TW200532005A

TW200532005A - Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same

Info

Publication number: TW200532005A
Application number: TW094105922A
Authority: TW
Inventors: Kimiaki Tsutsui; Rie Gunji; Takahiro Sakai
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2004-02-26
Filing date: 2005-02-25
Publication date: 2005-10-01
Also published as: TWI367934B; JPWO2005083504A1; CN1922540A; WO2005083504A1; JP4404090B2; KR20060133567A; KR101158382B1; CN100437301C

Abstract

This invention provides a liquid crystal aligning agent for obtaining a liquid crystal alignment film excelling in not only liquid crystal alignment performance but also electrical properties through photoalignment procedure; and a liquid crystal display device making use of this liquid crystal aligning agent, which can resolve problems invited by rubbing treatment of liquid crystal alignment film, exhibiting high reliability and which can minimize display unevenness and exudation around sealing material. There is provided a liquid crystal aligning agent for photoalignment, characterized by containing at least one of a polyamic acid, the polyamic acid obtained by reacting a diamine component containing a diamine of the following formula (1) with a tetracarboxylic acid dianhydride component containing a tetracarboxylic acid dianhydride with alicyclic structure into a polymer, and a polyimide obtained from the polyamic acid. There is further provided a liquid crystal display device having a liquid crystal alignment film obtained from the above liquid crystal aligning agent through photoalignment procedure. (in which two of R1 to R10 are primary amino, and each of the rest is a hydrogen atom or a monovalent organic group other than primary amino, provided that they may be identical with or different from each other).

Description

200532005 (1) 九、發明說明【發明所屬之技術領域】本發明係爲有關由光配向法形成液晶配向膜之光定向用液晶配向膜、及使用其之液晶顯示元件。【先前技術】液晶顯示元件爲現在廣泛使用作爲實現薄型·輕量的顯不裝置。液晶顯不兀件的顯示特性爲液晶的配向性，受液晶的預傾角（pretilt )的大小，預傾角（pretilt )的安定性，電特性等的影響大。提高這種液晶顯示元件的顯示特性’不僅使用的液晶材料，決定該液晶配向狀態之近接液晶配向膜亦爲重要的因素。現在’液晶配向膜主要以聚醯胺酸或聚醯亞胺的樹脂溶液作爲液晶配向劑使用，將其塗敷於基板後，進行燒結，將該塗膜表面以人造纖維布或尼龍布施壓硏磨，由進行所謂摩擦處理（rubbing )而形成。由聚醯亞胺或其先驅物的聚醯胺酸得到液晶配向膜的方法，可由塗敷·燒結樹脂溶液之簡便製程製成耐熱性、耐溶劑性優之塗膜，由於可容易由摩擦處理（rubbing )將液晶配向，工業化，廣泛普及使用至今。但是，以現在廣泛普及的配向方法之摩擦處理（ rubbing )時，因附著液晶配向膜的削屑或灰塵而成爲產生顯示缺陷的問題。又，硏磨時產生靜電，TF T (薄膜電晶體）元件被破壞，其結果，產生顯示不良成爲問題。又 -6- 200532005 (2) 近年基板的大型化摩擦處理（rubbing)不能均句的的實施成爲問題。作爲迴避這種摩擦處理（rubbing )的問題之方法，提案將於基板上所形成的膜以紫外線照射，不用摩擦處理 (rubbing)製作液晶配向膜的方法（光配向法）。提案種種有關該光配向法用的膜材料，例如有報告使用聚醯亞胺’係使用四羧酸來源構造位置具有脂環構造之 φ 聚醯亞胺，可將液晶分子均勻且安定的配向（參閱專利文獻1 )。一方面’作爲液晶配向膜必要的特性，不僅液晶配向性良好，作爲液晶元件時的電特性亦爲重要。自向來，作爲改善聚醢亞胺系之液晶配向膜的電特性的手段，提案由化合物的添加物，即選擇作爲聚醯亞胺的原料之二酸酐或二胺。例如，二胺的選擇例，使用具有對苯基二胺之聚醯亞胺，知其高溫的電壓保持率高參閱專利文獻2 )。 φ 但是’由紫外線等之照射引起化學變化之光配向法時，電特性相關者與向來的摩擦處理（rubbing )之液晶配向膜成爲預想以外的結果多，由光配向法之液晶配向膜之電特性，與摩擦處理（rubbing )的液晶配向膜比較時，一般電特性差的情形較多。特別是，伴隨因紫外線等之聚合物分解時，與向來的硏磨法比較，液晶胞中雜質離子的量增加，電壓保持率有降低的問題。該電壓保持率的降低，成爲引起液晶顯示面板的信頼性的降低，產生顯示不均，產生封裝劑週邊的不均等問題的原因。因此，有關由光 200532005 (3) 配向法的液晶配向膜之電特性的改善，與向來摩擦處理（ rubbing )的液晶配向膜不同的觀點必要進行材料開發。光配向法用之膜材的電特性改善的手段，提案由含# 軛烯酮構造之側鏈具有聚苯乙烯衍生物構造單元或馬來@ 酐醯亞胺構造單元的聚合物，得到電特性良好的液晶配@ 膜（參閱專利文獻3 )。又，亦提案由使用由具有聚合性馬來酸酐醯亞胺基之單體所成的光配向膜材料，成爲具有良好電壓保持率的光配向膜（參閱專利文獻4 )。但是’由光配向法的液晶配向膜，與摩擦處理（ rubbing )的液晶配向膜比較，不能說有較多配向膜材料的選擇。特別是，有關由使用現在摩擦處理（rubbing ) 的液晶配向膜有實績之聚醯亞胺系的材料電特性的觀點，無提案適合由光配向法製作液晶配向膜的構造。【專利文獻1】日本特開平9-297313號公報【專利文獻2】日本特開平5-341291號公報【專利文獻3】日本特開2〇〇〇_281724號公報【專利文獻4】日本特開2002-3 1 70 1 3號公報【發明內容】〔發明所欲解決之課題〕本發明係有鑑於上述事情，有關由使用摩擦處理（ rubbing)的液晶配向膜有實績的聚酿亞胺系材料，提供由光配向法得到不僅液晶配向性良好，具有良好的電特性 ’離子量少'’存儲電荷少的特性之液晶配向膜的液晶配向 200532005 (4) 理（顯示發現及液二胺酐成之聚劑爲目的。又，消除伴隨液晶配向膜的摩擦處 rubbing )的不理想，提供信頼性高，不易產生引起不均或封閉材料週邊的斑點的液晶顯示元件爲目的。〔課題解決手段〕本發明者等爲解決上述課題經深入硏究的結果，本發明。即本發明爲以下所示之光配向膜液晶配向劑晶顯不兀件。 1·至少含有一種，由下述式（1)所示含二胺之成分，與含具有脂環式構造之四羧酸二酐之四羧酸二分，經反應聚合所得之聚醯胺酸；或由該醯胺酸所得醯亞胺爲特徵的光定向用液晶配向劑。200532005 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment film for light alignment in which a liquid crystal alignment film is formed by a photo-alignment method, and a liquid crystal display element using the same. [Prior art] Liquid crystal display elements are widely used today as display devices that realize thin and lightweight displays. The display characteristics of the liquid crystal display device are the orientation of the liquid crystal, which is greatly affected by the size of the pretilt of the liquid crystal, the stability of the pretilt, and the electrical characteristics. Improving the display characteristics of such a liquid crystal display element is not only a liquid crystal material used, but also a close-up liquid crystal alignment film that determines the alignment state of the liquid crystal. At present, a liquid crystal alignment film mainly uses a polyamic acid or polyimide resin solution as a liquid crystal alignment agent. After being applied to a substrate, it is sintered, and the surface of the coating film is pressed with artificial fiber cloth or nylon cloth. Honing is performed by performing so-called rubbing. A method for obtaining a liquid crystal alignment film from polyimide or polyimide of its precursor, which can be made into a coating film excellent in heat resistance and solvent resistance by a simple process of applying and sintering a resin solution, because it can be easily processed by friction (Rubbing) Aligns and industrializes liquid crystals, and has been widely used. However, rubbing with the currently widely used alignment method causes display defects due to chipping or dust of the liquid crystal alignment film. In addition, static electricity is generated during honing, and a TTF (thin-film transistor) device is broken. As a result, display failure is a problem. -6- 200532005 (2) In recent years, the implementation of large-scale rubbing of substrates cannot be uniformly implemented. As a method for avoiding such a rubbing problem, a method (photo-alignment method) for producing a liquid crystal alignment film without rubbing is proposed by irradiating a film formed on a substrate with ultraviolet rays. Various proposals have been made on film materials for this photo-alignment method. For example, it has been reported that polyfluorene imine 'is used, and φpolyfluorene imine having an alicyclic structure at the position of the tetracarboxylic acid source structure. See Patent Document 1). On the one hand, as a necessary characteristic of the liquid crystal alignment film, not only the liquid crystal alignment is good, but also the electrical characteristics when the liquid crystal element is important. Conventionally, as a means for improving the electrical characteristics of polyfluorene-based liquid crystal alignment films, it has been proposed to select a dianhydride or diamine as a raw material of polyfluorene imine by the addition of a compound. For example, as a selection example of a diamine, a polyfluorene imine having p-phenylenediamine is used, and it is known that the high-temperature voltage retention rate is high (see Patent Document 2). φ However, in the photo-alignment method where chemical changes are caused by the irradiation of ultraviolet rays or the like, the electrical characteristics related to the conventional rubbing liquid crystal alignment film have many unexpected results. When compared with a rubbing liquid crystal alignment film, the electrical characteristics are often poor. In particular, when the polymer is decomposed by ultraviolet rays or the like, the amount of impurity ions in the liquid crystal cell is increased and the voltage holding ratio is lowered compared with the conventional honing method. This decrease in the voltage holding ratio causes a decrease in the reliability of the liquid crystal display panel, causes display unevenness, and causes problems such as unevenness around the encapsulant. Therefore, material improvement is required for the improvement of the electrical characteristics of the liquid crystal alignment film by the 200532005 (3) alignment method, which is different from the conventional liquid crystal alignment film for rubbing. Means to improve the electrical characteristics of the film used in the photo-alignment method. A polymer containing a polystyrene derivative structural unit or a male @ anhydride imine structural unit in the side chain with # conjugatenone structure is proposed to obtain electrical characteristics. Good liquid crystal with a film (see Patent Document 3). It is also proposed to use a photo-alignment film material made of a monomer having a polymerizable maleic anhydride / imine group to form a photo-alignment film having a good voltage holding ratio (see Patent Document 4). However, compared with the liquid crystal alignment film of rubbing, the liquid crystal alignment film by the photo-alignment method cannot be said to have more choices of alignment film materials. In particular, there is no proposal regarding a structure suitable for producing a liquid crystal alignment film by a photo-alignment method from the viewpoint of the electrical characteristics of a polyimide-based material that has a proven track record using a rubbing liquid crystal alignment film. [Patent Document 1] Japanese Patent Application Laid-Open No. 9-297313 [Patent Literature 2] Japanese Patent Application Laid-Open No. 5-341291 [Patent Literature 3] Japanese Patent Application Laid-Open No. 2000-281724 [Patent Literature 4] Japanese Patent Laid-Open 2002-3 1 70 1 [Contents of the Invention] [Problems to be Solved by the Invention] In view of the foregoing, the present invention relates to a polyimide-based material that has a proven track record in rubbing-treated liquid crystal alignment films. Provide liquid crystal alignment obtained by photo-alignment method with liquid crystal alignment film that not only has good liquid crystal alignment, but also has good electrical characteristics, such as low ionic content, and low storage charge. 200532005 (4) Principles (display discovery and liquid diamine anhydride formation The purpose of the polymerizing agent is to eliminate the undesired rubbing of the liquid crystal alignment film, and to provide a liquid crystal display element with high reliability and less likely to cause unevenness or spots around the sealing material. [Problem Solving Means] The present inventors have made intensive studies to solve the above-mentioned problems. That is, the present invention is a crystal display element for a liquid crystal alignment agent for a light alignment film as shown below. 1. A polyamic acid obtained by reaction polymerization containing at least one kind of a diamine-containing component represented by the following formula (1) and a tetracarboxylic acid halide containing a tetracarboxylic dianhydride having an alicyclic structure; Or the liquid crystal aligning agent for light orientation characterized by the fluorene imine obtained from this fluoric acid.

