyl-ming' and add NMP. W dissolves the compound of formula 3a in 21 1 (about 15 〇 eps). 1 reverse k for a suitable viscosity The solution has a 3 G wt% content. The replacement temperature is maintained for 24 hours under the tyrosine solution. 201226473 [Chemical Formula 3a]

將所得聚醯胺酸溶液蒸餾以提供純的聚醯胺駿，所得聚醢胺酸具有200,000的重量平均分子量。將甲& 2 吡咯烷酮（NMP )、γ - 丁内酯和2 - 丁基溶纖劑的有機現人办劑（體積比3:4:3)加入聚醯胺酸中，並在室溫下攪掉α = 小時以提供作為液晶配向劑的光配向聚醯胺酸（PSa 溶液。）實施例2 :聚醯胺酸（PSA-2至PSA-3)的製備根據與實施例】相同的步驟製備光配向聚隨胺 (PSA-2至PSA-3，液晶配向劑）溶液冰(1調-5_(2,4-二氨基苯乙氧基>5、氧苯醋和如化學式4續_ M，·(叫，EKj ’ ^ ¥基)丙-1，3-二基)雙(氧代)雙(3_氧代 ’ 伸苯基)雙(4-(4,4,4-三氟丁氧基)笨甲酸酯。，-一土）雙 [化學式4a]The resulting polyaminic acid solution was distilled to provide pure polyamine, and the obtained polyglycolic acid had a weight average molecular weight of 200,000. Add the organic active agent (3:4:3 by volume) of methyl & 2 pyrrolidone (NMP), γ-butyrolactone and 2-butyl cellosolve to polylysine and agitate at room temperature α = hour to provide a photo-aligned poly-proline (PSa solution) as a liquid crystal alignment agent. Example 2: Preparation of poly-proline (PSA-2 to PSA-3) Light was prepared according to the same procedure as in Example Oriented polyamine (PSA-2 to PSA-3, liquid crystal alignment agent) solution ice (1 -5 - (2,4-diaminophenethyloxy) 5, oxybenzene vinegar and as in Chemical Formula 4 _ M, ·(called, EKj ' ^ ¥ base) propane-1,3-diyl) bis(oxo)bis(3_oxo'phenylene) bis(4-(4,4,4-trifluorobutoxy) Base) stupid formate., - one soil) double [chemical formula 4a]

22 201226473t22 201226473t

-----r*A 實施例4至實施例6 :聚醯胺酸（psA"4至PSA-6) 的製備根據與實施例1相同的步驟製備光配向聚醯胺酸 (PSA-4至6，液晶配向劑）溶液，區別在於如下表！中包括化學式3a所示的4-(4,4,4-三氟丁氧基）苯曱酸 -4-(1£，3丑)-5_(2,4-二氨基笨乙氧基)_5_氧代戊-1，3_二烯基) 苯酯、如化學式4a所示的4,4，-郎，1，£)-3,3，-(2,2-雙(4-氨基苄基)丙-.1，3-二基)雙(氧代)雙(6-氧代丙稀_3，1..二基)雙(4山伸本基)雙(4-(4,4,4_二I丁氧基)苯曱酸g旨和如化學式&所示的1-(3,5_二氨基苯基)-3-十八烧基η比略院_25_二酮。 [化學式5a]-----r*A Example 4 to Example 6: Preparation of Polyproline (psA " 4 to PSA-6) Photo-aligned poly-proline (PSA-4) was prepared according to the same procedure as in Example 1. To 6, liquid crystal alignment agent) solution, the difference is in the following table! Including 4-(4,4,4-trifluorobutoxy)benzoic acid 4-(1£,3 ugly)-5-(2,4-diamino-homoethoxy)_5 as shown in Chemical Formula 3a _oxopenta-1,3-dienyl) phenyl ester, 4,4,-lang,1,3)-3,3,-(2,2-bis(4-aminobenzyl) as shown in Chemical Formula 4a Base) propyl-.1,3-diyl)bis(oxo)bis(6-oxopropan-3-3,1..diyl) bis(4-strandy) bis(4-(4,4) , 4_di-butoxy)benzoic acid g and 1-(3,5-diaminophenyl)-3-octadecyl η as shown in the chemical formula & [Chemical Formula 5a]

