TWI442143B - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Liquid crystal alignment agent and liquid crystal display element Download PDF

Info

Publication number
TWI442143B
TWI442143B TW097105110A TW97105110A TWI442143B TW I442143 B TWI442143 B TW I442143B TW 097105110 A TW097105110 A TW 097105110A TW 97105110 A TW97105110 A TW 97105110A TW I442143 B TWI442143 B TW I442143B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
crystal alignment
alignment agent
polymer
diamine
Prior art date
Application number
TW097105110A
Other languages
Chinese (zh)
Other versions
TW200844606A (en
Inventor
Tsutomu Kumagai
Satoshi Fukuma
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200844606A publication Critical patent/TW200844606A/en
Application granted granted Critical
Publication of TWI442143B publication Critical patent/TWI442143B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

液晶配向劑及液晶顯示元件Liquid crystal alignment agent and liquid crystal display element

本發明涉及液晶配向劑和具有液晶配向膜的液晶顯示元件。更具體地說，涉及能夠製成具有高垂直配向性、且耐熱性優良的液晶配向膜的液晶配向劑和具有由該液晶配向劑形成的液晶配向膜的液晶顯示元件。The present invention relates to a liquid crystal alignment agent and a liquid crystal display element having a liquid crystal alignment film. More specifically, it relates to a liquid crystal alignment agent capable of producing a liquid crystal alignment film having high vertical alignment and excellent heat resistance, and a liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent.

目前，作為液晶顯示元件，已知具有所謂TN(Twisted Nematic：扭轉向列)型液晶胞的TN型液晶顯示元件，其在設置了ITO(氧化銦-氧化錫)等透明導電膜的基板表面上形成由聚醯胺酸、聚醯亞胺等形成的液晶配向膜，作為液晶顯示元件用的基板，將2片該基板相對設置，在其間隙內形成具有正介電各向異性的向列型液晶層，構成夾層結構的晶胞，液晶分子的長軸從一片基板向另一片基板連續地扭轉90度。並且，還開發了與TN型液晶顯示元件相比對比度更高、其視角依賴性更小的STN(Super Twisted Nematic：超扭轉向列)型液晶顯示元件。這種STN型液晶顯示元件將在向列型液晶中摻合了作為光學活性物質的手性劑的液晶作為液晶使用，其利用通過使液晶分子的長軸在基板間處於連續扭轉180度以上幅度的狀態而產生的雙折射效應。At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN (Twisted Nematic) type liquid crystal cell is known, which is provided on a surface of a substrate on which a transparent conductive film such as ITO (indium oxide-tin oxide) is provided. A liquid crystal alignment film formed of polyacrylic acid, polyimine or the like is formed, and as a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic type having positive dielectric anisotropy is formed in the gap. The liquid crystal layer constitutes a unit cell of a sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element having a higher contrast ratio and a smaller viewing angle dependency than a TN type liquid crystal display element has been developed. Such an STN type liquid crystal display element uses a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal as a liquid crystal by using a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. The birefringence effect produced by the state.

並且近年來，提出了一種橫電場型液晶顯示元件，其驅動液晶的2個電極在一側基板上以梳齒狀設置，產生與基板面平行的電場，控製液晶分子。該元件通常被稱作為面內切換型(IPS型)，已知其廣視角性能優異。特別是當將 IPS型元件與光學補償膜併用時，可以使視角性能進一步提高，具有獲得了與無灰階反轉和色調變化的陰極射線管都能相匹敵的廣視角這種顯赫特徵。Further, in recent years, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving liquid crystal are provided in a comb shape on one side substrate, and an electric field parallel to the substrate surface is generated to control liquid crystal molecules. This element is generally referred to as an in-plane switching type (IPS type), and is known to have excellent wide viewing angle performance. Especially when When the IPS type element is used in combination with the optical compensation film, the viewing angle performance can be further improved, and the spectroscopy feature of obtaining a wide viewing angle comparable to that of a cathode ray tube having no gray scale inversion and color tone change can be obtained.

除此以外，還提出了具有負介電各向異性的液晶分子在基板上垂直配向的被稱作為MVA(Multi-Domain Vertical Alignment：多疇垂直配向)型或PVA(Patterned Vertical Alignment：圖案化垂直配向)型的垂直配向型液晶顯示元件(參考專利文獻1和非專利文獻1)。這些垂直配向型液晶顯示元件，不僅視角、對比度等優良，而且在形成液晶配向膜的過程中可以不需要進行打磨處理等，在製程方面也是優良的。In addition, it is also proposed that a liquid crystal molecule having a negative dielectric anisotropy is vertically aligned on a substrate, which is referred to as MVA (Multi-Domain Vertical Alignment) type or PVA (Patterned Vertical Alignment: Patterned Vertical). A vertical alignment type liquid crystal display element of the alignment type (refer to Patent Document 1 and Non-Patent Document 1). These vertical alignment type liquid crystal display elements are excellent not only in viewing angle and contrast, but also in the process of forming a liquid crystal alignment film, and are not required to be polished, and are excellent in process.

然而，在液晶顯示元件的製造過程中，通常為了除去打磨等製程中產生的異物等或者除去在製程中附著的灰塵，要進行用溶劑清洗的製程。作為清洗溶劑，通常使用超純水或異丙醇，清洗時有時採用將刷洗和超音波併用以進一步提高清洗效率的手法。在清洗製程中，通過浸漬於溶劑中等進行清洗之後，要進行溶劑的去除(基板的乾燥)。在乾燥製程中，大多是將通過加熱使溶劑蒸發與通過氣刀使溶劑擴散同時進行。已知在該清洗製程中，液晶配向膜(特別是表面狀態)會受到影響，導致預傾角不均或電學性能不均，當作為液晶顯示元件時，會出現顯示不均或顯示不良的情況。因此，從提高成品良率和顯示品質的角度出發，要求液晶配向膜對清洗製程，特別是清洗溶劑有高度的耐久性。However, in the manufacturing process of the liquid crystal display element, in order to remove foreign matter or the like generated in the process such as polishing or to remove dust adhering to the process, a process of cleaning with a solvent is performed. As the cleaning solvent, ultrapure water or isopropyl alcohol is usually used, and washing and ultrasonic waves are sometimes used for cleaning to further improve the cleaning efficiency. In the cleaning process, after immersion in a solvent or the like, the solvent is removed (drying of the substrate). In the drying process, most of the evaporation of the solvent by heating and the diffusion of the solvent by the air knife are simultaneously performed. It is known that in the cleaning process, the liquid crystal alignment film (especially in the surface state) is affected, resulting in uneven pretilt angle or uneven electrical properties, and when it is used as a liquid crystal display element, display unevenness or display failure may occur. Therefore, from the viewpoint of improving the yield of the finished product and the display quality, the liquid crystal alignment film is required to have a high durability against the cleaning process, particularly the cleaning solvent.

另外，近年來對提高顯示品質的要求更加嚴苛，特別是對液晶配向性和電學性能，要求具有迄今以上性能的液晶配向膜。Further, in recent years, the demand for improving the display quality has become more severe, and in particular, for liquid crystal alignment properties and electrical properties, a liquid crystal alignment film having the above-described performance has been required.

【專利文獻1】日本特開平11-258605號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258605

【非專利文獻1】“液晶”，Vol.3(No.2)，p117(1999年)。[Non-Patent Document 1] "Liquid Crystal", Vol. 3 (No. 2), p117 (1999).

本發明是基於上述情況而作出的，其目的是提供能夠製成不容易受溶劑清洗的影響、且液晶配向性優良、具有良好電學性能的液晶配向膜的液晶配向劑以及具有高品質的顯示性能的液晶顯示元件。The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal alignment agent capable of producing a liquid crystal alignment film which is not easily affected by solvent cleaning, has excellent liquid crystal alignment property, and has good electrical properties, and has high quality display performance. Liquid crystal display element.

本發明的其他目的和優點可以由以下的說明看出。Other objects and advantages of the invention will be apparent from the description which follows.

根據本發明，本發明的上述目的，第一，由一種液晶配向劑達成，其含有：(A)由四羧酸二酐與選自下述式(1)~(4)表示的二胺的至少1種反應所得的聚合物和/或其醯亞胺化聚合物， According to the present invention, the above object of the present invention, first, is achieved by a liquid crystal alignment agent comprising: (A) a tetracarboxylic dianhydride and a diamine selected from the following formulas (1) to (4); At least one polymer obtained by the reaction and/or its quinone imidized polymer,

(其中，R1 ~R4 各自獨立地是碳數為1~40的直鏈狀、支鏈狀或環狀的烷基或者碳數為4~40的直鏈狀、支鏈狀或環狀的烯基，R1 ~R4 所具有的氫原子中的1~15個可以被氟原子取代，A1 和A2 各自獨立地為氫原子或甲基)；和 (B)分子內具有2個以上環氧基的化合物。(wherein R 1 to R 4 are each independently a linear, branched or cyclic alkyl group having a carbon number of 1 to 40 or a linear, branched or cyclic group having a carbon number of 4 to 40; The alkenyl group, 1 to 15 of the hydrogen atoms of R 1 to R 4 may be substituted by a fluorine atom, and A 1 and A 2 are each independently a hydrogen atom or a methyl group; and (B) has 2 in the molecule. More than one epoxy group compound.

本發明的上述目的，第二，由一種液晶顯示元件達成，其具有由上述液晶配向劑製得的液晶配向膜。The above object of the present invention, and secondly, is achieved by a liquid crystal display element having a liquid crystal alignment film produced from the above liquid crystal alignment agent.

由本發明的液晶配向劑形成的液晶配向膜，由於表面自由能較低，對清洗製程的耐久性高，因此能夠製得對製 程適應性優良的液晶配向膜。並且同時，由於具有液晶配向性和高電壓保持性能，因而可以製得非常適用於液晶顯示元件的液晶配向膜。The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention has high surface free energy and high durability to a cleaning process, so that it can be produced. A liquid crystal alignment film excellent in process adaptability. At the same time, since it has liquid crystal alignment property and high voltage retention performance, a liquid crystal alignment film which is very suitable for a liquid crystal display element can be obtained.

本發明的液晶顯示元件可非常適用於各種液晶顯示裝置，例如桌上型計算機、手錶、座鐘、行動電話、計數顯示板、文字處理器、個人電腦、液晶電視機等。The liquid crystal display element of the present invention can be very suitably applied to various liquid crystal display devices such as a desktop computer, a watch, a desk clock, a mobile phone, a counting display panel, a word processor, a personal computer, a liquid crystal television, and the like.

實施發明之最佳形態Best form for implementing the invention ＜(A)聚合物＞<(A) Polymer>

本發明的液晶配向劑含有(A)由四羧酸二酐與選自上述式(1)~(4)表示的二胺的至少一種反應所得的聚合物(以下稱為“特定聚醯胺酸”)和/或其醯亞胺化聚合物(以下稱為“(A)聚合物”)。The liquid crystal alignment agent of the present invention contains (A) a polymer obtained by reacting at least one of tetracarboxylic dianhydride and a diamine selected from the above formulas (1) to (4) (hereinafter referred to as "specific poly-proline ") and / or its oxime imidized polymer (hereinafter referred to as "(A) polymer").

以下，對用於合成本發明液晶配向劑中所含的(A)聚合物所用的四羧酸二酐和二胺進行說明。Hereinafter, the tetracarboxylic dianhydride and the diamine used for synthesizing the (A) polymer contained in the liquid crystal alignment agent of the present invention will be described.

＜四羧酸二酐＞<tetracarboxylic dianhydride>

作為特定聚醯胺酸和/或其醯亞胺化聚合物的合成中所用的四羧酸二酐，可以舉出例如脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。Examples of the tetracarboxylic dianhydride used in the synthesis of the specific polyamic acid and/or its quinone imidized polymer include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic. Tetracarboxylic dianhydride and the like.

作為上述脂肪族四羧酸二酐，可以舉出例如丁烷四羧酸二酐等。Examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride and the like.

作為上述脂環式四羧酸二酐，可以舉出例如下述式(5)表示的化合物The alicyclic tetracarboxylic dianhydride may, for example, be a compound represented by the following formula (5).

