TWI454529B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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TWI454529B
TWI454529B TW097150526A TW97150526A TWI454529B TW I454529 B TWI454529 B TW I454529B TW 097150526 A TW097150526 A TW 097150526A TW 97150526 A TW97150526 A TW 97150526A TW I454529 B TWI454529 B TW I454529B
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formula
liquid crystal
crystal alignment
diamine
alignment agent
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TW200930760A (en
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Hitoshi Yano
Rika Hisada
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Jnc Corp
Jnc Petrochemical Corp
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    • 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

本發明有關於一種含有聚醯胺酸(polyamic acid)或其衍生物和環氧化合物的液晶配向劑、由此液晶配向劑所形成的液晶配向膜、以及具備此液晶配向膜的液晶顯示元件。The present invention relates to a liquid crystal alignment agent containing polyamic acid or a derivative thereof and an epoxy compound, a liquid crystal alignment film formed by the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

液晶顯示元件被使用在筆記型電腦(note personal computer)或桌上型電腦(desktop computer)的監視器(monitor)、以及攝像機(video camera)的取景器(view finder)、投影式顯示器(projection display)等各種液晶顯示裝置中，近來也開始用在電視中。此外，液晶顯示元件也可以用作光學打印頭(optical printer head)、光學傅立葉變換元件(optical Fourier transform device)、光閥(light valve)等光電子學(optoelectronics)相關元件。The liquid crystal display element is used in a monitor of a note personal computer or a desktop computer, a view finder of a video camera, and a projection display. Among various liquid crystal display devices, etc., they have recently been used in televisions. Further, the liquid crystal display element can also be used as an optoelectronics related element such as an optical printer head, an optical Fourier transform device, and a light valve.

液晶顯示元件通常具有：1)對向配置的一對基板；2)形成在所述一對基板各自所對向的面中的一面或者兩面上的電極；3)形成在所述一對基板各自所對向的面上的液晶配向膜；以及4)形成在所述一對基板之間的液晶層。The liquid crystal display element generally has: 1) a pair of substrates disposed oppositely; 2) electrodes formed on one or both of the faces of the pair of substrates; 3) formed on each of the pair of substrates a liquid crystal alignment film on the opposite surface; and 4) a liquid crystal layer formed between the pair of substrates.

在先前的液晶顯示元件中，使用向列型液晶的顯示元件占主流，目前已經實際應用的有：1)扭轉90度的TN(Twisted Nematic，扭轉向列)型液晶顯示元件、2)通常扭轉180度以上的STN(Super Twisted Nematic，超扭轉向列)型液晶顯示元件、3)使用薄膜晶體管的所謂TFT(Thin Film Transistor，薄膜晶體管)型液晶顯示元件。但這些液晶顯示元件存在以下缺點：可以正確辨識圖像的視角狹窄，從斜方向上觀看時會産生亮度或對比度降低以及半色調下的亮度反轉(brightness inverse)。Among the former liquid crystal display elements, display elements using nematic liquid crystals are dominant, and currently practical applications include: 1) twisted 90 degree TN (Twisted Nematic) type liquid crystal display elements, 2) normal twisting An STN (Super Twisted Nematic) type liquid crystal display element of 180 degrees or more, and a so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor. However, these liquid crystal display elements have the disadvantage that the angle of view of the image can be correctly recognized, and the brightness or contrast reduction and the brightness inverse at halftone are generated when viewed from an oblique direction.

近年來，此視角問題已經通過1)使用光學補償膜的TN-TFT型液晶顯示元件、2)採用垂直配向和光學補償膜的垂直配向(Vertical Alignment，VA)型液晶顯示元件、3)並用垂直配向和突起結構物技術的MVA(Multi Domain Vertical Alignment，多區域垂直配向)型液晶顯示元件、或者4)橫向電場方式的IPS(In-Plane Switching，面內切換)型液晶顯示元件、5)ECB(Electrically Controlled Birefringence，電控雙折射)型液晶顯示元件、6)光學補償彎曲(Optically Compensated Bend或者Optically self-Compensated Birefringence：OCB)型液晶顯示元件等技術而獲得了改良，經過改良的技術正實際應用，或者正在進行研究。In recent years, this viewing angle problem has been achieved by 1) TN-TFT type liquid crystal display elements using optical compensation films, 2) Vertical Alignment (VA) type liquid crystal display elements using vertical alignment and optical compensation films, and 3) vertical use MVA (Multi Domain Vertical Alignment) type liquid crystal display element of the alignment and protrusion structure technology, or 4) IPS (In-Plane Switching) type liquid crystal display element of the transverse electric field type, 5) ECB Improved (Electrically Controlled Birefringence) liquid crystal display device, 6) Optically Compensated Bend or Optically Self-Compensated Birefringence (OCB) liquid crystal display device, and improved technology Application, or ongoing research.

液晶顯示元件技術的發展不僅僅是只通過改良這些驅動方式或元件結構，也可以通過改良液晶顯示元件所使用的構成構件來達成。液晶顯示元件所使用的構成構件中，特別是液晶配向膜是關係到液晶顯示元件的顯示品質的重要因素之一，隨著液晶顯示元件品質的不斷提高，液晶配向膜的作用也變得越來越重要。The development of the liquid crystal display element technology is not only achieved by improving these driving methods or element structures, but also by improving the constituent members used for the liquid crystal display elements. Among the constituent members used for the liquid crystal display element, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and as the quality of the liquid crystal display element continues to increase, the role of the liquid crystal alignment film becomes more and more The more important.

液晶配向膜可以利用液晶配向劑來製備。目前主要使用的液晶配向劑是將聚醯胺酸或者可溶性聚醯亞胺(polyimide)溶解於有機溶劑中而成的溶液。將這種溶液塗布在基板上之後，通過加熱等手段進行成膜，而形成聚醯亞胺系配向膜。這種液晶配向劑例如已知有：作爲聚醯胺酸或其衍生物的原料的四羧酸二酐(tetracarboxylic dianhydride)及二胺(diamine)、和所表現的預傾角(pretilt angle)有所規定的液晶配向劑(例如，參照日本專利特開2002-62537號公報)。目前對聚醯胺酸以外的各種液晶配向劑也進行了研究，但是考慮到耐熱性、耐化學性(耐液晶性)、塗布性、液晶配向性、電特性、光學特性、顯示特性等方面，這些液晶配向劑幾乎未實際應用。The liquid crystal alignment film can be prepared by using a liquid crystal alignment agent. The liquid crystal alignment agent mainly used at present is a solution obtained by dissolving polylysine or a soluble polyimide in an organic solvent. After this solution is applied onto a substrate, film formation is carried out by heating or the like to form a polyimide film. Such a liquid crystal alignment agent is known, for example, as a tetracarboxylic dianhydride and a diamine as a raw material of polylysine or a derivative thereof, and a pretilt angle expressed. A liquid crystal alignment agent is prescribed (for example, refer to Japanese Laid-Open Patent Publication No. 2002-62537). At present, various liquid crystal alignment agents other than polyglycolic acid have also been studied, but in consideration of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, display characteristics, and the like, These liquid crystal alignment agents are hardly practical.

爲提高液晶顯示元件的顯示品質而要求液晶配向膜具備的重要特性，可以列舉離子密度。如果離子密度高，則在幀時間內施加在液晶上的電壓會降低，結果導致亮度下降，而阻礙正常的灰階顯示。另外，即使初始離子密度低，但是高溫加速試驗後離子密度(長期可靠性)增大等情況也是一個問題。In order to improve the display quality of the liquid crystal display element, an important characteristic of the liquid crystal alignment film is required, and an ion density can be cited. If the ion density is high, the voltage applied to the liquid crystal during the frame time is lowered, resulting in a decrease in brightness and hindering the normal gray scale display. In addition, even if the initial ion density is low, the ion density (long-term reliability) after the high-temperature acceleration test is increased, and the like is also a problem.

解決所述問題的嘗試已知有含有聚醯胺酸或其衍生物和規定量的具有噁嗪(oxazine)結構的化合物的液晶配向劑(例如，參照日本專利特開2007-286597號公報)，但是隨著液晶顯示元件的技術的發展，業界對提供可解決所述問題的液晶配向劑的要求越來越迫切。An attempt to solve the problem is known as a liquid crystal alignment agent containing a poly-proline or a derivative thereof and a predetermined amount of a compound having an oxazine structure (for example, refer to Japanese Laid-Open Patent Publication No. 2007-286597). However, with the development of the technology of liquid crystal display elements, the industry is increasingly demanding to provide liquid crystal alignment agents that can solve the problems.

考慮到以上情況，業界期待開發出一種離子密度及長期可靠性的問題獲得改善的液晶顯示元件用液晶配向劑，使用此液晶配向劑所形成的液晶配向膜，以及具備此液晶配向膜的液晶顯示元件。In view of the above, the industry is expected to develop a liquid crystal alignment agent for liquid crystal display elements having improved ion density and long-term reliability, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display having the liquid crystal alignment film. element.

本發明者們爲了解決所述課題而進行了潛心研究。The present inventors conducted intensive studies in order to solve the above problems.

結果發現：含有聚醯胺酸或其衍生物和規定的環氧化合物的液晶配向劑，可以使具備使用此液晶配向劑所製作的液晶配向膜的液晶顯示元件具有良好的離子密度及長期可靠性，從而完成了本發明。As a result, it has been found that a liquid crystal display element containing a polyisamic acid or a derivative thereof and a predetermined epoxy compound can have a good ion density and long-term reliability of a liquid crystal display element having a liquid crystal alignment film produced using the liquid crystal alignment agent. Thus, the present invention has been completed.

本發明包括以下構成。The present invention includes the following constitutions.

[1]一種液晶配向劑，其含有作爲二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物、以及平均官能基數大於1的具有環氧基的環氧化合物，[1] A liquid crystal alignment agent comprising, as a reaction product of a diamine and a tetracarboxylic dianhydride, a polyaminic acid or a derivative thereof, and an epoxy compound having an epoxy group having an average functional group number of more than 1,

其特徵在於：所述二胺是下述通式(I)所表示的二胺It is characterized in that the diamine is a diamine represented by the following formula (I)

(通式(I)中，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H、下述結構式(II-1)、通式(II-2)或者通式(II-3)，Z1 表示可以具有甲基的碳數爲1～12的亞烷基、下述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基，m、n及p分別表示0或者1。(In the formula (I), X 1 and X 2 each represent -O- or -CH 2 -, Y 1 represents -H, the following structural formula (II-1), general formula (II-2) or (II-3), Z 1 represents an alkylene group having 1 to 12 carbon atoms which may have a methyl group, 4-substituted-1 represented by the following formula (III-1) or formula (III-2) , 1-cyclohexylene, m, n and p represent 0 or 1, respectively.

其中，m＋n＋p爲0、1或者3，Where m+n+p is 0, 1, or 3,

當m＋n＋p爲0時，Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)，When m+n+p is 0, Y 1 represents the general formula (II-1), the general formula (II-2) or the general formula (II-3).

當m＋n＋p爲1時，m及n表示0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基是鍵結在X2 的間位，When m + n + p is 1, m and n are 0, and X 2 represents -O-, X 2 are bonded aminophenyl amino group is bonded at the meta position X 2,

當m＋n＋p爲3時，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基、或者通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基。)When m+n+p is 3, X 1 and X 2 each represent -O- or -CH 2 -, Y 1 represents -H, and Z 1 represents an alkylene group having 1 to 12 carbon atoms which may have a methyl group, or 4-substituted-1,1-cyclohexylene represented by the formula (III-1) or the formula (III-2). )

(通式(II-2)以及通式(II-3)中，Y2 及Y3 分別表示碳數爲1～30的烷基。)(In the general formula (II-2) and the general formula (II-3), Y 2 and Y 3 each represent an alkyl group having 1 to 30 carbon atoms.)

(通式(III-1)以及通式(III-2)中，Y4 及Y5 分別表示碳數爲1～30的烷基。)(In the general formula (III-1) and the general formula (III-2), Y 4 and Y 5 each represent an alkyl group having 1 to 30 carbon atoms.)

[2]根據[1]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺。[2] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula (I) is m+n+p is 3, and X 1 and X 2 represent -O- or -CH 2 , respectively. -, Y 1 represents -H, and Z 1 represents a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (III-1) or (III-2).

[3]根據[2]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺是下述結構式A1以及結構式A2所表示的二胺中的一方或者兩方。[3] The liquid crystal alignment agent according to [2], wherein the diamine represented by the formula (I) is one or both of the diamines represented by the following structural formula A1 and structural formula A2. square.

[4]根據[2]或[3]所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-3)、結構式(VIII-7)以及結構式(VIII-31)所表示的二胺中的一種以上，所述四羧酸二酐爲下述結構式(1)及結構式(14)中的一方或者兩方。[4] The liquid crystal alignment agent according to [2] or [3] wherein the diamine further comprises the following structural formula (VIII-3), structural formula (VIII-7), and structural formula (VIII) One or more of the diamines represented by the above formula, wherein the tetracarboxylic dianhydride is one or both of the following structural formula (1) and structural formula (14).

[5]根據[1]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基的二胺。[5] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula (I) is m+n+p is 3, and X 1 and X 2 represent -O- or -CH 2 , respectively. -, Y 1 represents -H, and Z 1 represents a diamine which may have an alkylene group having a methyl group of 1 to 12 carbon atoms.

[6]根據[5]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是X1 及X2 分別表示-CH2 -，且Z1 表示可以具有甲基的碳數爲1～10的亞烷基的二胺。[6] The liquid crystal alignment agent according to [5], wherein the diamine represented by the formula (I) is such that X 1 and X 2 each represent -CH 2 -, and Z 1 represents that it may have The alkylene having a carbon number of 1 to 10 is an alkylene group.

[7]根據[6]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺爲下述結構式B1所表示的二胺。[7] The liquid crystal alignment agent according to [6], wherein the diamine represented by the formula (I) is a diamine represented by the following structural formula B1.

[8]根據[5]至[7]中任一項所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-13)所表示的二胺，所述四羧酸二酐爲下述結構式(1)及結構式(14)中的一方或者兩方。[A] The liquid crystal alignment agent according to any one of [5], wherein the diamine further includes a diamine represented by the following structural formula (VIII-13), the four The carboxylic acid dianhydride is one or both of the following structural formula (1) and structural formula (14).

[9]根據[1]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m＋n＋p爲0，且Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)的二胺。[9] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula (I) is m+n+p is 0, and Y 1 represents a formula (II-1) (II-2) or a diamine of the formula (II-3).

[10]根據[9]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是所述通式(II-2)及通式(II-3)中的Y2 及Y3 分別表示碳數爲1～20的烷基的二胺。[10] The liquid crystal alignment agent according to [9], wherein the diamine represented by the formula (I) is in the formula (II-2) and the formula (II-3) Y 2 and Y 3 each represent a diamine having an alkyl group having 1 to 20 carbon atoms.

[11]根據[9]或[10]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是選自下述結構式C1～結構式C4所表示的二胺中的一種以上。[11] The liquid crystal alignment agent according to [9] or [10], wherein the diamine represented by the formula (I) is selected from the group consisting of the following structural formula C1 to structural formula C4. More than one of diamines.

[12]根據[9]至[11]中任一項所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-1)以及結構式(VIII-7)所表示的二胺中的一方或者兩方，所述四羧酸二酐爲下述結構式(1)及結構式(14)中的一方或者兩方。[12] The liquid crystal alignment agent according to any one of [9] to [11] wherein the diamine further comprises the following structural formula (VIII-1) and structural formula (VIII-7); One or both of the diamines shown may be one or both of the following structural formula (1) and structural formula (14).

[13]根據[1]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m＋n＋p爲1，m及n爲0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵結在X2 的間位的二胺。[13] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula (I) is m+n+p is 1, m and n are 0, and X 2 represents -O-, The amino group of the aminophenyl group to which X 2 is bonded is bonded to the diamine of the meta position of X 2 .

[14]根據[13]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺爲下述結構式D1以及結構式D2所表示的二胺中的一方或者兩方。[14] The liquid crystal alignment agent according to [13], wherein the diamine represented by the formula (I) is one or both of the following formula D1 and the diamine represented by the formula D2. square.

[15]根據[13]或[14]所述的液晶配向劑，其特徵在於：所述四羧酸二酐爲下述結構式(1)及結構式(14)中的一方或者兩方。[15] The liquid crystal alignment agent according to [13] or [14], wherein the tetracarboxylic dianhydride is one or both of the following structural formula (1) and structural formula (14).

[16]根據[1]所述的液晶配向劑，其特徵在於：所述二胺包括所述通式(I)中的m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基的二胺，以及選自下述四種二胺中的一種以上：[16] The liquid crystal alignment agent according to [1], wherein the diamine includes m+n+p in the general formula (I) of 3, and X 1 and X 2 represent -O- or -CH 2 , respectively. -, Y 1 represents -H, and Z 1 represents a diamine which may have an alkylene group having a methyl group of 1 to 12 carbon atoms, and one or more selected from the group consisting of the following four kinds of diamines:

(1)所述通式(I)中的m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示以所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺；(1) m+n+p in the formula (I) is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents the formula (III- 1) or a 4-substituted-1,1-cyclohexylene diamine represented by the formula (III-2);

(2)所述通式(I)中的m＋n＋p爲0，Y1 表示所述通式(II-1)、通式(II-2)或者通式(II-3)的二胺；(2) m+n+p in the formula (I) is 0, and Y 1 represents the diamine of the formula (II-1), the formula (II-2) or the formula (II-3);

(3)所述通式(I)中的m＋n＋p爲1，m及n爲0。且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵結在X2 的間位的二胺；(3) m+n+p in the above formula (I) is 1, and m and n are 0. And X 2 represents -O-, the amino group of the aminophenyl group to which X 2 is bonded is bonded to the diamine of the meta position of X 2 ;

(4)所述通式(I)中的m＋n＋p爲0，Y1 表示通式(II-4)的二胺。(4) m+n+p in the above formula (I) is 0, and Y 1 represents a diamine of the formula (II-4).

(通式(II-4)中，Y6 表示碳數爲1～30的烷基。)(In the formula (II-4), Y 6 represents an alkyl group having 1 to 30 carbon atoms.)

[17]根據[16]所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺包括下述結構式B1所表示的二胺、以及選自下述四種二胺中的一種以上：[17] The liquid crystal alignment agent according to [16], wherein the diamine represented by the formula (I) includes a diamine represented by the following structural formula B1, and four or more selected from the group consisting of More than one of the amines:

(1)下述結構式A1或者結構式A2所表示的二胺；(1) a diamine represented by the following structural formula A1 or structural formula A2;

(2)下述結構式C1或者結構式C2所表示的二胺；(2) a diamine represented by the following structural formula C1 or structural formula C2;

(3)下述結構式D1或者結構式D2所表示的二胺；(3) a diamine represented by the following structural formula D1 or structural formula D2;

(4)下述結構式(XI-47)所表示的二胺。(4) A diamine represented by the following structural formula (XI-47).

[18]根據[1]至[17]中任一項所述的液晶配向劑，其特徵在於：含有兩種以上聚醯胺酸或其衍生物。[18] The liquid crystal alignment agent according to any one of [1] to [17] wherein two or more kinds of polyaminic acid or a derivative thereof are contained.

[19]根據[17]所述的液晶配向劑，其特徵在於：含有作爲所述通式(I)中的m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基的二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物，以及下述三種聚醯胺酸或其衍生物中的一方或者兩方：[19] The liquid crystal alignment agent according to [17], which is characterized in that m+n+p in the above formula (I) is 3, and X 1 and X 2 each represent -O- or -CH 2 -, Y 1 represents -H, and Z 1 represents a polylysine or a derivative thereof which may be a reaction product of a diamine having a methyl group having 1 to 12 carbon atoms and a tetracarboxylic dianhydride, and the following three One or both of polyamines or their derivatives:

(1)作爲所述通式(I)中的m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示以所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物；(1) as m+n+p in the above formula (I) is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents the formula (III) -1) or a polyaminic acid or a derivative thereof, which is a reaction product of a 4-substituted-1,1-cyclohexylene diamine represented by the formula (III-2) and a tetracarboxylic dianhydride;

(2)作爲所述通式(I)中的m＋n＋p爲0，Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)的二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物；(2) As m+n+p in the above formula (I) is 0, Y 1 represents a diamine and a tetracarboxylic acid of the formula (II-1), the formula (II-2) or the formula (II-3) a polylysine or a derivative thereof, a reaction product of a dianhydride;

(3)作爲所述通式(I)中的m＋n＋p爲1，m及n爲0，且X2 表示-O-，所鍵結的氨基苯基的氨基鍵結在X2 的間位的二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物。(3) as m+n+p in the above formula (I) is 1, m and n are 0, and X 2 represents -O-, and the amino group of the bonded aminophenyl group is bonded to the meta position of X 2 Polylysine or a derivative thereof of the reaction product of an amine and a tetracarboxylic dianhydride.

[20]根據[1]至[19]中任一項所述的液晶配向劑，其特徵在於：所述環氧化合物是選自縮水甘油醚、縮水甘油酯、縮水甘油胺、含環氧基的丙烯酸系樹脂、縮水甘油醯胺、異氰脲酸縮水甘油酯、鏈狀脂肪族型環氧化合物以及環狀脂肪族型環氧化合物所組成的族群中的一種以上。[20] The liquid crystal alignment agent according to any one of [1] to [19] wherein the epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidylamine, and epoxy group-containing One or more of the group consisting of acrylic resin, glycidylamine, glycidyl isocyanurate, chain aliphatic epoxide, and cyclic aliphatic epoxide.

[21]根據[20]所述的液晶配向劑，其特徵在於：所述環氧化合物是選自N,N,N',N'-四縮水甘油基間二甲苯二胺、1,3-雙(N,N-二縮水甘油基氨基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷、2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧丙氧基]苯基)]乙基]苯基]丙烷、3,4-環氧環己烯甲基-3',4'-環氧環己烯基甲酸酯、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物、雙酚A酚醛型環氧化合物、甲酚酚醛型環氧化合物以及N,N,O-三縮水甘油基對氨基苯酚中的一種以上。[21] The liquid crystal alignment agent according to [20], wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl metaxylene diamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[4- (2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl Propane, 3,4-epoxycyclohexenemethyl-3',4'-epoxycyclohexenylcarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, A bisphenol A phenolic epoxy compound, a cresol novolac epoxy compound, and one or more of N, N, O-triglycidyl p-aminophenol.

[22]一種液晶配向膜，其特徵在於：此液晶配向膜是對根據[1]至[21]中任一項所述的液晶配向劑的膜進行煆燒而形成的。[22] A liquid crystal alignment film formed by calcining a film of the liquid crystal alignment agent according to any one of [1] to [21].

[23]一種液晶顯示元件，其具備對向配置的一對基板，形成在所述一對基板各自所對向的面中的一面或者兩面上的電極，形成在所述一對基板各自所對向的面上的液晶配向膜，以及形成在所述一對基板之間的液晶層，其特徵在於：所述液晶配向膜是根據[22]所述的液晶配向膜。[23] A liquid crystal display device comprising: a pair of substrates disposed oppositely, an electrode formed on one or both surfaces of the pair of substrates facing each other, and each of the pair of substrates is formed The liquid crystal alignment film on the surface and the liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [22].

此外，本說明書中，在提到“烷基”、“烯基”、“炔基”時，這些基團可以爲線形，也可以爲分枝形。Further, in the present specification, when referring to "alkyl group", "alkenyl group", or "alkynyl group", these groups may be linear or branched.

[發明的效果][Effects of the Invention]

本發明可以提供一種離子密度低、長期可靠性良好的各種驅動方式的液晶顯示元件。The present invention can provide a liquid crystal display element of various driving methods having low ion density and long-term reliability.

為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。The above described features and advantages of the present invention will be more apparent from the following description.

