TWI421280B - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display - Google Patents

Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display Download PDF

Info

Publication number
TWI421280B
TWI421280B TW097129711A TW97129711A TWI421280B TW I421280 B TWI421280 B TW I421280B TW 097129711 A TW097129711 A TW 097129711A TW 97129711 A TW97129711 A TW 97129711A TW I421280 B TWI421280 B TW I421280B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
formula
group
crystal alignment
diamine
Prior art date
Application number
TW097129711A
Other languages
Chinese (zh)
Other versions
TW200906914A (en
Inventor
Takahiro Mori
Daisuke Touma
Original Assignee
Jnc Corp
Jnc Petrochemical 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 Jnc Corp, Jnc Petrochemical Corp filed Critical Jnc Corp
Publication of TW200906914A publication Critical patent/TW200906914A/en
Application granted granted Critical
Publication of TWI421280B publication Critical patent/TWI421280B/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

Description

液晶配向劑、液晶配向膜及液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

本發明涉及一種聚合物、使用此聚合物而形成的液晶配向劑、利用此液晶配向劑獲得的液晶配向膜及具有此液晶配向膜的液晶顯示元件，所述聚合物含有以主鏈上具有三級胺與亞烷基的二胺作為主成分的聚醯胺酸或其衍生物、即聚醯胺酸及聚醯亞胺。The present invention relates to a polymer, a liquid crystal alignment agent formed using the polymer, a liquid crystal alignment film obtained by using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, the polymer having three in the main chain A polyamine or a derivative thereof having a diamine of an alkylamine and an alkylene group as a main component, that is, polylysine and polyimine.

液晶顯示元件用在以筆記本電腦(notebook)或桌上電腦(desktop computer)的顯示器(monitor)為代表的攝像機(video camera)的取景器(view finder)、投影式(projection)顯示器(display)等各種液晶顯示裝置中，最近也用作電視的顯示元件。此外，也用作光學打印頭(optical printer head)、光學傅立葉變換(optical Fourier transform)元件、光閥(light valve)等光電子學(optoelecctronics)相關元件。作為先前的液晶顯示元件，主流是使用向列型液晶(nematic liquid crystal)的顯示元件，正在實用化的是扭轉90度的扭轉向列(Twisted Nematic，TN)型液晶顯示元件、通常扭轉180度或180度以上的超扭轉向列(Super Twisted Nematic，STN)型液晶顯示元件、使用薄膜電晶體的所謂TFT(Thin film transistor，薄膜電晶體)型液晶顯示元件。The liquid crystal display element is used in a view finder, a projection display, etc. of a video camera represented by a notebook or a desktop computer. Among various liquid crystal display devices, it has recently been used as a display element of a television. In addition, it is also used as an optoelecctronics related component such as an optical printer head, an optical Fourier transform element, and a light valve. As a conventional liquid crystal display element, a mainstream display device using a nematic liquid crystal is a twisted nematic (TN) liquid crystal display element which is twisted by 90 degrees, and is usually twisted by 180 degrees. Or a super Twisted Nematic (STN) type liquid crystal display element of 180 degrees or more, or a so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor.

然而，這些液晶顯示元件存在以下缺點：能夠比較好地觀察圖像的視角較為狹窄，斜向觀看時，亮度及對比度 (contrast)會降低，並且產生半色調的亮度反轉。近年來，針對所述視角問題，利用使用光學補償膜的TN型液晶顯示元件、並用垂直配向與突起構造物的技術的多區域垂直排列(Multi domain Vertical Alignment，MVA)型液晶顯示元件、或者橫向電場方式的平面轉換(In Plane Switching，IPS)型液晶顯示元件等技術進行改良，並將此改良技術實用化(例如，參照日本專利特公昭63－21907號公報、日本專利特開平6－160878號公報及日本專利特開平9－15650號公報)。However, these liquid crystal display elements have the following disadvantages: the viewing angle of the image which can be observed relatively well is relatively narrow, and the brightness and contrast when viewed obliquely (contrast) will decrease and produce a halftone brightness inversion. In recent years, for the viewing angle problem, a multi-domain vertical alignment (MVA) type liquid crystal display element or a lateral direction using a TN type liquid crystal display element using an optical compensation film and a technique of using a vertical alignment and a protrusion structure is used. Techniques such as an In Plane Switching (IPS) type liquid crystal display device are improved, and the improved technique is put into practical use (for example, refer to Japanese Patent Publication No. Sho 63-21907, Japanese Patent Laid-Open No. Hei 6-160878 Bulletin and Japanese Patent Laid-Open No. Hei 9-15650).

液晶顯示元件的技術發展不僅僅是通過這些驅動方式及元件結構的改良來實現，也可以通過用於液晶顯示元件的構成構件的改良來實現。用於液晶顯示元件的構成構件中，尤其是液晶配向膜，它是與液晶顯示元件的顯示品質相關的重要要素之一，隨著液晶顯示元件的高品質化，液晶配向膜的作用逐年重要。The technical development of the liquid crystal display element can be realized not only by improvement of these driving methods and element structures, but also by improvement of constituent members for liquid crystal display elements. Among the constituent members used for the liquid crystal display element, in particular, a liquid crystal alignment film, which is one of important elements relating to the display quality of the liquid crystal display element, the role of the liquid crystal alignment film is important year by year with the improvement of the quality of the liquid crystal display element.

為了提高液晶顯示元件的顯示品質，作為對於液晶配向膜所要求的重要特性，可舉出電壓保持率及殘留直流電(direct current，DC)。如果電壓保持率較低，那麽在幀期間(frame time)中，施加至液晶的電壓會下降，其結果，亮度降低，有時會對正常的諧調顯示造成障礙。另一方面，如果殘留DC較大，那麽在施加電壓後，有時會存在所謂的“殘像(persistence)”，即儘管將電壓設置為OFF，但仍殘留應消失的圖像。In order to improve the display quality of the liquid crystal display element, a voltage holding ratio and a residual direct current (DC) are mentioned as important characteristics required for the liquid crystal alignment film. If the voltage holding ratio is low, the voltage applied to the liquid crystal drops during the frame time, and as a result, the brightness is lowered, which sometimes causes an obstacle to the normal harmonic display. On the other hand, if the residual DC is large, there is a so-called "persistence" sometimes after the voltage is applied, that is, although the voltage is set to OFF, an image that should disappear is left.

另外，作為其他表示液晶顯示元件的性能的指標之 一，可使用白顯示的亮度相對於黑顯示的亮度的比率即對比度。一般來說，白顯示的亮度不會產生很大變化，所以對比度在很大程度上是受黑顯示的亮度的影響。因此，為了提高對比度，重要的是降低黑顯示的亮度。In addition, as other indicators indicating the performance of the liquid crystal display element First, the ratio of the brightness of the white display to the brightness of the black display, that is, the contrast can be used. In general, the brightness of the white display does not change much, so the contrast is largely affected by the brightness of the black display. Therefore, in order to improve the contrast, it is important to reduce the brightness of the black display.

眾所周知，為了提高液晶顯示元件的對比度，而使用單軸配向性較高的液晶配向膜，使液晶顯示元件中的液晶分子更加均勻地配向，提高黑顯示特性，由此可解决所述問題(例如，參照日本專利特開2005－258397號公報)。也就是說，對於提高液晶配向膜的單軸配向性，增大液晶配向膜的延遲(retardation)即可。It is known that in order to improve the contrast of a liquid crystal display element, a liquid crystal alignment film having a high uniaxial alignment property is used to more uniformly align liquid crystal molecules in a liquid crystal display element, thereby improving black display characteristics, thereby solving the problem (for example, Japanese Patent Laid-Open Publication No. 2005-258397. That is, it is sufficient to increase the uniaxial alignment of the liquid crystal alignment film and increase the retardation of the liquid crystal alignment film.

根據以上情況，為了提高液晶顯示元件的顯示品質，需要一種電壓保持率高、殘留DC小、且延遲較大的材料。In view of the above, in order to improve the display quality of the liquid crystal display element, a material having a high voltage holding ratio, a small residual DC, and a large retardation is required.

另一方面，作為液晶配向劑的材料，已知有具有含有亞苯基二氨基的二價有機基的聚醯胺酸或其衍生物(例如，參照國際公開第2004/053583號小册子)，但就單軸配向性的表現及其進一步提高的觀點來說，需要進一步進行研究。On the other hand, as a material of the liquid crystal alignment agent, a polyaminic acid having a divalent organic group containing a phenylene diamino group or a derivative thereof is known (for example, refer to International Publication No. 2004/053583 pamphlet). However, in terms of the performance of uniaxial alignment and its further improvement, further research is needed.

本發明的課題在於提供一種可形成電壓保持率高、殘留DC低、此外具有較大延遲的液晶配向膜的聚醯胺酸及其衍生物即聚醯胺酸及聚醯亞胺系聚合物，使用此聚合物而形成的液晶配向膜，及具有此液晶配向膜、具有優異的對比度、不會引起引起殘像的液晶顯示元件。An object of the present invention is to provide a polylysine and a derivative thereof which are capable of forming a liquid crystal alignment film having a high voltage holding ratio, a low residual DC, and a large retardation, that is, a poly-proline and a polyimine polymer. A liquid crystal alignment film formed using the polymer, and a liquid crystal display element having the liquid crystal alignment film and having excellent contrast without causing an afterimage.

本發明者等人為了解决所述課題而進行積極研究，發 現通過對聚合物原料即二胺導入亞烷基結構，由聚合物所構成的液晶配向膜可使液晶顯示元件中的液晶分子更加均勻地配向，其結果，使用此液晶配向膜的液晶顯示元件具有較大的延遲。並且發現，通過對所述二胺導入三級胺，並使用組入所述二胺的聚合物，可使液晶配向膜在用於液晶顯示元件時具有高電壓保持率與低殘留DC。The inventors of the present invention conducted active research in order to solve the problem. By introducing an alkylene structure to a polymer raw material, that is, a diamine, a liquid crystal alignment film composed of a polymer can more uniformly align liquid crystal molecules in a liquid crystal display element, and as a result, a liquid crystal display element using the liquid crystal alignment film Has a large delay. Further, it has been found that by introducing a tertiary amine into the diamine and using a polymer incorporated in the diamine, the liquid crystal alignment film can have a high voltage holding ratio and a low residual DC when used for a liquid crystal display element.

本發明由下述內容構成。The present invention consists of the following contents.

[1]一種液晶配向劑，其含有四羧酸二酐(tetracarboxylic acid dianhydride)與二胺的反應產物、即聚醯胺酸或其衍生物，其特徵在於，所述二胺包含以下述通式(1)表示的二胺。[1] A liquid crystal alignment agent comprising a reaction product of a tetracarboxylic acid dianhydride and a diamine, that is, a polyaminic acid or a derivative thereof, wherein the diamine comprises the following formula (1) A diamine represented.

通式(1)中，R1 獨立地表示一價有機基，R2 獨立地表示一價基，Z表示包含碳數1~5的亞烷基的二價基。In the formula (1), R 1 independently represents a monovalent organic group, R 2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms.

[2]如[1]所述的液晶配向劑，其特徵在於，R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3之烷基、氟、氯或溴。[2] The liquid crystal alignment agent according to [1], wherein R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine or bromine.

[3]如[1]或[2]所述的液晶配向劑，其特徵在於，以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。[3] The liquid crystal alignment agent according to [1] or [2], wherein the diamine represented by the formula (1) is on the phenyl groups at both ends and corresponds to the N-Z-N main chain. Each of the opposite positions has an amino group.

[4]如[3]所述的液晶配向劑，其特徵在於，以通式(1) 表示的二胺是從下述結構式239~253及258~262所組成的族群中選擇的一個或一個以上。[4] The liquid crystal alignment agent according to [3], which is characterized by the formula (1) The diamine to be represented is one or more selected from the group consisting of the following structural formulae 239 to 253 and 258 to 262.

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

[6]如[5]所述的液晶配向劑，其特徵在於，所述四羧酸 二酐是所述結構式500及511的一者或兩者。[6] The liquid crystal alignment agent according to [5], wherein the tetracarboxylic acid The dianhydride is one or both of the structural formulae 500 and 511.

[7]如[1]至[6]中任一項所述的液晶配向劑，其特徵在於，所述二胺進一步包含以下述通式(2)表示的二胺。The liquid crystal alignment agent according to any one of the above aspects, wherein the diamine further contains a diamine represented by the following formula (2).

[化5]H2 N－R3 －NH2 (2)[Chemical 5] H 2 N-R 3 -NH 2 (2)

通式(2)中，R3 表示具有取代基及不包含兩個或兩個以上的亞氨基的二價有機基。In the formula (2), R 3 represents a divalent organic group having a substituent and not containing two or more imino groups.

[8]如[7]所述的液晶配向劑，其特徵在於，以通式(2)表示的二胺包含以下述通式(3)~(5)表示的二胺。[8] The liquid crystal alignment agent according to the above [7], wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5).

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

通式(4)中，X1 獨立地表示亞甲基或氧，X2 表示可具有甲基或CF3 作為取代基的碳數1~8的亞烷基。In the formula (4), X 1 independently represents a methylene group or oxygen, and X 2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF 3 as a substituent.

[化8] [化8]

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

[9]如[8]所述的液晶配向劑，其特徵在於，通式(3)~(5)中，兩個氨基的位置相對於Y或X1 是對位。[Nine] to [8] The liquid crystal alignment agent, wherein in the general formula (3) to (5), with respect to the positions of the two amino groups X 1 or Y is para.

[10]如[9]所述的液晶配向劑，其特徵在於，以通式(3)表示的二胺是從下述結構式301~304、306、307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從下述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從下述結構式381、384、390及398所組成的族群中選擇的一個或一個以上。[10] The liquid crystal alignment agent according to [9], wherein the diamine represented by the formula (3) is selected from the group consisting of the following structural formulae 301 to 304, 306, 307 and 313. One or more diamines represented by the formula (4) are one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367 and 372, represented by the formula (5). The diamine is one or more selected from the group consisting of the following structural formulas 381, 384, 390 and 398.

[11]如[8]至[10]中任一項所述的液晶配向劑，其特徵在於，所述二胺中，以通式(1)表示的二胺的含有率為20~99莫耳%，以通式(2)表示的二胺的含有率為1~80莫耳%。[11] The liquid crystal alignment agent according to any one of [8], wherein the content of the diamine represented by the formula (1) in the diamine is 20 to 99 moles. The content of the diamine in the formula (2) is 1 to 80 mol%.

[12]一種液晶配向劑，其含有：四羧酸二酐A與二胺A的反應產物即聚醯胺酸或其衍生物A、以及四羧酸二酐B與二胺B的反應產物即聚醯胺酸或其衍生物B的液晶配向劑，其特徵在於，所述二胺A包含以上述通式(1)表示的二胺， 所述二胺B不包含以上述通式(1)表示的二胺。[12] A liquid crystal alignment agent comprising: a reaction product of a tetracarboxylic dianhydride A and a diamine A, that is, a reaction product of polyamic acid or a derivative A thereof, and a tetracarboxylic dianhydride B and a diamine B, that is, A liquid crystal alignment agent of poly-proline or a derivative B thereof, wherein the diamine A contains a diamine represented by the above formula (1), The diamine B does not contain the diamine represented by the above formula (1).

[13]如[12]所述的液晶配向劑，其特徵在於，通式(1)中，R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3的烷基、氟、氯或溴。[13] The liquid crystal alignment agent according to [12], wherein, in the formula (1), R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen and a carbon number of 1 to 3. Alkyl, fluorine, chlorine or bromine.

[14]如[12]或[13]所述的液晶配向劑，其特徵在於，以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。[14] The liquid crystal alignment agent according to [12] or [13], wherein the diamine represented by the formula (1) is on the phenyl groups at both ends and corresponds to the N-Z-N main chain. Each of the opposite positions has an amino group.

[15]如[14]所述的液晶配向劑，其特徵在於，以通式(1)表示的二胺是從上述結構式239~253及258~262所組成的族群中選擇的一個或一個以上。[15] The liquid crystal alignment agent according to [14], wherein the diamine represented by the formula (1) is one selected from the group consisting of the above structural formulas 239 to 253 and 258 to 262. the above.

[16]如[12]至[15]中任一項所述的液晶配向劑，其特徵在於，所述二胺B包含以上述通式(2)表示的二胺。[16] The liquid crystal alignment agent according to any one of [12], wherein the diamine B contains a diamine represented by the above formula (2).

[17]如[16]所述的液晶配向劑，其特徵在於，以通式(2)表示的二胺包含以上述通式(3)~(5)表示的二胺。[17] The liquid crystal alignment agent according to [16], wherein the diamine represented by the formula (2) contains a diamine represented by the above formulas (3) to (5).

[18]如[17]所述的液晶配向劑，其特徵在於，通式(3)~(5)中，兩個氨基的位置相對於Y或X1 是對位。[18] as described in [17] The liquid crystal alignment agent, wherein in the general formula (3) to (5), with respect to the positions of the two amino groups X 1 or Y is para.

[19]如[18]所述的液晶配向劑，其特徵在於，以通式(3)表示的二胺是從上述結構式301~304、306、307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從上述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從上述結構式381、384、390及398所組成的族群中選擇的一個或一個以上。[19] The liquid crystal alignment agent according to [18], wherein the diamine represented by the formula (3) is one selected from the group consisting of the structural formulas 301 to 304, 306, 307 and 313. Or one or more, the diamine represented by the formula (4) is one or more selected from the group consisting of the above structural formulas 360, 364, 365, 367 and 372, and the diamine represented by the formula (5) It is one or more selected from the group consisting of the above structural formulas 381, 384, 390, and 398.

[20]如[12]至[19]中任一項所述的液晶配向劑，其特徵 在於，所述四羧酸二酐A及四羧酸二酐B是從上述結構式500、505~508、511、515及517中選擇的一個或一個以上。[20] The liquid crystal alignment agent according to any one of [12] to [19] which is characterized The tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are one or more selected from the above structural formulas 500, 505 to 508, 511, 515, and 517.

[21]如[20]所述的液晶配向劑，其特徵在於，所述四羧酸二酐A及四羧酸二酐B是上述結構式500及511的一者或兩者。[21] The liquid crystal alignment agent according to [20], wherein the tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are one or both of the structural formulae 500 and 511.

[22]如[1]至[21]中任一項所述的液晶配向劑，其特徵在於，其進一步包含環氧化合物。[22] The liquid crystal alignment agent according to any one of [1] to [21] which further comprises an epoxy compound.