(式(5)中，R5 為相互獨立的氫原子、鹵素原子或者1價的有機基團)、下述式(6)表示的化合物 (In the formula (5), R 5 is a mutually independent hydrogen atom, a halogen atom or a monovalent organic group), and a compound represented by the following formula (6)

(式(6)中，R6 為相互獨立的碳數為1~10的烷基，n為0~2的整數)、下述式(7)或(8)表示的化合物 (In the formula (6), R 6 is an alkyl group having 1 to 10 carbon atoms independently of each other, and n is an integer of 0 to 2), and a compound represented by the following formula (7) or (8)

(式(7)和(8)中，R7 和R9 代表具有芳香環的2價有機基團，R8 和R10 相互獨立地代表氫原子或者烷基)、1,2,3,4-環戊烷 四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3',4,4'-二環己基四羧酸二酐、2,3,5-三羧基環戊基醋酸二酐、1,2,4-三羧基環戊基醋酸二酐、雙環[2.2.1]-庚烷-2,3,5,6-四羧酸二酐、3,5,6-三羧基降冰片烷-2-醋酸二酐、四環[4.4.0.12,5 .17,10 ]十二烷-3,4,8,9-四羧酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、雙環[2.2.2]-辛-4-烯-2,3,5,6-四羧酸二酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、3,5,6-三羧基-2-羧基降冰片烷-2:3,5:6-二酐、4,9-二氧雜三環[5.3.1.02,6 ]十一烷-3,5,8,10-四酮等。 (In the formulae (7) and (8), R 7 and R 9 represent a divalent organic group having an aromatic ring, and R 8 and R 10 independently of each other represent a hydrogen atom or an alkyl group), 1, 2, 3, 4 - cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2.2.1]-heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane-3,4,8,9-tetracarboxylic dianhydride , 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, bicyclo[2.2.2]-oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 2, 6 ] undecane-3,5,8,10-tetraketone, and the like.

作為上述式(5)中R5 的鹵素原子，可以舉出例如氯原子、溴原子或碘原子，作為R5 的一價有機基團，可以舉出例如碳數為1~10的烷基、烷氧基等，具體地可以舉出例如甲基、乙基、甲氧基等。The halogen atom of R 5 in the above formula (5) may, for example, be a chlorine atom, a bromine atom or an iodine atom, and the monovalent organic group of R 5 may, for example, be an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkoxy group and the like include a methyl group, an ethyl group, a methoxy group and the like.

作為上述式(5)表示的化合物的具體例子，可以舉出例如1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2-二乙基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二乙基-1,2,3,4-環丁烷四羧酸二酐、1,3-二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐等。Specific examples of the compound represented by the above formula (5) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-. Cyclobutane tetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the like.

作為上述式(6)表示的化合物的具體例子，可以舉出例如1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-5-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、 1,3,3a,4,5,9b-六氫-5-乙基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-乙基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-乙基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-5,8-二甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮等。Specific examples of the compound represented by the above formula (6) include, for example, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl group )-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-B 5-(4-hydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione Wait.

作為上述芳香族四羧酸二酐，可以舉出例如均苯四酸二酐、3,3',4,4'-二苯酮四羧酸二酐、3,3',4,4'-聯苯基碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3',4,4'-聯苯基醚四羧酸二酐、3,3',4,4'-二甲基二苯基矽烷四羧酸二酐、3,3',4,4'-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4'-二(3,4-二羧基苯氧基)二苯基硫醚二酐、4,4'-二(3,4-二羧基苯氧基)二苯基碸二酐、4,4'-二(3,4-二羧基苯氧基)二苯基丙烷二酐、3,3',4,4'-全氟異亞丙基二苯二甲酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、二(苯二甲酸)苯膦氧化物二酐、乙二醇-二(脫水偏苯三酸酯)、丙二醇-二(脫水偏苯三酸酯)、1,4-丁二醇-二(脫水偏苯三酸酯)、1,6-己二醇-二(脫水偏苯三酸酯)、1,8-辛二醇-二(脫水偏苯三酸酯)、2,2-二(4-羥苯基)丙烷-二(脫水偏苯三酸酯)、下述式(9)~(12)表示的化合物等。Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'- Biphenyl sulfonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'- Biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid Dihydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-di 3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4' - perfluoroisopropylidene di phthalic anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, Di(phthalic acid) phenylphosphine oxide dianhydride, ethylene glycol-di (hydrogen trimellitate), propylene glycol-di (hydrogen trimellitate), 1,4-butanediol-di (dehydration) Trimellitic acid ester), 1,6-hexanediol-di(anhydrotrimellitic acid ester), 1,8-octanediol-di(anhydrotrimellitic acid ester), 2,2-di(4) -Hydroxyphenyl)propane-di(hydrogen trimellitate), represented by the following formulas (9) to (12) And the like.

這些四羧酸二酐可以一種單獨或者2種以上組合使用。These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

作為特定聚醯胺酸的合成中所用的四羧酸二酐，較佳為含有選自由1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3',4,4'-二環己基四羧酸二酐、2,3,5-三羧基環戊基醋酸二酐、1,2,4-三羧基環戊基醋酸二酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二甲酸酐、雙環[2.2.2]-辛-4-烯-2,3,5,6-四羧酸二酐、 1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、均苯四酸二酐、3,3',4,4'-二苯酮四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐所構成群組的至少一種化合物的四羧酸二酐。另外，作為特佳的四羧酸二酐，可以舉出2,3,5-三羧基環戊基醋酸二酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮。這些較佳的四羧酸二酐的含有比率，相對於全部四羧酸二酐，較佳為20莫耳%以上，更佳為40莫耳%以上。The tetracarboxylic dianhydride used in the synthesis of the specific polyamic acid preferably contains a compound selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1. 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3 , 3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-4-ene-2 , 3,5,6-tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3- Diketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c ]-furan-1,3-diketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-biphenyl A tetracarboxylic dianhydride of at least one compound of the group consisting of carboxylic acid dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride. Further, as a particularly preferable tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 5-(2,5-dioxotetrahydro-3-furanyl)-3 are mentioned. -methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo De-3-furyl)-naphthalene [1,2-c]-furan-1,3-dione. The content ratio of these preferable tetracarboxylic dianhydrides is preferably 20 mol% or more, and more preferably 40 mol% or more based on the total tetracarboxylic dianhydride.

＜二胺＞<Diamine>

特定聚醯胺酸和/或其醯亞胺化聚合物的合成中所用的二胺為選自上述式(1)~(4)表示的化合物中的至少1種(以下，也稱為“特定二胺”)。The diamine used in the synthesis of the specific polyamic acid and/or its quinone imidized polymer is at least one selected from the compounds represented by the above formulas (1) to (4) (hereinafter, also referred to as "specific Diamine").

上述式(1)~(4)表示的二胺中，作為R1 ~R4 表示的碳數為1~40的直鏈狀烷基，可以舉出例如正己基、正辛基、正癸基、正十二烷基、正十五烷基、正十六烷基、正十八烷基、正二十烷基等；作為支鏈狀烷基，可以舉出例如1-甲基己基、1-乙基己基、2-甲基己基、2-乙基己基、1-乙基辛基、2-乙基辛基、3-乙基辛基、1,2-二甲基己基、1,2-二乙基己基、1,2-二甲基辛基、1,2-二乙基辛基、1-甲基癸基、1-乙基癸基、2-甲基癸基、2-乙基癸基等； 作為環狀烷基，可以舉出例如從環丁烷、環戊烷、環己烷、環癸烷、降冰片烷、雙環辛烷、雙環十一烷、金剛烷等環狀烷上除去1個氫原子所得的基團、具有甾族骨架(steroid)的基團等。作為上述具有甾族骨架的基團，可以舉出從膽甾醇、膽甾烷醇、羊毛甾醇、24脫氫甾醇(desmosterol)等甾族化合物上除去1個氫原子所得的基團。In the diamine represented by the above formulas (1) to (4), the linear alkyl group having 1 to 40 carbon atoms represented by R 1 to R 4 may, for example, be n-hexyl, n-octyl or n-decyl. , n-dodecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-icosyl, etc.; as a branched alkyl group, for example, 1-methylhexyl, 1 -ethylhexyl, 2-methylhexyl, 2-ethylhexyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 1,2-dimethylhexyl, 1,2 -diethylhexyl, 1,2-dimethyloctyl, 1,2-diethyloctyl, 1-methylindenyl, 1-ethylindenyl, 2-methylindenyl, 2-ethyl Examples of the cyclic alkyl group include a ring of cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornane, bicyclooctane, dicycloundecane, and adamantane. A group obtained by removing one hydrogen atom from the alkane, a group having a steroid, and the like. Examples of the group having a steroid skeleton include a group obtained by removing one hydrogen atom from a steroid such as cholesterol, cholesteryl alcohol, lanosterol or 24 dehydroesterol.

作為碳數為4~40的直鏈狀、支鏈狀或環狀烯基，可以舉出上述例示的烷基所具有的碳-碳鍵中的1個以上改為雙鍵的基團。The linear, branched or cyclic alkenyl group having a carbon number of 4 to 40 may be a group in which one or more of the carbon-carbon bonds of the above-exemplified alkyl group are changed to a double bond.

作為特定二胺，較佳為上述式(1)~(4)中R1 ~R4 為具有甾族骨架的基團的二胺，或者上述式(1)表示的、且R1 是碳數為1~20的直鏈狀、支鏈狀或環狀烷基或碳數為4~20的直鏈狀、支鏈狀或環狀烯基的二胺。The specific diamine is preferably a diamine in which R 1 to R 4 in the above formulas (1) to (4) are a group having a steroid skeleton, or a formula represented by the above formula (1), and R 1 is a carbon number. It is a linear, branched or cyclic alkyl group of 1 to 20 or a linear, branched or cyclic alkenyl diamine having 4 to 20 carbon atoms.

在特定聚醯胺酸和/或其醯亞胺化聚合物的合成時，除了上述特定二胺以外，還可以併用其他的二胺。作為其他的二胺，可以舉出例如脂肪族或脂環式二胺、分子內具有2個1級胺基以及該1級胺基以外的氮原子的二胺、二胺基有機矽氧烷、芳香族二胺等。In the synthesis of the specific polyamine and/or its quinone imidized polymer, in addition to the above specific diamine, other diamines may be used in combination. Examples of the other diamines include an aliphatic or alicyclic diamine, a diamine having two primary amino groups in the molecule, and a nitrogen atom other than the primary amino group, and a diamine organooxane. Aromatic diamines, etc.

作為上述脂肪族或脂環式二胺，可以舉出例如1,3-丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺、壬二胺、4,4-二胺基庚二胺、1,4-二胺基環己烷、1,4-二(胺甲基)-雙環[2.2.1]庚烷、1,4-二(胺丙基)-雙環[2.2.1]庚烷、1,3-二(胺甲基)環己烷、1,4-二(胺甲基)環己烷、1,3-二(胺丙基)環己烷、間苯二甲胺、對苯二甲胺、異佛爾酮二胺、四氫 二環戊二烯二胺、六氫-4,7-甲撐茚二亞甲基二胺、三環[6.2.1.02,7 ]-伸十一烷基二甲二胺、4,4'-亞甲基二(環己胺)等；作為上述分子內具有2個1級胺基以及該1級胺基以外的氮原子的二胺，可以舉出例如2,3-二胺基吡啶、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、5,6-二胺基-2,3-二氰基吡嗪、5,6-二胺基-2,4-二羥基嘧啶、2,4-二胺基-6-二甲基胺基-1,3,5-三嗪、1,4-二(3-胺基丙基)呱嗪、2,4-二胺基-6-異丙氧基-1,3,5-三嗪、2,4-二胺基-6-甲氧基-1,3,5-三嗪、2,4-二胺基-6-苯基-1,3,5-三嗪、2,4-二胺基-6-甲基-s-三嗪、2,4-二胺基-1,3,5-三嗪、4,6-二胺基-2-乙烯基-s-三嗪、2,4-二胺基-5-苯基噻唑、2,6-二胺基嘌呤、5,6-二胺基-1,3-二甲基尿嘧啶、3,5-二胺基-1,2,4-***、6,9-二胺基-2-乙氧基吖啶乳酸酯、3,8-二胺基-6-苯基菲啶、1,4-二胺基呱嗪、3,6-二胺基吖啶、二(4-胺基苯基)苯基胺等； 作為上述二胺基有機矽氧烷，可以舉出例如下述式(13)表示的化合物等Examples of the aliphatic or alicyclic diamine include 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, and 4,4. -diaminoheptyldiamine, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)-bicyclo[2.2.1]heptane, 1,4-bis(aminopropyl)- Bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminopropyl)cyclohexane , m-xylylenediamine, p-xylylenediamine, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclic [ 6.2.1.0 2,7 ]-e-decyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), etc.; as the above molecule, having two first-order amine groups and the first-order amine Examples of the diamine of a nitrogen atom other than the group include 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 5 ,6-Diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1 , 3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2, 4-diamino-6-methoxy- 1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2 , 4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2, 6-Diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino- 2-ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, di(4- An aminophenyl phenylamine or the like; and the compound represented by the following formula (13):