實施例7 :聚醯亞胺聚合物（psi-1)的製備在通入氮氣的同時’在暗室中將0.5莫耳的由以下化學式3a所示的4-(4,4,4-三氟丁氧基 > 苯甲酸 _4-(1E，3E)-5-(2,4-二氨基笨乙氧基)-5•氧代-1，3-二稀基^ 酯和N-甲基吡咯烷酮（NMP)加入裝有攪拌器、^产控制器、氮氣注射器和冷却器的四口燒瓶中，以將化 3a所示的化合物溶解入NMP。予"" 將l.Omol的固態4，10-二氧雜-三環[6.3.1.〇2,7]十二烷 -3,5,9，11-四_ (也稱為“2,3,5_三羧基環戊基乙酸軒，，）:= 到此混合溶液中並劇烈攪拌。 σ 23 201226473 在攪拌1小時後，反應以提供適合的黏度（約150 cps)。所得溶液具有30 wt%的固含量，且所得溶液在室溫下反應24小時以提供聚醯胺酸溶液。將3.0莫耳乙酸酐催化劑和5.〇莫耳吡啶催化劑加入到聚醯胺酸溶液中’加熱至8(TC並反應6小時。通過真空蒸顧反應産物將乙酸野和η比变催化劑和NMP溶劑去除，以k供具有20 wt%固含量的聚醯亞胺樹脂溶液。將所得的可溶性聚醯亞胺樹脂蒸餾，以提供純的聚醯亞胺樹脂（重量平均分子量200,000)〇將N-曱基各燒 _(ΝΜΡ)、γ-丁内酯和2-丁基溶纖劑的有機混合溶劑積比3:4:3)加入所得的可溶性聚醯亞胺樹脂中，並在室溫下攪拌24小時以提供作為液晶配向劑的光配向聚醯亞胺樹脂（PSI_1)。實施例8至實施例9:聚醯亞胺聚合物（PSI_2至⑸ 的製備 _ 根據與實施例7相同的步驟進行，區別在於如下表工中包括化學式3a所示的4_(4,4,4_三氟丁氧基）苯甲酸 ^•(阳叫似-二氨基笨乙氧基…氧代戊妙二缚基) 笨酯和如化學式4&所示的4,4，-(1民1,£)-3,3,-(2 2-雙(4畜莫节基)丙-u-工基)雙(氧代)雙(3·氧代丙稀处;^基)雙^ 伸苯基)雙(4_(4,4,4-三氟丁氧基)苯曱酸醋，以提供聚酿酸’隨後根據與實施例7相同的步驟使用聚酿胺酸獲溶性光配向聚醯亞胺樹脂溶液（液晶配向劑）。 24 201226473 實施例10至實施例12 :聚醯亞胺聚合 m PSI-6)的製備根據與實施例7相同的步驟進行，區別在於如中包括化學式3a所示@ 4·(4，Μ_三氟了氧基）苯甲酸 -4-(1Ε，3Ε)-5·(2,4-二乳基笨乙氧基)5氧代戊_13_二缔基) 苯醋、如化學式4a所示的认眼㈣似似美节基)丙·1，3-二基)雙(氧代)雙(3_氧代丙稀3n)雙^ 伸苯基)雙(4-(4,4,4·三氟丁氧基)苯甲酸酿和如化學式5&所示的1-(3,5_二氨基笨基)_3·十八烷基吡咯烧_2,5·二嗣，以 k供聚醯胺1，h後根據與實施例7相同的步驟使用聚醯胺酸獲得可溶性光配向聚醯亞胺樹脂溶液（液晶配向劑）。 (表1)Example 7: Preparation of Polyimine Polymer (psi-1) While passing nitrogen gas, '0.5 mol of 4-(4,4,4-trifluoro) represented by the following Chemical Formula 3a was placed in a dark room Butoxy> benzoic acid_4-(1E,3E)-5-(2,4-diamino oxaethoxy)-5•oxo-1,3-disyl ester and N-methyl Pyrrolidone (NMP) was added to a four-necked flask equipped with a stirrer, a controller, a nitrogen syringe, and a cooler to dissolve the compound represented by the compound 3a into NMP. To "" , 10-dioxa-tricyclo[6.3.1.〇2,7]dodecane-3,5,9,11-tetra- (also known as "2,3,5-tricarboxycyclopentyl acetic acid Xuan,,): = To this mixed solution and vigorously stirred. σ 23 201226473 After stirring for 1 hour, the reaction was carried out to provide a suitable viscosity (about 150 cps). The resulting solution had a solid content of 30 wt%, and the resulting solution was The reaction was allowed to proceed for 24 hours at room temperature to provide a polyamidonic acid solution. 3.0 mM acetic anhydride catalyst and 5. 