本發明的液晶配向劑含有聚醯胺酸或其衍生物、和平均官能基數大於1的具有環氧基的環氧化合物。聚醯胺酸或其衍生物可以採用一種，也可以採用兩種以上。所述聚醯胺酸或其衍生物的含量優選在液晶配向劑中占0.1重量%～50重量%，更優選1重量%～30重量%。另外，所述環氧化合物的含量相對於所述聚醯胺酸或其衍生物100重量份，優選0.1重量份～100重量份，更優選0.5重量份～80重量份。The liquid crystal alignment agent of the present invention contains polylysine or a derivative thereof, and an epoxy compound having an epoxy group having an average functional group number of more than 1. Polylysine or a derivative thereof may be used singly or in combination of two or more. The content of the polyamic acid or a derivative thereof is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 30% by weight, based on the liquid crystal alignment agent. Further, the content of the epoxy compound is preferably 0.1 parts by weight to 100 parts by weight, more preferably 0.5 parts by weight to 80 parts by weight, per 100 parts by weight of the polyaminic acid or a derivative thereof.

所述聚醯胺酸或其衍生物是二胺與四羧酸二酐的反應產物。所述所謂聚醯胺酸衍生物是一種如下的成分：在製成下述液晶配向劑時，此聚醯胺酸衍生物爲溶解在溶劑中的形態，並且將此液晶配向劑製成下述液晶配向膜時，可以形成以聚醯亞胺作爲主要成分的液晶配向膜。這種聚醯胺酸衍生物例如可以列舉可溶性聚醯亞胺、聚醯胺酸酯以及聚醯胺酸醯胺等，更具體而言，包括：1)聚醯胺酸的全部氨基和羧基進行脫水閉環反應而成的聚醯亞胺；2)聚醯胺酸的部分氨基和羧基進行脫水閉環反應而成的部分聚醯亞胺；3)聚醯胺酸的羧基轉化成酯而成的聚醯胺酸酯；4)將四羧酸二酐化合物中所含的二酐的一部分置換成有機二羧酸並進行反應而成的聚醯胺酸-聚醯胺共聚物；進一步5)使此聚醯胺酸-聚醯胺共聚物的一部分或者全部進行脫水閉環反應而成的聚醯胺醯亞胺。The polyaminic acid or a derivative thereof is a reaction product of a diamine and a tetracarboxylic dianhydride. The poly-proline derivative is a component which is dissolved in a solvent when the liquid crystal alignment agent described below is formed, and the liquid crystal alignment agent is made into the following In the case of a liquid crystal alignment film, a liquid crystal alignment film containing polyimine as a main component can be formed. Examples of such a polyamic acid derivative include soluble polyimine, polyphthalate, and polyamidamine, and more specifically, include: 1) all amino and carboxyl groups of polyproline are subjected to Polyimine which is formed by dehydration ring closure reaction; 2) partial polyimine which is obtained by dehydration ring closure reaction of a part of amino and carboxyl groups of polyproline; 3) polymerization of carboxyl group of polylysine into ester a phthalic acid ester; 4) a poly-proline-polyamine copolymer obtained by replacing a part of a dianhydride contained in a tetracarboxylic dianhydride compound with an organic dicarboxylic acid; further 5) A polyamidoquinone imine obtained by performing a dehydration ring-closure reaction of a part or all of a poly-proline-polyamine copolymer.

所述聚醯胺酸或其衍生物中，所述四羧酸二酐與二胺以莫耳比計優選0.8：1.2～1.2：0.8，更優選0.9：1.1～1.1：0.9。In the polyamic acid or a derivative thereof, the tetracarboxylic dianhydride and the diamine are preferably 0.8: 1.2 to 1.2: 0.8, more preferably 0.9: 1.1 to 1.1: 0.9 in terms of a molar ratio.

所述二胺可以採用一種，也可以採用兩種以上，並且所述二胺包括下述通式(I)所表示的二胺。此通式(I)所表示的二胺可以採用一種，也可以採用兩種以上。所述二胺中，所述通式(I)所表示的二胺優選0.5莫耳%～100莫耳%，更優選1莫耳%～100莫耳%。The diamine may be used singly or in combination of two or more kinds, and the diamine includes a diamine represented by the following formula (I). The diamine represented by the above formula (I) may be used singly or in combination of two or more kinds. In the diamine, the diamine represented by the above formula (I) is preferably from 0.5 mol% to 100 mol%, more preferably from 1 mol% to 100 mol%.

所述通式(I)中，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H、下述結構式(II-1)、通式(II-2)或者通式(II-3)，Z1 表示可以具有甲基的碳數爲1～12的亞烷基、下述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基，m、n及p分別表示0或者1。In the above formula (I), X 1 and X 2 each represent -O- or -CH 2 -, Y 1 represents -H, the following structural formula (II-1), general formula (II-2) or Formula (II-3), Z 1 represents an alkylene group having a methyl group of 1 to 12, a 4-substituted group represented by the following formula (III-1) or (III-2)- 1,1-cyclohexylene, m, n and p represent 0 or 1, respectively.

但是，所述通式(I)中，m＋n＋p爲0、1或者3，當m＋n＋p爲0時，Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)；當m＋n＋p爲1時，m及n表示0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基是鍵結在X2 的間位；當m＋n＋p爲3時，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基、或者通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基。However, in the general formula (I), m+n+p is 0, 1, or 3. When m+n+p is 0, Y 1 represents the general formula (II-1), the general formula (II-2) or the general formula (II-3). When m+n+p is 1, m and n represent 0, and X 2 represents -O-, and the amino group of the aminophenyl group to which X 2 is bonded is bonded to the meta position of X 2 ; when m+n+p is 3, X 1 and X 2 respectively represent -O- or -CH 2 -, Y 1 represents -H, and Z 1 represents an alkylene group having 1 to 12 carbon atoms which may have a methyl group, or a formula (III-1) or 4-substituted-1,1-cyclohexylene represented by the formula (III-2).

所述通式(I)所表示的二胺，例如是m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的A型二胺。A型二胺主要可以應用於TN型液晶顯示元件。The diamine represented by the above formula (I) is, for example, m+n+p is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents the formula ( III-1) or a 4-substituted-1,1-cyclohexylene group-type diamine represented by the formula (III-2). The type A diamine can be mainly applied to a TN type liquid crystal display element.

所述A型二胺例如可以列舉下述結構式A1以及A2所表示的二胺。Examples of the A-type diamine include diamines represented by the following structural formulas A1 and A2.

另外，所述通式(I)所表示的二胺，例如是m＋n＋p爲3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數爲1～12的亞烷基的B型二胺。B型二胺主要可以應用於IPS、VA型液晶顯示元件。Further, the diamine represented by the above formula (I) is, for example, m+n+p is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents that it may have a The B-type diamine having an alkylene group having 1 to 12 carbon atoms. The B-type diamine can be mainly applied to IPS and VA type liquid crystal display elements.

所述B型二胺優選X1 及X2 分別表示-CH2 -，且Z1 表示可以具有甲基的碳數爲1～10的亞烷基的二胺，這種B型二胺例如可以列舉下述結構式B1所表示的二胺。Preferably, the B-type diamines X 1 and X 2 each represent -CH 2 -, and Z 1 represents a diamine which may have an alkylene group having a methyl group of 1 to 10 carbon atoms, and the B-type diamine may be, for example, The diamine represented by the following structural formula B1 is listed.

另外，所述通式(I)所表示的二胺，例如是m＋n＋p爲0，且Y1 表示所述通式(II-1)、通式(II-2)或者通式(II-3)的二胺的C型二胺。C型二胺主要可以應用於VA型液晶顯示元件。Further, the diamine represented by the above formula (I) is, for example, m+n+p is 0, and Y 1 represents the above formula (II-1), formula (II-2) or formula (II-3) The diamine C type diamine. The C-type diamine can be mainly applied to a VA type liquid crystal display element.

所述C型二胺優選所述通式(II-2)及通式(II-3)中的Y2 及Y3 分別表示碳數爲1～20的烷基的二胺。這種C型二胺例如可以列舉下述結構式C1～結構式C4所表示的二胺。The C-type diamine is preferably a diamine in which the Y 2 and Y 3 in the formula (II-2) and the formula (II-3) each represent an alkyl group having 1 to 20 carbon atoms. Examples of such a C-type diamine include diamines represented by the following structural formula C1 to structural formula C4.

另外，所述通式(I)所表示的二胺，例如是m＋n＋p爲1，m及n爲0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵結在X2 的間位的D型二胺。D型二胺主要可以應用於IPS型液晶顯示元件。所述D型二胺例如可以列舉下述結構式D1以及結構式D2所表示的二胺。Further, the diamine represented by the above formula (I) is, for example, m+n+p is 1, m and n are 0, and X 2 represents -O-, and the amino group of the aminophenyl group bonded by X 2 is bonded to X. meta-diamines D-2. The D-type diamine can be mainly applied to an IPS type liquid crystal display element. Examples of the D-type diamine include a diamine represented by the following structural formula D1 and structural formula D2.

所述二胺可以進一步包括所述通式(I)所表示的二胺以外的其他二胺。這種其他二胺例如可以列舉下述通式(IV)～通式(X)所表示的直鏈型二胺。直鏈型二胺可以採用一種，也可以採用兩種以上。The diamine may further include other diamines other than the diamine represented by the above formula (I). Examples of such other diamines include linear diamines represented by the following general formulae (IV) to (X). The linear diamine may be used singly or in combination of two or more.

通式(IV)中，A1 表示-(CH2 )m -。此處，m表示1～12的整數。另外，通式(VI)以及通式(VIII)中，A1 獨立地表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-N(CH3 )-(CH2 )m -N(CH3 )-、-S-(CH2 )m -S-。此處，m表示1～12的整數。In the formula (IV), A 1 represents -(CH 2 ) m -. Here, m represents an integer of 1 to 12. Further, in the general formula (VI) and the general formula (VIII), A 1 independently represents a single bond, -O-, -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - N (CH 3) - (CH 2 m - N(CH 3 )-, -S-(CH 2 ) m -S-. Here, m represents an integer of 1 to 12.

另外，通式(IX)中，A2 獨立地表示-S-、-CO-、-C(CH3 )2 -、-C(CF3 )2 -或者碳數爲1～3的亞烷基。Further, in the formula (IX), A 2 independently represents -S-, -CO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - or an alkylene group having 1 to 3 carbon atoms. .

另外，通式(X)中，A1 獨立地表示-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-C(CF3 )2 -、-O-(CH2 )m -O-、-S-(CH2 )m -S-。此處，m表示1～12的整數。另外，通式(X)中，A2 表示單鍵、-O-、-S-、-CO-、、-C(CH3 )2 -、-C(CF3 )2 -或者碳數爲1～3的亞烷基。Further, in the general formula (X), A 1 independently represents -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO-, -C(CF 3 ) 2 -, -O -(CH 2 ) m -O-, -S-(CH 2 ) m -S-. Here, m represents an integer of 1 to 12. Further, in the general formula (X), A 2 represents a single bond, -O-, -S-, -CO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - or a carbon number of 1 ～3 alkylene.

另外，通式(V)～(X)中的環己環或者苯環上所鍵結的氫，可以獨立地被-F、-Cl、-CH3 、-OH、-COOH、-SO3 H、-PO3 H2 或者4-羥基苄基取代。Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (V) to (X) may be independently -F, -Cl, -CH 3 , -OH, -COOH, -SO 3 H , -PO 3 H 2 or 4-hydroxybenzyl substituted.

通式(IV)所表示的直鏈型二胺例如可以列舉結構式(IV-1)～結構式(IV-3)所表示的二胺。The linear diamine represented by the formula (IV) may, for example, be a diamine represented by the structural formula (IV-1) to the structural formula (IV-3).

通式(V)所表示的直鏈型二胺例如可以列舉結構式(V-1)以及結構式(V-2)所表示的二胺。Examples of the linear diamine represented by the formula (V) include a diamine represented by the structural formula (V-1) and the structural formula (V-2).

通式(VI)所表示的直鏈型二胺例如可以列舉結構式(VI-1)～結構式(VI-3)所表示的二胺。The linear diamine represented by the formula (VI) may, for example, be a diamine represented by the structural formula (VI-1) to the structural formula (VI-3).

通式(VII)所表示的直鏈型二胺例如可以列舉結構式(VII-1)～結構式(VII-14)所表示的二胺。The linear diamine represented by the formula (VII) may, for example, be a diamine represented by the structural formula (VII-1) to the structural formula (VII-14).

通式(VIII)所表示的直鏈型二胺例如可以列舉結構式(VIII-1)～結構式(VIII-31)所表示的二胺。The linear diamine represented by the formula (VIII) may, for example, be a diamine represented by the structural formula (VIII-1) to the structural formula (VIII-31).

通式(IX)所表示的直鏈型二胺例如可以列舉結構式(IX-1)～結構式(IX-6)所表示的二胺。The linear diamine represented by the formula (IX) may, for example, be a diamine represented by the structural formula (IX-1) to the structural formula (IX-6).

通式(X)所表示的直鏈型二胺例如可以列舉結構式(X-1)～結構式(X-6)所表示的二胺。The linear diamine represented by the formula (X) may, for example, be a diamine represented by the structural formula (X-1) to the structural formula (X-6).

這些直鏈型二胺中，更優選的直鏈型二胺可以列舉結構式(VII-1)～結構式(VII-5)、結構式(VIII-1)～結構式(VIII-13)、結構式(VIII-24)、結構式(VIII-25)、結構式(VIII-29)、結構式(VIII-31)、結構式(IX-1)、結構式(IX-2)、結構式(IX-6)以及結構式(X-1)所表示的二胺，進一步優選的直鏈型二胺可以列舉結構式(VII-1)、結構式(VII-2)、結構式(VIII-1)～結構式(VIII-13)、結構式(VIII-29)以及結構式(VIII-31)所表示的二胺。Among these linear diamines, more preferred linear diamines include structural formula (VII-1) to structural formula (VII-5), structural formula (VIII-1) to structural formula (VIII-13), Structural formula (VIII-24), structural formula (VIII-25), structural formula (VIII-29), structural formula (VIII-31), structural formula (IX-1), structural formula (IX-2), structural formula (IX-6) and the diamine represented by the structural formula (X-1), and further preferred linear diamines include the structural formula (VII-1), the structural formula (VII-2), and the structural formula (VIII-). 1) to a diamine represented by the structural formula (VIII-13), the structural formula (VIII-29), and the structural formula (VIII-31).

就製成液晶顯示元件時可以獲得合適的配向性的觀點而言，在TN以及IPS型液晶顯示元件中，所述二胺中的所述直鏈型二胺的莫耳比優選1%～90%，更優選5%～80%。The molar ratio of the linear diamine in the diamine is preferably from 1% to 90 in terms of TN and IPS type liquid crystal display elements from the viewpoint of obtaining an appropriate alignment property when a liquid crystal display element is produced. %, more preferably 5% to 80%.

在VA型液晶顯示元件、OCB型液晶顯示元件、STN型液晶顯示元件等需要大的預傾角的用途中，所述二胺優選包括具有側鏈結構的二胺，所以所述通式(I)所表示的二胺以外的二胺可以使用這種具有側鏈結構的二胺。這種具有側鏈結構的二胺例如可以列舉下述通式(XI)～通式(XV)所表示的側鏈型二胺。側鏈型二胺可以採用一種，也可以採用兩種以上。In applications in which a large pretilt angle is required, such as a VA liquid crystal display device, an OCB liquid crystal display device, or an STN liquid crystal display device, the diamine preferably includes a diamine having a side chain structure, so the general formula (I) As the diamine other than the diamine represented, such a diamine having a side chain structure can be used. Examples of the diamine having a side chain structure include a side chain type diamine represented by the following formula (XI) to formula (XV). The side chain type diamine may be used singly or in combination of two or more.

通式(XI)中，A3 表示單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-、或者-(CH2 )m -。此處，m表示1～6的整數。R7 表示具有甾體(steroid)骨架的基團，以下述通式(XVI)所表示的基團或者碳數爲1～30的烷基。此烷基中的任意-CH2 -可以獨立地被置換爲-CF2 -、-CHF-、-O-、-CH=CH-或者-C≡C-，-CH3 可以獨立地被置換爲-CH2 F、-CHF2 或者-CF3 。其中，此烷基中的-O-不相鄰。In the formula (XI), A 3 represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, or -(CH 2 ) m -. Here, m represents an integer of 1 to 6. R 7 represents a group having a steroid skeleton, a group represented by the following formula (XVI) or an alkyl group having 1 to 30 carbon atoms. Any -CH 2 - in the alkyl group may be independently substituted with -CF 2 -, -CHF-, -O-, -CH=CH- or -C≡C-, and -CH 3 may be independently substituted with -CH 2 F, -CHF 2 or -CF 3 . Wherein -O- in the alkyl group is not adjacent.

通式(XVI)中，A4 與A5 分別獨立地表示單鍵、-O-、-COO-、-OCO-、-CONH-、-CH=CH-或者碳數爲1～20的亞烷基。R8 與R9 分別獨立地表示-F或-CH3 。環S表示1,4-亞苯基、1,4-亞環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,5-二基、萘-2,7-二基或者蒽-9,10-二基。R10 表示-F、碳數爲1～30的烷基、碳數爲1～30的氟代烷基、碳數爲1～30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 。另外，a與b分別獨立地表示0～4的整數，當a或b爲2～4時，相鄰的A4 或相鄰的A5 爲不同的基團；c、d與e分別獨立地表示0～3的整數，當e爲2或者3時，多個環S可以是相同的基團，也可以是不同的基團。f與g分別獨立地表示0～2的整數，而且c＋d＋e≧1。In the formula (XVI), A 4 and A 5 each independently represent a single bond, -O-, -COO-, -OCO-, -CONH-, -CH=CH- or an alkylene group having 1 to 20 carbon atoms. base. R 8 and R 9 each independently represent -F or -CH 3 . Ring S represents 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-di Base, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl. R 10 represents -F, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH 2 F, and -OCHF 2 Or -OCF 3 . Further, a and b each independently represent an integer of 0 to 4, and when a or b is 2 to 4, adjacent A 4 or adjacent A 5 are different groups; c, d and e are independently An integer of 0 to 3 is represented. When e is 2 or 3, the plurality of rings S may be the same group or different groups. f and g each independently represent an integer of 0 to 2, and c+d+e≧1.

其中，當通式(XI)中的m爲1時，排除通式(XVI)中的c、d及e分別爲1的情況，或者排除A4 及A5 分別爲單鍵或者碳數爲2的亞烷基的情況。Wherein, when m in the general formula (XI) is 1, the case where c, d and e in the general formula (XVI) are respectively 1 is excluded, or the exclusion of A 4 and A 5 is a single bond or a carbon number of 2, respectively. The case of an alkylene group.

通式(XII)中，形成甾體骨架的碳上所鍵結的氫可以獨立地被-CH3 取代。通式(XII)以及通式(XIII)中，R11 分別獨立地表示-H或者-CH3 ，R12 表示-H或者碳數爲1～20的烷基或烯基。A6 分別獨立地表示單鍵、-C(=O)-或者-CH2 -。通式(XIII)中，R13 及R14 分別獨立地表示-H、碳數爲1～20的烷基或者苯基。In the formula (XII), the hydrogen bonded to the carbon forming the steroid skeleton may be independently substituted by -CH 3 . In the formula (XII) and the formula (XIII), R 11 each independently represents -H or -CH 3 , and R 12 represents -H or an alkyl group or alkenyl group having 1 to 20 carbon atoms. A 6 independently represents a single bond, -C(=O)- or -CH 2 -. In the formula (XIII), R 13 and R 14 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group.

通式(XIV)中，R15 表示-H或者碳數爲1～30的烷基。此烷基中，碳數爲2～30的烷基的任意-CH2 -可以獨立地被置換爲-O-、-CH=CH-或者-C≡C-。但是，此烷基中的-O-不相鄰。通式(XIV)以及通式(XV)中，A7 獨立地表示-O-或者碳數爲1～6的亞烷基。通式(XIV)中，A8 表示單鍵或者碳數爲1～3的亞烷基。環T表示1,4-亞苯基或者1,4-亞環己基。h表示0或者1。通式(XV)中，R16 表示碳數爲6～22的烷基，R17 表示-H或者碳數爲1～22的烷基。但是，通式(XIV)中，當h爲0時R15 爲-H，當h爲1時，排除A8 爲單鍵的情況，或者R15 爲-H。In the formula (XIV), R 15 represents -H or an alkyl group having 1 to 30 carbon atoms. In the alkyl group, any -CH 2 - of the alkyl group having 2 to 30 carbon atoms may be independently substituted with -O-, -CH=CH- or -C≡C-. However, -O- in this alkyl group is not adjacent. In the general formula (XIV) and the general formula (XV), A 7 independently represents -O- or an alkylene group having 1 to 6 carbon atoms. In the formula (XIV), A 8 represents a single bond or an alkylene group having 1 to 3 carbon atoms. Ring T represents 1,4-phenylene or 1,4-cyclohexylene. h means 0 or 1. In the formula (XV), R 16 represents an alkyl group having 6 to 22 carbon atoms, and R 17 represents -H or an alkyl group having 1 to 22 carbon atoms. However, in the general formula (XIV), when h is 0, R 15 is -H, and when h is 1, the case where A 8 is a single bond or R 15 is -H is excluded.

所述通式(XI)所表示的側鏈型二胺中，鍵結在苯環的碳上的兩個氨基的鍵結位置關係優選間位或者對位。兩個氨基的鍵結位置關係更優選如下：當“R7 -A3 -”的鍵結位置爲1位時，所述兩個氨基鍵結在3位和5位，或者2位和5位。In the side chain type diamine represented by the above formula (XI), the bonding positional relationship of the two amino groups bonded to the carbon of the benzene ring is preferably meta or para. The bonding positional relationship of the two amino groups is more preferably as follows: when the bonding position of "R 7 -A 3 -" is 1 position, the two amino groups are bonded at 3 and 5 positions, or 2 and 5 positions. .

所述通式(XI)所表示的二胺例如可以列舉下述通式(XI-1)～通式(XI-9)所表示的二胺。Examples of the diamine represented by the above formula (XI) include a diamine represented by the following formula (XI-1) to formula (XI-9).

所述通式(XI-1)、通式(XI-2)、通式(XI-5)以及通式(XI-6)中，R18 優選碳數爲1～30的烷基或者碳數爲1～30的烷氧基，更優選碳數爲3～30的烷基或者碳數爲3～30的烷氧基，更優選碳數爲5～25的烷基或者碳數爲5～25的烷氧基。另外，所述通式(XI-3)、通式(XI-4)以及通式(XI-7)～通式(XI-9)中，R19 優選碳數爲1～30的烷基或者碳數爲1～30的烷氧基，更優選碳數爲3～25的烷基或者碳數爲3～25的烷氧基。In the above formula (XI-1), formula (XI-2), formula (XI-5) and formula (XI-6), R 18 is preferably an alkyl group having 1 to 30 carbon atoms or a carbon number. The alkoxy group of 1 to 30 is more preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms or a carbon number of 5 to 25. Alkoxy group. Further, in the above formula (XI-3), formula (XI-4), and formula (XI-7) to formula (XI-9), R 19 is preferably an alkyl group having 1 to 30 carbon atoms or The alkoxy group having 1 to 30 carbon atoms is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

另外，所述通式(XI)所表示的側鏈型二胺例如可以列舉下述通式(XI-10)～通式(XI-15)所表示的二胺。In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following formula (XI-10) to formula (XI-15).

所述通式(XI-10)～通式(XI-13)中，R20 優選碳數爲4～30的烷基，更優選碳數爲6～25的烷基。所述通式(XI-14)以及通式(XI-15)中，R21 優選碳數爲6～30的烷基，更優選碳數爲8～25的烷基。In the above formula (XI-10) to formula (XI-13), R 20 is preferably an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 25 carbon atoms. In the above formula (XI-14) and formula (XI-15), R 21 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms.

另外，所述通式(XI)所表示的側鏈型二胺例如可以列舉下述通式(XI-16)～通式(XI-36)所表示的二胺。In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following formula (XI-16) to formula (XI-36).