[23]如[22]所述的液晶配向劑，其特徵在於，所述環氧化合物是從下述結構式(E1)~(E3)、(E5)及下述通式(E4)所組成的族群中選擇的一個或一個以上。[23] The liquid crystal alignment agent according to [22], wherein the epoxy compound is composed of the following structural formulae (E1) to (E3), (E5), and the following general formula (E4); One or more of the selected ethnic groups.

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

[24]如[22]或[23]所述的液晶配向劑，其特徵在於，相對於所述聚醯胺酸或其衍生物的總量而包含0.1~40 wt%的所述環氧化合物。[24] The liquid crystal alignment agent according to [22], wherein the epoxy compound is contained in an amount of 0.1 to 40% by weight based on the total amount of the polyamic acid or a derivative thereof. .

[25]一種液晶配向膜，其是由[1]至[24]中任一項的液晶配向劑而獲得的。[25] A liquid crystal alignment film obtained by the liquid crystal alignment agent of any one of [1] to [24].

[26]一種液晶顯示元件，其具有：一對基板；含有液晶分子，且形成於所述一對基板之間的液晶層；對液晶層施加電壓的電極；使所述液晶分子於特定方向上配向的液晶配向膜；其特徵在於，所述液晶配向膜是[25]的液晶配向膜。[26] A liquid crystal display element comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and the liquid crystal molecules being oriented in a specific direction An aligned liquid crystal alignment film; characterized in that the liquid crystal alignment film is a liquid crystal alignment film of [25].

[27]如[26]所述的液晶顯示元件，其特徵在於，其是所述電極在相對於所述基板的表面水平的方向上對所述液晶層施加電壓的用於橫向電場方式的液晶顯示元件。[27] The liquid crystal display element according to [26], wherein the electrode is a liquid crystal for transverse electric field mode in which a voltage is applied to the liquid crystal layer in a direction horizontal to a surface of the substrate. Display component.

[28]如[26]所述的液晶顯示元件，其特徵在於，其是所述電極在相對於所述基板的表面垂直的方向上對所述液晶層施加電壓的用於縱向電場方式的液晶顯示元件。[28] The liquid crystal display element according to [26], wherein the electrode is a liquid crystal for a vertical electric field type in which a voltage is applied to the liquid crystal layer in a direction perpendicular to a surface of the substrate. Display component.

[29]一種聚合物，其是四羧酸二酐與二胺的反應產物，其特徵在於，所述二胺包含以上述通式(1)表示的二胺與以上述通式(2)表示的二胺。[29] A polymer which is a reaction product of a tetracarboxylic dianhydride and a diamine, wherein the diamine comprises a diamine represented by the above formula (1) and is represented by the above formula (2) Diamine.

[30]如[29]所述的聚合物，其特徵在於，通式(1)中，R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3的烷基、氟、氯或溴。[30] The polymer according to [29], wherein, in the formula (1), R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen and an alkane having 1 to 3 carbon atoms. Base, fluorine, chlorine or bromine.

[31]如[29]或[30]所述的聚合物，其特徵在於，以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。[31] The polymer according to [29] or [30], wherein the diamine represented by the formula (1) is on the phenyl groups at both ends, and corresponds to the N-Z-N main chain. Each pair has an amino group.

[32]如[32]所述的聚合物，其特徵在於，以通式(1)表示的二胺是從上述結構式239~253及258~262所組成的族群中選擇的一個或一個以上。[32] The polymer according to the above [32], wherein the diamine represented by the formula (1) is one or more selected from the group consisting of the structural formulas 239 to 253 and 258 to 262. .

[33]如[32]所述的聚合物，其特徵在於，以通式(1)表示的二胺是上述結構式240。[33] The polymer according to [32], wherein the diamine represented by the formula (1) is the above structural formula 240.

[34]如[29]至[33]中任一項所述的聚合物，其特徵在於，以通式(2)表示的二胺包含以上述通式(3)~(5)表示的二胺。The polymer of the formula (2), wherein the diamine represented by the formula (2) includes the two groups represented by the above formula (3) to (5), wherein the diamine represented by the above formula (3) to (5) amine.

[35]如[34]所述的聚合物，其特徵在於，通式(3)~(5)中，兩個氨基的位置相對於Y或X1 是對位。[35] The polymer according to [34], wherein, in the general formulae (3) to (5), the positions of the two amino groups are para-position with respect to Y or X 1 .

[36]如[35]所述的聚合物，其特徵在於，以通式(3)表示的二胺是從上述結構式301~304、306、307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從上述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從上述結構式381、384、390及398所組成的族群中選擇的一個或一個以上。[36] The polymer according to the above [35], wherein the diamine represented by the formula (3) is one selected from the group consisting of the above structural formulas 301 to 304, 306, 307 and 313 or One or more diamines represented by the formula (4) are one or more selected from the group consisting of the above structural formulas 360, 364, 365, 367 and 372, and the diamine represented by the formula (5) is One or more selected from the group consisting of the above structural formulas 381, 384, 390, and 398.

[37]如[36]所述的的聚合物，其特徵在於，以通式(3) 表示的二胺是所述結構式301及306的一者或兩者，以通式(4)表示的二胺是上述結構式364，以通式(5)表示的二胺是上述結構式381。[37] The polymer according to [36], which is characterized by the formula (3) The diamine represented by the formulae 301 and 306 is one or both of the structural formulae 301 and 306, and the diamine represented by the formula (4) is the above structural formula 364, and the diamine represented by the formula (5) is the above structural formula 381. .

[38]如[29]至[37]中任一項所述的聚合物，其特徵在於，所述四羧酸二酐是從上述結構式500、505~508、511、515及517中選擇的一個或一個以上。[38] The polymer according to any one of [29] to [37] wherein the tetracarboxylic dianhydride is selected from the above structural formulas 500, 505 to 508, 511, 515 and 517. One or more of them.

[39]如[38]所述的聚合物，其特徵在於，所述四羧酸二酐是上述結構式500及511的一者或兩者。[39] The polymer according to [38], wherein the tetracarboxylic dianhydride is one or both of the structural formulae 500 and 511.

通過本發明，可提供一種具有特別優異的對比度、電壓保持率高、殘留DC下降、不會引起所謂的殘像的蓄積電荷減少的液晶顯示元件，用以形成此液晶顯示元件的液晶配向膜以及可形成此液晶配向膜的聚合物及液晶配向劑。According to the present invention, it is possible to provide a liquid crystal display element having a particularly excellent contrast ratio, a high voltage holding ratio, a residual DC drop, and a reduction in accumulated charge of a so-called afterimage, and a liquid crystal alignment film for forming the liquid crystal display element and A polymer and a liquid crystal alignment agent which form the liquid crystal alignment film.

本發明的液晶配向劑含有四羧酸二酐與二胺的反應產物、即聚醯胺酸或其衍生物。所謂所述聚醯胺酸的衍生物，是指在製成含有溶劑的後述液晶配向劑時溶解於溶劑的成分，是指在將此液晶配向劑製成後述液晶配向膜時，可形成以聚醯亞胺作為主成分的液晶配向膜的成分。作為這種聚醯胺酸的衍生物，例如可舉出：可溶性聚醯亞胺、聚醯胺酸酯及聚醯胺酸醯胺等，更具體來說，可舉出：1)聚醯胺酸的所有氨基與羧基進行脫水閉環反應而獲得的聚醯亞胺、2)聚醯胺酸的一部分氨基與羧基進行脫水閉環反應而獲得的部分聚醯亞胺、3)將聚醯胺酸的羧基轉換為酯的聚 醯胺酸酯、4)將四羧酸二酐化合物所包含的酸二酐的一部分替換為有機二羧酸且使其反應而獲得的聚醯胺酸－聚醯胺共聚物、此外5)使此聚醯胺酸－聚醯胺共聚物的一部分或全部進行脫水閉環反應而獲得的聚醯胺醯亞胺。所述聚醯胺酸或其衍生物既可以是一種化合物，也可以是兩種或兩種以上的化合物。The liquid crystal alignment agent of the present invention contains a reaction product of a tetracarboxylic dianhydride and a diamine, that is, polylysine or a derivative thereof. The derivative of the poly-proline is a component which is dissolved in a solvent when a liquid crystal alignment agent to be described later is prepared, and is used to form a liquid crystal alignment film to form a liquid crystal alignment film. A component of a liquid crystal alignment film containing quinone imine as a main component. Examples of the derivative of the polyaminic acid include soluble polyimine, polyphthalate, and polyamidamine, and more specifically, 1) polyamine a polyimine obtained by performing a dehydration ring-closing reaction of all amino groups of an acid with a carboxyl group, 2) a partial polyimine obtained by performing a dehydration ring-closing reaction of a part of an amino group of a poly-proline, and 3) a poly-proline Conversion of carboxyl groups to esters a phthalic acid ester, 4) a poly-proline-polyamine copolymer obtained by replacing a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound with an organic dicarboxylic acid and reacting it, and 5) A polyamidoquinone imine obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyaminic acid or a derivative thereof may be either a compound or two or more compounds.

所述二胺包含以下述通式(1)表示的二胺。以通式(1)表示的二胺可以是一種化合物，也可以是兩種或兩種以上的化合物。The diamine contains a diamine represented by the following formula (1). The diamine represented by the formula (1) may be one compound or two or more compounds.

所述通式(1)中，R1 獨立地表示一價有機基，R2 獨立地表示一價基，Z表示包含碳數1~5的亞烷基的二價基。In the above formula (1), R 1 independently represents a monovalent organic group, R 2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms.

所述R1 可以使用各種一價有機基，優選R1 獨立為碳數1~3的烷基。所述R2 可以使用各種一價基，R2 較好的是獨立為氫、碳數1~3的烷基、氟、氯或溴。The R 1 may use various monovalent organic groups, and it is preferred that R 1 is independently an alkyl group having 1 to 3 carbon atoms. The R 2 may use various monovalent groups, and R 2 is preferably independently hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine or bromine.

所述Z可以使用包含碳數1~5的亞烷基的各種結構的二價基。Z既可以是碳數1~5的亞烷基，也可以是具有碳數1~5的亞烷基與其他二價基的基團。所述亞烷基既可以是一種，也可以是兩種或兩種以上(其中，不相連)。這種Z例如可舉出以下述通式(8)表示的二價基。As the Z, a divalent group of various structures containing an alkylene group having 1 to 5 carbon atoms can be used. Z may be an alkylene group having 1 to 5 carbon atoms or a group having an alkylene group having 1 to 5 carbon atoms and another divalent group. The alkylene group may be one type or two or more types (wherein not connected). Such Z is, for example, a divalent group represented by the following formula (8).

[化14] [Chemistry 14]

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

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

本發明中，作為以通式(1)表示的二胺，例如可舉出以下化合物。In the present invention, examples of the diamine represented by the formula (1) include the following compounds.

作為更優選的以通式(1)表示的二胺，可舉出以下化合物。The diamine represented by the formula (1) is more preferable, and the following compounds are mentioned.

[化24] [Chem. 24]

此外，作為進一步優選的以通式(1)表示的二胺，可舉出所述結構式239~253及258~262的化合物，作為進一步更優選的以通式(1)表示的二胺，可舉出所述結構式240~243及259~262的化合物。In addition, the diamine represented by the formula (1) is further preferably a compound of the above formulas 239 to 253 and 258 to 262, and further preferably a diamine represented by the formula (1). The compounds of the structural formulae 240 to 243 and 259 to 262 can be mentioned.

所述二胺既可以僅包含以所述通式(1)表示的二胺，也可以進一步包含以下述通式(2)表示的其他二胺。以通式(2)表示的二胺既可以是一種化合物，也可以是兩種或兩種以上的化合物。The diamine may contain only the diamine represented by the above formula (1), or may further contain another diamine represented by the following formula (2). The diamine represented by the formula (2) may be either a compound or two or more compounds.

[化26]H2 N－R3 －NH2 (2)[Chem. 26] H 2 N-R 3 -NH 2 (2)

通式(2)中，R3 表示具有取代基及不包含兩個或兩個以上的亞氨基的二價有機基。In the formula (2), R 3 represents a divalent organic group having a substituent and not containing two or more imino groups.

以通式(2)表示的二胺中包含各種二胺，優選舉出以下述通式(3)~(6)表示的二胺。The diamine represented by the formula (2) contains various diamines, and preferably a diamine represented by the following general formulae (3) to (6).

[化27] [化27]

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

通式(4)中，X1 獨立地表示亞甲基或氧，X2 表示可具有甲基或CF3 作為取代基的碳數1~8的亞烷基。In the formula (4), X 1 independently represents a methylene group or oxygen, and X 2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF 3 as a substituent.

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

通式(6)中，R5 表示氫或一價基。所述一價基可以使用各種有機基，優選碳數1~30的烴基。此烴基優選為具有亞烷基、環亞烷基、亞芳基等二價烴基與烷基的基團。In the formula (6), R 5 represents hydrogen or a monovalent group. The monovalent group may use various organic groups, preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group is preferably a group having a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group or an arylene group and an alkyl group.

所述通式(3)~(5)中，鍵結於兩端的苯基上的兩個氨基的位置相對於Y或X1 可以是鄰位、間位及對位的任一位置，但就提高液晶顯示元件的施加電壓時的黑顯示特性的觀點而言，優選相對於Y或X1 為對位。In the general formulae (3) to (5), the positions of the two amino groups bonded to the phenyl groups at both ends may be any position of the ortho, meta and para positions with respect to Y or X 1 , but From the viewpoint of improving the black display characteristics when the voltage is applied to the liquid crystal display element, it is preferable to be aligned with respect to Y or X 1 .

另外，所述通式(6)中，鍵結於末端的苯基上的兩個氨基的位置相互之間可以是鄰位、間位及對位的任一位置，但就使液晶顯示元件中表現出較大的預傾角的觀點而言，優選相互之間為間位。Further, in the above formula (6), the positions of the two amino groups bonded to the phenyl group at the terminal may be any position of the ortho, meta and para positions, but in the liquid crystal display element From the viewpoint of exhibiting a large pretilt angle, it is preferable to be meta-position with each other.

作為以通式(3)表示的二胺，例如可舉出以下化合物。The diamine represented by the formula (3) is exemplified by the following compounds.

作為更優選的以通式(3)表示的二胺，可舉出以下化合物。The diamine represented by the formula (3) is more preferable, and the following compounds are mentioned.

作為進一步優選的以通式(3)表示的二胺，可舉出所述結構式301~307及311~319的化合物，作為進一步更優選的以通式(3)表示的二胺，可舉出所述結構式301~304、306、307及313的化合物。The diamine represented by the formula (3) is further preferably a compound of the above structural formulas 301 to 307 and 311 to 319, and more preferably a diamine represented by the formula (3). The compounds of the structural formulae 301 to 304, 306, 307 and 313 are derived.

作為以通式(4)表示的二胺，例如可舉出以下化合物。The diamine represented by the formula (4) is exemplified by the following compounds.

作為更優選的以通式(4)表示的二胺，可舉出以下化合物。The diamine represented by the formula (4) is more preferable, and the following compounds are mentioned.

作為進一步優選的以通式(4)表示的二胺，可舉出所述結構式360、364~367及372的化合物，作為進一步更優選的以通式(4)表示的二胺，可舉出所述結構式360、364、365、367及372的化合物。Further, the diamine represented by the formula (4) is exemplified by the compounds of the structural formulas 360, 364 to 367 and 372, and the diamine represented by the formula (4) is more preferable. The compounds of structural formulas 360, 364, 365, 367 and 372 are derived.

作為以通式(5)表示的二胺，例如可舉出以下化合物。The diamine represented by the formula (5) is exemplified by the following compounds.

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

作為進一步優選的以通式(5)表示的二胺，可舉出所述結構式381、382、384、390及398的化合物，作為進一步更優選的以通式(5)表示的二胺，可舉出所述結構式381、384、390及398的化合物。Further, the diamine represented by the formula (5) is exemplified by the compounds of the structural formulas 381, 382, 384, 390 and 398, and the diamine represented by the formula (5) is further more preferable. The compounds of the structural formulas 381, 384, 390 and 398 can be mentioned.

作為以通式(6)表示的二胺，例如可舉出以下化合物。The diamine represented by the formula (6) is exemplified by the following compounds.

作為更優選的以通式(6)表示的二胺，可舉出以下化合物。The diamine represented by the formula (6) is more preferable, and the following compounds are mentioned.

作為進一步優選的以通式(6)表示的二胺，可舉出所述結構式438、443、447及449~451的化合物。Further, the diamine represented by the formula (6) is exemplified by the compounds of the structural formulae 438, 443, 447 and 449 to 451.

本發明中，作為所述二胺，可進一步使用以通式(1)及(2)表示的二胺以外的其他二胺。作為這種其他二胺，可舉出以下述通式(9a)或(9b)表示的二胺及具有矽氧烷鍵的矽氧烷系二胺。In the present invention, as the diamine, other diamines other than the diamines represented by the general formulae (1) and (2) can be further used. Examples of such other diamines include a diamine represented by the following general formula (9a) or (9b) and a decane oxide-based diamine having a decane bond.

通式(9a)及(9b)中，Q表示氧、硫、磺醯基、可具有取代基的碳數6~20的亞芳基、可具有取代基的碳數3~20的環亞烷基、或可具有取代基的亞氨基。所述亞芳基、環亞烷基及亞氨基可具有的取代基可舉出獨立為碳數1~3的烷基、氟、氯及溴等一價有機基。所述亞芳基可舉出1,4－亞苯基，所述環亞烷基可舉出1,4－亞環己基。通式(9a)及(9b)中的R1 、R2 及R8 與所述通式(1)及(8)相同。作為以通式(9a)或(9b)表示的二胺，例如可舉 出以下化合物。In the general formulae (9a) and (9b), Q represents an oxygen, sulfur, sulfonyl group, a hexylene group having 6 to 20 carbon atoms which may have a substituent, and a cycloalkylene having 3 to 20 carbon atoms which may have a substituent. A group or an imino group which may have a substituent. The substituent which the arylene group, the cycloalkylene group and the imino group may have is a monovalent organic group such as an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine or bromine. The arylene group may be a 1,4-phenylene group, and the cycloalkylene group may be a 1,4-cyclohexylene group. R 1 , R 2 and R 8 in the general formulae (9a) and (9b) are the same as the above formulas (1) and (8). Examples of the diamine represented by the formula (9a) or (9b) include the following compounds.

以通式(9a)或(9b)表示的二胺在兩端的苯基上分別具有氨基。這些氨基的位置相對於所述二價有機基，可以是鄰位、間位、對位的任一位置，但就提高液晶顯示元件的施加電壓時的黑顯示特性的觀點而言，優選均為對位。The diamine represented by the formula (9a) or (9b) has an amino group at each of the phenyl groups at both ends. The position of the amino group may be any position of the ortho, meta or para position with respect to the divalent organic group, but it is preferably from the viewpoint of improving the black display property when the voltage is applied to the liquid crystal display element. Counterpoint.