〇Morepyridine catalyst were added to the poly-proline solution to 'heat up to 8 (TC and react for 6 hours. Evaporating the reaction product to convert acetic acid field and η ratio change catalyst and The NMP solvent is removed, and the polyiminoimine resin solution having a solid content of 20 wt% is supplied in k. The obtained soluble polyimide resin is distilled to provide a pure polyimine resin (weight average molecular weight: 200,000). - The organic solvent mixture ratio of thiol ketone (γ), γ-butyrolactone and 2-butyl cellosolve is 3:4:3) added to the obtained soluble polyimide resin and stirred at room temperature 24 hours to provide a photo-aligned polyimide resin (PSI_1) as a liquid crystal alignment agent. Example 8 to Example 9: Polyimine polymer (Preparation of PSI_2 to (5)_ According to the same procedure as in Example 7. The difference is that the following work includes 4_(4,4,4-trifluorobutoxy)benzoic acid as shown in Chemical Formula 3a (yang-like-diamino-stupyloxy) oxo-amethylene ) stupid ester and 4,4,-(1,1,£)-3,3,-(2 2-double (4 animal moji)-propyl-u-worker) double as shown in Chemical Formula 4& Oxo) bis (3. oxo propylene; yl) bis(phenyl) bis(4_(4,4,4-trifluorobutoxy)benzoic acid vinegar to provide poly-branched acid' The polyaniline acid-soluble light was used according to the same procedure as in Example 7. Polyimine resin solution (liquid crystal alignment agent). 24 201226473 Example 10 to Example 12: Polyimine polymerization m PSI-6) was prepared according to the same procedure as in Example 7, except that it was included @4·(4,Μ_Trifluoroethoxy)benzoic acid 4-(1Ε,3Ε)-5·(2,4-dilacyloxyethyl)5-oxopenta- 13 as shown in Chemical Formula 3a Benzene acetonate, an eye-catching formula as shown in Chemical Formula 4a (4) Like a melamine-based) 1,3-1,3-diyl) bis(oxo)bis(3-oxopropene 3n) double extension Phenyl) bis(4-(4,4,4·trifluorobutoxy)benzoic acid and 1-(3,5-diaminophenyl)_3·octadecylpyrrole as shown in Chemical Formula 5& After burning _2,5·2, and supplying polyamine to k, h, a soluble photo-aligned polyimine resin solution (liquid crystal alignment agent) was obtained by using polylysine according to the same procedure as in Example 7. (Table 1)