(式(13)中，R11 相互獨立地代表氫原子或1價有機基團，R12 相互獨立地為亞甲基或碳數為2~20的伸烷基，p 為1~20的整數)；作為上述芳香族二胺，可以舉出例如對苯二胺、2-甲基-1,4-苯二胺、2-乙基-1,4-苯二胺、2,5-二甲基-1,4-苯二胺、2,5-二乙基-1,4-苯二胺、2,3,5,6-四甲基-1,4-苯二胺、間苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基乙烷、4,4'-二胺基二苯基硫醚、4,4'-二胺基二苯基碸、3,3'-二甲基-4,4'-二胺基聯苯、4,4'-二胺基苯甲醯苯胺、4,4'-二胺基二苯醚、1,5-二胺基萘、2,2'-二甲基-4,4'-二胺基聯苯、5-胺基-1-(4'-胺基苯基)-1,3,3-三甲基茚滿、6-胺基-1-(4'-胺基苯基)-1,3,3-三甲基茚滿、3,4'-二胺基二苯基醚、3,3'-二胺基二苯酮、3,4'-二胺基二苯酮、4,4'-二胺基二苯酮、2,2-二[4-(4-胺基苯氧基)苯基]丙烷、2,2-二[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-二(4-胺基苯基)六氟丙烷、2,2-二[4-(4-胺基苯氧基)苯基]碸、1,4-二(4-胺基苯氧基)苯、1,3-二(4-胺基苯氧基)苯、1,3-二(3-胺基苯氧基)苯、9,9-二(4-胺基苯基)-10-氫蒽、2,7-二胺基芴、9,9-二(4-胺基苯基)芴、4,4'-亞甲基-二(2-氯苯胺)、2,2',5,5'-四氯-4,4'-二胺基聯苯、2,2'-二氯-4,4'-二胺基-5,5'-二甲氧基聯苯、3,3'-二甲氧基-4,4'-二胺基聯苯、1,4,4'-(對伸苯基異亞丙基)二苯胺、4,4'-(間伸苯基異亞丙基)二苯胺、2,2'-二[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷、4,4'-二胺基-2,2'-二(三氟甲基)聯苯、4,4'-二[(4-胺基-2-三氟甲基)苯氧基]-八氟聯苯、4-(4-正庚基環己基)苯氧基-2,4-二胺基苯、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基 咔唑、N-苯基-3,6-二胺基咔唑、下述式(14)~(16)表示的化合物等(In the formula (13), R 11 independently represents a hydrogen atom or a monovalent organic group, and R 12 is independently a methylene group or an alkylene group having a carbon number of 2 to 20, and p is an integer of 1 to 20 The aromatic diamine may, for example, be p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine or 2,5-dimethyl -1,4-phenylenediamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m-phenylenediamine , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenylanthracene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3, 3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxyl) Benzo, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9, 9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diamine Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diamine Biphenyl, 1,4,4'-(p-phenylisopropylene)diphenylamine, 4,4'-(meta-phenylisopropylene)diphenylamine, 2,2'-di[4 -(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4, 4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4-(4-n-heptylcyclohexyl)phenoxy-2,4-diamino Benzene, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6 -diaminocarbazole, a compound represented by the following formulas (14) to (16), etc.

(式(14)~(16)中，X1 相互獨立地是單鍵、-O-、-CO-、-COO-、-OCO-、-NHCO-、-CONH-、-S-、亞甲基、碳數為2~6的伸烷基或伸苯基，R13 是碳數為10~20的烷基、碳數為4~40的具有脂環式骨架的1價有機基團或者碳數為6~20的含氟原子的1價有機基團，R14 是碳數為4~40的具有脂環式骨架的2價有機基團或者碳數為5~30的含氟原子的2價有機基團，q為1~20的整數)。(In the formulae (14) to (16), X 1 is independently a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, and methylene a base having 2 to 6 carbon atoms or a phenyl group, R 13 being an alkyl group having 10 to 20 carbon atoms, a tetravalent organic group having an alicyclic skeleton having a carbon number of 4 to 40, or carbon The number 1 to 20 is a fluorine atom-containing monovalent organic group, and R 14 is a divalent organic group having an alicyclic skeleton having a carbon number of 4 to 40 or a fluorine atom having 5 to 30 carbon atoms; A valence organic group, q is an integer from 1 to 20).

作為上述式(14)表示的二胺，可以舉出例如下述式(17)~(31)表示的化合物， The diamine represented by the above formula (14) is, for example, a compound represented by the following formulas (17) to (31).

另外，作為上述式(15)表示的化合物，可以舉出下述式(32)~(36)表示的化合物， In addition, examples of the compound represented by the above formula (15) include compounds represented by the following formulas (32) to (36).

在特定聚醯胺酸的合成時，當將特定二胺與其他的二胺併用時，特定二胺的使用比率，相對於全部二胺，較佳為1莫耳%以上，特佳為5莫耳%以上。In the synthesis of a specific polyamine, when a specific diamine is used in combination with another diamine, the use ratio of the specific diamine is preferably 1 mol% or more, and particularly preferably 5 mol, based on the entire diamine. More than 8% of the ear.

＜特定聚醯胺酸的合成＞<Synthesis of specific polylysine>

以下，對本發明液晶配向劑中可以含有的特定聚醯胺酸的合成方法進行說明。Hereinafter, a method for synthesizing a specific polyamic acid which can be contained in the liquid crystal alignment agent of the present invention will be described.

特定聚醯胺酸可以通過將上述四羧酸二酐與特定二胺以及根據情況的其他二胺較佳為在有機溶劑中，較佳為在-20℃~150℃、更佳為0~100℃的溫度條件下，較佳為使其反應0.5~72小時而合成。The specific polyamic acid can be preferably used in an organic solvent by using the above tetracarboxylic dianhydride with a specific diamine and, if appropriate, other organic amines, preferably at -20 ° C to 150 ° C, more preferably 0 to 100. Under the temperature condition of °C, it is preferred to carry out the reaction for 0.5 to 72 hours to synthesize.

供給特定聚醯胺酸合成反應的四羧酸二酐與二胺的使用比率，較佳為相對於1當量二胺的胺基，使四羧酸二酐的酸酐基為0.5~2當量的比率，更佳為使其為0.7~1.2當量的比率。The ratio of use of the tetracarboxylic dianhydride to the diamine to be supplied to the specific polyaminic acid synthesis reaction is preferably 0.5 to 2 equivalents based on the amine group of 1 equivalent of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 equivalents. More preferably, it is made to have a ratio of 0.7 to 1.2 equivalents.

這裏，作為有機溶劑，只要能夠溶解合成的特定聚醯胺酸，則對其沒有特別的限製，可以例示例如1-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、3-丁氧基-N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-己基氧基-N,N-二甲基丙醯胺等醯胺類溶劑；二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺等非質子系極性溶劑；間甲基酚、二甲苯酚、苯酚、鹵代苯酚等酚類溶劑。有機溶劑的用量(α)較佳為使四羧酸二酐和二胺化合物的總量(β)相對於反應溶液的總量(α+β)的比率(單體濃度)為0.1~30重量%的量。Here, the organic solvent is not particularly limited as long as it can dissolve the specific polylysine synthesized, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. N-dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N , a phthalamide solvent such as N-dimethylpropionamide; an aprotic polar solvent such as dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol a phenolic solvent such as xylenol, phenol or halogenated phenol. The amount (α) of the organic solvent is preferably such that the ratio (monomer concentration) of the total amount (β) of the tetracarboxylic dianhydride and the diamine compound to the total amount (α + β) of the reaction solution is 0.1 to 30 by weight. The amount of %.

上述有機溶劑中，在不使生成的特定聚醯胺酸析出的範圍內，還可以併用特定聚醯胺酸的不良溶劑(poor solvent)之醇類、酮類、酯類、醚類、鹵代烴類、烴類等。作為這種不良溶劑的具體例子，可以舉出例如甲醇、乙醇、異丙醇、環己醇、4-羥基-4-甲基-2-戊酮、乙二醇、丙二醇、1,4-丁二醇、三甘醇、乙二醇單甲基醚、乳酸乙酯、乳酸丁酯、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、醋酸甲酯、醋酸乙酯、醋酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙酯、丙二酸二乙酯、二乙基醚、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單甲基醚乙酸酯、二甘醇單乙基醚乙酸酯、四氫呋喃、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、辛烷、苯、甲苯、二甲苯、丙酸異戊基酯、異丁酸異戊基酯、二異戊基醚等。In the above organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons of a poor solvent of a specific polyglycolic acid may be used in combination in a range in which the specific polyamine acid to be produced is not precipitated. Hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butylene. Glycol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether , ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, two Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane 1,2-Dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, propionic acid Isoamyl ester, isoamyl isobutyrate, diisoamyl ether, etc.

如上所述，得到溶解了特定聚醯胺酸的反應溶液。然後，將該反應溶液投入到大量的不良溶劑中，得到析出物，通過減壓下乾燥該析出物或者將反應溶液用蒸發器減壓蒸餾，可得聚醯胺酸。並且，能使該特定聚醯胺酸再次溶解於有機溶劑中，然後進行一次或者數次用不良溶劑使其析出之製程或用蒸發器減壓蒸餾之製程，藉以精製特定聚醯胺酸。As described above, a reaction solution in which a specific polyamine is dissolved is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled under reduced pressure with an evaporator to obtain a polyamine. Further, the specific polylysine can be re-dissolved in an organic solvent, and then subjected to a process of precipitating with a poor solvent one or several times or a process of vacuum distillation using an evaporator, thereby purifying a specific polyamine.

＜特定聚醯胺酸的醯亞胺化聚合物的合成方法＞<Synthesis method of quinone imidized polymer of specific polyaminic acid>

接下來，對本發明液晶配向劑中可以含有的特定聚醯胺酸之醯亞胺化聚合物的合成方法進行說明。Next, a method for synthesizing a specific polyaminic acid quinone imidized polymer which may be contained in the liquid crystal alignment agent of the present invention will be described.

特定聚醯胺酸的醯亞胺化聚合物可以通過將上述特定聚醯胺酸所具有的醯胺酸結構中一部分或全部脫水閉環而合成。The quinone imidized polymer of a specific polyamic acid can be synthesized by dehydrating and ring-closing a part or all of the proline structure of the above specific polyamic acid.

特定聚醯胺酸的脫水閉環反應可以通過(i)加熱特定聚醯胺酸的方法，或者(ii)將特定聚醯胺酸溶解於有機溶劑中，向該溶液中加入脫水劑和脫水閉環催化劑並根據需要加熱的方法而進行。The dehydration ring-closure reaction of the specific polyamine can be carried out by (i) heating a specific poly-proline, or (ii) dissolving a specific poly-lysine in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. And according to the method of heating required.

上述(i)的加熱特定聚醯胺酸的方法中反應溫度較佳為50~200℃，更佳為60~170℃。當反應溫度不足50℃時，則脫水閉環反應不能進行完全，如果反應溫度超過200℃，則會出現所得醯亞胺化聚合物的分子量下降的情況。The reaction temperature in the method of heating the specific polyaminic acid of the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be completed. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may decrease.

另一方面，在上述(ii)的在特定聚醯胺酸溶液中添加脫水劑和脫水閉環催化劑的方法中，作為脫水劑，可以使用例如醋酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的用量，根據所需的醯亞胺化率而定，較佳為相對於1莫耳特定聚醯胺酸的重複單元，為0.01~20莫耳。作為脫水閉環催化劑，可以使用例如吡啶、三甲基吡啶、二甲基吡啶、三乙胺等3級胺。但是，並不局限於這些。脫水閉環催化劑的用量，相對於1莫耳所用脫水劑，較佳為0.01~10莫耳。上述脫水劑、脫水閉環催化劑的用量越多，則可使醯亞胺化率越高。作為脫水閉環反應中所用的有機溶劑，可以舉 出作為特定聚醯胺酸合成中所用溶劑而例示於上述中的有機溶劑。脫水閉環反應的反應溫度較佳為0~180℃，更佳為10~150℃。通過對如此得到的反應溶液進行與特定聚醯胺酸精製方法中同樣的操作，可以精製所得醯亞胺化聚合物。On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the specific polyaminic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is preferably from 0.01 to 20 moles per mole of the repeating unit of the specific poly-prolinic acid of 1 mole, depending on the desired hydrazine imidization ratio. As the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0.01 to 10 mols per mol of the dehydrating agent used. The higher the amount of the above dehydrating agent and the dehydration ring-closure catalyst, the higher the yield of ruthenium. As the organic solvent used in the dehydration ring closure reaction, An organic solvent exemplified above as a solvent used in the synthesis of a specific polyamine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The obtained ruthenium iodide polymer can be purified by subjecting the reaction solution thus obtained to the same operation as in the specific polyamic acid purification method.