子或 )° )所 (式中’ R]〜R1G中之2個爲一級胺基、其餘爲氫原一級胺基以外之一價有機基，各自爲相同或相異均可 2·具有S曰式構造之四竣酸一肝，爲下述式（2 示之四羧酸二酐爲特徵的上述1項所述的光定向用液晶配向劑。 200532005 (5)Sub-or) °) (wherein 'R] ~ R1G are primary amine groups and the rest are monovalent organic groups other than hydrogenogen primary amine groups, each of which may be the same or different. 2 · S S The quaternary acid and liver of the formula structure is the liquid crystal alignment agent for photo-orientation described in the above item 1, which is characterized by the following formula (2) tetracarboxylic dianhydride. 200532005 (5)

(式中’R11〜R14，各自爲獨立之氫原子或碳數1〜4之院基）。 3 ·具有將上述1或2項中任一項之光定向用液晶配向劑，經由塗敷於基板的步驟，及將該基板照射偏光紫外線的步驟所形成之液晶配向膜的液晶顯示元件。〔發明之效果〕本發明的光定向用液晶配劑可由光配向法得到電壓保持率優，離子量降低，且存儲電荷少的液晶配向膜。又，以光配向法所得具有由本發明的液晶配向劑之液晶配向膜之液晶顯示元件，消除伴隨液晶配向膜的摩擦處理（ rubbing )的不理想，且具有良好的電特性。因此，可作爲信頼性高，不易產生引起顯示不均或封閉材料週邊的斑點的液晶顯示裝置，適合使用於TN元件、S TN元件、 TFT液晶元件’更可作爲由水平電場型的液晶顯示元件、垂直配向型的液晶顯示元件使用的種種顯示元件。又，選擇使用的液晶’亦可使用作爲強介電性及反強介電性液晶顯示元件。 ’ 〔用以實施發明之最佳型態〕 -10- 200532005 (6) 以上詳細說明本發明。本發明的液晶配向劑至少含有由四羧酸二酐成分，與二胺成分反應聚合所得之聚醯胺酸，或由該聚醯胺酸所得的聚醯亞胺的一方，爲達成由偏光紫外線照射的配向性，高電壓保持性，少存儲電荷性，該四羧酸二酐成分至少一部份爲具有脂環式構造的四羧酸二酐，該二胺成分至少一部份爲一般（1 )所示的二胺爲其特徵。本發明液晶配向劑所使用的具有脂環式構造之四羧酸二酐的具體例，可列舉如1，2，3，4一環丁烷四羧酸二酐、1，2—二甲基一1，2，3，4一環丁烷四羧酸二酐、1 ，3 —二甲基 1，2，3，4一環丁烷四羧酸二酐、1，2，3 ，4 —四甲基—1，2，3，4 —環丁烷四续酸二酐、1，2 ’ 3 ，4 —環戊烷四羧酸二酐、2，3，4，5 —四氫呋喃四羧酸二酐、1，2，4，5 —環己烷四羧酸二酐、2，3，5 —三羧基環戊基醋酸二酐、3，4 —二羧基—1 一環己基琥珀酸二酐、3，4 —二羧基一 1，2，3，4 —四氫一 1—萘琥珀酸二酐等，但不限定於此等物質。又，此等的四羧酸二酐可單獨或組合使用。又’具有脂環式構造四羧酸二酐之中，爲顯示高電壓保持率，且由紫外線照射得到優液晶配向性’以使用下述式（2 )所示四羧酸二酐爲理想。 -11 - 200532005 (7)(Wherein 'R11 to R14, each is an independent hydrogen atom or a radical of 1 to 4 carbon atoms). 3. A liquid crystal display element having a liquid crystal alignment film formed by applying the liquid crystal alignment agent for light alignment according to any one of the above 1 or 2 to a substrate and a step of irradiating the substrate with polarized ultraviolet rays. [Effects of the Invention] The liquid crystal alignment agent for photo-alignment of the present invention can be obtained by a photo-alignment method. The liquid-crystal alignment film has excellent voltage holding ratio, reduced ion content, and low stored charge. In addition, the liquid crystal display element having the liquid crystal alignment film of the liquid crystal alignment agent of the present invention obtained by the photo-alignment method can eliminate the undesired rubbing of the liquid crystal alignment film, and has good electrical characteristics. Therefore, it can be used as a liquid crystal display device with high reliability and less likely to cause uneven display or spots around the sealing material. It is suitable for use in TN devices, S TN devices, and TFT liquid crystal devices. Various display elements used in vertical alignment type liquid crystal display elements. Alternatively, the liquid crystal of choice can be used as a ferroelectric and anti-ferroelectric liquid crystal display element. [The best mode for carrying out the invention] -10- 200532005 (6) The present invention has been described in detail above. The liquid crystal alignment agent of the present invention contains at least one of a polyamic acid obtained by reacting and polymerizing a tetracarboxylic dianhydride component and a diamine component, or a polyimide obtained from the polyamic acid. Irradiation alignment, high voltage retention, less charge storage, at least part of the tetracarboxylic dianhydride component is tetracarboxylic dianhydride having an alicyclic structure, and at least part of the diamine component is general ( 1) The diamine shown is characteristic. Specific examples of the tetracarboxylic dianhydride having an alicyclic structure used in the liquid crystal alignment agent of the present invention include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1 1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,3-dimethyl1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl —1,2,3,4 —cyclobutanetetracarboxylic dianhydride, 1,2 ′ 3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5 —tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1 monocyclohexyl succinic dianhydride, 3,4 —Dicarboxyl-1,2,3,4—tetrahydro-1—naphthalenesuccinic dianhydride and the like, but not limited thereto. These tetracarboxylic dianhydrides can be used alone or in combination. Among the tetracarboxylic dianhydrides having an alicyclic structure, in order to exhibit high voltage retention and obtain excellent liquid crystal alignment by ultraviolet irradiation, it is preferable to use a tetracarboxylic dianhydride represented by the following formula (2). -11-200532005 (7)

(式中，R11〜R14，各自爲獨立之氫原子或碳數1〜4之烷基）° 上述式中的R11〜R14，各自爲獨立之氫原子或碳數1 〜4之烷基，以氫原子或甲基爲理想，更理想爲氫原子。具體的以使用1，2，3，4 一環丁烷四羧酸二酐、1 ’ 2 — 二甲基一 1，2，3，4一環丁烷四羧酸二酐、1，3 —二甲基 ρ 2，3，4一環丁烷四羧酸二酐、1，2，3，4 —四甲基― i，2，3，4 一環丁烷四殘酸二酐爲理想，更理想爲1，2 ，3，4 一環丁烷四羧酸二酐。本發明液晶配向劑所使用的四羧酸二酐成分，係可使用由具有上述脂環式構造之四羧酸二酐，與其他的四羧酸二酐的組合。其他的四羧酸二酐，可列舉如二環[3，3，〇]辛烷一 2’ 4，6，8-四羧酸二酐等的具有脂環式構造的四羧酸二酐、1，2，3 ’ 4 — 丁烷四羧酸二酐等的脂肪族四续酸二酐、均苯四甲酸二酐、3，3 / ，4，4〃一聯苯基四錢酸二酐、2，2 /，3，3 / —聯苯基四羧酸二酐、2，3， 3〆，4/ —聯苯四羧酸二酐、3，3^ ，4，4'—二苯甲酮四羧酸二酐、2，3，3 / ，f —二苯甲酮四羧酸酐、雙（ 3，4一二羧基苯）醚二酐、雙（3，4 —二羧基苯）硕二酐、：I，2，5，6 —苯四羧酸二酐 2，3，6，7 —苯四羧酸二 -12- 200532005 (8) 酐、1，4，5，S —苯四羧酸二酐等的芳香族四羧酸二酐，但不限定於此等物質。又，此等的四羧酸二酐可組合數種類，具有脂環式構造的四羧酸二酐使用。此等其他四羧酸二酐之中，均苯四甲酸二酐、3，3/ ，4，4 / 一二苯甲酮四羧酸二酐、1，4，5，8 —苯四羧酸二酐電壓保持率有降低的傾向，有液晶配向性優，存儲電荷少的效果。因此，重視減少存儲電荷時，將此等的四羧酸二酐與具有脂環式構造的四羧酸二酐組合使用爲理想。本發明的液晶配向劑所使用的四羧酸二酐成分，具有脂式構造之四羧酸二酐的理想比率爲2 0〜1 0 〇莫耳％，更理想爲5 0〜1 00莫耳％。增加具有脂環式四羧酸二酐的比率，可得到更良好的光配向性，得到高電壓保持性。本發明的液晶配向劑所使用的一般式（1 ) R2 R1 R10 r9(Wherein R11 to R14 are each an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms) ° R11 to R14 in the above formula are each an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable. Specifically, 1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1 ′ 2-dimethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, and 1,3-dimethylformate are used. The group ρ 2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl ― i, 2,3,4 monocyclobutanetetracarboxylic acid dianhydride is desirable, and more preferably 1 , 2, 3, 4 monocyclobutane tetracarboxylic dianhydride. The tetracarboxylic dianhydride component used in the liquid crystal alignment agent of the present invention may be a combination of a tetracarboxylic dianhydride having the above-mentioned alicyclic structure and another tetracarboxylic dianhydride. Other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides having an alicyclic structure such as bicyclo [3,3, 〇] octane-2'4,6,8-tetracarboxylic dianhydride, 1,2,3 '4-butanetetracarboxylic dianhydride, aliphatic tetracontinic acid dianhydride, pyromellitic dianhydride, 3,3 /, 4,4〃 monobiphenyltetracarboxylic dianhydride , 2, 2 /, 3, 3 / --biphenyltetracarboxylic dianhydride, 2,3,3,4, --biphenyltetracarboxylic dianhydride, 3,3 ^, 4,4'-diphenyl Methyl ketone tetracarboxylic dianhydride, 2,3,3 /, f-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxybenzene) ether dianhydride, bis (3,4-dicarboxybenzene) Dianhydride: 1,1,2,5,6-benzenetetracarboxylic dianhydride 2,3,6,7-benzenetetracarboxylic acid di-12- 200532005 (8) anhydride, 1,4,5, S-benzenetetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as carboxylic dianhydrides are not limited thereto. These tetracarboxylic dianhydrides can be used in combination of several types, and tetracarboxylic dianhydrides having an alicyclic structure can be used. Among these other tetracarboxylic dianhydrides, pyromellitic dianhydride, 3,3 /, 4,4 / monobenzophenonetetracarboxylic dianhydride, 1,4,5,8-benzenetetracarboxylic acid The dianhydride voltage retention rate tends to decrease, the liquid crystal has excellent alignment, and has the effects of less stored charge. Therefore, when it is important to reduce the storage charge, it is desirable to use these tetracarboxylic dianhydrides in combination with a tetracarboxylic dianhydride having an alicyclic structure. The tetracarboxylic dianhydride component used in the liquid crystal alignment agent of the present invention has an ideal ratio of tetracarboxylic dianhydride having a fatty structure of 20 to 100 mole%, and more preferably 50 to 100 mole. %. Increasing the ratio of the alicyclic tetracarboxylic dianhydride can provide better photo-alignment and high voltage retention. General formula (1) used in the liquid crystal alignment agent of the present invention R2 R1 R10 r9