25 201226473 < 一一 r** 如表1所示，化學式3a、化學式4a和化學式5a的含量單位為分別根據用於製備聚醯胺酸的二胺的總莫耳的莫耳％。實驗例1 :液晶配向膜的垂直配向性能評價（測量與標準液晶盒的預傾角差（△預傾角））使用液晶盒評價液晶配向劑的垂直配向性質。液晶盒如下製備。用光刻法使具有標準化尺寸的ITO玻璃基板形成圖案以僅保留3 cmx6 cm正方形ITO和用於施加電壓的ITO 電極，並除去銦錫氧化物（ITO)的其他部分。用由實施例1至實施例12和對比例1至對比例3製得的液晶光配向劑以Ο.ίμιη厚度旋塗在圖案化的IT〇基板上，並在8(TC和220°C下固化。為了測定垂直配向性質’通過摩擦製程、組裝製程和液晶注射製程製作測試液晶盒。用垂直偏振光顯微鏡觀察通過上述製程所得的液晶盒的垂直配向性能。在觀察垂直配向性能後，選擇具有良好垂直配向性此的液晶盒作為標準液晶盒，並將標準液晶 i的預傾角定義為90。隨後，在施加電場下使用能量輻射每個液晶盒，並使用晶體旋轉方法測量預傾角。在表 1中，△預傾角表明每個液晶盒測定的預傾角和標準液晶盒的預傾角之間的差異。用於評價垂直配向性能的標準如下： <用於評價垂直配向性能的標準> 26 201226473 良好：與標準液晶盒的預傾角差在〇. 3。至4。的範圍内。差：與標準液晶盒的預傾角差小於0 3。或大於4。。實驗例2 :液晶配向性能在施加電場下使用UV能量輻射所得液晶盒，並使用垂直偏振光顯微鏡測量每個液晶盒的液晶配向性能。用於評價液晶配向性能的標準如下： <用於評價液晶配向性能的標準〉良好：未發現向錯差：發現向錯實驗例3 :電壓保持比和殘留DC電壓對所得液晶盒施加1伏電壓，並在室溫下測量每個液晶盒的電壓保持比（VHR);對所得液晶盒施加〇伏至+1〇伏電壓，並測量每個液晶盒的殘留DC (RDC)電壓。電壓保持比表明在主動矩陣型TFT-LCD内，隨外電源浮動的液晶層保持充電電壓的程度，優選接近100%。 <用於評價電壓保持比的標準> 良好：97%或更高差··小於97% 殘留DC電壓表明通過將離子化液晶層的雜質吸附到配向層來對液晶層施加的電壓，越低越好。殘留DC電壓的測量方法包括使用閃變光度計（flicker) ’即使用液晶層的電容量隨DC電壓的變化曲綫(C-V)的方法。 <用於評價殘留DC電壓的標準> 良好：小於100 mV 差：100 mV或更高 27 201226473 (表2) 製備例垂直配向液晶配向性能電壓保持比 RDC PSA-1 良好良好良好良好 PSA-2 良好良好良好良好 PSA-3 良好良好良好良好 PSA-4 良好良好良好良好 PSA-5 良好良好良好良好 PSA-6 良好良好良好良好 PSI-1 良好良好良好良好 PSI-2 良好良好良好良好 PSI-3 良奸良好良好良好 PSI-4 良好良好良好良好 PSI-5 良好良好良好良好 PSI-6 良好良好良好良好對比例1 良好良好良好差對比例2 良好良好良好差如表2所示，與對比例〖和對比例2相比，從實施例 1至實施例12獲得的液晶配向劑具有改進的RD C特性。長期施例1 i ^ RDC特性是指評價液晶配向膜的電學特性的參考。較向的值表稀晶由有機或無機材料所⑽污染較重，可罪性受相。因此’與對比例i和2相比，從實 12獲得f液晶配㈣具錢*的電學特性。文明^當前認為是實際可行的示例性實施方-V、說明了本發明’應理解的是本發明不限於已公開 28 201226473 ----- 式，相反，應該覆蓋包括在所附權利要求的精神和範圍内的各種修改和等價替換。因此，應理解前述實施方式不以任何方式限制本發明。【圖式簡單說明】無【主要元件符號說明】無 2925 201226473 < One-to-one r** As shown in Table 1, the units of the chemical formula 3a, the chemical formula 4a and the chemical formula 5a are the molar % of the total molar amount of the diamine used for the preparation of the poly-proline. Experimental Example 1: Evaluation of vertical alignment property of liquid crystal alignment film (measurement of pretilt angle difference (Δ pretilt angle) with standard liquid crystal cell) The liquid crystal cell was used to evaluate the vertical alignment property of the liquid crystal alignment agent. The liquid crystal cell was prepared as follows. The ITO glass substrate having a standardized size was patterned by photolithography to retain only 3 cm x 6 cm square ITO and an ITO electrode for applying a voltage, and to remove other portions of indium tin oxide (ITO). The liquid crystal photoalignments prepared by Example 1 to Example 12 and Comparative Example 1 to Comparative Example 3 were spin-coated on a patterned IT substrate at a thickness of (. ίμιη, and at 8 (TC and 220 ° C). Curing. In order to determine the vertical alignment property, a test cell was fabricated by a rubbing process, an assembly process, and a liquid crystal injection process. The vertical alignment performance of the liquid crystal cell obtained by the above process was observed by a vertically polarized light microscope. After observing the vertical alignment property, the selection was performed. A good vertical alignment of this liquid crystal cell as a standard liquid crystal cell, and the pretilt angle of the standard liquid crystal i is defined as 90. Subsequently, each liquid crystal cell is irradiated with energy under an applied electric field, and the pretilt angle is measured using a crystal rotation method. In 1, the Δ pretilt angle indicates the difference between the pretilt angle measured by each liquid crystal cell and the pretilt angle of the standard liquid crystal cell. The criteria for evaluating the vertical alignment performance are as follows: <Standard for evaluating vertical alignment performance> 201226473 Good: The pretilt angle difference from the standard liquid crystal cell is in the range of 〇. 3 to 4. Poor: The pretilt angle difference from the standard liquid crystal cell is less than 0 3 . 