＜聚合物的平均醯亞胺化率＞<Average oxime imidization ratio of polymer>

可以在本發明使用的特定聚醯胺酸的醯亞胺化聚合物，其全部重複單元中具有醯亞胺環的重複單元的比率(以下，也稱為“醯亞胺化率”)也可以是不足100%的部分脫水閉環產物。醯亞胺化率可以由聚合物的1 H-NMR通過下述公式(1)求出。The quinone imidized polymer of the specific polyamine which can be used in the present invention, the ratio of the repeating unit having a quinone ring in all the repeating units (hereinafter, also referred to as "deuterated imidization ratio") may also be used. It is a partially dehydrated closed-loop product of less than 100%. The ruthenium amination ratio can be determined from 1 H-NMR of the polymer by the following formula (1).

醯亞胺化率(%)=(1-A1/A2×α)×100　　　(1)醯 imidization rate (%) = (1-A1/A2 × α) × 100 (1)

(公式(1)中，A1為源於NH基質子的化學位移10ppm附近的峰面積，A2為源於芳香族質子的化學位移7~8ppm附近的峰面積，α為相對於醯亞胺化反應前聚醯胺酸中的1個NH基之質子，芳香族質子的個數比率)。(In equation (1), A1 is the peak area near the chemical shift of 10 ppm from the NH proton, A2 is the peak area near the chemical shift of the aromatic proton from 7 to 8 ppm, and α is relative to the ruthenium reaction. Proton of one NH group in the former poly-proline, the ratio of the number of aromatic protons).

本發明液晶配向劑中所含的特定聚醯胺酸和/或其醯亞胺化聚合物的平均醯亞胺化率較佳為40~100%，更佳為50~100%。另外，這裏所謂的“平均醯亞胺化率”，是指對由本發明中所含有的全部特定聚醯胺酸及其醯亞胺化聚合物所構成的聚合物混合物通過上述方法測定的醯亞胺化率。如下所述，本發明液晶配向劑中所含有的特定聚醯胺酸和/或其醯亞胺化聚合物，其一部分可以從由其他聚醯胺 酸及其醯亞胺化聚合物所構成群組中選出的至少一種替換，但此時的平均醯亞胺化率，應當理解為是指對由所有特定聚醯胺酸及其醯亞胺化聚合物以及其他聚醯胺酸及其醯亞胺化聚合物所構成的聚合物混合物通過上述方法測定的醯亞胺化率。The specific polyamidation rate of the specific polyaminic acid and/or its quinone imidized polymer contained in the liquid crystal alignment agent of the present invention is preferably from 40 to 100%, more preferably from 50 to 100%. In addition, the "average oxime imidization rate" as used herein means a polymer mixture composed of all the specific polylysines and quinone imidized polymers contained in the present invention, which are determined by the above method. Amination rate. As described below, the specific polyaminic acid and/or its quinone imidized polymer contained in the liquid crystal alignment agent of the present invention may be partially derived from other polyamines. At least one substitution selected from the group consisting of an acid and its quinone imidized polymer, but the average oxime imidization ratio at this time is understood to mean the imidization of all specific poly-proline and its hydrazine. The ratio of the imidization of the polymer mixture composed of the polymer and other poly-proline and its quinone imidized polymer by the above method.

＜末端修飾型聚合物＞<End modified polymer>

本發明中所用的特定聚醯胺酸或其醯亞胺化聚合物還可以是進行了分子量調節的末端修飾型聚合物。通過使用末端修飾型聚合物，可以在不損害本發明效果的前提下改善液晶配向劑的塗敷特性等。這種末端修飾型聚合物可以通過在特定聚醯胺酸的合成時，向反應體系中加入一元酸酐、單胺化合物、單異氰酸酯化合物等而合成。其中，作為一元酸酐，可以舉出例如馬來酸酐、苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐、正十六烷基琥珀酸酐等。作為單胺化合物，可以舉出例如苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十五烷胺、正十六烷胺、正十七烷胺、正十八烷胺、正二十烷胺等。作為單異氰酸酯化合物，可以舉出例如異氰酸苯酯、異氰酸萘基酯等。The specific polyaminic acid or its quinone imidized polymer used in the present invention may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to a reaction system at the time of synthesis of a specific poly-proline. Among them, examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten. Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate.

＜聚合物的溶液黏度＞<Solid viscosity of polymer>

如上所得的特定聚醯胺酸及其醯亞胺化聚合物，較佳為當配成10%的溶液時，具有20~800mPa．s的黏度，更佳 為具有30~500mPa．s的黏度。The specific polyamic acid and its quinone imidized polymer obtained as above, preferably having a solution of 10%, having a solution of 20 to 800 mPa. s viscosity, better For having 30~500mPa. s viscosity.

另外，聚合物的溶液黏度(mPa．s)是採用規定的溶劑，對固體成分濃度稀釋為10%的溶液採用E型旋轉黏度計在25℃下測定的。Further, the solution viscosity (mPa.s) of the polymer was measured by using a predetermined solvent, and the solution having a solid component concentration diluted to 10% was measured at 25 ° C using an E-type rotational viscometer.

＜其他聚合物＞<Other polymers>

本發明的液晶配向劑中，在不損害本發明的效果的情況下，上述特定聚醯胺酸或其醯亞胺化聚合物的一部分可以從由其他聚醯胺酸及其醯亞胺化聚合物所構成群組中選出的至少一種(以下稱為“其他聚合物”)替換。In the liquid crystal alignment agent of the present invention, a part of the above specific polyaminic acid or its ruthenium iodide polymer can be polymerized from other polyglycines and their hydrazines without impairing the effects of the present invention. At least one selected from the group consisting of substances (hereinafter referred to as "other polymer") is replaced.

上述其他聚合物，只要是特定聚醯胺酸以外的聚醯胺酸或其醯亞胺化聚合物，則對其沒有特別的限製，較佳為由上述四羧酸二酐與其他二胺反應所得的聚合物或其醯亞胺化聚合物。作為這裏使用的四羧酸二酐，較佳為脂環式四羧酸二酐或者芳香族四羧酸二酐，特佳為1,2,3,4-環丁烷四羧酸二酐或均苯四酸二酐。作為這裏使用的其他二胺，較佳為芳香族二胺，特佳為4,4'-二胺基二苯基甲烷。The above other polymer is not particularly limited as long as it is a polyamic acid other than a specific polyamic acid or a quinone imidized polymer thereof, and it is preferred to react the above tetracarboxylic dianhydride with another diamine. The resulting polymer or its oxime imidized polymer. The tetracarboxylic dianhydride used herein is preferably an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, particularly preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride or Pyromellitic dianhydride. As the other diamine used herein, an aromatic diamine is preferable, and 4,4'-diaminodiphenylmethane is particularly preferable.

這種其他聚合物的合成，可以使用其他二胺替代特定二胺，與特定聚醯胺酸及其醯亞胺化聚合物合成同樣地進行。The synthesis of such other polymers can be carried out in the same manner as the synthesis of the specific polyamine and its ruthenium-imided polymer by using other diamines instead of the specific diamine.

當本發明液晶配向劑含有其他聚合物時，其他聚合物的使用比例，相對於特定聚醯胺酸及其醯亞胺化聚合物以及其他聚合物的合計量，較佳為40重量%以下，更佳為30重量%以下。When the liquid crystal alignment agent of the present invention contains other polymers, the ratio of use of the other polymers is preferably 40% by weight or less based on the total amount of the specific polyaminic acid and its ruthenium iodide polymer and other polymers. More preferably, it is 30% by weight or less.

＜(B)分子內具有2個以上環氧基的化合物＞<(B) Compound having two or more epoxy groups in the molecule>

本發明的液晶配向劑除了上述(A)聚合物以外，還含有(B)分子內具有2個以上環氧基的化合物(以下稱為“環氧化合物”)。In addition to the above (A) polymer, the liquid crystal alignment agent of the present invention further contains (B) a compound having two or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound").

作為(B)環氧化合物，可以舉出縮水甘油醚化合物、縮水甘油基胺化合物等。Examples of the (B) epoxy compound include a glycidyl ether compound and a glycidylamine compound.

作為上述縮水甘油醚交版印化合物，可以舉出例如乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己二醇、苯-1,4-二醇二縮水甘油醚、2-甲基苯-1,4-二醇二縮水甘油醚、2-乙基苯-1,4-二醇二縮水甘油醚、2-正己基苯-1,4-二醇二縮水甘油醚、2-正癸基苯-1,4-二醇二縮水甘油醚、2-三氟甲基苯-1,4-二醇二縮水甘油醚、2,5-二乙基苯-1,4-二醇二縮水甘油醚等。這些縮水甘油醚化合物中，較佳的可以舉出聚乙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己二醇、苯-1,4-二醇二縮水甘油醚或2-甲基苯-1,4-二醇二縮水甘油醚。Examples of the glycidyl ether cross-printing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, benzene-1,4-diol diglycidyl ether, 2-methylbenzene-1,4-diol diglycidyl ether, 2-ethylbenzene- 1,4-diol diglycidyl ether, 2-n-hexylbenzene-1,4-diol diglycidyl ether, 2-n-nonylbenzene-1,4-diol diglycidyl ether, 2-trifluoro Methylbenzene-1,4-diol diglycidyl ether, 2,5-diethylbenzene-1,4-diol diglycidyl ether, and the like. Among these glycidyl ether compounds, preferred are polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,3,5,6-tetraglycidyl-2,4. - hexanediol, benzene-1,4-diol diglycidyl ether or 2-methylbenzene-1,4-diol diglycidyl ether.

上述縮水甘油基胺化合物，是具有1個以上、較佳為2個之下述式(37)表示的二縮水甘油基胺基的化合物。The glycidylamine compound is a compound having one or more, preferably two, diglycidylamino groups represented by the following formula (37).

作為縮水甘油基胺化合物的具體例子，可以舉出例如N,N,N',N'-四縮水甘油基-對苯二胺、N,N,N',N'-四縮水甘油基-2-甲基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-2-正丙基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-2-正己基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-2-三氟甲基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-2,5-二甲基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-間苯二甲胺、N,N,N',N'-四縮水甘油基-2,2'-二甲基-4,4'-二胺基聯苯、N,N,N',N'-四縮水甘油基-2,2'-二乙基-4,4'-二胺基聯苯、N,N,N',N'-四縮水甘油基-3,3'-二甲基-4,4'-二胺基聯苯、N,N,N',N'-四縮水甘油基-3,3'-二乙基-4,4'-二胺基聯苯、2,2-二[4-(N,N-二縮水甘油基-4-胺基苯氧基)苯基]丙烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基醚、1,3-二(N,N-二縮水甘油基胺基甲基)環己烷、1,4-二(N,N-二縮水甘油基胺基甲基)環己烷、1,3-二(N,N-二縮水甘油基胺基甲基)苯、1,4-二(N,N-二縮水甘油基胺基甲基)苯、3-(N-烯丙基-N-縮水甘油基)胺基丙基三甲氧基矽烷、3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷、N,N-二縮水甘油基-苄基胺、N,N-二縮水甘油基-胺基甲基環己烷等。這些縮水甘油基胺化合物中，較佳的可以舉出 N,N,N',N'-四縮水甘油基-對苯二胺、N,N,N',N'-四縮水甘油基-2-甲基-1,4-苯二胺、N,N,N',N'-四縮水甘油基-2,2'-二甲基-4,4'-二胺基聯苯、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、1,3-二(N,N-二縮水甘油基胺基甲基)環己烷、1,4-二(N,N-二縮水甘油基胺基甲基)環己烷或N,N,N',N'-四縮水甘油基-間苯二甲胺。Specific examples of the glycidylamine compound include, for example, N,N,N',N'-tetraglycidyl-p-phenylenediamine, N,N,N',N'-tetraglycidyl-2 -Methyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2-n-propyl-1,4-phenylenediamine, N,N,N',N' -tetraglycidyl-2-n-hexyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2-trifluoromethyl-1,4-phenylenediamine, N ,N,N',N'-tetraglycidyl-2,5-dimethyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine , N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N,N,N',N'-tetraglycidyl -2,2'-diethyl-4,4'-diaminobiphenyl, N,N,N',N'-tetraglycidyl-3,3'-dimethyl-4,4'- Diaminobiphenyl, N,N,N',N'-tetraglycidyl-3,3'-diethyl-4,4'-diaminobiphenyl, 2,2-di[4-( N,N-diglycidyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane 1,4-bis(N,N-diglycidylaminomethyl) Cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 3-(N -allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, N,N-diglycidyl- Benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. Among these glycidylamine compounds, preferred examples thereof N,N,N',N'-tetraglycidyl-p-phenylenediamine, N,N,N',N'-tetraglycidyl-2-methyl-1,4-phenylenediamine, N, N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N,N,N',N'-tetraglycidyl-4, 4'-Diaminodiphenylmethane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylamino) Methyl)cyclohexane or N,N,N',N'-tetraglycidyl-m-xylylenediamine.