(1) 一級胺基以外之一價有機基，各自爲相同或相異均可）。所示的二胺的具體例，可列舉如式（3 )所示不同的苯環各自附有一級胺基的二胺，(1) Monovalent organic groups other than the primary amine group, each may be the same or different). Specific examples of the diamine shown include diamines each having a primary amine group attached to a different benzene ring represented by formula (3).

•N• N

H2N^~~\ /==yNH2 (3) 200532005 (9) 與式（4 )所示同一的苯環具有2個一級胺基的二胺H2N ^ ~~ \ / == yNH2 (3) 200532005 (9) Diamine having two primary amine groups in the same benzene ring as shown in formula (4)

又，此等二胺的苯環上之氫原子爲一級胺基以外的一價有機基所取代亦可。該一價基，可列舉如碳酸1〜2 0的 φ 烷基或鏈烯基、環烷基、苯基、聯苯基、叔苯基、氟原子，或此等之組合所成的基。此等一般式（1 )所不的一胺中，由於四羧酸二酐的反應性及成爲配向膜時的液晶配向性觀點以4，4 / 一二胺基二苯基胺、2，4 一二胺基二苯基胺爲理想，最理想爲4，4 -二胺基一苯基胺。本發明的液晶配向劑所使用的二胺成分，必要爲含一般式（1 )所示之二胺，可與其他之二胺組合使用。可與一般式（1 )所示二胺組合的二胺無特別的限制，可列舉 φ 具體例如下。脂環式二胺的例，可舉1，4 —二胺環己烷、：I，3—二胺環己烷、4，4 / _二胺二環己基甲烷，4， f —二胺基一 3，3 / —二甲基環己基胺、及異富爾酮二胺等，又，碳環式芳香族二胺的例，可舉如〇 -苯二胺、 m —苯二胺、p -苯二胺、二胺基甲苯類（例如，2，4 一一月女基甲本）、1’ 4一一胺基—2—甲氧基苯、2，5— 一· 胺基二甲苯類，1，3-二胺基—4 一氯苯、1，4 —二胺基 —2，5—二氯苯、1，3-二胺基—4 —異丙基苯，4，I 一二胺基基一 2，-丙烷，4，I —二胺二苯甲烷、2 -14- 200532005 (10) ，2 / —二胺基芪、4，4 / 一二胺基芪、4，f —二胺基二苯醚、4，4，一二苯硫醚、4，4 / 一二胺基二苯硕、3 ，3 / —二胺基二苯硕、4，4 ——二胺基苯甲酸苯酯、2, 2一 —二胺基二苯甲酮、4，4 ——二胺基苄、雙（4 —胺苯基）膦氧化物、雙（3 -胺基）甲基亞磺基氧化物（ methyl sulfine oxide)、雙（4 —胺基）苯膦氧化物、雙 (4 一胺基）環己基膦氧化物、N，N / —雙（胺苯基）-N ^ —苯胺、N，N -雙（胺苯基）一 N —甲胺、4，4 —二胺基二苯尿素、1，8—二胺基萘、1，5—二胺基萘、二胺基蒽醌、二胺基芴、雙（4 一胺苯基）二乙基矽烷、雙（4 一胺苯基）二甲基矽烷、雙（4 一胺苯基）四甲基二矽氧烷、3，4] 一二苯醚、聯苯胺、2，2 / —二甲基聯苯胺、2 ，2—雙[4 一十4一胺苯氧基]苯基]丙烷、雙[4 一（4 一胺苯氧基）苯基]硕、4，4 / 一雙（4 一胺苯氧基）聯苯、2 ，2—雙[4— (4 一胺苯氧基）苯六氟丙烷、1，4 —雙（4 φ —胺苯氧基）苯、1，3-雙（4 —胺苯氧基）苯等。又，雜環式二胺，可列舉如2，6 -二胺基吡啶、2， 4 —二胺基吡啶、2，4 —二胺基—s —三嗪、2，7 —二胺基苯并呋喃、2，7-二胺基咔唑、3，7-二胺基吩噻嗪、2 ，5 —二胺基—1，3，4 —噻二唑、2，4一二胺基—6-苯基- s —三嗪等，脂肪族二胺之例，可列6如二胺基甲烷、1，2 —二胺基乙烷、1，3 -二胺基丙烷、1，4 —二胺基丁烷、1，6 —二胺基己烷、1，7 —二胺基庚烷、1，8 —二胺基辛烷、1，9 一二胺基壬烷、1，1 0 -二胺基癸烷、1， -15- 200532005 (11) 3 —二胺基—2，2—二甲基丙烷、丨，4一二胺基—2, 2一二甲基丁烷、1，6—二胺基一 2，5 —二甲基己烷、〗，7 — 二胺基一2，5—二甲基庚烷、；[，7 —二胺基_4，4 一二甲基庚火兀、1，7 - 一*fe:基—3-甲基庚院、1，9 一二胺其—3 一甲基壬烷、2，11 一二胺基十二碳烷、；[，12 一二胺基十八碳烷、1，2 -雙（3 一胺基丙氧基）乙烷等。The hydrogen atom on the benzene ring of these diamines may be substituted by a monovalent organic group other than the primary amine group. Examples of the monovalent group include a φ alkyl group or alkenyl group of 1 to 20 carbonic acid, a cycloalkyl group, a phenyl group, a biphenyl group, a tertiary phenyl group, a fluorine atom, or a combination thereof. Among these monoamines not represented by the general formula (1), the viewpoint of the reactivity of the tetracarboxylic dianhydride and the orientation of the liquid crystal when it becomes an alignment film is 4,4 / monodiaminodiphenylamine, 2,4 Monodiaminodiphenylamine is preferred, and 4,4-diaminomonophenylamine is most preferred. The diamine component used in the liquid crystal alignment agent of the present invention must contain a diamine represented by the general formula (1), and can be used in combination with other diamines. The diamine that can be combined with the diamine represented by the general formula (1) is not particularly limited, and examples of φ include the following. Examples of the alicyclic diamine include 1,4-diamine cyclohexane, 1,3-diamine cyclohexane, 4,4 / _diamine dicyclohexylmethane, and 4, f-diamine group. Examples of 3,3 / -dimethylcyclohexylamine, isofulrone diamine, and the like, and examples of carbocyclic aromatic diamines include o-phenylenediamine, m-phenylenediamine, p -Phenylenediamine, diaminotoluenes (for example, 2,4 yamidine), 1 '4-monoamino-2-methoxybenzene, 2,5-monoaminoxylene Class, 1,3-diamino-4 monochlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,3-diamino-4, cumene, 4, I a Diamino-2, -propane, 4, I-diaminediphenylmethane, 2 -14-200532005 (10), 2 / -diaminostilbene, 4,4 / -diaminostilbene, 4, f —Diaminodiphenyl ether, 4,4,1-diphenyl sulfide, 4,4 / monodiaminodiphenyl master, 3,3 / —diaminodiphenyl master, 4, 4 —diamine Benzyl benzoate, 2, 2-diaminobenzophenone, 4, 4-diaminobenzyl, bis (4-aminophenyl) phosphine oxide, bis (3-amino) methylimine Sulfoxy (Methyl sulfine oxide), bis (4-amino) phenylphosphine oxide, bis (4-amino) cyclohexylphosphine oxide, N, N /-bis (aminephenyl) -N ^ -aniline, N , N-bis (aminophenyl) -N-methylamine, 4,4-diaminodiphenylurea, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, diaminoanthraquinone, Diaminophosphonium, bis (4-monoaminophenyl) diethylsilane, bis (4-monoaminophenyl) dimethylsilane, bis (4-monoaminophenyl) tetramethyldisilazane, 3,4 ] Diphenyl ether, benzidine, 2, 2 /-dimethyl benzidine, 2, 2-bis [4 ten fourteen monoamine phenoxy] phenyl] propane, bis [4 one (4 monoamine benzene (Oxy) phenyl], 4,4 / mono-bis (4- monoaminophenoxy) biphenyl, 2,2-bis [4- (4-monoaminophenoxy) phenylhexafluoropropane, 1, 4- — Bis (4-φ-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, etc. Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-s-triazine, and 2,7-diaminobenzene Benzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino 6-phenyl-s-triazine and the like, examples of aliphatic diamines, such as diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4 --- Diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,1 0 -Diaminodecane, 1, -15- 200532005 (11) 3-diamino-2,2-dimethylpropane, 丨, 4-diamino-2, 2-dimethylbutane, 1 , 6-diamino-2,5-dimethylhexane, 7-diamino-2,5-dimethylheptane, [, 7-diamino-4,4-dimethylamine Ketoheptene, 1,7-a * fe: yl-3-methylheptane, 1,9-diamine and its 3-methylnonane, 2,11-diaminododecane, [, 12-diaminooctadecane, 1,2- (3-amino-propoxy) ethane.