4. Experimental Example 2: Liquid crystal alignment performance The obtained liquid crystal cell was irradiated with UV energy under an applied electric field, and the liquid crystal alignment property of each liquid crystal cell was measured using a vertical polarization microscope. The criteria for evaluating the liquid crystal alignment performance were as follows: Standard for evaluating the alignment performance of liquid crystals> Good: No difference in error was found: Dislocation test Example 3 was found: voltage holding ratio and residual DC voltage were applied to the obtained liquid crystal cell by 1 volt, and each liquid crystal was measured at room temperature. The voltage holding ratio of the cell is maintained (VHR); the resulting liquid crystal cell is applied with a voltage of +1 〇V, and the residual DC (RDC) voltage of each liquid crystal cell is measured. The voltage holding ratio is shown in the active matrix type TFT-LCD. The degree to which the liquid crystal layer floating with the external power source maintains the charging voltage is preferably close to 100%. <Standard for evaluating the voltage holding ratio> Good: 97% or higher difference · less than 97% Residual DC voltage indicates that the ion is passed The impurity of the liquid crystal layer is adsorbed to the alignment layer to apply a voltage to the liquid crystal layer as low as possible. The method of measuring the residual DC voltage includes using a flicker photometer (ie, using a liquid crystal layer) Method of capacitance versus DC voltage curve (CV) <Standard for evaluating residual DC voltage> Good: less than 100 mV Difference: 100 mV or higher 27 201226473 (Table 2) Preparation of Vertical Alignment Liquid Crystal Alignment Performance voltage retention is better than RDC PSA-1 Good Good Good PSA-2 Good Good Good Good PSA-3 Good Good Good Good Good PSA-4 Good Good Good Good Good PSA-5 Good Good Good Good Good PSA-6 Good Good Good Good Good PSI-1 Good Good Good Good PSI-2 Good Good Good Good PSI-3 Good Good Good Good PSI-4 Good Good Good Good Good PSI-5 Good Good Good Good Good PSI-6 Good Good Good Good Comparative 1 Good Good Good Poor Comparative 2 Good Good and Poor Difference As shown in Table 2, the liquid crystal alignment agents obtained from Examples 1 to 12 had improved RD C characteristics as compared with Comparative Examples 2 and Comparative Example 2. Long-term Example 1 i ^ RDC characteristics refer to a reference for evaluating the electrical properties of a liquid crystal alignment film. The relative value of the thinner crystal is more polluted by the organic or inorganic material (10), and the sinful phase is affected. Therefore, compared with the comparative examples i and 2, the electric properties of the f liquid crystal (f) have been obtained from the real 12 . Civilization ^ is currently considered to be a practical exemplary embodiment - V, illustrating the invention 'it is understood that the invention is not limited to the disclosed 28 201226473 -----, but instead should be covered by the appended claims Various modifications and equivalent substitutions within the spirit and scope. Therefore, it is to be understood that the foregoing embodiments are not intended to limit the invention in any way. [Simple description of the diagram] None [Key component symbol description] None 29