作為優選的以通式(9a)或(9b)表示的二胺，可舉出以下化合物。Preferred examples of the diamine represented by the formula (9a) or (9b) include the following compounds.

對於所述矽氧烷系二胺並沒有特別限制，可以在本發明中比較好地使用以通式(7)表示的二胺。The dioxane-based diamine is not particularly limited, and the diamine represented by the formula (7) can be preferably used in the present invention.

通式(7)中，R22 及R23 獨立地表示碳數1~3的烷基或苯基，R21 獨立地表示亞甲基、亞苯基或被烷基取代的亞苯基，X獨立地表示1~6的整數，y表示1~10的整數。In the formula (7), R 22 and R 23 independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R 21 independently represents a methylene group, a phenylene group or a phenylene group substituted by an alkyl group, X Independently represents an integer from 1 to 6, and y represents an integer from 1 to 10.

本發明中，所使用的所述二胺的種類可以根據液晶顯示元件的電場方式進行確定。已知液晶顯示元件的電場方式有橫向電場方式與縱向電場方式，在橫向電場方式的液晶顯示元件中，必須表現出較小的預傾角，也就是所謂的低預傾角，所以如果是以通式(2)表示的二胺，那麽主要使用以通式(3)或(4)表示的二胺。In the present invention, the type of the diamine used can be determined in accordance with the electric field mode of the liquid crystal display element. It is known that the electric field mode of the liquid crystal display element has a transverse electric field mode and a longitudinal electric field mode, and in the liquid crystal display element of the transverse electric field mode, it is necessary to exhibit a small pretilt angle, that is, a so-called low pretilt angle, so if it is a general formula The diamine represented by (2) is mainly a diamine represented by the formula (3) or (4).

本發明中，由使用100莫耳%的以通式(1)表示的二胺作為所述二胺的液晶配向劑而獲得的液晶顯示元件同時具有較大的對比度、低殘留DC、及低預傾角的特性。因此，有效作為橫向電場方式的液晶配向膜。關於需要較大 的預傾角的用於縱向電場方式的液晶顯示元件，必須與表現出較大的預傾角的所謂具有支鏈的二胺並用。作為所述具有支鏈的二胺，如果是以通式(2)表示的二胺，那麽可以舉出以通式(5)或(6)表示的二胺，作為並用的形態，必須是使用具有支鏈的二胺所獲得的聚醯胺酸或其衍生物與其他(例如低預傾角)聚醯胺酸或其衍生物的混合物，或者是具有支鏈的二胺與低預傾角的二胺的共聚物。In the present invention, a liquid crystal display element obtained by using 100 mol% of a diamine represented by the general formula (1) as a liquid crystal alignment agent of the diamine has a large contrast ratio, a low residual DC, and a low pretreatment. The characteristics of the dip. Therefore, it is effective as a liquid crystal alignment film of a transverse electric field type. About the need for a larger The pretilt angle liquid crystal display element for the longitudinal electric field mode must be used in combination with a so-called branched diamine which exhibits a large pretilt angle. When the diamine represented by the formula (2) is a diamine represented by the formula (2), a diamine represented by the formula (5) or (6) may be mentioned, and the form to be used in combination must be used. a mixture of a polyamine or a derivative thereof having a branched diamine with another (for example, a low pretilt) polyaminic acid or a derivative thereof, or a branched diamine with a low pretilt angle a copolymer of an amine.

此外，本發明的聚合物中，並用以通式(1)表示的二胺與以通式(2)表示的二胺的一種或一種以上。此時，就使液晶顯示元件中的殘留DC明顯地降低的觀點而言，優選所述二胺中的以通式(1)表示的二胺的含有率為20莫耳%或20莫耳%以上。如果以通式(1)表示的二胺的含有率小於20莫耳%，那麽有時殘留DC的降低效果會較小，而不會表現出針對殘像的效果。Further, in the polymer of the present invention, one or more kinds of the diamine represented by the formula (1) and the diamine represented by the formula (2) are used. In view of the fact that the residual DC in the liquid crystal display element is remarkably lowered, the content of the diamine represented by the general formula (1) in the diamine is preferably 20 mol% or 20 mol%. the above. When the content of the diamine represented by the general formula (1) is less than 20 mol%, the effect of reducing the residual DC may be small, and the effect on the afterimage may not be exhibited.

在橫向電場方式的液晶顯示元件中，就提高不施加電壓時的黑顯示特性的觀點而言，優選在以通式(1)表示的二胺的基礎上進一步並用以通式(3)及(4)表示的二胺的一種或一種以上。進一步使用這些二胺，會成為低預傾角，所以對橫向電場方式非常有效。所述二胺中的以通式(3)及(4)表示的二胺越多則越是提高液晶顯示元件的電壓保持率，但是考慮到殘留DC的降低，那麽所述含有率較好的是在1莫耳%~80莫耳%的範圍內。In the liquid crystal display device of the transverse electric field type, it is preferable to further use the general formula (3) and (in addition to the diamine represented by the general formula (1) from the viewpoint of improving the black display characteristics when no voltage is applied. 4) One or more of the diamines indicated. Further use of these diamines results in a low pretilt angle and is therefore very effective for the transverse electric field mode. The more diamines represented by the general formulae (3) and (4) in the diamine, the more the voltage holding ratio of the liquid crystal display element is improved, but in view of the decrease in residual DC, the content ratio is good. It is in the range of 1% by mole to 80% by mole.

另外，在縱向電場方式即TN方式、光學補償彎曲(Optically Compensated Bend，OCB)方式、垂直排列 (Vertiical Alignment，VA)方式中，必須表現出較大的預傾角。此時，必須將帶有支鏈的以通式(5)及(6)表示的二胺的一種或一種以上與以通式(1)表示的二胺並用。通過控制這些二胺的種類及比例，能夠表現出預定的預傾角，但考慮到降低殘留DC，那麽優選所述含有率在1莫耳%~80莫耳%的範圍內。應用通過並用以通式(5)及(6)表示的二胺而獲得的聚合物的液晶顯示元件可成為進一步提高電壓保持率的縱向電場方式的液晶顯示元件。In addition, in the vertical electric field mode, that is, TN mode, optically compensated Bend (OCB) mode, vertical alignment In the (Vertiical Alignment, VA) mode, a large pretilt angle must be exhibited. In this case, one or more kinds of the diamines represented by the general formulae (5) and (6) having a branching property must be used in combination with the diamine represented by the general formula (1). By controlling the type and ratio of these diamines, a predetermined pretilt angle can be exhibited. However, in view of reducing residual DC, the content ratio is preferably in the range of 1 mol% to 80 mol%. A liquid crystal display element using a polymer obtained by using the diamines represented by the general formulae (5) and (6) can be a vertical electric field type liquid crystal display element which further increases the voltage holding ratio.

另外，在進一步含有所述通式(1)~(6)以外的其他二胺時，在應用所獲得的聚合物的液晶顯示元件中，就充分表現出殘留DC的降低或黑顯示特性的提高效果的觀點而言，其他二胺的含有率優選二胺整體的30莫耳%或30莫耳%以下。In addition, when the other diamines other than the above formulas (1) to (6) are further contained, the liquid crystal display element of the polymer obtained by the application sufficiently exhibits a decrease in residual DC or an improvement in black display characteristics. From the viewpoint of the effect, the content of the other diamine is preferably 30 mol% or less of 30 mol% or less of the entire diamine.

作為所述四羧酸二酐，在不損及本發明的效果的情況下，可使用芳香族系四羧酸二酐、脂環式四羧酸二酐及脂肪族四羧酸二酐等各種四羧酸二酐的一種或者兩種或兩種以上。As the tetracarboxylic dianhydride, various kinds of aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride can be used without impairing the effects of the present invention. One or two or more kinds of tetracarboxylic dianhydrides.

作為可用於本發明的四羧酸二酐，例如可舉出以下化合物。As the tetracarboxylic dianhydride which can be used in the present invention, for example, the following compounds can be mentioned.

所述四羧酸二酐優選所述結構式500、505~508、 511、515及517的化合物，更優選所述結構式500及511的化合物。The tetracarboxylic dianhydride is preferably the structural formula 500, 505-508, The compounds of 511, 515 and 517 are more preferably compounds of the formulae 500 and 511.

所述聚醯胺酸或其衍生物的分子量，例如為利用凝膠滲透色譜法(Gel Permeation Chromatography，GPC)的所獲得的聚苯乙烯換算的重量平均分子量(Mw)，優選10,000~500,000，更優選20,000~200,000。The molecular weight of the polyaminic acid or a derivative thereof is, for example, a polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC), preferably 10,000 to 500,000, more preferably It is preferably 20,000 to 200,000.

所述聚醯胺酸或其衍生物，除了使用所述四羧酸二酐與二胺以外，也可以與聚醯亞胺膜的形成中所使用的公知的聚醯胺酸或其衍生物同樣進行製造。例如，向具備原料投入口、氮氣導入口、溫度計、攪拌機及冷凝器的反應容器中投入以通式(1)及(2)~(6)表示的二胺的一種或者兩種或兩種以上、以及根據情況從其他二胺中選擇的一種或者兩種或兩種以上的二胺，此外根據需要投入所需量的單胺。The polyamic acid or a derivative thereof may be the same as the known poly-proline or the derivative thereof used in the formation of the polyimide film, in addition to the tetracarboxylic dianhydride and the diamine. Made for manufacturing. For example, one or two or more kinds of diamines represented by the general formulae (1) and (2) to (6) are introduced into a reaction container having a raw material inlet, a nitrogen gas inlet, a thermometer, a stirrer, and a condenser. And one or two or more kinds of diamines selected from other diamines as the case may be, and further, a desired amount of the monoamine is supplied as needed.

接著，投入溶劑(例如，醯胺系極性溶劑即N－甲基－2－吡咯烷酮或二甲基甲醯胺等)及四羧酸二酐的一種或者兩種或兩種以上，此外根據需要投入羧酸酐。此時，四羧酸二酐的總投入量優選與二胺的總莫耳數大致相等的莫耳數(莫耳比0.9~1.1左右)。Then, one or two or more kinds of a solvent (for example, a guanamine-based polar solvent, that is, N-methyl-2-pyrrolidone or dimethylformamide) and a tetracarboxylic dianhydride are charged, and further, if necessary, Carboxylic anhydride. At this time, the total amount of the tetracarboxylic dianhydride to be charged is preferably a molar number (molar ratio of about 0.9 to 1.1) which is substantially equal to the total number of moles of the diamine.

所述聚醯胺酸或其衍生物包含以通式(1)表示的二胺與四羧酸二酐反應而生成的結構，此外可包含以通式(2)表示的二胺與四羧酸二酐反應而生成的結構。作為以通式(1)表示的二胺與四羧酸二酐反應而生成的結構，例如可舉出以下述通式(10)及(11)表示的結構，作為以通式 (2)表示的二胺與四羧酸二酐的反應而生成的結構，例如可舉出以下述通式(12)及(13)表示的結構。另外，通式(10)~(13)中，R10 表示來源於四羧酸二酐的四價有機基，R1 及R2 與通式(1)相同，R3 與通式(2)相同。The polyaminic acid or a derivative thereof comprises a structure obtained by reacting a diamine represented by the formula (1) with a tetracarboxylic dianhydride, and further comprises a diamine and a tetracarboxylic acid represented by the formula (2) A structure formed by the reaction of dianhydride. The structure which is produced by the reaction of the diamine represented by the formula (1) and the tetracarboxylic dianhydride is, for example, a structure represented by the following general formulae (10) and (11), and is represented by the general formula (2). The structure formed by the reaction of the diamine and the tetracarboxylic dianhydride is, for example, a structure represented by the following general formulae (12) and (13). Further, in the general formulae (10) to (13), R 10 represents a tetravalent organic group derived from tetracarboxylic dianhydride, R 1 and R 2 are the same as those of the general formula (1), and R 3 and the general formula (2) the same.

所述聚醯胺酸或其衍生物中的以通式(10)~(13)表示的結構可通過確定聚合物的結構時的通常技術來加以確定，更具體來說，可通過紅外光譜(Infrared Spectroscopy，IR)或核磁共振(nuclear magnetic resonance，NMR)來確定。The structure represented by the general formulae (10) to (13) in the poly-proline or a derivative thereof can be determined by a usual technique for determining the structure of the polymer, and more specifically, by infrared spectroscopy ( Infrared Spectroscopy (IR) or nuclear magnetic resonance (NMR) was used to determine.

更詳細來說，對於本發明中的聚醯胺酸或其衍生物，以大量的不良溶劑使其沉澱，通過過濾等將固體成分與溶劑完全分離，並以IR、NMR進行分析，由此可加以鑒定。此外，利用KOH或NaOH等强鹼水溶液使固體成分的聚 醯胺酸或其衍生物分解後，以有機溶劑進行萃取，並以氣相色譜(Gas Chromatography，GC)、高效液相色譜法(High performance Liquid Chromatography，HPLC)或氣相色譜/質譜分析法(Gas Chromatography－Mass Spectrometry，GC－MS)進行分析，由此可鑒定所使用的單體。More specifically, the poly-proline or the derivative thereof in the present invention is precipitated with a large amount of a poor solvent, and the solid component is completely separated from the solvent by filtration or the like, and analyzed by IR or NMR. Identification. In addition, the solid component is aggregated by using a strong alkali aqueous solution such as KOH or NaOH. After the proline or its derivative is decomposed, it is extracted with an organic solvent and subjected to gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography/mass spectrometry ( Gas Chromatography-Mass Spectrometry (GC-MS) was analyzed to identify the monomers used.

本發明的液晶配向劑也可以進一步含有所述聚醯胺酸或其衍生物以外的其他成分。其他成分可以是一種，也可以是兩種或兩種以上。The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid or a derivative thereof. The other components may be one type or two or more types.

例如，就提高液晶配向膜的耐久性的觀點而言，例如本發明的液晶配向劑也可以進一步含有環氧化合物。如果所述環氧化合物具有環氧基，那麽並沒有特別限制，但優選具有兩個或兩個以上環氧乙烷基的化合物。所述環氧化合物可以是一種化合物，也可以是兩種或兩種以上的化合物。For example, from the viewpoint of improving the durability of the liquid crystal alignment film, for example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound. If the epoxy compound has an epoxy group, it is not particularly limited, but a compound having two or more ethylene oxide groups is preferred. The epoxy compound may be one compound or two or more compounds.

本發明中，液晶配向劑中的所述環氧化合物的含量並沒有特別限制，在由液晶配向劑所形成的液晶配向膜中，就優化不易因摩擦處理而使膜受到磨損等的耐久性的觀點而言，優選所述環氧化合物的含量相對於液晶配向劑為0.1~40 wt%，更優選0.2~30 wt%。In the present invention, the content of the epoxy compound in the liquid crystal alignment agent is not particularly limited, and in the liquid crystal alignment film formed of the liquid crystal alignment agent, the durability of the film which is not easily rubbed by the rubbing treatment is optimized. From the viewpoint, the content of the epoxy compound is preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight based on the liquid crystal alignment agent.

作為所述環氧化合物，例如可舉出：雙酚A型環氧化合物、縮水甘油酯型環氧化合物、脂環式環氧化合物、具有環氧乙烷基的單體的聚合物、及具有環氧乙烷基的單體與其他單體的共聚物、以下述結構式(E1)~(E3)、(E5)表示的化合物、及以下述通式(E4)表示的化合物等。Examples of the epoxy compound include a bisphenol A epoxy compound, a glycidyl ester epoxy compound, an alicyclic epoxy compound, a polymer having a monomer having an oxirane group, and A copolymer of an oxiranyl group monomer and another monomer, a compound represented by the following structural formulae (E1) to (E3), (E5), a compound represented by the following formula (E4), and the like.

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

更具體來說，作為所述環氧化合物，可舉出：商品名“Epikote 807”、“Epikote 815”、“Epikote 825”、“Epikote 827”。More specifically, examples of the epoxy compound include "Epikote 807", "Epikote 815", "Epikote 825", and "Epikote 827".

作為以通式(E4)表示的化合物，可舉出：商品名 “Epikote 828”、“Epikote 190P”、“Epikote 191P”(以上為YUKA SHELL EPOXY股份有限公司製造)、商品名“Epikote 1004”、“Epikote 1256”(以上為JAPAN EPOXY RESINS股份有限公司製造)、商品名“Araldite CY177”。The compound represented by the formula (E4): a trade name "Epikote 828", "Epikote 190P", "Epikote 191P" (above, manufactured by YUKA SHELL EPOXY Co., Ltd.), trade name "Epikote 1004", "Epikote 1256" (above, manufactured by JAPAN EPOXY RESINS Co., Ltd.), and products Named "Araldite CY177".

作為以結構式(E1)表示的化合物，可舉出商品名“Araldite CY184”(日本CIBA－GEIGY股份有限公司製造)。The compound represented by the structural formula (E1) is exemplified by the trade name "Araldite CY184" (manufactured by CIBA-GEIGY Co., Ltd., Japan).

作為以結構式(E2)表示的化合物，可舉出商品名“Celloxide 2021P”、“EHPE－3150”(DAICEL化學工業股份有限公司製造)。The compound represented by the structural formula (E2) is exemplified by the trade name "Celloxide 2021P" and "EHPE-3150" (manufactured by DAICEL Chemical Industry Co., Ltd.).

作為以結構式(E3)表示的化合物，可舉出商品名“TECMOA VG3101L”(三井化學股份有限公司製造)。The compound represented by the structural formula (E3) is exemplified by the trade name "TECMOA VG3101L" (manufactured by Mitsui Chemicals, Inc.).

作為以結構式(E5)表示的化合物，可舉出“4,4'－亞甲基雙(N,N－二縮水甘油基苯胺)”(SIGMA－ALDRICH公司製造)。The compound represented by the structural formula (E5) is "4,4'-methylenebis(N,N-diglycidylaniline)" (manufactured by SIGMA-ALDRICH).