可與一般式（〗）所示之二胺組合使用之二胺之中，依光定向性的觀點，以〇 —苯二胺、m —苯=胺、p 一苯二胺與二胺基甲苯類（例如2，4 —二胺基甲苯）、1，4 — 二胺基一 2 —甲氧基苯、2，5 —二胺基二甲苯類等之苯二胺衍生物爲理想’最理想者爲p —苯二胺。爲得到良好的光定向性使用P—苯二胺時，理想的比率爲1〇莫耳％以上，更理想爲3 0莫耳％以上。又’爲提局液晶的預傾角（p r e t i 11 )的目的，亦可於上述二胺可倂用結合已知可提高長鏈烷基、全氟烷基、類固醇骨幹基等之傾斜角效果的有機基。其具體的例可列舉如’ πι —本一 fee的本5我介由酸鍵結合具有長鍵院基構造的1，3—二胺基一 4 一十二碳烷氧基苯等。本發明的液晶配向劑所利用的二胺成分，爲得到高電壓保持率，一般式（1 )所示之二胺的理想比率爲〗〇〜 1〇〇莫耳％，更理想爲30〜100莫耳％。本發明的液晶配向劑所利用的四羧酸二酐成分與二胺成分，於有機溶劑中混合時可反應成爲聚醯胺酸，由該聚醯胺酸的脫水閉環可成爲聚醯亞胺。 -16- 200532005 (12) 將四羧酸二酐成分與二胺成於有機溶劑中混合的方法，可列舉將以有機溶劑分散或溶解二胺成分的溶液攪拌，將四羧酸二酐原樣，或於有機溶劑分散或溶解添加的方法 ’反之於有機溶劑分散或溶解的四羧酸二酐成分的溶液添加二胺成分的方法，將四羧酸二酐成分與二胺成分交互添加的的方法，於本發明此等的任一方法均可。又，四羧酸二酐成分或二胺成分爲由數種化合物所成時，此等數種的 φ 成分預先混合的狀態反應亦可，個順序反應亦可。將四羧酸二酐成分與二胺成分於有機溶劑中反應時的溫度，通常爲0〜1 5 0 °c，理想爲5〜1 0 0 °c，更理想爲1 〇〜8 0 °C。溫度高聚合反應較快結束，過高時有不能得到高分子量的聚合物的情形。又，反應可於任意的濃度進行，濃度過低時難於得到高分子量的聚合物，濃度過高時反應液黏性變爲過高均勻的攪拌變爲困難，理想爲1〜5 0重量 %，更理想爲5〜3 0重量％。反應初期於高濃度進行，爾 φ 後，追加有機溶劑亦沒關係。上述反應所使用的有機溶劑，可溶解生成之聚醯胺酸者無特別的限制，具體例可列舉如N，N _二甲基甲醯胺、Ν’ N —二甲基乙醯胺、N —甲基一2—卩比咯院酮、N —甲基己內醯胺、二甲基亞硕、四甲基尿素、吡啶、二甲基硕、六甲基亞硕、7 — 丁內酯等。此等可單獨，或混合使用均可。又，其爲不能溶解聚醯胺酸的溶劑時，在不析出生成之聚醯胺酸的範圍，混合於上述溶劑使用亦可。因有機溶劑中的水分阻碍聚合反應，又成爲生成之聚醯胺酸水解 •17- 200532005 (13) 的原因，有機溶劑儘量使用脫水乾燥者爲理想ό 於聚醯胺酸聚合反應所使用的四羧酸二酐成分與二胺成分之比率，其莫耳比以1 : 0 · 8〜1 : 1 .2者爲理想。與通常的聚縮合反應同樣，其莫耳比以越接近1 : 1所得的聚醯胺酸的分子量變大。聚醯胺酸的分子量，過小時由其所得塗膜的強度有成爲不充分的情形，反之聚醯胺酸的分子量過大時，由其所製造的液量配向劑的黏度變爲過高， φ 塗膜形成時的作業性、塗膜的均勻性有變差的情形。因此，本發明的液晶配向劑所使用的聚醯胺酸以GPC所測定的重量平均分子量（聚乙二醇、聚環氧乙烷換算）以 2000〜.250000爲理想，更理想爲4000〜200000。如上述所得的聚醯胺酸，原樣於本發明的液晶配向劑亦沒關係，脫水閉環成爲聚醯亞胺再使用亦可。但是，依聚醯胺酸的構造，因醯亞胺化而不溶化，使用於液晶配向劑有困難的情形。此時醯胺酸中之醯胺酸基不完全醯亞胺 φ 化，爲保持適度溶解性範圍之醯亞胺化者亦無妨。將聚醯胺酸脫水閉環之醯亞胺化，係將聚醯胺酸的溶液原樣加熱之熱醯胺化，一般爲於聚醯胺酸的溶液添加觸媒的化學醯亞胺化。其中，於比較低溫進行醯亞胺化反應的化學醯亞胺化者，所得的聚亞胺的分子量不易引起分子量降低爲理想。化學的醯胺化，係將聚醯胺酸於有機溶劑中，於鹼性觸媒與酸酐的存在下由攪拌進行。此的反應溫度爲-20〜 2 5 0 °C，理想爲0〜1 8 0 t，反應時間可於1〜1 〇〇小時進 - 18- 200532005 (14) 行。鹼性觸媒的量爲醯胺酸基的0.5〜3 0莫耳倍。，埋下爲2〜2 0莫耳倍，酸酐的量爲醯胺酸的1〜5 0莫耳倍，理想爲3〜3 0莫耳倍。鹼性觸媒或酸酐的量少時反應不能充分進行，又過多時反應結束後完全去除有困難。此時使用的鹼性觸媒可列舉如吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等，其中亦以吡啶在反應進行時可保持適度的鹼性爲理想。又，酸酐可列舉如醋酸酐、偏苯三酸、均 g 苯四甲酸酐等。其中亦以使用醋酸酐時反應結束後的純化容易爲理想。有機溶劑可使用上述聚醯胺酸合成時使用的溶劑。由化學的醯胺化的醯亞胺化率，可由調節觸媒量與反應溫度、反應時間而控制。如此所得的聚醯亞胺化溶液，添加之觸媒殘留於溶液內，爲使用於本發明的液晶配向劑，將聚醯亞胺溶液投入攪拌中的貧溶劑，沈澱回收聚醯亞胺爲理想。於聚醯亞胺的沈澱回收使用的貧溶劑無特別的限制，可例示如甲醇、 φ 丙酮、己烷、丁基溶纖素、庚烷、甲乙基酮、甲異丁酮、乙醇、甲苯、苯等。由投入於貧溶劑所沈澱的聚醯亞胺經過濾·洗淨回收後，於常壓或減壓下，常溫或加熱乾燥可成爲粉體。將該粉體更以良溶劑溶解，再沈澱的操作重複 2〜1 0次時，可純化聚醯亞胺。一次的沈澱回收操作不能去除雜質時，以進行此純化步驟爲理想。此時的貧溶劑例如使用醇類、酮類、烴等三種以上貧溶劑時，更可提高純化的效率爲理想。 . 又，聚醯胺酸亦可由相同的操作回收及純化。於本發 -19- 200532005 (15) 明的液晶配向劑中不欲含有於聚醯胺酸的聚合所使用的溶劑’或於反應溶液中存在未反應的單體或雜質時，進行該沈丨殿回收及純化即可。本發明的液晶配向劑，係至少含有如以上所得的具有特定構造之醯胺酸或將該醯胺酸脫水閉環之聚醯亞胺之一方者’通常係採取將此等之樹脂溶解於有機溶劑之樹脂溶液的構成。作爲樹脂溶液，可原樣使用聚醯胺酸或聚醯亞 φ 胺的反應溶液亦可，由反應液回收之沈澱於有機溶劑再溶解者亦可。該有機溶劑爲，可溶解所含有之樹脂成分者無特別的限制，特舉具體例如N，N—二甲基甲醯胺、N，N—二甲基乙醯胺、N —甲基一2 —吡咯院酮，、N —甲基一己內醯胺、2 —吡咯烷酮、N —乙基吡咯烷酮、N —乙烯基吡咯烷酮、二甲基亞硕、四甲基尿素、吡啶、二甲基砸、六甲基亞硕、7 -丁內酯等。此等使用1種類或數種類混合均可。 φ 又，單獨時爲不溶解樹脂成分的溶劑時，在樹脂成分不析出的範圍者，可混合於本發明的液晶配向劑。特別是，適度的混合乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙基卡必醇醋酸酯、乙二醇、1 一甲氧基一 2 -丙醇、1—乙氧基一 2 -丙醇、1 一丁氧基一 2 一丙醇、1_ 苯氧基一 2—丙醇、丙二醇單醋酸酯、丙二醇二醋酸酯、丙二醇一 1 一單甲基醚一2 —醋酸酯 '丙二醇一 1 一單乙基醚一 2 —醋酸酯、二丙二醇、2— (2—乙氧基丙氧基）丙醇、乳酸甲醋、乳酸乙酯、乳酸η -丙酯、乳酸η —丁酯 -20- 200532005 (16) 、乳酸異戊酯等的具有低表面張力的基板塗敷時的塗膜均勻性，可適合使向劑。本發明液晶配向劑的固體成分濃晶配合膜的厚度之設定適當的變更，理想。未達1重量％時，形成均勻且，超過1 〇重量％時溶液的保存安定名 I 其他，本發明的液晶配向劑，爲合性，亦可添加矽烷偶合劑，或混合或聚醯亞胺，亦可添加其他的樹脂成如上所得的本發明液晶配方劑，，經乾燥、燒結可成爲塗膜，將該塗電子射線對基板面以一定的方向照射爲液晶配向膜使用。此時，使用的基板爲高透明性基 Φ 可使用玻璃基板、丙烯酸基板或聚碳板。爲驅動液晶使用被形成ITO電極便化觀點爲理想。又，基板僅爲單側元件者可使用矽晶片等的不透明物，等的光反射材料。液晶配向劑的敷方法，可列舉如、噴墨法等。其中，依生產性面亦廣印刷法，在本發明的液晶配向亦可適液晶配向劑塗敷後的乾燥步驟，溶劑，已知可提高對用於本發明的液晶配度，可依欲形成的液以1〜10重量％者爲無缺陷的塗膜有困難有變差的情形。提高塗膜對基板的密 2種以上的聚醯胺酸分。過濾後，塗敷於基板膜面由偏光紫外線或施以光定向處理，作板者無特別的限制，酸酯基板等的塑膠基等的基板依製程的簡的反射型的液晶顯示此時的電極可使用鋁旋轉塗敷法、印刷法泛使用工業化之轉印用。並非必要的，塗敷後 -21 - 200532005 (17) 〜燒結爲止的時間依基板爲不一定時，不在塗敷後立即燒結時’以含有乾燥步驟者爲理想。該乾燥爲，依基板的運輸等塗膜形狀不變形的程度將溶劑蒸發爲佳，其乾燥手段無特別的限制。可舉具體例如，可採用5 〇〜1 5 〇〇C，理想爲於8 0〜1 2 0 °C的熱板上乾燥〇 . 5〜3 〇分鐘，理想爲i〜5 分鐘的方法。液晶配向劑的燒結，可於1 〇〇〜3 5 0 °C的任意溫度進行’理想爲1 5 0〜3 0 0。(：，更理想爲2 0 0〜2 5 0。(：。液晶配向劑中含有聚醯胺酸時，由聚醯胺酸至聚醯亞胺依該燒結溫度其轉化率有變化，本發明的液晶配向劑，無必要爲 1 〇〇 %的醯亞胺化。但是，必要液晶胞的製造步驟，以比封裝劑等的處理溫度高1 0 °c以上的溫度燒結爲理想。燒結後的塗膜厚度，過厚時不利於液晶顯示元件的消費電力，過薄時液晶顯示元件的信頼性有下降的情形，理想爲 1 0 〜1 0 0 n m 〇如上述所得的聚醯亞胺膜，相對於基板由一定的方向介以偏光板照射被偏光的紫外線。使用的紫外線的波長，一般可使用1 〇〇 n m〜4 0 0 n m範圍的紫外線，特別依使用之聚醯亞胺的種類介由濾波器選擇最適當的波長爲理想。又，紫外線的照射時間一般由數秒至數小時的範圍，考慮工業的生產性，或由照射量的增大可能引起電壓保持率的下降時，依使用的聚醯亞胺的種類選擇得到良好配向性的必要量爲理想。本發明的液晶配向元件’由上述的手法由液晶配向劑 -22- 200532005 (18) 得到具液晶配向膜的基板後，以公知的方法製作液晶胞，成爲液晶顯示元件。舉一液晶胞的製作例，將一對形成液晶配向膜的基板，挾1〜3 0 // m，理想爲2〜1 0 // m的隔片，由光照射將配向方向配置成爲0〜270°的任意角度將周圍以封裝劑固定，一般爲將液晶注入後封閉。有關液晶注入的方法無特別的限制，可例示如，將製作之液晶胞內減壓後將液晶注入的真空法，將液晶滴下後進行封閉的滴 • 入法。如此，使用本發明的光定向用液晶配向劑製作之液晶元件，由於具有優電特性，信頼性高，可作爲不易引起顯示不均或封閉材邊的滲出產生斑點的顯示裝置。其中，可使用於TN元件、STN元件、TFT液晶元件，v又亦適用於由使用水平電場型的液晶顯示元件、垂直配向性的液晶配向型的液晶顯示元件等的向列液晶之種種方式的顯示元件。又，由選擇使用之液晶’可使用於強介電性及反強介電 φ 性的液晶顯示元件。【實施方式】以下以實施例更詳細說明本發明’本發明不限於實施例。本實施例所使用簡略符號說明如下。 (四羧酸二酐） C B D A : 1，2，3，4 一環院四殘酸二酐 -23- 200532005 (19) 1，3 — DM — CBDA: 1，3 —二甲基—1，2，3，4 —環烷四羧酸二酐 (二胺） 4，- PADPA: 4，4^ —二胺基二苯胺 p— PDA: p —苯二胺 DDE : 4，4 / 一二胺基二苯胺 (有機溶劑） NMP : N —甲基一 2 —吡咯烷酮 BCS : 丁基溶纖素Among the diamines that can be used in combination with the diamines represented by the general formula (), from the viewpoint of photo-directivity, 0-phenylenediamine, m-benzene = amine, p-phenylenediamine and diaminotoluene Benzene diamine derivatives (such as 2,4-diaminotoluene), 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene, etc. are ideal and most ideal This is p-phenylenediamine. When P-phenylenediamine is used in order to obtain good photo-directivity, the desirable ratio is 10 mol% or more, and more preferably 30 mol% or more. For the purpose of mentioning the pretilt angle of the liquid crystal (preti 11), the above diamine can also be used in combination with organic materials known to improve the tilt angle effect of long chain alkyl, perfluoroalkyl, steroid backbone, etc. base. Specific examples thereof include, for example, 'πι-Ben-Fee's Ben-I 5 and 1,3-diamino-1,2-dodecylalkoxybenzene, etc., which have a long-bond radical structure through an acid bond. The diamine component used in the liquid crystal alignment agent of the present invention has an ideal ratio of diamine represented by general formula (1) in order to obtain a high voltage holding ratio, and is more preferably 30 to 100 mole%, more preferably 30 to 100. Mole%. The tetracarboxylic dianhydride component and the diamine component used in the liquid crystal alignment agent of the present invention can be reacted to form a polyamic acid when mixed in an organic solvent, and the dehydration ring closure of the polyamino acid can be a polyimide. -16- 200532005 (12) A method of mixing a tetracarboxylic dianhydride component and a diamine in an organic solvent includes agitating a solution in which the diamine component is dispersed or dissolved in an organic solvent, and the tetracarboxylic dianhydride is used as it is. Or a method of adding or dispersing or dissolving in an organic solvent 'Conversely, a method of adding a diamine component to a solution of a tetracarboxylic dianhydride component dispersed or dissolved in an organic solvent, or a method of adding a tetracarboxylic dianhydride component and a diamine component alternately Any of these methods in the present invention may be used. When the tetracarboxylic dianhydride component or the diamine component is made of several kinds of compounds, these φ components may be reacted in a mixed state in advance, or they may be sequentially reacted. The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent is usually 0 to 150 ° C, preferably 5 to 100 ° C, and more preferably 10 to 80 ° C. . When the temperature is high, the polymerization reaction ends quickly, and when the temperature is too high, a polymer having a high molecular weight may not be obtained. In addition, the reaction can be performed at an arbitrary concentration. When the concentration is too low, it is difficult to obtain a polymer of high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high and uniform stirring becomes difficult. Ideally, it is 1 to 50% by weight. More preferably, it is 5 to 30% by weight. The reaction proceeds at a high concentration in the initial stage, and it is not necessary to add an organic solvent after φ. The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the generated polyamidic acid. Specific examples include N, N_dimethylformamide, N'N-dimethylacetamide, N —Methyl-2-pyrimidone, N-methylcaprolactam, dimethylasyl, tetramethylurea, pyridine, dimethylasyl, hexamethylasyl, 7-butyrolactone Wait. These can be used alone or in combination. When it is a solvent that does not dissolve the polyamic acid, it may be used in a mixture with the above-mentioned solvent in a range in which the polyamic acid is not formed. Because the water in the organic solvent hinders the polymerization reaction, and it becomes the hydrolysis of the resulting polyamic acid • 17- 200532005 (13), it is ideal to use dehydration and drying of the organic solvent as much as possible. The molar ratio of the carboxylic dianhydride component to the diamine component is preferably one in the range of 1: 0 · 8 to 1: 1.2. As with the ordinary polycondensation reaction, the molecular weight of the polyamidic acid obtained when the molar ratio is closer to 1: 1 is larger. When the molecular weight of the polyamic acid is too small, the strength of the coating film obtained may be insufficient. On the other hand, when the molecular weight of the polyamic acid is too large, the viscosity of the liquid amount alignment agent produced by the polyamic acid becomes too high, φ The workability at the time of coating film formation and the uniformity of a coating film may worsen. Therefore, the weight average molecular weight (polyethylene glycol, polyethylene oxide conversion) of the polyamic acid used in the liquid crystal alignment agent of the present invention measured by GPC is preferably 2000 to .250000, and more preferably 4,000 to 200,000. . It does not matter if the polyamidic acid obtained as described above is used as it is in the liquid crystal alignment agent of the present invention, and it is also possible to reuse and dehydrate and close the polyamidoimide. However, depending on the structure of the polyamidic acid, it does not dissolve due to the imidization, and it is difficult to use the liquid crystal alignment agent. At this time, the amido group in the amido acid is not completely amidated, and it is not necessary to maintain a moderate solubility range. Polyimide dehydration and ring-closing hydrazine imidization is a thermal hydrazine that heats a solution of polyamic acid as it is. Generally, it is a chemical hydrazine that adds a catalyst to a solution of polyamic acid. Among them, it is preferable that the chemical imidization of the ammonium imidization reaction at a relatively low temperature is not likely to cause a decrease in molecular weight of the obtained polyimine. The chemical amidation is carried out by stirring polyamine in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature is -20 ~ 250 ° C, ideally 0 ~ 180 °. The reaction time can be from 1 ~ 1000 hours-18- 200532005 (14). The amount of the alkaline catalyst is 0.5 to 30 mole times of the amino acid group. It is buried at 2 to 20 mol times, and the amount of anhydride is 1 to 50 mol times of glutamic acid, ideally 3 to 30 mol times. When the amount of the basic catalyst or the acid anhydride is small, the reaction cannot proceed sufficiently, and when the amount is too large, it is difficult to completely remove the reaction after the reaction is completed. Examples of the basic catalyst used at this time include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, it is also preferable that pyridine can maintain a moderate alkalinity while the reaction proceeds. . Examples of the acid anhydride include acetic anhydride, trimellitic acid, and pyromellitic anhydride. Among them, the use of acetic anhydride is also preferred because the purification after the reaction is easy. As the organic solvent, a solvent used in the synthesis of the above-mentioned polyamic acid can be used. The rate of imidization by chemical amidation can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time. In the thus obtained polyimide solution, the added catalyst remains in the solution. In order to use the liquid crystal alignment agent of the present invention, the polyimide solution is thrown into the lean solvent in the stirring, and the polyimide is preferably precipitated and recovered. . The lean solvent used for the precipitation and recovery of polyimide is not particularly limited, and examples thereof include methanol, φ acetone, hexane, butylcellolysin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. . The polyimide precipitated by being poured into a lean solvent can be filtered, washed, and recovered, and can be dried under normal pressure or reduced pressure, and dried at room temperature or by heating to form a powder. When this powder is further dissolved in a good solvent and the operation of reprecipitation is repeated 2 to 10 times, the polyimide can be purified. This purification step is ideal when impurities cannot be removed in a single precipitation recovery operation. In this case, when three or more kinds of lean solvents such as alcohols, ketones, and hydrocarbons are used, the purification efficiency can be further improved. Polyamines can also be recovered and purified by the same operation. The liquid crystal alignment agent described in the present invention-19- 200532005 (15) does not want to be contained in the solvent used for the polymerization of polyamic acid, or when unreacted monomers or impurities are present in the reaction solution, the precipitation is performed. And purification. The liquid crystal alignment agent of the present invention contains at least one of the amino acids having a specific structure obtained as described above, or a polyimide having dehydration and ring closure of the amino acids. Generally, the resin is dissolved in an organic solvent. The composition of the resin solution. As the resin solution, a reaction solution of polyamidic acid or polyamidoφamine may be used as it is, and the precipitate recovered from the reaction solution may be re-dissolved in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the contained resin components. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2. --Pyrrolidinone, N-methyl-caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylaso, tetramethylurea, pyridine, dimethylpyridine, six Methylasyl, 7-butyrolactone, etc. These may be used singly or in combination. φ In the case where the solvent alone does not dissolve the resin component, the liquid crystal alignment agent of the present invention can be mixed in a range where the resin component does not precipitate. In particular, moderately mixed ethylcellulose, butylcellosolvin, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol 1-ethoxy-2-propanol, 1-butoxy-2 propanol, 1-phenoxy-2 propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol 1-monomethyl Ether-2 — Acetate 'propylene glycol — 1 — Monoethyl ether — 2 — Acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, lactic acid η- The uniformity of the coating film when coating a substrate having a low surface tension, such as propyl ester, η-butyl lactate-20-200532005 (16), isoamyl lactate, and the like, can be suitably used as an agent. The thickness of the solid-state concentrated crystal compounding film of the liquid crystal alignment agent of the present invention is appropriately changed, which is desirable. When it is less than 1% by weight, the solution is formed uniformly and when it exceeds 10% by weight, the storage stability of the solution is I. Others, the liquid crystal alignment agent of the present invention is synthetic, and a silane coupling agent may be added, or mixed or polyimide. Alternatively, other resins can be added to form the liquid crystal formulation of the present invention obtained as above. After drying and sintering, a coating film can be formed. The coated electron beam is irradiated to the substrate surface in a certain direction and used as a liquid crystal alignment film. In this case, the substrate used is a highly transparent substrate. Φ A glass substrate, an acrylic substrate, or a polycarbonate plate can be used. It is desirable to use an ITO electrode formed for driving the liquid crystal, which is convenient. In addition, if the substrate is a single-sided device, an opaque material such as a silicon wafer or the like can be used as a light reflecting material. Methods for applying the liquid crystal alignment agent include, for example, the inkjet method. Among them, in accordance with the productivity method, the liquid crystal alignment of the present invention can also be adapted to the drying step after the application of the liquid crystal alignment agent. The solvent is known to increase the degree of alignment of the liquid crystal used in the present invention and can be formed as desired. If the amount of the liquid is 1 to 10% by weight, the coating film is non-defective, and it may be difficult or deteriorated. Two or more kinds of polyamines are used to increase the density of the coating film to the substrate. After filtering, the substrate film is coated with polarized ultraviolet rays or subjected to light directional treatment. There is no particular limitation on the platers. Plastic-based substrates such as acid ester substrates and other substrates can be used in simple reflective liquid crystal displays. The aluminum spin coating method and printing method are widely used for industrial transfer. It is not necessary. The time after coating -21-200532005 (17) to sintering depends on the substrate, and it is not necessary to sinter immediately after coating. It is desirable to include a drying step. This drying is preferably carried out by evaporating the solvent to such an extent that the shape of the coating film does not deform such as during transportation of the substrate, and the drying means is not particularly limited. Specifically, for example, a method of 50 to 150 ° C, ideally, drying on a hot plate at 80 to 120 ° C, 0.5 to 300 minutes, and ideally i to 5 minutes can be used. The sintering of the liquid crystal alignment agent can be performed at an arbitrary temperature of 100 to 350 ° C ', and is preferably 150 to 300. (:, More preferably from 200 to 250. (:. When the liquid crystal alignment agent contains polyamic acid, the conversion rate from polyamic acid to polyimide varies according to the sintering temperature. The present invention The liquid crystal alignment agent does not need to be 100% fluorinated. However, it is necessary to sinter the liquid crystal cell at a temperature higher than the processing temperature of the encapsulant by more than 10 ° c. The sintered If the thickness of the coating film is too thick, it is not conducive to the power consumption of the liquid crystal display element. If the thickness of the coating film is too thin, the reliability of the liquid crystal display element may be reduced. The thickness is preferably 10 to 100 nm. The polyimide film obtained as described above, With respect to the substrate, the polarized ultraviolet rays are irradiated through a polarizing plate through a certain direction. The wavelength of the ultraviolet rays used can generally be ultraviolet rays in the range of 100 nm to 400 nm, and is particularly dependent on the type of polyimide used. It is ideal to select the most suitable wavelength by a filter. In addition, the irradiation time of ultraviolet rays generally ranges from a few seconds to several hours. When industrial productivity is considered, or when the voltage holding rate may decrease due to an increase in irradiation amount, use it according to the application. of The type of fluorene imine is preferably selected as necessary to obtain good alignment. The liquid crystal alignment element of the present invention 'from the liquid crystal alignment agent by the above-mentioned method-22- 200532005 (18) After a substrate having a liquid crystal alignment film is obtained, The method is to make a liquid crystal cell into a liquid crystal display element. As an example of the production of a liquid crystal cell, a pair of substrates forming a liquid crystal alignment film is 挟 1 ~ 3 0 // m, ideally a spacer of 2 ~ 1 0 // m, The alignment direction is arranged at an arbitrary angle of 0 to 270 ° by light irradiation, and the surroundings are fixed with a sealing agent. Generally, the liquid crystal is sealed after being injected. There is no particular limitation on the method of liquid crystal injection. For example, the produced liquid crystal cells are intracellularly The vacuum method of injecting liquid crystals after depressurizing, and dropping the liquid crystals, and the closed dripping method. In this way, the liquid crystal element produced by using the liquid crystal alignment agent for photo-alignment of the present invention has excellent electrical characteristics, high reliability, and can be used. As a display device that does not easily cause uneven display or exudation on the side of the sealing material, it can be used for TN elements, STN elements, TFT liquid crystal elements, and v is also suitable for using water. Various types of nematic liquid crystal display devices, such as a flat electric field liquid crystal display device and a vertical alignment liquid crystal alignment liquid crystal display device. In addition, the liquid crystal used can be used for strong dielectric properties and anti-ferroelectricity. An electric φ liquid crystal display element. [Embodiment] The following describes the present invention in more detail with examples. The present invention is not limited to the examples. The abbreviations used in this example are described below. (Tetracarboxylic dianhydride) CBDA: 1, 2,3,4 Tetra-Residual Acid Dianhydride-23- 200532005 (19) 1,3 — DM — CBDA: 1,3 —dimethyl —1,2,3,4 —naphthenic tetracarboxylic dianhydride (Diamine) 4,-PADPA: 4,4 ^ —diaminodiphenylamine p — PDA: p —phenylenediamine DDE: 4,4 / monodiaminodiphenylamine (organic solvent) NMP: N —methyl One 2-Pyrrolidone BCS: Butyl Fibrinolysin