Claims

201226473 七、申請專利範圍： 1. 一種液晶配向劑，包括：聚合物，所述聚合物選自包括以下化學式1所示的重複單元的聚醯胺酸、包括以下化學式2所示的重複單元的聚醯亞胺和它們的組合： [化學式1]201226473 VII. Patent Application Range: 1. A liquid crystal alignment agent comprising: a polymer selected from the group consisting of polylysine including a repeating unit represented by the following Chemical Formula 1, comprising a repeating unit represented by the following Chemical Formula 2 Polyimine and combinations thereof: [Chemical Formula 1]

[化學式2][Chemical Formula 2]

其中，在化學式1和2中， X1和X2為相同或不同，且各自獨立地為由脂環酸二酐或芳族酸二酐衍生的四價有機基團；且 Y1和Y2為相同或不同，且各自獨立地為由二胺衍生的二價有機基團，且所述二胺包括以下化學式3所示的一種； [化學式3]Wherein, in Chemical Formulas 1 and 2, X1 and X2 are the same or different, and each independently is a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride; and Y1 and Y2 are the same or different And each independently is a divalent organic group derived from a diamine, and the diamine includes one represented by the following Chemical Formula 3; [Chemical Formula 3]

201226473. 其中，在化學式3中， Α1為經取代或未經取代的C1至C20伸烷基； Α2 為單鍵、〇、S02 或 C(R103)(R104)，其中 RI〇3 和 R 、1〇4 為相同或不同’且獨立地為氫、或經取代或未經取代的Cl 至C6伸烷基； A3 為-〇-、-OCO-、-COO-、-CONH-或-NHCO-; 各R1為經取代或未經取代的C1至C30烷基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至C3〇雜芳基； ^ R2為經取代或未經取代的C1_C30伸烷基、至少一個_CIi2_ 基團獨立地被-CO-、-CO-0-、-NZ-、-NZ-CO-、-CO-NZ-或 -CH=CH-取代的C1-C30伸烷基，其中Z為氫或C1-C10烷基，條件是氧原子彼此不直接鍵合；各R3為相同或不同，且獨立地為經取代或未經取代的至C30燒基、經取代或未經取代的C6-C30芳基或經取代或未經取代的C2至C3〇雜芳基；、Q2和Q3獨立地為氫或鹵素； η為0至3的整數； ml為〇至3的整數；且 m2為〇至4的整數。 > 2.如申請專利範圍第1項所述的液晶配向劑，所述二月女進二步包括選自以下化學式4所示的二胺和以下化學式 5所示的二胺中的至少一種： [化學式4] 31 201226473 JOJl jpil201226473. wherein, in Chemical Formula 3, Α1 is a substituted or unsubstituted C1 to C20 alkyl group; Α2 is a single bond, 〇, S02 or C(R103)(R104), wherein RI〇3 and R, 1 〇4 is the same or different 'and independently hydrogen, or substituted or unsubstituted C1 to C6 alkyl; A3 is -〇-, -OCO-, -COO-, -CONH- or -NHCO-; Each R1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C3 oxaaryl group; ^ R2 is substituted or Unsubstituted C1_C30 alkylene group, at least one _CIi2_ group independently substituted by -CO-, -CO-0-, -NZ-, -NZ-CO-, -CO-NZ- or -CH=CH- C1-C30 alkylene, wherein Z is hydrogen or C1-C10 alkyl, provided that the oxygen atoms are not directly bonded to each other; each R3 is the same or different and independently substituted or unsubstituted to C30 a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2 to C3 〇 aryl group; Q2 and Q3 are independently hydrogen or halogen; η is an integer from 0 to 3; An integer of 〇 to 3; and m2 is an integer from 〇 to 4. 2. The liquid crystal alignment agent according to claim 1, wherein the second step comprises at least one selected from the group consisting of a diamine represented by the following Chemical Formula 4 and a diamine represented by the following Chemical Formula 5; : [Chemical Formula 4] 31 201226473 JOJl jpil

R4為經取代或未經取代的C1-C30伸烷基、至少一個 -CH2-基團獨立地被-CO-、-CO-0-、-NZ-、-NZ-CO-、-CO-NZ-或-CH=CH-取代的C1-C30伸烷基，其中Z為氫或C1-C10 烷基’條件是氧原子彼此不直接鍵合；且 Q4、Q5、Q6、Q7、Q8和Q9獨立地為氫或鹵素； [化學式5] nh2R4 is a substituted or unsubstituted C1-C30 alkylene group, at least one -CH2- group is independently -CO-, -CO-0-, -NZ-, -NZ-CO-, -CO-NZ -or -CH=CH-substituted C1-C30 alkylene, wherein Z is hydrogen or C1-C10 alkyl', provided that the oxygen atoms are not directly bonded to each other; and Q4, Q5, Q6, Q7, Q8 and Q9 are independent The ground is hydrogen or halogen; [chemical formula 5] nh2