就優化液晶配向膜的透明性與平坦性的觀點而言，這些化合物中，所述環氧化合物優選包含：以通式(E4)表示的化合物(n＝0~4的化合物的混合物)即“Epikote 828”、以結構式(E1)表示的化合物即“Araldite CY184”(日本CIBA－GEIGY股份有限公司製造)、以結構式(E2)表示的化合物即商品名“Celloxide 2021P”(DAICEL化學工業股份有限公司製造)、以結構式(E3)表示的化合物即商品名“TECMOA VG3101L”(三井化學股份有限公 司製造)及以結構式(E5)表示的化合物“4,4'－亞甲基雙(N,N－二縮水甘油基苯胺)”(SIGMA－ALDRICH公司製造)。In view of optimizing the transparency and flatness of the liquid crystal alignment film, in the compound, the epoxy compound preferably contains a compound represented by the formula (E4) (a mixture of compounds of n=0 to 4), that is, " Epikote 828", a compound represented by the structural formula (E1), "Araldite CY184" (manufactured by CIBA-GEIGY Co., Ltd., Japan), and a compound represented by the structural formula (E2), trade name "Celloxide 2021P" (DAICEL Chemical Industry Co., Ltd.) Manufactured by the company, the compound represented by the structural formula (E3) is the trade name "TECMOA VG3101L" (Mitsui Chemical Co., Ltd. The product "4,4'-methylenebis(N,N-diglycidylaniline)" (manufactured by SIGMA-ALDRICH Co., Ltd.) represented by the formula (E5).

此外，作為所述環氧化合物，例如可舉出：縮水甘油醚、縮水甘油酯、縮水甘油胺、含有環氧基的丙烯酸系樹脂、縮水甘油基醯胺、縮水甘油基異氰尿酸酯、鏈狀脂肪族型環氧化合物及環狀脂肪族型環氧化合物。而且，環氧化合物是指具有環氧基的化合物，環氧樹脂是指具有環氧基的樹脂。Further, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, and glycidyl isocyanurate. A chain aliphatic epoxy compound and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

作為所述縮水甘油醚，例如可舉出：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、雙酚型環氧化合物、氫化雙酚－A型環氧化合物、氫化雙酚－F型環氧化合物、氫化雙酚－S型環氧化合物、氫化雙酚型環氧化合物、溴化雙酚－A型環氧化合物、溴化雙酚－F型環氧化合物、苯酚酚醛清漆(phenol novolac)型環氧化合物、甲酚酚醛清漆(cresol novolac)型環氧化合物、溴化苯酚酚醛清漆型環氧化合物、溴化甲酚酚醛清漆型環氧化合物、雙酚A酚醛清漆型環氧化合物、含有萘骨架的環氧化合物、芳香族聚縮水甘油醚化合物、二環戊二烯苯酚型環氧化合物、脂環式二縮水甘油醚化合物、脂肪族聚縮水甘油醚化合物、多硫化物(polysulfide)型二縮水甘油醚化合物及聯苯酚(biphenol)型環氧化合物。Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A ring. Oxygen compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type ring Oxygen compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolak type epoxy compound, brominated cresol novolak type epoxy compound, double Phenolic A novolak type epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidol An ether compound, a polysulfide type diglycidyl ether compound, and a biphenol type epoxy compound.

作為所述縮水甘油酯，例如可舉出二縮水甘油酯化合物及縮水甘油酯環氧化合物。Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

作為所述縮水甘油胺，例如可舉出聚縮水甘油胺化合物。As the glycidylamine, for example, a polyglycidylamine compound can be mentioned.

作為所述含有環氧基的丙烯酸系化合物，例如可舉出具有環氧乙烷基(oxiranyl)的單體的均聚物(homopolymer)及共聚物。Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxiranyl group.

作為所述縮水甘油基醯胺，例如可舉出縮水甘油基醯胺型環氧化合物。Examples of the glycidyl decylamine include a glycidyl guanamine type epoxy compound.

作為所述鏈狀脂肪族型環氧化合物，例如可舉出使烯烴化合物的碳－碳雙鍵氧化而獲得的含有環氧基的化合物。The chain aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

作為所述環狀脂肪族型環氧化合物，例如可舉出使環烯烴化合物的碳－碳雙鍵氧化而獲得的含有環氧基的化合物。The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cyclic olefin compound.

作為所述雙酚A型環氧化合物，例如可舉出：828、1001、1002、1003、1004、1007、1010(均為JAPAN EPOXY RESINS製造)、Epotohto YD－128(東都化成公司製造)、DER－331、DER－332、DER－324(均為DOW CHEMICAL公司製造)、Epikuron 840、Epikuron 850、Epikuron 1050(均為大日本油墨公司製造)、Epomic R－140、Epomic R－301及Epomic R－304(均為三井化學公司製造)。Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by JAPAN EPOXY RESINS), Epotohto YD-128 (manufactured by Tosho Kasei Co., Ltd.), and DER. -331, DER-332, DER-324 (all manufactured by DOW CHEMICAL), Epikuron 840, Epikuron 850, Epikuron 1050 (all manufactured by Dainippon Ink Co., Ltd.), Epomic R-140, Epomic R-301, and Epomic R- 304 (all manufactured by Mitsui Chemicals Co., Ltd.).

作為所述雙酚F型環氧化合物，例如可舉出806、807、4004P(均為JAPAN EPOXY RESINS製造)、Epotohto YDF－170、Epotohto YDF－175S、Epotohto YDF－2001(均為東都化成公司製造)、DER－354(DOW CHEMICAL公司製造)、Epikuron 830及Epikuron 835(均為大日本油墨公司 製造)。Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by JAPAN EPOXY RESINS), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). ), DER-354 (manufactured by DOW CHEMICAL), Epikuron 830 and Epikuron 835 (both are Dainippon Ink Co., Ltd.) Manufacturing).

作為所述雙酚型環氧化合物，例如可舉出：2,2－雙(4－羥基苯基)－1,1,1,3,3,3－六氟丙烷的環氧化物。Examples of the bisphenol epoxy compound include an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

作為所述氫化雙酚－A型環氧化合物，例如可舉出：Suntohto ST－3000(東都化成公司製造)、Ricaresin HBE－100(新日本理化公司製造)及Denacol EX－252(NAGASE CHEMTEX公司製造)。Examples of the hydrogenated bisphenol-A type epoxy compound include Suntohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Ricaresin HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (manufactured by NAGASE CHEMTEX Co., Ltd.). ).

作為所述氫化雙酚型環氧化合物，例如可舉出氫化2,2－雙(4－羥基苯基)－1,1,1,3,3,3－六氟丙烷的環氧化物。Examples of the hydrogenated bisphenol epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

作為所述溴化雙酚－A型環氧化合物，例如可舉出：5050、5051(均為JAPAN EPOXY RESINS製造)、Epotohto YDB－360、Epotohto YDB－400(均為東都化成公司製造)、DER－530、DER－538(均為DOW CHEMICAL公司製造)、Epikuron 152及Epikuron 153(均為大日本油墨公司製造)。Examples of the brominated bisphenol-A type epoxy compound include 5050 and 5051 (all manufactured by JAPAN EPOXY RESINS), Epotohto YDB-360, and Epotohto YDB-400 (all manufactured by Tohto Kasei Co., Ltd.), and DER. -530, DER-538 (all manufactured by DOW CHEMICAL), Epikuron 152, and Epikuron 153 (all manufactured by Dainippon Ink Co., Ltd.).

作為所述苯酚酚醛清漆型環氧化合物，例如可舉出：152、154(均為JARAN EPOXY RESINS製造)、YDPN－638(東都化成公司製造)、DEN431、DEN438(均為DOW CHEMICAL公司製造)、Epikuron N－770(大日本油墨化學工業股份有限公司製造)、EPPN－201及EPPN－202(均為日本化藥股份有限公司製造)。Examples of the phenol novolak-type epoxy compound include 152 and 154 (both manufactured by JARAN EPOXY RESINS), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431, and DEN438 (all manufactured by DOW CHEMICAL Co., Ltd.). Epikuron N-770 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

作為所述甲酚酚醛清漆型環氧化合物，例如可舉出：180S75(JAPAN EPOXY RESINS製造)、YDCN－701、YDCN－702(均為東都化成公司製造)、Epikuron N－665、Epikuron N－695(均為大日本油墨化學工業股份有限公司 製造)、EOCN－102S、EOCN－103S、EOCN－104S、EOCN－1020、EOCN－1025及EOCN－1027(均為日本化藥股份有限公司製造)。Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by JAPAN EPOXY RESINS), YDCN-701, and YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), Epikuron N-665, and Epikuron N-695. (All are Dainippon Ink Chemical Industry Co., Ltd. Manufacturing), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

作為所述雙酚A酚醛清漆型環氧化合物，例如可舉出：157S70(JAPAN EPOXY RESINS股份有限公司製造)及Epikuron N－880(大日本油墨化學工業股份有限公司製造)。Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by JAPAN EPOXY RESINS Co., Ltd.) and Epikuron N-880 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

作為所述含有萘骨架的環氧化合物，例如可舉出：Epikuron HP－4032、Epikuron HP－4700、Epikuron HP－4770(均為大日本油墨化學工業股份有限公司製造)及NC－7000(日本化藥公司製造)。Examples of the epoxy compound containing a naphthalene skeleton include Epikuron HP-4032, Epikuron HP-4700, Epikuron HP-4770 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), and NC-7000 (Japanese). Manufactured by a pharmaceutical company).

作為所述芳香族聚縮水甘油醚化合物，例如可舉出：對苯二酚二縮水甘油醚(下述結構式E101)、鄰苯二酚二縮水甘油醚(下述結構式E102)、間苯二酚二縮水甘油醚(下述結構式E103)、三(4－縮水甘油氧基苯基)甲烷(下述結構式E105)、1031S、1032H60(均為JAPAN EPOXY RESINS製造)、TACTIX－742(DOW CHEMICAL公司製造)、Denacol EX－201(NAGASE CHEMTEX公司製造)、DPPN－503、DPPN－502H、DPPN－501H、NC6000(均為日本化藥股份有限公司製造)、TECMOA VG3101L(三井化學公司製造)、以下述結構式E106表示的化合物及以下述結構式E107表示的化合物。Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following structural formula E101), catechol diglycidyl ether (the following structural formula E102), and isophthalic acid. Diphenol diglycidyl ether (the following structural formula E103), tris(4-glycidoxyphenyl)methane (the following structural formula E105), 1031S, 1032H60 (all manufactured by JAPAN EPOXY RESINS), TACTIX-742 ( Manufactured by DOW CHEMICAL, Denacol EX-201 (manufactured by NAGASE CHEMTEX), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), TECMOA VG3101L (manufactured by Mitsui Chemicals, Inc.) A compound represented by the following structural formula E106 and a compound represented by the following structural formula E107.

[化58] [化58]

作為所述二環戊二烯苯酚型環氧化合物，例如可舉出：TACTIX－556(DOW CHEMICAL公司製造)及Epikuron HP－7200(大日本油墨化學工業股份有限公司製造)。Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by DOW CHEMICAL Co., Ltd.) and Epikuron HP-7200 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

作為所述脂環式二縮水甘油醚化合物，例如可舉出：環己烷二甲醇二縮水甘油醚化合物及Ricaresin DME－100(新日本理化公司製造)。Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Ricaresin DME-100 (manufactured by Shin-Nippon Chemical Co., Ltd.).

作為所述脂肪族聚縮水甘油醚化合物，例如可舉出： 乙二醇二縮水甘油醚(下述結構式E108)、二乙二醇二縮水甘油醚(下述結構式E109)、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚(下述結構式E110)、三丙二醇二縮水甘油醚(下述結構式E111)、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚(下述結構式E112)、1,4－丁二醇二縮水甘油醚(下述結構式E113)、1,6－己二醇二縮水甘油醚(下述結構式E114)、二溴新戊二醇二縮水甘油醚(下述結構式E115)、Denacol EX－810、Denacol EX－851、Denacol EX－8301、Denacol EX－911、Denacol EX－920、Denacol EX－931、Denacol EX－211、Denacol EX－212、Denacol EX－313(均為NAGASE CHEMTEX公司製造)、DD－503(旭電化公司製造)、Ricaresin W－100(新日本理化公司製造)、1,3,5,6－四縮水甘油基－2,4－己二醇(下述結構式E116)、甘油聚縮水甘油醚、山梨醇聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、季戊四醇聚縮水甘油醚、Denacol EX－313、Denacol EX－611、Denacol EX－321及Denacol EX－411(均為NAGASE CHEMTEX公司製造)。As the aliphatic polyglycidyl ether compound, for example, Ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol diglycidyl ether (the following structural formula E109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (the following structural formula) E110), tripropylene glycol diglycidyl ether (the following structural formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula E112), 1,4-butanediol diglycidyl Ether (structure E113 below), 1,6-hexanediol diglycidyl ether (structure E114 below), dibromo neopentyl glycol diglycidyl ether (structure E115 below), Denacol EX-810 , Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all manufactured by NAGASE CHEMTEX), DD -503 (manufactured by Asahi Kasei Co., Ltd.), Ricaresin W-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (structure E116 below), glycerin Polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by NAGASE CHEMTEX).

作為所述多硫化物型二縮水甘油醚化合物，例如可舉出：FLDP－50及FLDP－60(均為Toray Thiokol製造)。Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol).

作為所述聯苯酚型環氧化合物，例如可舉出：YX－4000、YL－6121H(均為JAPAN EPOXY RESINS製造)、NC－3000P及NC－3000S(均為日本化藥股份有限公司製造)。Examples of the biphenol-based epoxy compound include YX-4000, YL-6121H (all manufactured by JAPAN EPOXY RESINS), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

作為所述二縮水甘油酯化合物，例如可舉出：對苯二甲酸二縮水甘油酯(下述結構式117)、鄰苯二甲酸二縮水甘油酯(下述結構式E118)、雙(2－甲基環氧乙烷基甲基)鄰苯二甲酸酯(下述結構式E119)、以下述結構式E121表示的化合物、以下述結構式E122表示的化合物及以下述結構式E123表示的化合物。Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula E118), and bis (2- Methyl oxiranylmethyl) phthalate (the following structural formula E119), a compound represented by the following structural formula E121, a compound represented by the following structural formula E122, and a compound represented by the following structural formula E123 .

[化60] [60]

作為所述縮水甘油酯環氧化合物，例如可舉出：871、872(均為JAPAN EPOXY RESINS製造)、Epikuron 200、Epikuroonn 400(均為大日本油墨化學工業股份有限公司製造)、Denacol EX－711及Denacol EX－721(均為NAGASE CHEMTEX公司製造)。Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by JAPAN EPOXY RESINS), Epikuron 200, and Epikuroonn 400 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), and Denacol EX-711. And Denacol EX-721 (both manufactured by NAGASE CHEMTEX).

作為所述聚縮水甘油胺化合物，例如可舉出：N,N－二縮水甘油基苯胺(下述結構式E124)、N,N－二縮水甘油基－鄰甲苯胺(下述結構式E125)、N,N－二縮水甘油基－間甲苯胺(下述結構式E126)、N,N－二縮水甘油基－2,4,6－三溴苯胺(下述結構式E127)、3一(N,N－二縮水甘油基)氨基丙基三甲氧基矽烷(下述結構式E128)、N,B,O－三縮水甘油基－ 對氨基苯酚(下述結構式E129)、N,N,O－三縮水甘油基－間氨基苯酚(下述結構式E130)、N,N,N',N－四縮水甘油基－間苯二甲胺(TETRAD－X(三菱瓦斯化學)、下述結構式E132)、1,3－雙(N,N－二縮水甘油基氨基甲基)環己烷(TETRAD－C(三菱瓦斯化學)、下述結構式E133)、1,4－雙(N,N－二縮水甘油基氨基甲基)環己烷(下述結構式E134)、1,3－雙(N,N－二縮水甘油基氨基)環己烷(下述結構式E135)、1,4－雙(N,N－二縮水甘油基氨基)環己烷(下述結構式E136)、1,3－雙(N,N－二縮水甘油基氨基)苯(下述結構式E137)、1,4－雙(N,N－二縮水甘油基氨基)苯(下述結構式E138)、2,6－雙(N,N－二縮水甘油基氨基甲基)雙環[2.2.1]庚烷(下述結構式E139)、N,N,N',N'－四縮水甘油基－4,4'－二氨基二環己基甲烷(下述結構式E140)、2,2'－二甲基－(N,N,N',N'－四縮水甘油基)－4,4'－二氨基聯苯(下述結構式E141)、N,N,N',N'－四縮水甘油基－4,4'－二氨基二苯醚(下述結構式E142)、1,3,5－三(4－(N,N－二縮水甘油基)氨基苯氧基)苯(下述結構式E143)、2,4,4'－三(N,N－二縮水甘油基氨基)二苯醚(下述結構式E144)、三(4－(N,N－二縮水甘油基)氨基苯基)甲烷(下述結構式E145)、3,4,3',4'－四(N,N－二縮水甘油基氨基)聯苯(下述結構式E146)、3,4,3',4'－四(N,N－二縮水甘油基氨基)二苯醚(下述結構式E147)、以下述結構式E148表示的化合物及以下述結構式E149表示的化合物。Examples of the polyglycidylamine compound include N,N-diglycidylaniline (the following structural formula E124) and N,N-diglycidyl-o-toluidine (the following structural formula E125). , N,N-diglycidyl-m-toluidine (structure E126 below), N,N-diglycidyl-2,4,6-tribromoaniline (structure E127 below), 3 one ( N,N-diglycidyl)aminopropyltrimethoxydecane (structure E128 below), N,B,O-triglycidyl- P-Aminophenol (Structure of Formula E129 below), N,N,O-triglycidyl-m-aminophenol (Structure of Formula E130 below), N,N,N',N-tetraglycidyl-m-phenylene Methylamine (TETRAD-X (Mitsubishi Gas Chemical), the following structural formula E132), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), The following structural formula E133), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (the following structural formula E134), 1,3-bis(N,N-diglycidyl) Amino)cyclohexane (structural formula E135 below), 1,4-bis(N,N-diglycidylamino)cyclohexane (structure E136 below), 1,3-bis(N,N-) Diglycidylamino)benzene (structural formula E137 below), 1,4-bis(N,N-diglycidylamino)benzene (structure E138 below), 2,6-bis(N,N- Diglycidylaminomethyl)bicyclo[2.2.1]heptane (structure E139 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (Structure E140 below), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (Structure E141 below) , N, N, N', N'-tetraglycidyl 4,4'-diaminodiphenyl ether (the following structural formula E142), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (the following structural formula E143) ), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (the following structural formula E144), tris(4-(N,N-diglycidyl)aminophenyl) Methane (structure E145 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (Structure E146 below), 3,4,3',4' - Tetrakis(N,N-diglycidylamino)diphenyl ether (the following structural formula E147), a compound represented by the following structural formula E148, and a compound represented by the following structural formula E149.