作為本發明液晶配向劑中所含的(B)環氧化合物，較佳為縮水甘油基胺化合物。The (B) epoxy compound contained in the liquid crystal alignment agent of the present invention is preferably a glycidylamine compound.

作為本發明液晶配向劑中(B)環氧化合物的使用比率，相對於100重量份全部聚合物(是指所有的特定聚醯胺酸及其醯亞胺化聚合物以及其他聚醯胺酸及其醯亞胺化聚合物。下同)，較佳為0.01~100重量份，更佳為0.1~50重量份。As the use ratio of the (B) epoxy compound in the liquid crystal alignment agent of the present invention, relative to 100 parts by weight of the total polymer (refers to all the specific polyamine acids and their ruthenium iodide polymers and other polyamic acids and The ruthenium imidized polymer, the same as below, is preferably from 0.01 to 100 parts by weight, more preferably from 0.1 to 50 parts by weight.

＜其他成分＞<Other ingredients>

本發明的液晶配向劑含有上述(A)特定聚醯胺酸和/或其醯亞胺化聚合物以及(B)環氧化合物作為必需成分，還可以任意含有其他的成分。作為這種其他的添加劑，可以舉出例如(C)縮水甘油基胺化合物以外的胺化合物(以下簡稱為“胺化合物”)、(D)含官能性矽烷的化合物等。The liquid crystal alignment agent of the present invention contains the above (A) specific polyamic acid and/or its quinone imidized polymer and (B) an epoxy compound as an essential component, and may further contain other components. Examples of such other additives include an amine compound other than the (C) glycidylamine compound (hereinafter simply referred to as "amine compound"), and (D) a functional decane-containing compound.

(C)胺化合物可以從提高液晶配向劑的保存穩定性以及所得液晶配向膜的電學性能的角度考慮而添加。The (C) amine compound can be added from the viewpoint of improving the storage stability of the liquid crystal alignment agent and the electrical properties of the obtained liquid crystal alignment film.

作為這種(C)胺化合物，可以舉出例如正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十五烷 胺、正十六烷胺、正十七烷胺、正十八烷胺、正二十烷胺、2-甲氧基乙胺、2-甲氧基苄胺、4-甲氧基苄胺、二乙胺、二異丙基胺、甲基乙基胺、n-乙基環己基胺、三乙胺、三乙醇胺、苯胺、鄰甲苯胺、間甲苯胺、對甲苯胺、2-乙基苯胺、3-乙基苯胺、4-乙基苯胺、對己基苯胺、2-氟苯胺、4-氟苯胺、2,4,6-三氟苯胺、鄰胺苯基乙基醚、間胺苯基乙基醚、對胺苯基乙基醚、對三氟甲氧基苯胺、對三氟乙氧基苯胺、環己基胺、環辛基胺、吡啶、呱啶、呱嗪、1-環己基呱嗪、2-氮雜雙環[2.2.2]辛烷、9-氮雜雙環[3,3,1]壬烷、9-甲基-9-氮雜雙環[3.3.1]壬烷、1,4-二氮雜雙環[2.2.2]辛烷、3,7-二氮雜雙環[3.3.1]壬烷、1,8-二氮雜雙環[5.4.0]十一碳烯等。Examples of such (C) amine compounds include n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecane. Amine, n-tridecylamine, n-tetradecylamine, n-pentadecane Amine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-eicosylamine, 2-methoxyethylamine, 2-methoxybenzylamine, 4-methoxybenzylamine, Diethylamine, diisopropylamine, methylethylamine, n-ethylcyclohexylamine, triethylamine, triethanolamine, aniline, o-toluidine, m-toluidine, p-toluidine, 2-ethylaniline , 3-ethylaniline, 4-ethylaniline, p-hexylaniline, 2-fluoroaniline, 4-fluoroaniline, 2,4,6-trifluoroaniline, o-amine phenylethyl ether, m-aminophenyl Ether, p-aminophenyl ethyl ether, p-trifluoromethoxyaniline, p-trifluoroethoxyaniline, cyclohexylamine, cyclooctylamine, pyridine, acridine, pyridazine, 1-cyclohexylpyridazine , 2-azabicyclo[2.2.2]octane, 9-azabicyclo[3,3,1]nonane, 9-methyl-9-azabicyclo[3.3.1]nonane, 1,4 -diazabicyclo[2.2.2]octane, 3,7-diazabicyclo[3.3.1]nonane, 1,8-diazabicyclo[5.4.0]undecene and the like.

上述(D)含官能性矽烷的化合物，可以為提高所得液晶配向膜對基板表面的接著性而添加。作為這種(D)含官能性矽烷的化合物的具體例子，可以舉出例如3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧羰基-3-胺基丙基三甲氧基矽烷、N-乙氧羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、 9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-二(氧乙烯基)-3-胺基丙基三甲氧基矽烷、N-二(氧乙烯基)-3-胺基丙基三乙氧基矽烷、3-(N-烯丙基-N-縮水甘油基)胺基丙基三甲氧基矽烷、3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷等。The (D) functional decane-containing compound may be added to improve the adhesion of the obtained liquid crystal alignment film to the surface of the substrate. Specific examples of such a (D) functional decane-containing compound include, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethyl. Oxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Baseline, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriazine Triamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxy Mercaptoalkyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltri Ethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-amine Propyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxy Basear, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like.

＜液晶配向劑＞<Liquid alignment agent>

將本發明的液晶配向劑調製成特定聚醯胺酸和/或其醯亞胺化聚合物以及任意添加的其他成分較佳為溶解含於有機溶劑中的溶液狀態。The liquid crystal alignment agent of the present invention is prepared into a specific polyamic acid and/or its quinone imidized polymer, and any other component added is preferably dissolved in a solution state contained in an organic solvent.

作為本發明液晶配向劑中所使用的有機溶劑，可以舉出作為特定聚醯胺酸合成反應中所用溶劑而例示的溶劑。另外，還可以適當地選擇併用作為在特定聚醯胺酸合成反應時可以併用的不良溶劑而例示的不良溶劑。The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the specific polyamine acid synthesis reaction. Further, a poor solvent exemplified as a poor solvent which can be used in combination in a specific polyamine acid synthesis reaction can be appropriately selected and used.

作為本發明液晶配向劑中所用的特佳的有機溶劑，可以舉出例如N-甲基-2-吡咯烷酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚(丁基溶纖劑)、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單甲基醚乙酸酯、二甘醇單乙基醚乙酸酯 等。這些溶劑可以單獨使用，或者也可以2種以上混合使用。The particularly preferable organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide or N,N-dimethylformamidine. Amine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Wait. These solvents may be used singly or in combination of two or more.

本發明液晶配向劑中固體成分濃度(液晶配向劑中除溶劑以外的成分的合計重量除以液晶配向劑的總重量的值)考慮黏性、揮發性等，較佳為選擇1~10重量%的範圍。將本發明液晶配向劑塗敷於基板表面，形成作為液晶配向膜的塗膜，當固體成分濃度不足1重量%時，將導致該塗膜的厚度過小，從而不能獲得良好的液晶配向膜；另一方面，當固體成分濃度超過10重量%時，將導致塗膜厚度過厚，從而不能獲得良好的液晶配向膜，並且，會出現液晶配向劑的黏性增大導致塗敷特性變差的情況，因而都不佳。In the liquid crystal alignment agent of the present invention, the solid content concentration (the total weight of the components other than the solvent in the liquid crystal alignment agent divided by the total weight of the liquid crystal alignment agent) is preferably 1 to 10% by weight in consideration of viscosity, volatility, and the like. The scope. Applying the liquid crystal alignment agent of the present invention to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that a good liquid crystal alignment film cannot be obtained; On the one hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases to cause deterioration of coating properties. And thus not good.

本發明液晶配向劑更佳的固體成分濃度值，根據將本發明液晶配向劑塗敷於基板時所採用的方法而不同。例如，當採用旋塗法時，固體成分濃度特佳為1.5~4.5重量%的範圍。當採用印刷法時，特佳為使固體成分濃度為4~10重量%的範圍，這樣，可以使溶液黏度落在10~50mPa．s的範圍。當採用噴墨法時，特佳為使固體成分濃度為2~5重量%的範圍，這樣，可以使溶液黏度落在3~15mPa．s的範圍。The solid content concentration value of the liquid crystal alignment agent of the present invention differs depending on the method used when the liquid crystal alignment agent of the present invention is applied to the substrate. For example, when the spin coating method is employed, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When using the printing method, it is particularly preferable to make the solid content concentration range of 4 to 10% by weight, so that the solution viscosity can be reduced to 10 to 50 mPa. The scope of s. When the inkjet method is used, it is particularly preferable to make the solid content concentration in the range of 2 to 5% by weight, so that the solution viscosity can be reduced to 3 to 15 mPa. The scope of s.

本發明液晶配向劑的表面張力較佳為25~40mN/m。The surface tension of the liquid crystal alignment agent of the present invention is preferably from 25 to 40 mN/m.

調製本發明液晶配向劑時的溫度，較佳為0℃~200℃，更佳為20℃~60℃。The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C.

＜液晶顯示元件＞<Liquid crystal display element>

本發明的液晶顯示元件特徵在於具有由如上所述製得 的本發明液晶配向劑製得的液晶配向膜。The liquid crystal display element of the present invention is characterized in that it has been produced as described above The liquid crystal alignment film produced by the liquid crystal alignment agent of the present invention.

本發明的液晶顯示元件，可以通過例如以下的製程(1)~(4)製造。The liquid crystal display element of the present invention can be produced, for example, by the following processes (1) to (4).

(1)通過平版印刷法、旋塗法或者噴墨印刷法等合適的塗敷方法，將本發明的液晶配向劑塗敷在設有形成圖案的透明導電膜的基板一面上，接著，通過加熱塗敷面形成塗膜。這裏，作為基板，可以使用例如浮法玻璃、鈉鈣玻璃等玻璃；聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚醚碸、聚碳酸酯等由塑膠所形成的透明基板等。作為基板一面上所設置的透明導電膜，可以使用由氧化鍚(SnO2 )所形成的NESA膜(美國PPG公司註冊商標)、由氧化銦-氧化錫(In2 O3 -SnO2 )所形成的ITO膜等，這些透明導電膜圖案的形成採用光蝕刻法或在透明導電膜形成時預先使用遮罩的方法。在液晶配向劑的塗敷時，為了進一步改善基板表面和透明導電膜與塗膜的接著性，還可以在基板的該表面上預先塗敷含官能性矽烷的化合物、含官能性鈦的化合物等。塗敷液晶配向劑後的加熱溫度較佳為80~300℃，更佳為120~250℃。另外，當本發明的液晶配向劑含有具有醯胺酸單元的聚合物時，通過塗敷後除去有機溶劑，形成作為配向膜的塗膜，且還可以進一步通過加熱使其脫水閉環，形成進一步醯亞胺化的塗膜。(1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by a suitable coating method such as a lithography method, a spin coating method or an inkjet printing method, followed by heating The coated surface forms a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, or the like formed of plastic can be used. Transparent substrate, etc. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) formed of yttrium oxide (SnO 2 ), formed of indium oxide-tin oxide (In 2 O 3 -SnO 2 ) can be used. For the ITO film or the like, the transparent conductive film pattern is formed by photolithography or a method in which a mask is used in advance when the transparent conductive film is formed. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in advance. . The heating temperature after the application of the liquid crystal alignment agent is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. Further, when the liquid crystal alignment agent of the present invention contains a polymer having a guanine unit, the organic solvent is removed after coating to form a coating film as an alignment film, and further dehydration and ring closure by heating to form a further ruthenium The imidized coating film.

形成的塗膜的厚度較佳為0.001~1μm，更佳為0.005~0.5μm。The thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(2)接著，對如上所述形成的塗膜面用纏有由例如尼 龍、人造纖維、棉花等纖維所形成的布的輥進行以一定方向摩擦的打磨處理，或者通過對塗膜表面照射偏光紫外線的方法或對塗膜表面照射離子束的方法，可以使塗膜上產生液晶分子配向能，從而可以製得液晶配向膜。(2) Next, the coating film surface formed as described above is wrapped with, for example, Nepal Rolls of cloth formed by fibers such as dragons, rayon, cotton, etc. are subjected to a rubbing treatment in a certain direction, or by irradiating a surface of the coating film with a polarized ultraviolet ray or by irradiating an ion beam on the surface of the coating film. The alignment energy of the liquid crystal molecules is generated, whereby a liquid crystal alignment film can be obtained.