其中，在化學式5中， R5為氫、經取代或未經取代的cl C3〇烷基、經取代或未經取代的芳基或經取代或未經取代的C2_C3< 雜芳基； _ R6為經取代或未經取代的C1_⑽絲、經取代或未 ^取代的C6_C3G芳基或經取代或未經取代的C2_C3〇雜芳叫為0至3的整數。 32 201226473. 3.如曰申請專利範圍第2項所述的液晶配向劑，其中以二胺的總量計’所述二胺包括3G莫耳％至9()莫耳％的由以上化學式3表示的二胺、5莫耳％至2〇莫耳。/❶的由以上化學式4表示的二胺和5莫耳％至5〇莫耳％的由以上化學式5表示的二胺。 4·如申凊專利範圍第1項所述的液晶配向劑，其中以上化學式3所示的二胺為以下化學式6所示的二胺： [化學式6]Wherein, in Chemical Formula 5, R5 is hydrogen, substituted or unsubstituted cl C3 alkyl group, substituted or unsubstituted aryl or substituted or unsubstituted C2_C3<heteroaryl; _R6 is The substituted or unsubstituted C1_(10) filament, the substituted or unsubstituted C6_C3G aryl group or the substituted or unsubstituted C2_C3 oxa group is an integer of 0 to 3. The liquid crystal alignment agent of claim 2, wherein the diamine comprises 3G mol% to 9 () mol% by the total amount of diamine, the above chemical formula 3 Derived as diamine, 5 moles to 2 moles. The diamine represented by the above Chemical Formula 4 and the diamine represented by the above Chemical Formula 5 are from 5 mol% to 5 mol%. 4. The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine represented by the above Chemical Formula 3 is a diamine represented by the following Chemical Formula 6: [Chemical Formula 6]

其中’在化學式6中， 1為0至10的整數，且 m為0至3的整數。 5·如申請專利範圍第1項所述的液晶配向劑，其中所述聚醯胺酸和所述聚醯亞胺分別具有1〇,〇〇〇至300,000的重量平均分子量。 6. 如申請專利範圍第1項所述的液晶配向劑，其中所述液晶配向劑包括重量比為1:99至50:50的所述聚醯胺酸和戶斤述聚酿亞胺。 7. 如申請專利範圍第1項所述的液晶配向劑’其中所述浪晶配向劑包括1 wt%至30 wt%的固體。 8. 如申請專利範圍第1項所述的液晶配向劑’其中所 33 201226473 «f x ^/yrxx 述液晶配向劑具有3 cps至3〇 cps的黏度。 9. 一種液晶配向膜’所述液晶配向膜通過將如申請專利範圍第1項至第8項中任何一項所述的液晶配向劑塗布到基板上來製備。 10. —種液晶顯示器，所述液晶顯不器包括申請專利範圍第9項所述的液晶配向膜。 201226473t 四、指定代表圖： (一）本案之指定代表圖：無 (二）本代表圖之元件符號簡單說明：無五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： [化學式1]Wherein 'in Chemical Formula 6, 1 is an integer of 0 to 10, and m is an integer of 0 to 3. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid and the polyimine have a weight average molecular weight of from 1 Torr to 300300,000, respectively. 6. The liquid crystal alignment agent according to claim 1, wherein the liquid crystal alignment agent comprises the polyamic acid and the chitosan in a weight ratio of 1:99 to 50:50. 7. The liquid crystal alignment agent according to claim 1, wherein the wave crystal alignment agent comprises 1 wt% to 30 wt% of a solid. 8. The liquid crystal alignment agent according to claim 1, wherein 33 201226473 «f x ^/yrxx said liquid crystal alignment agent has a viscosity of 3 cps to 3 〇 cps. A liquid crystal alignment film is produced by applying a liquid crystal alignment agent according to any one of items 1 to 8 of the patent application to a substrate. A liquid crystal display comprising the liquid crystal alignment film according to claim 9 of the patent application. 201226473t IV. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Chemical formula 1]

Ο 0 [化學式2]Ο 0 [Chemical Formula 2]