[化61] [化61]

作為所述具有環氧乙烷基的單體的均聚物，例如可舉出：聚甲基丙烯酸縮水甘油酯。作為所述具有環氧乙烷基的單體的共聚物，例如可舉出：N－苯基順丁烯二醯亞胺－甲基丙烯酸縮水甘油酯共聚物、N－環己基順丁烯二醯亞胺－甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸苄酯－甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸丁酯－甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸2－羥基乙酯－甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸(3－乙基－3－氧雜環丁基)甲酯－甲基丙烯酸縮水甘油酯共聚物及苯乙烯－甲基丙烯酸縮水甘油酯共聚物。The homopolymer of the monomer having an oxiranyl group may, for example, be polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxiranyl group include N-phenyl maleimide-glycidyl methacrylate copolymer and N-cyclohexyl-butenylene.醯imino-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate Ester-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymerization Things.

作為所述具有環氧乙烷基的單體，例如可舉出：(甲基) 丙烯酸縮水甘油酯、(甲基)丙烯酸3,4－環氧基環己酯及(甲基)丙烯酸甲基縮水甘油酯。Examples of the monomer having an oxiranyl group include (meth) Glycidyl acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

作為所述具有環氧乙烷基的單體的共聚物中的所述具有環氧乙烷基的單體以外的其他單體，例如可舉出：(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2－羥基乙酯、(甲基)丙烯酸2－羥基丙酯、苯乙烯、甲基苯乙烯、氯甲基苯乙烯、(甲基)丙烯酸(3－乙基－3－氧雜環丁基)甲酯、N－環己基順丁烯二醯亞胺及N－苯基順丁烯二醯亞胺。Examples of the monomer other than the oxiranyl group-containing monomer in the copolymer of the oxiranyl group-containing monomer include (meth)acrylic acid and (meth)acrylic acid. Methyl ester, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) Cyclohexyl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloromethyl styrene, ( (3-Ethyl-3-oxetanyl)methyl (meth)acrylate, N-cyclohexylmethyleneimine, and N-phenylmaleimide.

作為所述縮水甘油基異氰尿酸酯，例如可舉出：1,3,5－三縮水甘油基－1,3,5－三嗪－2,4,6－(1H,3H,5H)－三酮(下述結構式E150)、1,3－二縮水甘油基－5－烯丙基－1,3,5－三嗪－2,4,6－(1H,3H,5H)－三酮(下述結構式E151)及縮水甘油基異氰尿酸酯型環氧樹脂。Examples of the glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H, 3H, 5H). -triketone (structure E150 below), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-three A ketone (structure E151 below) and a glycidyl isocyanurate type epoxy resin.

作為所述鏈狀脂肪族型環氧化合物，例如可舉出：環氧化聚丁二烯及Epolead PB3600(DAICEL化學工業股份有限公司製造)。Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by DAICEL Chemical Industry Co., Ltd.).

作為所述環狀脂肪族型環氧化合物，例如可舉出：2－ 甲基－3,4－環氧環己基甲基－2'－甲基－3',4'－環氧環己基羧酸酯(下述結構式E153)、2,3－環氧環戊基－2',3'－環氧環戊醚(下述結構式E154)、ε－己內酯改質3,4－環氧環己基甲基－3',4'－環氧環己烷羧酸酯、1,2：8,9－二環氧檸檬烯(Celloxide 3000(DAICEL化學工業股份有限公司製造)、下述結構式E155)、以下述結構式E156表示的化合物、CY－175、CY－177、CY－179(均為CIBA－GEIGY公司製造)、EHPD－3150(DAICEL化學工業股份有限公司製造)及環狀脂肪族型環氧樹脂。As the cyclic aliphatic epoxy compound, for example, 2- Methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (Structure E153 below), 2,3-epoxycyclopentyl -2',3'-epoxycyclopentyl ether (structure E154 below), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate Acid ester, 1,2:8,9-diepoxylimene (Celloxide 3000 (manufactured by DAICEL Chemical Industry Co., Ltd.), the following structural formula E155), a compound represented by the following structural formula E156, CY-175, CY- 177, CY-179 (both manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by DAICEL Chemical Industry Co., Ltd.), and a cyclic aliphatic epoxy resin.

另外，例如，就提高對基板的密接性的觀點而言，本發明的液晶配向劑也可以進一步含有矽烷偶合劑、鈦系偶合劑及氨基矽化合物等偶合劑。所述偶合劑可以是一種化合物，也可以是兩種或兩種以上的化合物。Further, for example, the liquid crystal alignment agent of the present invention may further contain a coupling agent such as a decane coupling agent, a titanium coupling agent, or an aminoguanidine compound, from the viewpoint of improving the adhesion to the substrate. The coupling agent may be one compound or two or more compounds.

作為所述氨基矽化合物，可舉出：對氨基苯基三甲氧基矽烷、對氨基苯基三乙氧基矽烷、間氨基苯基三甲氧基矽烷、間氨基苯基三乙氧基矽烷、氨基丙基三甲氧基矽烷、氨基丙基三乙氧基矽烷等。Examples of the aminoguanidine compound include p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, and amino group. Propyltrimethoxydecane, aminopropyltriethoxydecane, and the like.

所述偶合劑的含有率，在液晶配向劑中優選0.01~3 wt%。The content of the coupling agent is preferably 0.01 to 3 in the liquid crystal alignment agent. Wt%.

另外，例如，在不損及本發明的特性的範圍(優選所述聚醯胺酸或其衍生物的20 wt%以內)內，本發明的液晶配向劑也可以進一步含有聚酯、丙烯酸聚合物、丙烯酸酯聚合物等聚合物成分。Further, for example, the liquid crystal alignment agent of the present invention may further contain a polyester or an acrylic polymer in a range not detracting from the characteristics of the present invention (preferably within 20% by weight of the polyaminic acid or a derivative thereof). A polymer component such as an acrylate polymer.

並且，例如，在不損及本發明目的的範圍內，本發明的液晶配向劑也可以進一步含有二羧酸或其衍生物與二胺的反應產物即聚醯胺，或四羧酸二酐、二羧酸或其衍生物與二胺的反應產物即聚醯胺醯亞胺等其他聚合物成分。Further, for example, the liquid crystal alignment agent of the present invention may further contain a reaction product of a dicarboxylic acid or a derivative thereof and a diamine, that is, a polydecylamine or a tetracarboxylic dianhydride, within a range not impairing the object of the present invention. The reaction product of a dicarboxylic acid or a derivative thereof and a diamine is another polymer component such as polyamidoximine.

另外，例如，就實現液晶配向劑的塗佈性的提高的觀點而言，本發明的液晶配向劑也可以進一步含有用以實現此目的的表面活性劑，就提高液晶配向劑的抗靜電性的觀點而言，本發明的液晶配向劑也可以進一步含有抗靜電劑。Further, for example, from the viewpoint of improving the coatability of the liquid crystal alignment agent, the liquid crystal alignment agent of the present invention may further contain a surfactant for achieving the object, thereby improving the antistatic property of the liquid crystal alignment agent. In view of the above, the liquid crystal alignment agent of the present invention may further contain an antistatic agent.

另外，例如，就液晶配向劑的塗佈性及所述聚醯胺酸或其衍生物的濃度的調整的觀點而言，本發明的液晶配向劑也可以進一步含有溶劑。所述溶劑如果是具有可溶解高分子成分的能力的溶劑，那麽並沒有特別限制，可以應用。所述溶劑廣泛包含在聚醯胺酸、可溶性聚醯亞胺等高分子成分的製造步驟及用途方面通常所使用的溶劑，根據使用目的可適當選擇。所述溶劑可以是一種，也可以是兩種或兩種以上的混合溶劑。Further, for example, the liquid crystal alignment agent of the present invention may further contain a solvent from the viewpoint of the applicability of the liquid crystal alignment agent and the adjustment of the concentration of the polyaminic acid or its derivative. The solvent is not particularly limited as long as it has a solvent capable of dissolving a polymer component, and can be used. The solvent widely includes a solvent which is usually used in the production steps and uses of a polymer component such as polyamic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types.

作為所述溶劑，可舉出所述聚醯胺酸或其衍生物的良溶劑(good solvent)、或以改善塗佈性為目的的其他溶劑。The solvent may, for example, be a good solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

作為對於所述聚醯胺酸或其衍生物而言為良溶劑的非 質子性極性有機溶劑，可舉出：N－甲基－2－吡咯烷酮、二甲基咪唑啉酮、N－甲基己內醯胺、N－甲基丙醯胺、N,N－二甲基乙醯胺、二甲基亞碸、N,N－二甲基甲醯胺、N,N－二乙基甲醯胺、二乙基乙醯胺、γ－丁內酯等內酯。As a non-good solvent for the poly-proline or its derivative Examples of the protic polar organic solvent include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methyl caprolactam, N-methylpropionamide, and N,N-dimethyl group. Lactam, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone and the like.

作為以所述改善塗佈性等為目的的其他溶劑例，可舉出：乳酸烷基酯、3－甲基－3－甲氧基丁醇、萘滿(tetralin)、異佛爾酮、乙二醇單丁醚等乙二醇單烷基醚、二乙二醇單***等二乙二醇單烷基醚、乙二醇單烷基醚或乙酸苯酯、三乙二醇單烷基醚、丙二醇單丁醚等丙二醇單烷基醚、丙二酸二乙酯等丙二酸二烷基酯、二丙二醇單甲醚等二丙二醇單烷基醚、這些乙酸酯類等的酯化合物。Examples of other solvents for the purpose of improving the coating property and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and B. Ethylene glycol monoalkyl ether such as diol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl ether or phenyl acetate, triethylene glycol monoalkyl ether And a propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, a dialkyl malonate such as dipropyl malonate, a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or an ester compound such as these acetates.

這些溶劑中，所述溶劑尤其優選使用N－甲基－2－吡咯烷酮、二甲基咪唑啉酮、γ－丁內酯、乙二醇單丁醚、二乙二醇單***、丙二醇單丁醚及二丙二醇單甲醚等。Among these solvents, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether. And dipropylene glycol monomethyl ether and the like.

本發明中，液晶配向劑中的包含所述聚醯胺酸或其衍生物的高分子成分的濃度並沒有特別限制，優選0.1~40 wt%。將此液晶配向劑塗佈在基板上時，為了調整膜厚，有時必須事先進行利用溶劑稀釋所含有的高分子成分的操作。為了調整膜厚而必須稀釋液晶配向劑時，就調整液晶配向劑的黏度以使其成為適於容易地混合溶劑的黏度的觀點而言，所述高分子成分的濃度優選40 wt%或40 wt%以下。In the present invention, the concentration of the polymer component containing the polyamic acid or a derivative thereof in the liquid crystal alignment agent is not particularly limited, but is preferably 0.1 to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the polymer component contained in the solvent in advance. When it is necessary to dilute the liquid crystal alignment agent in order to adjust the film thickness, the viscosity of the liquid crystal alignment agent is adjusted so as to be a viscosity suitable for easily mixing the solvent, and the concentration of the polymer component is preferably 40 wt% or 40 wt. %the following.

另外，液晶配向劑中的所述高分子成分的濃度有時也根據液晶配向劑的塗佈方法來進行調整。液晶配向劑的塗 佈方法為旋塗法(spinner)或印刷法時，為了良好地保持膜厚，通常多數情況是將所述高分子成分的濃度調整為10 wt%以下。在其他塗佈方法、例如浸塗法(dipping)或噴墨法(inkjet)的情況下，有時也可以謂整為更低的濃度。另一方面，如果所述高分子成分的濃度為0.1 wt%以上，那麽容易將所獲得的液晶配向膜的膜厚調整為最佳厚度。所以，在通常的旋轉塗佈法或印刷法等的情況下，所述高分子成分的濃度為0.1 wt%以上，優選0.5~10 wt%。然而，根據液晶配向劑的塗佈方法，也可以在更加稀薄的濃度下使用。Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. Coating of liquid crystal alignment agent When the cloth method is a spinner method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually adjusted to 10 wt% or less. In the case of other coating methods, such as dipping or inkjet, it may be a lower concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film is easily adjusted to an optimum thickness. Therefore, in the case of a usual spin coating method, printing method, or the like, the concentration of the polymer component is 0.1 wt% or more, preferably 0.5 to 10 wt%. However, depending on the method of applying the liquid crystal alignment agent, it can also be used at a more dilute concentration.

而且，在用於製作液晶配向膜時，本發明的液晶配向劑的黏度可根據形成此液晶配向劑的膜的手段及方法而確定。例如，在使用印刷機來形成液晶配向劑的膜時，就獲得充分的膜厚的觀點而言，優選5 mPa．s或5 mPa．S以上，另外，就抑制印刷不均的觀點而言，優選100 mPa．s以下，更優選10~80 mPa．s。利用旋塗法塗佈液晶配向劑而形成液晶配向劑的膜時，就同樣的觀點而言，優選5~200 mPa．s，更優選10~100 mPa．s。液晶配向劑的黏度，可通過以溶劑進行稀釋或通過伴隨攪拌的熟化來降低。Further, when used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to the means and method for forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed using a printing machine, from the viewpoint of obtaining a sufficient film thickness, it is preferably 5 mPa. s or 5 mPa. S or more, in addition, from the viewpoint of suppressing uneven printing, it is preferably 100 mPa. Below s, more preferably 10 to 80 mPa. s. When a liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, from the same viewpoint, it is preferably 5 to 200 mPa. s, more preferably 10~100 mPa. s. The viscosity of the liquid crystal alignment agent can be lowered by dilution with a solvent or by aging with stirring.

本發明的液晶配向劑也可以是所謂的聚合物摻合的形態。這種形態的液晶配向劑是含有四羧酸二酐A與二胺A的反應產物即聚醯胺酸或其衍生物A、與四羧酸二酐B與二胺B的反應生成物即聚醯胺酸或其衍生物B的液晶配向劑，可舉出二胺A包含以通式(1)表示的二胺、二胺B 不包含以通式(1)表示的二胺的液晶配向劑。The liquid crystal alignment agent of the present invention may also be in the form of a so-called polymer blend. The liquid crystal alignment agent of this form is a reaction product containing a reaction product of tetracarboxylic dianhydride A and diamine A, that is, polyamine or a derivative thereof, and a reaction product of tetracarboxylic dianhydride B and diamine B. The liquid crystal alignment agent of valine acid or its derivative B, the diamine A contains the diamine represented by the formula (1), and the diamine B. A liquid crystal alignment agent which does not contain the diamine represented by the general formula (1).

聚醯胺酸或其衍生物A與所述的本發明的聚醯胺酸或其衍生物相同。聚醯胺酸或其衍生物B除了所述二胺中不包含以通式(1)表示的二胺以外、即所述二胺使用所述其他二胺以外，與所述的本發明的聚醯胺酸或其衍生物相同。The polyaminic acid or its derivative A is the same as the polylysine of the present invention or a derivative thereof. Poly-proline or its derivative B, in addition to the diamine of the formula (1), that is, the use of the other diamine as the diamine, and the polymerization of the present invention The proline or its derivative is the same.

四羧酸二酐A及B可使用所述的四羧酸。所述二胺A中包含以通式(1)表示的二胺即可，也可以進一步包含所述其他二胺。所述二胺B可使用以通式(1)表示的二胺以外的所述其他二胺。The tetracarboxylic acid can be used for the tetracarboxylic dianhydrides A and B. The diamine A may contain the diamine represented by the formula (1), and may further contain the other diamine. As the diamine B, the other diamine other than the diamine represented by the general formula (1) can be used.

本發明的所述液晶配向劑中的聚醯胺酸或其衍生物B的含量如果是可表現出本發明效果的量，那麽並沒有特別限制，就同時具有表現本發明的效果與調整配向性兩方面的觀點而言，聚醯胺酸或其衍生物B的含量相對於液晶配向劑中的聚合物總量優選1~50 wt%，更優選2~30wt%。The content of the polyaminic acid or the derivative B thereof in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an amount which exhibits the effects of the present invention, and at the same time, exhibits the effect of the present invention and the adjustment of the alignment. From the viewpoint of both, the content of the polyaminic acid or its derivative B is preferably from 1 to 50% by weight, more preferably from 2 to 30% by weight, based on the total amount of the polymer in the liquid crystal alignment agent.

本發明的液晶配向膜可由所述本發明的液晶配向劑獲得。本發明的液晶配向膜可通過利用液晶配向劑製作液晶配向膜的通常的方法而獲得，例如，本發明的液晶配向膜可通過形成本發明的液晶配向劑的塗膜的步驟與對其加熱並鍛燒的步驟而獲得。對於本發明的液晶配向膜，根據需要，也可以對所述鍛燒步驟中所獲得的膜進行摩擦處理。The liquid crystal alignment film of the present invention can be obtained by the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method of producing a liquid crystal alignment film by using a liquid crystal alignment agent, for example, the liquid crystal alignment film of the present invention can be heated and formed by the step of forming a coating film of the liquid crystal alignment agent of the present invention. Obtained by the step of calcination. For the liquid crystal alignment film of the present invention, the film obtained in the calcination step may be subjected to a rubbing treatment as needed.

所述塗膜，與通常製作液晶配向膜的情況相同，可通過於液晶顯示元件中的基板上塗佈本發明的液晶配向劑而形成。所述基板可舉出：可設置氧化銦錫(Indium Tin Oxide，ITO)電極等電極或彩色濾光片(color filter)等的 以玻璃製造的基板。The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid crystal display device, as in the case of generally producing a liquid crystal alignment film. The substrate may be an electrode such as an Indium Tin Oxide (ITO) electrode or a color filter. A substrate made of glass.

作為將液晶配向劑塗佈於基板上的方法，一般已知有旋塗法、印刷法、浸塗法、滴下法、噴墨法等。這些方法在本發明中也可以同樣應用。As a method of applying a liquid crystal alignment agent onto a substrate, a spin coating method, a printing method, a dip coating method, a dropping method, an inkjet method, or the like is generally known. These methods can also be applied similarly in the present invention.

所述塗膜的鍛燒可在所述聚醯胺酸或其衍生物進行脫水、閉環反應所需的條件下進行。所述塗膜的鍛燒一般已知有：在烘箱(oven)或紅外線爐中進行加熱處理的方法、在加熱板上進行加熱處理的方法等。這些方法在本發明中也可以同樣應用。一般優選在150~300℃左右的溫度下進行1分鐘~3小時。The calcination of the coating film can be carried out under the conditions required for the dehydration and ring closure reaction of the polyaminic acid or its derivative. The calcination of the coating film is generally known as a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. These methods can also be applied similarly in the present invention. It is generally preferred to carry out at a temperature of about 150 to 300 ° C for 1 minute to 3 hours.

所述摩擦處理可與通常的用於液晶配向膜的配向處理的摩擦處理同樣進行，在本發明的液晶配向膜可獲得充分的延遲的條件下即可。特別優選的的條件是毛壓入量0.2~0.8 mm、載物台(stage)移動速度5~250 mm/sec、輥子(roller)旋轉速度500~2,000 rpm。作為液晶配向膜的配向處理方法，除了摩擦法以外，一般已知有光配向法或轉印法等。在可獲得本發明效果的範圍內，也可以在所述摩擦處理中並用這些其他配向處理方法。The rubbing treatment can be carried out in the same manner as the rubbing treatment for the alignment treatment of the liquid crystal alignment film, and the liquid crystal alignment film of the present invention can be sufficiently delayed. Particularly preferred conditions are a hair injection amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm/sec, and a roller rotation speed of 500 to 2,000 rpm. As a method of the alignment treatment of the liquid crystal alignment film, in addition to the rubbing method, a photoalignment method, a transfer method, or the like is generally known. These other alignment treatment methods may be used in combination in the rubbing treatment within the range in which the effects of the present invention can be obtained.

利用包含所述步驟以外的其他步驟的方法可比較好地獲得本發明的液晶配向膜。作為所述其他步驟，可舉出：使所述塗膜乾燥的步驟、或以清洗液清洗摩擦處理前後的膜的步驟等。The liquid crystal alignment film of the present invention can be obtained relatively well by a method including other steps than the above steps. Examples of the other steps include a step of drying the coating film, a step of washing the film before and after the rubbing treatment with a cleaning liquid, and the like.

所述乾燥步驟與所述鍛燒步驟同樣，一般已知有在烘箱或紅外線爐中進行加熱處理的方法、在加熱板上進行加 熱處理的方法等。這些方法也同樣可應用於所述乾燥步驟中。乾燥步驟優選在可溶劑蒸發的範圍內的溫度下實施，更優選在相對於所述鍛燒步驟的溫度比較低的溫度下實施。The drying step is the same as the calcining step, and a method of performing heat treatment in an oven or an infrared oven is generally known, and the heating is performed on a hot plate. Heat treatment method, etc. These methods are equally applicable to the drying step. The drying step is preferably carried out at a temperature within the range in which the solvent can be evaporated, more preferably at a relatively low temperature relative to the temperature of the calcining step.

作為於配向處理前後利用清洗液清洗液晶配向膜的方法，可舉出：刷洗(brushing)、噴霧(jet spray)、蒸氣清洗或超聲波清洗等。這些方法既可以單獨進行，也可以並用。作為清洗液，可使用純水，或甲醇、乙醇、異丙醇等各種醇類，苯、甲苯、二甲苯等芳香族烴類，二氯甲烷等鹵素系溶劑，丙酮、甲基乙基酮等酮類，但並不限定於這些。當然，這些清洗液是使用充分純化的雜質較少的清洗液。這種清洗方法也可以應用於形成本發明的液晶配向膜的所述清洗步驟中。The method of washing the liquid crystal alignment film by the cleaning liquid before and after the alignment treatment includes brushing, jet spray, steam cleaning, ultrasonic cleaning, and the like. These methods can be performed either singly or in combination. As the cleaning liquid, pure water, various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, acetone, methyl ethyl ketone, etc. may be used. Ketones, but are not limited to these. Of course, these cleaning solutions are cleaning fluids that use less purified impurities. This cleaning method can also be applied to the cleaning step of forming the liquid crystal alignment film of the present invention.

本發明的液晶配向膜的膜厚並沒有特別限制，優選10~300 nm，更優選30~150 nm。本發明的液晶配向膜的膜厚可通過輪廓儀(profilometer)或橢圓計(ellipsometer)等公知的膜厚測定裝置進行測定。The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, and is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer.

本發明的液晶顯示元件包括：一對基板；含有液晶分子，且形成於所述一對基板之間的液晶層；對液晶層施加電壓的電極；及使所述液晶分子於特定方向上配向的液晶配向膜。所述液晶配向膜使用所述的本發明的液晶配向膜。A liquid crystal display device of the present invention includes: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and an alignment of the liquid crystal molecules in a specific direction Liquid crystal alignment film. The liquid crystal alignment film described above uses the liquid crystal alignment film of the present invention.

對於所述基板，在本發明的液晶配向膜的情況下，可使用所述玻璃制的基板；對於所述電極，在本發明的液晶配向膜的情況下，如上所述，可使用形成於玻璃制基板上 的ITO電極。For the substrate, in the case of the liquid crystal alignment film of the present invention, the glass substrate can be used; and in the case of the liquid crystal alignment film of the present invention, as described above, it can be used in the glass as described above. On the substrate ITO electrode.

所述液晶層由密封在下述相對向的一對基板之間的縫隙中的液晶組合物所形成，所述一對基板的對向方式是所述一對基板中的一塊基板的形成有液晶配向膜的面朝向另一塊基板。The liquid crystal layer is formed by a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein a pair of substrates is formed by liquid crystal alignment of one of the pair of substrates The face of the film faces the other substrate.

對於所述液晶組合物並沒有特別限制，可使用介電各向異性為正或負的各種液晶組合物。介電各向異性為正的優選液晶組合物可舉出下述文獻中記載的液晶組合物：日本專利第3086228號公報、日本專利第2635435號公報、日本專利特表平5－501735號公報、日本專利特開平8－157826號公報、日本專利特開平8－231960號公報、日本專利特開平9－241644號公報(EP885272A1說明書)、日本專利特開平9－302346號公報(EP806466A1說明書)、日本專利特開平8－199168號公報(EP722998A1說明書)、日本專利特開平9－235552號公報、日本專利特開平9－255956號公報、日本專利特開平9－241643號公報(EP885271A1說明書)、日本專利特開平10－204016號公報(EP844229A1說明書)、日本專利特開平10－204436號公報、日本專利特開平10－231482號公報、日本專利特開2000－087040公報、日本專利特開2001－48822公報等。The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A liquid crystal composition which is positive in dielectric anisotropy is exemplified by a liquid crystal composition described in Japanese Patent No. 3086228, Japanese Patent No. 2635435, and Japanese Patent Laid-Open No. Hei 5-501735. Japanese Patent Laid-Open No. Hei 8-157826, Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei No. Hei 9-241644 (Patent No. EP 852 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP806466A1), Japanese Patent Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. Hei 10-204436, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei.

介電各向異性為負的優選液晶組合物可舉出下述文獻中所記載的液晶組合物：日本專利特開昭57－114532號公報、日本專利特開平2－4725號公報、日本專利特開平4－224885號公報、日本專利特開平8－40953號公報、日本 專利特開平8－104869號公報、日本專利特開平10－168076號公報、日本專利特開平10－168453號公報、日本專利特開平10－236989號公報、日本專利特開平10－236990號公報、日本專利特開平10－236992號公報、日本專利特開平10－236993號公報、日本專利特開平10－236994號公報、日本專利特開平10－237000號公報、日本專利特開平10－237004號公報、日本專利特開平10－237024號公報、日本專利特開平10－237035號公報、日本專利特開平10－237075號公報、日本專利特開平10－237076號公報、日本專利特開平10－237448號公報(EP967261A1說明書)、日本專利特開平10－287874號公報、日本專利特開平10－287875號公報、日本專利特開平10－291945號公報、日本專利特開平11－029581號公報、日本專利特開平11－080049號公報、日本專利特開2000－256307公報、日本專利特開2001－019965公報、日本專利特開2001－072626公報、日本專利特開2001－192657公報等。The liquid crystal composition described in the following documents is exemplified by the following Japanese Patent Publication No. Sho 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, and Japanese Patent Application. Japanese Patent Laid-Open No. Hei 4-224885, Japanese Patent Laid-Open No. Hei 8-40953, Japan Japanese Patent Laid-Open No. Hei 10-104076, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Publication No. Hei 10-168453 Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei 10--237000, Japanese Patent Laid-Open No. Hei 10-237004, Japan Japanese Laid-Open Patent Publication No. Hei 10-237025, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Laid-Open No. Hei 10-237076, and Japanese Patent Laid-Open No. Hei 10-237448 (EP967261A1) Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. Japanese Patent Laid-Open Publication No. 2000-256307, Japanese Patent Laid-Open Publication No. 2001-019965, Japanese Patent Laid-Open No. 2001-0 Japanese Patent Publication No. 2001-192657, and the like.

也可以向所述介電各向異性為正或負的液晶組合物中添加一種或一種以上的光學活性化合物而使用。It is also possible to use one or more optically active compounds in the liquid crystal composition having positive or negative dielectric anisotropy.

本發明的液晶顯示元件可通過下述方式獲得：在一對基板的至少一塊基板上形成本發明的液晶配向膜，以液晶配向膜朝內的方式介隔間隔物(spacer)而使所獲得的一對基板對向，在形成於基板之間的間隙中封裝入液晶組合物，形成液晶層。在製造本發明的液晶顯示元件時，根據需要，也可以包含於基板上貼附偏光膜等的其他步驟。The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film of the present invention on at least one substrate of a pair of substrates, and separating the spacers in such a manner that the liquid crystal alignment film faces inwardly. The pair of substrates are opposed to each other, and a liquid crystal composition is encapsulated in a gap formed between the substrates to form a liquid crystal layer. When manufacturing the liquid crystal display element of the present invention, other steps of attaching a polarizing film or the like to the substrate may be included as needed.

本發明的液晶顯示元件可形成用於各種電場方式的液晶顯示元件。這種用於電場方式的液晶顯示元件可舉出：在相對於所述基板的表面水平的方向上，所述電極對所述液晶層施加電壓的用於橫向電場方式的液晶顯示元件，或在相對於所述基板的表面垂直的方向上，所述電極對所述液晶層施加電壓的用於縱向電場方式的液晶顯示元件。The liquid crystal display element of the present invention can form a liquid crystal display element for various electric field modes. Such a liquid crystal display element for an electric field method may be a liquid crystal display element for a transverse electric field mode in which a voltage is applied to the liquid crystal layer in a direction horizontal to a surface of the substrate, or A liquid crystal display element for a longitudinal electric field mode in which a voltage is applied to the liquid crystal layer by the electrode in a direction perpendicular to a surface of the substrate.

用於橫向電場方式的液晶顯示元件也可以不表現出比較大的預傾角，所以可以比較好地使用利用下述本發明的液晶配向劑所獲得的液晶配向膜，此本發明的液晶配向劑由不包含具有支鏈的二胺的二胺而獲得。The liquid crystal display element used in the transverse electric field mode may not exhibit a relatively large pretilt angle, so that the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention described below can be used relatively well, and the liquid crystal alignment agent of the present invention is composed of Obtained without the diamine having a branched diamine.

用於縱向電場方式的液晶顯示元件需要表現出比較大的預傾角，所以可以比較好地使用利用下述本發明的液晶配向劑所獲得的液晶配向膜，此本發明的液晶配向劑是由除了以通式(1)表示的二胺以外、也包含具有支鏈的二胺的二胺所獲得的液晶配向劑，或者所述二胺B中包含具有支鏈的二胺的液晶配向劑。The liquid crystal display element for the longitudinal electric field mode needs to exhibit a relatively large pretilt angle, so that the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention described below can be used relatively well, and the liquid crystal alignment agent of the present invention is composed of A liquid crystal alignment agent obtained by using a diamine having a branched diamine in addition to the diamine represented by the general formula (1), or a liquid crystal alignment agent containing a branched diamine in the diamine B.

這樣，將本發明的液晶配向劑作為原料而製作的液晶配向膜，通過適當選擇其原料即聚合物，可應用在各種顯示驅動方式的液晶顯示元件中。In this way, the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material.

[實施例][Examples]

以下，根據實施例詳細說明通過使用本發明的聚合物而獲得的液晶配向劑及液晶顯示元件，但本發明並不限定於這些實施例。實施例中，分子量的測定使用GPC，將聚苯乙烯作為標準溶液，洗提液使用二甲基甲醯胺 (Dimethylformamide，DMF)。另外，以下的實施例中，容積的單位升以L表示。所以，mL表示毫升。Hereinafter, the liquid crystal alignment agent and the liquid crystal display element obtained by using the polymer of the present invention will be described in detail based on examples, but the present invention is not limited to these examples. In the examples, the molecular weight was determined by using GPC, polystyrene as a standard solution, and eluate using dimethylformamide. (Dimethylformamide, DMF). In addition, in the following examples, the unit liter of the volume is represented by L. Therefore, mL means milliliters.

以下記載實施例中使用的液晶顯示元件的評價方法。The evaluation method of the liquid crystal display element used in the examples is described below.

(1)殘留DC 對30 Hz、3 V的矩形波重叠3 V的直流電壓30分鐘後，測定5分鐘後的閃爍消失電壓，將此值的絕對值作為殘留DC。殘留DC越小，殘像越少，可以說良好。(1) Residual DC After a DC voltage of 3 V was superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes, the flickering disappearance voltage after 5 minutes was measured, and the absolute value of this value was taken as residual DC. The smaller the residual DC, the less the residual image, and it can be said to be good.

(2)電壓保持率(VHR，Voltage Holding Ratio) 使用“水島等人，第14次液晶討論會會議錄p78(1988)”中記載的方法。測定是對單元(cell)施加栅極(gate)寬度69 μs、頻率60 Hz、波高±5 V的矩形波。在測定溫度為60℃。(2) Voltage holding ratio (VHR, Voltage Holding Ratio) The method described in "Water Island et al., 14th Liquid Crystal Symposium Proceedings p78 (1988)" is used. The measurement was performed by applying a rectangular wave having a gate width of 69 μs, a frequency of 60 Hz, and a wave height of ±5 V to a cell. The measurement temperature was 60 °C.

(3)延遲(R)測定 使用分光橢圓計M－2000U(J.A.Woollam Co.Inc.製造)，求得配向膜的延遲(R)。R的值越大，配向膜越向摩擦方向延伸，而具有較高的單軸配向性。結果可以說黑顯示良好。(3) Delay (R) measurement The retardation (R) of the alignment film was determined using a spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.). The larger the value of R, the more the alignment film extends toward the rubbing direction and the higher the uniaxial alignment. The result can be said that the black display is good.

(4)預傾角(Pt角) 以中央精機股份有限公司製造的液晶評價裝置(OMS－CA3)，在室溫下進行測定。(4) Pretilt angle (Pt angle) The liquid crystal evaluation apparatus (OMS-CA3) manufactured by Central Seiki Co., Ltd. was used for measurement at room temperature.

實施例及比較例中所使用的四羧酸二酐、二胺及溶劑的名稱以縮寫表示。以下的記述中有時使用這些縮寫。The names of the tetracarboxylic dianhydride, the diamine, and the solvent used in the examples and the comparative examples are abbreviated. These abbreviations are sometimes used in the following descriptions.

四羧酸二酐1,2,3,4－環丁烷四甲酸二酐：CBDA 均苯四甲酸二酐：PMDA二胺4,4'－二氨基二苯基甲烷：DDM 1,3－雙(4－(4－氨基苄基)苯基)丙烷：BZ3 4,4'－二氨基二苯醚：APE 1,1－雙[4－[(4－氨基苯基)甲基]苯基]－4－正丁基環己烷：PMBCh N,N'－雙(4－氨基苯基)－N,N'－二甲基乙二胺：NN2DAMe2,6－二氨基吡啶：DAPY4,4'－二氨基二苯基胺：DADPA溶劑成分N－甲基－2－吡咯烷酮：NMP γ－丁內酯：GBL丁基溶纖劑－：BCTetracarboxylic dianhydride 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA Pyromellitic dianhydride: PMDA diamine 4,4'-diaminodiphenylmethane: DDM 1,3-bis(4-(4-aminobenzyl)phenyl)propane: BZ3 4,4'- Aminodiphenyl ether: APE 1,1-bis[4-[(4-aminophenyl)methyl]phenyl]-4-n-butylcyclohexane: PMBCh N, N'-bis(4-aminobenzene -N,N'-dimethylethylenediamine: NN2DAMe2,6-diaminopyridine: DAPY4,4'-diaminodiphenylamine: DADPA solvent component N-methyl-2-pyrrolidone: NMP γ- Butyrolactone: GBL butyl cellosolve -: BC

合成例1Synthesis Example 1

液晶配向膜用組合物A1(清漆A1)的製備 向具備溫度計、攪拌機、原料投入口及氮氣導入口的100 mL的四口燒瓶中投入2.83 g的NN2DAMe、53.4 mL的脫水NMP，在乾燥氮氣流下攪拌溶解。一邊將反應系統的溫度保持在5℃，一邊添加1.03 g的CBDA、1.14 g的PMDA，使其反應30小時後，添加27.7 mL的BC、13.3 mL的GBL，製備高分子成分的濃度為5 wt%的聚醯胺酸的清漆。在原料的反應中，利用反應熱使反應溫度上升時，將 反應溫度控制在約70℃或70℃以下而使其反應。Preparation of composition A1 (varnish A1) for liquid crystal alignment film 2.83 g of NN2DAMe and 53.4 mL of dehydrated NMP were placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and stirred and dissolved under a dry nitrogen stream. While maintaining the temperature of the reaction system at 5 ° C, 1.03 g of CBDA and 1.14 g of PMDA were added, and after reacting for 30 hours, 27.7 mL of BC and 13.3 mL of GBL were added to prepare a polymer component having a concentration of 5 wt. % phthalate varnish. In the reaction of the raw material, when the reaction temperature is raised by the heat of reaction, The reaction temperature is controlled to be about 70 ° C or lower to react.

而且，在本發明的實施例中，一邊確認反應中的黏度一邊進行反應，在添加BC後的清漆的黏度達到30~35 mPa．s(使用E型黏度計，25℃)的時間點結束反應，在低溫下保存。所獲得的聚醯胺酸的重量平均分子量為62,320。另外，重量平均分子量是使用WATERS製造的GPC測定裝置(軟件Empower)且在管柱溫度500℃下進行測定。Further, in the examples of the present invention, the reaction was carried out while confirming the viscosity in the reaction, and the viscosity of the varnish after the addition of BC reached 30 to 35 mPa. The reaction was terminated at the time point of s (using an E-type viscometer, 25 ° C) and stored at a low temperature. The polyamic acid obtained had a weight average molecular weight of 62,320. Further, the weight average molecular weight was measured using a GPC measuring device (software Empower) manufactured by WATERS and at a column temperature of 500 °C.

以NMP/BC/GBL(＝60/25/15，重量比)的混合溶劑稀釋如上所述獲得的清漆，進行調整以使總高分子成分的濃度達到3 wt%，從而製備用於塗佈的清漆A1。The varnish obtained as described above was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio), and adjusted so that the total polymer component concentration reached 3 wt%, thereby preparing for coating. Varnish A1.

合成例2~8Synthesis Example 2~8

各種清漆的製備 除了以下述表1的莫耳比使用表1的原料以外，以與清漆A1相同的方法，製備並獲得清漆A2~A8。清漆A1~A8的原料種類、其莫耳比及所獲得的聚醯胺酸的重量平均分子量示於表1中。Preparation of various varnishes Varnishes A2 to A8 were prepared and obtained in the same manner as in the varnish A1 except that the materials of Table 1 were used in the molar ratios shown in Table 1 below. The raw material type of the varnishes A1 to A8, the molar ratio thereof, and the weight average molecular weight of the obtained polyamic acid are shown in Table 1.

實施例1Example 1

用於測定預傾角、電壓保持率及殘留DC的單元a的製作所述用於測定的單元a的基板使用帶有ITO電極的玻璃基板。The substrate a for measuring the pretilt angle, the voltage holding ratio, and the residual DC was used as the substrate for the unit a for measurement, and a glass substrate with an ITO electrode was used.

以旋轉器將合成例1中所獲得的清漆A1塗佈於所述帶有ITO電極的玻璃基板上。塗佈條件為1,700 rpm、15秒鐘。塗膜後，在80℃下預鍛燒約3分鐘後，在230℃下進行20分鐘加熱處理，形成膜厚大約為70 nm的液晶配向膜。使用飯沼GAUGE製作所股份有限公司製造的摩擦處理裝置，在摩擦布(毛長1.8 mm：人造纖維(Rayon))的毛壓入量為0.40 mm、載物台移動速度為60 mm/sec、輥子旋轉速度為1,000 rpm的條件下，對所獲得的聚醯亞胺膜進行摩擦處理，獲得液晶夾持用基板。The varnish A1 obtained in Synthesis Example 1 was applied onto the glass substrate with an ITO electrode by a spinner. The coating conditions were 1,700 rpm and 15 seconds. After coating, the film was pre-calcined at 80 ° C for about 3 minutes, and then heat-treated at 230 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 70 nm. Using a friction treatment device manufactured by Iguchi GAUGE Co., Ltd., the frictional cloth (hair length 1.8 mm: Rayon) has a hair insertion amount of 0.40 mm, the stage moving speed is 60 mm/sec, and the roller rotates. The obtained polyimide film was subjected to a rubbing treatment at a speed of 1,000 rpm to obtain a substrate for liquid crystal clamping.

在超純水中對所獲得的液晶夾持用基板進行5分鐘超聲波清洗後，在烘箱中在120℃下乾燥30分鐘。在其中一塊帶有ITO電極的玻璃基板上散布7 μm的間隙劑，以環氧硬化劑密封另一塊帶有ITO電極的玻璃基板，製作間隙為7 μm的逆平行單元(antiparallel cell)。向所述單元中注入液晶材料，以光硬化劑密封注入口。接著，在110℃下加熱處理30分鐘，製成用於測定預傾角、電壓保持率及殘留DC的單元a。用作液晶材料的液晶組合物A的組成示於下文。此組合物的NI點為100.0℃，雙折射為0.093。The obtained liquid crystal holding substrate was subjected to ultrasonic cleaning for 5 minutes in ultrapure water, and then dried in an oven at 120 ° C for 30 minutes. A 7 μm gap agent was spread on one of the glass substrates with ITO electrodes, and another glass substrate with ITO electrodes was sealed with an epoxy hardener to prepare an antiparallel cell having a gap of 7 μm. A liquid crystal material is injected into the unit, and the injection port is sealed with a light hardener. Subsequently, the mixture was heat-treated at 110 ° C for 30 minutes to prepare a unit a for measuring the pretilt angle, the voltage holding ratio, and the residual DC. The composition of the liquid crystal composition A used as a liquid crystal material is shown below. This composition has an NI point of 100.0 ° C and a birefringence of 0.093.

預傾角、電壓保持率及殘留DC的測定使用所述用於測定的單元a，以所述記載的方法測定預傾角、電壓保持率及殘留DC，結果預傾角為2.3∘，電壓保持率為99.0%，殘留DC為2 mV。Measurement of pretilt angle, voltage holding ratio, and residual DC Using the unit a for measurement described above, the pretilt angle, the voltage holding ratio, and the residual DC were measured by the method described above, and as a result, the pretilt angle was 2.3 ∘, and the voltage holding ratio was 99.0. %, residual DC is 2 mV.

用於測定延遲的基板b的製作所述用於測定的基板b的基板使用透明玻璃基板。The substrate for measuring the retardation b is used as a substrate for the substrate b to be measured, and a transparent glass substrate is used.

以旋轉器將合成例1中所獲得的清漆A1塗佈於所述透明玻璃基板上。塗佈條件為1,700 rpm、15秒鐘。在80℃下預鍛燒約3分鐘後，在230℃下進行20分鐘的加熱處理，形成膜厚大約為70 nm的液晶配向膜。使用飯沼GAUGE製作所股份有限公司製造的摩擦處理裝置，在摩擦布(毛長1.8 mm：人造纖維)的毛壓入量為0.40 mm、載物台移動速度為60 mm/sec、輥子旋轉速度為1,000 rpm的條件下，對所獲得的聚醯亞胺膜進行摩擦處理，獲得用於測定的基板b。The varnish A1 obtained in Synthesis Example 1 was applied onto the transparent glass substrate by a spinner. The coating conditions were 1,700 rpm and 15 seconds. After calcination at 80 ° C for about 3 minutes, heat treatment was carried out at 230 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 70 nm. A friction treatment device manufactured by Iguchi GAUGE Co., Ltd. was used. The frictional cloth (hair length 1.8 mm: rayon) had a hair injection amount of 0.40 mm, the stage moving speed was 60 mm/sec, and the roller rotation speed was 1,000. The obtained polyimide film was subjected to a rubbing treatment under the conditions of rpm to obtain a substrate b for measurement.

延遲測定 使用所獲得的用於測定的基板b，利用分光橢圓計求得延遲。所獲得的R為0.65 nm。Delayed measurement Using the obtained substrate b for measurement, a retardation was obtained using a spectroscopic ellipsometer. The obtained R was 0.65 nm.

實施例2~7Example 2~7

使用合成例2~7中所獲得的清漆A2~A7，與實施例1同樣製作用於測定的單元a及用於測定的基板b，與實施例1同樣測定預傾角、電壓保持率(VHR)、殘留DC及7 遲(R)。測定結果示於表2中。Using the varnishes A2 to A7 obtained in Synthesis Examples 2 to 7, the unit a for measurement and the substrate b for measurement were prepared in the same manner as in Example 1, and the pretilt angle and voltage holding ratio (VHR) were measured in the same manner as in Example 1. , residual DC and 7 Late (R). The measurement results are shown in Table 2.

另外，本發明的實施例的試驗方法中，如果電壓保持率為99.0%以上的值，那麽算是良好，如果殘留DC為10 mV以下的值，那麽算是良好，如果延遲為0.2 nm以上的值，那麽算是良好。如果延遲的值為0.2 nm以下，那麽算是配向力較弱，流動配向或不施加電壓時，有時會產生漏光。尤其是在橫向電場方式下，延遲的值是重要的參數(parameter)。關於預傾角，根據各驅動方式不同，所需要的值也不同，因此無法對所獲得的數值具體判斷好或不好，但在IPS等橫向電場方式下，優選較小的值(3.0∘以下)，在TN為代表的縱向電場方式下，優選比較大的值(4.0∘以上)。Further, in the test method of the embodiment of the present invention, if the voltage holding ratio is 99.0% or more, it is considered to be good, and if the residual DC is 10 mV or less, it is considered to be good, and if the retardation is 0.2 nm or more, Then it is good. If the value of the retardation is 0.2 nm or less, it is considered that the alignment force is weak, and when the flow is aligned or no voltage is applied, light leakage sometimes occurs. Especially in the transverse electric field mode, the value of the delay is an important parameter. Regarding the pretilt angle, depending on the driving method, the required values are also different, so that it is not possible to specifically judge the obtained value or not, but in the transverse electric field mode such as IPS, a smaller value (3.0 ∘ or less) is preferable. In the longitudinal electric field mode represented by TN, a relatively large value (4.0 ∘ or more) is preferable.

實施例8及9Examples 8 and 9

分別以後述的表3中所示的聚合物組成(重量比)來製備清漆A1、A2及A8，使用這些清漆，與實施例1同樣進行預傾角、電壓保持率、殘留DC及延遲的測定。測定結果示於表3中。Varnishes A1, A2, and A8 were prepared from the polymer compositions (weight ratios) shown in Table 3, which will be described later, and the pre-tilt angle, voltage holding ratio, residual DC, and retardation were measured in the same manner as in Example 1 using these varnishes. The measurement results are shown in Table 3.

實施例10Example 10

向20 g(固體成分濃度5 wt%)合成例1中所獲得的清漆A1中混合0.1 g(相對於清漆A1的聚合物為10 wt%)環氧化合物即4,4'－亞甲基雙(N,N－二縮水甘油基苯胺)(SIGMA－ALDRICH公司製造)，製備清漆B1，使用此清漆B1，與實施例1同樣進行預傾角、電壓保持率、殘留DC及延遲的測定。To 20 g (solid content concentration: 5 wt%) of the varnish A1 obtained in Synthesis Example 1, 0.1 g (10 wt% based on the polymer of the varnish A1) was mixed with an epoxy compound, that is, 4,4'-methylene double (N,N-diglycidylaniline) (manufactured by SIGMA-ALDRICH Co., Ltd.), varnish B1 was prepared, and the pre-tilt angle, voltage holding ratio, residual DC, and retardation were measured in the same manner as in Example 1 using this varnish B1.

合成例10~14Synthesis Example 10~14

各種清漆的製備 除了以下述表5的莫耳比使用下述表5的原料以外，利用與清漆A1相同的方法，製備並獲得清漆C1~C5。清漆C1~C5的原料種類、其莫耳比及所獲得的聚醯胺酸的重量平均分子量示於表5中。Preparation of various varnishes Varnishes C1 to C5 were prepared and obtained in the same manner as in the varnish A1, except that the materials of the following Table 5 were used in the molar ratios shown in Table 5 below. The raw material types of the varnishes C1 to C5, the molar ratio thereof, and the weight average molecular weight of the obtained polyamic acid are shown in Table 5.

比較例1~5Comparative example 1~5

使用合成例10~14中所獲得的清漆C1~C5來替代清漆A1，與實施例1同樣製作用於測定的單元a及用於測定的基板b，與實施例1同樣測定預傾角、電壓保持率、殘留DC及延遲。測定結果示於表6中。Using the varnishes C1 to C5 obtained in Synthesis Examples 10 to 14 instead of the varnish A1, the unit a for measurement and the substrate b for measurement were prepared in the same manner as in Example 1, and the pretilt angle and voltage retention were measured in the same manner as in Example 1. Rate, residual DC and delay. The measurement results are shown in Table 6.

根據實施例1~10及比較例1~5的結果可知，通過使用本發明的具有包含三級胺的二胺的聚醯胺酸，可製作能夠同時滿足殘留DC降低與較大延遲的液晶顯示元件。According to the results of Examples 1 to 10 and Comparative Examples 1 to 5, it was found that by using the polyamic acid having the diamine containing a tertiary amine of the present invention, a liquid crystal display capable of simultaneously satisfying the residual DC reduction and large retardation can be produced. element.

Claims (37)

一種液晶配向劑，其含有四羧酸二酐與二胺的反應產物、即聚醯胺酸或其衍生物，其特徵在於，所述二胺包含以下述通式(1)表示的二胺， 通式(1)中，R1 獨立地表示一價有機基，R2 獨立地表示一價基，Z表示包含碳數1~5的亞烷基的二價基。A liquid crystal alignment agent containing a reaction product of a tetracarboxylic dianhydride and a diamine, that is, a poly-proline or a derivative thereof, wherein the diamine comprises a diamine represented by the following formula (1), In the formula (1), R 1 independently represents a monovalent organic group, R 2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms. 如申請專利範圍第1項所述的液晶配向劑，其中R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3之烷基、氟、氯或溴。The liquid crystal alignment agent according to claim 1, wherein R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine or bromine. 如申請專利範圍第1項所述的液晶配向劑，其中以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (1) has an amino group at each of the opposite positions of the N-Z-N main chain at the phenyl groups at both ends. . 如申請專利範圍第3項所述的液晶配向劑，其中以通式(1)表示的二胺是從下述結構式239~253及258~262所組成的族群中選擇的一個或一個以上， The liquid crystal alignment agent according to the third aspect of the invention, wherein the diamine represented by the formula (1) is one or more selected from the group consisting of the following structural formulas 239 to 253 and 258 to 262, 如申請專利範圍第1項所述的液晶配向劑，其中所述四羧酸二酐是從下述結構式500、505~508、511、515及517中選擇的一個或一個以上， 。The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride is one or more selected from the following structural formulas 500, 505 to 508, 511, 515, and 517. . 如申請專利範圍第5項所述的液晶配向劑，其中所述四羧酸二酐是所述結構式500及511的一者或者兩者。The liquid crystal alignment agent according to claim 5, wherein the tetracarboxylic dianhydride is one or both of the structural formulas 500 and 511. 如申請專利範圍第1項所述的液晶配向劑，其中所述二胺進一步包含以下述通式(2)表示的二胺，[化5]H2 N－R3 －NH2 (2)通式(2)中，R3 表示可具有取代基及不包含兩個或 兩個以上的亞氨基的二價有機基。The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a diamine represented by the following formula (2), [Chem. 5] H 2 N-R 3 -NH 2 (2) In the formula (2), R 3 represents a divalent organic group which may have a substituent and does not contain two or more imino groups. 如申請專利範圍第7項所述的液晶配向劑，其中以通式(2)表示的二胺包含以下述通式(3)~(5)表示的二胺， 通式(3)中，Y表示包含碳數1~5的伸烷基、氧及硫的一種或一種以上的二價基， 通式(4)中，X1 獨立地表示亞甲基或者氧，X2 表示可具有甲基或者CF3 作為取代基的碳數1~8的亞烷基， 通式(5)中，X1 獨立地表示碳數1~6的亞烷基或者氧；X3 表示單鍵或者碳數1~3的亞烷基；環T表示1,4－亞苯基或者1,4－亞環己基；R4 表示氫或者碳數1~30的烷基，其 中，所述烷基中，碳數2~30的烷基中的任意的亞甲基可獨立地被氧、－CH＝CH－或者－C≡C一取代，所述烷基中，氧並不相鄰；h表示0或者1。The liquid crystal alignment agent according to claim 7, wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5), In the formula (3), Y represents one or more divalent groups containing an alkylene group having 1 to 5 carbon atoms, oxygen and sulfur, In the formula (4), X 1 independently represents a methylene group or oxygen, and X 2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF 3 as a substituent. In the formula (5), X 1 independently represents an alkylene group having 1 to 6 carbon atoms or oxygen; X 3 represents a single bond or an alkylene group having 1 to 3 carbon atoms; and ring T represents a 1,4-phenylene group. Or 1,4-cyclohexylene; R 4 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, wherein any methylene group of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be independently Oxygen, -CH=CH- or -C≡C is monosubstituted, in which the oxygen is not adjacent; h represents 0 or 1. 如申請專利範圍第8項所述的液晶配向劑，其中通式(3)~(5)中，兩個氨基的位置相對於Y或者X1 是對位。The liquid crystal alignment agent according to claim 8, wherein in the general formulae (3) to (5), the positions of the two amino groups are aligned with respect to Y or X 1 . 如申請專利範圍第9項所述的液晶配向劑，其中以通式(3)表示的二胺是從下述結構式301~304、306、307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從下述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從下述結構式381、384、390及398所組成的族群中選擇的一個或一個以上， [化10] The liquid crystal alignment agent according to claim 9, wherein the diamine represented by the general formula (3) is one selected from the group consisting of the following structural formulas 301 to 304, 306, 307 and 313. In the above, the diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367 and 372, and the diamine represented by the formula (5) is One or more selected from the group consisting of the following structural formulas 381, 384, 390, and 398, [化10] 如申請專利範圍第8項所述的液晶配向劑，其中所述二胺中，以通式(1)表示的二胺的含有率為20~99莫耳%，以通式(2)表示的二胺的含有率為1~80莫耳%。The liquid crystal alignment agent according to claim 8, wherein the content of the diamine represented by the formula (1) in the diamine is 20 to 99 mol%, represented by the formula (2). The content of the diamine is 1 to 80 mol%. 一種液晶配向劑，其含有：四羧酸二酐A與二胺A的反應產物即聚醯胺酸或其衍生物A、以及四羧酸二酐B與二胺B的反應產物即聚醯胺酸或其衍生物B，其特徵在於，所述二胺A包含以下述通式(1)表示的二胺，所述二胺B不包含以下述通式(1)表示的二胺， 通式(1)中，R1 獨立地表示一價有機基，R2 獨立地表示一價基，Z表示包含碳數1~5的亞烷基的二價基。A liquid crystal alignment agent comprising: a reaction product of tetracarboxylic dianhydride A and diamine A, that is, polyaminic acid or a derivative thereof, and a reaction product of tetracarboxylic dianhydride B and diamine B, that is, polydecylamine The acid or the derivative B thereof, wherein the diamine A contains a diamine represented by the following formula (1), and the diamine B does not contain a diamine represented by the following formula (1). In the formula (1), R 1 independently represents a monovalent organic group, R 2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms. 如申請專利範圍第12項所述的液晶配向劑，其中通式(1)中，R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3的烷基、氟、氯或溴。The liquid crystal alignment agent according to claim 12, wherein, in the formula (1), R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen and an alkyl group having 1 to 3 carbon atoms; Fluorine, chlorine or bromine. 如申請專利範圍第12項所述的液晶配向劑，其中 以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。The liquid crystal alignment agent according to claim 12, wherein The diamine represented by the formula (1) has an amino group at each of the phenyl groups at both ends corresponding to the N-Z-N main chain. 如申請專利範圍第14項所述的液晶配向劑，其中以通式(1)表示的二胺是從下述結構式239~253及258~262所組成的族群中選擇的一個或一個以上， [化14] The liquid crystal alignment agent according to claim 14, wherein the diamine represented by the formula (1) is one or more selected from the group consisting of the following structural formulas 239 to 253 and 258 to 262, [Chemistry 14] 如申請專利範圍第12項所述的液晶配向劑，其中所述二胺B包含以下述通式(2)表示的二胺，[化15]H2 N－R3 －NH2 (2)通式(2)中，R3 表示具有取代基及不包含兩個或兩個以上的亞氨基的二價有機基。The liquid crystal alignment agent according to claim 12, wherein the diamine B comprises a diamine represented by the following formula (2), [Chem. 15] H 2 N-R 3 -NH 2 (2) In the formula (2), R 3 represents a divalent organic group having a substituent and not containing two or more imino groups. 如申請專利範圍第16項所述的液晶配向劑，其中以通式(2)表示的二胺包含以下述通式(3)~(5)表示的二胺， 通式(3)中，Y表示包含碳數1~5的亞烷基、氧及 硫的一種或一種以上的二價基， 通式(4)中，X1 獨立地表示亞甲基或者氧，X2 表示可具有甲基或者CF3 作為取代基的碳數1~8的亞烷基， 通式(5)中，X1 獨立地表示碳數1~6的亞烷基或者氧；X3 表示單鍵或者碳數1~3的亞烷基；環T表示1,4－亞苯基或者1,4－亞環己基；R4 表示氫或者碳數1~30的烷基，其中，所述烷基中，碳數2~30的烷基中的任意的亞甲基可獨立地被氧、－CH＝CH－或者－C≡C－取代，所述烷基中，氧並不相鄰)；h表示0或者1。The liquid crystal alignment agent according to claim 16, wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5), In the formula (3), Y represents one or more divalent groups including an alkylene group having 1 to 5 carbon atoms, oxygen, and sulfur. In the formula (4), X 1 independently represents a methylene group or oxygen, and X 2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF 3 as a substituent. In the formula (5), X 1 independently represents an alkylene group having 1 to 6 carbon atoms or oxygen; X 3 represents a single bond or an alkylene group having 1 to 3 carbon atoms; and ring T represents a 1,4-phenylene group. Or 1,4-cyclohexylene; R 4 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, wherein any methylene group of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be independently Oxygen, -CH=CH- or -C≡C-substituted, in which the oxygen is not adjacent); h represents 0 or 1. 如申請專利範圍第17項所述的液晶配向劑，其中通式(3)~(5)中，兩個氨基的位置相對於Y或者X1 是對位。The liquid crystal alignment agent according to claim 17, wherein in the general formulae (3) to (5), the positions of the two amino groups are aligned with respect to Y or X 1 . 如申請專利範圍第18項所述的液晶配向劑，其中以通式(3)表示的二胺是從下述結構式301~304、306、 307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從下述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從下述結構式381、384、390及398所組成的族群中選擇的一個或一個以上， The liquid crystal alignment agent according to claim 18, wherein the diamine represented by the general formula (3) is one selected from the group consisting of the following structural formulas 301 to 304, 306, 307 and 313. In the above, the diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367 and 372, and the diamine represented by the formula (5) is One or more selected from the group consisting of the following structural formulas 381, 384, 390, and 398, 如申請專利範圍第12項所述的液晶配向劑，其中所述四羧酸二酐A及四羧酸二酐B是從下述結構式500、 505~508、511、515及517中選擇的一個或一個以上， 。The liquid crystal alignment agent according to claim 12, wherein the tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are selected from the following structural formulas 500, 505 to 508, 511, 515 and 517. One or more, . 如申請專利範圍第20項所述的液晶配向劑，其中所述四羧酸二酐A及四羧酸二酐B是所述結構式500及511的一者或者兩者。The liquid crystal alignment agent according to claim 20, wherein the tetracarboxylic dianhydride A and the tetracarboxylic dianhydride B are one or both of the structural formulas 500 and 511. 如申請專利範圍第1項或第12項所述的液晶配向劑，其中還包括環氧化合物。The liquid crystal alignment agent according to claim 1 or 12, which further comprises an epoxy compound. 如申請專利範圍第22項所述的液晶配向劑，其中所述環氧化合物是從下述結構式(E1)~(E3)、(E5)及下述通式(E4)所組成的族群中選擇的一個或一個以上，[化23] 通式(E4)中，n表示0~10的整數。The liquid crystal alignment agent according to claim 22, wherein the epoxy compound is in a group consisting of the following structural formulae (E1) to (E3), (E5), and the following general formula (E4); One or more selected, [Chem. 23] In the formula (E4), n represents an integer of 0 to 10. 如申請專利範圍第22項所述的液晶配向劑，其中相對於所述聚醯胺酸或其衍生物的總量而包含0.1~40 wt%的所述環氧化合物。The liquid crystal alignment agent according to claim 22, wherein the epoxy compound is contained in an amount of 0.1 to 40% by weight based on the total amount of the polyamic acid or a derivative thereof. 一種液晶配向膜，其特徵在於，其是由申請專利範圍第1至24項中任一項的液晶配向劑而獲得的。A liquid crystal alignment film obtained by the liquid crystal alignment agent of any one of claims 1 to 24. 一種液晶顯示元件，包括：一對基板；含有液晶分子，且形成於所述一對基板之間的液晶層；對液晶層施加電壓的電極；使所述液晶分子於特定方向上配向的液晶配向膜；其特徵在於，所述液晶配向膜是申請專利範圍第25項所述的液晶配向膜。A liquid crystal display element comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and a liquid crystal alignment for aligning the liquid crystal molecules in a specific direction The liquid crystal alignment film is the liquid crystal alignment film according to claim 25 of the patent application. 如申請專利範圍第26項所述的液晶顯示元件，其中所述電極在相對於所述基板的表面水平的方向上，對所述液晶層施加電壓的用於橫向電場方式的液晶顯示元件。The liquid crystal display element according to claim 26, wherein the electrode is a liquid crystal display element for a transverse electric field mode in which a voltage is applied to the liquid crystal layer in a direction horizontal to a surface of the substrate. 如申請專利範圍第26項所述的液晶顯示元件，其中所述電極在相對於所述基板的表面垂直的方向上，對所述液晶層施加電壓的用於縱向電場方式的液晶顯示元件。The liquid crystal display element according to claim 26, wherein the electrode is a liquid crystal display element for a vertical electric field mode in which a voltage is applied to the liquid crystal layer in a direction perpendicular to a surface of the substrate. 一種聚合物，其是四羧酸二酐與二胺的反應產物，其特徵在於，所述二胺包含以下述通式(1)表示的二胺與以下述通式(2)表示的二胺， 通式(1)中，R1 獨立地表示一價有機基，R2 獨立地表示一價基，Z表示包含碳數1~5的亞烷基的二價基，[化25]H2 N－R3 －NH2 (2)通式(2)中，R3 表示具有取代基及不包含亞氨基的 二價有機基。A polymer which is a reaction product of a tetracarboxylic dianhydride and a diamine, characterized in that the diamine comprises a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2) , In the formula (1), R 1 independently represents a monovalent organic group, R 2 independently represents a monovalent group, and Z represents a divalent group containing an alkylene group having 1 to 5 carbon atoms, [Chem. 25] H 2 N -R 3 -NH 2 (2) In the formula (2), R 3 represents a divalent organic group having a substituent and not containing an imino group. 如申請專利範圍第29所述的聚合物，其中通式(1)中，R1 獨立為碳數1~3的烷基，R2 獨立為氫、碳數1~3的烷基、氟、氯或溴。 如申請專利範圍第29項所述的聚合物，其中以通式(1)表示的二胺，在兩端的苯基上，在對應於N－Z－N主鏈的各個對位上具有氨基。 如申請專利範圍第31項項所述的聚合物，其中以通式(1)表示的二胺是從下述結構式239~253及258~262所組成的族群中選擇的一個或一個以上， The polymer according to claim 29, wherein, in the formula (1), R 1 is independently an alkyl group having 1 to 3 carbon atoms, and R 2 is independently hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, Chlorine or bromine. The polymer according to claim 29, wherein the diamine represented by the formula (1) has an amino group at each of the phenyl groups at both ends corresponding to the N-Z-N main chain. The polymer according to claim 31, wherein the diamine represented by the formula (1) is one or more selected from the group consisting of the following structural formulae 239 to 253 and 258 to 262, 如申請專利範圍第32項所述的聚合物，其中以通式(1)表示的二胺是所述結構式240。The polymer according to claim 32, wherein the diamine represented by the formula (1) is the structural formula 240. 如申請專利範圍第29項所述的聚合物，其中以通式(2)表示的二胺包含以下述通式(3)~(5)表示的二胺， 通式(3)中，Y表示包含碳數1~5的亞烷基、氧及硫的一種或一種以上的二價基， 通式(4)中，X1 獨立地表示亞甲基或者氧，X2 表示可具有甲基或者CF3 作為取代基的碳數1~8的亞烷基， 通式(5)中，X1 獨立地表示碳數1~6的亞烷基或者氧；X3 表示單鍵或者碳數1~3的亞烷基；環T表示1,4－亞苯基或者1,4－亞環己基；R4 表示氫或者碳數1~30的烷基，其中所述烷基中，碳數2~30的烷基中的任意的亞甲基可獨立地被氧、－CH＝CH－或者－C≡C－取代，所述烷基中，氧並不相鄰；h表示0或者1。The polymer according to claim 29, wherein the diamine represented by the formula (2) contains a diamine represented by the following general formulae (3) to (5), In the formula (3), Y represents one or more divalent groups including an alkylene group having 1 to 5 carbon atoms, oxygen, and sulfur. In the formula (4), X 1 independently represents a methylene group or oxygen, and X 2 represents an alkylene group having 1 to 8 carbon atoms which may have a methyl group or CF 3 as a substituent. In the formula (5), X 1 independently represents an alkylene group having 1 to 6 carbon atoms or oxygen; X 3 represents a single bond or an alkylene group having 1 to 3 carbon atoms; and ring T represents a 1,4-phenylene group. Or 1,4-cyclohexylene; R 4 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, wherein any methylene group of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be independently oxygenated , -CH=CH- or -C≡C-substituted, wherein the oxygen is not adjacent; h represents 0 or 1. 如申請專利範圍第34項所述的聚合物，其中通式(3)~(5)中，兩個氨基的位置相對於Y或者X1 是對位。The polymer according to claim 34, wherein in the general formulae (3) to (5), the positions of the two amino groups are para-position with respect to Y or X 1 . 如申請專利範圍第35項所述的聚合物，其中以通 式(3)表示的二胺是從下述結構式301~304、306、307及313所組成的族群中選擇的一個或一個以上，以通式(4)表示的二胺是從下述結構式360、364、365、367及372所組成的族群中選擇的一個或一個以上，以通式(5)表示的二胺是從下述結構式381、384、390及398所組成的族群中選擇的一個或一個以上， The polymer according to claim 35, wherein the diamine represented by the formula (3) is one or more selected from the group consisting of the following structural formulas 301 to 304, 306, 307 and 313. The diamine represented by the formula (4) is one or more selected from the group consisting of the following structural formulas 360, 364, 365, 367 and 372, and the diamine represented by the formula (5) is derived from One or more selected from the group consisting of the following structural formulas 381, 384, 390, and 398, 如申請專利範圍第36項所述的聚合物，其中以通式(3)表示的二胺是所述結構式301及306的一者或者兩者，以通式(4)表示的二胺是所述結構式364，以通式(5) 表示的二胺是所述結構式381。The polymer according to claim 36, wherein the diamine represented by the formula (3) is one or both of the structural formulae 301 and 306, and the diamine represented by the formula (4) is The structural formula 364 is represented by the general formula (5) The diamine represented is the structural formula 381. 如申請專利範圍第29項所述的聚合物，其中所述四羧酸二酐是從下述結構式500、505~508、511、515及517中選擇的一個或一個以上， 。The polymer according to claim 29, wherein the tetracarboxylic dianhydride is one or more selected from the following structural formulas 500, 505 to 508, 511, 515 and 517, . 如申請專利範圍第38項所述的聚合物，其中所述四羧酸二酐是所述結構式500及511的一者或者兩者。The polymer of claim 38, wherein the tetracarboxylic dianhydride is one or both of the structural formulae 500 and 511.
TW097129711A 2007-08-08 2008-08-05 Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display TWI421280B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007206242 2007-08-08
JP2007334695A JP5130907B2 (en) 2007-08-08 2007-12-26 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Publications (2)

Publication Number Publication Date
TW200906914A TW200906914A (en) 2009-02-16
TWI421280B true TWI421280B (en) 2014-01-01

Family

ID=40390448

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097129711A TWI421280B (en) 2007-08-08 2008-08-05 Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display

Country Status (4)

Country Link
JP (1) JP5130907B2 (en)
KR (1) KR101489716B1 (en)
CN (1) CN101364009B (en)
TW (1) TWI421280B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5446925B2 (en) * 2009-04-15 2014-03-19 Ｊｎｃ株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN101864319B (en) * 2009-04-15 2014-09-17 Jnc株式会社 Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device
JP5569095B2 (en) * 2010-03-29 2014-08-13 Ｊｎｃ株式会社 Diamine having diphenylamine structure at two positions in the molecule, polymer obtained by reacting this diamine, liquid crystal aligning agent containing this polymer, liquid crystal aligning film formed using this liquid crystal aligning agent, and this liquid crystal aligning film Liquid crystal display device having
JP2012155311A (en) * 2011-01-05 2012-08-16 Jnc Corp Liquid crystal aligning agent for forming photo-aligning liquid crystal alignment layer, liquid crystal alignment layer and liquid crystal display element using the same
JP5929298B2 (en) 2011-03-02 2016-06-01 Jnc株式会社 Diamine, liquid crystal aligning agent, liquid crystal display element using the same, and method for forming liquid crystal alignment film
CN103718093B (en) * 2011-08-04 2016-11-23 日产化学工业株式会社 The aligning agent for liquid crystal of light orientation position logos and use the liquid crystal orientation film of this aligning agent for liquid crystal
TWI545104B (en) * 2011-12-22 2016-08-11 Diphenylamine-based compound, a polyamic acid composition, a polyimide composition and a liquid crystal aligning agent
CN108034435A (en) 2012-04-24 2018-05-15 捷恩智株式会社 Light orientation aligning agent for liquid crystal, light orientation liquid crystal orientation film, its forming method and LCD assembly
JP6347917B2 (en) * 2013-05-27 2018-06-27 株式会社ジャパンディスプレイ Liquid crystal display device and manufacturing method thereof
TWI487731B (en) * 2013-09-04 2015-06-11 Daxin Materials Corp Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device having the same
JP6315193B2 (en) * 2013-10-03 2018-04-25 Jsr株式会社 Liquid crystal alignment agent
CN104714338A (en) * 2013-12-16 2015-06-17 群创光电股份有限公司 Liquid crystal display panel
JP6492564B2 (en) * 2014-02-13 2019-04-03 Jsr株式会社 Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, Liquid Crystal Display Element, Retardation Film, Method of Producing Retardation Film, Polymer, and Compound
JP2015215462A (en) * 2014-05-09 2015-12-03 Jsr株式会社 Liquid crystal display device and manufacturing method of the same
KR102282111B1 (en) * 2014-11-19 2021-07-26 제이에스알 가부시끼가이샤 Liquid crystal aligning agent, liquid crystal alignment film, method for producing liquid crystal alignment film and liquid crystal display element
KR20170097552A (en) * 2016-02-18 2017-08-28 제이엔씨 주식회사 Liquid crystal aligning agents for forming liquid crystal alignment films, liquid crystal alignment films and liquid crystal display devices using the same
CN111303081B (en) * 2020-03-27 2022-02-01 中国科学院化学研究所 High-strength high-modulus epoxy resin composition and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1173886A (en) * 1995-10-20 1998-02-18 智索股份有限公司 Polyamic acid, polyimide film and liquid crystal aligning film and liquid crystal display element
JP2007140156A (en) * 2005-11-18 2007-06-07 Chisso Corp Liquid crystal alignment agent and liquid crystal display element

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3613421B2 (en) * 1996-05-31 2005-01-26 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP3978754B2 (en) * 1997-12-29 2007-09-19 チッソ株式会社 Polyamic acid composition, liquid crystal alignment film, and liquid crystal display element
FR2806908B1 (en) * 2000-03-30 2002-12-20 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
DE10160815A1 (en) * 2001-12-11 2003-06-18 Henkel Kgaa Oxidation dye composition, useful for dyeing keratin fibers, especially human hair, comprises 2,4-dichloro-3-aminophenol and a bis-p-phenylenediamine or bis-p-aminophenol compound
JP4600637B2 (en) 2002-04-30 2010-12-15 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP4599904B2 (en) * 2003-07-14 2010-12-15 チッソ株式会社 Polyimide varnish for forming an alignment film for a horizontal electric field type liquid crystal display element, an alignment film, and a horizontal electric field type liquid crystal display element having the alignment film
WO2005083504A1 (en) * 2004-02-26 2005-09-09 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same
EP2305632A1 (en) * 2005-12-23 2011-04-06 Rolic AG Photocrosslinkable materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1173886A (en) * 1995-10-20 1998-02-18 智索股份有限公司 Polyamic acid, polyimide film and liquid crystal aligning film and liquid crystal display element
JP2007140156A (en) * 2005-11-18 2007-06-07 Chisso Corp Liquid crystal alignment agent and liquid crystal display element

Also Published As

Publication number Publication date
KR20090015829A (en) 2009-02-12
CN101364009B (en) 2012-03-28
JP2009058928A (en) 2009-03-19
JP5130907B2 (en) 2013-01-30
TW200906914A (en) 2009-02-16
CN101364009A (en) 2009-02-11
KR101489716B1 (en) 2015-02-04

Similar Documents

Publication Publication Date Title
TWI421280B (en) Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display
JP5556482B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI492966B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display
TWI596138B (en) Method to form liquid crystal photo-alignment film, and liquid crystal display
TWI458754B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
TWI606081B (en) Method of forming liquid crystal alignment film for photo-alignment, and liquid crystal displays
JP5482109B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN106047372B (en) Liquid crystal aligning agent, liquid crystal alignment film and method for producing same, and liquid crystal element and method for producing same
JP6252009B2 (en) Novel diamine, polymer using the same, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI676654B (en) Liquid crystal aligning agents containing polyamic acid or derivative thereof, liquid crystal alighment films and liquid crystal display devices
KR101823949B1 (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device
TWI515228B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polylysine and polyimine
TW201211108A (en) Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element
JP5428643B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP7409325B2 (en) Liquid crystal aligning agent and method for manufacturing liquid crystal elements
KR20130070230A (en) Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film
JP5630139B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2017170841A1 (en) Liquid crystal alignment agent, liquid crystal alignment membrane, and liquid crystal display element using same
WO2019106952A1 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device
WO2019193855A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and production method for liquid crystal element
TWI409298B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device
JP7409378B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element
WO2019193854A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and production method for liquid crystal element
JP2023109149A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer, and compound
JP2022191063A (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer and compound