(3)如上述(1)至(2)所述製得的液晶配向膜，還可以根據需要進行清洗。作為清洗溶劑，可以使用例如水、丙酮、甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、甲基乙基酮、環己酮、醋酸甲酯、醋酸乙酯、醋酸丁酯、四氫呋喃、己烷、庚烷、辛烷等。為了提高清洗效率，還可以在清洗溶劑中添加界面活性劑，或者採用加熱溶劑進行洗滌的方法、與刷洗併用的方法、與超音波併用的方法。清洗後，可以直接使用，或者還可以採用適當的溶劑進行沖洗等後，根據需要進行加熱乾燥。(3) The liquid crystal alignment film obtained as described in the above (1) to (2) may be washed as needed. As the washing solvent, for example, water, acetone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate can be used. , tetrahydrofuran, hexane, heptane, octane, and the like. In order to improve the cleaning efficiency, a surfactant may be added to the cleaning solvent, or a method of washing with a heating solvent, a method of using a brush, and a method of using ultrasonic waves. After washing, it may be used as it is, or it may be washed with a suitable solvent, and then dried by heating as needed.

(4)製作2片如上形成液晶配向膜的基板，將2片基板隔著間隙(晶胞間隙)相對放置，使各自液晶配向膜的打磨方向相互垂直或逆平行，將2片基板周邊部位用密封劑貼合，向由基板表面和密封劑分割出的晶胞間隙內注入充填液晶，封閉注入孔，構成液晶胞。然後，在液晶胞的外表面，即構成液晶胞的各基板的另一側面上貼合偏光板，使其偏光方向與該基板一面上所形成的液晶配向膜的打磨方向一致或者垂直，製得液晶顯示元件。這裏，作為密封劑，可以使用例如作為固化劑和間隙物的含氧化鋁球的環氧樹脂等。作為液晶，可以舉出向列型液晶和層列型液晶，其中較佳為向列型液晶，可以使用例如希夫氏鹼類液晶、氧 化偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶、酯類液晶、三聯苯類液晶、聯苯基環己烷類液晶、嘧啶類液晶、二烷類液晶、雙環辛烷類液晶、立方烷類液晶等。此外，這些液晶中還可以添加例如氯化胆甾醇、胆甾醇壬酸酯、胆甾醇碳酸酯等胆甾型液晶和以商品名"C-15"、"CB-15"(默克公司製)銷售的手性劑等而進行使用。並且，還可以使用對癸氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯等之強介電性液晶。(4) Two substrates in which the liquid crystal alignment film is formed as described above are formed, and the two substrates are placed opposite to each other with a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other, and the peripheral portions of the two substrates are used. The sealant is bonded, and a liquid crystal is filled into the cell gap which is divided by the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, so that the polarizing direction is the same as or perpendicular to the polishing direction of the liquid crystal alignment film formed on one side of the substrate. Liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer may be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. Hexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, two An alkane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added under the trade names "C-15" and "CB-15" (manufactured by Merck). It is used by selling chiral agents and the like. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used.

作為液晶胞外表面上貼合的偏光板，可以舉出將聚乙烯醇延伸配向同時吸收碘所得的稱作為H膜的偏光膜夾在醋酸纖維素保護膜中而製成的偏光板或者H膜自身製成的偏光板。The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or an H film formed by sandwiching a polarizing film called an H film obtained by stretching a polyvinyl alcohol while absorbing iodine, and sandwiching it on a cellulose acetate protective film. A polarizing plate made by itself.

【實施例】[Examples]

以下，通過實施例對本發明進行更具體的說明，但是本發明並不局限於這些實施例。Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples.

在以下的實施例、比較例中，對所調製的液晶配向劑的評價按照以下的方法進行。In the following examples and comparative examples, the evaluation of the prepared liquid crystal alignment agent was carried out in the following manner.

[液晶配向膜表面自由能的評價][Evaluation of Surface Free Energy of Liquid Crystal Alignment Film]

在一面上具有由ITO膜所形成的透明導電膜的1mm厚的玻璃基板的透明導電膜上，通過旋塗法塗敷各實施例或比較例中調製的液晶配向劑溶液，通過在200℃下加熱60分鐘，得到具有膜厚為0.06μm的覆膜的基板。對該覆膜測定水和二碘甲烷的接觸角，使用該測定值通 過擴張的霍克斯(Extended Fowkes)公式求出覆膜(液晶配向膜)的表面自由能。On the transparent conductive film of a 1 mm thick glass substrate having a transparent conductive film formed of an ITO film on one side, the liquid crystal alignment agent solution prepared in each of the examples or the comparative examples was applied by spin coating at 200 ° C. After heating for 60 minutes, a substrate having a film having a film thickness of 0.06 μm was obtained. The contact angle of water and diiodomethane was measured for the film, and the measured value was used. The surface free energy of the film (liquid crystal alignment film) was obtained by the over-expanded Extended Fowkes formula.

[電壓保持率的測定][Measurement of voltage holding ratio]

預製6片一面具有由ITO膜所形成的透明導電膜的1mm厚的玻璃基板，通過旋塗法在各基板的透明導電膜上塗敷各實施例或比較例中調製的液晶配向劑溶液，通過在200℃下加熱60分鐘，得到6片具有膜厚為0.06μm的覆膜的基板。Six glass substrates of 1 mm thick having a transparent conductive film formed of an ITO film were prefabricated, and a liquid crystal alignment agent solution prepared in each of the examples or the comparative examples was applied onto the transparent conductive film of each substrate by a spin coating method. The film was heated at 200 ° C for 60 minutes to obtain 6 substrates having a film thickness of 0.06 μm.

這些基板中，2片以超純水為清洗溶劑，另外2片以異丙醇為清洗溶劑，分別在40℃下進行1分鐘超音波清洗後，於100℃下加熱10分鐘除去溶劑。剩下的2片不進行清洗而用於下一製程。這樣，得到清洗條件不同的3對液晶配向膜塗敷基板。Two of these substrates were treated with ultrapure water as a cleaning solvent, and two sheets of isopropyl alcohol were used as a cleaning solvent. After ultrasonic cleaning at 40 ° C for 1 minute, the solvent was removed by heating at 100 ° C for 10 minutes. The remaining 2 pieces were used for the next process without cleaning. Thus, three pairs of liquid crystal alignment film coated substrates having different cleaning conditions were obtained.

接下來以相同清洗條件的2塊基板為一對，在各基板的具有液晶配向膜的各外緣上，除液晶注入口外，塗敷加入了直徑為5.5μm的氧化鋁球的環氧樹脂接著劑後，以液晶配向膜為內側，並使打磨方向相互逆平行而重合並壓合，使接著劑固化。接著，通過液晶注入口向基板間填充向列型液晶(負型，默克公司製，MLC-6608)後，用丙烯酸類光固化接著劑封閉液晶注入口，在基板外側的兩面上貼合偏光板，製成清洗條件不同的3組液晶顯示元件。Next, two substrates of the same cleaning condition were used as a pair, and on the outer edges of the liquid crystal alignment films of the respective substrates, an epoxy resin coated with alumina balls having a diameter of 5.5 μm was applied in addition to the liquid crystal injection port. After the agent, the liquid crystal alignment film is inside, and the rubbing directions are antiparallel to each other, and the pressure is combined and pressed to cure the adhesive. Next, a nematic liquid crystal (negative type, MLC-6608, manufactured by Merck & Co., Inc.) was filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port was closed with an acrylic photocurable adhesive, and the polarized light was bonded to both sides of the substrate. The board is made into three sets of liquid crystal display elements having different cleaning conditions.

在60℃下以16.7毫秒的時間間隔內，對這些液晶 顯示元件分別施加5V的電壓，電壓施加時間為60微秒，然後測定從電壓解除至16.7毫秒後的電壓保持率。These liquid crystals were applied at 60 ° C at intervals of 16.7 milliseconds. The display elements were each applied with a voltage of 5 V, the voltage application time was 60 microseconds, and then the voltage holding ratio from the voltage release to 16.7 milliseconds was measured.

[液晶配向性評價][Liquid alignment evaluation]

使由上述方法製作的各液晶顯示元件的施加電壓在AC 0V~8V的範圍變化時，當由垂直方向目視觀察液晶顯示元件時以及由斜方向觀察時，當兩者情況下整面都為沒有顯示不良的均勻顯示時評價為“良好”，當上述觀察方向之一者或者雙方發生顯示不均時，評價為“出現不均”。When the applied voltage of each liquid crystal display element produced by the above method is changed in the range of AC 0V to 8V, when the liquid crystal display element is visually observed from the vertical direction and when viewed from the oblique direction, the entire surface is not present when both are used. When the display of the uniform display was poor, the evaluation was "good", and when one or both of the above-mentioned observation directions showed uneven display, the evaluation was "unevenness".

單體合成例1(1-(3,5-二胺基苯基)-3-十八烷基琥珀醯亞胺的合成)Monomer Synthesis Example 1 (Synthesis of 1-(3,5-Diaminophenyl)-3-octadecylsuccinimide)

向由氮氣換氣的300ml三頸燒瓶中加入12.81g(0.07mol)3,5-二硝基苯胺和70ml醋酸，一邊通入氮氣一邊攪拌，使固體物質溶解。向其中加入24.64g(0.07mol)十八烷基琥珀酸酐，在氮氣下回流20小時使其反應。將反應液冷卻至室溫後，加入70ml甲醇，靜置一夜。濾出析出的固體成分，用甲醇洗滌後乾燥，得到30g(收率83%)1-(3,5-二硝基苯基)-3-十八烷基琥珀醯亞胺。To a 300 ml three-necked flask ventilated with nitrogen, 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid were added, and the mixture was stirred while passing nitrogen gas to dissolve the solid matter. Thereto was added 24.64 g (0.07 mol) of octadecyl succinic anhydride, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After cooling the reaction mixture to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The precipitated solid component was filtered, washed with methanol and dried to give 30 g (yield: 83%) of 1-(3,5-dinitrophenyl)-3-octadecyl amber.

然後，向由氮氣換氣的500ml燒瓶中，加入30g(0.058mol)以上述合成的1-(3,5-二硝基苯基)-3-十八烷基琥珀醯亞胺、100ml乙醇、100ml四氫呋喃(THF)以及25g還原催化劑鈀碳(Pd/C)，在70℃下攪拌1小時。向其中加入42.5ml(43.75g)肼一水合物，加熱回流6小 時使其反應。濾出Pd/C，將濾液在旋轉蒸發器中進行濃縮。將所得粗產物加熱溶解於N-甲基-2-吡咯烷酮中後，冷卻再結晶，得到14.6g(0.032mol，收率55%)目標產物1-(3,5-二胺基苯基)-3-十八烷基琥珀醯亞胺。Then, to a 500 ml flask ventilated with nitrogen, 30 g (0.058 mol) of 1-(3,5-dinitrophenyl)-3-octadecylsuccinimide synthesized above, 100 ml of ethanol, 100 ml of tetrahydrofuran (THF) and 25 g of a reduction catalyst palladium carbon (Pd/C) were stirred at 70 ° C for 1 hour. 42.5 ml (43.75 g) of hydrazine monohydrate was added thereto, and the mixture was heated under reflux for 6 hours. When it is allowed to react. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and then recrystallized by cooling to obtain 14.6 g (0.032 mol, yield 55%) of the desired product 1-(3,5-diaminophenyl)- 3-octadecyl amber imine.

單體合成例2(1-(3,5-二胺基苯基)-3-十二烷基琥珀醯亞胺的合成)Monomer Synthesis Example 2 (Synthesis of 1-(3,5-Diaminophenyl)-3-dodecylsuccinimide)

除了使用18.76g(0.07mol)十二烷基琥珀酸酐替代24.64g(0.07mol)十八烷基琥珀酸酐以外，與單體合成例1同樣地操作，製得11g(0.030mol，收率51%)1-(3,5-二胺基苯基)-3-十二烷基琥珀醯亞胺。11 g (0.030 mol, yield 51%) was obtained in the same manner as in Monomer Synthesis Example 1, except that 18.76 g (0.07 mol) of dodecylsuccinic anhydride was used instead of 24.64 g (0.07 mol) of octadecyl succinic anhydride. ) 1-(3,5-Diaminophenyl)-3-dodecyl amber imine.