Ο 〇 3 201226473 修正日期：100年1〇月6曰 38315pifl 爲第100130079號中文說明書無劃線修正頁發明專利說明書 (2006.Ci； (本說明書格式、順序及粗體字’請勿任意更動’※記號部分請勿填寫） ※申請案號：/外/多0以/ ※申請日期：/夕义々%IPC分類：一、發明名稱：（中文/英文）液晶配向劑、使用其製造的液晶配向膜和包括該液晶配向膜的液晶顯示器 LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM MANUFACTURED USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE LIQUID CRYSTAL ALIGNMENT FILM 二、中文發明摘要：一種液晶配向劑，其包括聚合物，所述聚合物選自包括以下化學式1所示的重複單元的聚醯胺酸、包括以下化學式2所示的重複單元的聚醯亞胺和它們的組合。 [化學式1]Ο 〇3 201226473 Revision date: 100 years 1 month 6曰38315pifl is the 100130079 Chinese manual without scribe correction page invention patent specification (2006.Ci; (this specification format, order and bold type 'do not change any more' ※Please do not fill in the number of the mark. ※Application number: /Outside/Multiple 0/※Application date: / 夕义々%IPC classification: I. Name of the invention: (Chinese / English) Liquid crystal alignment agent, liquid crystal manufactured using the same Alignment film and liquid crystal display including the liquid crystal alignment film LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM MANUFACTURED USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE LIQUID CRYSTAL ALIGNMENT FILM II. Abstract: A liquid crystal alignment agent comprising polymerization The polymer is selected from the group consisting of polylysine including a repeating unit represented by the following Chemical Formula 1, a polyimine comprising a repeating unit represented by the following Chemical Formula 2, and a combination thereof.

[化學式2] HOOC COOH[Chemical Formula 2] HOOC COOH

201226473 修正日期：100年1〇月6曰 38315pifl 爲第100130079號中文說明書無劃線修正頁發明專利說明書 (2006.Ci； (本說明書格式、順序及粗體字’請勿任意更動’※記號部分請勿填寫） ※申請案號：/外/多0以/ ※申請日期：/夕义々%IPC分類：一、發明名稱：（中文/英文）液晶配向劑、使用其製造的液晶配向膜和包括該液晶配向膜的液晶顯示器 LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM MANUFACTURED USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE LIQUID CRYSTAL ALIGNMENT FILM 二、中文發明摘要：一種液晶配向劑，其包括聚合物，所述聚合物選自包括以下化學式1所示的重複單元的聚醯胺酸、包括以下化學式2所示的重複單元的聚醯亞胺和它們的組合。 [化學式1]201226473 Revision date: 100 years 1 month 6曰38315pifl is the 100130079 Chinese manual no-line correction page invention patent specification (2006.Ci; (this specification format, order and bold type 'do not change any more' ※ mark part Please do not fill in. ※Application number: /Outside/Multiple 0/※Application date: / 夕义々%IPC classification: 1. Name of the invention: (Chinese/English) Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same Liquid crystal display including the liquid crystal alignment film LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM MANUFACTURED USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE LIQUID CRYSTAL ALIGNMENT FILM II. Abstract: A liquid crystal alignment agent comprising a polymer, The polymer is selected from the group consisting of polylysine including a repeating unit represented by the following Chemical Formula 1, a polyimine comprising a repeating unit represented by the following Chemical Formula 2, and a combination thereof.

[化學式2] HOOC COOH[Chemical Formula 2] HOOC COOH

201226473 J 38315pifl 爲第100130079號中文說明書無劃線修正頁修正日期：100年10月6日在化學式1和2中，X1、X2、Y1和Y2與說明書中的定義相同。三、英文發明摘要： Disclosed is a liquid crystal alignment agent that includes a polymer selected from polyamic acid including a repeating unit represented by the following Chemical Formula 1, polyimide including a repeating unit represented by the following Chemical Formula 2, and a combination thereof. [Chemical Formula 1] NH—Y- HOOC 、c〇OH [Chemical Formula 2] o o N^X2 'N—Y- Λ. o o Y In Chemical Formulae 1 and 2, X\ X2, Y1 and Y2 are the same as defined in the detailed description.201226473 J 38315pifl is the Chinese version of the 100130079 No-line correction page. Revision date: October 6, 100. In Chemical Formulas 1 and 2, X1, X2, Y1, and Y2 are the same as defined in the specification. III. English Abstract: Disclosed is a liquid crystal alignment agent that includes a polymer selected from polyamic acid including a repeating unit represented by the following Chemical Formula 1, polyimide including a repeating unit represented by the following Chemical Formula 2, and a combination thereof [Chemical Formula 1] NH—Y- HOOC, c〇OH [Chemical Formula 2] oo N^X2 'N—Y- Λ. oo Y In Chemical Formulae 1 and 2, X\ X2, Y1 and Y2 are the same As defined in the detailed description.