(合成例 1 ) CBDA/ 4，4 / 一 PADPA 將四羧酸二酐成分的CBDA 19.61 g ( 〇.〗mol )、二胺成分的 4，一 DADPA 19.13 g (0.096 mol)於 348.6 φ g的Ν Μ P中混合，於室溫反應5小時得到聚醯胺酸溶液a 。聚合反應容易且均勻的進行，所得的聚醯胺酸的重量平均分子量以GPC — 101 (日本Shodex製）測定的結果，爲 50000 (聚乙二醇、聚環氧乙烷換算）。更將該溶液添加 NMP與BCS使其成爲聚醯胺酸4重量％、NMP76重量％、BCS20重量％，得到本發明的液晶配向劑。 (合成例 2) CBDA/4，DADPA、CBDA/p - PDA 將四羧酸二酐成分的CBDA 19.61 g(0.1 mol)、二 -24- 200532005 (20) 胺成分的 P— PDA 10.38 g( 0.096 mol)於 269.9 g 的 NMP中混合，聚合反應容易且均勻的進行，於室溫反應5 小時得到聚醯胺酸溶液B。所得的聚醯胺酸與合成例1同樣測定的結果，爲47000。將合成例1所得的聚醯胺酸與合成例2所得的聚醯胺酸以1 : 1的固體成分比混合，得到均勻的溶液。更將該溶液添加NMP與BCS使其成爲聚醯胺酸4重量％、NMP76重量％、BCS20重量％，得到 φ 本發明的液晶配向劑。(Synthesis Example 1) CBDA / 4,4 / mono PADPA The tetracarboxylic dianhydride component of CBDA 19.61 g (〇.〗 Mol), the diamine component of 4, mono DADPA 19.13 g (0.096 mol) was 348.6 φ g NM was mixed and reacted at room temperature for 5 hours to obtain a polyamine solution a. The polymerization reaction proceeded easily and uniformly. The weight average molecular weight of the obtained polyamic acid was measured by GPC-101 (manufactured by Shodex, Japan), and was 50,000 (equivalent to polyethylene glycol and polyethylene oxide). Furthermore, NMP and BCS were added to the solution to make it 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention. (Synthesis example 2) CBDA / 4, DADPA, CBDA / p-PDA 19.61 g (0.1 mol) of CBDA with tetracarboxylic dianhydride component, di-24-200532005 (20) P-PDA with 10.38 g (0.096) mol) was mixed in 269.9 g of NMP, the polymerization reaction was easy and uniform, and the reaction was performed at room temperature for 5 hours to obtain a polyamidic acid solution B. When the obtained polyamic acid was measured in the same manner as in Synthesis Example 1, it was 47,000. The polyamino acid obtained in Synthesis Example 1 and the polyamino acid obtained in Synthesis Example 2 were mixed at a solid content ratio of 1: 1 to obtain a uniform solution. Furthermore, NMP and BCS were added to the solution to make it 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention.

(比較合成例1) CBDA/p - PDA 將合成例2所得的聚醯胺酸添加NMP與BCS使其成爲聚醯胺酸4重量％、NMP76重量％、BCS20重量％，作爲比較的液晶配向劑。(Comparative Synthesis Example 1) CBDA / p-PDA Polyamic acid obtained in Synthesis Example 2 was added with NMP and BCS to make it 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS. As a comparative liquid crystal alignment agent .

(比較合成例2) CBDA/DDE(Comparative Synthesis Example 2) CBDA / DDE

將四羧酸二酐成分的CBDA 19.41 g (0.099 mol)、二胺成分的 DDE 20.02 g(0.1 mol)於 223.48 g 的 NMP 中混合’聚合反應容易且均勻的進行，於室溫反應5小時得到聚醯胺酸溶液C。所得的聚醯胺酸與合成例1同樣測定的結果，爲65000。添加NMP與BCS使其成爲聚醯胺酸4重量％、NMP76重量％、BCS20重量％，作爲比較的液晶配向劑。 (實施例1 ) -25- 200532005 (21) 將合成例1所得的本發明的液晶配向劑噴鍍於具透明電極玻璃基板，於8(TC的熱板上乾燥5分鐘後，於22〇t 的熱風循環烘箱進行3 0分鐘的燒結，形成1 0 0 nm的塗膜。該該塗膜面介由偏光板照射5 J / c m 2之3 1 3 n ni紫外線，得到具液晶配向膜的基板。爲評價液晶胞的電特性，準備上述具液晶配向膜的基板2片，於其中的一液晶配向膜面上散佈4 // m的隔離片。在其上印刷封裝劑，將另1片基板的液晶配向膜面以面對光配向方向正直的貼合後，將封裝劑硬化製作空晶胞。該空晶胞以減壓注入法，將液晶MLC - 2003 (日本默克 (Japan Merck製）注入，將注入口封閉，得到扭曲向列 (twist pneumatic )液晶胞。將該液晶胞於1 20 °C處理30 分鐘，其後徐冷至室溫進行晶胞的觀察時，配向性良好。電壓保持特性的評價於上述液晶胞在23°C的溫度下附加4V的電壓60 // s ，測定1 6 · 6 7 m s後的電壓，由電壓保持程度計算電壓保持率。又，於9 0 °C溫度下作同樣的測定。其結果，於2 3 °C的電壓保持率爲9 9 · 2 %，於9 0 °c的電壓保持率爲8 6 · 4 %。離子密度的評價於上述液晶胞在2 3 °C的溫度下，使用「液晶胞·離子密度測定系統（2 · 0版）」（臼本（株）東陽技硏（ -26- 200532005 (22)Mixing 19.41 g (0.099 mol) of CBDA with tetracarboxylic dianhydride and 20.02 g (0.1 mol) of DDE with diamine in 223.48 g of NMP. The polymerization reaction is easy and uniform, and the reaction is performed at room temperature for 5 hours to obtain Polyamine solution C. When the obtained polyamic acid was measured in the same manner as in Synthesis Example 1, it was 65,000. NMP and BCS were added to make it 4% by weight of polyamide, 76% by weight of NMP, and 20% by weight of BCS, and used as a comparative liquid crystal alignment agent. (Example 1) -25- 200532005 (21) The liquid crystal alignment agent of the present invention obtained in Synthesis Example 1 was spray-coated on a glass substrate with a transparent electrode, and dried on a hot plate of 8 ° C for 5 minutes, and then at 22 ° The hot-air circulation oven was sintered for 30 minutes to form a 100 nm coating film. The coating film surface was irradiated with 3 J 3 cm 3 ni UV at 5 J / cm 2 through a polarizer to obtain a substrate with a liquid crystal alignment film. In order to evaluate the electrical characteristics of the liquid crystal cell, two substrates with the above-mentioned liquid crystal alignment film were prepared, and a 4 // m spacer was spread on one of the liquid crystal alignment films. A sealant was printed thereon, and the other substrate After the surface of the liquid crystal alignment film is adhered to face the light alignment direction, the encapsulant is hardened to form an empty cell. The empty cell is a liquid crystal MLC-2003 (Japan Merck) manufactured by a reduced pressure injection method. After injection, the injection port was closed to obtain a twisted nematic liquid crystal cell. The liquid crystal cell was treated at 120 ° C for 30 minutes, and then slowly cooled to room temperature to observe the cell, and the alignment was good. Voltage The retention characteristics were evaluated by adding 4V to the liquid crystal cell at a temperature of 23 ° C. Press 60 // s to measure the voltage after 1 6 · 67 ms, and calculate the voltage retention rate from the voltage retention level. The same measurement was performed at a temperature of 90 ° C. As a result, the voltage at 2 3 ° C The retention is 99.2%, and the voltage retention at 90 ° C is 86.4%. Evaluation of Ion Density The above-mentioned liquid crystal cells were measured at a temperature of 23 ° C using a "liquid crystal cell · ion density measurement". System (version 2 · 0) "(Usumoto Co., Ltd. Toyo Techno (-26- 200532005 (22)

Technic)製，於三角波振幅ίον、頻率〇.G1 Hz的條件下測定離子密度。其結果離子密度爲1 10 PC/ cm2。電荷存儲特性的評價於上述液晶胞在2 3 °C的溫度下將直流3 V的電壓重疊 3 0 Hz/ ±3 V的矩形波附加60分鐘，切斷直流3V後立即以光學閃光（Fricker )消去法測定液晶胞內殘留電壓。其結果存儲電何爲0V。 (實施例2 ) 使用合成例2所得本發明的液晶配向劑，與實施例i 同樣進行評價。但是，光照射係介由偏光板進行】j/ cm2 的2 5 4 nm紫外線照射。其結果如後述表1所示。 (比較例1 ) 使用比較合成例1所得的液晶配向劑，與實施例1同樣進行評價。但是，光照射係介由偏光板進行1 j / c m 2 的2 5 4 nm紫外線照射。其結果如後述表1所示。 (比較例2 ) 使用比較合成例2所得的液晶配向劑，與實施例1同樣進行評價。但是，光照射係介由偏光板進行1 j / cm2 的2 5 4 n m糸外線照射。其結果如後述表1所示。 -27- 200532005 (23) [表1] 液晶配向劑配向電壓保持率（％) 離子密度存儲電性 2 3〇C 90°C (pC/cm2) 荷（V) 實施例1 合成例1 良好 99.2 86.4 1 10 0 實施例2 合成例2 良好 98.6 70.6 460 0.1 比較例1 比較合成例1 良好 96.8 43.8 1900 1.8 比較例2 比較合成例2 良好 94.2 33.9 3500 1.2(Technic), the ion density was measured under the conditions of triangular wave amplitude ίον and frequency 0.1 G1 Hz. As a result, the ion density was 1 10 PC / cm2. The evaluation of the charge storage characteristics was based on the above-mentioned liquid crystal cell superimposing a rectangular wave of 3 V DC at a voltage of 30 Hz / ± 3 V for 60 minutes at a temperature of 2 3 ° C, and an optical flash (Fricker) immediately after the DC 3 V was cut off. Elimination method measures the residual voltage in the liquid crystal cell. As a result, the stored voltage is 0V. (Example 2) The liquid crystal alignment agent of the present invention obtained in Synthesis Example 2 was used for evaluation in the same manner as in Example i. However, light irradiation is performed through a polarizing plate] 2 5 4 nm ultraviolet light at j / cm2. The results are shown in Table 1 described later. (Comparative Example 1) Evaluation was performed in the same manner as in Example 1 using the liquid crystal alignment agent obtained in Comparative Synthesis Example 1. However, the light irradiation was performed by 2 5 4 nm ultraviolet rays of 1 j / cm 2 through a polarizing plate. The results are shown in Table 1 described later. (Comparative Example 2) Evaluation was performed in the same manner as in Example 1 using the liquid crystal alignment agent obtained in Comparative Synthesis Example 2. However, the light irradiation was performed by a polarizing plate with a radiation of 2 5 4 n m n at 1 j / cm2. The results are shown in Table 1 described later. -27- 200532005 (23) [Table 1] Alignment voltage retention ratio of liquid crystal alignment agent (%) Ion density storage electrical property 2 30 ° C 90 ° C (pC / cm2) charge (V) Example 1 Synthesis example 1 Good 99.2 86.4 1 10 0 Example 2 Synthesis Example 2 Good 98.6 70.6 460 0.1 Comparative Example 1 Comparative Synthesis Example 1 Good 96.8 43.8 1900 1.8 Comparative Example 2 Comparative Synthesis Example 2 Good 94.2 33.9 3500 1.2

(合成例 3) CBDA/p - PDA(0.7) 、4，一 DADPA( 0.3 ) 將四羧酸二酐成分的CBDA 18.63 g( 0.095 mol)、二胺成分的 p— PDA 7.57 g( 0.07 mol)及 4，4，一 DADPA 5.98 g ( 0.03 mol )於 289.6 g 的 NMP 中混合，於(Synthesis example 3) CBDA / p-PDA (0.7), 4, 1-DADPA (0.3), 18.3 g (0.095 mol) of CBDA tetracarboxylic dianhydride component, p-PDA 7.57 g (0.07 mol) of diamine component And 4,4,1-DADPA 5.98 g (0.03 mol) in 289.6 g of NMP.

室溫反應5小時得到聚醯胺酸溶液D。聚合反應容易且均勻的進行，所得的聚醯胺酸的重量平均分子量以 GPC -101 (日本Shodex製）測定的結果，爲28800 (聚乙二醇、聚環氧乙烷換算）。更將該溶液添加NMP與BCS使其成爲聚醯胺酸6重量％、NMP74重量％、BCS20重量％，得到本發明的液晶配向劑。 (合成例 4) CBDA/p— PDA (0·5) 、4，— DADPA ( 0.5 ) 將四羧酸二酐成分的CBDA 18.63 g( 0.095 mol)、二胺成分的 P— PDA 5.41 g( 0.05 mol)及 4，4 / — -28- 200532005 (24) DADPA 9.96 g(0.〇5 m〇i)於 306.0 g 的 NMP 中混合，於室溫反應5小時得到聚醯胺酸溶液E。聚合反應容易且均勻的進行’所得的聚醯胺酸的重量平均分子量以GP C -101 (日本Shodex製）測定的結果，爲28600 (聚乙二醇、聚環氧乙烷換算）。更將該溶液添加NMP與BCS使其成爲聚醯胺酸6重量％、NMP74重量％、BCS20重量％ ’得到本發明的液晶配向劑。The reaction was performed at room temperature for 5 hours to obtain a polyamine solution D. The polymerization reaction proceeded easily and uniformly. The weight average molecular weight of the obtained polyamic acid was measured by GPC-101 (manufactured by Shodex, Japan) and was 28,800 (polyethylene glycol, polyethylene oxide equivalent). Furthermore, NMP and BCS were added to this solution to make it 6% by weight of polyamic acid, 74% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention. (Synthesis example 4) CBDA / p—PDA (0.5), 4, —DADPA (0.5), tetracarboxylic dianhydride component of CBDA 18.63 g (0.095 mol), and diamine component of P—PDA 5.41 g (0.05 mol) and 4, 4 / — -28- 200532005 (24) DADPA 9.96 g (0. 05 m0i) was mixed in 306.0 g of NMP, and reacted at room temperature for 5 hours to obtain a polyamine solution E. The polymerization reaction was carried out easily and uniformly. The weight average molecular weight of the obtained polyamic acid was measured by GP C-101 (manufactured by Shodex Japan) and was 28600 (polyethylene glycol and polyethylene oxide equivalent). Furthermore, NMP and BCS were added to this solution to make it 6% by weight of polyamic acid, 74% by weight of NMP, and 20% by weight of BCS 'to obtain a liquid crystal alignment agent of the present invention.

(合成例 5) 1，3 - DM— CBDA、CBDA/4，4 "-(Synthesis example 5) 1, 3-DM— CBDA, CBDA / 4, 4 "-

DADPA 將四羧酸二酐成分的1，3DM— CBDA11.21 g(0.05 mol) CBDA 8.82 g( 0.045 mol)、二胺成分的 4，4' 一 DADPA 19.93 g(0.1 mol)於 359·6 g 的 NMP 中混合，於室溫反應5小時得到聚醯胺酸溶液F。聚合反應容易且均勻的進行，所得的聚醯胺酸的重量平均分子量以 GPC -101 (日本Shodex製）測定的結果，爲30300 (聚乙二醇、聚環氧乙烷換算）。更將該溶液添加NMP與BCS使其成爲聚醯胺酸6重量％、NMP74重量％、BCS20重量％，得到本發明的液晶配向劑。DADPA mixes 1,3DM- CBDA with tetracarboxylic dianhydride11.21 g (0.05 mol) CBDA 8.82 g (0.045 mol) and 4,4'-diamine DADPA 19.93 g (0.1 mol) in 359.6 g Mixed with NMP and reacted at room temperature for 5 hours to obtain a polyamine solution F. The polymerization reaction proceeded easily and uniformly. The weight average molecular weight of the obtained polyamic acid was measured by GPC-101 (manufactured by Shodex, Japan) and was 30,300 (polyethylene glycol, polyethylene oxide equivalent). Furthermore, NMP and BCS were added to this solution to make it 6% by weight of polyamic acid, 74% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention.

(合成例 6) 1，3— DM— CBDA、CBDA/p— DPA(Synthesis example 6) 1, 3— DM— CBDA, CBDA / p— DPA

將四羧酸二酐成分的 1，3DM—CBDA 11.21 g ( 0.05 mol) CBDA 9.02 g ( 0.046 mol )、二胺成分的 p — DPA 1 0.8 1 g ( 0· 1 mol )於2 79.4 g的NMP中混合，於室溫反 -29- 200532005 (25) 應5小時得到聚醯胺酸溶液· G。聚合反應容易且均勻的進行，所得的聚醯胺酸的重量平均分子量以GP C - 1 0 1 (日本 Shodex製）測定的結果，爲31300(聚乙二醇、聚環氧乙烷換算）。更將該溶液添加NMP與BCS使其成爲聚醯胺酸6重量％、NMP74重量％、BCS20重量％，得到本發明的液晶配向劑。Tetracarboxylic dianhydride component 1,3DM-CBDA 11.21 g (0.05 mol) CBDA 9.02 g (0.046 mol), diamine component p-DPA 1 0.8 1 g (0.1 mol) to 2 79.4 g of NMP Mix at room temperature and invert -29- 200532005 at room temperature (25) The polyamine solution · G should be obtained in 5 hours. The polymerization reaction was carried out easily and uniformly. The weight average molecular weight of the obtained polyamic acid was measured by GP C-101 (manufactured by Shodex, Japan) and was 3,300 (polyethylene glycol, polyethylene oxide equivalent). Furthermore, NMP and BCS were added to this solution to make it 6% by weight of polyamide, 74% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention.

φ (合成例 7) CBDA/4，4， DADPA、CBDA/DDE 將合成例1所得的聚醯胺酸溶液A與比較合成例2 所得的聚醯胺酸溶液C以1 : 1的固體成分比混合，得到均勻的溶液。更將該溶液添加NMP與BCS使其成爲聚醯胺酸4重量％、NMP76重量％、BCS20重量％，得到本發明的液晶配向劑。 (合成例 7) CBDA/4，DADPA、DDE φ 將四羧酸二酐成分的CBDA 18.63 g(0.095 mol)、二胺成分的 DDE 10.01 g(〇.〇5 m〇l)及 4，— DADPA 9 · 9 6 g ( 0 · 0 5 m ο 1 )於3 4 7.4 g的Ν Μ P中混合，聚合反應容易且均勻的進行，於室溫反應5小時得到聚醯胺酸溶液 Η。所得的聚醯胺酸與合成例1同樣測定的結果，爲 2 8 00 0。添加ΝΜΡ與BCS使其成爲聚醯胺酸6重量％、 ΝΜΡ74重量％、BCS20重量％，作爲比較的液晶配向劑 -30- 200532005 (26)φ (Synthesis Example 7) CBDA / 4, 4, DADPA, CBDA / DDE The polyamic acid solution A obtained in Synthesis Example 1 and the polyamic acid solution C obtained in Comparative Synthesis Example 2 were used at a solid content ratio of 1: 1. Mix to get a homogeneous solution. Furthermore, NMP and BCS were added to this solution to make it 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS to obtain a liquid crystal alignment agent of the present invention. (Synthesis Example 7) CBDA / 4, DADPA, DDE φ The tetracarboxylic dianhydride component of CBDA 18.63 g (0.095 mol), the diamine component DDE 10.01 g (0.05 mol) and 4, — DADPA 9 · 9 6 g (0 · 0 5 m ο 1) was mixed with 3 4 7.4 g of NM P, and the polymerization reaction was easy and uniform, and the reaction was performed at room temperature for 5 hours to obtain a polyamic acid solution. As a result of measurement of the obtained polyamic acid in the same manner as in Synthesis Example 1, it was 2800. Add NMP and BCS to make it 6% by weight of polyamic acid, 74% by weight of NMP, and 20% by weight of BCS, as a comparative liquid crystal alignment agent -30- 200532005 (26)

(比較合成例 3) 1，3 DM— CBDA、CBDA/p—PUA 將合成例6所在溶液G，添加NMP與BCS使其成爲聚醯胺酸6重量％、NMP74重量％、BCS20重量％，作爲比較的液晶配向劑。 (實施例3 ) 使用合成例3所得本發明的液晶配向劑，與實施例1 φ 同樣進行評價。但是，光照射係介由偏光板進行1 J/ cm2 的2 5 4 n m紫外線照射。其結果如後述表2所示。 (實施例4 ) 使用合成例4所得本發明的液晶配向劑，.與實施例1 同樣進行評價。但是，光照射係介由偏光板進行5 j/ cm2 的3 1 3 nm紫外線照射。其結果如後述表2所示。 φ (實施例5 ) 使用合成例5所得本發明的液晶配向劑，與實施例1 同樣進行評價。但是，光照射係介由偏光板進行2.5 j/ c m的3 1 3 n m紫外線照射。其結果如後述表2所示。 (實施例6 ) 使用合成例6所得本發明的液晶配向劑，與實施例1 同樣進行評價。但是，光照射係介由偏光板進行〇 · 5 j / cm**的2 5 4 nm紫外線照射。其結果如後述表2所示。 -31 - 200532005 (27) (實施例7 ) 使用合成例7所得本發明的液晶配向劑，與實施例1 同樣進行評價。但是，光照射係介由偏光板進行5 j/ em2 的3 1 3 nm紫外線照射。其結果如後述表2所示。 (實施例8 ) 使用合成例8所得本發明的液晶配向劑，與實施例1 同樣進彳了評價。但是，光照射係介由偏光板進行1 J/ cm2 的254 nm紫外線照射。其結果如後述表2所示。 (比較例3 ,) 使用比較合成例3所得本發明的液晶配向劑，與實施例】同樣進行評價。但是，光照射係介由偏光板進行〇 . 5 / 的2 5 4 n m糸外線照射。其結果如後述表2所示。 -32- 200532005 (28) 表2 ](Comparative Synthesis Example 3) 1, 3 DM—CBA, CBDA / p-PUA The solution G in Synthesis Example 6 was added with NMP and BCS to make it 6% by weight of polyamic acid, 74% by weight of NMP, and 20% by weight of BCS. Comparative liquid crystal alignment agent. (Example 3) Using the liquid crystal alignment agent of the present invention obtained in Synthesis Example 3, evaluation was performed in the same manner as in Example 1 φ. However, the light irradiation was carried out at a wavelength of 2 5 4 n m at 1 J / cm2 through a polarizing plate. The results are shown in Table 2 described later. (Example 4) Using the liquid crystal alignment agent of the present invention obtained in Synthesis Example 4, the same evaluation as in Example 1 was performed. However, the light irradiation was carried out at 3 1 3 nm with 5 j / cm 2 through a polarizing plate. The results are shown in Table 2 described later. φ (Example 5) Evaluation was performed in the same manner as in Example 1 using the liquid crystal alignment agent of the present invention obtained in Synthesis Example 5. However, the light irradiation was performed by a polarizing plate with 3 1 3 n m ultraviolet radiation of 2.5 j / cm. The results are shown in Table 2 described later. (Example 6) Evaluation was performed in the same manner as in Example 1 using the liquid crystal alignment agent of the present invention obtained in Synthesis Example 6. However, the light irradiation was carried out at a wavelength of 2 5 4 nm of 0.5 j / cm ** through a polarizing plate. The results are shown in Table 2 described later. -31-200532005 (27) (Example 7) The liquid crystal alignment agent of the present invention obtained in Synthesis Example 7 was used for evaluation in the same manner as in Example 1. However, the light irradiation was carried out at 3 1 3 nm with 5 j / em2 through a polarizing plate. The results are shown in Table 2 described later. (Example 8) Evaluation was performed in the same manner as in Example 1 using the liquid crystal alignment agent of the present invention obtained in Synthesis Example 8. However, light irradiation was performed at 1 J / cm2 at 254 nm with ultraviolet light through a polarizing plate. The results are shown in Table 2 described later. (Comparative Example 3) Using the liquid crystal alignment agent of the present invention obtained in Comparative Synthesis Example 3, evaluation was performed in the same manner as in Example. However, the light irradiation was performed by a polarizing plate with 0.5 / 2 5 4 n m 糸 external radiation. The results are shown in Table 2 described later. -32- 200532005 (28) Table 2]

液晶配向劑配向電壓保持率離子密度存儲性 (%) (pC/cm2) 電荷 2 3 °C 9 0°C (V) 實施例 3 合成例 3 良好 98.1 70 • 4 490 0.1 實施例 4 合成例 4 良好 98.2 72.5 400 0.1 實施例 5 合成例 5 良好 98.9 84.1 110 0 實施例 6 合成例 6 良好 98.8 80. ,3 250 0.1 實施例 7 合成例 7 良好 96.5 70. .1 700 0.1 實施例 8 合成例 8 良好 96.5 69. ,8 680 0.1 比較例 3 比較合成例3 良好 97.5 53 . 4 1000 1.7Liquid crystal alignment agent Alignment voltage retention rate Ion density storage (%) (pC / cm2) Charge 2 3 ° C 9 0 ° C (V) Example 3 Synthesis example 3 Good 98.1 70 • 4 490 0.1 Example 4 Synthesis example 4 Good 98.2 72.5 400 0.1 Example 5 Synthesis Example 5 Good 98.9 84.1 110 0 Example 6 Synthesis Example 6 Good 98.8 80., 3 250 0.1 Example 7 Synthesis Example 7 Good 96.5 70. .1 700 0.1 Example 8 Synthesis Example 8 Good 96.5 69., 8 680 0.1 Comparative Example 3 Comparative Synthesis Example 3 Good 97.5 53. 4 1000 1.7

-33--33-

Claims

200532005 (1) 十、申請專利範圍 I 一種光定向用液晶配向劑，其特徵係至少含有一種’由下述式（丨）所示含二胺之二胺成分，與含具有脂環式構造之四羧酸二酐之四羧酸二酐成分，經反應聚合所得之聚醯胺酸；或由該醯胺酸所得之聚醯亞胺200532005 (1) X. Patent application scope I A liquid crystal alignment agent for photo-alignment, characterized in that it contains at least one type of diamine-containing diamine component represented by the following formula (丨), and one containing an alicyclic structure Tetracarboxylic dianhydride, tetracarboxylic dianhydride component, polyfluorinated acid obtained by reaction polymerization; or polyimide obtained from the fluorinated acid

(式中，R1〜R1G中之2個爲一級胺基、其餘爲氫原子或一級胺基以外之一價有機基，各自爲相同或相異均可）。 2 ·如申請專利範圍第1項之光定向用液晶配向劑，其中具有脂環式構造之四羧酸二酐，爲下述式（2)所示之四羧酸二酐(In the formula, two of R1 to R1G are primary amine groups, and the rest are hydrogen atoms or monovalent organic groups other than primary amine groups, and each of them may be the same or different). 2. The liquid crystal alignment agent for photo-alignment according to item 1 of the patent application, wherein the tetracarboxylic dianhydride having an alicyclic structure is a tetracarboxylic dianhydride represented by the following formula (2)

(式中，R11〜R14，各自爲獨立之氫原子或碳數1〜4之烷基）。 3 · —種液晶顯示元件，其特徵爲具有，將申請專利範圍第1或第2項中任一項之光定向用液晶配向劑，經由塗敷於基板的步驟，與對該基板照射偏光紫外線的步驟所形成之液晶配向膜。 -34- 200532005 七無明說單簡號符表為代圖件表元代之定圖指表 :案代圖本本表、、代定一二無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無(Wherein R11 to R14 are each an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms). 3. A liquid crystal display element, comprising: applying a liquid crystal alignment agent for light alignment according to any one of the scope of claims 1 or 2 of a patent application to a substrate through a step of applying polarized ultraviolet rays to the substrate; The liquid crystal alignment film formed in the step. -34- 200532005 Qiwuming said that the single abbreviation symbol table is the definitive drawing reference table of the original drawing table: the case drawing, the table, and the decrement, if there is a chemical formula in this case, please reveal the best display Inventive chemical formula: None