單體合成例3(1-(3,5-二胺基苯基)-3-十七烷基-4-甲基馬來醯亞胺的合成)Monomer Synthesis Example 3 (Synthesis of 1-(3,5-Diaminophenyl)-3-heptadecyl-4-methylmaleimide)

向由氮氣換氣的2000ml三頸燒瓶中加入31.5g(0.25mol)二甲基馬來酸酐、89.0g(0.5mol)N-溴代琥珀醯亞胺、1.0g(4.15mmol)過氧化苯甲醯和1500ml四氯化碳，加熱回流5小時。將反應液冷卻至室溫，在室溫下靜置一夜後，過濾。將濾液用水洗滌後，將有機層在旋轉蒸發器中濃縮。將所得油狀粗產物在高真空下蒸餾(120~125℃/2mmHg)，得到20.0g(0.1mol，收率39%)中間體3-溴甲基-4-甲基馬來酸酐。To a 2000 ml three-necked flask ventilated with nitrogen, 31.5 g (0.25 mol) of dimethyl maleic anhydride, 89.0 g (0.5 mol) of N-bromosinium imide, 1.0 g (4.15 mmol) of benzoyl peroxide were added.醯 and 1500 ml of carbon tetrachloride were heated to reflux for 5 hours. The reaction solution was cooled to room temperature, allowed to stand at room temperature overnight, and then filtered. After the filtrate was washed with water, the organic layer was concentrated in a rotary evaporator. The crude oily product obtained was distilled under high vacuum (120-125 ° C / 2 mmHg) to afford 20.0 g (0.1 mol, yield 39%) of intermediate 3-bromomethyl-4-methylmaleic anhydride.

然後，向由氬氣換氣的2000ml三頸燒瓶中加入16.4g(80mmol)上述製得的3-溴甲基-4-甲基馬來酸酐、1.52g(8.0mmol)碘化銅、400ml二乙基醚和160ml HMPA(六甲基磷醯三胺)後，在通入氬氣的條件下冷卻至-5~0℃。一邊攪拌該混合物，一邊經20分鐘滴加另外準備的溶於400ml二乙基醚的400mmol溴化十六烷基鎂的溶液。使混合液體回升至室溫，再攪拌8小時。然後，加入用600ml二乙基醚稀釋的4N硫酸600ml，使溶液成為酸性。將分離的水層進一步用600ml二乙基醚洗滌，合併有機層。將有機層用水洗滌，並用硫酸鈉除水後，在旋轉蒸發器中濃縮溶液，得到油狀的粗產物。將該粗產物在以石油醚/乙酸乙酯(19:1)混合溶液作為展開溶劑的氧化矽凝膠管柱中進行精製，得到14.0g(0.04mol，收率50%)3-十七烷基-4-甲基馬來酸酐。Then, to a 2000 ml three-necked flask ventilated with argon, 16.4 g (80 mmol) of 3-bromomethyl-4-methylmaleic anhydride obtained above, 1.52 g (8.0 mmol) of copper iodide, and 400 ml of two were added. Ethyl ether and 160ml After HMPA (hexamethylphosphonium triamine), it was cooled to -5 to 0 ° C under argon gas. While stirring the mixture, a separately prepared solution of 400 mmol of cetylmagnesium bromide dissolved in 400 ml of diethyl ether was added dropwise over 20 minutes. The mixed liquid was allowed to warm to room temperature and stirred for additional 8 hours. Then, 600 ml of 4N sulfuric acid diluted with 600 ml of diethyl ether was added to make the solution acidic. The separated aqueous layer was further washed with 600 ml of diethyl ether and organic layers were combined. The organic layer was washed with water and water was evaporated over sodium sulfate. The crude product was purified in a cerium oxide gel column using a petroleum ether/ethyl acetate (19:1) mixture as a solvent, to afford 14.0 g (0.04 mol, yield 50%) of 3-heptadecane. Base-4-methyl maleic anhydride.

然後向由氮氣換氣的200ml三頸燒瓶中加入6.4g(0.035mol)3,5-二硝基苯胺和35ml醋酸。一邊通入氮氣一邊攪拌，使固體物質溶解。向其中加入12.3g(0.035mol)上述製得的3-十七烷基-4-甲基馬來酸酐，在氮氣下回流20小時使其反應。將反應液冷卻至室溫後，加入35ml甲醇，靜置一夜。濾出固體成分，用甲醇洗滌後乾燥，得到14.6g(0.029mol，收率81%)1-(3,5-二硝基苯基)-3-十七烷基-4-甲基馬來醯亞胺。Then, to a 200 ml three-necked flask ventilated with nitrogen, 6.4 g (0.035 mol) of 3,5-dinitroaniline and 35 ml of acetic acid were added. The mixture was stirred while passing nitrogen gas to dissolve the solid matter. 12.3 g (0.035 mol) of the above-prepared 3-heptadecyl-4-methyl maleic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After cooling the reaction mixture to room temperature, 35 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 14.4 g (0.029 mol, yield 81%) of 1-(3,5-dinitrophenyl)-3-heptadecyl-4-methyl. Yttrium.

然後，向由氮氣換氣的300ml燒瓶中，加入13.4g(0.026mol)1-(3,5-二硝基苯基)-3-十七烷基-4-甲基馬來醯亞胺、50ml乙醇、50ml THF以及12.5g還原催化 劑Pd/C，在70℃下攪拌1小時。然後加入19ml(19.6g)肼一水合物，加熱回流6小時使其反應。濾出Pd/C，將濾液在旋轉蒸發器中進行濃縮。將所得粗產物加熱溶解於N-甲基-2-吡咯烷酮中，冷卻而藉以再結晶，得到6.6g(0.015mol，收率56%)目標產物1-(3,5-二胺基苯基)-3-十七烷基-4-甲基馬來醯亞胺。Then, to a 300 ml flask ventilated with nitrogen, 13.4 g (0.026 mol) of 1-(3,5-dinitrophenyl)-3-heptadecyl-4-methylmaleimide was added. 50ml ethanol, 50ml THF and 12.5g reduction catalysis The agent Pd/C was stirred at 70 ° C for 1 hour. Then, 19 ml (19.6 g) of hydrazine monohydrate was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and cooled to be recrystallized to obtain 6.6 g (0.015 mol, yield 56%) of the desired product 1-(3,5-diaminophenyl). 3-heptadecyl-4-methylmaleimide.

單體合成例4(1-(3,5-二胺基苯基)-3-十六烷氧基甲基-4-甲基馬來醯亞胺的合成)Monomer Synthesis Example 4 (Synthesis of 1-(3,5-Diaminophenyl)-3-hexadecyloxymethyl-4-methylmaleimide)

向由氮氣換氣的300ml三頸燒瓶中加入12.81g(0.07mol)3,5-二硝基苯胺和70ml醋酸後，一邊通入氮氣一邊攪拌，使固體物質溶解。向其中加入14.35g(0.07mol)與單體合成例3的中間體同樣地合成的3-(溴甲基)-4-甲基馬來酸酐，在氮氣下回流20小時使其反應。將反應溶液冷卻至室溫後，加入70ml甲醇，靜置一夜。濾出固體成分，用甲醇洗滌後乾燥，得到18.9g(0.051mol，收率73%)1-(3,5-二硝基苯基)-3-溴甲基-4-甲基馬來醯亞胺。After adding 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid to a 300 ml three-necked flask which was purged with nitrogen, the mixture was stirred while passing nitrogen gas to dissolve the solid matter. 14.35 g (0.07 mol) of 3-(bromomethyl)-4-methylmaleic anhydride synthesized in the same manner as the intermediate of the monomer synthesis example 3 was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After the reaction solution was cooled to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered, washed with methanol and dried to give 18.9 g (0.051 mol, yield 73%) of 1-(3,5-dinitrophenyl)-3-bromomethyl-4-methylmale. Imine.

接著，向由氮氣換氣的500ml三頸燒瓶中加入18.1g(0.049mol)1-(3,5-二硝基苯基)-3-溴甲基-4-甲基馬來醯亞胺、12.9g(0.049mol)1-十六烷醇鈉鹽和100ml二甲基亞碸後，在100℃下攪拌10小時使其反應。將反應液冷卻至室溫後，加入70ml甲醇，靜置一夜。濾出固體成分，用甲醇洗滌後乾燥，得到20.8g(0.039mol，收 率80%)1-(3,5-二硝基苯基)-3-十六烷氧基甲基-4-甲基馬來醯亞胺。Next, 18.1 g (0.049 mol) of 1-(3,5-dinitrophenyl)-3-bromomethyl-4-methylmaleimide was added to a 500 ml three-necked flask ventilated with nitrogen. After 12.9 g (0.049 mol) of sodium 1-hexadecanolate and 100 ml of dimethylarylene, the mixture was stirred at 100 ° C for 10 hours to cause a reaction. After cooling the reaction mixture to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 20.8 g (0.039 mol. Rate 80%) 1-(3,5-Dinitrophenyl)-3-hexadecyloxymethyl-4-methylmaleimide.

然後，向由氮氣換氣的300ml燒瓶中，加入13.8g(0.026mol)1-(3,5-二硝基苯基)-3-十六烷氧基甲基-4-甲基馬來醯亞胺、50ml乙醇、50ml THF以及12.5g還原催化劑Pd/C，在70℃下攪拌1小時。然後加入19ml(19.6g)肼一水合物，加熱回流6小時使其反應。濾出Pd/C，將濾液在旋轉蒸發器中進行濃縮。將所得粗產物加熱溶解於N-甲基-2-吡咯烷酮中，冷卻而藉以再結晶，得到8.2g(0.018mol，收率67%)目標產物1-(3,5-二胺基苯基)-3-十六烷氧基甲基-4-甲基馬來醯亞胺。Then, to a 300 ml flask ventilated with nitrogen, 13.8 g (0.026 mol) of 1-(3,5-dinitrophenyl)-3-hexadecyloxymethyl-4-methylmalay was added. The imine, 50 ml of ethanol, 50 ml of THF and 12.5 g of a reduction catalyst Pd/C were stirred at 70 ° C for 1 hour. Then, 19 ml (19.6 g) of hydrazine monohydrate was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and cooled to be recrystallized to obtain 8.2 g (0.018 mol, yield 67%) of the desired product 1-(3,5-diaminophenyl). -3-hexadecyloxymethyl-4-methylmaleimide.

聚合物合成例1~19、聚合物比較合成例1~4Polymer Synthesis Examples 1 to 19, Polymer Comparative Synthesis Examples 1 to 4

向N-甲基吡咯烷酮中依次加入表1中所示組成的二胺和四羧酸二酐，配成單體濃度為20重量%的溶液，使其在60℃下反應4小時，得到含有聚醯胺酸(A-1)~(A-19)或(a-1)~(a-4)的溶液。向所得各聚醯胺酸溶液中，相對於溶液中醯胺酸單元的總量(莫耳)，分別加入表1所示莫耳倍數(當量)的吡啶和醋酸酐後，在110℃下加熱4小時進行脫水閉環反應。通過將所得溶液在二乙基醚中再次沉澱、回收、並減壓乾燥，藉以得到醯亞胺化聚合物(B-1)~(B-19)和(b-1)~(b-4)。這些醯亞胺化聚合物的醯亞胺化率如表1所示。To the N-methylpyrrolidone, a diamine and a tetracarboxylic dianhydride having the compositions shown in Table 1 were successively added to prepare a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours to obtain a polycondensation. A solution of proline (A-1)~(A-19) or (a-1)~(a-4). To each of the obtained polyaminic acid solutions, pyridine and acetic anhydride as shown in Table 1 were added to the total amount (molar) of the proline units in the solution, and then heated at 110 ° C. The dehydration ring closure reaction was carried out for 4 hours. The obtained solution is again precipitated in diethyl ether, recovered, and dried under reduced pressure to obtain ruthenium iodide polymers (B-1) to (B-19) and (b-1) to (b-4). ). The oxime imidization ratio of these quinone imidized polymers is shown in Table 1.

聚合物合成例20~22Polymer Synthesis Example 20~22

向N-甲基吡咯烷酮中依次加入表1中所示組成的二胺和四羧酸二酐，配成單體濃度為20重量%的溶液，使其在60℃下反應4小時，通過將所得溶液在二乙基醚中再次沈澱，回收，並減壓乾燥，藉以得到聚醯胺酸(A-20)~(A-22)。另外，在聚合物合成例20~22中不進行醯亞胺化反應。To the N-methylpyrrolidone, a diamine and a tetracarboxylic dianhydride having the compositions shown in Table 1 were successively added to prepare a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours, and the obtained was obtained. The solution was again precipitated in diethyl ether, recovered, and dried under reduced pressure to give polyamic acid (A-20)~(A-22). Further, in the polymer synthesis examples 20 to 22, the oxime imidization reaction was not carried out.

表1中，對於二胺和酸酐，括弧內的數字表示單體的使用比率(莫耳比)，表中的符號含義如下。In Table 1, for diamines and acid anhydrides, the numbers in parentheses indicate the use ratio (molar ratio) of the monomers, and the symbols in the table have the following meanings.