所述通式(XI-16)、通式(XI-17)、通式(XI-20)、通式(XI-22)、通式(XI-23)、通式(XI-26)、通式(XI-28)、通式(XI-29)、通式(XI-34)以及通式(XI-35)中，R22 優選碳數爲1～30的烷基、碳數爲1～30的烷氧基，更優選碳數爲3～25的烷基或者碳數爲3～25的烷氧基。所述通式(XI-18)、通式(XI-19)、通式(XI-21)、通式(XI-24)、通式(XI-25)、通式(XI-27)、通式(XI-30)～通式(XI-33)以及通式(XI-36)中，R23 優選-H、-F、碳數爲1～30的烷基、碳數爲1～30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ，更優選碳數爲3～25的烷基或者碳數爲3～25的烷氧基。所述通式(XI-31)以及通式(XI-32)中，A9 表示碳數爲1～20的亞烷基。The general formula (XI-16), the general formula (XI-17), the general formula (XI-20), the general formula (XI-22), the general formula (XI-23), the general formula (XI-26), In the formula (XI-28), the formula (XI-29), the formula (XI-34), and the formula (XI-35), R 22 is preferably an alkyl group having 1 to 30 carbon atoms and a carbon number of 1 The alkoxy group of ～30 is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. The general formula (XI-18), the general formula (XI-19), the general formula (XI-21), the general formula (XI-24), the general formula (XI-25), the general formula (XI-27), In the general formula (XI-30) to the general formula (XI-33) and the general formula (XI-36), R 23 is preferably -H, -F, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30. The alkoxy group, -CN, -OCH 2 F, -OCHF 2 or -OCF 3 , more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. In the above formula (XI-31) and formula (XI-32), A 9 represents an alkylene group having 1 to 20 carbon atoms.

另外，所述通式(XI)所表示的側鏈型二胺例如可以列舉下述結構式(XI-37)～通式(XI-46)所表示的二胺。In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following structural formulae (XI-37) to (XI-46).

所述通式(XI)所表示的側鏈型二胺優選通式(XI-1)～通式(XI-9)所表示的二胺，更優選通式(XI-2)或者通式(XI-4)所表示的二胺。The side chain type diamine represented by the above formula (XI) is preferably a diamine represented by the formula (XI-1) to the formula (XI-9), more preferably a formula (XI-2) or a formula ( The diamine represented by XI-4).

所述通式(XII)所表示的側鏈型二胺，優選兩個“NH2 -Ph-A6 -O-”中的一個鍵結在甾核(steroid nucleus)的3位，另一個鍵結在甾核的6位。另外，分別鍵結在兩個苯基上的兩個氨基優選鍵結在A6 的間位或者對位。The side chain type diamine represented by the general formula (XII), preferably one of the two "NH 2 -Ph-A 6 -O-" bonds to the 3 position of the steroid nucleus, the other bond It is 6 in the nucleus. In addition, the two amino groups respectively bonded to the two phenyl groups are preferably bonded to the meta or para position of A 6 .

所述通式(XII)所表示的側鏈型二胺例如可以列舉下述結構式(XII-1)～結構式(XII-4)所表示的二胺。Examples of the side chain type diamine represented by the above formula (XII) include diamines represented by the following structural formula (XII-1) to structural formula (XII-4).

所述通式(XIII)所表示的側鏈型二胺，優選兩個“NH2 -(R14 -)Ph-A6 -O-”分別鍵結在苯基的碳上，並且這兩個“NH2 -(R14 -)Ph-A6 -O-”鍵結在苯基上的鍵結有甾核的碳的間位或者對位。另外，分別鍵結在兩個苯基上的兩個氨基，優選鍵結在A6 的間位或者對位。The side chain type diamine represented by the formula (XIII), preferably two "NH 2 -(R 14 -)Ph-A 6 -O-" respectively bonded to the carbon of the phenyl group, and the two "NH 2 -(R 14 -)Ph-A 6 -O-" is bonded to the phenyl group to the meta or para position of the carbon of the nucleus. Further, the two amino groups are respectively bonded on both phenyl, preferably bonded to A in the meta or para position 6.

所述通式(XIII)所表示的側鏈型二胺例如可以列舉下述結構式(XIII-1)～結構式(XIII-8)所表示的二胺。The side chain type diamine represented by the above formula (XIII) may, for example, be a diamine represented by the following structural formula (XIII-1) to structural formula (XIII-8).

所述通式(XIV)所表示的側鏈型二胺，優選分別鍵結在兩個苯基上的兩個氨基鍵結在A7 的間位或者對位。The side chain type diamine represented by the above formula (XIV) preferably has two amino groups bonded to the two phenyl groups respectively bonded to the meta or para position of A 7 .

所述通式(XIV)所表示的側鏈型二胺例如可以列舉下述通式(XIV-1)～通式(XIV-9)所表示的二胺。Examples of the side chain type diamine represented by the above formula (XIV) include diamines represented by the following formula (XIV-1) to formula (XIV-9).

所述通式(XIV-1)以及通式(XIV-2)中，R24 爲-H，所述通式(XIV-4)以及通式(XIV-5)中，R25 爲-H。另外，所述通式(XIV-3)中，R24 優選-H或者碳數爲1～30的烷基，所述通式(XIV-6)～通式(XIV-9)中，R25 優選-H或者碳數爲1～20的烷基。In the above formula (XIV-1) and formula (XIV-2), R 24 is -H, and in the formula (XIV-4) and formula (XIV-5), R 25 is -H. Further, in the above formula (XIV-3), R 24 is preferably -H or an alkyl group having 1 to 30 carbon atoms, and in the above formula (XIV-6) to formula (XIV-9), R 25 Preference is given to -H or an alkyl group having 1 to 20 carbon atoms.

所述通式(XV)所表示的側鏈型二胺，優選分別鍵結在兩個苯基上的兩個氨基鍵結在A7 的間位或者對位。The side chain type diamine represented by the above formula (XV) preferably has two amino groups bonded to the two phenyl groups respectively bonded to the meta or para position of A 7 .

所述通式(XV)所表示的側鏈型二胺例如可以列舉下述通式(XV-1)～通式(XV-3)所表示的二胺。Examples of the side chain type diamine represented by the above formula (XV) include diamines represented by the following formula (XV-1) to formula (XV-3).

所述通式中，R26 優選碳數爲6～20的烷基，R27 優選-H或者碳數爲1～10的烷基。In the above formula, R 26 is preferably an alkyl group having 6 to 20 carbon atoms, and R 27 is preferably -H or an alkyl group having 1 to 10 carbon atoms.

就製成液晶顯示元件時可以獲得合適的預傾角的觀點而言，在TN以及VA型液晶顯示元件中，在所述二胺中的所述側鏈型二胺的莫耳比優選1%～90%，更優選5%～80%。From the viewpoint of obtaining a suitable pretilt angle when forming a liquid crystal display element, in the TN and VA type liquid crystal display elements, the molar ratio of the side chain type diamine in the diamine is preferably 1%. 90%, more preferably 5% to 80%.

所述二胺可以更包括所述通式(I)所表示的二胺以外的其他二胺，例如具有萘結構的萘系二胺、具有芴結構的芴系二胺、具有矽氧烷鍵的矽氧烷系二胺、或者具有所述通式(XI)～通式(XV)所表示的側鏈結構以外的側鏈結構的二胺。如果所述其他二胺具有側鏈結構，則可以用作所述胺的B成分；如果所述其他二胺不具有側鏈結構，則可以用作所述胺的A成分。The diamine may further include other diamines other than the diamine represented by the above formula (I), for example, a naphthalene type diamine having a naphthalene structure, an anthracene diamine having a fluorene structure, and a decane bond. A dioxin-based diamine or a diamine having a side chain structure other than the side chain structure represented by the above formula (XI) to formula (XV). If the other diamine has a side chain structure, it can be used as the component B of the amine; if the other diamine does not have a side chain structure, it can be used as the component A of the amine.

例如，所述矽氧烷系二胺例如可以列舉下述通式(XVII)所表示的二胺。For example, the dioxane-based diamine is exemplified by a diamine represented by the following formula (XVII).

所述通式(XVII)中，R28 及R29 獨立表示碳數爲1～3的烷基或者苯基，A10 獨立表示亞甲基、亞苯基或者烷基取代亞苯基。i表示1～6的整數，j表示1～10的整數。In the above formula (XVII), R 28 and R 29 independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A 10 independently represents a methylene group, a phenylene group or an alkyl group-substituted phenylene group. i represents an integer of 1 to 6, and j represents an integer of 1 to 10.

所述通式(XVII)所表示的二胺例如可以列舉下述結構式(XVII-1)～結構式(XVII-7)所表示的二胺。Examples of the diamine represented by the above formula (XVII) include a diamine represented by the following structural formula (XVII-1) to structural formula (XVII-7).

此外，所述其他二胺並沒有特別限定，例如可以列舉下述通式(1')～通式(8')所表示的二胺。In addition, the other diamine is not particularly limited, and examples thereof include a diamine represented by the following formula (1') to formula (8').

所述通式中，R30 獨立地表示碳數爲3～30的烷基，所述通式(4')、通式(6')及通式(8')中，R31 表示碳數爲3～30的烷基。In the above formula, R 30 independently represents an alkyl group having 3 to 30 carbon atoms, and in the above formula (4'), formula (6') and formula (8'), R 31 represents a carbon number. It is an alkyl group of 3 to 30.

此外，所述其他二胺並不限定爲所述的二胺，在本發明的目的可以獲得實現的範圍內，當然可以使用所述其他二胺以外的各種形態的二胺。Further, the other diamine is not limited to the above-described diamine, and it is of course possible to use various forms of diamines other than the other diamines within the range in which the object of the present invention can be attained.

所述二胺的一部分也可以置換爲單胺。如果將二胺的一部分置換爲單胺，則可以終止生成聚醯胺酸或其衍生物的聚合反應，而抑制進一步的反應，由此可以容易地控制所獲得的聚醯胺酸或其衍生物的分子量，就這個觀點而言，優選將二胺的一部分置換爲單胺。單胺相對於二胺的比率只要在無損本發明的效果的範圍內即可，標準爲占全部胺的10莫耳%以下。A part of the diamine may also be substituted with a monoamine. If a part of the diamine is substituted with a monoamine, the polymerization reaction for producing poly-proline or a derivative thereof can be terminated, and further reaction can be suppressed, whereby the obtained poly-proline or its derivative can be easily controlled. From this point of view, it is preferred to replace a part of the diamine with a monoamine. The ratio of the monoamine to the diamine may be within the range which does not impair the effects of the present invention, and the standard is 10 mol% or less of the total amine.

所述四羧酸二酐只要是四羧酸二酐，則沒有特別限定。所述四羧酸二酐可以採用一種，也可以採用兩種以上。基於使本發明的聚醯胺酸或其衍生物形成爲可溶解於溶劑中的形態的觀點，優選是適當地選擇所述四羧酸二酐。所述四羧酸二酐例如可以列舉：芳香族四羧酸二酐、脂肪族四羧酸二酐以及脂環族四羧酸二酐。The tetracarboxylic dianhydride is not particularly limited as long as it is a tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used singly or in combination of two or more. From the viewpoint of forming the poly-proline or the derivative thereof of the present invention into a form soluble in a solvent, it is preferred to appropriately select the tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride.

所述芳香族四羧酸二酐例如可以列舉下述結構式(1)～(13)所表示的化合物。Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following structural formulae (1) to (13).

所述芳香族四羧酸二酐，優選下述結構式(1)、結構式(2)、結構式(5)、結構式(6)以及結構式(7)所表示的化合物，更優選結構式(1)所表示的均苯四甲酸二酐。The aromatic tetracarboxylic dianhydride is preferably a compound represented by the following structural formula (1), structural formula (2), structural formula (5), structural formula (6), and structural formula (7), and more preferably a structure. Pyromellitic dianhydride represented by the formula (1).

所述脂肪族四羧酸二酐以及所述脂環族四羧酸二酐，例如可以列舉下述結構式(14)～結構式(62)所表示的化合物。Examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include compounds represented by the following structural formulas (14) to (62).

所述脂肪族四羧酸二酐以及所述脂環族四羧酸二酐，優選所述結構式(14)～結構式(29)、以及結構式(60)所表示的化合物，更優選結構式(14)所表示的1,2,3,4-環丁烷四甲酸二酐。The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are preferably compounds represented by the structural formula (14) to the structural formula (29) and the structural formula (60), and more preferably a structure. 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by formula (14).

另外，就使本發明的聚醯胺酸或其衍生物成爲可溶解於溶劑的聚醯亞胺的觀點而言，所述脂肪族四羧酸二酐以及所述脂環族四羧酸二酐優選所述結構式(19)、結構式(20)、結構式(27)～結構式(29)以及結構式(60)所表示的化合物。Further, from the viewpoint of making the polyaminic acid of the present invention or a derivative thereof into a polyimine which is soluble in a solvent, the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride Preference is given to the compounds represented by the structural formula (19), the structural formula (20), the structural formula (27) to the structural formula (29) and the structural formula (60).

並且，所述四羧酸二酐也可以含有具有側鏈結構的四羧酸二酐。具有側鏈結構的四羧酸二酐可以增大液晶顯示元件的預傾角。具有側鏈結構的四羧酸二酐例如可以列舉下述結構式(63)以及結構式(64)所表示的具有甾骨架的化合物。Further, the tetracarboxylic dianhydride may also contain a tetracarboxylic dianhydride having a side chain structure. The tetracarboxylic dianhydride having a side chain structure can increase the pretilt angle of the liquid crystal display element. Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having an anthracene skeleton represented by the following structural formula (63) and structural formula (64).

就使液晶顯示元件具有良好的離子密度的觀點而言，所述四羧酸二酐優選含有所述芳香族四羧酸二酐、和脂肪族四羧酸二酐以及脂環族四羧酸二酐中的一方或者兩方。The tetracarboxylic dianhydride preferably contains the aromatic tetracarboxylic dianhydride, and an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic acid in terms of a liquid crystal display element having a good ion density. One or both of the anhydrides.

所述四羧酸二酐還包括除此以外的各種形態的四羧酸二酐，而並不限定於所述的四羧酸二酐。所述四羧酸二酐可以在本發明的目的能够實現的範圍內，使用其他各種形態的四羧酸二酐。The tetracarboxylic dianhydride further includes various forms of tetracarboxylic dianhydride other than the above, and is not limited to the tetracarboxylic dianhydride described above. The tetracarboxylic dianhydride may use other various forms of tetracarboxylic dianhydride within the range that can be achieved by the object of the present invention.

所述四羧酸二酐的一部分可以置換爲羧酸酐。如果將四羧酸二酐的一部分置換爲羧酸酐，則可以終止生成所述聚醯胺酸或其衍生物的聚合反應，而抑制進一步的反應，由此可以容易地控制所獲得的聚醯胺酸或其衍生物的分子量，就這個觀點而言，優選將四羧酸二酐的一部分置換爲羧酸酐。所述羧酸酐相對於四羧酸二酐的比率只要在無損本發明的效果的範圍內即可，標準爲所述四羧酸二酐的10莫耳%以下。A part of the tetracarboxylic dianhydride may be replaced with a carboxylic anhydride. If a part of the tetracarboxylic dianhydride is replaced with a carboxylic acid anhydride, the polymerization reaction for producing the polyaminic acid or its derivative can be terminated, and further reaction can be suppressed, whereby the obtained polyamine can be easily controlled. From the viewpoint of the molecular weight of the acid or its derivative, it is preferred to replace a part of the tetracarboxylic dianhydride with a carboxylic anhydride. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride may be within the range which does not impair the effects of the present invention, and the standard is 10 mol% or less of the tetracarboxylic dianhydride.

關於前文所說明的所述二胺和所述四羧酸二酐的組合，更具體而言，就離子密度降低、配向性提高的觀點而言，優選所述二胺包含所述A型二胺和所述結構式(VIII-3)、結構式(VIII-7)、結構式(VIII-31)所表示的二胺中的一種以上，並且所述四羧酸二酐包含所述結構式(1)及結構式(14)中的一方或者兩方。With respect to the combination of the diamine and the tetracarboxylic dianhydride described above, more specifically, from the viewpoint of a decrease in ion density and an improvement in the alignment property, it is preferred that the diamine contains the A-type diamine. And one or more of the diamines represented by the structural formula (VIII-3), the structural formula (VIII-7), and the structural formula (VIII-31), and the tetracarboxylic dianhydride comprises the structural formula ( 1) and one or both of the structural formulas (14).

另外，就離子密度降低、配向性提高、以及防止燒黏的觀點而言，優選所述二胺包含所述B型二胺和所述結構式(VIII-13)所表示的二胺，並且所述四羧酸二酐包含所述結構式(1)及結構式(14)中的一方或者兩方。Further, in view of reduction in ion density, improvement in orientation, and prevention of sticking, it is preferred that the diamine comprises the B-type diamine and the diamine represented by the structural formula (VIII-13), and The tetracarboxylic dianhydride includes one or both of the structural formula (1) and the structural formula (14).

另外，就離子密度降低、配向性提高的觀點而言，優選所述二胺包含所述C型二胺和所述結構式(VIII-1)、結構式(VIII-7)所表示的二胺中的一方或者兩方，並且所述四羧酸二酐包含所述結構式(1)及結構式(14)中的一方或者兩方。Further, from the viewpoint of a decrease in ion density and an improvement in the alignment property, the diamine preferably contains the C-type diamine and the diamine represented by the structural formula (VIII-1) and the structural formula (VIII-7). One or both of the above, and the tetracarboxylic dianhydride includes one or both of the structural formula (1) and the structural formula (14).

另外，就離子密度下降、配向性提高、以及防止燒黏的觀點而言，優選所述二胺包含所述結構式D1及結構式D2所表示的所述D型二胺中的一方或者兩方，並且所述四羧酸二酐包含所述結構式(1)及結構式(14)中的一方或者兩方。Moreover, it is preferable that the diamine includes one or both of the D-type diamines represented by the structural formula D1 and the structural formula D2 from the viewpoint of a decrease in ion density, an improved alignment, and prevention of sticking. And the tetracarboxylic dianhydride includes one or both of the structural formula (1) and the structural formula (14).

所述聚醯胺酸或其衍生物的重量平均分子量並沒有特別限定，在將其用作液晶配向劑的成分時，就在對液晶配向膜進行煆燒的步驟中，所述聚醯胺酸或其衍生物不會蒸發，並且可以獲得作爲液晶配向劑的成分的良好物理性質的觀點而言，所述重量平均分子量優選大於等於5×103 ，更優選大於等於1×104 。而且，就使具有黏性等的液晶配向劑的操作變得容易的觀點而言，所述重量平均分子量優選小於等於1×106 。The weight average molecular weight of the polyaminic acid or a derivative thereof is not particularly limited, and when it is used as a component of a liquid crystal alignment agent, in the step of calcining the liquid crystal alignment film, the polylysine The weight average molecular weight is preferably 5 × 10 3 or more, more preferably 1 × 10 4 or more, from the viewpoint that the physical property of the component as the liquid crystal alignment agent can be obtained without evaporating. Moreover, from the viewpoint of facilitating the operation of the liquid crystal alignment agent having viscosity or the like, the weight average molecular weight is preferably 1 × 10 6 or less.

所述聚醯胺酸或其衍生物的重量平均分子量可以通過凝膠滲透色譜分析(Gel Permeation Chromatography，GPC)法來測定。例如，用二甲基甲醯胺(Dimethylformamide，DMF)稀釋所獲得的聚醯胺酸或其衍生物，使聚醯胺酸或其衍生物的濃度達到約1重量%，使用Chromatopac C-R7A(島津製作所製造)，以DMF作爲展開溶劑，通過凝膠滲透色譜分析(GPC)法進行測定，並進行聚苯乙烯換算，由此可以求出所述聚醯胺酸或其衍生物的重量平均分子量。並且，就提高GPC測定的精度的觀點而言，也可以將磷酸、鹽酸、硝酸、硫酸等無機酸或者溴化鋰、氯化鋰等無機鹽溶解於DMF溶劑中，製備成展開溶劑而進行使用。The weight average molecular weight of the polyaminic acid or a derivative thereof can be measured by a gel permeation chromatography (GPC) method. For example, the obtained polyaminic acid or a derivative thereof is diluted with dimethylformamide (DMF) to a concentration of polyglycine or a derivative thereof of about 1% by weight, using Chromatopac C-R7A ( The product of the Shimadzu Corporation is determined by the gel permeation chromatography (GPC) method using DMF as a developing solvent, and the weight average molecular weight of the polyaminic acid or its derivative can be determined by polystyrene conversion. . Further, from the viewpoint of improving the accuracy of the GPC measurement, an inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, or an inorganic salt such as lithium bromide or lithium chloride may be dissolved in a DMF solvent to prepare a developing solvent.

可以採用衆所周知的方法來製造所述聚醯胺酸或其衍生物。例如，可以將所述二胺投入具備原料投入口、氮氣導入口、溫度計、攪拌機及冷凝器的反應容器中，並且根據需要投入所需量的單胺。The polylysine or a derivative thereof can be produced by a well-known method. For example, the diamine may be introduced into a reaction vessel having a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser, and a required amount of a monoamine may be added as needed.

然後，投入溶劑(例如醯胺系極性溶劑N-甲基-2-吡咯烷酮或者二甲基甲醯胺等)以及所述四羧酸二酐，並且根據需要添加所需量的羧酸酐。此時，優選四羧酸二酐的投入總量與二胺的總莫耳數大致相等(莫耳比爲0.9～1.1左右)。Then, a solvent (for example, a guanamine-based polar solvent N-methyl-2-pyrrolidone or dimethylformamide or the like) and the tetracarboxylic dianhydride are charged, and a desired amount of a carboxylic anhydride is added as needed. In this case, the total amount of the tetracarboxylic dianhydride to be charged is preferably substantially equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

於攪拌下、於0℃～70℃下使之反應1小時～48小時，由此可以較好地獲得聚醯胺酸溶液。另外，也可以通過加熱來提高反應溫度上升(例如50℃～80℃)，而獲得分子量小的聚醯胺酸。用大量不良溶劑來使所生成的聚醯胺酸沉澱，通過過濾等將固體成分和溶劑完全分離開來，由此可以獲得聚醯胺酸。The reaction is carried out at 0 ° C to 70 ° C for 1 hour to 48 hours with stirring, whereby a polyaminic acid solution can be preferably obtained. Further, it is also possible to increase the reaction temperature (for example, 50 to 80 ° C) by heating to obtain a polylysine having a small molecular weight. The produced polyamine acid is precipitated with a large amount of a poor solvent, and the solid component and the solvent are completely separated by filtration or the like, whereby polylysine can be obtained.

作爲聚醯胺酸衍生物的可溶性聚醯亞胺，通常可以通過如下方式獲得：使聚醯胺酸溶液，與作爲脫水劑的乙酸酐、丙酸酐、三氟乙酸酐等酸酐，以及作爲脫水閉環催化劑的三乙基胺、吡啶、三甲基吡啶(collidine)等叔胺一起在20℃～150℃的溫度下進行醯亞胺化反應。The soluble polyimine which is a polyproline derivative can be usually obtained by using a polyaminic acid solution, an anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride as a dehydrating agent, and as a dehydration ring closure. The tertiary amine such as triethylamine, pyridine or collidine of the catalyst is subjected to a ruthenium iodization reaction at a temperature of from 20 ° C to 150 ° C.

另外，所述可溶性聚醯亞胺也可以通過如下方式獲得：使用大量的不良溶劑(甲醇、乙醇、異丙醇等醇系溶劑或者二醇系溶劑)，使聚醯胺酸從聚醯胺酸溶液中析出，並在甲苯、二甲苯等溶劑中，使所析出的聚醯胺酸，與和所述相同的脫水劑及脫水閉環催化劑一起在20℃～150℃的溫度下進行醯亞胺化反應。Further, the soluble polyimine may also be obtained by using a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol, or isopropanol or a glycol solvent) to make the polyamic acid from polylysine. Precipitating in a solution, and precipitating the polylysine which is precipitated in a solvent such as toluene or xylene with the same dehydrating agent and dehydration ring-closure catalyst at a temperature of from 20 ° C to 150 ° C reaction.

在所述醯亞胺化反應中，脫水劑與脫水閉環催化劑的比例優選0.1～10(莫耳比)。脫水劑與脫水閉環催化劑這兩者的合計使用量，優選相對於所使用的四羧酸二酐中所含的酸二酐的莫耳總量爲1.5倍莫耳～10倍莫耳。通過調整此化學醯亞胺化的脫水劑、催化劑量、反應溫度以及反應時間，可以控制醯亞胺化程度，而獲得部分聚醯亞胺。In the oxime imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closure catalyst is preferably 0.1 to 10 (mole ratio). The total amount of the dehydrating agent and the dehydration ring-closing catalyst to be used is preferably 1.5 times to 10 times the molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride to be used. By adjusting the chemical hydrazide dehydrating agent, the amount of the catalyst, the reaction temperature, and the reaction time, the degree of hydrazide can be controlled to obtain a partial polyimine.

另外，如果將所述四羧酸二酐的一部分置換爲有機二羧酸，則可以獲得聚醯胺酸-聚醯胺共聚物。其中，有機二羧酸相對於四羧酸二酐的比率只要在無損本發明的效果的範圍內即可，標準爲所述四羧酸二酐的10莫耳%以下。Further, if a part of the tetracarboxylic dianhydride is replaced with an organic dicarboxylic acid, a poly-proline-polyamine copolymer can be obtained. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic dianhydride may be within the range which does not impair the effects of the present invention, and the standard is 10 mol% or less of the tetracarboxylic dianhydride.

並且，可以通過將聚醯胺酸-聚醯胺共聚物化學醯亞胺化來獲得聚醯胺醯亞胺。Further, polyamidoquinone imine can be obtained by chemically imidating a poly-proline-polyamine copolymer.

可以通過紅外光譜法(Infrared Spectroscopy，IR)、磁核共振法(nuclear magnetic resonance，NMR)進行分析，由此鑒定所述聚醯胺酸或其衍生物。另外，可以用KOH或NaOH等強鹼的水溶液使固態的聚醯胺酸或其衍生物分解，然後用有機溶劑萃取聚醯胺酸，並通過GC、高效液相色譜法(High Performance Liquid Chromatography，HPLC)、氣相色譜-質譜法(Gas Chromatography-Mass Spectrometry，GC-MS)進行分析，由此鑒定所使用的單體。The polylysine or a derivative thereof can be identified by analyzing by infrared spectroscopy (IR) or nuclear magnetic resonance (NMR). Alternatively, the solid polyamine or its derivative may be decomposed with an aqueous solution of a strong base such as KOH or NaOH, and then the polylysine may be extracted with an organic solvent and passed through GC, High Performance Liquid Chromatography (High Performance Liquid Chromatography, HPLC, Gas Chromatography-Mass Spectrometry (GC-MS) was used for analysis to identify the monomers used.

可以用溶劑稀釋所獲得的聚醯胺酸或其衍生物，將其調整成所需的黏度後再使用。The obtained polyglycine or a derivative thereof can be diluted with a solvent and adjusted to a desired viscosity before use.

另外，可以將所獲得的聚醯胺酸或其衍生物與溶劑分離，然後和下述環氧化合物一起再次溶解在下述溶劑中，製成液晶配向劑而使用；或者，也可以不與溶劑分離，而添加環氧化合物，製成液晶配向劑而使用。Further, the obtained polyaminic acid or a derivative thereof may be separated from the solvent, and then re-dissolved in the following solvent together with the epoxy compound described below to prepare a liquid crystal alignment agent, or may be separated from the solvent. An epoxy compound is added to prepare a liquid crystal alignment agent.

關於所述聚醯胺酸或其衍生物，可以通過使用所述側鏈型二胺等具有側鏈結構的二胺或者四羧酸二酐，來適當地調整液晶顯示元件的預傾角，而使所述聚醯胺酸或其衍生物可以適用於任意種類的液晶顯示元件。作爲預傾角，VA型液晶顯示元件大多需要80°～90°左右的大的預傾角，OCB型液晶顯示元件大多需要7°～20°左右的預傾角，TN型液晶顯示元件或STN型液晶顯示元件大多需要3°～10°左右的預傾角，IPS型液晶顯示元件大多需要0°～3°左右的小的預傾角。With respect to the poly-proline or a derivative thereof, the pretilt angle of the liquid crystal display element can be appropriately adjusted by using a diamine having a side chain structure such as a side chain type diamine or a tetracarboxylic dianhydride. The polyamic acid or a derivative thereof can be applied to any type of liquid crystal display element. As the pretilt angle, a large pretilt angle of about 80° to 90° is required for a VA liquid crystal display element, and a pretilt angle of about 7° to 20° is often required for an OCB liquid crystal display element, and a TN liquid crystal display element or an STN liquid crystal display is required. Most of the elements require a pretilt angle of about 3 to 10 degrees, and an IPS type liquid crystal display element often requires a small pretilt angle of about 0 to 3 degrees.

像所述預傾角這樣的由聚醯胺酸或其衍生物的單體所表現出來的特性，可以通過使用具有這種特性的單體製造聚醯胺酸或其衍生物而獲得。由單體所表現出來的特性，可以由使用多種具有這種特性的單體而獲得的一種聚醯胺酸或其衍生物來獲得，另外，也可以由使用多種具有這種特性的單體而獲得的兩種以上的聚醯胺酸或其衍生物來獲得。The properties exhibited by the monomer of polylysine or a derivative thereof such as the pretilt angle can be obtained by producing polyamic acid or a derivative thereof using a monomer having such a property. The characteristics exhibited by the monomer can be obtained by using a polylysine or a derivative thereof obtained by using a plurality of monomers having such characteristics, and it is also possible to use a plurality of monomers having such characteristics. Two or more kinds of polyaminic acid or a derivative thereof obtained are obtained.

就使本發明的液晶配向劑具有優異的特性的觀點而言，優選使液晶配向劑中含有單體的一部分或者全部不同的兩種以上的聚醯胺酸或其衍生物。至於兩種以上的聚醯胺酸或其衍生物的混合比，只要爲可以獲得液晶配向劑的用途所對應的所需特性的程度即可。In view of the fact that the liquid crystal alignment agent of the present invention has excellent properties, it is preferred that the liquid crystal alignment agent contains two or more kinds of polyaminic acid or a derivative thereof which are different from a part or all of the monomers. The mixing ratio of two or more kinds of polyamic acid or a derivative thereof may be such a degree as to obtain a desired property corresponding to the use of the liquid crystal alignment agent.

更具體而言，通過適當選擇所述二胺或四羧酸二酐的種類以及所述二胺與四羧酸二酐的組合，可以使本發明的液晶配向劑具有所要求的更加良好的離子密度或更加合適的預傾角等所需特性，而且可以提高這些特性。More specifically, by appropriately selecting the kind of the diamine or tetracarboxylic dianhydride and the combination of the diamine and the tetracarboxylic dianhydride, the liquid crystal alignment agent of the present invention can have a desired more excellent ion. Density or a more suitable pretilt angle and other desired characteristics, and these characteristics can be improved.

所述兩種以上的聚醯胺酸或其衍生物的組合例如可以列舉：(1)包含所述B型二胺的聚醯胺酸或其衍生物，與包含所述A型二胺的聚醯胺酸或其衍生物、包含所述C型二胺的聚醯胺酸或其衍生物、或者包含所述D型二胺的聚醯胺酸或其衍生物的組合；(2)包含所述B型二胺的聚醯胺酸或其衍生物、包含所述A型二胺的聚醯胺酸或其衍生物、以及包含所述C型二胺的聚醯胺酸或其衍生物的組合；以及，(3)包含所述B型二胺的聚醯胺酸或其衍生物，與包含所述D型二胺的聚醯胺酸或其衍生物，與包含所述A型二胺的聚醯胺酸或其衍生物、或者包含所述C型二胺的聚醯胺酸或其衍生物的組合。The combination of the two or more kinds of polyaminic acid or a derivative thereof may, for example, be: (1) a poly-proline or a derivative thereof containing the B-type diamine, and a poly-containing polyamine a combination of proline or a derivative thereof, polylysine comprising the C-type diamine or a derivative thereof, or polylysine comprising the D-diamine or a derivative thereof; (2) a polyaminic acid of a B-type diamine or a derivative thereof, a poly-proline or a derivative thereof comprising the A-type diamine, and a poly-proline or a derivative thereof comprising the C-type diamine And (3) a poly-proline or a derivative thereof comprising the B-type diamine, and a poly-proline or a derivative thereof comprising the D-diamine, and the type-containing diamine A combination of polylysine or a derivative thereof, or polylysine comprising the C-type diamine or a derivative thereof.

所述環氧化合物是具有兩個以上環氧基的化合物等平均官能基數大於1的具有環氧基的化合物。環氧化合物可以採用一種，也可以採用兩種以上。在液晶配向劑中，環氧化合物的種類及含量，是採用可以形成環氧化合物與所述聚醯胺酸或其衍生物的溶液的種類及含量。另外，環氧樹脂是指具有環氧基的樹脂。The epoxy compound is a compound having an epoxy group having an average functional group number of more than 1 such as a compound having two or more epoxy groups. The epoxy compound may be used singly or in combination of two or more. In the liquid crystal alignment agent, the type and content of the epoxy compound and the content of the solution which can form the epoxy compound and the polyamic acid or its derivative are used. Further, the epoxy resin means a resin having an epoxy group.

所述環氧化合物例如可以列舉：縮水甘油醚、縮水甘油酯、縮水甘油胺、含環氧基的丙烯酸系樹脂、縮水甘油醯胺、異氰脲酸縮水甘油酯、鏈狀脂肪族型環氧化合物以及環狀脂肪族型環氧化合物。Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, and chain aliphatic epoxy. Compounds and cyclic aliphatic epoxy compounds.

所述縮水甘油醚例如可以列舉：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、苯酚酚醛型環氧化合物、甲酚酚醛型環氧化合物、溴化苯酚酚醛型環氧化合物、溴化甲酚酚醛型環氧化合物、雙酚A酚醛型環氧化合物、含萘骨架的環氧化合物、芳香族多縮水甘油醚化合物、二環戊二烯-苯酚型環氧化合物、脂環族二縮水甘油醚化合物、脂肪族多縮水甘油醚化合物、多硫化物(polysulfide)型二縮水甘油醚化合物以及雙酚型環氧化合物。Examples of the glycidyl ether include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a bisphenol type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and hydrogenation. 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 epoxy compound, phenol novolac type epoxy Compound, cresol novolac type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polycondensation A glyceryl ether compound, a dicyclopentadiene-phenol type epoxy compound, an alicyclic diglycidyl ether compound, an aliphatic polyglycidyl ether compound, a polysulfide type diglycidyl ether compound, and a bisphenol type ring Oxygen compound.

所述縮水甘油酯例如可以列舉二縮水甘油酯化合物以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.

所述縮水甘油胺例如可以列舉多縮水甘油胺化合物以及縮水甘油胺型環氧樹脂。Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin.

所述含環氧基的丙烯酸系化合物例如可以列舉具有環氧乙烷基(oxiranyl)的單體的均聚物及共聚物。Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having an oxiranyl group.

所述縮水甘油醯胺例如可以列舉縮水甘油醯胺型環氧化合物。The glycidylamine can be exemplified by a glycidylamine type epoxy compound.

所述鏈狀脂肪族型環氧化合物例如可以列舉將烯烴化合物的碳-碳雙鍵氧化而成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.

所述環狀脂肪族型環氧化合物例如可以列舉將環烯烴化合物的碳-碳雙鍵氧化而成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 cycloolefin compound.

所述雙酚A型環氧化合物例如可以列舉：828、1001、1002、1003、1004、1007、1010(均由日本環氧樹脂製造)，Epo Tohto YD-128(東都化成公司製造)，DER-331、DER-332、DER-324(均由陶氏化學(Dow Chemical)公司製造)，Epiclon 840、Epiclon 850、Epiclon 1050(均由大日本油墨製造)，Epomik R-140、Epomik R-301以及EpomikR-304(均由三井化學製造)。Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by Japanese epoxy resin), Epo Tohto YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER- 331, DER-332, DER-324 (all manufactured by Dow Chemical), Epiclon 840, Epiclon 850, Epiclon 1050 (all manufactured by Dainippon Ink), Epomik R-140, Epomik R-301 and EpomikR-304 (both manufactured by Mitsui Chemicals).

所述雙酚F型環氧化合物例如可以列舉：806、807、4004P(均由日本環氧樹脂製造)，Epo Tohto YDF-170、Epo Tohto YDF-175S、Epo Tohto YDF-2001(均由東都化成公司製造)，DER-354(陶氏化學公司製造)，Epiclon 830以及Epiclon 835(均由大日本油墨製造)。Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Japanese epoxy resin), Epo Tohto YDF-170, Epo Tohto YDF-175S, and Epo Tohto YDF-2001 (both by Toho Chemical Co., Ltd.). Made by the company), DER-354 (manufactured by The Dow Chemical Company), Epiclon 830 and Epiclon 835 (all manufactured by Dainippon Ink).

所述雙酚型環氧化合物例如可以列舉：2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷的環氧化合物。The bisphenol type epoxy compound may, for example, be an epoxy compound of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

所述氫化雙酚A型環氧化合物例如可以列舉：Sun Tohto ST-3000(東都化成公司製造)、Rikare sin HBE-100(新日本理化製造)以及Denacol EX-252(長瀨化成公司製造)。Examples of the hydrogenated bisphenol A type epoxy compound include Sun Tohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rikare sin HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (manufactured by Nagase Chemical Co., Ltd.).

所述氫化雙酚型環氧化合物例如可以列舉：氫化2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷的環氧化合物。The hydrogenated bisphenol type epoxy compound may, for example, be an epoxy compound of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

所述溴化雙酚A型環氧化合物例如可以列舉：5050、5051(均由日本環氧樹脂製造)，Epo Tohto YDB-360、Epo Tohto YDB-400(均由東都化成公司製造)，DER-530、DER-538(均由陶氏化學公司製造)，Epiclon 152以及Epiclon 153(均由大日本油墨製造)。Examples of the brominated bisphenol A type epoxy compound include 5050 and 5051 (all manufactured by Japanese epoxy resin), Epo Tohto YDB-360, and Epo Tohto YDB-400 (all manufactured by Tohto Kasei Co., Ltd.), DER- 530, DER-538 (all manufactured by The Dow Chemical Company), Epiclon 152 and Epiclon 153 (both manufactured by Dainippon Ink).

所述苯酚酚醛型環氧化合物例如可以列舉：152、154(均由日本環氧樹脂製造)，YDPN-638(東都化成公司製造)，DEN431、DEN438(均由陶氏化學公司製造)，EpiclonN-770(大日本油墨化學工業股份有限公司製造)，EPPN-201以及EPPN-202(均由日本化藥股份有限公司製造)。Examples of the phenol novolak type epoxy compound include 152 and 154 (all manufactured by Japanese epoxy resin), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical Co., Ltd.), and Epiclon N- 770 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EPPN-201 and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.).

所述甲酚酚醛型環氧化合物例如可以列舉：180S75(日本環氧樹脂製造)，YDCN-701、YDCN-702(均由東都化成公司製造)，Epiclon N-665、Epiclon N-695(均由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以及EOCN-1027(均由日本化藥股份有限公司製造)。Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Nippon Epoxy Resin), YDCN-701, YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), Epiclon N-665, and Epiclon N-695 (both by Manufactured by Dainippon Ink Chemical Industry Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

所述雙酚A酚醛型環氧化合物例如可以列舉：157S70(日本環氧樹脂股份有限公司製造)、Epiclon N-880(大日本油墨化學工業股份有限公司製造)。Examples of the bisphenol A phenolic epoxy compound include 157S70 (manufactured by Nippon Epoxy Resin Co., Ltd.) and Epiclon N-880 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

所述含萘骨架的環氧化合物例如可以列舉：Epiclon HP-4032、Epiclon HP-4700、Epiclon HP-4770(均由大日本油墨化學工業股份有限公司製造)，以及NC-7000(日本化藥公司製造)。Examples of the naphthalene skeleton-containing epoxy compound include Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (both manufactured by Dainippon Ink and Chemicals Co., Ltd.), and NC-7000 (Nippon Chemical Co., Ltd.). Manufacturing).

所述芳香族多縮水甘油醚化合物例如可以列舉：對苯二酚二縮水甘油醚(下述結構式101)，鄰苯二酚二縮水甘油醚(下述結構式102)，間苯二酚二縮水甘油醚(下述結構式103)，2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧丙氧基]苯基)]乙基]苯基]丙烷(下述結構式104)，三(4-縮水甘油氧基苯基)甲烷(下述結構式105)，1031S、1032H60(均由日本環氧樹脂製造)，TACTIX-742(陶氏化學公司製造)，Denacol EX-201(長瀨化成公司製造)，DPPN-503、DPPN-502H、DPPN-501H、NC6000(均由日本化藥股份有限公司製造)，Tecmore VG3101L(三井化學公司製造)，下述結構式106所表示的化合物以及下述結構式107所表示的化合物。Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following structural formula 101), catechol diglycidyl ether (the following structural formula 102), and resorcinol II. Glycidyl ether (Structure 103 below), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3) -glycidoxy]phenyl)]ethyl]phenyl]propane (Structure 104 below), tris(4-glycidoxyphenyl)methane (Structural Formula 105 below), 1031S, 1032H60 ( Made of Japanese epoxy resin), TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 (manufactured by Changchun Chemical Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (both made in Japan) (manufactured by Pharmaceutical Co., Ltd.), Tecmore VG3101L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following structural formula 106, and a compound represented by the following structural formula 107.

所述二環戊二烯-苯酚型環氧化合物例如可以列舉：TACTIX-556(陶氏化學公司製造)、Epiclon 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 The Dow Chemical Co., Ltd.) and Epiclon HP-7200 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

所述脂環族二縮水甘油醚化合物例如可以列舉：環己二甲醇二縮水甘油醚化合物、以及Rikaresin DME-100(新日本理化製造)。Examples of the alicyclic diglycidyl ether compound include a cyclohexanedimethanol diglycidyl ether compound and Rikaresin DME-100 (manufactured by Shin Nippon Chemical Co., Ltd.).

所述脂肪族多縮水甘油醚化合物例如可以列舉：乙二醇二縮水甘油醚(下述結構式108)，二乙二醇二縮水甘油醚(下述結構式109)，聚乙二醇二縮水甘油醚，丙二醇二縮水甘油醚(下述結構式110)，三丙二醇二縮水甘油醚(下述結構式111)，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112)，1,4-丁二醇二縮水甘油醚(下述結構式113)，1,6-己二醇二縮水甘油醚(下述結構式114)，二溴新戊二醇二縮水甘油醚(下述結構式115)，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(均由長瀨化成公司製造)，DD-503(旭電化公司製造)，Rikaresin W-100(新日本理化製造)，1,3,5,6-四縮水甘油基-2,4-己二醇(下述結構式116)，丙三醇多縮水甘油醚，山梨糖醇多縮水甘油醚，三羥甲基丙烷多縮水甘油醚，季戊四醇多縮水甘油醚，Denacol EX-313、Denacol EX-611、Denacol EX-321、Denacol EX-411(均由長瀨化成公司製造)。Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula 108), diethylene glycol diglycidyl ether (the following structural formula 109), and polyethylene glycol condensed water. Glycerol ether, propylene glycol diglycidyl ether (the following structural formula 110), tripropylene glycol diglycidyl ether (the following structural formula 111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula) 112), 1,4-butanediol diglycidyl ether (structure 113 below), 1,6-hexanediol diglycidyl ether (structure 114 below), dibromo neopentyl glycol diglycidyl Ether (Structure 115 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 Chemical Co., Ltd.), DD-503 (made by Asahi Kasei Co., Ltd.), Rikaresin W-100 (Nippon Chemical and Chemical Manufacturing), 1,3,5,6-tetraglycidyl-2,4 - hexanediol (Structure 116 below), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polycondensate Glycerol ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by Nagase Chemical Co., Ltd.).

所述多硫化物型二縮水甘油醚化合物例如可以列舉：FLDP-50及FLDP-60(均由Toray Thiokol製造)。Examples of the polysulfide type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol).

所述雙酚型環氧化合物例如可以列舉：YX-4000、YL-6121(均由日本環氧樹脂製造)，NC-3000P、NC-3000S(均由日本化藥股份有限公司製造)。Examples of the bisphenol type epoxy compound include YX-4000, YL-6121 (all manufactured by Japanese epoxy resin), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

所述二縮水甘油酯化合物例如可以列舉：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118)、鄰苯二甲酸雙(2-甲基環氧乙烷基甲酯)(下述結構式119)、六氫鄰苯二甲酸二縮水甘油酯(下述結構式120)、下述結構式121所表示的化合物、下述結構式122所表示的化合物以及下述結構式123所表示的化合物。Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula 118), and phthalic acid bis (2). -Methyl oxiranylmethyl ester) (the following structural formula 119), hexahydrophthalic acid diglycidyl ester (the following structural formula 120), a compound represented by the following structural formula 121, and the following structure The compound represented by Formula 122 and the compound represented by the following Structural Formula 123.

所述縮水甘油酯環氧化合物例如可以列舉：871、872(均由日本環氧樹脂製造)，Epiclon 200、Epiclon 400(均由大日本油墨化學工業股份有限公司製造)，Denacol EX-711以及Denacol EX-721(均由長瀨化成公司製造)。Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by Nippon Epoxy Resin), Epiclon 200 and Epiclon 400 (both manufactured by Dainippon Ink and Chemicals Co., Ltd.), Denacol EX-711 and Denacol. EX-721 (all manufactured by Changchun Chemical Company).

所述多縮水甘油胺化合物例如可以列舉：N,N-二(縮水甘油基)苯胺(下述結構式124)、N,N-二縮水甘油基鄰甲苯胺(下述結構式125)、N,N-二縮水甘油基間甲苯胺(下述結構式126)、N,N-二縮水甘油基-2,4,6-三溴苯胺(下述結構式127)、3-(N,N-二縮水甘油基)氨基丙基三甲氧基矽烷(下述結構式128)、N,N,O-三縮水甘油基對氨基苯酚(下述結構式129)、N,N,O-三縮水甘油基間氨基苯酚(下述結構式130)、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷(下述結構式131)、N,N,N',N'-四縮水甘油基間二甲苯二胺(TETRAD-X(三菱瓦斯化學)，下述結構式132)、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133)、1,4-雙(N,N-二縮水甘油基氨基甲基)環己烷(下述結構式134)、1,3-雙(N,N-二縮水甘油基氨基)環己烷(下述結構式135)、1,4-雙(N,N-二縮水甘油基氨基)環己烷(下述結構式136)、1,3-雙(N,N-二縮水甘油基氨基)苯(下述結構式137)、1,4-雙(N,N-二縮水甘油基氨基)苯(下述結構式138)、2,6-雙(N,N-二縮水甘油基氨基甲基)二環[2.2.1]庚烷(下述結構式139)、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140)、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141)、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基醚(下述結構式142)、1,3,5-三(4-(N,N-二縮水甘油基)氨基苯氧基)苯(下述結構式143)、2,4,4'-三(N,N-二縮水甘油基氨基)二苯基醚(下述結構式144)、三(4-(N,N-二縮水甘油基)氨基苯基)甲烷(下述結構式145)、3,4,3',4'-四(N,N-二縮水甘油基氨基)聯苯(下述結構式146)、3,4,3',4'-四(N,N-二縮水甘油基氨基)二苯基醚(下述結構式147)、下述結構式148所表示的化合物以及下述結構式149所表示的化合物。Examples of the polyglycidylamine compound include N,N-bis(glycidyl)aniline (hereinafter, Structural Formula 124), N,N-diglycidyl o-toluidine (hereinafter, Structural Formula 125), and N. , N-diglycidyl m-toluidine (structure formula 126 below), N,N-diglycidyl-2,4,6-tribromoaniline (structure 127 below), 3-(N,N - diglycidyl) aminopropyltrimethoxydecane (structure 128 below), N, N, O-triglycidyl p-aminophenol (structure 129 below), N, N, O-tri-shrink Glyceryl-m-aminophenol (Structural Formula 130 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (Structural Formula 131 below), N, N , N', N'-tetraglycidyl m-xylenediamine (TETRAD-X (Mitsubishi Gas Chemical), the following structural formula 132), 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), the following structural formula 133), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (the following structural formula 134), 1,3-bis(N,N-diglycidylamino)cyclohexane (structure formula 135 below), 1,4-bis(N,N-diglycidylamino)cyclohexane (structure described below) Formula 136), 1,3-double (N, N- Diglycidylamino)benzene (Structural Formula 137 below), 1,4-bis(N,N-diglycidylamino)benzene (Structural Formula 138 below), 2,6-bis (N,N- Diglycidylaminomethyl)bicyclo[2.2.1]heptane (structural formula 139 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexyl Methane (Structural Formula 140 below), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (Structural Formula 141 below) ), N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (Structural Formula 142 below), 1,3,5-tris(4-(N,N) - diglycidyl)aminophenoxy)benzene (Structural Formula 143 below), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (Structure 144 below) , tris(4-(N,N-diglycidyl)aminophenyl)methane (formula 145 below), 3,4,3',4'-tetrakis (N,N-diglycidylamino) Biphenyl (the following structural formula 146), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (the following structural formula 147), the following structural formula 148 The compound shown and the compound represented by the following structural formula 149.

所述具有環氧乙烷基的單體的均聚物例如可以列舉聚甲基丙烯酸縮水甘油酯。所述具有環氧乙烷基的單體的共聚物例如可以列舉：N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物、N-環己基馬來醯亞胺-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-環氧丙烷基)甲酯-甲基丙烯酸縮水甘油酯共聚物以及苯乙烯-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. The copolymer of the monomer having an oxiranyl group may, for example, be N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-methacrylic acid Glycidyl ester copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-methacrylic acid shrinkage A glyceride copolymer, a (3-ethyl-3-epoxypropenyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

所述具有環氧乙烷基的單體例如可以列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-3,4-環氧環己酯、(甲基)丙烯酸甲基縮水甘油酯。Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate. .

所述具有環氧乙烷基的單體的共聚物中，所述具有環氧乙烷基的單體以外的單體，例如可以列舉：(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-環氧丙烷基)甲酯、N-環己基馬來醯亞胺以及N-苯基馬來醯亞胺。In the copolymer of the monomer having an oxiranyl group, examples of the monomer other than the monomer having an oxiranyl group include (meth)acrylic acid and methyl (meth)acrylate. Ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclomethacrylate Ester, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloromethyl styrene, (A) (3-ethyl-3-epoxypropenyl)methyl acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

所述異氰脲酸縮水甘油酯例如可以列舉：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150)、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151)以及異氰脲酸縮水甘油酯型環氧樹脂。The glycidyl isocyanurate may, for example, be 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following structural formula 150), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (described below) Structural Formula 151) and an isocyanuric acid glycidyl ester type epoxy resin.

所述鏈狀脂肪族型環氧化合物例如可以列舉：環氧化聚丁二烯、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.).

所述環狀脂肪族型環氧化合物例如可以列舉：3,4-環氧環己烯甲基-3',4'-環氧環己烯基甲酸酯(Celloxide 2021(Daicel化學工業股份有限公司製造)，下述結構式152)，2-甲基-3,4-環氧環己基甲基-2'-甲基-3',4'-環氧環己基甲酸酯(下述結構式153)，2,3-環氧環戊基-2',3'-環氧環戊基醚(下述結構式154)，ε-己內酯改性3,4-環氧環己基甲基-3',4'-環氧環己基甲酸酯，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155)，下述結構式156所表示的化合物，CY-175、CY-177、CY-179(均由CIBA-GEIGY公司製造)，EHPD-3150(Daicel化學工業股份有限公司製造)以及環狀脂肪族型環氧樹脂。Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenemethyl-3',4'-epoxycyclohexenylcarboxylate (Celloxide 2021 (Daicel Chemical Industry Co., Ltd.) Manufactured by the company, the following structural formula 152), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylformate (structure Formula 153), 2,3-epoxycyclopentyl-2',3'-epoxycyclopentyl ether (structure 154 below), ε-caprolactone modified 3,4-epoxycyclohexyl Base-3',4'-epoxycyclohexylformate, 1,2:8,9-diepoxylimene (Celloxide 3000 (manufactured by Daicel Chemical Industry Co., Ltd.), the following structural formula 155), the following The compound represented by Structural Formula 156, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by Daicel Chemical Industry Co., Ltd.), and cyclic aliphatic epoxy resin .

所述環氧化合物優選多縮水甘油胺化合物、雙酚A酚醛型環氧化合物、甲酚酚醛型環氧化合物以及環狀脂肪族型環氧化合物中的一種以上，更優選N,N,N',N'-四縮水甘油基間二甲苯二胺、1,3-雙(N,N-二縮水甘油基氨基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷、商品名“Tecmore VG3101L”、3,4-環氧環己烯甲基-3',4'-環氧環己烯基甲酸酯、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物、N,N,O-三縮水甘油基對氨基苯酚、雙酚A酚醛型環氧化合物以及甲酚酚醛型環氧化合物中的一種以上。The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A phenolic epoxy compound, a cresol novolac epoxy compound, and a cyclic aliphatic epoxy compound, and more preferably N, N, N' , N'-tetraglycidyl meta-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl -4,4'-diaminodiphenylmethane, trade name "Tecmore VG3101L", 3,4-epoxycyclohexenemethyl-3',4'-epoxycyclohexenylcarboxylate, N- a phenyl maleimide-glycidyl methacrylate copolymer, one of N, N, O-triglycidyl p-aminophenol, a bisphenol A phenolic epoxy compound, and a cresol novolac epoxy compound the above.

本發明的液晶配向劑可以進一步包含所述聚醯胺酸或其衍生物、以及環氧化合物以外的成分。這種進一步包含的成分可以列舉溶劑以及普通液晶配向劑中所含有的各種添加劑。The liquid crystal alignment agent of the present invention may further comprise a component other than the polyamic acid or a derivative thereof and an epoxy compound. Such a further contained component may, for example, be a solvent and various additives contained in a general liquid crystal alignment agent.

所述溶劑廣泛包括聚醯胺酸、可溶性聚醯亞胺以及聚醯胺醯亞胺等通常用在高分子成分的製造步驟或用途中的溶劑，所述溶劑可以根據使用目的來適當選擇。例如，可以基於調整液晶配向劑的黏度等物理性質、易操作性以及簡化步驟等觀點來使用所述溶劑。溶劑可以採用一種，也可以採用兩種以上。所述溶劑例如可以列舉對聚醯胺酸或其衍生物具有易溶性的非質子極性有機溶劑、以及改變表面張力而改善塗布性等的塗布性改善溶劑，所述溶劑優選爲含有這些溶劑的混合溶劑。The solvent includes a solvent which is generally used in a production step or a use of a polymer component, such as polyacrylic acid, soluble polyimine, and polyamidoximine, and the solvent can be appropriately selected depending on the purpose of use. For example, the solvent can be used from the viewpoints of adjusting physical properties such as viscosity of the liquid crystal alignment agent, ease of handling, and simplification of steps. The solvent may be used singly or in combination of two or more. The solvent may, for example, be an aprotic polar organic solvent which is soluble in polylysine or a derivative thereof, and a coating property improving solvent which changes surface tension to improve coatability and the like, and the solvent is preferably a mixture containing these solvents. Solvent.

所述非質子極性有機溶劑例如可以列舉：N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone)、N,N'-二甲基咪示啉酮(N,N'-dimethyl imidazolidinone)、N-甲基己內醯胺(N-methyl caprolactam)、N,N-二甲基丙醯胺(N,N-dimethyl propionamide)、N,N-二甲基乙醯胺、二甲基亞碸(dimethyl sulfoxide)、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二乙基乙醯胺、N,N,N'N'-四甲基脲、γ-丁內酯以及γ-戊內酯。所述非質子極性有機溶劑優選爲選自N-甲基-2-吡咯烷酮、N,N'-二甲基咪唑啉酮、γ-丁內酯以及γ-戊內酯中的一種以上。Examples of the aprotic polar organic solvent include N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) and N,N'-dimethylimidazolidinone. , N-methyl caprolactam, N,N-dimethyl propionamide, N,N-dimethylacetamide, dimethyl Dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N,N,N'N'-four Base urea, γ-butyrolactone and γ-valerolactone. The aprotic polar organic solvent is preferably one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N'-dimethylimidazolidinone, γ-butyrolactone, and γ-valerolactone.

所述塗布性改善溶劑例如可以列舉：乳酸烷基酯、3-甲基-3-甲氧基丁醇、四氫萘(tetralin)、異佛爾酮(isophorone)、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、乙二醇乙酸單烷基酯或者乙二醇乙酸單苯酯、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、以及這些的乙酸酯類等酯化合物。所述塗布性改善溶劑優選爲選自乙二醇單丁醚、二乙二醇單***、丙二醇單丁醚以及二丙二醇單甲醚中的一種以上。Examples of the coatability improving solvent include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and the like. Diethylene glycol monoalkyl ether such as ethylene glycol monoalkyl ether or diethylene glycol monoethyl ether; monoalkyl glycol glycol acetate or monophenyl glycol acetate, triethylene glycol monoalkyl ether, An propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, a dialkyl malonate such as dialkyl malonate or a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or an ester compound such as an acetate. The applicability improving solvent is preferably one or more selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

非質子極性溶劑與塗布性改善溶劑的種類和比例，可以考慮液晶配向劑的印刷性、塗布性、溶解性以及保存穩定性等而適當設定。非質子極性溶劑的溶解性以及保存穩定性相對優於塗布性改善溶劑，而塗布性改善溶劑的印刷性以及塗布性相對優於非質子極性溶劑。The type and ratio of the aprotic polar solvent and the applicability improving solvent can be appropriately set in consideration of printability, coatability, solubility, storage stability, and the like of the liquid crystal alignment agent. The solubility and storage stability of the aprotic polar solvent are relatively better than the coating property improving solvent, and the printability and coatability of the coating property improving solvent are relatively superior to those of the aprotic polar solvent.

所述添加劑只要是用來提高液晶配向劑的特定性質的成分即可，可以採用一種，也可以採用兩種以上。所述添加劑可以列舉根據各自目的而使用的聚醯胺酸或其衍生物以外的高分子化合物及低分子化合物。The additive may be used alone or in combination of two or more kinds as long as it is a component for improving the specific properties of the liquid crystal alignment agent. The additive may, for example, be a polymer compound or a low molecular compound other than polyamine or a derivative thereof used for each purpose.

就控制所形成的液晶配向劑的電特性或配向性的觀點而言，所述高分子化合物優選爲可溶於有機溶劑的高分子化合物。這種高分子化合物例如可以列舉：聚醯胺、聚氨酯(polyurethane)、聚脲(polyurea)、聚酯、聚環氧化物(polyepoxide)、聚酯多元醇(polyesterpolyol)、聚矽氧(silicone)改性聚氨酯、聚矽氧改性聚酯。The polymer compound is preferably a polymer compound soluble in an organic solvent from the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment agent formed. Examples of such a polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyesterpolyol, and silicone modification. Polyurethane, polyoxymethylene modified polyester.

所述低分子化合物例如可以列舉：表面活性劑、抗靜電劑、矽烷偶聯劑(silane coupling agent)、鈦系偶聯劑以及醯亞胺化催化劑。就提高液晶配向劑的塗布性的觀點而言，優選表面活性劑。就提高液晶配向劑及液晶配向膜的抗靜電性的觀點而言，優選抗靜電劑。就提高液晶配向膜與基板的密接性或耐摩擦性的觀點而言，優選矽烷偶聯劑及鈦系偶聯劑。就形成液晶配向膜時，可以在低溫下進行醯亞胺化的觀點而言，優選醯亞胺化催化劑。Examples of the low molecular compound include a surfactant, an antistatic agent, a silane coupling agent, a titanium coupling agent, and a ruthenium amide catalyst. From the viewpoint of improving the coatability of the liquid crystal alignment agent, a surfactant is preferred. From the viewpoint of improving the antistatic property of the liquid crystal alignment agent and the liquid crystal alignment film, an antistatic agent is preferred. From the viewpoint of improving the adhesion between the liquid crystal alignment film and the substrate or the abrasion resistance, a decane coupling agent and a titanium coupling agent are preferable. In the case of forming a liquid crystal alignment film, a ruthenium imidization catalyst is preferred from the viewpoint of performing ruthenium imidization at a low temperature.

所述矽烷偶聯劑例如可以列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基甲基三甲氧基矽烷、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、3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-(甲基丙烯醯氧基)丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、N-(1,3-二甲基亞丁基)-3-(三乙氧基甲矽烷基)-1-丙基胺以及N,N'-雙[3-(三甲氧基甲矽烷基)丙基]乙二胺。The decane coupling agent may, for example, be vinyltrimethoxydecane, vinyltriethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N- (2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-amino Phenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-(Methethyloxy)propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylidene)-3-(triethoxymethane 1-propylamine and N,N'-bis[3-(trimethoxycarbamidyl)propyl]ethylenediamine.

所述醯亞胺化催化劑例如可以列舉：三甲基胺、三乙基胺、三丙基胺、三丁基胺等脂肪族胺類；N,N-二甲基苯胺、N,N-二乙基苯胺、甲基取代苯胺、羥基取代苯胺等芳香族胺類；吡啶、甲基取代吡啶、羥基取代吡啶、喹啉(quinoline)、甲基取代喹啉、羥基取代喹啉、異喹啉、甲基取代異喹啉、羥基取代異喹啉、咪唑(imidazole)、甲基取代咪唑、羥基取代咪唑等環式胺類。所述醯亞胺化催化劑優選爲選自N,N-二甲基苯胺，鄰、間、對羥基苯胺，鄰、間、對羥基吡啶以及異喹啉中的一種以上。Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-di Aromatic amines such as ethyl aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, A cyclic amine such as a methyl-substituted isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably one or more selected from the group consisting of N,N-dimethylaniline, o-, m-p-hydroxyaniline, o-, m-, p-hydroxypyridine and isoquinoline.

矽烷偶聯劑的添加量通常爲聚醯胺酸或其衍生物的總重量的0重量%～10重量%，優選0.1重量%～3重量%。The amount of the decane coupling agent to be added is usually from 0% by weight to 10% by weight, preferably from 0.1% by weight to 3% by weight based on the total mass of the polyaminic acid or its derivative.

醯亞胺催化劑的添加量相對於聚醯胺酸或其衍生物的羰基通常爲0.01當量～5當量，優選0.05當量～3當量。The amount of the ruthenium imine catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, per mole of the carbonyl group of the polyaminic acid or its derivative.

其他添加劑的添加量根據用途而有所不同，通常爲聚醯胺酸或其衍生物的總重量的0重量%～30重量%，優選0.1重量%～10重量%。The amount of the other additives to be added varies depending on the use, and is usually 0% by weight to 30% by weight, preferably 0.1% by weight to 10% by weight based on the total weight of the polyaminic acid or its derivative.

例如，從就使液晶顯示元件的電特性長期穩定的觀點而言考慮，本發明的液晶配向劑可以進一步含有烯基取代納迪克醯亞胺(nadiimide)化合物。所述烯基取代納迪克醯亞胺化合物可以是採用一種化合物，也可以是採用兩種或者兩種以上的化合物。就從所述觀點考慮而言，所述烯基取代納迪克醯亞胺化合物的含量，以相對於液晶配向劑中的聚醯胺酸或者其衍生物的重量比計，優選爲0.01～1.00，更加優選爲0.01～0.70，進一步優選爲0.01～0.50。For example, from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadiimide compound. The alkenyl-substituted nadicylimine compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the alkenyl-substituted nadicylimine compound is preferably from 0.01 to 1.00, based on the weight ratio of the poly-proline or the derivative thereof in the liquid crystal alignment agent. It is more preferably 0.01 to 0.70, still more preferably 0.01 to 0.50.

所述烯基取代納迪克醯亞胺化合物，優選爲可以溶解在溶解本發明中使用的聚醯胺酸或者其衍生物的溶劑中溶解的化合物。這樣的烯基取代納迪克醯亞胺化合物的例子可以列舉以下述通式(Ina)所表示的化合物。The alkenyl-substituted nadicylimine compound is preferably a compound which can be dissolved in a solvent which dissolves the poly-proline or the derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (Ina).

通式(Ina)中，L1 以及L2 分別獨立地表示氫、碳數爲1～12的烷基、碳數爲3～6的烯基、碳數爲5～8的環烷基、芳基或者苄基，n表示1或者2。In the general formula (Ina), L 1 and L 2 each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an aromatic group. Base or benzyl, n represents 1 or 2.

當n=1時，W表示碳數爲1～12的烷基、碳數爲2～6的烯基、碳數爲5～8的環烷基、碳數爲6～12的芳基、苄基、以-Z1 -(0)q -(Z2 O)r -Z3 -H(Z1 、Z2 以及Z3 獨立地表示碳數爲2～6的亞烷基，q表示0或者1，並且而且r表示1～30的整數)所表示的基團、以-(Z4 )s -B-Z5 -H(Z4 以及Z5 獨立地表示碳數爲1～4的亞烷基或者碳數爲5～8的環亞烷基，B表示亞苯基，並且而且s表示0或者1)所表示的基團、以-B-T-B-H(B表示亞苯基，而且並且T表示-CH2 -、-C(CH3 )2 -、-O-、-CO-、-S-或者SO2 -)所表示的基團、或者這些基團的1個～3個氫經被羥基所取代而成的基團。When n=1, W represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and benzyl group. a group, -Z 1 -(0) q -(Z 2 O) r -Z 3 -H (Z 1 , Z 2 and Z 3 independently represent an alkylene group having 2 to 6 carbon atoms, and q represents 0 or 1, and r is a group represented by an integer of 1 to 30), and -(Z 4 ) s -BZ 5 -H (Z 4 and Z 5 independently represent an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having a carbon number of 5 to 8, B represents a phenylene group, and s represents a group represented by 0 or 1), with -BTBH (B represents a phenylene group, and T represents -CH 2 - a group represented by -C(CH 3 ) 2 -, -O-, -CO-, -S- or SO 2 -), or one to three hydrogens of these groups are substituted by a hydroxyl group Group.

此時，優選的W是碳數爲1～8的烷基、碳數爲3～4的烯基、環己基、苯基、苄基、碳數爲4～10的聚(乙烯氧)乙基、苯氧基苯基、苯基甲基苯基、苯基異亞丙基苯基以及這些基團的1個或者2個氫經被羥基所取代而成的基團。In this case, preferred W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, and a poly(ethyleneoxy)ethyl group having 4 to 10 carbon atoms. And a phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenephenyl group, and a group in which one or two hydrogens of these groups are substituted by a hydroxyl group.

當通式(Ina)中n=2時，W表示碳數爲2～20的亞烷基、碳數爲5～8的環亞烷基、碳數爲6～12的亞芳基、以-Z1 -O-(Z2 O)r -Z3 -(Z1 ～Z3 以及r的含義如上所述)所表示的基團、以-Z4 -B-Z5 -(Z4 、Z5 以及B的含義如上所述)所表示的基團、以-B-(O-B)s -T-(B-O)s -B-(B表示亞苯基，T表示碳數爲1～3的亞烷基、-O-或者-SO2 -，s表示0或者1)所表示的基團、或者這些基團的1個～3個氫經被羥基取代而成所取代的基團。When n=2 in the general formula (Ina), W represents an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, and - Z 1 -O- (Z 2 O) r -Z 3 - ( Z 1 ~ Z 3 meanings and r as described above) a group represented to -Z 4 -BZ 5 - (Z 4 , Z 5 and The meaning of B is as defined above. The group represented by -B-(OB) s -T-(BO) s -B- (B represents a phenylene group, and T represents an alkylene group having 1 to 3 carbon atoms) And -O- or -SO 2 -, s represents a group represented by 0 or 1), or a group in which one to three hydrogens of these groups are substituted by a hydroxyl group.

此時，優選的W是碳數爲2～12的亞烷基、亞環己基、亞苯基、苯亞甲基、亞二甲苯基、以-C3 H6 -O-(Z2 -O)r -O-C3 H6 -(Z2 表示碳數爲2～6的亞烷基，r表示1或者2)所表示的基團、以-B-T-B-(B表示亞苯基，而且T表示-CH2 -、-O-或者-SO2 -)所表示的基團、以-B-O-B-C3 H6 -B-O-B-(B表示亞苯基)所表示的基團、以及這些基團的1個或者2個氫被經羥基所取代而成的基團。In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a benzylidene group, a xylylene group, and a -C 3 H 6 -O-(Z 2 -O) group. r- OC 3 H 6 - (Z 2 represents an alkylene group having 2 to 6 carbon atoms, r represents 1 or 2), and -BTB- (B represents a phenylene group, and T represents - a group represented by CH 2 -, -O- or -SO 2 -), a group represented by -BOBC 3 H 6 -BOB- (B represents a phenylene group), and 1 or 2 of these groups A group in which hydrogen is replaced by a hydroxyl group.

這樣的烯基取代納迪克醯亞胺化合物例如可以使用：如日本專利第2729565號公報所記載的，通過將烯基取代納迪克酸酐衍生物和二胺在80℃～220℃的溫度下保持0.5小時～20小時而合成獲得的化合物；或者市售的化合物。烯基取代納迪克醯亞胺化合物的具體例可以列舉以下所示的化合物。Such an alkenyl-substituted nadicylimine compound can be used, for example, by maintaining an alkenyl-substituted nadic anhydride derivative and a diamine at a temperature of from 80 ° C to 220 ° C as described in Japanese Patent No. 2729565. The obtained compound is synthesized in hours to 20 hours; or a commercially available compound. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-甲基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-甲基-烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-甲基-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-甲基-甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-乙基己基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-methyl-allyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methyl-allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-methyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-A -Methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-ethylhexyl)-allyl bicyclo [2.2. 1]hept-5-ene-2,3-dimethylimine,

N-(2-乙基己基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苯基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-allyl Ring [2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allyl Ring [2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allyl Ring [2.2.1]hept-5-ene-2,3-dimethylimine,

N-苯基-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-phenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-allyl bicyclo [2.2.1] Hg-5-ene-2,3-dimethylimine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N -benzyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(2-hydroxyethyl)-allylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-(2-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine,

N-(2,2-二甲基-3-羥基丙基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,2-二甲基-3-羥基丙基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,3-二羥基丙基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,3-二羥基丙基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基-1-丙烯基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基環己基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,2 -Dimethyl-3-hydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,3-di Hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,3-dihydroxypropyl)-allyl (methyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine,

N-(4-羥基苯基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基苯基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基苯基)-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(對羥基苄基)-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4-hydroxyphenyl)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(3-hydroxyphenyl)- Allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine,

N-{2-(2-羥基乙氧基)乙基}-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{4-(4-羥基苯基異亞丙基)苯基}-烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{4-(4-羥基苯基異亞丙基)苯基}-烯丙基(甲基)二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{4-(4-羥基苯基異亞丙基)苯基}-甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺，以及這些化合物的低聚物(oligomer)、N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{ 2-(2-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2-(2- Hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-[2-{2-(2- Hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-[2-{2-(2- Hydroxyethoxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-[2-{2 -(2-hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{4- (4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{4-(4-hydroxyl Phenyl isopropylidene)phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{4-(4-hydroxyl Phenyl isopropylidene)phenyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, and oligomers of these compounds,

N,N'-亞乙基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(ene) Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'- Hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-docamethylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

1,2-雙{3'-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、1,2-雙{3'-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、1,2-雙{3'-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、雙[2'-{3'-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙基]醚、雙[2'-{3'-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙基]醚、1,4-雙{3'-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}丁烷、1,4-雙{3'-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}丁烷、1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}ethane, 1,2-double {3 '-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine imine)propoxy}ethane, 1,2-bis{3'-(methyl Allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine]propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine)propoxy}ethyl]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine)propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine imine)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyl imine) propoxy}butane,

N,N'-對亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allyl bicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) , N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-miya Xylyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

2,2-雙[4-{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, 2,2 - bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, double {4-( Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine imine)phenyl}methane,

雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4-(methylallylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl} Ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allyl bicyclic [2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethyl quinone imine) phenyl} hydrazine,

雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、1,6-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-3-羥基己烷、1,12-雙(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-3,6-二羥基十二烷、1,3-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-5-羥基環己烷、1,5-雙{3'-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}-3-羥基戊烷、1,4-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2-羥基苯、Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}anthracene, 1,6-bis(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dimethylimine)-3-hydroxyhexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine)-3,6-dihydroxydodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino)-5-hydroxycyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)propoxy -3-hydroxypentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2-hydroxybenzene,

1,4-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2,5-二羥基苯、N,N'-對-(2-羥基)亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對-(2-羥基)亞二甲苯基-雙(烯丙基甲基環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間-(2-羥基)亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間-(2-羥基)亞二甲苯基-雙(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對-(2,3-二羥基)亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、1,4-Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2,5-dihydroxybenzene, N,N'-p- (2-hydroxy) xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-(2-hydroxyl ) xylylene-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-(2-hydroxy) sub-di Tolyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-(2-hydroxy)xylylene-double (Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-(2,3-dihydroxy)xylylene- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

2,2-雙[4-{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2-羥基-苯氧基}苯基]丙烷、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2-羥基-苯基}甲烷、雙{3-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-4-羥基-苯基}醚、雙{3-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-5-羥基-苯基}碸、1,1,1-三{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)}苯氧基甲基丙烷、N,N',N"-三(亞乙基甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)異氰尿酸酯，以及這些的低聚物等。2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2-hydroxy-phenoxy}phenyl] Propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2-hydroxy-phenyl}methane, double {3-( Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine]}phenoxymethylpropane, N,N',N"-tris(ethylene allylenylbicyclo[2.2.1 ]Hept-5-ene-2,3-dimethylimine)isocyanurate, and oligomers thereof and the like.

另外，本發明所使用的烯基取代納迪克醯亞胺化合物也可以是不對稱的含有亞烷基、亞苯基的下述結構式所表示的化合物。Further, the alkenyl-substituted nadicylimine compound used in the present invention may be an asymmetric compound represented by the following structural formula containing an alkylene group or a phenylene group.

以下列舉所述烯基取代納迪克醯亞胺化合物中優選的化合物。Preferred compounds among the alkenyl substituted nadic quinone imine compounds are listed below.

N,N'-亞乙基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(ene) Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'- Hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-docamethylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

N,N'-對亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、2,2-雙[4-{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allyl bicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) , N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-miya Xylyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene -2,3 -dimethylimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl} Methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane,

雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸。Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4-(methylallylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl} Ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allyl bicyclic [2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine)phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl} Hey.

以下列舉更優選的烯基取代納迪克醯亞胺化合物。More preferred alkenyl substituted nadic quinone imine compounds are listed below.

N,N'-亞乙基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(ene) Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'- Hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-docamethylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

N,N'-對亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allyl bicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) , N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-miya Xylyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine),

2,2-雙[4-{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷。2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, 2,2 - bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, double {4-( Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine) phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}methane.

並且，特別優選的烯基取代納迪克醯亞胺化合物可以列舉如下所示的結構式(Ina-1)所表示的雙{4-(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、結構式(Ina-2)所表示的N,N'-間亞二甲苯基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、及以結構式(Ina-3)所表示的N,N'-六亞甲基-雙(烯丙基二環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)。Further, a particularly preferred alkenyl-substituted nadic ylidene compound may be a bis{4-(allylbicyclo[2.2.1]hept-5-ene represented by the structural formula (Ina-1) shown below. -2,3-dimethylimine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]g, represented by the formula (Ina-2) -5-ene-2,3-dimethylimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1] represented by the structural formula (Ina-3) Hg-5-ene-2,3-dimethylimine).

另外，例如就使液晶顯示元件的電特性長期穩定的觀點而言，本發明的液晶配向劑也可以進一步含有具有自由基聚合性不飽和雙鍵的化合物。所述具有自由基聚合性不飽和雙鍵的化合物可以採用一種化合物，也可以採用兩種或者兩種以上的化合物。此外，所述具有自由基聚合性不飽和雙鍵的化合物中，不包括所述烯基取代納迪克醯亞胺化合物。就所述觀點而言，所述具有自由基聚合性不飽和雙鍵的化合物的含量，以相對於聚醯胺酸或者其衍生物的重量比計，優選0.01～1.00，更加優選0.01～0.70，進一步優選爲0.01～0.50。In addition, for example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one compound or two or more compounds. Further, in the compound having a radical polymerizable unsaturated double bond, the alkenyl-substituted nadic ylidene compound is not included. In view of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 0.01 to 1.00, more preferably from 0.01 to 0.70, based on the weight ratio of the polyglycine or a derivative thereof. More preferably, it is 0.01 to 0.50.

另外，就降低液晶顯示元件的離子密度、抑制離子密度隨時間增大、並且抑制殘像的觀點而言，具有自由基聚合性不飽和雙鍵的化合物相對於烯基取代納迪克醯亞胺化合物的比率，以重量比計，優選0.1～10，更加優選0.5～5。Further, in terms of lowering the ion density of the liquid crystal display element, suppressing an increase in ion density with time, and suppressing afterimage, a compound having a radical polymerizable unsaturated double bond is substituted with an alkenyl group to replace a nadic ylidene compound. The ratio is preferably from 0.1 to 10, more preferably from 0.5 to 5, by weight.

所述具有自由基聚合性不飽和雙鍵的化合物可以列舉(甲基)丙烯酸酯、(甲基)丙烯醯胺等(甲基)丙烯酸衍生物，以及雙馬來醯亞胺(bismaleimide)。所述具有自由基聚合性不飽和雙鍵的化合物更加優選具有兩個以上的自由基聚合性不飽和雙鍵的(甲基)丙烯酸衍生物。Examples of the compound having a radical polymerizable unsaturated double bond include a (meth)acrylic acid ester, a (meth)acrylic acid derivative such as (meth)acrylamide, and a bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

(甲基)丙烯酸酯的具體例，例如可以列舉：(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯(isobornyl(meth)acrylate)、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-羥基乙酯以及(甲基)丙烯酸-2-羥基丙酯。Specific examples of the (meth) acrylate include, for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (methyl). Dicyclopentyloxyethyl acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate-2- Hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate.

雙官能(甲基)丙烯酸酯的具體例，例如可以列舉：雙丙烯酸乙二酯，東亞合成化學工業股份有限公司的產品ARONIX M-210、ARONIX M-240和ARONIX M-6200，日本化藥股份有限公司的產品KAYARAD HDDA、KAYARAD HX-220、KAYARAD R-604和KAYARAD R-684，大阪有機化學工業股份有限公司的產品V260、V312和V335HP，以及共榮社油脂化學工業股份有限公司的產品Light Acrylate BA-4EA、Light Acrylate BP-4PA和Light Acrylate BP-2PA。Specific examples of the difunctional (meth) acrylate include, for example, ethylene diacrylate, products of Atomic Synthetic Chemical Co., Ltd., ARONIX M-210, ARONIX M-240, and ARONIX M-6200, Nippon Chemical Co., Ltd. Products of the company KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoeisha Oil Chemical Industry Co., Ltd. Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

三官能以上的多官能(甲基)丙烯酸酯的具體例，例如可以列舉：4,4'-亞甲基雙(N,N-二羥基丙烯酸乙二酯基苯胺)、ARONIX M-400、ARONIX M-405、ARONIX M-450、ARONIX M-7100、ARONIX M-8030、ARONIX M-8060、KAYARAD TMPTA、KAYARAD DPCA-20、KAYARADDPCA-30、KAYARA DDPCA-60、KAYARAD DPCA-120、以及大阪有機化學工業股份有限公司的產品VGPT。Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-methylenebis(N,N-dihydroxyethyl acrylate benzoate), ARONIX M-400, and ARONIX. M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARADDPCA-30, KAYARA DDPCA-60, KAYARAD DPCA-120, and Osaka Organic Chemistry Industrial Co., Ltd. product VGPT.

(甲基)丙烯醯胺衍生物的具體例，例如可以列舉：N-異丙基丙烯醯胺，N-異丙基甲基丙烯醯胺、N-正丙基丙烯醯胺、N-正丙基甲基丙烯醯胺、N-環丙基丙烯醯胺、N-環丙基甲基丙烯醯胺、N-乙氧基乙基丙烯醯胺、N-乙氧基乙基甲基丙烯醯胺、N-四氫糠基丙烯醯胺(N-tetrahydrofurfuryl acrylamide)、N-四氫糠基甲基丙烯醯胺、N-乙基丙烯醯胺、N-乙基-N-甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N-甲基-N-正丙基丙烯醯胺、N-甲基-N-異丙基丙烯醯胺、N-丙烯醯基呱啶(N-acryloyl piperidine)、N-丙烯醯基吡咯烷(N-acryloyl pyrrolidine)、N,N'-亞甲基雙丙烯醯胺、N,N'-亞乙基雙丙烯醯胺、N,N'-二羥基亞乙基雙丙烯醯胺、N-(4-羥基苯基)甲基丙烯醯胺、N-苯基甲基丙烯醯胺、N-丁基甲基丙烯醯胺、N-(異丁氧基甲基)甲基丙烯醯胺、N-[2-(N,N-二甲基氨基)乙基]甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、N-[3-(二甲基氨基)丙基]甲基丙烯醯胺、N-(甲氧基甲基)甲基丙烯醯胺、N-(羥基甲基)-2-甲基丙烯醯胺、N-苄基-2-甲基丙烯醯胺以及N,N'-亞甲基雙(甲基丙烯醯胺)。Specific examples of the (meth) acrylamide derivative include, for example, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, N-n-propyl Methyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide , N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N,N-diethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloyl Piperidine), N-acryloyl pyrrolidine, N,N'-methylenebispropenylamine, N,N'-ethylenebisacrylamide, N,N'-dihydroxy Ethylenebis acrylamide, N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl) ) methacrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-( Dimethyl Aminoamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methylpropenamide, N-benzyl-2- Methyl acrylamide and N,N'-methylene bis(methacrylamide).

所述(甲基)丙烯酸衍生物中，特別優選N,N'-亞甲基雙丙烯醯胺、N,N'-二羥基亞乙基雙丙烯醯胺、雙丙烯酸乙二酯以及4,4'-亞甲基雙(N,N-二羥基丙烯酸乙二酯基苯胺)。Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylenebisacrylamide, ethylene diacrylate, and 4,4 are particularly preferable. '-Methylene double (N,N-dihydroxy acrylate phenyl aniline).

雙馬來醯亞胺例如可以列舉：KI CHEMICALINDUSTRY股份有限公司製造的BMI-70和BMI-80，以及大和化成工業股份有限公司製造的BMI-1000、BMI-3000、BMI-4000、BMI-5000和BMI-7000。Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by KI CHEMICALINDUSTRY Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 manufactured by Daiwa Kasei Kogyo Co., Ltd., and BMI-7000.

而且，例如從液晶顯示元件的電特性的長期穩定性的觀點考慮，本發明的液晶配向劑可以進一步含有噁嗪化合物。所述噁嗪化合物可以採用一種化合物，也可以採用兩種或者兩種以上的化合物。就所述觀點而言，所述噁嗪化合物的含量相對於所述聚醯胺酸或者其衍生物，優選0.1重量%～50重量%，更加優選1重量%～40重量%，進一步優選爲1重量%～20重量%。Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazine compound may be one compound or two or more compounds. In view of the above, the content of the oxazine compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, even more preferably 1% based on the polyamic acid or a derivative thereof. Weight% to 20% by weight.

所述噁嗪化合物，優選可溶解於溶解聚醯胺酸或者其衍生物的溶劑中，並且具有開環聚合性的噁嗪化合物。The oxazine compound is preferably soluble in a solvent in which polyacrylic acid or a derivative thereof is dissolved, and has a ring-opening polymerizable oxazine compound.

另外，所述噁嗪化合物中的噁嗪結構的數量並沒有特別限定。Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

關於噁嗪的結構，已知有各種結構。在本發明中，噁嗪的結構並沒有特別限定，所述噁嗪化合物中的噁嗪結構可以列舉苯並噁嗪(benzoxazine)或者萘並噁嗪(naphthoxazine)等具有包含縮合多環芳香族基的芳香族基的噁嗪結構。Regarding the structure of the oxazine, various structures are known. In the present invention, the structure of the oxazine is not particularly limited, and the oxazine structure in the oxazine compound may be exemplified by a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The aromatic-based oxazine structure.

所述噁嗪化合物例如可以列舉下述通式(a)～通式(f)所示的化合物。另外，下述通式中，朝向環的中心所表示的鍵，表示鍵結在構成環並且可以鍵結取代基的任一個碳上。The oxazine compound may, for example, be a compound represented by the following formula (a) to formula (f). Further, in the following formula, the bond represented toward the center of the ring means that the bond is bonded to any one of the carbons constituting the ring and capable of bonding the substituent.

所述通式(a)～通式(c)中，R1 以及R2 表示碳數爲1～30的有機基。另外，所述通式(a)～通式(f)中，R3 至R6 表示氫或者碳數爲1～6的烴基。另外，所述通式(c)、通式(d)以及通式(f)中，X表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-N HCO-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m-S-。此處，m爲1～6的整數。另外，所述通式(e)以及通式(f)中，Y獨立地表示單鍵、-O-、-S-、-CO-、-C(CH3 )2 -、-C(CF3 )2 -或者碳數爲1～3的亞烷基。所述Y的苯環、萘環上所鍵結的氫可以獨立地被-F、-CH3 、-OH、-COOH、-SO3 H、-PO3 H2 取代。In the above formula (a) to formula (c), R 1 and R 2 each represent an organic group having 1 to 30 carbon atoms. Further, in the above formulae (a) to (f), R 3 to R 6 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (c), formula (d) and formula (f), X represents a single bond, -O-, -S-, -SS-, -SO 2 -, -CO-, - CONH-, -N HCO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 ) m -, -O-(CH 2 ) m -O-, -S-( CH 2 )mS-. Here, m is an integer of 1 to 6. Further, in the above formula (e) and formula (f), Y independently represents a single bond, -O-, -S-, -CO-, -C(CH 3 ) 2 -, -C(CF 3 2 - or an alkylene group having 1 to 3 carbon atoms. The hydrogen bonded to the benzene ring or the naphthalene ring of Y may be independently substituted with -F, -CH 3 , -OH, -COOH, -SO 3 H, -PO 3 H 2 .

另外，所述噁嗪化合物包括：側鏈上具有噁嗪結構的低聚物或者聚合物、主鏈中具有噁嗪結構的低聚物或者聚合物。Further, the oxazine compound includes an oligomer or a polymer having an oxazine structure in a side chain, an oligomer or a polymer having an oxazine structure in the main chain.

通式(a)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。Examples of the oxazine compound represented by the formula (a) include the following oxazine compounds.

式中，R1 優選碳數爲1～30的烷基，更加優選碳數爲1～20的烷基。In the formula, R 1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

通式(b)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。Examples of the oxazine compound represented by the formula (b) include the following oxazine compounds.

式中，R1 優選碳數爲1～30的烷基，更加優選碳數爲1～20的烷基。In the formula, R 1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

通式(c)所表示的噁嗪化合物可以列舉下述通式(I)所表示的噁嗪化合物。The oxazine compound represented by the following formula (I) is exemplified by the oxazine compound represented by the formula (c).

所述通式(I)中，R1 以及R2 表示碳數爲1～30的有機基，R3 至R6 表示氫或者碳數爲1～6的烴基，X表示單鍵、-CH2 -、-C(CH3 )2 -、-CO-、-O-、-SO2 -或者-C(CF3 )2 -。所述通式(I)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。In the above formula (I), R 1 and R 2 represent an organic group having 1 to 30 carbon atoms, R 3 to R 6 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH 2 -, -C(CH 3 ) 2 -, -CO-, -O-, -SO 2 - or -C(CF 3 ) 2 -. Examples of the oxazine compound represented by the above formula (I) include the following oxazine compounds.

式中，R1 優選碳數爲1～30的烷基，更加優選碳數爲1～20的烷基。In the formula, R 1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

通式(d)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。Examples of the oxazine compound represented by the formula (d) include the following oxazine compounds.

通式(e)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。Examples of the oxazine compound represented by the formula (e) include the following oxazine compounds.

通式(f)所表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。Examples of the oxazine compound represented by the formula (f) include the following oxazine compounds.

這些噁嗪化合物中，更加優選的噁嗪化合物可以列舉式(b-1)、式(c-1)、式(c-3)、式(c-5)、式(c-7)、式(c-9)、式(d-1)～式(d-6)、式(e-3)、式(e-4)、式(f-2)～式(f-4)所表示的噁嗪化合物。Among the oxazine compounds, more preferred oxazine compounds include the formula (b-1), the formula (c-1), the formula (c-3), the formula (c-5), the formula (c-7), and the formula. (c-9), represented by formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula (f-2) to formula (f-4) Oxazine compound.

所述噁嗪化合物可以通過與國際公開2004/009708號手冊、日本專利特開平11-12258號公報、日本專利特開2004-352670號公報所記載的方法相同的方法來製造。The oxazine compound can be produced by the same method as the method described in the International Publication No. 2004/009708, the Japanese Patent Application Laid-Open No. Hei 11-12258, and the Japanese Patent Publication No. 2004-352670.

例如，通式(a)所表示的噁嗪化合物可以通過使苯酚化合物、伯胺以及醛(aldehyde)進行反應而獲得(參照國際公開2004/009708號手冊)。For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (refer to International Publication No. 2004/009708).

另外，通式(b)所表示的噁嗪化合物可以通過以下的方式獲得：通過將伯胺緩慢添加到甲醛中的方法使其反應後，再添加具有萘酚(naphthol)系羥基的化合物而進行反應(參照國際公開2004/009708號手冊)。Further, the oxazine compound represented by the formula (b) can be obtained by a method in which a primary amine is slowly added to formaldehyde, and then a compound having a naphthol-based hydroxyl group is added. Reaction (refer to International Publication No. 2004/009708).

另外，通式(c)所表示的噁嗪化合物可以通過以下的方式獲得：在有機溶劑中，在脂肪族仲胺、脂肪族叔胺或者鹼性含氮雜環化合物的存在下，使1莫耳苯酚化合物、相對於其一個酚羥基至少爲2莫耳以上的醛、以及1莫耳伯胺進行反應(參照國際公開2004/009708號手冊和日本專利特開平11-12258號公報)。Further, the oxazine compound represented by the formula (c) can be obtained by, in an organic solvent, in the presence of an aliphatic secondary amine, an aliphatic tertiary amine or a basic nitrogen-containing heterocyclic compound, The phenolic compound is reacted with respect to an aldehyde having a phenolic hydroxyl group of at least 2 mol or more, and 1 morolamine (refer to the International Publication No. 2004/009708, and Japanese Patent Laid-Open No. Hei 11-12258).

另外，通式(d)～通式(f)所表示的噁嗪化合物可以通過以下的方式獲得：在正丁醇中，在90℃以上的溫度下，使4,4'-二氨基二苯基甲烷等具有多個苯環和鍵結這些苯環的有機基的二胺、甲醛(formalin)等醛以及苯酚進行脫水縮合反應(參照日本專利特開2004-352670號公報)。Further, the oxazine compound represented by the general formula (d) to the general formula (f) can be obtained by subjecting 4,4'-diaminodiphenyl to n-butanol at a temperature of 90 ° C or higher. A hydrazine having a plurality of benzene rings and an organic group such as a benzene ring, an aldehyde such as a formalin, and a phenol are subjected to a dehydration condensation reaction, such as a benzene ring (refer to Japanese Laid-Open Patent Publication No. 2004-352670).

另外，例如就液晶顯示元件的電特性的長期穩定性的觀點而言，本發明的液晶配向劑可以進一步含有噁唑啉化合物。所述噁唑啉化合物是具有噁唑啉結構的化合物。所述噁唑啉化合物可以採用一種化合物，也可以採用兩種或者兩種以上的化合物。就所述觀點而言，所述噁唑啉化合物的含量相對於所述聚醯胺酸或者其衍生物，優選0.1重量%～50重量%，更加優選1重量%～40重量%，進一步優選爲1重量%～20重量%。或者，就上述觀點而言，所述噁唑啉化合物的含量優選爲，將噁唑啉化合物中的噁唑啉結構換算爲噁唑啉時，其相對於所述聚醯胺酸或者其衍生物而爲0.1重量%～40重量%。Further, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. In view of the above, the content of the oxazoline compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, even more preferably 1% by weight to 40% by weight based on the polyamic acid or a derivative thereof. 1% by weight to 20% by weight. Alternatively, in view of the above, the content of the oxazoline compound is preferably such that when the oxazoline structure in the oxazoline compound is converted to an oxazoline, it is relative to the polylysine or a derivative thereof. It is from 0.1% by weight to 40% by weight.

關於所述噁唑啉化合物，可以在一個化合物中僅具有一種噁唑啉結構，也可以在一個化合物中具有兩種或者兩種以上的噁唑啉結構。另外，所述噁唑啉化合物只要在一個化合物中具有一個所述噁唑啉結構即可，優選具有兩個以上的噁唑啉結構。另外，噁唑啉化合物可以是側鏈上具有噁唑啉環結構的聚合物，也可以是共聚物。側鏈上具有噁唑啉結構的聚合物可以是側鏈上具有噁唑啉結構的單體的均聚物，也可以是側鏈上具有噁唑啉結構的單體與不具有噁唑啉結構的單體的共聚物。側鏈上具有噁唑啉結構的共聚物可以是側鏈上具有噁唑啉結構的兩種或者兩種以上的單體的共聚物，也可以是側鏈上具有噁唑啉結構的兩種或者兩種以上的單體與不具有噁唑啉結構的單體的共聚物。Regarding the oxazoline compound, there may be only one oxazoline structure in one compound, or two or more oxazoline structures in one compound. Further, the oxazoline compound preferably has one or more oxazoline structures in one compound, and preferably has two or more oxazoline structures. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure on the side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two types having an oxazoline structure in a side chain or A copolymer of two or more monomers and a monomer having no oxazoline structure.

所述噁唑啉結構優選爲，以噁唑啉結構中的氧以及氮中的一方或者兩方可以與聚醯胺酸的羰基進行反應方式存在於的噁唑啉化合物中的結構。The oxazoline structure is preferably a structure in which an oxazoline compound in which one or both of oxygen and nitrogen in the oxazoline structure can react with a carbonyl group of polyglycine.

所述噁唑啉化合物例如可以列舉：2,2'-雙(2-噁唑啉)、1,2,4-三-(2-噁唑啉基-2-)苯、4-呋喃-2-基亞甲基-2-苯基-4H-噁唑-5-酮、1,4-雙(4,5-二氫-2-噁唑基)苯、1,3-雙(4,5-二氫-2-噁唑基)苯、2,3-雙(4-異丙烯基-2-噁唑啉-2-基)丁烷、2,2'-雙-4-苄基-2-噁唑啉、2,6-雙(異丙基-2-噁唑啉-2-基)吡啶、2,2'-異亞丙基雙(4-叔丁基-2-噁唑啉)、2,2'-異亞丙基雙(4-苯基-2-噁唑啉)、2,2'-亞甲基雙(4-叔丁基-2-噁唑啉)以及2,2'-亞甲基雙(4-苯基-2-噁唑啉)。除了這些噁唑啉化合物以外，還可以列舉EPOCROS(商品名，日本觸媒股份有限公司製造)這樣的具有噁唑基的聚合物或者低聚物。Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2-)benzene, and 4-furan-2. - benzylidene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis (4,5 -dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2 -oxazoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline) , 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2 '-Methylene bis(4-phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned.

更優選的所述噁。坐啉化合物例如可以列舉2,2'-雙(2-噁唑啉)以及1,3-雙(4,5-二氫-2-噁唑基)苯。More preferred of the evil. Examples of the porphyrin compound include 2,2'-bis(2-oxazoline) and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

本發明的液晶配向劑中的聚醯胺酸或其衍生物的含有率，可以根據將液晶配向劑塗布到基板上的塗布方法來選擇。例如，如果是用於普通液晶顯示元件的製造步驟所使用的印刷機(包括膠版印刷機(offset printer)或噴墨印刷機(ink jet printer)。以下有時簡稱爲“印刷機”。)的液晶配向劑，則聚醯胺酸或其衍生物的含有率優選0.5重量%～30重量%，更優選1重量%～15重量%，所述聚醯胺酸或其衍生物的含有率可以根據與液晶配向劑的黏度(下述)之間的關係來適當調整。The content of polyphthalic acid or a derivative thereof in the liquid crystal alignment agent of the present invention can be selected according to a coating method in which a liquid crystal alignment agent is applied onto a substrate. For example, it is a printing machine (including an offset printer or an ink jet printer) used for a manufacturing step of a general liquid crystal display element. Hereinafter, it is sometimes simply referred to as a "printing machine". In the liquid crystal alignment agent, the content of the polyaminic acid or a derivative thereof is preferably 0.5% by weight to 30% by weight, more preferably 1% by weight to 15% by weight, and the content of the polyaminic acid or a derivative thereof may be based on The relationship between the viscosity of the liquid crystal alignment agent (described below) is appropriately adjusted.

本發明的液晶配向劑的黏度根據塗布方法、聚醯胺酸或其衍生物的濃度、所使用的聚醯胺酸或其衍生物的種類、溶劑的種類和比例的不同而多種多樣。例如，當使用印刷機來進行塗布時，液晶配向劑的黏度優選5mPa‧s～100mPa‧s，更優選10mPa‧s～80mPa‧s。如果液晶配向劑的黏度小於5mPa‧s，則液晶配向膜會難以獲得足够的膜厚；如果液晶配向劑的黏度大於100mPa‧s，則印刷不勻會增大。通過旋轉塗布法來塗布液晶配向劑時，液晶配向劑的黏度優選5mPa‧s～200mPa‧s，更優選10mPa‧s～100mPa‧s。The viscosity of the liquid crystal alignment agent of the present invention varies depending on the coating method, the concentration of the polyaminic acid or its derivative, the type of the polyaminic acid or its derivative used, and the type and ratio of the solvent. For example, when coating is carried out using a printing machine, the viscosity of the liquid crystal alignment agent is preferably 5 mPa‧s to 100 mPa‧s, more preferably 10 mPa‧s to 80 mPa‧s. If the viscosity of the liquid crystal alignment agent is less than 5 mPa‧s, it may be difficult to obtain a sufficient film thickness for the liquid crystal alignment film; if the viscosity of the liquid crystal alignment agent is more than 100 mPa‧s, the unevenness of printing may increase. When the liquid crystal alignment agent is applied by a spin coating method, the viscosity of the liquid crystal alignment agent is preferably 5 mPa ‧ to 200 mPa ‧ s, and more preferably 10 mPa ‧ to 100 mPa ‧ s

液晶配向劑的黏度可以通過旋轉黏度測定法來測定，例如可以使用旋轉黏度計(東機產業製造的TVE-20L型)來進行測定(測定溫度：25℃)。The viscosity of the liquid crystal alignment agent can be measured by a rotational viscosity measurement method. For example, a rotational viscosity meter (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) can be used for measurement (measurement temperature: 25 ° C).

本發明的液晶配向膜是對所述本發明的液晶配向劑的膜進行煆燒而形成的。液晶配向劑的膜的形成其及煆燒，可以通過光阻(photoresist)的常用方法來進行。The liquid crystal alignment film of the present invention is formed by calcining a film of the liquid crystal alignment agent of the present invention. The formation of the film of the liquid crystal alignment agent and the calcination can be carried out by a usual method of photoresist.

所述液晶配向膜例如可以通過將本發明的液晶配向劑塗布在液晶顯示元件用基板、或者氟化鈣或矽等的測定用基板上，並將此液晶配向劑的膜加熱到例如150℃～400℃、優選180℃～280℃而形成。此處，液晶配向劑的膜厚優選10nm～300nm，更優選30nm～100nm。另外，當液晶配向膜的用途是用在像IPS型液晶顯示元件這樣的橫向電場方式的液晶顯示元件中時，優選對液晶配向膜實施摩擦處理。The liquid crystal alignment film can be applied, for example, to a substrate for a liquid crystal display device or a substrate for measurement such as calcium fluoride or ruthenium, and the film of the liquid crystal alignment agent can be heated to, for example, 150 ° C to the liquid crystal alignment film. It is formed at 400 ° C, preferably 180 ° C to 280 ° C. Here, the film thickness of the liquid crystal alignment agent is preferably 10 nm to 300 nm, and more preferably 30 nm to 100 nm. Further, when the use of the liquid crystal alignment film is used in a liquid crystal display device of a transverse electric field type such as an IPS type liquid crystal display element, it is preferable to subject the liquid crystal alignment film to a rubbing treatment.

所述液晶配向膜的膜厚可以根據液晶配向劑的黏度或者液晶配向劑的塗布方法來進行調整。另外，液晶配向膜的膜厚可以使用階差計或橢偏儀(ellipsometer)等衆所周知的膜厚測定裝置來測定。並且，可以根據需要對液晶配向膜進行水解等處理，並利用IR或者質譜法(Mass Spectrometry，MS)等常用的分析方法來分析液晶配向膜中的成分。例如，“Performance improvement of polybenzoxazine by alloying with polyamide:effect of preparation method on the properties”(Tsutomu Takeichi et. al.,polymer,2005,46,p.4909-4916)中，記載了通過IR來對將聚醯胺酸醯亞胺化而成的膜中的噁嗪化合物進行分析的方法。The film thickness of the liquid crystal alignment film can be adjusted according to the viscosity of the liquid crystal alignment agent or the coating method of the liquid crystal alignment agent. Further, the film thickness of the liquid crystal alignment film can be measured using a well-known film thickness measuring device such as a step meter or an ellipsometer. Further, the liquid crystal alignment film may be subjected to hydrolysis or the like as needed, and the components in the liquid crystal alignment film may be analyzed by a usual analysis method such as IR or mass spectrometry (MS). For example, "Performance improvement of polybenzoxazine by alloying with polyamide: effect of preparation method on the properties" (Tsutomu Takeichi et. al., polymer, 2005, 46, p. 4909-4916), it is described that A method for analyzing an oxazine compound in a film obtained by imidating ruthenium amide.

本發明的液晶顯示元件具有對向配置的一對基板、形成在所述一對基板各自所對向的面中的一面或者兩面上的電極、形成在所述一對基板各自所對向的面上的液晶配向膜、以及形成在所述一對基板之間的液晶層。The liquid crystal display device of the present invention has a pair of substrates disposed in opposite directions, and electrodes formed on one or both of the surfaces facing the pair of substrates, and surfaces formed on the pair of substrates a liquid crystal alignment film on the upper surface and a liquid crystal layer formed between the pair of substrates.

所述對向配置的一對附帶電極的基板優選透明基板(例如玻璃基板)。The pair of substrates with electrodes disposed oppositely are preferably transparent substrates (for example, glass substrates).

在所述一對基板中的至少一方或者兩方的表面，對應於液晶顯示元件的形態而設置有電極。所述電極只要是形成在基板的一個面上的電極，則沒有特別限定。這種電極例如可以列舉氧化銦錫(indium tin oxide，ITO)或金屬的蒸鍍膜等。可以將電極形成在基板的整個表面上，也可以將電極形成爲經圖案化的既定形狀。另外，可以僅在一對基板中的一塊基板上設置電極，也可以在兩塊基板上均設置電極。例如對於未設置電極的基板，可以在基板表面形成本發明的液晶配向膜，而對於設置了電極的基板，可以在電極上形成本發明的液晶配向膜。本發明的液晶配向膜的形成如上所述。At least one or both of the pair of substrates are provided with electrodes corresponding to the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include indium tin oxide (ITO) or a vapor deposited film of a metal. The electrode may be formed on the entire surface of the substrate, or the electrode may be formed into a patterned predetermined shape. Further, an electrode may be provided only on one of the pair of substrates, or an electrode may be provided on both of the substrates. For example, for a substrate on which no electrode is provided, the liquid crystal alignment film of the present invention can be formed on the surface of the substrate, and for the substrate provided with the electrode, the liquid crystal alignment film of the present invention can be formed on the electrode. The formation of the liquid crystal alignment film of the present invention is as described above.

夾在所述一對基板之間的液晶層包含液晶組合物。此處，液晶組合物並沒有特別限制，可以根據驅動模式而使用介電各向異性(dielectric anisotropy)爲正的液晶組合物以及介電各向異性爲負的液晶組合物中的任意一種組合物。The liquid crystal layer sandwiched between the pair of substrates contains a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and any one of a liquid crystal composition having a positive dielectric anisotropy and a liquid crystal composition having a negative dielectric anisotropy may be used depending on a driving mode. .

介電各向異性爲正的液晶組合物的優選的例子公開在以下公報中：日本專利特許第3086228號公報、日本專利特許第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)、日本專利特開平9-302346號公報(EP806466A1)、日本專利特開平8-199168號公報(EP722998A1)、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)、日本專利特開平10-204016號公報(EP844229A1)、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號公報、日本專利特開2001-48822號公報等。A preferred example of the liquid crystal composition having a positive dielectric anisotropy is disclosed in the following publications: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Japanese Laid-Open Patent Publication No. Hei 8-- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Hei. Japanese Patent Publication No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), and Japanese Patent Laid-Open No. Hei 10-204016 Japanese Patent Laid-Open No. Hei 10-204436, Japanese Patent Laid-Open No. Hei 10-231482, Japanese Patent Laid-Open No. 2000-087040, and Japanese Patent Laid-Open No. 2001-48822.

用於VA型液晶顯示元件的液晶組合物，可以是介電各向異性爲負的各種液晶組合物。液晶組合物的優選的例子公開在以下公報中：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)、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號公報、日本專利特開2001-019965號公報、日本專利特開2001-072626號公報、日本專利特開2001-192657號公報等。The liquid crystal composition used for the VA liquid crystal display element may be various liquid crystal compositions having a negative dielectric anisotropy. A preferred example of the liquid crystal composition is disclosed in the following publications: Japanese Patent Laid-Open Publication No. SHO 57-114532, Japanese Patent Laid-Open No. Hei No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, and Japanese Patent Laid-Open No. Hei 8- Japanese Patent Publication No. Hei 10-104869, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei No. Hei No. Hei 10-237000, Japanese Patent Laid-Open No. Hei 10- Japanese Patent Laid-Open No. Hei 10-237024, 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- Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-291945, and Japanese Patent No. 237,448. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2001-192657 and the like.

也可以在所述介電常數爲正或者爲負的液晶組合物中添加一種以上的光學活性化合物再使用。It is also possible to add one or more optically active compounds to the liquid crystal composition having a positive or negative dielectric constant for reuse.

本發明的液晶顯示元件當然也可以具有其他構件。例如，在使用薄膜晶體管的彩色顯示TFT型液晶元件中，可以在第一透明基板上形成薄膜晶體管、絕緣膜、保護膜、信號電極和像素電極等，而第二透明基板上可以具有遮蔽像素區域以外的光的黑色矩陣(black matrix)、彩色濾光片(color filter)、平坦化膜以及像素電極等。The liquid crystal display element of the present invention may of course have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like may be formed on the first transparent substrate, and the second transparent substrate may have a masking pixel region A black matrix other than light, a color filter, a flattening film, and a pixel electrode.

另外，在VA型液晶顯示元件、特別是MVA型液晶顯示元件中，第一透明基板上形成有被稱爲區域(domain)的微小突起物。另外，爲了調整基板間的盒間隙(cell gap)，也可以在第一透明基板上形成間隔物(spacer)。Further, in the VA liquid crystal display element, particularly the MVA liquid crystal display element, minute projections called domains are formed on the first transparent substrate. Further, in order to adjust the cell gap between the substrates, a spacer may be formed on the first transparent substrate.

本發明的液晶顯示元件可以通過任意方法來製作，例如可以通過包括以下步驟的方法來製作：1)將液晶配向劑塗布在所述兩塊透明基板上的步驟；2)將所塗布的液晶配向劑乾燥的步驟；3)進行爲使乾燥的液晶配向劑進行脫水、閉環反應所必需的加熱處理的步驟；4)對所獲得的液晶配向膜進行配向處理的步驟；5)將兩塊基板貼合後，將液晶組合物封入基板之間，或者將液晶組合物滴加到其中一塊基板上之後，再將此基板與另一塊基板相貼合的步驟。The liquid crystal display element of the present invention can be produced by any method, for example, by a method comprising the steps of: 1) coating a liquid crystal alignment agent on the two transparent substrates; 2) aligning the applied liquid crystal a step of drying the agent; 3) a step of performing heat treatment necessary for dehydrating and ring-closing the dried liquid crystal alignment agent; 4) a step of performing alignment treatment on the obtained liquid crystal alignment film; 5) pasting two substrates After the sealing, the liquid crystal composition is sealed between the substrates, or the liquid crystal composition is dropped onto one of the substrates, and then the substrate is bonded to the other substrate.

所述塗布液晶配向劑的步驟中所採用的塗布方法，一般已知有旋轉塗布法、印刷法、浸漬塗布法(dipping)、滴加法、噴塗法等。這些方法也可以應用在本發明中。The coating method used in the step of applying the liquid crystal alignment agent is generally known by a spin coating method, a printing method, a dipping method, a dropping method, a spray method, or the like. These methods can also be applied to the present invention.

另外，實施所述乾燥步驟以及脫水反應所必需的加熱處理的步驟的方法，一般已知有在烘箱(oven)或者紅外線爐中進行加熱處理的方法、在加熱板(hot plate)上進行加熱處理的方法等。這些方法也可以應用在本發明中。乾燥步驟優選在溶劑可以蒸發的範圍內的較低的溫度(50℃～140℃)下實施。加熱處理的步驟通常優選在150℃～300℃左右的溫度下進行。Further, a method of performing the drying step and the step of heat treatment necessary for the dehydration reaction is generally known as a method of performing heat treatment in an oven or an infrared furnace, and heat treatment on a hot plate. Method etc. These methods can also be applied to the present invention. The drying step is preferably carried out at a lower temperature (50 ° C to 140 ° C) in the range in which the solvent can be evaporated. The step of heat treatment is usually preferably carried out at a temperature of from about 150 ° C to about 300 ° C.

關於IPS型液晶顯示元件、OCB型液晶顯示元件、TN型液晶顯示元件、STN型液晶顯示元件，對液晶配向膜的配向處理通常是進行摩擦處理。對於VA型液晶顯示元件中大多不進行摩擦處理，但是也可以進行摩擦處理。Regarding the IPS type liquid crystal display element, the OCB type liquid crystal display element, the TN type liquid crystal display element, and the STN type liquid crystal display element, the alignment treatment of the liquid crystal alignment film is usually performed by rubbing treatment. Although most of the VA liquid crystal display elements are not subjected to rubbing treatment, rubbing treatment may be performed.

然後，在其中一塊基板上塗布黏接劑後，將此基板與另一塊基板相貼合，在真空中注入液晶。當採用滴加注入法時，在貼合之前將液晶組合物滴加到其中一塊基板上，然後將此基板與另一塊基板相貼合。利用熱或者紫外線使用於貼合的黏接劑硬化，由此製作出本發明的液晶顯示元件。Then, after applying the adhesive on one of the substrates, the substrate is bonded to the other substrate, and the liquid crystal is injected in a vacuum. When the dropping injection method is employed, the liquid crystal composition is dropped onto one of the substrates before the bonding, and then the substrate is bonded to the other substrate. The liquid crystal display element of the present invention is produced by curing with a bonding agent by heat or ultraviolet rays.

在本發明的液晶顯示元件上，也可以安裝偏光板(偏光膜)、波片、光散射膜以及驅動電路等。In the liquid crystal display element of the present invention, a polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, or the like may be attached.

[實施例][Examples]

下面，通過實施例來說明本發明，但是本發明並不限定於這些實施例。實施例中所使用的化合物如下。Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. The compounds used in the examples are as follows.

＜四羧酸二酐＞<tetracarboxylic dianhydride>

化合物：均苯四甲酸二酐(Pyromellitic Dianhydride)：PMDACompound: Pyromellitic Dianhydride: PMDA

化合物：1,2,3,4-環丁烷四甲酸二酐(1,2,3,4-cyclobutane tetracarboxylic dianhydride)：CBDACompound: 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA

＜二胺＞<Diamine>

化合物：4,4'-二氨基二苯基甲烷：DDMCompound: 4,4'-diaminodiphenylmethane: DDM

化合物：4,4'-二氨基二苯基乙烷：DDETCompound: 4,4'-diaminodiphenylethane: DDET

化合物：1,1-雙[4-(4-氨基苯氧基)苯基]-4-(反-4-正戊基環己基)環己烷：5HHBACompound: 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(trans-4-n-pentylcyclohexyl)cyclohexane: 5HHBA

化合物：1,1-雙[4-(4-氨基苯氧基)苯基]-4-[(4-正庚基環己基)乙基]環己烷：7H2HBACompound: 1,1-bis[4-(4-aminophenoxy)phenyl]-4-[(4-n-heptylcyclohexyl)ethyl]cyclohexane: 7H2HBA

化合物：1,1-雙[4-(4-氨基苯基甲基)苯基]-4-正庚基環己烷：7HBZCompound: 1,1-bis[4-(4-aminophenylmethyl)phenyl]-4-n-heptylcyclohexane: 7HBZ

化合物：1,3-雙[4-(4-氨基苯基甲基)苯基]丙烷：BABZP3Compound: 1,3-bis[4-(4-aminophenylmethyl)phenyl]propane: BABZP3

化合物：2,2-雙[4-(4-氨基苯氧基)苯基]丙烷：BAPPCompound: 2,2-bis[4-(4-aminophenoxy)phenyl]propane: BAPP

化合物：1-苯基甲基-2,5-二氨基苯：2,5-P1PDACompound: 1-phenylmethyl-2,5-diaminobenzene: 2,5-P1PDA

化合物：1-苯基甲基-3,5-二氨基苯：3,5-P1PDACompound: 1-phenylmethyl-3,5-diaminobenzene: 3,5-P1PDA

化合物：5-[4-(4-正戊基環己基)環己基]苯基甲基-1,3-二氨基苯：5HHP1PDACompound: 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethyl-1,3-diaminobenzene: 5HHP1PDA

化合物：5-{[4-(4-正庚基環己基)乙基]環己基}苯基甲基-1,3-二氨基苯：7H2HP1PDACompound: 5-{[4-(4-n-heptylcyclohexyl)ethyl]cyclohexyl}phenylmethyl-1,3-diaminobenzene: 7H2HP1PDA

化合物：5-[4-(正十六烷基)苯基甲基]-1,3-二氨基苯：16P1PDACompound: 5-[4-(n-hexadecyl)phenylmethyl]-1,3-diaminobenzene: 16P1PDA

化合物：3,3'-二氨基二苯基醚：3,3'-DDECompound: 3,3'-diaminodiphenyl ether: 3,3'-DDE

化合物：3,4'-二氨基二苯基醚：3,4'-DDECompound: 3,4'-diaminodiphenyl ether: 3,4'-DDE

化合物：4,4'-二氨基二苯基醚：4,4'-DDECompound: 4,4'-diaminodiphenyl ether: 4,4'-DDE

＜環氧化合物＞<epoxy compound>

化合物：N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷：TGDDMCompound: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane: TGDDM

化合物：雙酚A酚醛型環氧化合物：157S70(商品名，日本環氧樹脂股份有限公司製造)Compound: bisphenol A phenolic epoxy compound: 157S70 (trade name, manufactured by Nippon Epoxy Resin Co., Ltd.)

化合物：3,4-環氧環己烯甲基-3',4'-環氧環己烯基甲酸酯：Celloxide 2021(商品名，Daicel化學工業股份有限公司製造)Compound: 3,4-epoxycyclohexenemethyl-3',4'-epoxycyclohexenylcarboxylate: Celloxide 2021 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.)

化合物：甲酚酚醛型環氧化合物：EOCN-104S(商品名，日本化藥股份有限公司製造)，平均官能基數大於等於2的具有環氧基的化合物)Compound: cresol novolac type epoxy compound: EOCN-104S (trade name, manufactured by Nippon Kayaku Co., Ltd.), an epoxy group-containing compound having an average functional group number of 2 or more)

＜溶劑><solvent>

NMP:N-甲基-2-吡咯烷酮NMP: N-methyl-2-pyrrolidone

GBL:γ-丁內酯GBL: γ-butyrolactone

BC：丁基溶纖劑(乙二醇單丁醚)BC: butyl cellosolve (ethylene glycol monobutyl ether)

＜1.聚醯胺酸的合成><1. Synthesis of polyaminic acid>

[合成例1][Synthesis Example 1]

在具備溫度計、攪拌機、原料投入口以及氮氣導入口的100mL的四口燒瓶中，加入2.426g的DDM、54.0g的脫水NMP，在乾燥氮氣流下將其攪拌溶解。然後，添加1.735g的PMDA、0.840g的CBDA以及15.0g的脫水GBL，在室溫環境下反應30小時。在反應過程中反應溫度上升時，將反應溫度抑制在約70℃以下進行反應。在所獲得的溶液中加入25.Og的BC，獲得濃度爲6重量%的聚醯胺酸溶液。將此聚醯胺酸溶液設爲PA1。2.427 g of DDM and 54.0 g 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 the mixture was stirred and dissolved under a dry nitrogen stream. Then, 1.735 g of PMDA, 0.840 g of CBDA, and 15.0 g of dehydrated GBL were added, and the mixture was reacted for 30 hours at room temperature. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70 ° C or lower to carry out the reaction. To the obtained solution, 2.Og of BC was added to obtain a polyglycine solution having a concentration of 6% by weight. This polyaminic acid solution was set to PA1.

[合成例2～19][Synthesis Examples 2 to 19]

除了根據表1改變四羧酸二酐以及二胺以外，依據合成例1來製備聚醯胺酸溶液PA2～PA19。將包括合成例在內的結果匯總在表1中。The polyaminic acid solutions PA2 to PA19 were prepared in accordance with Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed according to Table 1. The results including the synthesis examples are summarized in Table 1.

<2.液晶顯示元件的製作><2. Production of liquid crystal display element>

[比較例1][Comparative Example 1]

以8/2的重量比混合PA1和PA2。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以使聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過如下方式來製作液晶顯示元件。PA1 and PA2 were mixed at a weight ratio of 8/2. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of the polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

<液晶顯示元件的製作方法>(實施例1~實施例12、比較例1~比較例12)<Method for Producing Liquid Crystal Display Element> (Examples 1 to 12, Comparative Example 1 to Comparative Example 12)

使用旋轉塗布機，將液晶配向劑塗布到兩塊附帶ITO電極的玻璃基板上，形成膜厚為70nm的膜。塗布形成膜之後，在80℃下加熱乾燥約5分鐘後，在210℃下進行20分鐘的加熱處理，而形成液晶配向膜。然後，使用摩擦裝置，對形成有液晶配向膜的基板表面進行摩擦處理，來實施配向處理。之後，在超純水中對液晶配向膜進行5分鐘超聲波清洗，然後在烘箱中，在120℃下乾燥30分鐘。The liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode using a spin coater to form a film having a film thickness of 70 nm. After coating and forming a film, it was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 210 ° C for 20 minutes to form a liquid crystal alignment film. Then, the surface of the substrate on which the liquid crystal alignment film was formed was subjected to a rubbing treatment using a rubbing device to carry out an alignment treatment. Thereafter, the liquid crystal alignment film was ultrasonically washed in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes.

在其中一塊玻璃基板上散布7μm的間隙材料(gap material)，以形成有液晶配向膜的面位於內側，並且摩擦方向爲反平行的方式將兩塊玻璃基板對向配置，然後用環氧硬化劑加以密封，製作出間隙爲7μm的反平行液晶盒(antiparallel cell)。向此液晶盒中注入以下所示的液晶組合物，用光硬化劑密封注入口。接著，在110℃下加熱處理30分鐘，而製成液晶顯示元件。A gap material of 7 μm is spread on one of the glass substrates, the surface on which the liquid crystal alignment film is formed is located on the inner side, and the two glass substrates are disposed opposite to each other in the rubbing direction, and then the epoxy hardener is used. It was sealed to produce an antiparallel cell having a gap of 7 μm. The liquid crystal composition shown below was injected into the liquid crystal cell, and the injection port was sealed with a light hardener. Subsequently, the film was heat-treated at 110 ° C for 30 minutes to prepare a liquid crystal display element.

[實施例1][Example 1]

在比較例1所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 1, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例2][Embodiment 2]

在比較例1所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的157S70，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 1, 20 parts by weight of 157S70 was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例2][Comparative Example 2]

以8/2的重量比混合PA1和PA3。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。PA1 and PA3 were mixed at a weight ratio of 8/2. To the obtained mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例3][Example 3]

在比較例2所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 2, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例4][Example 4]

在比較例2所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的Celloxide 2021P，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 2, 20 parts by weight of Celloxide 2021P was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例3][Comparative Example 3]

在PA4中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA4, and the entire solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例5][Example 5]

在比較例3所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸溶解爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 3, 20 parts by weight of TGDDM dissolved in 100 parts by weight of polylysine was dissolved to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例6][Embodiment 6]

在比較例3所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的EOCN-104S，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 3, 20 parts by weight of EOCN-104S was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例4][Comparative Example 4]

在PA5中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA5, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例7][Embodiment 7]

在比較例4所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 4, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例8][Embodiment 8]

在比較例4所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的EOCN-104S，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 4, 20 parts by weight of EOCN-104S was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例5][Comparative Example 5]

在PA6中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA6, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例9][Embodiment 9]

在比較例5所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 5, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例10][Embodiment 10]

在比較例5所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的EOCN-104S，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 5, 20 parts by weight of EOCN-104S was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例6][Comparative Example 6]

在PA7中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA7, and the whole of the solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例11][Example 11]

在比較例6所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 6, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例7][Comparative Example 7]

在PA8中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA8, and the whole of the solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[實施例12][Embodiment 12]

在比較例7所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 7, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例8][Comparative Example 8]

在PA9中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA9, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例9][Comparative Example 9]

在比較例8所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸為20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 8, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例10][Comparative Example 10]

在PA10中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA10, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.

[比較例12][Comparative Example 12]

在PA11中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以如 上所述的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA11, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, such as The liquid crystal display element was fabricated in the manner described above.

[比較例14][Comparative Example 14]

以9/1的重量比混合PA6和PA12。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，按照下述方式製作液晶顯示元件。PA6 and PA12 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner.

<液晶顯示元件的製作方法>(實施例13~實施例20、比較例14~比較例21)<Method for Producing Liquid Crystal Display Element> (Examples 13 to 20, Comparative Example 14 to Comparative Example 21)

使用旋轉塗布機，將液晶配向劑塗布到兩塊附帶ITO電極的玻璃基板上，形成膜厚為70nm的膜。塗布形成膜之後，在80℃下加熱乾燥約5分鐘後，在210℃下進行20分鐘加熱處理，形成液晶配向膜。之後，在超純水中對液晶配向膜進行5分鐘超聲波清洗，然後在烘箱中，在120℃下乾燥30分鐘。The liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode using a spin coater to form a film having a film thickness of 70 nm. After coating and forming a film, it was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 210 ° C for 20 minutes to form a liquid crystal alignment film. Thereafter, the liquid crystal alignment film was ultrasonically washed in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes.

在其中一塊玻璃基板上散布4μm的間隙材料，以使形成有液晶配向膜的面位於內側的方式加以配置後，用環氧硬化劑加以密封，製作出間隙為4μm的液晶盒。向此液晶盒中注入以下所示的液晶組合物，用光硬化劑密封注入口。接著，在110℃下進行30分鐘加熱處理，製成液晶顯示元件。A gap material of 4 μm was spread on one of the glass substrates, and the surface on which the liquid crystal alignment film was formed was placed inside, and then sealed with an epoxy curing agent to prepare a liquid crystal cell having a gap of 4 μm. The liquid crystal composition shown below was injected into the liquid crystal cell, and the injection port was sealed with a light hardener. Subsequently, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

[實施例13][Example 13]

在比較例14所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過和比較例10相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 14, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 10, using the obtained liquid crystal alignment agent.

[比較例15][Comparative Example 15]

以9/1的重量比混合PA6和PA13。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過和比較例14相同的方式製作液晶顯示元件。PA6 and PA13 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例14][Embodiment 14]

在比較例15所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 15, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例16][Comparative Example 16]

以9/1的重量比混合PA6和PA14。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過和比較例14相同的方式製作液晶顯示元件。PA6 and PA14 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例15][Example 15]

在比較例16所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的157S70，而獲得液晶配向劑。使用所獲得的液晶配向劑，通過和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 16, 20 parts by weight of 157S70 was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例17][Comparative Example 17]

以9/1的重量比混合PA15和PA16。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。PA15 and PA16 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例16][Example 16]

在比較例17所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 17, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例17][Example 17]

在比較例17所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的Celloxide 2021P，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 17, 20 parts by weight of Celloxide 2021P was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例18][Comparative Example 18]

以9/1的重量比混合PA15和PA17。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。PA15 and PA17 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例18][Embodiment 18]

在比較例18所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的EOCN-104S，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 18, 20 parts by weight of EOCN-104S was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例19][Comparative Example 19]

在PA18中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA18, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例19][Embodiment 19]

在比較例19所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 19, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[實施例20][Example 20]

在比較例19所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的EOCN-104S，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 19, 20 parts by weight of EOCN-104S was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例20][Comparative Example 20]

以9/1的重量比混合PA15和PA19。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，以聚醯胺酸的濃度達到4重量%的方式對溶液整體進行稀釋，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。PA15 and PA19 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

[比較例21][Comparative Example 21]

在比較例20所獲得的4重量%的液晶配向劑中，溶解相對於100重量份聚醯胺酸爲20重量份的TGDDM，而獲得液晶配向劑。使用所獲得的液晶配向劑，以和比較例14相同的方式製作液晶顯示元件。In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 20, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent.

<3.電特性的評價><3. Evaluation of electrical characteristics>

以如下方式測定實施例1～實施例20、比較例1～比較例21所製作的液晶顯示元件的離子密度和長期可靠性。The ion density and long-term reliability of the liquid crystal display elements produced in Examples 1 to 20 and Comparative Examples 1 to 21 were measured in the following manner.

1)離子密度的測定1) Determination of ion density

使用Toyo Technica製造的液晶物性評價裝置6254型來測定離子密度。測定條件如下：波形爲三角波；頻率爲0.01Hz；電壓爲±10V；測定溫度爲60℃。測得的離子密度的值越小，電特性就越好。將結果示於表2、表3。The ion density was measured using a liquid crystal property evaluation device 6254 manufactured by Toyo Technica. The measurement conditions were as follows: the waveform was a triangular wave; the frequency was 0.01 Hz; the voltage was ±10 V; and the measurement temperature was 60 °C. The smaller the value of the measured ion density, the better the electrical characteristics. The results are shown in Table 2 and Table 3.

2)離子密度的保持特性的測定2) Determination of retention characteristics of ion density

針對所製作的液晶顯示元件，隨著時間經過測定離子密度[pC]，並且對離子密度的保持特性進行評價。保持特性的試驗方法可以採用如下方法：將液晶顯示元件放置在溫度爲100℃的環境中，隨著時間經過中途取出此液晶顯示元件並測定其離子密度[pC]。200小時後的離子密度的數值越小，離子密度的保持特性就越好，並且電特性的長期可靠性就越好。將100小時後和200小時後的數據示於表2、表3。With respect to the produced liquid crystal display element, the ion density [pC] was measured over time, and the ion density retention characteristics were evaluated. As a test method for maintaining characteristics, a liquid crystal display element can be placed in an environment at a temperature of 100 ° C, and the liquid crystal display element is taken out over time and its ion density [pC] is measured. The smaller the value of the ion density after 200 hours, the better the ion density retention property and the longer the long-term reliability of the electrical characteristics. The data after 100 hours and after 200 hours are shown in Table 2 and Table 3.

如表2、表3所示，使用添加了環氧化合物的實施例1~實施例20的液晶配向劑的液晶顯示元件可以抑制離子密度隨著時間經過而增大。As shown in Table 2 and Table 3, the liquid crystal display element using the liquid crystal alignment agents of Examples 1 to 20 to which the epoxy compound was added can suppress the increase in ion density with time.

<4.配向特性的評價><4. Evaluation of alignment characteristics>

對於實施例1、3、5、7、9、11、12以及比較例1~比較例12中所製作的液晶顯示元件，將注入液晶組合物後、加 熱處理前的此元件夾在兩塊偏向板之間，貼裝背光源(back light)，觀察液晶的配向狀態，根據是否存在流動配向(flow orientation)來評價配向特性。不存在流動配向的液晶顯示元件可以認為配向性良好。將結果示於表4。In the liquid crystal display elements produced in Examples 1, 3, 5, 7, 9, 11, 12 and Comparative Examples 1 to 12, after the liquid crystal composition was injected, This element before heat treatment was sandwiched between two deflecting plates, and a back light was attached to observe the alignment state of the liquid crystal, and the alignment characteristics were evaluated based on whether or not there was a flow orientation. A liquid crystal display element in which no flow alignment is present can be considered to have good alignment. The results are shown in Table 4.

如表4所示，此次所研發的添加有環氧化合物的液晶配向劑，即使添加環氧化合物，也未確認到流動配向，可以維持高配向性。As shown in Table 4, the liquid crystal alignment agent to which the epoxy compound was added, which was developed this time, did not confirm the flow alignment even when an epoxy compound was added, and the high alignment property was maintained.

雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (23)

一種液晶配向劑，其含有作為二胺和四羧酸二酐的反應產物的聚醯胺酸或其衍生物、以及平均官能基數大於1的具有環氧基的環氧化合物，其中所述液晶配向劑不含有噁嗪化合物，此液晶配向劑的特徵在於：所述二胺是下述通式(I)所表示的二胺： (通式(I)中，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H、下述結構式(II-1)、通式(II-2)或者通式(II-3)，Z1 表示可以具有甲基的碳數為1~12的亞烷基、下述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基，m、n及p分別表示0或者1；其中，m+n+p為0、1或者3，當m+n+p為0時，Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)，當m+n+p為1時，m及n表示0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基是鍵結在X2 的間位，當m+n+p為3時，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數為1~12的亞烷基、或者通式(III-1)或通式(III-2)所表示的4-取代 -1,1-亞環己基)， (通式(II-2)以及通式(II-3)中，Y2 及Y3 分別表示碳數為1~30的烷基)， (通式(III-1)以及通式(III-2)中，Y4 及Y5 分別表示碳數為1~30的烷基)。A liquid crystal aligning agent containing polyamic acid or a derivative thereof as a reaction product of a diamine and a tetracarboxylic dianhydride, and an epoxy compound having an epoxy group having an average functional group number of more than 1, wherein the liquid crystal alignment The agent does not contain an oxazine compound, and the liquid crystal alignment agent is characterized in that the diamine is a diamine represented by the following formula (I): (In the formula (I), X 1 and X 2 each represent -O- or -CH 2 -, Y 1 represents -H, the following structural formula (II-1), general formula (II-2) or (II-3), Z 1 represents an alkylene group having a methyl group of 1 to 12, a 4-substituted-1 represented by the following formula (III-1) or (III-2) , 1-cyclohexylene, m, n and p respectively represent 0 or 1; wherein m+n+p is 0, 1 or 3, and when m+n+p is 0, Y 1 represents a general formula (II- 1), General formula (II-2) or Formula (II-3), when m+n+p is 1, m and n represent 0, and X 2 represents -O-, an amino group bonded to X 2 The amino group of the phenyl group is bonded to the meta position of X 2 . When m+n+p is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents An alkylene group having a methyl group having 1 to 12 carbon atoms or a 4-substituted-1,1-cyclohexylene group represented by the formula (III-1) or the formula (III-2), (In the general formula (II-2) and the general formula (II-3), Y 2 and Y 3 each represent an alkyl group having 1 to 30 carbon atoms), (In the general formula (III-1) and the general formula (III-2), Y 4 and Y 5 each represent an alkyl group having 1 to 30 carbon atoms). 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺。The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (I) is m+n+p is 3, and X 1 and X 2 respectively represent -O- Or -CH 2 -, Y 1 represents -H, and Z 1 represents a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (III-1) or (III-2) . 如申請專利範圍第2項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺是下述結構式A1以及結構式A2所表示的二胺中的一方或者兩方， The liquid crystal alignment agent according to the second aspect of the invention, wherein the diamine represented by the formula (I) is one or two of the diamines represented by the following structural formula A1 and structural formula A2. square, 如申請專利範圍第2項或第3項所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-3)、結構式(VIII-7)以及結構式(VIII-31)所表示的二胺中的一種以上，所述四羧酸二酐為下述結構式(1)及結構式(14)中的一方或者兩方， The liquid crystal alignment agent according to Item 2 or 3, wherein the diamine further comprises the following structural formula (VIII-3), structural formula (VIII-7), and structural formula (VIII). -31) one or more of the following diamines, wherein the tetracarboxylic dianhydride is one or both of the following structural formula (1) and structural formula (14), 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數為1~12的亞烷基的二胺。The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (I) is m+n+p is 3, and X 1 and X 2 respectively represent -O- Or -CH 2 -, Y 1 represents -H, and Z 1 represents a diamine which may have an alkylene group having a methyl group of 1 to 12 carbon atoms. 如申請專利範圍第5項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是X1 及X2 分別表示-CH2 -，且Z1 表示可以具有甲基的碳數為1~10的亞烷基的二胺。The liquid crystal alignment agent according to claim 5, wherein the diamine represented by the formula (I) is such that X 1 and X 2 each represent -CH 2 -, and Z 1 represents that it may have The alkylene having a carbon number of 1 to 10 is an alkylene group. 如申請專利範圍第6項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺為下述結構式B1所表示的二胺， The liquid crystal alignment agent according to the sixth aspect of the invention, wherein the diamine represented by the formula (I) is a diamine represented by the following structural formula B1, 如申請專利範圍第5項至第7項中任一項所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-13)所表示的二胺，所述四羧酸二酐為下述結構式(1)及結構式(14)中的一方或者兩方， The liquid crystal alignment agent according to any one of the items 5 to 7, wherein the diamine further comprises a diamine represented by the following structural formula (VIII-13), the fourth The carboxylic acid dianhydride is one or both of the following structural formula (1) and structural formula (14). 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m+n+p為0，且Y1 表示所述通式(II-1)、通式(II-2)或者通式(II-3)的二胺。The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (I) is m+n+p is 0, and Y 1 represents the formula (II) -1), a diamine of the formula (II-2) or the formula (II-3). 如申請專利範圍第9項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是所述通式(II-2)及通式(II-3)中的Y2 及Y3 分別表示碳數為1~20的烷基的二胺。The liquid crystal alignment agent according to claim 9, wherein the diamine represented by the formula (I) is in the formula (II-2) and the formula (II-3). Y 2 and Y 3 each represent a diamine having an alkyl group having 1 to 20 carbon atoms. 如申請專利範圍第9項或第10項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是選自下述結構式C1~結構式C4所表示的二胺中的一種以上， The liquid crystal alignment agent according to claim 9 or 10, wherein the diamine represented by the formula (I) is selected from the group consisting of the following structural formula C1 to structural formula C4. More than one of diamines, 如申請專利範圍第9項所述的液晶配向劑，其特徵在於：所述二胺進一步包括下述結構式(VIII-1)以及結構式(VIII-7)所表示的二胺中的一方或者兩方，所述四羧酸二酐為下述結構式(1)及結構式(14)中的一方或者兩方， The liquid crystal alignment agent according to claim 9, wherein the diamine further includes one of the diamines represented by the following structural formula (VIII-1) and structural formula (VIII-7) or In both, the tetracarboxylic dianhydride is one or both of the following structural formula (1) and structural formula (14). 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺，是m+n+p為1，m及n為0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵 結在X2 的間位的二胺。The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine represented by the formula (I) is m+n+p is 1, m and n are 0, and X 2 represents -O-, the amino group of the aminophenyl group to which X 2 is bonded is bonded to the diamine of the meta position of X 2 . 如申請專利範圍第13項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺為下述結構式D1以及結構式D2所表示的二胺中的一方或者兩方， The liquid crystal alignment agent according to claim 13, wherein the diamine represented by the formula (I) is one or both of the following structural formula D1 and the diamine represented by the structural formula D2. square, 如申請專利範圍第13項或第14項所述的液晶配向劑，其特徵在於：所述四羧酸二酐為下述結構式(1)及結構式(14)中的一方或者兩方， The liquid crystal alignment agent according to claim 13 or 14, wherein the tetracarboxylic dianhydride is one or both of the following structural formula (1) and structural formula (14). 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述二胺包括所述通式(I)中的m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數為1~12的亞烷基的二胺，以及選自下述四種二胺中的一種以上：(1)所述通式(I)中的m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺；(2)所述通式(I)中的m+n+p為0，且Y1 表示所 述通式(II-1)、通式(II-2)或者通式(II-3)的二胺；(3)所述通式(I)中的m+n+p為1，m及n為0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵結在X2 的間位的二胺；(4)所述通式(I)中的m+n+p為0，Y1 表示通式(II-4)的二胺， (通式(II-4)中，Y6 表示碳數為1~30的烷基)。The liquid crystal alignment agent according to claim 1, wherein the diamine comprises m+n+p in the formula (I) of 3, and X 1 and X 2 respectively represent -O- Or -CH 2 -, Y 1 represents -H, and Z 1 represents a diamine which may have an alkylene group having a methyl group of 1 to 12 carbon atoms, and one or more selected from the following four kinds of diamines: 1) m+n+p in the formula (I) is 3, X 1 and X 2 represent -O- or -CH 2 - respectively, Y 1 represents -H, and Z 1 represents the formula ( III-1) or a 4-substituted-1,1-cyclohexylene diamine represented by the formula (III-2); (2) m+n+p in the formula (I) is 0, And Y 1 represents the diamine of the above formula (II-1), formula (II-2) or formula (II-3); (3) m+n+p in the formula (I) Is 1, m and n are 0, and X 2 represents -O-, the amino group of the aminophenyl group to which X 2 is bonded is bonded to the diamine of the meta position of X 2 ; (4) the general formula (I) m+n+p is 0, and Y 1 represents a diamine of the formula (II-4), (In the formula (II-4), Y 6 represents an alkyl group having 1 to 30 carbon atoms). 如申請專利範圍第16項所述的液晶配向劑，其特徵在於：所述通式(I)所表示的二胺包括下述結構式B1所表示的二胺、以及選自下述四種二胺中的一種以上：(1)下述結構式A1或者結構式A2所表示的二胺；(2)下述結構式C1或者結構式C2所表示的二胺；(3)下述結構式D1或者結構式D2所表示的二胺；(4)下述結構式(XI-47)所表示的二胺， The liquid crystal alignment agent according to the above aspect of the invention, wherein the diamine represented by the formula (I) includes a diamine represented by the following structural formula B1, and a One or more of the amines: (1) a diamine represented by the following structural formula A1 or structural formula A2; (2) a diamine represented by the following structural formula C1 or structural formula C2; (3) the following structural formula D1 Or a diamine represented by the structural formula D2; (4) a diamine represented by the following structural formula (XI-47), 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：含有兩種以上聚醯胺酸或其衍生物。 The liquid crystal alignment agent according to claim 1, which comprises two or more kinds of polyaminic acid or a derivative thereof. 如申請專利範圍第18項所述的液晶配向劑，其特徵在於：含有作為所述通式(I)中的m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示可以具有甲基的碳數為1~12的亞烷基的二胺與四羧酸二酐的反 應產物的聚醯胺酸或其衍生物，以及下述三種聚醯胺酸或其衍生物中的一方或者兩方：(1)作為所述通式(I)中的m+n+p為3，X1 及X2 分別表示-O-或-CH2 -，Y1 表示-H，且Z1 表示所述通式(III-1)或通式(III-2)所表示的4-取代-1,1-亞環己基的二胺與四羧酸二酐的反應產物的聚醯胺酸或者其衍生物；(2)作為所述通式(I)中的m+n+p為0，且Y1 表示通式(II-1)、通式(II-2)或者通式(II-3)的二胺與四羧酸二酐的反應產物的聚醯胺酸或者其衍生物；(3)作為所述通式(I)中的m+n+p為1，m及n為0，且X2 表示-O-，X2 所鍵結的氨基苯基的氨基鍵結在X2 的間位的二胺與四羧酸二酐的反應產物的聚醯胺酸或其衍生物。The liquid crystal alignment agent according to claim 18, which is characterized in that m+n+p in the formula (I) is 3, and X 1 and X 2 respectively represent -O- or -CH. 2 -, Y 1 represents -H, and Z 1 represents a polyamic acid or a derivative thereof which may have a reaction product of a diamine having a methyl group having 1 to 12 carbon atoms and a tetracarboxylic dianhydride. And one or both of the following poly-proline acids or derivatives thereof: (1) as m+n+p in the above formula (I) is 3, and X 1 and X 2 respectively represent -O- Or -CH 2 -, Y 1 represents -H, and Z 1 represents a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (III-1) or (III-2) Poly-proline or a derivative thereof, which is a reaction product of tetracarboxylic dianhydride; (2) as m+n+p in the formula (I) is 0, and Y 1 represents a formula (II-1) a polylysine or a derivative thereof, a reaction product of a diamine of the formula (II-2) or the formula (II-3) with a tetracarboxylic dianhydride; (3) as the above formula (I) m+n+p is 1, m and n are 0, and X 2 represents -O-, and the amino group of the aminophenyl group bonded by X 2 is bonded to the diamine and tetracarboxylic acid at the meta position of X 2 . Polyacetic acid of the reaction product of dianhydride or Creatures. 如申請專利範圍第1項所述的液晶配向劑，其特徵在於：所述環氧化合物是選自縮水甘油醚、縮水甘油酯、縮水甘油胺、含環氧基的丙烯酸系樹脂、縮水甘油醯胺、異氰脲酸縮水甘油酯、鏈狀脂肪族型環氧化合物以及環狀脂肪族型環氧化合物所組成的族群中的一種以上。 The liquid crystal alignment agent according to claim 1, wherein the epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, and glycidyl hydrazine. One or more of a group consisting of an amine, an isocyanuric acid glycidyl ester, a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. 如申請專利範圍第20項所述的液晶配向劑，其特徵在於：所述環氧化合物是選自N,N,N',N'-四縮水甘油基間二甲苯二胺、1,3-雙(N,N-二縮水甘油基氨基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷、2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧丙氧基]苯基)]乙基]苯基]丙烷、3,4-環氧環己烯甲基-3',4'-環氧 環己烯基甲酸酯、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物、雙酚A酚醛型環氧化合物、甲酚酚醛型環氧化合物以及N,N,O-三縮水甘油基對氨基苯酚中的一種以上。 The liquid crystal alignment agent according to claim 20, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl metaxylene diamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[4- (2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl Propane, 3,4-epoxycyclohexenemethyl-3',4'-epoxy Cyclohexenylcarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, bisphenol A phenolic epoxy compound, cresol novolac epoxy compound, and N, N, O- More than one of triglycidyl p-aminophenol. 一種液晶配向膜，其特徵在於：此液晶配向膜是對如申請專利範圍第1項至第21項中任一項所述的液晶配向劑的膜進行煆燒而形成的。 A liquid crystal alignment film which is formed by calcining a film of the liquid crystal alignment agent according to any one of claims 1 to 21 of the invention. 一種液晶顯示元件，其具備對向配置的一對基板，形成在所述一對基板各自所對向的面中的一面或者兩面上的電極，形成在所述一對基板各自所對向的面上的液晶配向膜，以及形成在所述一對基板之間的液晶層，其特徵在於：所述液晶配向膜是申請專利範圍第22項所述的液晶配向膜。 A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both surfaces of the pair of substrates facing each other, and being formed on a surface facing each of the pair of substrates And a liquid crystal alignment film formed in the liquid crystal alignment film according to claim 22, wherein the liquid crystal alignment film is a liquid crystal alignment film formed between the pair of substrates.
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