＜二胺化合物＞<Diamine compound>

D-1:1-(3,5-二胺基苯基)-3-十八烷基琥珀醯亞胺D-1:1-(3,5-diaminophenyl)-3-octadecyl amber imine

D-2:1-(3,5-二胺基苯基)-3-十二烷基琥珀醯亞胺D-2: 1-(3,5-Diaminophenyl)-3-dodecyl amber imine

D-3:1-(3,5-二胺基苯基)-3-十七烷基-4-甲基馬來醯亞胺D-3: 1-(3,5-Diaminophenyl)-3-heptadecyl-4-methylmaleimide

D-4:1-(3,5-二胺基苯基)-3-十六烷氧基甲基-4-甲基馬來醯亞胺D-4: 1-(3,5-Diaminophenyl)-3-hexadecyloxymethyl-4-methylmaleimide

D-5：十八烷氧基-2,4-二胺基苯D-5: octadecyloxy-2,4-diaminobenzene

D-6：對苯二胺D-6: p-phenylenediamine

D-7:4,4-二胺基二苯基甲烷D-7: 4,4-diaminodiphenylmethane

D-8:4,4-二胺基二苯基醚D-8: 4,4-diaminodiphenyl ether

D-9:2,2'-二甲基-4,4'-二胺基聯苯D-9: 2,2'-dimethyl-4,4'-diaminobiphenyl

＜四羧酸二酐＞<tetracarboxylic dianhydride>

T-1:5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐T-1: 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride

T-2:2,3,5-三羧基環戊基醋酸二酐T-2: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

T-3:1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮T-3: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2- c]-furan-1,3-dione

T-4:1,2,3,4-環丁烷四羧酸二酐T-4: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

實施例1Example 1

將作為(A)聚合物的合成例1中製得的醯亞胺化聚合物B-1溶於γ-丁內酯/N-甲基-2-吡咯烷酮/丁基溶纖劑混合 溶液(重量比40:30:30)中，向該溶液中相對於100重量份全部聚合物加入20重量份作為(B)環氧化合物的聚乙二醇二縮水甘油醚(分子量約400)，製成固體成分濃度為4.0重量%的溶液。目視觀察該溶液，為無渾濁的透明溶液。接著通過用孔徑為0.2μm的濾器過濾該溶液，製得液晶配向劑。The ruthenium imidized polymer B-1 obtained in Synthesis Example 1 as the (A) polymer was dissolved in γ-butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve. In the solution (weight ratio 40:30:30), 20 parts by weight of polyethylene glycol diglycidyl ether (molecular weight of about 400) as the (B) epoxy compound is added to the solution in 100 parts by weight of the total polymer, A solution having a solid concentration of 4.0% by weight was prepared. The solution was visually observed to be a turbid transparent solution. Then, the solution was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

採用該液晶配向劑按照上述方法進行各種評價。結果列於表2和表3。Various evaluations were carried out by the above method using this liquid crystal alignment agent. The results are shown in Tables 2 and 3.

實施例2~39、比較例1~12Examples 2 to 39 and Comparative Examples 1 to 12

除了向液晶配向劑中混合的(A)聚合物和(B)環氧化合物的種類及用量如表2所示以外，與實施例1同樣地調製各液晶配向劑。採用這些液晶配向劑按照上述方法進行評價的結果列於表2和表3。Each liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the type and amount of the (A) polymer and the (B) epoxy compound mixed in the liquid crystal alignment agent were as shown in Table 2. The results of evaluation using these liquid crystal alignment agents in accordance with the above methods are shown in Tables 2 and 3.

表2中，對於(B)環氧化合物，括弧內的數字表示含量比率(相對於100重量份全部聚合物的重量份)，表中的符號 含義如下所示。In Table 2, for the (B) epoxy compound, the number in parentheses indicates the content ratio (parts by weight relative to 100 parts by weight of the total polymer), the symbols in the table. The meaning is as follows.

環氧A：聚乙二醇二縮水甘油醚(分子量約400)Epoxy A: polyethylene glycol diglycidyl ether (molecular weight of about 400)

環氧B:1,6-己二醇二縮水甘油醚Epoxy B: 1,6-hexanediol diglycidyl ether

環氧C:N,N,N',N'-四縮水甘油基-2,2'-二甲基-4,4'-二胺基聯苯Epoxy C: N, N, N', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl

環氧D:N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷Epoxy D: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

環氧E:1,3-二(N,N'-二縮水甘油基胺基甲基)環己烷Epoxy E: 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane

環氧F:N,N,N',N'-四縮水甘油基-間苯二甲胺Epoxy F: N, N, N', N'-tetraglycidyl-m-xylylenediamine

Claims (7)

一種液晶配向劑，其特徵在於含有：(A)由四羧酸二酐與選自下述式(1)~(4)表示的二胺的至少1種反應所得的聚合物和/或其醯亞胺化聚合物， 其中，R1 ~R4 各自獨立地是碳數為1~40的直鏈狀、支鏈狀或環狀的烷基或者碳數為4~40的直鏈狀、支鏈狀或環狀的烯基，R1 ~R4 所具有的氫原子中的1~15個可以被氟原子取代，A1 和A2 各自獨立地為氫原子或甲基；和(B)分子內具有2個以上環氧基的化合物。A liquid crystal alignment agent comprising: (A) a polymer obtained by reacting at least one of a tetracarboxylic dianhydride and a diamine selected from the following formulas (1) to (4) and/or a ruthenium thereof Imined polymer, Wherein R 1 to R 4 are each independently a linear, branched or cyclic alkyl group having a carbon number of 1 to 40 or a linear, branched or cyclic group having a carbon number of 4 to 40; In the alkenyl group, 1 to 15 of the hydrogen atoms of R 1 to R 4 may be substituted by a fluorine atom, and A 1 and A 2 are each independently a hydrogen atom or a methyl group; and (B) has 2 or more molecules in the molecule. An epoxy group compound. 如申請專利範圍第1項之液晶配向劑，其中(B)分子內具有2個以上環氧基的化合物為縮水甘油基胺化合物。 The liquid crystal alignment agent of claim 1, wherein (B) the compound having two or more epoxy groups in the molecule is a glycidylamine compound. 如申請專利範圍第1或2項之液晶配向劑，其中相對於100重量份(A)聚合物，(B)分子內具有2個以上環氧基的化合物的含有量為0.01~100重量份。 The liquid crystal alignment agent according to claim 1 or 2, wherein the content of the compound having two or more epoxy groups in the molecule (B) is 0.01 to 100 parts by weight based on 100 parts by weight of the (A) polymer. 如申請專利範圍第1或2項之液晶配向劑，其中上述式(1)~(4)表示的二胺所含有的基團R1 ~R4 是具有甾族(steroid)骨架的基團。The liquid crystal alignment agent of the first or second aspect of the invention, wherein the groups R 1 to R 4 contained in the diamine represented by the above formulas (1) to (4) are groups having a steroid skeleton. 如申請專利範圍第1或2項之液晶配向劑，其中二胺是上述式(1)表示的、R1 為碳數為1~20的直鏈狀、支鏈狀或環狀烷基或碳數為4~20的直鏈狀、支鏈狀或環狀烯基的二胺。The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine is a linear, branched or cyclic alkyl group or carbon represented by the above formula (1), and R 1 is a carbon number of 1 to 20. A linear, branched or cyclic alkenyl diamine of 4 to 20 is used. 如申請專利範圍第1或2項之液晶配向劑，其中(A)聚合物的平均醯亞胺化率為40~100%。 The liquid crystal alignment agent of claim 1 or 2, wherein the (A) polymer has an average oxime imidization ratio of 40 to 100%. 一種液晶顯示元件，其特徵在於具有由如申請專利範圍第1至6項中任一項之液晶配向劑所製得的液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film produced by the liquid crystal alignment agent according to any one of claims 1 to 6.
TW097105110A 2007-02-15 2008-02-14 Liquid crystal alignment agent and liquid crystal display element TWI442143B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007035362 2007-02-15

Publications (2)

Publication Number Publication Date
TW200844606A TW200844606A (en) 2008-11-16
TWI442143B true TWI442143B (en) 2014-06-21

Family

ID=39844089

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097105110A TWI442143B (en) 2007-02-15 2008-02-14 Liquid crystal alignment agent and liquid crystal display element

Country Status (4)

Country Link
JP (1) JP5077558B2 (en)
KR (1) KR101010382B1 (en)
CN (1) CN101246283B (en)
TW (1) TWI442143B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009093707A1 (en) * 2008-01-25 2009-07-30 Nissan Chemical Industries, Ltd. Liquid-crystal alignment material and liquid-crystal display element made with the same
JP5311110B2 (en) * 2008-10-22 2013-10-09 日立化成株式会社 Method for forming spacer for liquid crystal display device, liquid crystal display device and manufacturing method thereof
CN105778929A (en) * 2016-04-27 2016-07-20 深圳市道尔顿电子材料有限公司 Liquid crystal orientation agent, diamine compound and polyamide acid
CN111007677B (en) * 2019-12-05 2022-04-26 Tcl华星光电技术有限公司 Color film substrate, preparation method thereof and display panel
WO2024135713A1 (en) * 2022-12-20 2024-06-27 三菱ケミカル株式会社 Epoxy resin, production method for same, curable resin composition, and cured product

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002062537A (en) * 2000-08-21 2002-02-28 Jsr Corp Liquid crystal aligning agent for stn (supertwisted nematic) liquid crystal display element and stn liquid crystal display element
KR100491944B1 (en) * 2002-12-09 2005-05-30 한국화학연구원 Polyimide derivatives with pendant imide group and method for preparing them
TWI359189B (en) * 2004-01-27 2012-03-01 Jsr Corp Liquid crystal alignment agent, liquid crystal ali
TWI360680B (en) * 2004-02-24 2012-03-21 Jsr Corp Liquid crystal alignment agent and manufacturing m
KR100559264B1 (en) * 2004-10-29 2006-03-15 한국화학연구원 Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them
KR100622026B1 (en) * 2004-10-29 2006-09-19 한국화학연구원 Insulator containing soluble polyimides and organic thin film transistor using them
KR20070035683A (en) * 2005-09-28 2007-04-02 삼성전자주식회사 Liquid crystal display and method for manufacturing the same
KR100782437B1 (en) * 2005-12-30 2007-12-05 제일모직주식회사 Alignment Agent of Liquid Crystal

Also Published As

Publication number Publication date
JP5077558B2 (en) 2012-11-21
CN101246283A (en) 2008-08-20
KR20080076800A (en) 2008-08-20
CN101246283B (en) 2011-02-16
JP2008225458A (en) 2008-09-25
TW200844606A (en) 2008-11-16
KR101010382B1 (en) 2011-01-21

Similar Documents

Publication Publication Date Title
TWI434111B (en) Liquid crystal aligning agent and liquid crystal display element
TWI427375B (en) Vertical alignment mode liquid crystal alignment agent and liquid crystal display device
JP4978433B2 (en) Liquid crystal aligning agent and liquid crystal display element
TWI461802B (en) Liquid crystal aligning agent and liquid crystal display element
TWI457667B (en) Liquid crystal alignment agent and liquid crystal display element
TWI476489B (en) Liquid crystal aligning agent and liquid crystal display element
JP5013106B2 (en) Liquid crystal aligning agent and liquid crystal display element
JP2009031319A (en) Manufacturing method for liquid crystal alignment agent, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TWI442143B (en) Liquid crystal alignment agent and liquid crystal display element
TWI501011B (en) Liquid crystal aligning agent and liquid crystal display element
TWI444727B (en) Liquid crystal alignment agent and liquid crystal display element
TWI427103B (en) Liquid crystal aligning agent and liquid crystal display element
TWI467290B (en) Liquid crystal aligning agent, liquid crystal display element, polyamic acid, polyimide and compound
TWI439770B (en) Liquid crystal alignment agent and liquid crystal alignment film
TWI429685B (en) Liquid crystal aligning agent and liquid crystal display element
TWI442144B (en) Liquid crystal alignment agent and liquid crystal display element
TWI461460B (en) Liquid aligning agent liquid crystal aligning film and liquid crystal display element
TWI428370B (en) Liquid crystal aligning agent and liquid crystal display element
TWI466921B (en) Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element
JP2008225010A (en) Liquid crystal aligning agent and liquid crystal display element
TW200819510A (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TWI354843B (en) Liquid crystal alignment agent and liquid crystal
TWI422930B (en) Liquid crystal alignment agent and liquid crystal display element
TW200831562A (en) Liquid crystal alignment agent and liquid crystal display element
TW200932789A (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees