TWI492966B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display - Google Patents

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

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TWI492966B
TWI492966B TW097143519A TW97143519A TWI492966B TW I492966 B TWI492966 B TW I492966B TW 097143519 A TW097143519 A TW 097143519A TW 97143519 A TW97143519 A TW 97143519A TW I492966 B TWI492966 B TW I492966B
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liquid crystal
formula
crystal alignment
structural formula
alignment agent
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TW097143519A
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TW200927790A (en
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Fumitaka Kondo
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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、液晶配向膜以及液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

本發明有關於一種液晶配向劑、由該液晶配向劑所獲得的液晶配向膜以及具有該液晶配向膜的液晶顯示元件，所述液晶配向劑含有使主鏈上具有呱嗪(piperazine)的二胺(diamine)與四羧酸二酐(tetracarboxylic dianhydride)反應而獲得的聚醯胺酸(polyamic acid)或者其衍生物。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, the liquid crystal alignment agent containing a diamine having a piperazine in a main chain (diamine) Polyamic acid obtained by reacting with tetracarboxylic dianhydride or a derivative thereof.

液晶顯示元件被用於以筆記型電腦(note personal computer)或桌上型電腦(desktop personal computer)的監視器(monitor)為代表的攝像機(video camera)的取景器(viewfinder)、投影式顯示器等的各種液晶顯示裝置，近來也被用於電視。另外，液晶顯示元件也被用於光學打印頭(optical printer head)、光學傅利葉變換元件(optical Fourier transform device)、光閥(light valve)等光電子相關元件。The liquid crystal display element is used for a viewfinder, a projection display, etc. of a video camera represented by a monitor of a note personal computer or a desktop personal computer. Various liquid crystal display devices have recently been used for televisions. Further, the liquid crystal display element is also used for an optoelectronic related element such as an optical printer head, an optical Fourier transform device, or a light valve.

液晶顯示元件中已知了各種元件，而液晶顯示元件的技術發展不僅是通過對液晶顯示元件的驅動方式或者液晶顯示元件的結構進行改良來實現的，而且是通過對液晶顯示元件所使用的構成構件進行改良來實現的。通常，液晶顯示元件具有用來將液晶層中的液晶組成物配向在特定方向上的液晶配向膜。液晶配向膜是與液晶顯示元件的顯示品質相關的一個重要的要素，液晶配向膜的作用隨著液晶顯示元件的品質提高而逐年變得重要。Various components are known in the liquid crystal display element, and the technical development of the liquid crystal display element is realized not only by the driving method of the liquid crystal display element or the structure of the liquid crystal display element, but also by the composition used for the liquid crystal display element. The components are improved to achieve. Generally, a liquid crystal display element has a liquid crystal alignment film for aligning a liquid crystal composition in a liquid crystal layer in a specific direction. The liquid crystal alignment film is an important element related to the display quality of the liquid crystal display element, and the action of the liquid crystal alignment film becomes important year by year as the quality of the liquid crystal display element is improved.

液晶配向膜是由液晶配向劑所製備的。目前，主要使用的液晶配向劑是將聚醯胺酸或者可溶性的聚醯亞胺(polyimide)溶解在有機溶劑中的溶液。將這樣的溶液塗布在基板之後，利用加熱等方法進行成膜，由此形成液晶配向膜。The liquid crystal alignment film is prepared from a liquid crystal alignment agent. Currently, a liquid crystal alignment agent mainly used is a solution in which polylysine or a soluble polyimide is dissolved in an organic solvent. After such a solution is applied onto a substrate, film formation is performed by a method such as heating to form a liquid crystal alignment film.

為了提高液晶顯示元件的顯示品質，液晶配向膜所需要的重要特性可以列舉離子密度。如果離子密度高，那麼有時在幀(frame)期間中施加給液晶的電壓會下降，結果亮度下降而妨礙正常的灰度顯示。而且，例如即使初期的離子密度低，但高溫加速試驗後的離子密度(長期可靠性)增大的情況也是不好。In order to improve the display quality of the liquid crystal display element, important characteristics required for the liquid crystal alignment film include ion density. If the ion density is high, sometimes the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered to hinder the normal gradation display. Further, for example, even if the initial ion density is low, the ion density (long-term reliability) after the high-temperature acceleration test is increased.

人們嘗試著解决所述的問題，例如，已知一種聚醯胺酸組成物，其用來形成液晶配向膜，且組合含有物性不同的兩種或者兩種以上的聚醯胺酸(例如參照日本專利特開平11-193345號公報和日本專利特開平11-193347號公報)。Attempts have been made to solve the problems described. For example, a polylysine composition for forming a liquid crystal alignment film and combining two or more kinds of polylysine having different physical properties (for example, reference to Japan) is known. Patent Publication No. Hei 11-193345 and Japanese Patent Laid-Open No. Hei 11-193347.

另一方面，用來形成即使在低溫下進行煆燒但醯亞胺化率仍高的膜的液晶配向劑，已知一種如下的液晶配向劑：其含有使二胺與四羧酸二酐反應而獲得的聚醯胺酸，所述二胺具有呱嗪之類的含鹼性氮原子的二價有機基團(例如參照日本專利特開平9-194725號公報)。On the other hand, a liquid crystal alignment agent for forming a film having a high yield of oxime iodization even at a low temperature is known as a liquid crystal alignment agent containing a reaction of a diamine with a tetracarboxylic dianhydride. In the case of the obtained polyamine, the diamine has a divalent organic group containing a basic nitrogen atom such as a pyridazine (for example, refer to Japanese Laid-Open Patent Publication No. Hei 9-194725).

另外，已知一種使具有呱嗪的芳香族二胺與四羧酸二酐反應而獲得的聚醯胺酸及其熱特性(例如參照Journal of Polymer Science:Part A:Polymer Chemistry,vol. 30,p1099-1102(1992))。Further, a polylysine obtained by reacting an aromatic diamine having a pyridazine with a tetracarboxylic dianhydride and its thermal properties are known (for example, refer to Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30, P1099-1102 (1992)).

這些現有技術中，對於形成要求進一步改良的如今的液晶配向膜的液晶配向劑而言，在所得液晶配向膜的電特性或者用來獲得所需電特性的材料方面尚留有進一步研究的餘地。In these prior art, there is still room for further research on the liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention which is required to be further improved, in terms of electrical characteristics of the obtained liquid crystal alignment film or materials for obtaining desired electrical characteristics.

本發明提供一種表現出所需的離子密度以及實現該離子密度的長期穩定性的液晶顯示元件、在該液晶顯示元件中表現出所需的離子密度以及實現該離子密度的長期穩定性的液晶配向膜、以及可以形成該液晶配向膜的液晶配向劑。The present invention provides a liquid crystal display element exhibiting a desired ion density and achieving long-term stability of the ion density, a liquid crystal alignment exhibiting a desired ion density in the liquid crystal display element, and long-term stability of the ion density. A film, and a liquid crystal alignment agent capable of forming the liquid crystal alignment film.

本發明者們發現，將含有以具有呱嗪的芳香族二胺作為原料的聚醯胺酸或者其衍生物的組成物用於液晶配向劑，可以對具有由此所形成的液晶配向膜的液晶顯示元件賦予良好的離子密度以及長期可靠性，從而完成了本發明。The present inventors have found that a composition containing polyaminic acid or a derivative thereof containing an aromatic diamine having a pyridazine as a raw material can be used for a liquid crystal alignment agent, and can have a liquid crystal having a liquid crystal alignment film formed thereby. The display element imparts good ion density and long-term reliability, thereby completing the present invention.

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

[1]一種液晶配向劑，其含有作為四羧酸二酐與二胺的反應產物的聚醯胺酸或者其衍生物，該液晶配向劑的特徵在於：[1] A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent being characterized by:

所述二胺包含以下述通式(N)表示的二胺。The diamine contains a diamine represented by the following formula (N).

通式(N)中，A1 獨立地表示一價有機基團，A2 獨立地表示一價有機基團，m表示0～3的整數，n表示0～4的整數。In the formula (N), A 1 independently represents a monovalent organic group, A 2 independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4.

[2]根據[1]所述的液晶配向劑，其特徵在於：A1 獨立地為碳數為1～10的烷基、碳數為1～10的烷氧基、乙醯胺、氟、氯或者溴，A2 獨立地為碳數為1～3的烷基。[2] The liquid crystal alignment agent according to [1], wherein A 1 is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, acetaminophen, fluorine, or the like. Chlorine or bromine, A 2 is independently an alkyl group having 1 to 3 carbon atoms.

[3]根據[1]或者[2]所述的液晶配向劑，其特徵在於：以通式(N)表示的二胺於兩端的苯基中在對位上具有氨基。[3] The liquid crystal alignment agent according to [1] or [2], wherein the diamine represented by the formula (N) has an amino group at a p-position in a phenyl group at both ends.

[4]根據[1]～[3]中任一項所述的液晶配向劑，其特徵在於：以通式(N)表示的二胺是選自由以下述結構式(N)-1、結構式(N)-2、結構式(N)-5～結構式(N)-7、結構式(N)-9、結構式(N)-10、結構式(N)-14、結構式(N)-17、結構式(N)-18、結構式(N)-21～結構式(N)-23、結構式(N)-26以及結構式(N)-28表示的化合物所組成的族群中的一種或者一種以上。[4] The liquid crystal alignment agent according to any one of [1] to [3], wherein the diamine represented by the formula (N) is selected from the group consisting of the following structural formula (N)-1; Formula (N)-2, Structural Formula (N)-5 to Structural Formula (N)-7, Structural Formula (N)-9, Structural Formula (N)-10, Structural Formula (N)-14, Structural Formula ( N)-17, a structural formula (N)-18, a structural formula (N)-21 to a structural formula (N)-23, a structural formula (N)-26, and a compound represented by the structural formula (N)-28 One or more of the ethnic groups.

[5]根據[4]所述的液晶配向劑，其特徵在於：以通式(N)表示的二胺是以所述結構式(N)-1以及結構式(N)-2表示的化合物中的一方或者兩方。[5] The liquid crystal alignment agent according to [4], wherein the diamine represented by the formula (N) is a compound represented by the structural formula (N)-1 and the structural formula (N)-2 One or both of them.

[6]根據[1]～[5]中任一項所述的液晶配向劑，其特徵在於：所述二胺進一步包含以下述通式(VIII)以及通式(X)～通式(XIII)表示的具有側鏈結構的二胺。[6] The liquid crystal alignment agent according to any one of [1] to [5] wherein the diamine further comprises the following general formula (VIII) and the general formula (X) to the general formula (XIII). a diamine having a side chain structure.

通式(VIII)中，A3 表示單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-或者-(CH2 )m -(m表示1～6的整數)，R1 表示具有類固醇(steroid)骨架的基團、以下述通式(IX)表示的基團，當苯環上所鍵合的兩個氨基的位置關係為對位時，R1 進一步包含碳數為1～30的烷基，當該位置關係為間位時，R1 進一步包含碳數為1～30的烷基或者苯基，該烷基中，任意的-CH2 -可以獨立地經-CF2 -、-CHF-、-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，-CH3 可以經-CH2 F、-CHF2 或者-CF3 所取代，該苯基的氫可以獨立地被取代為-F、-CH3 、-OCH3 、-OCH2 F、-OCHF2 或者-OCF3 。In the formula (VIII), A 3 represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH 2 ) m - (m represents an integer of 1 to 6), R 1 represents a group having a steroid skeleton and a group represented by the following formula (IX). When the positional relationship of two amino groups bonded to the benzene ring is para, R 1 further contains a carbon number. When the positional relationship is a meta position, R 1 further includes an alkyl group having 1 to 30 carbon atoms or a phenyl group, and any -CH 2 - in the alkyl group may independently pass through - CF 2 -, -CHF-, -O- (here non-continuous), -CH=CH- or -C≡C-, -CH 3 may be via -CH 2 F, -CHF 2 or -CF 3 Substituted, the hydrogen of the phenyl group may be independently substituted with -F, -CH 3 , -OCH 3 , -OCH 2 F, -OCHF 2 or -OCF 3 .

通式(IX)中，A4 以及A5 分別獨立地表示單鍵、-O-(此處為非連續)、-COO-、-OCO-、-CONH-、-CH=CH-或者碳數為1～12的亞烷基，R2 以及R3 分別獨立地表示-F或者-CH3 ，環S獨立地表示1,4-亞苯基、1,4-亞環己基、1,3-二噁烷-2,5-二基(1,3-dioxane-2,5-diyl)、嘧啶-2,5-二基(pyrimidine-2,5-diyl)、吡啶-2,5-二基(pyridine-2,5-diyl)、萘-1,5-二基(naphthalene-1,5-diyl)、萘-2,7-二基或者蒽-9,10-二基(anthracene-9,10-diyl)，R4 表示-H、-F、碳數為1～30的烷基、碳數為1～30的氟取代烷基、碳數為1～30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ，a以及b分別表示0～4的整數，c、d以及e分別表示0～3的整數，f以及g分別獨立地表示0～2的整數，並且c+d+e≧1。In the formula (IX), A 4 and A 5 each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon number. Is an alkylene group of 1 to 12, and R 2 and R 3 each independently represent -F or -CH 3 , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl (pyridine-2,5-diyl), naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl (anthracene-9, 10-diyl), R 4 represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH 2 F, -OCHF 2 or -OCF 3 , a and b respectively represent integers of 0 to 4, c, d and e represent integers of 0 to 3, respectively, and f and g each independently represent an integer of 0 to 2, And c+d+e≧1.

通式(X)以及(XI)中，R5 獨立地表示-H或者-CH3 ，R6 表示-H或者碳數為1～20的烷基或烯基，A6 獨立地表示單鍵、-C(=O)-或者-CH2 -，通式(XI)中，R7 以及R8 分別獨立地表示碳數為1～20的烷基或者苯基。In the general formulae (X) and (XI), R 5 independently represents -H or -CH 3 , R 6 represents -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A 6 independently represents a single bond, -C(=O)- or -CH 2 -, in the formula (XI), R 7 and R 8 each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group.

通式(XII)以及(XIII)中，A7 獨立地表示-O-或者碳數為1～6的亞烷基，通式(XII)中，R9 表示-H或者碳數為1～30的烷基，該烷基中，碳數為2～30的烷基的任意的-CH2 -可以經-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，A8 表示單鍵或者碳數為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(XIII)中，R10 表示碳數為6～22的烷基，R11 表示碳數為1～22的烷基。In the general formulae (XII) and (XIII), A 7 independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and in the formula (XII), R 9 represents -H or a carbon number of 1 to 30. An alkyl group in which any -CH 2 - of an alkyl group having 2 to 30 carbon atoms may be subjected to -O- (here, discontinuous), -CH=CH- or -C≡C- Substituted, 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, and h represents 0 or 1, in the formula (XIII) R 10 represents an alkyl group having 6 to 22 carbon atoms, and R 11 represents an alkyl group having 1 to 22 carbon atoms.

[7]根據[6]所述的液晶配向劑，其特徵在於：所述具有側鏈結構的二胺是選自以下述通式(VIII-2)、通式(VIII-4)～通式(VIII-6)、通式(XII-2)、通式(XII-4)以及通式(XII-6)表示的化合物中的至少一種。[7] The liquid crystal alignment agent according to [6], wherein the diamine having a side chain structure is selected from the group consisting of the following formula (VIII-2) and formula (VIII-4) to (VIII-6), at least one of the compounds represented by the formula (XII-2), the formula (XII-4), and the formula (XII-6).

所述通式中，R23 、R29 以及R30 分別表示碳數為1～30的烷基或者碳數為1～30的烷氧基。In the above formula, R 23 , R 29 and R 30 each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.

[8]根據[1]～[7]中任一項所述的液晶配向劑，其特徵在於：所述二胺進一步包含以下述通式(I)～通式(VII)以及通式(XV)表示的不具有側鏈結構的二胺。The liquid crystal alignment agent according to any one of [1] to [7] wherein the diamine further comprises the following general formula (I) to general formula (VII) and general formula (XV) a diamine represented by a side chain structure.

通式(I)中，X表示-(CH2 )m -(m表示1～6的整數)，通式(III)以及通式(V)～通式(VII)中，Y獨立地表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-NH-、-N(CH3 )-(CH2 )m -N(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m -S-(m表示1～6的整數)，通式(V)中，Z表示單鍵或者不存在，通式(XV)中，R33 以及R34 分別獨立地表示碳數為1～3的烷基或者苯基，A3 獨立地表示亞甲基、亞苯基或者經烷基取代的亞苯基。1表示1～6的整數，m表示1～10的整數，通式(II)～(VII)中，環己烷環或者苯環上所鍵合的氫可以獨立地被取代為-F、-CH3 、-CF3 、-OH、-COOH、-SO3 H、-PO3 H2 ，通式(IV)中的苯環上所鍵合的氫可以經苄基所取代。In the formula (I), X represents -(CH 2 ) m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents a single Bond, -O-, -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH 3 )-(CH 2 ) m -N( CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 ) m -, -O-(CH 2 ) m -O-, -S-(CH 2 ) m -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R 33 and R 34 each independently represent a carbon number of 1 to Alkyl or phenyl of 3 , A 3 independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group. 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the general formulae (II) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, - CH 3 , -CF 3 , -OH, -COOH, -SO 3 H, -PO 3 H 2 , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted with a benzyl group.

[9]根據[8]所述的液晶配向劑，其特徵在於：所述不具有側鏈結構的二胺是選自以下述結構式(IV-1)、結構式(IV-2)、結構式(IV-15)～結構式(IV-17)、結構式(V-1)～結構式(V-12)、結構式(V-33)、結構式(V-35)～結構式(V-37)、結構式(VII-2)以及結構式(XV-1)表示的化合物中的至少一種。[9] The liquid crystal alignment agent according to [8], wherein the diamine having no side chain structure is selected from the group consisting of the following structural formula (IV-1), structural formula (IV-2), and structure Formula (IV-15) to Structural Formula (IV-17), Structural Formula (V-1) to Structural Formula (V-12), Structural Formula (V-33), Structural Formula (V-35) to Structural Formula ( At least one of a compound represented by V-37), Structural Formula (VII-2), and Structural Formula (XV-1).

[10]根據[1]～[9]中任一項所述的液晶配向劑，其特徵在於：所述四羧酸二酐包含芳香族四羧酸二酐。[10] The liquid crystal alignment agent according to any one of [1] to [9] wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride.

[11]根據[10]所述的液晶配向劑，其特徵在於：所述芳香族四羧酸二酐是以下述結構式(1)、結構式(2)、結構式(5)～結構式(7)以及結構式(14)表示的化合物中的至少一種。[11] The liquid crystal alignment agent according to [10], wherein the aromatic tetracarboxylic dianhydride is represented by the following structural formula (1), structural formula (2), and structural formula (5) to structural formula. (7) and at least one of the compounds represented by the formula (14).

[12]根據[11]所述的液晶配向劑，其特徵在於：所述芳香族四羧酸二酐是以所述結構式(1)表示的化合物。[12] The liquid crystal alignment agent according to [11], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the structural formula (1).

[13]根據[1]～[12]中任一項所述的液晶配向劑，其特徵在於：所述四羧酸二酐包含脂環式四羧酸二酐以及脂肪族四羧酸二酐中的一方或者兩方。[13] The liquid crystal alignment agent according to any one of [1] to [12] wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. One or both of them.

[14]根據[13]所述的液晶配向劑，其特徵在於：所述脂環式四羧酸二酐以及脂肪族四羧酸二酐是以下述結構式(19)、結構式(23)、結構式(25)、結構式(35)～結構式(39)、結構式(44)以及結構式(49)表示的化合物中的至少一種。[14] The liquid crystal alignment agent according to [13], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (19), structural formula (23) At least one of the compounds represented by the structural formula (25), the structural formula (35) to the structural formula (39), the structural formula (44), and the structural formula (49).

[15]根據[14]所述的液晶配向劑，其特徵在於：所述脂環式四羧酸二酐以及脂肪族四羧酸二酐是以所述結構式(19)、結構式(23)、結構式(37)以及結構式(49)表示的化合物中的至少一種。[15] The liquid crystal alignment agent according to [14], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the structural formula (19), structural formula (23) At least one of the compounds represented by the structural formula (37) and the structural formula (49).

[16]根據[6]～[15]中任一項所述的液晶配向劑，其特徵在於：該液晶配向劑含有所述聚醯胺酸或者其衍生物A以及B，並且所述聚醯胺酸或者其衍生物A包含所述二胺中的所述具有側鏈結構的二胺，且所述聚醯胺酸或者其衍生物A以及B的二胺中的一方或者兩方包含以通式(N)表示的二胺。[16] The liquid crystal alignment agent according to any one of [6], wherein the liquid crystal alignment agent contains the polyamic acid or derivatives A and B thereof, and the polyfluorene The amine acid or derivative A thereof comprises the diamine having a side chain structure in the diamine, and one or both of the polyamine or a derivative thereof and a diamine of B are included A diamine represented by the formula (N).

[17]根據[1]～[16]中任一項所述的液晶配向劑，其特徵在於：該液晶配向劑進一步含有選自烯基取代納迪克(nadic)醯亞胺化合物、具有自由基聚合性不飽和雙鍵的化合物、噁嗪(oxazine)化合物、噁唑啉(oxazoline)化合物以及環氧化合物中的一種或者一種以上。The liquid crystal alignment agent according to any one of [1] to [16] wherein the liquid crystal alignment agent further contains an alkenyl-substituted nadic quinone imine compound and has a radical. One or more of a compound having a polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound.

[18]根據[17]所述的液晶配向劑，其特徵在於：所述烯基取代納迪克醯亞胺化合物是選自由雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷(bis{4-(allylbicyclo[2.2.1]ept-5-ene-2,3-dicarboxyimide)phenyl}methane)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)以及N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)所組成的族群中的一種或者一種以上。[18] The liquid crystal alignment agent according to [17], wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5- Ethene-2,3-dimethylimine)phenyl}methane (bis{4-(allylbicyclo[2.2.1] ept-5-ene-2,3-dicarboxyimide)phenyl}methane), N,N'- M-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine) and N,N'-hexamethylene-bis(allylbicyclo[ 2.2.1] One or more of the group consisting of hept-5-ene-2,3-dimethylimine.

[19]根據[18]所述的液晶配向劑，其特徵在於：所述烯基取代納迪克醯亞胺化合物為雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷。[19] The liquid crystal alignment agent according to [18], wherein the alkenyl-substituted nadicilide compound is bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)phenyl}methane.

[20]根據[17]所述的液晶配向劑，其特徵在於：所述具有自由基聚合性不飽和雙鍵的化合物是選自由N,N'-亞甲基雙丙烯醯胺(N,N'-methylene bisacrylamide)、N,N'-二羥基亞乙基雙丙烯醯胺(N,N'-dihydroxyethylene bisacrylamide)、雙丙烯酸乙二酯(ethylene bisacrylate)以及4,4'-亞甲基雙(N,N-二羥基亞乙基丙烯酸酯苯胺)(4,4'-methylene bis(N,N-dihydroxyethylene acrylate aniline))所組成的族群中的一種或者一種以上。[20] The liquid crystal alignment agent according to [17], wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-methylenebis acrylamide (N, N) '-methylene bisacrylamide), N,N'-dihydroxyethylene bisacrylamide, ethylene bisacrylate, and 4,4'-methylene double ( One or more of the groups consisting of 4,4'-methylene bis(N,N-dihydroxyethylene acrylate aniline).

[21]根據[20]所述的液晶配向劑，其特徵在於：所述具有自由基聚合性不飽和雙鍵的化合物為N,N'-二羥基亞乙基雙丙烯醯胺。[21] The liquid crystal alignment agent according to [20], wherein the compound having a radical polymerizable unsaturated double bond is N,N'-dihydroxyethylenebisacrylamide.

[22]根據[17]所述的液晶配向劑，其特徵在於：所述噁嗪化合物是選自由以下述式(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)以及式(f-2)～式(f-4)表示的化合物所組成的族群中的一種或者一種以上。[22] The liquid crystal alignment agent according to [17], wherein the oxazine compound is selected from the group consisting of the following formula (b-1), formula (c-1), formula (c-3), and (c-5), formula (c-7), formula (c-9), formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula ( F-2) One or more of the group consisting of the compounds represented by the formula (f-4).

[23]根據[22]所述的液晶配向劑，其特徵在於：所述噁嗪化合物為以所述式(c-1)表示的化合物。[23] The liquid crystal alignment agent according to [22], wherein the oxazine compound is a compound represented by the formula (c-1).

[24]根據[17]所述的液晶配向劑，其特徵在於：所述噁唑啉化合物為2,2'-雙(2-噁唑啉)以及1,3-雙(4,5-二氫-2-噁唑基)苯(1,3-bis(4,5-dihydro-2-oxazolyl)benzene)中的一方或者兩方。[24] The liquid crystal alignment agent according to [17], wherein the oxazoline compound is 2,2'-bis(2-oxazoline) and 1,3-double (4,5-di One or both of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[25]根據[24]所述的液晶配向劑，其特徵在於：所述噁唑啉化合物為1,3-雙(4,5-二氫-2-噁唑基)苯。[25] The liquid crystal alignment agent according to [24], wherein the oxazoline compound is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[26]根據[17]所述的液晶配向劑，其特徵在於：所述環氧化合物是選自由N,N,N',N'-四縮水甘油基-間苯二甲胺(N,N,N',N'-tetraglycidyl-m-xylenediamine)、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(2-[4-(2,3-epoxy propoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxy propoxy]phenyl)]ethyl]henyl]ropane)、3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯(3,4-epoxy cyclohexenyl methyl-3',4'-epoxy cyclohexene carboxylate)、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物(N-phenylmaleimide-glycidyl methacrylate copolymer)以及2-(3,4-環氧環己基)乙基三甲氧基矽烷(2-(3,4-epoxy cyclohexyl)ethyl trimethoxy silane)所組成的族群中的一種或者一種以上。[26] The liquid crystal alignment agent according to [17], wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine (N, N) , N', N'-tetraglycidyl-m-xylenediamine), 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-glycidyloxy]phenyl)]ethyl]phenyl]propane (2-[4-(2,3-epoxy propoxy)phenyl]-2-[4-[1,1-bis[4 -([2,3-epoxy propoxy]phenyl)]ethyl]henyl]ropane), 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (3, 4-epoxy cyclohexenyl methyl-3', 4'-epoxy cyclohexene carboxylate), N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3, One or more of the group consisting of 2-(3,4-epoxy cyclohexyl)ethyl trimethoxy silane.

[27]根據[26]所述的液晶配向劑,其特徵在於：所述環氧化合物為3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯或者2-(3,4-環氧環己基)乙基三甲氧基矽烷。[27] The liquid crystal alignment agent according to [26], wherein the epoxy compound is 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid Ester or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

[28]一種液晶配向膜,其特徵在於：該液晶配向膜是對根據[1]～[27]中任一項所述的液晶配向劑的塗膜進行加熱而形成的。[28] A liquid crystal alignment film formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [27].

[29]一種液晶顯示元件，其具有一對基板、含有液晶分子且形成在所述一對基板間的液晶層、對液晶層施加電壓的電極、以及將所述液晶分子配向在預定方向上的液晶配向膜，此液晶顯示元件的特徵在於：所述液晶配向膜是根據[28]所述的液晶配向膜。[29] A liquid crystal display element having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and an alignment of the liquid crystal molecules in a predetermined direction A liquid crystal alignment film characterized in that the liquid crystal alignment film is the liquid crystal alignment film according to [28].

[發明效果][Effect of the invention]

根據本發明，可以提供一種離子密度高、與該離子密度的隨時間變動相對應的長期可靠性良好、可應用於各種驅動方式中的液晶顯示元件。According to the present invention, it is possible to provide a liquid crystal display element which has a high ion density and is excellent in long-term reliability corresponding to the change in the ion density with time, and can be applied to various driving methods.

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作為四羧酸二酐與二胺的反應產物的聚醯胺酸或者其衍生物。所述聚醯胺酸的衍生物是指，在製成含有溶劑的後述液晶配向劑時溶解於溶劑中的成分、且在將該液晶配向劑製成後述液晶配向膜時可以形成以聚醯亞胺作為主成分的液晶配向膜的成分。這樣的聚醯胺酸的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，更具體而言可以列舉1)聚醯胺酸的所有氨基與羧基進行脫水閉環反應而成的聚醯亞胺、2)部分地進行脫水閉環反應而成的部分聚醯亞胺、3)將聚醯胺酸的羧基轉變為酯而成的聚醯胺酸酯、4)將四羧酸二酐化合物所含的酸二酐的一部分替換為有機二羧酸來進行反應而獲得的聚醯胺酸-聚醯胺共聚物，進一步可以列舉5)使該聚醯胺酸-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。所述聚醯胺酸或者其衍生物可以是一種化合物，也可以是兩種或者兩種以上的化合物。The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. The poly-proline derivative is a component which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent which will be described later, and can be formed into a polysiloxane when the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later. A component of a liquid crystal alignment film having an amine as a main component. Examples of such a derivative of polylysine include soluble polyimine, polyphthalate, and polyamidamine, and more specifically, 1) all amino and carboxyl groups of polyglycine Polyimine which is obtained by dehydration ring closure reaction, 2) partial polyimine which is partially subjected to dehydration ring closure reaction, 3) polyphthalate which converts carboxyl group of polylysine into ester, 4 a poly-proline-polyamine copolymer obtained by replacing a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound with an organic dicarboxylic acid, and further, 5) making the poly-proline A polyamidoquinone imine obtained by subjecting a part or all of the polyamidamide copolymer to a dehydration ring-closure reaction. The polyamic acid or a derivative thereof may be one compound or two or more compounds.

所述二胺包含以下述通式(N)表示的二胺。本發明中使用的二胺可以是一種化合物，也可以是兩種或者兩種以上的化合物。The diamine contains a diamine represented by the following formula (N). The diamine used in the present invention may be one compound or two or more compounds.

通式(N)中，A1 獨立地表示一價有機基團，A2 獨立地表示一價有機基團，m表示0～3的整數，n表示0～4的整數。另外，在本發明中，鹵素包括在有機基團中。In the formula (N), A 1 independently represents a monovalent organic group, A 2 independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. Further, in the present invention, halogen is included in the organic group.

所述A1 以及A2 可以分別使用各種一價有機基團。A1 優選的是獨立地為碳數為1～10的烷基、碳數為1～10的烷氧基、乙醯胺、氟、氯或者溴。A2 優選的是獨立地為碳數為1～3的烷基。The A 1 and A 2 may each use various monovalent organic groups. A 1 is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, acetamide, fluorine, chlorine or bromine. A 2 is preferably an alkyl group independently having 1 to 3 carbon atoms.

以通式(N)表示的二胺於兩端的苯基上分別具有氨基。這些氨基的位置可以相對於呱嗪，獨立地處於鄰位、間位、對位中的任一位置。從所述二胺的製造比較容易的觀點考慮，這些氨基的位置優選的是均為對位。The diamine represented by the formula (N) has an amino group at each of the phenyl groups at both ends. The positions of these amino groups can be independently at any of the ortho, meta and para positions relative to the pyridazine. From the viewpoint that the production of the diamine is relatively easy, the positions of these amino groups are preferably all para-position.

在本發明中，以通式(N)表示的二胺例如可以列舉以下化合物。In the present invention, examples of the diamine represented by the formula (N) include the following compounds.

以所述通式(N)表示的二胺優選以所述結構式(N)-1、結構式(N)-2、結構式(N)-5～結構式(N)-7、結構式(N)-9、結構式(N)-10、結構式(N)-14、結構式(N)-17、結構式(N)-18、結構式(N)-21～結構式(N)-23、結構式(N)-26以及結構式(N)-28表示的化合物，更加優選以所述結構式(N)-1以及結構式(N)-2表示的化合物。The diamine represented by the above formula (N) is preferably represented by the structural formula (N)-1, structural formula (N)-2, structural formula (N)-5 to structural formula (N)-7, structural formula. (N)-9, structural formula (N)-10, structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structural formula (N)-21-structure formula (N And a compound represented by the structural formula (N)-26 and the structural formula (N)-28, and a compound represented by the structural formula (N)-1 and the structural formula (N)-2 is more preferable.

從使液晶顯示元件中表現出所需的離子密度、而且表現出該離子密度的長期穩定性的觀點考慮，以所述通式(N)表示的二胺在構成本發明液晶配向劑中的聚醯胺酸的二胺中，以莫耳比計優選為含有20%～100%，更加優選為含有35%～100%。The diamine represented by the above formula (N) is agglomerated in the liquid crystal alignment agent of the present invention from the viewpoint of exhibiting a desired ion density in the liquid crystal display element and exhibiting long-term stability of the ion density. The diamine of the proline is preferably contained in an amount of from 20% to 100%, more preferably from 35% to 100%, in terms of a molar ratio.

以所述通式(N)表示的二胺可以用衆所周知的方法來製造。這樣的製造方法例如可以列舉如下方法：如日本專利特開昭52-14780號公報所記載的那樣，在使用錫、鹽酸等還原劑的普通的還原條件下，將使可以具有對應的取代基的硝基苯(Nitrobenzene)或者其衍生物與呱嗪進行加熱反應所得的化合物的硝基還原為氨基。The diamine represented by the above formula (N) can be produced by a known method. For example, as described in JP-A-52-14780, it is possible to have a corresponding substituent under ordinary reducing conditions using a reducing agent such as tin or hydrochloric acid. The nitro group of the compound obtained by subjecting Nitrobenzene or a derivative thereof to a pyridine reaction is reduced to an amino group.

所述二胺可以僅包含以所述通式(N)表示的二胺，也可以進一步包含其他二胺。其他二胺例如可以列舉具有側鏈結構的二胺以及不具有側鏈結構的二胺。這樣的其他二胺可以是一種化合物，也可以是兩種或者兩種以上的化合物。The diamine may contain only the diamine represented by the above formula (N), and may further contain other diamines. Examples of the other diamine include a diamine having a side chain structure and a diamine having no side chain structure. Such other diamines may be one compound or two or more compounds.

所述具有側鏈結構的二胺是指具有如下取代基(側鏈)的二胺，該取代基在將連結兩個氨基的取代基作為主鏈時自主鏈分支，並且可以表現出所需的預傾角(pretilt angl)。具有側鏈結構的二胺中的側鏈只要根據所需要的預傾角而適當地選擇即可，例如，該側鏈可以列舉碳數為3或3以上的基團。所述具有側鏈結構的二胺可以列舉以下述通式(VIII)以及通式(X)～通式(XIII)表示的化合物。The diamine having a side chain structure means a diamine having a substituent (side chain) which branches autonomously when a substituent linking two amino groups is used as a main chain, and can exhibit desired Pretilt angl. The side chain in the diamine having a side chain structure may be appropriately selected according to the required pretilt angle. For example, the side chain may be a group having a carbon number of 3 or more. Examples of the diamine having a side chain structure include compounds represented by the following formula (VIII) and formula (X) to formula (XIII).

通式(VIII)中，A3 表示單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-或者-(CH2 )m -(m表示1～6的整數)，R1 表示具有類固醇骨架的基團、以下述通式(IX)表示的基團，而且，當苯環上所鍵合的兩個氨基的位置關係為對位時，R1 進一步包含碳數為1～30的烷基，當該位置關係為間位時，R1 進一步包含碳數為1～30的烷基或者苯基。該烷基中，任意的-CH2 -可以獨立地經-CF2 -、-CHF-、-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，-CH3 可以經-CH2 F、-CHF2 或者-CF3 所取代。而且，該苯基的氫可以獨立地被取代為-F、-CH3 、-OCH3 、-OCH2 F、-OCHF2 或者-OCF3 。In the formula (VIII), A 3 represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH 2 ) m - (m represents an integer of 1 to 6), R 1 represents a group having a steroid skeleton, a group represented by the following formula (IX), and when the positional relationship of the two amino groups bonded to the benzene ring is para, R 1 further contains a carbon number of In the alkyl group of 1 to 30, when the positional relationship is meta, R 1 further contains an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, any -CH 2 - may be independently substituted by -CF 2 -, -CHF-, -O- (here, discontinuous), -CH=CH- or -C≡C-, - CH 3 may be substituted with -CH 2 F, -CHF 2 or -CF 3 . Moreover, the hydrogen of the phenyl group may be independently substituted with -F, -CH 3 , -OCH 3 , -OCH 2 F, -OCHF 2 or -OCF 3 .

通式(IX)中，A4 以及A5 分別獨立地表示單鍵、-O-(此處為非連續)、-COO-、-OCO-、-CONH-、-CH=CH-或者碳數為1～12的亞烷基，R2 以及R3 分別獨立地表示-F或者-CH3 ，環S獨立地表示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，R4 表示-H、-F、碳數為1～30的烷基、碳數為1～30的氟取代烷基、碳數為1～30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ，a以及b分別表示0～4的整數，c、d以及e分別表示0～3的整數，f以及g分別獨立地表示0～2的整數，並且c＋d＋e≧1。In the formula (IX), A 4 and A 5 each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon number. Is an alkylene group of 1 to 12, and R 2 and R 3 each independently represent -F or -CH 3 , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or oxime-9 , 10-diyl, R 4 represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or -CN -OCH 2 F, -OCHF 2 or -OCF 3 , a and b respectively represent integers of 0 to 4, c, d and e represent integers of 0 to 3, respectively, and f and g each independently represent an integer of 0 to 2 And c+d+e≧1.

通式(X)以及(XI)中，R5 獨立地表示-H或者-CH3 ，R6 表示-H或者碳數為1～20的烷基或烯基，A6 獨立地表示單鍵、-C(=O)-或者-CH2 -。而且通式(XI)中，R7 以及R8 分別獨立地表示碳數為1～20的烷基或者苯基。In the general formulae (X) and (XI), R 5 independently represents -H or -CH 3 , R 6 represents -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A 6 independently represents a single bond, -C(=O)- or -CH 2 -. Further, in the formula (XI), R 7 and R 8 each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group.

通式(XII)以及(XIII)中，A7 獨立地表示-O-或者碳數為1～6的亞烷基。而且通式(XII)中，R9 表示-H或者碳數為1～30的烷基，該烷基中，碳數為2～30的烷基的任意的-CH2 -可以經-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，A8 表示單鍵或者碳數為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。而且，通式(XIII)中，R10 表示碳數為6～22的烷基，R11 表示碳數為1～22的烷基。In the general formulae (XII) and (XIII), A 7 independently represents -O- or an alkylene group having 1 to 6 carbon atoms. Further, in the formula (XII), R 9 represents -H or an alkyl group having 1 to 30 carbon atoms, and in the alkyl group, any -CH 2 - of the alkyl group having 2 to 30 carbon atoms may be subjected to -O- (here is discontinuous), -CH=CH- or -C≡C- is substituted, A 8 represents a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T represents 1,4-phenylene group or 1,4-cyclohexylene, h represents 0 or 1. Further, in the formula (XIII), R 10 represents an alkyl group having 6 to 22 carbon atoms, and R 11 represents an alkyl group having 1 to 22 carbon atoms.

以通式(VIII)表示的二胺例如可以列舉以下述通式(VIII-1)～通式(VIII-37)以及以結構式(VIII-38)～結構式(VIII-43)表示的二胺。Examples of the diamine represented by the formula (VIII) include the following formula (VIII-1) to formula (VIII-37) and two groups represented by the structural formula (VIII-38) to the structural formula (VIII-43). amine.

通式(VIII-1)～通式(VIII-11)中，R23 優選的是表示碳數為1～30的烷基或者碳數為1～30的烷氧基，更加優選的是表示碳數為5～25的烷基或者碳數為5～25的烷氧基。而且，R24 優選的是表示碳數為1～30的烷基或者碳數為1～30的烷氧基，更加優選的是表示碳數為3～25的烷基或者碳數為3～25的烷氧基。In the general formulae (VIII-1) to (VIII-11), R 23 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and more preferably represents carbon. The number is 5 to 25 alkyl groups or the carbon number is 5 to 25 alkoxy groups. Further, R 24 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms or a carbon number of 3 to 25 Alkoxy group.

通式(VIII-12)～通式(VIII-15)中，R25 優選的是表示碳數為4～30的烷基，更加優選的是表示碳數為6～25的烷基。通式(VIII-16)以及通式(VIII-17)中，R26 優選的是表示碳數為6～30的烷基，更加優選的是表示碳數為8～25的烷基。In the general formulae (VIII-12) to (VIII-15), R 25 preferably represents an alkyl group having 4 to 30 carbon atoms, and more preferably an alkyl group having 6 to 25 carbon atoms. In the general formula (VIII-16) and the general formula (VIII-17), R 26 preferably represents an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 8 to 25 carbon atoms.

通式(VIII-18)～通式(VIII-37)中，R27 優選的是表示碳數為1～30的烷基或者碳數為1～30的烷氧基，更加優選的是表示碳數為3～25的烷基或者碳數為3～25的烷氧基。而且，R28 優選的是表示-H、-F、碳數為1～30的烷基、碳數為1～30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ，更加優選的是表示碳數為3～25的烷基或者碳數為3～25的烷氧基。In the general formulae (VIII-18) to (VIII-37), R 27 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and more preferably represents carbon. The number is 3 to 25 alkyl groups or the alkoxy group having 3 to 25 carbon atoms. Further, R 28 preferably represents -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH 2 F, -OCHF 2 or -OCF 3 More preferably, it is an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

這些二胺中，優選以通式(VIII-1)～通式(VIII-11)表示的二胺，更加優選以通式(VIII-2)以及通式(VIII-4)～通式(VIII-6)表示的二胺。Among these diamines, a diamine represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and a formula (VIII-2) and a formula (VIII-4) to a formula (VIII) are more preferred. -6) The diamine represented.

以所述通式(X)表示的二胺優選的是，在通式(X)中兩個“NH2 -Ph-A6 -O-”中的一個鍵合於類固醇骨架的3位，另一個鍵合於6位。而且，兩個氨基分別鍵合於苯環碳上，優選的是相對於A6 的鍵合位置而鍵合在間位或者對位上。The diamine represented by the above formula (X) is preferably one of two "NH 2 -Ph-A 6 -O-" in the formula (X) bonded to the 3-position of the steroid skeleton, One is bonded to 6 digits. Further, the two amino groups are bonded to the benzene ring carbon, respectively, and are preferably bonded to the meta or para position with respect to the bonding position of A 6 .

以通式(X)表示的二胺例如可以列舉以下述結構式(X-1)～結構式(X-4)表示的二胺。The diamine represented by the formula (X) is, for example, a diamine represented by the following structural formula (X-1) to structural formula (X-4).

以所述通式(XI)表示的二胺中，在通式(XI)中兩個“NH2 -(R6 -)Ph-A6 -O-”分別鍵合於苯環的碳上，優選的是相對於類固醇骨架所鍵合的碳而鍵合於間位或者對位的碳上。而且，兩個氨基分別鍵合於苯環的碳上，優選的是相對於A6 而鍵合在間位或者對位上。In the diamine represented by the above formula (XI), in the formula (XI), two "NH 2 -(R 6 -)Ph-A 6 -O-" are bonded to the carbon of the benzene ring, respectively. It is preferred to bond to the meta or para carbon with respect to the carbon to which the steroid skeleton is bonded. Further, the two amino groups are bonded to the carbon of the benzene ring, respectively, and are preferably bonded to the meta or para position with respect to A 6 .

以通式(XI)表示的二胺例如可以列舉以下述結構式(XI-1)～結構式(XI-8)表示的二胺。The diamine represented by the formula (XI) is, for example, a diamine represented by the following structural formula (XI-1) to structural formula (XI-8).

以所述通式(XII)表示的二胺中，在通式(XII)中兩個氨基分別鍵合於苯環的碳上，優選的是相對於A7 而鍵合在間位或者對位上。In the diamine represented by the above formula (XII), in the formula (XII), two amino groups are bonded to the carbon of the benzene ring, respectively, preferably bonded to the meta or para position relative to A 7 . on.

以通式(XII)表示的二胺例如可以列舉以下述通式(XII-1)～通式(XII-8)表示的二胺。The diamine represented by the formula (XII) is, for example, a diamine represented by the following formula (XII-1) to formula (XII-8).

通式(XII-1)～通式(XII-3)中，R29 優選的是表示-H、碳數為1～30的烷基或者碳數為1～30的烷氧基，更加優選的是表示碳數為3～30的烷基或者碳數為3～30的烷氧基。而且，通式(XII-4)～通式(XII-8)中，R30 優選的是表示-H、碳數為1～30的烷基或者碳數為1～30的烷氧基，更加優選的是表示碳數為3～30的烷基或者碳數為3～30的烷氧基。In the general formulae (XII-1) to (XII-3), R 29 preferably represents -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably It is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. Further, in the general formulae (XII-4) to (XII-8), R 30 preferably represents -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably Preferably, it is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms.

以所述通式(XIII)表示的二胺中，在通式(XIII)中兩個氨基分別鍵合於苯環的碳上，優選的是相對於A7 而鍵合在間位或者對位上。In the diamine represented by the above formula (XIII), in the formula (XIII), two amino groups are bonded to the carbon of the benzene ring, respectively, preferably bonded to the meta or para position relative to A 7 . on.

以通式(XIII)表示的二胺例如可以列舉以下述通式(XIII-1)～通式(XIII-3)表示的二胺。The diamine represented by the formula (XIII) is, for example, a diamine represented by the following formula (XIII-1) to (XIII-3).

通式(XIII-1)～通式(XIII-3)中，R31 優選的是表示碳數為6～22的烷基，更加優選的是表示碳數為6～20的烷基。R32 優選的是表示-H或者碳數為1～22的烷基，更加優選的是表示碳數為1～10的烷基。In the general formulae (XIII-1) to (XIII-3), R 31 preferably represents an alkyl group having 6 to 22 carbon atoms, and more preferably an alkyl group having 6 to 20 carbon atoms. R 32 is preferably an alkyl group having -H or a carbon number of 1 to 22, and more preferably an alkyl group having 1 to 10 carbon atoms.

所述具有側鏈結構的二胺優選的是選自以通式(VIII-2)、通式(VIII-4)～通式(VIII-6)、通式(XII-2)、通式(XII-4)以及通式(XII-6)表示的化合物中的至少一種。The diamine having a side chain structure is preferably selected from the group consisting of the general formula (VIII-2), the general formula (VIII-4) to the general formula (VIII-6), the general formula (XII-2), and the general formula ( XII-4) and at least one of the compounds represented by the formula (XII-6).

從使液晶顯示元件中表現出所需的預傾角的觀點考慮，所述具有側鏈結構的二胺在構成本發明液晶配向劑中的聚醯胺酸的二胺中，以莫耳比計優選為含有1%～90%，更加優選為含有5%～70%。From the viewpoint of exhibiting a desired pretilt angle in the liquid crystal display element, the diamine having a side chain structure is preferably selected from a molar ratio of a polyamine of a polylysine constituting the liquid crystal alignment agent of the present invention. It is contained in an amount of 1% to 90%, more preferably 5% to 70%.

所述不具有側鏈結構的二胺是指不具有如下取代基(側鏈)的二胺，該取代基在將連結氨基的取代基作為主鏈時自主鏈分支，並且可以表現出所需的預傾角。所述不具有側鏈結構的二胺可以列舉以下述通式(I)～通式(VII)以及通式(XV)表示的化合物。The diamine having no side chain structure means a diamine having no substituent (side chain) which branches autonomously when a substituent linking an amino group is used as a main chain, and can exhibit a desired Pretilt angle. Examples of the diamine having no side chain structure include compounds represented by the following formula (I) to formula (VII) and formula (XV).

通式(I)中，X表示-(CH2 )m -(m表示1～6的整數)，通式(III)以及通式(V)～通式(VII)中，Y獨立地表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-NH-、-N(CH3 )-(CH2 )m -N(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m -S-(m表示1～6的整數)，通式(V)中，Z表示單鍵或者不存在，通式(XV)中，R33 以及R34 分別獨立地表示碳數為1～3的烷基或者苯基，A3 獨立地表示亞甲基、亞苯基或者經烷基取代的亞苯基。1表示1～6的整數，m表示1～10的整數，通式(II)～(VII)中，環己烷環或者苯環上所鍵合的氫可以獨立地被取代為-F、-CH3 、-CF3 、-OH、-COOH、-SO3 H、-PO3 H2 ，通式(IV)中的苯環上所鍵合的氫可以經芐基所取代。In the formula (I), X represents -(CH 2 ) m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents a single Bond, -O-, -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH 3 )-(CH 2 ) m -N( CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 ) m -, -O-(CH 2 ) m -O-, -S-(CH 2 ) m -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R 33 and R 34 each independently represent a carbon number of 1 to Alkyl or phenyl of 3 , A 3 independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group. 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the general formulae (II) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, - CH 3 , -CF 3 , -OH, -COOH, -SO 3 H, -PO 3 H 2 , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted with a benzyl group.

以通式(I)表示的二胺例如可以列舉以下述結構式(I-1)～結構式(I-3)表示的二胺。The diamine represented by the formula (I) is, for example, a diamine represented by the following structural formula (I-1) to structural formula (I-3).

以通式(II)表示的二胺例如可以列舉以下述結構式(II-1)、結構式(II-2)表示的二胺。The diamine represented by the formula (II) is, for example, a diamine represented by the following structural formula (II-1) or structural formula (II-2).

以通式(III)表示的二胺例如可以列舉以下述結構式(III-1)～結構式(III-3)表示的二胺。The diamine represented by the formula (III) is, for example, a diamine represented by the following structural formula (III-1) to structural formula (III-3).

以通式(IV)表示的二胺例如可以列舉以下述結構式(IV-1)～結構式(IV-17)表示的二胺。The diamine represented by the formula (IV) is, for example, a diamine represented by the following structural formula (IV-1) to structural formula (IV-17).

以通式(V)表示的二胺例如可以列舉以下述結構式(V-1)～結構式(V-37)表示的二胺。The diamine represented by the formula (V) is, for example, a diamine represented by the following structural formula (V-1) to structural formula (V-37).

以通式(VI)表示的二胺例如可以列舉以下述結構式(VI-1)～結構式(VI-6)表示的二胺。The diamine represented by the formula (VI) is, for example, a diamine represented by the following structural formula (VI-1) to structural formula (VI-6).

以通式(VII)表示的二胺例如可以列舉以下述結構式(VII-1)～結構式(VII-16)表示的二胺。The diamine represented by the formula (VII) is, for example, a diamine represented by the following structural formula (VII-1) to structural formula (VII-16).

以通式(XV)表示的二胺例如可以列舉以下述結構式(XV-1)表示的化合物。The diamine represented by the formula (XV) is, for example, a compound represented by the following structural formula (XV-1).

這些二胺中，所述不具有側鏈結構的二胺優選以結構式(IV-1)～結構式(IV-5)、結構式(IV-15)～結構式(IV-17)、結構式(V-1)～結構式(V-12)、結構式(V-26)、結構式(V-27)、結構式(V-31)、結構式(V-33)、結構式(V-35)～結構式(V-37)、結構式(VI-1)、結構式(VI-2)、結構式(VI-6)、結構式(VII-1)～結構式(VII-5)以及結構式(XV -1)表示的二胺，更加優選以結構式(IV-1)、結構式(IV-2)、結構式(IV-15)～結構式(IV-17)、結構式(V-1)～結構式(V-12)、結構式(V-33)、結構式(V-35)～結構式(V-37)、結構式(VII-2)以及結構式(XV-1)表示的二胺。Among these diamines, the diamine having no side chain structure preferably has a structural formula (IV-1) to a structural formula (IV-5), a structural formula (IV-15) to a structural formula (IV-17), and a structure. Formula (V-1) to Structural Formula (V-12), Structural Formula (V-26), Structural Formula (V-27), Structural Formula (V-31), Structural Formula (V-33), Structural Formula ( V-35) to structural formula (V-37), structural formula (VI-1), structural formula (VI-2), structural formula (VI-6), structural formula (VII-1) to structural formula (VII- 5) and the diamine represented by the structural formula (XV-1), more preferably, the structural formula (IV-1), the structural formula (IV-2), the structural formula (IV-15) to the structural formula (IV-17), Structural formula (V-1) to structural formula (V-12), structural formula (V-33), structural formula (V-35) to structural formula (V-37), structural formula (VII-2), and structural formula The diamine represented by (XV-1).

從使液晶顯示元件中表現出離子密度等所需的電特性的觀點考慮，所述不具有側鏈結構的二胺在構成本發明液晶配向劑中的聚醯胺酸的二胺中，以莫耳比計優選為含有1%～98%，更加優選為含有10%～95%。The diamine having no side chain structure is a diamine of a poly-proline which constitutes the liquid crystal alignment agent of the present invention, from the viewpoint of exhibiting an electric property required for an ion density or the like in the liquid crystal display element. The ear ratio meter preferably contains from 1% to 98%, more preferably from 10% to 95%.

本發明中的二胺可以使用所述的以通式(I)～通式(VIII)以及通式(X)～通式(XIII)表示的二胺以外的其他二胺。這樣的其他二胺例如可以列舉：具有萘結構的萘系二胺、具有芴(fluorene)結構的芴系二胺、以及通式(VIII)～(XII)以外的具有側鏈結構的二胺。The diamine other than the diamine represented by the general formula (I) to the general formula (VIII) and the general formula (X) to the general formula (XIII) can be used as the diamine in the present invention. Examples of such other diamines include naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and diamines having a side chain structure other than the general formulae (VIII) to (XII).

其他二胺例如可以列舉以下述通式(1')～通式(8')表示的化合物。Examples of the other diamines include compounds represented by the following general formulae (1') to (8').

通式(1')～通式(8')中，R35 以及R36 分別獨立地表示碳數為3～30的烷基。In the general formulae (1') to (8'), R 35 and R 36 each independently represent an alkyl group having 3 to 30 carbon atoms.

在構成本發明液晶配向劑中的聚醯胺酸的二胺中，所述其他二胺可以在不損及本發明效果的程度的範圍內使用。In the diamine constituting the polyproline in the liquid crystal alignment agent of the present invention, the other diamine can be used within the range not to the extent that the effects of the present invention are impaired.

對於所述二胺來說，可以在各二胺中單胺(monoamine)相對於二胺的比率為40莫耳%或者40莫耳%以下的範圍內，將一部分二胺替換為單胺。這樣的替換能够引起生成聚醯胺酸時的聚合反應的終止(termination)，從而能句多抑制聚合反應的進一步進行。因此，通過這樣的替換，可以容易地控制所獲得的聚合物(聚醯胺酸或者其衍生物)的分子量，例如，可以不損及本發明的效果而改善液晶配向劑的塗布特性。只要不損及本發明的效果，則替換為單胺的二胺可以是一種，也可以是兩種或兩種以上。所述單胺例如可以列舉：苯胺、4-羥基苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一胺、正十二胺、正十三胺、正十四胺、正十五胺、正十六胺、正十七胺、正十八胺以及正二十胺。For the diamine, a part of the diamine may be replaced with a monoamine in a range of 40 mol% or 40 mol% or less of the monoamine to the diamine in each diamine. Such substitution can cause termination of the polymerization reaction in the formation of poly-proline, so that the polymerization can be further inhibited. Therefore, by such substitution, the molecular weight of the obtained polymer (polylysine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-decylamine. , n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine and n-dodecylamine.

本發明中使用的四羧酸二酐可以是一種化合物，也可以是兩種或者兩種以上的化合物。所述四羧酸可以列舉芳香族四羧酸二酐、脂環式四羧酸二酐以及脂肪族四羧酸二酐。The tetracarboxylic dianhydride used in the present invention may be one compound or two or more compounds. Examples of the tetracarboxylic acid include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride.

所述芳香族四羧酸二酐，是兩個酸酐中的至少一個為由鍵合於芳香族化合物上的兩個羧基所得的酸酐的化合物。所述芳香族四羧酸二酐例如可以列舉以下述結構式(1)～結構式(18)表示的化合物。The aromatic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride obtained by bonding two carboxyl groups bonded to the aromatic compound. Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following structural formulae (1) to (18).

所述芳香族四羧酸二酐優選以所述結構式(1)、結構式(2)、結構式(5)～結構式(7)以及結構式(14)表示的化合物，更加優選以所述結構式(1)表示的化合物。The aromatic tetracarboxylic dianhydride is preferably a compound represented by the structural formula (1), the structural formula (2), the structural formula (5) to the structural formula (7), and the structural formula (14), and more preferably The compound represented by the structural formula (1).

所述脂環式四羧酸二酐，是兩個酸酐中的至少一個為由鍵合於脂環式化合物上的兩個羧基所得的酸酐的化合物。所述脂環式四羧酸二酐例如可以列舉以下述結構式(19)～結構式(22)、結構式(24)～結構式(44)以及結構式(49)～結構式(65)表示的化合物。The alicyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride obtained by bonding two carboxyl groups bonded to the alicyclic compound. Examples of the alicyclic tetracarboxylic dianhydride include the following structural formulae (19) to (22), structural formulas (24) to (44), and structural formulae (49) to (65). The compound represented.

所述脂環式四羧酸二酐優選以所述結構式(19)、結構式(25)、結構式(35)～結構式(37)、結構式(39)、結構式(44)以及結構式(49)表示的化合物，更加優選以所述結構式(19)、結構式(37)以及結構式(49)表示的化合物。The alicyclic tetracarboxylic dianhydride preferably has the structural formula (19), structural formula (25), structural formula (35) to structural formula (37), structural formula (39), structural formula (44), and The compound represented by the structural formula (49) is more preferably a compound represented by the above structural formula (19), structural formula (37) and structural formula (49).

所述脂肪族四羧酸二酐，是具有兩個由鍵合於脂肪族化合物上的兩個羧基所得的酸酐的化合物。所述脂肪族四羧酸二酐例如可以列舉以下述結構式(23)、結構式(45)～結構式(48)、結構式(66)以及結構式(67)表示的化合物。The aliphatic tetracarboxylic dianhydride is a compound having two acid anhydrides obtained by bonding two carboxyl groups bonded to an aliphatic compound. Examples of the aliphatic tetracarboxylic dianhydride include compounds represented by the following structural formula (23), structural formula (45) to structural formula (48), structural formula (66), and structural formula (67).

所述脂肪族四羧酸二酐優選以所述結構式(23)表示的化合物。The aliphatic tetracarboxylic dianhydride is preferably a compound represented by the structural formula (23).

所述四羧酸二酐也可以使用以結構式(1)～結構式(67)表示的四羧酸二酐以外的其他四羧酸二酐。其他四羧酸二酐例如可以列舉具有側鏈結構的四羧酸二酐。通過使用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。As the tetracarboxylic dianhydride, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the structural formulae (1) to (67) can be used. Examples of the other tetracarboxylic dianhydride include tetracarboxylic dianhydride having a side chain structure. By using a tetracarboxylic dianhydride having a side chain structure, the pretilt angle of the liquid crystal display element can be increased.

具有側鏈結構的四羧酸二酐例如可以列舉以下述結構式(68)以及結構式(69)表示的具有類固醇骨架的化合物。Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having a steroid skeleton represented by the following structural formula (68) and structural formula (69).

所述四羧酸二酐可以在實現本發明效果的範圍內使用任意的種類和調配量。The tetracarboxylic dianhydride may be used in any kind and blending amount within the range in which the effects of the present invention are achieved.

也可以將所述四羧酸二酐的一部分替換為羧酸單酐。這樣的替換能夠引起生成聚醯胺酸時的聚合反應的終止，從而能够抑制聚合反應的進一步進行。因此，通過這樣的替換，可以容易地控制所獲得的聚合物(聚醯胺酸或者其衍生物)的分子量，例如，可以不損及本發明的效果而改善液晶配向劑的塗布特性。羧酸酐相對於四羧酸二酐的比率只要在不損及本發明效果的範圍內即可，其基準優選的是總四羧酸二酐量的10莫耳%或10莫耳%以下。只要不損及本發明的效果，則替換為羧酸酐的四羧酸二酐可以是一種，也可以是兩種或者兩種以上。所述羧酸單酐例如可以列舉：馬來酸酐、鄰苯二甲酸酐、衣康酸酐(itaconic anhydride)、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐、正十六烷基琥珀酸酐以及環己酸酐。It is also possible to replace a part of the tetracarboxylic dianhydride with a carboxylic acid monoanhydride. Such replacement can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymer (polylysine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride may be within the range not impairing the effects of the present invention, and the basis thereof is preferably 10 mol% or 10 mol% or less of the total amount of the tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is replaced with a carboxylic anhydride may be one type or two or more types as long as the effect of the present invention is not impaired. Examples of the carboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, N-hexadecyl succinic anhydride and cyclohexanoic anhydride.

所述四羧酸二酐可以在二羧酸相對於四羧酸二酐的比率為10莫耳%或10莫耳%以下的範圍內，將一部分四羧酸二酐替換為二羧酸。只要不損及本發明的效果，則替換為二羧酸的四羧酸二酐可以是一種，也可以是兩種或兩種以上。The tetracarboxylic dianhydride may be substituted with a portion of the tetracarboxylic dianhydride to the dicarboxylic acid in a range of 10 mol% or 10 mol% or less of the dicarboxylic acid to the tetracarboxylic dianhydride. The tetracarboxylic dianhydride substituted with a dicarboxylic acid may be one type or two or more types as long as the effects of the present invention are not impaired.

所述聚醯胺酸或者其衍生物的單體中也可以進一步包含單異氰酸酯(monoisocyanate)化合物。通過使單體中包含單異氰酸酯化合物，所獲得的聚醯胺酸或者其衍生物的末端得到修飾，分子量得以調節。通過使用此末端修飾型聚醯胺酸或者其衍生物，例如可以不損及本發明的效果而改善液晶配向劑的塗布特性。從所述觀點考慮，單體中的單異氰酸酯化合物的含量優選的是相對於單體中的二胺以及四羧酸二酐的總量而為1莫耳%～10莫耳%。所述單異氰酸酯化合物例如可以列舉異氰酸苯酯以及異氰酸萘酯。The monomer of the polyamic acid or a derivative thereof may further contain a monoisocyanate compound. By including a monoisocyanate compound in the monomer, the terminal of the obtained polyglycine or a derivative thereof is modified, and the molecular weight is adjusted. By using this terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From the viewpoint of the above, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

所述聚醯胺酸或者其衍生物除了使用以通式(N)表示的二胺以外，可以與聚醯亞胺的膜形成中所使用的衆所周知的聚醯胺酸或者其衍生物同樣地製造。四羧酸二酐的總添加量優選的是與二胺的總莫耳數大致為等莫耳(莫耳比為0.9～1.1左右)。The polyamic acid or a derivative thereof may be the same as the well-known polyperglycine or derivative thereof used in the formation of a film of polyimine, in addition to the diamine represented by the general formula (N). Made in the field. The total amount of the tetracarboxylic dianhydride added is preferably about the same as the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

所述聚醯胺酸或者其衍生物的分子量以聚苯乙烯換算的重量平均分子量(Mw)計，優選為10,000～500,000，更加優選為20,000～200,000。所述聚醯胺酸或者其衍生物的分子量可以通過利用凝膠滲透色譜(Gel Permeation Chromatography，GPC)法進行測定而求出。The molecular weight of the polyamic acid or a derivative thereof is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or a derivative thereof can be determined by measurement by a gel permeation chromatography (GPC) method.

對於所述聚醯胺酸或者其衍生物，可以通過對用大量不良溶劑進行沉澱而獲得的固體成分實行紅外光譜(Infrared spectroscopy，IR)、核磁共振(Nuclear Magnetic Resonance，NMR)分析來確認其存在。而且，可以通過對用KOH或NaOH等強鹼的水溶液對所述聚醯胺酸或者其衍生物的分解物的有機溶劑進行萃取所得的萃取物實行氣相色譜(Gas Chromatography，GC)、高效液相色譜(High Performance Liquid Chromatography，HPLC)或者氣相色譜-質譜(Gas Chromatograph-Mass Spectrometer，GC-MS)分析，來確認所使用的單體。For the polyamic acid or a derivative thereof, the solid component obtained by precipitating with a large amount of poor solvent can be confirmed by infrared spectroscopy (IR) or nuclear magnetic resonance (NMR) analysis. . Further, gas chromatography (Gas Chromatography, GC), high-efficiency liquid can be carried out by extracting an extract obtained by extracting an organic solvent of a polylysine or a derivative of a derivative thereof with an aqueous solution of a strong alkali such as KOH or NaOH. The cells used were confirmed by high performance liquid Chromatography (HPLC) or gas chromatography-mass spectrometer (GC-MS) analysis.

本發明的液晶配向劑可以進一步含有所述聚醯胺酸或者其衍生物以外的其他成分。其他成分可以是一種，也可以是兩種或者兩種以上。The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid or a derivative thereof. The other components may be one type or two or more types.

例如，從使液晶顯示元件的電特性長期穩定的觀點考慮，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化合物。所述烯基取代納迪克醯亞胺化合物可以是一種化合物，也可以是兩種或者兩種以上的化合物。從所述觀點考慮，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，優選為0.01～1.00，更加優選為0.01～0.70，進一步優選為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 nadic ylidene imine 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, more preferably 0.01, based on the weight ratio of the poly-proline or the derivative thereof in the liquid crystal alignment agent. ～0.70, more preferably 0.01 to 0.50.

所述烯基取代納迪克醯亞胺化合物優選可以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)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、碳數為1～12的烷基、碳數為3～6的烯基、碳數為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表示碳數為1～12的烷基、碳數為2～6的烯基、碳數為5～8的環烷基、碳數為6～12的芳基、苄基、以-Z1 -(O)q -(Z2 O)r -Z3 -H(Z1 、Z2 以及Z3 獨立地表示碳數為2～6的亞烷基，q表示0或者1，而且r表示1～30的整數)表示的基團、以-(Z4 )s -B-Z5 -H(Z4 以及Z5 獨立地表示碳數為1～4的亞烷基或者碳數為5～8的環亞烷基，B表示亞苯基，而且s表示0或者1)表示的基團、以-B-T-B-H(B表示亞苯基，而且T表示-CH2 -、-C(CH3 )2 -、-O-、-CO-、-S-或者SO2 -)表示的基團、或者這些基團的1個～3個氫經羥基所取代的基團。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 -(O) 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 represents 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 carbon number Is a cycloalkylene group of 5-8, 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 -, -C(CH) 3 ) a group represented by 2 -, -O-, -CO-, -S- or SO 2 -), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group.

此時，優選的W是碳數為1～8的烷基、碳數為3～4的烯基、環己基、苯基、芐基、碳數為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個氫經羥基所取代的基團。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. a phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenephenyl group, and a group in which one or two hydrogens of these groups are substituted with a hydroxyl group.

當通式(Ina)中n=2時，W表示碳數為2～20的亞烷基、碳數為5～8的環亞烷基、碳數為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)表示的基團、以-Z4 -B-Z5 -(Z4 、Z5 以及B的含義如上所述)表示的基團、以-B-(O-B)s -T-(B-O)s -B-(B表示亞苯基，T表示碳數為1～3的亞烷基、-O-或者-SO2 -，s表示0或者1)表示的基團、或者這些基團的1個～3個氫經羥基所取代的基團。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 and r meaning as described above) is a group represented to -Z 4 -BZ 5 - (Z 4 , Z 5 and B The meaning of the group as described above, with -B-(OB) s -T-(BO) s -B- (B represents a phenylene group, and T represents an alkylene group having a carbon number of 1 to 3, - 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 with a hydroxyl group.

此時，優選的W是碳數為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 表示碳數為2～6的亞烷基，r表示1或者2)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 -)表示的基團、以-B-O-B-C3 H6 -B-O-B-(B表示亞苯基)表示的基團、以及這些基團的1個或者2個氫經羥基所取代的基團。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 -CH a group represented by 2 -, -O- or -SO 2 -), a group represented by -BOBC 3 H 6 -BOB- (B represents a phenylene group), and 1 or 2 hydrogen groups of these groups a group substituted 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號公報所記載的那樣，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小時而合成所得的化合物；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 resulting compound is synthesized in 0.5 hour to 20 hours; or a commercially available compound. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺(N-methyl-allylbicyclo[2.2.1]hept-5-ene-2，3-dicarboximide)、N-甲基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-甲基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-甲基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-乙基己基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-乙基己基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-烯丙基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-異丙烯基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-環己基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苯基-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-苄基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2-羥基乙基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,2-二甲基-3-羥基丙基)-烯丙基雙環[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)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(2,3-二羥基丙基)-烯丙基雙環[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)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基-1-丙烯基)-烯丙基雙環[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)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(4-羥基苯基)-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(3-羥基苯基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(對羥基芐基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-烯丙基雙環[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(甲基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基甲基雙環[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]-烯丙基雙環[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)雙環[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]-甲基烯丙基雙環[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}-烯丙基雙環[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)雙環[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}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、以及它們的低聚物(oligomer)；N-methyl-allyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine (N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide), N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methyl-methylallylbicyclo[2.2.1 Hept-5-ene-2,3-dimethylimine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-ethylhexyl)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-methylallyl bicyclo [2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , N-cyclohexyl- Propyl (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-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-methylallylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, 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-dimethyl-3-hydroxypropyl)-allyl Bicyclo[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-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine, N-(2,3-dihydroxypropyl)-allyl (A 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-dimethylimine, N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(4-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(3-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, 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]heptane- 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- Alkene-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-hydroxyphenylisopropylidene)phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Terpenoids, and their oligomers (oligomers);

N,N'-亞乙基-雙(烯丙基雙環[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-dicarboximide))、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、1,2-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、1,2-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、1，2-雙{3'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙烷、雙[2'-{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙基]醚、雙[2'-{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}乙基]醚、1,4-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}丁烷、1,4-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}丁烷、N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2，3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[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-(烯丙基甲基雙環[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-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、1,6-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-3-羥基-己烷、1,12-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-3,6-二羥基-十二烷、1,3-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-5-羥基-環己烷、1,5-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)丙氧基}-3-羥基-戊烷、1,4-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2-羥基-苯、1,4-雙(烯丙基甲基雙環[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(烯丙基雙環[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(烯丙基雙環[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(甲基烯丙基雙環[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(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[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-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-2-羥基-苯基}甲烷、雙{3-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-4-羥基-苯基}醚、雙{3-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)-5-羥基-苯基}碸、1,1,1-三{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)}苯氧基甲基丙烷、N,N',N"-三(亞乙基甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)異氰尿酸酯，以及它們的低聚物等。N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine) (N,N'-ethylene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboximide)), N,N'-ethylidene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino), N,N'-ethylene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-triam Methyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-hexamethylene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine), N,N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N, N'-docamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-cyclohexylene-double ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)propoxy}ethane, 1,2-bis{3'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine) propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}ethyl ]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}ethyl]ether, 1 ,4-double {3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}butane, 1,4-double {3'- (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}butane, N,N'-p-phenylene-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) , N, N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-{(1- Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-xylene Base-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-carboximine), N,N'-m-xylylene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), 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-dimethylimine)phenoxy}benzene 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, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, Double {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, {4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine)phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}anthracene, 1,6-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium imine) propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2- Hydroxy-benzene, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2,5-dihydroxy-benzene, N,N '-p-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-( 2-hydroxy) xylylene-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dimethylpyrene Amine), N,N'-m-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N, N'-m-(2-hydroxy)xylylene-bis(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-carboximine), 2,2-bis[4 -{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(ene Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine)}phenoxymethylpropane, N,N',N"-tris(ethylidenemethylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Iridium imide) isocyanurate, and oligomers thereof and the like.

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

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(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[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-(烯丙基甲基雙環[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-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}碸。N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), 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'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N '-Cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), 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-carboximine), N,N'-m-xylylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-di Amidoxime)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine 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-dimethylimineimine)phenyl}methane, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}methane, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}ether, double {4- (Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine)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}anthracene.

以下列舉更加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(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-對亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、N,N'-間亞二甲苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[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-(烯丙基甲基雙環[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-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷。N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), 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'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N '-Cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), 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-carboximine), N,N'-m-xylylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-di Amidoxime)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine 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-dimethylimineimine)phenyl}methane, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}methane, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}methane.

而且，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以結構式(Ina-1)表示的雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、以結構式(Ina-2)表示的N,N'-間亞二甲苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)、以及以結構式(Ina-3)表示的N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)。Further, a particularly preferred alkenyl-substituted nadicylimine compound can be exemplified by the following double {4-(allylbicyclo[2.2.1]hept-5-ene represented by the structural formula (Ina-1). 2,3-dimethylimine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5 represented by the structural formula (Ina-2) -ene-2,3-dimethylimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5- represented by the structural formula (Ina-3) Alkene-2,3-dimethylimine).

而且，例如從使液晶顯示元件的電特性長期穩定的觀點考慮，本發明的液晶配向劑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是一種化合物，也可以是兩種或者兩種以上的化合物。另外，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。從所述觀點考慮，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，優選為0.01～1.00，更加優選為0.01～0.70，進一步優選為0.01～0.50。Further, 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 kind of compound or two or more types of compounds. Further, the alkenyl-substituted nadic quinone imine compound is not included in the compound having a radical polymerizable unsaturated double bond. From the viewpoint 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 polyamic acid or a derivative thereof. More preferably, it is 0.01 to 0.50.

另外，從降低液晶顯示元件的離子密度、抑制離子密度的隨時間增大、而且抑制殘像的觀點考慮，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，優選為0.1～10，更加優選為0.5～5。Further, from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase of the ion density with time, and suppressing the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with the alkenyl group in the nadic ylidene compound. The ratio is preferably from 0.1 to 10, and 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()。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或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) acrylate, a (meth) acrylamide 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)丙烯酸芐酯、(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 cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (methyl). Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate 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.

三官能或者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-二羥基亞乙基丙烯酸酯苯胺)、ARONIX M-400、ARONIX M-405、ARONIX M-450、ARONIX M-7100、ARONIX M-8030、ARONIX M-8060、KAYARAD TMPTA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-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 trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline), ARONIX M- 400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, And VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

(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 acryla mide)，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 acryla mide, 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-propylene decyl acridine (N- Acryloyl piperidine), N-acryloyl pyrrolidine, N,N'-methylenebis acrylamide, N,N'-ethylenebis acrylamide, N,N'-di Hydroxyethylene bis acrylamide, N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl) Methyl acrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3- (two Aminoamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methylpropenamide, N-benzyl-2- Methyl acrylamide and N,N'-methylene bis methacrylamide.

所述的(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-二羥基亞乙基丙烯酸酯苯胺)。Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bisacrylamide, ethylene diacrylate, and 4 are particularly preferable. , 4'-methylenebis(N,N-dihydroxyethylene acrylate aniline).

雙馬來醯亞胺例如可以列舉：KI CHEMICAL INDUSTRY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 CHEMICAL INDUSTRY Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, and 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是一種化合物，也可以是兩種或者兩種以上的化合物。從所述觀點考慮，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，優選為0.1重量%～50重量%，更加優選為1重量%～40重量%，進一步優選為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. From the above viewpoints, 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 to 40% by weight, more preferably 1% by weight to 20% by weight.

所述噁嗪化合物優選的是，可溶於溶解聚醯胺酸或者其衍生物的溶劑中、而且具有開環聚合性的噁嗪化合物。The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves polyglycine or a derivative thereof and which has ring-opening polymerizability.

而且，所述噁嗪化合物中的噁嗪結構的數量並無特別限定。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。本發明中，噁嗪的結構並無特別限定，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團的芳香族基團的噁嗪結構。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 include a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The oxazine structure of the aromatic group.

所述噁嗪化合物例如可以列舉下述通式(a)～通式(f)所表示的化合物。另外，下述通式中，朝向環的中心所表示的鍵，表示鍵合於構成環並且能够鍵合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 by the center of the ring means that it is bonded to any of the carbon constituting the ring and capable of bonding the substituent.

所述通式(a)～通式(c)中，R1 以及R2 表示碳數為1～30的有機基團。而且，所述通式(a)～通式(f)中，R3 至R6 表示氫或者碳數為1～6的烴基。而且所述通式(c)、通式(d)以及通式(f)中，X表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m -S-。此處m為1～6的整數。而且，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 -或者碳數為1～3的亞烷基。所述Y的鍵合於苯環、萘環上的氫可以獨立地被取代為-F、-CH3 、-OH、-COOH、-SO3 H、-PO3 H2 。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 -, -NHCO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 ) m -, -O-(CH 2 ) m -O-, -S-(CH 2 ) m -S-. 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 .

而且，所述噁嗪化合物中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.

以通式(a)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 優選碳數為1～30的烷基，更加優選碳數為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.

以通式(b)表示的噁嗪化合物可以例如以下的噁嗪化合物。The oxazine compound represented by the formula (b) may, for example, be the following oxazine compound.

式中，R1 優選碳數為1～30的烷基，更加優選碳數為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.

以通式(c)表示的噁嗪化合物可以列舉以下述通式(I)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 (I).

所述通式(I)中，R1 以及R2 表示碳數為1～30的有機基團，R3 至R6 表示氫或者碳數為1～6的烴基，X表示單鍵、-CH2 -、-C(CH3 )2 -、-CO-、-O-、-SO2 -或者-C(CF3 )2 -。以所述通式(I)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 -. The oxazine compound represented by the above formula (I) is exemplified by the following oxazine compound.

式中，R1 優選碳數為1～30的烷基，更加優選碳數為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.

以通式(d)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.

以通式(e)表示的噁嗪化合物例如可以列舉以下的噁嗪化合物。The oxazine compound represented by the formula (e) includes, for example, the following oxazine compounds.

以通式(f)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，更加優選的是，可以列舉以式(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)表示的噁嗪化合物。Among these oxazine compounds, more preferably, formula (b-1), formula (c-1), formula (c-3), formula (c-5), formula (c-7), or formula (c-9), the evil represented by the formula (d-1) to the formula (d-6), the formula (e-3), the formula (e-4), and the formula (f-2) to the formula (f-4) Azin compound.

所述噁嗪化合物可以用與國際公開2004/009708號小冊子、日本專利特開平11-12258號公報、日本專利特開2004-352670號公報所述的方法相同的方法來製造。The oxazine compound can be produced by the same method as that described in the pamphlet of International Publication No. 2004/009708, Japanese Patent Laid-Open No. Hei 11-12258, and Japanese Patent Laid-Open No. 2004-352670.

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

而且，以通式(b)表示的噁嗪化合物可以通過以下的方法而獲得：使用將伯胺緩緩添加到甲醛中的方法進行反應之後，添加具有萘酚(naphthol)系羥基的化合物進行反應(參照國際公開2004/009708號小冊子)。Further, the oxazine compound represented by the formula (b) can be obtained by a method of slowly adding a primary amine to formaldehyde, and then adding a compound having a naphthol-based hydroxyl group to carry out a reaction. (Refer to International Publication No. 2004/009708 booklet).

而且，以通式(c)表示的噁嗪化合物可以通過以下的方法而獲得：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、相對於其一個酚性羥基至少為2莫耳或者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號小冊子和日本專利特開平11-12258號公報)。Further, the oxazine compound represented by the general formula (c) can be obtained by the following method: in the presence of an aliphatic secondary amine, an aliphatic tertiary amine or a basic nitrogen-containing heterocyclic compound in an organic solvent, 1 The mol phenol compound is reacted with respect to one aldehyde having at least 2 mol or more of phenolic hydroxyl groups, and 1 mol of the amine (refer to International Publication No. 2004/009708 pamphlet and Japanese Patent Laid-Open No. 11-12258 Bulletin).

而且，以通式(d)～通式(f)表示的噁嗪化合物可以通過以下的方法而獲得：使4,4'-二氨基二苯基甲烷等具有多個苯環和鍵合這些苯環的有機基團的二胺、福爾馬林(formalin)等醛以及苯酚在正丁醇中，在90℃或90℃以上的溫度下進行脫水縮合反應(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 having a plurality of benzene rings and bonding benzene with 4,4'-diaminodiphenylmethane or the like. a diamine of a ring organic group, an aldehyde such as formalin, or a phenol in a n-butanol, and a dehydration condensation reaction at a temperature of 90 ° C or higher (refer to Japanese Patent Laid-Open No. 2004-352670) Bulletin).

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是一種化合物，也可以是兩種或者兩種以上的化合物。從所述觀點考慮，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，優選為0.1重量%～50重量%，更加優選為1重量%～40重量%，進一步優選為1重量%～20重量%。或者，從上述觀點來說，所述噁唑啉化合物的含量優選的是，將噁唑啉化合物中的噁唑啉結構換算為噁唑啉時，相對於所述聚醯胺酸或者其衍生物而為0.1重量%～40重量%。Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. From the viewpoint 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 the polyaminic acid or a derivative thereof, and further preferably It is 1% by weight to 20% by weight. Alternatively, from the above viewpoint, the content of the oxazoline compound is preferably such that when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the poly-proline or a derivative thereof is used. It is from 0.1% by weight to 40% by weight.

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。而且，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，優選的是具有兩個或兩個以上的噁唑啉結構。而且，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。The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more oxazoline structures in one compound. Further, the oxazoline compound may have one oxazoline structure 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的是，存在於噁唑啉化合物中以使噁唑啉結構中的氧以及氮中的一方或者兩方與聚醯胺酸的羰基可以進行反應的結構。The oxazoline structure is preferably present in the oxazoline compound such that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polylysine.

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(1,2,4-tris-(2-oxazolinyl-2)-benzene)、4-呋喃-2-基亞甲基-2-苯基-4H-噁唑-5-酮(4-furan-2-yl methylene-2-phenyl-4H-oxazole-5-one)、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-芐基-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)。除這些噁唑啉化合物以外，也可以列舉如EPOCROS(商品名,日本催化劑股份有限公司製造)那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) and 1,2,4-tris-(2-oxazolinyl-2)-benzene (1,2,4). -tris-(2-oxazolinyl-2)-benzene), 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one (4-furan-2-yl methylene-2- phenyl-4H-oxazole-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'-isopropylene Bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline) and 2,2'-methylenebis(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 Catalyst Co., Ltd.) may be mentioned.

更加優選的所述噁唑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 preferably, the oxazoline compound is exemplified by 2,2'-bis(2-oxazoline) and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

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環氧化合物。所述環氧化合物可以是一種化合物，也可以是兩種或者兩種以上的化合物。從所述觀點考慮，所述環氧化合物的含量相對於所述聚醯胺酸或者其衍生物，優選為0.1重量%～50重量%，更加優選為1重量%～40重量%，進一步優選為1重量%～20重量%。Further, for example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The epoxy compound may be one compound or two or more compounds. From the above viewpoints, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, based on the polyamic acid or a derivative thereof, and further preferably 1% by weight to 20% by weight.

環氧化合物可以列舉分子內具有一個或者兩個或兩個以上環氧環的各種化合物。分子內具有一個環氧環的化合物例如可以列舉：苯基縮水甘油醚、丁基縮水甘油醚、3,3,3-三氟甲基環氧丙烷(3,3,3-trifluoro propylene oxide)、氧化苯乙烯(styrene oxide)、六氟環氧丙烷、氧化環己烯(cyclohexene oxide)、3-縮水甘油氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、N-縮水甘油基鄰苯二甲醯亞胺、(九氟-N-丁基)環氧化物((nonafluoro-N-butyl)epoxide)、全氟乙基縮水甘油醚、表氯醇(epichlorohydrin)、表溴醇、N,N-二縮水甘油基苯胺以及3-[2-(全氟己基)乙氧基]-1,2-環氧丙烷。The epoxy compound may be exemplified by various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, and 3,3,3-trifluoro propylene oxide. Styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxy decane, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, table Epichlorohydrin, epibromohydrin, N,N-diglycidylaniline and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane.

分子內具有兩個環氧環的化合物例如可以列舉：乙二醇二縮水甘油醚(ethyleneglycol diglycidyl ether)、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯以及3-(N,N-二縮水甘油基)氨基丙基三甲氧基矽烷。Examples of the compound having two epoxy rings in the molecule include ethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 3, 4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

分子內具有三個環氧環的化合物例如可以列舉：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(商品名“TECHMORE VG3101L”，(三井化學)公司製造)。Examples of the compound having three epoxy rings in the molecule include 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "TECHMORE VG3101L", manufactured by Mitsui Chemicals Co., Ltd.).

分子內具有四個環氧環的化合物例如可以列舉：1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N',N'-四縮水甘油基-間苯二甲胺、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'-二氨基二苯基甲烷以及3-(N-烯丙基-N-縮水甘油基)氨基丙基三甲氧基矽烷。Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl group- M-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diamino Diphenylmethane and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

除所述化合物以外，分子內具有環氧環的化合物的例子也可以列舉具有環氧環的低聚物或聚合物。具有環氧環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-環氧環己酯以及(甲基)丙烯酸甲基縮水甘油酯。In addition to the compound, examples of the compound having an epoxy ring in the molecule include an oligomer or a polymer having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

與具有環氧環的單體進行共聚合的其他單體，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)丙烯酸芐酯、(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。Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-epoxypropane)methyl (meth)acrylate N-cyclohexylmaleimide and N-phenylmaleimide.

具有環氧環的單體的聚合物的優選具體例，可以列舉聚甲基丙烯酸縮水甘油酯等。而且，具有環氧環的單體與其他單體的共聚物的優選具體例，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、甲基丙烯酸芐酯-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。Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmalanium. Imine-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate a glycidyl methacrylate copolymer, a (3-ethyl-3-epoxypropenyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

這些例子中，特別優選N,N,N',N'-四縮水甘油基-間苯二甲胺、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“TECHMORE VG3101L”、3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物以及2-(3,4-環氧環己基)乙基三甲氧基矽烷。Among these examples, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N are particularly preferred. ,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "TECHMORE VG3101L", 3,4-epoxycyclohexenylmethyl-3',4 '-Epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

更加系統地來說，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、異氰尿酸縮水甘油酯、鏈狀脂肪族型環氧化合物以及環狀脂肪族型環氧化合物。另外，環氧化合物是指具有環氧基的化合物，環氧樹脂是指具有環氧基的樹脂。More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, and chain fat. A family of epoxy compounds and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

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、苯酚酚醛清漆(phenol novolac)型環氧化合物、甲酚酚醛清漆(cresol novolac)型環氧化合物、溴化苯酚酚醛清漆型環氧化合物、溴化甲酚酚醛清漆型環氧化合物、雙酚A酚醛清漆型環氧化合物、含萘骨架的環氧化合物、芳香族聚縮水甘油醚化合物、雙環戊二烯酚型環氧化合物、脂環式二縮水甘油醚化合物、脂肪族聚縮水甘油醚化合物、多硫化物(polysulfide)型二縮水甘油醚化合物以及聯苯酚型環氧化合物。Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A epoxy compound. Hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type 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 phenolic Varnish type epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, and more A polysulfide type diglycidyl ether compound and a biphenol type epoxy 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基酯環氧化合物。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。The glycidylamine may, for example, be a polyglycidylamine compound.

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的單體的均聚物以及共聚物。Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxirane 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-碳雙鍵氧化而獲得的含有環氧基的化合物。The chain aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

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-碳雙鍵氧化而獲得的含有環氧基的化合物。The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cyclic olefin compound.

所述雙酚A型環氧化合物例如可以列舉：828、1001、1002、1003、1004、1007、1010(均為日本環氧樹脂製造)，EPOTOHTO YD-128(東都化成公司製造)，DER-331、DER-332、DER-324(均為Dow Chemical公司製造)，EPICLON 840、EPICLON 850、EPICLON 1050(均為大日本油墨製造)，EPOMIC R-140、EPOMIC R-301和EPOMIC R-304(均為三井化學製造)。Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by Japanese epoxy resin), EPOTOHTO YD-128 (manufactured by Tohto Kasei Co., Ltd.), and DER-331. , DER-332, DER-324 (all manufactured by Dow Chemical), EPICLON 840, EPICLON 850, EPICLON 1050 (all manufactured by Dainippon Ink), EPOMIC R-140, EPOMIC R-301 and EPOMIC R-304 (both Made for Mitsui Chemicals).

所述雙酚F型環氧化合物例如可以列舉：806、807、4004P(均為日本環氧樹脂製造)，EPOTOHTO YDF-l70、EPOTOHTO YDF-175S、EPOTOHTO YDF-2001(均為東都化成公司製造)，DER-354(Dow Chemical公司製造)，EPICLON 830和EPICLON 835(均為大日本油墨製造)。Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Japan epoxy resin), EPOTOHTO YDF-l70, EPOTOHTO YDF-175S, and EPOTOHTO YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). , DER-354 (manufactured by Dow Chemical Co., Ltd.), 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物。The bisphenol type epoxy compound may, for example, be an epoxide 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：SUNTOHTO ST-3000(東都化成公司製造)、RIKARESIN HBE-100(新日本理化製造)以及DENACOL EX-252(Nagasechemtex公司製造)。Examples of the hydrogenated bisphenol-A type epoxy compound include SUNTOHTO ST-3000 (manufactured by Tohto Kasei Co., Ltd.), RIKARESIN HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and DENACOL EX-252 (manufactured by Nagase Chemtex 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物。Examples of the hydrogenated bisphenol type epoxy compound include an epoxide 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(均為日本環氧樹脂製造)，EPOTOHTO YDB-360、EPOTOHTO YDB-400(均為東都化成公司製造)，DER-530、DER-538(均為Dow Chemical公司製造)，EPICLON152和EPICLON153(均為大日本油墨製造)。Examples of the brominated bisphenol-A type epoxy compound include 5050 and 5051 (all manufactured by Japanese epoxy resin), EPOTOHTO YDB-360, and EPOTOHTO YDB-400 (all manufactured by Dongdu Chemical Co., Ltd.), DER-530. DER-538 (all manufactured by Dow Chemical Co., Ltd.), EPICLON 152 and EPICLON 153 (all manufactured by Dainippon Ink).

所述苯酚酚醛清漆型環氧化合物例如可以列舉：152、154(均為日本環氧樹脂製造)，YDPN-638(東都化成公司製造)，DEN431、DEN438(均為Dow Chemical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和EPPN-202(均為日本化藥股份有限公司製造)。Examples of the phenol novolak-type epoxy compound include 152 and 154 (all manufactured by Japan Epoxy Resin), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical Co., Ltd.), and EPICLONN- 770 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EPPN-201 and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.).

所述甲酚酚醛清漆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(均為東都化成公司製造)，EPICLONN-665、EPICLON N-695(均為大日本油墨化學工業股份有限公司製造)，EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025和EOCN-1027(均為日本化藥股份有限公司製造)。Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Nippon Epoxy Resin), YDCN-701, YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), EPICLONN-665, and EPICLON N-695 (both 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酚醛清漆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)、以及EPICLONN-880(大日本油墨化學工業股份有限公司製造)。Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Nippon Epoxy Resin Co., Ltd.) and EPICLONN-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(均為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 epoxy compound containing a naphthalene skeleton include EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and NC-7000 (Nippon Chemical Co., Ltd.). Manufacturing).

所述芳香族聚縮水甘油醚化合物例如可以列舉：對苯二酚二縮水甘油醚(hydroquinone diglycidy1 ether，下述結構式E101)、鄰苯二酚二縮水甘油醚(catechol diglycidylether，下述結構式E102)、間苯二酚二縮水甘油醚(resorcinol diglycidyl ether，下述結構式E103)、三(4-縮水甘油氧基苯基)甲烷(下述結構式E105)，1031S、1032H60(均為日本環氧樹脂製造)，TACTIX-742(Dow Chemical公司製造)，DENACOL EX-201(Nagase chemtex公司製造)，DPPN-503、DPPN-502H、DPPN-501H、NC6000(均為日本化藥股份有限公司製造)，TECHMORE VG3101L(三井化學公司製造)，以下述結構式E106表示的化合物以及以下述結構式E107表示的化合物。Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidy1 ether (the following structural formula E101) and catechol diglycidylether (structure E102 below). ), resorcinol diglycidyl ether (the following structural formula E103), tris(4-glycidoxyphenyl)methane (the following structural formula E105), 1031S, 1032H60 (all are Japanese rings) Oxygen resin manufacturing), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), DENACOL EX-201 (manufactured by Nagase Chemex), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.) TECHMORE VG3101L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following structural formula E106, and a compound represented by the following structural formula E107.

所述雙環戊二烯酚型環氧化合物例如可以列舉：TACTIX-556(Dow Chemical公司製造)、以及EPICLON HP-7200(大日本油墨化學工業股份有限公司製造)。Examples of the biscyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Co., Ltd.) and EPICLON HP-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.).

所述脂環式二縮水甘油醚化合物例如可以列舉：環己烷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 cyclohexane dimethanol diglycidyl ether compound and RIKARESIN DME-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.).

所述脂肪族聚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E108)、二乙二醇二縮水甘油醚(下述結構式E109)、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚(下述結構式E110)、三丙二醇二縮水甘油醚(下述結構式E111)、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚(下述結構式E112)、1,4-丁二醇二縮水甘油醚(下述結構式E113)、1,6-己二醇二縮水甘油醚(下述結構式E114)、二溴新戊二醇二縮水甘油醚(下述結構式E115)，DENACOL EX-810、DENACOL EX-851、DENACOL EX-8301、DENACOL EX-911、DENACOL EX-920、DENACOL EX-931、DENACOL EX-211、DENACOL EX-212、DENACOL EX-313(均為Nagase chemtex公司製造)，DD-503(旭電化製造)，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E116)、甘油聚縮水甘油醚、山梨糖醇聚縮水甘油醚(sorbitol polyglycidyl ether)、三羥甲基丙烷聚縮水甘油醚、季戊四醇聚縮水甘油醚，DENACOL EX-313、DENACOL EX-611、DENACOL EX-321和DENACOL EX-411(均為Nagase chemtex公司製造)。Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol diglycidyl ether (the following structural formula E109), and polyethylene glycol condensed water. Glycerol ether, propylene glycol diglycidyl ether (the following structural formula E110), tripropylene glycol diglycidyl ether (the following structural formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula) E112), 1,4-butanediol diglycidyl ether (structure E113 below), 1,6-hexanediol diglycidyl ether (structure E114 below), dibromo neopentyl glycol diglycidyl Ether (Structure E115 below), DENACOL EX-810, DENACOL EX-851, DENACOL EX-8301, DENACOL EX-911, DENACOL EX-920, DENACOL EX-931, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313 (all manufactured by Nagase Chemex), DD-503 (made by Asahi Kasei), RIKARESIN W-100 (Nippon Chemical and Chemical Manufacturing), 1,3,5,6-tetraglycidyl-2,4-hexyl Glycol (Structure E116 below), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polycondensate Oleyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321 and DENACOL EX-411 (both manufactured by Nagase Chemtex Corporation).

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

所述聯苯酚型環氧化合物例如可以列舉：YX-4000、YL-6121H(均為日本環氧樹脂製造)，NC-3000P和NC-3000S(均為日本化藥股份有限公司製造)。Examples of the biphenol-based epoxy compound include YX-4000, YL-6121H (all manufactured by Japan Epoxy Resin), NC-3000P and NC-3000S (both 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E118)、鄰苯二甲酸雙(2-甲基環氧乙烷基甲基)酯(下述結構式E119)、以下述結構式E121表示的化合物、以下述結構式E122表示的化合物以及以下述結構式E123表示的化合物。Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula E118), and phthalic acid bis (2). -Methyl oxiranylmethyl)ester (the following structural formula E119), a compound represented by the following structural formula E121, a compound represented by the following structural formula E122, and a compound represented by the following structural formula E123.

所述縮水甘油酯環氧化合物例如可以列舉：871、872(均為日本環氧樹脂製造)，EPICLON 200、EPICLON 400(均為大日本油墨化學工業股份有限公司製造)，DENACOL EX-711和 DENACOL EX-721(均為Nagase chemtex公司製造)。Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by Japan Epoxy Resin), EPICLON 200, and EPICLON 400 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), DENACOL EX-711 and DENACOL. EX-721 (both manufactured by Nagase Chemex).

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E124)、N,N-二縮水甘油基-鄰甲苯胺(下述結構式E125)、N,N-二縮水甘油基-間甲苯胺(下述結構式E126)、N,N-二縮水甘油基-2,4,6-三溴苯胺(下述結構式E127)、3-(N,N-二縮水甘油基)氨基丙基三甲氧基矽烷(下述結構式E128)、N,N,O-三縮水甘油基-對氨基苯酚(下述結構式E129)、N,N,O-三縮水甘油基-間氨基苯酚(下述結構式E130)、N,N,N'，N'-四縮水甘油基-間亞二甲苯基二胺(TETRAD-X(三菱氣體化學)，下述結構式E132)、1,3-雙(N,N-二縮水甘油基氨基甲基)環己烷(TETRAD-C(三菱氣體化學)，下述結構式E133)、1,4-雙(N,N-二縮水甘油基氨基甲基)環己烷(下述結構式E134)、1,3-雙(N,N-二縮水甘油基氨基)環己烷(下述結構式E135)、1,4-雙(N,N-二縮水甘油基氨基)環己烷(下述結構式E136)、1,3-雙(N，N-二縮水甘油基氨基)苯(下述結構式E137)、1,4-雙(N,N-二縮水甘油基氨基)苯(下述結構式E138)、2,6-雙(N，N-二縮水甘油基氨基甲基)雙環[2.2.1]庚烷(下述結構式E139)、N,N,N',N'-四縮水甘油基-4,4'-二氨基二環己基甲烷(下述結構式E140)、2,2'-二甲基-(N,N,N',N'-四縮水甘油基)-4,4'-二氨基二苯基(下述結構式E141)、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基醚(下述結構式E142)、1,3,5-三(4-(N,N-二縮水甘油基)氨基苯氧基)苯(下述結構式E143)、2,4,4'-三(N,N-二縮水甘油基氨基)二苯基醚(下述結構式E144)、三(4-(N,N-二縮水甘油基)氨基苯基)甲烷(下述結構式E145)、3,4,3',4'-四(N,N-二縮水甘油基氨基)聯苯(下述結構式E146)、3,4,3',4'-四(N,N-二縮水甘油基氨基)二苯基醚(下述結構式E147)、以下述結構式E148表示的化合物以及以下述結構式E149表示的化合物。Examples of the polyglycidylamine compound include N,N-diglycidylaniline (structure E124 below), N,N-diglycidyl-o-toluidine (structure E125 below), N, N-diglycidyl-m-toluidine (structure E126 below), N,N-diglycidyl-2,4,6-tribromoaniline (structure E127 below), 3-(N,N - diglycidyl) aminopropyltrimethoxydecane (structure E128 below), N,N,O-triglycidyl-p-aminophenol (structure E129 below), N,N,O-three Glycidyl-m-aminophenol (structure E130 below), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (Mitsubishi Gas Chemical), the following structure Formula E132), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), the following structural formula E133), 1,4-double (N, N-diglycidylaminomethyl)cyclohexane (the following structural formula E134), 1,3-bis(N,N-diglycidylamino)cyclohexane (the following structural formula E135), 1, 4-bis(N,N-diglycidylamino)cyclohexane (the following structural formula E136), 1,3-bis(N,N-diglycidylamino)benzene (the following structural formula E137), 1,4- Bis(N,N-diglycidylamino)benzene (structure E138 below), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (described below) Structural formula E139), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (Strong formula E140 below), 2,2'-dimethyl-(N ,N,N',N'-tetraglycidyl)-4,4'-diaminodiphenyl (structure E141 below), N,N,N',N'-tetraglycidyl-4, 4'-Diaminodiphenyl ether (Formula E142 below), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (Structure of Formula E143 below) 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula E144 below), tris(4-(N,N-diglycidyl)aminophenyl) Methane (structure E145 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (Structure E146 below), 3,4,3',4' - Tetrakis(N,N-diglycidylamino)diphenyl ether (the following structural formula E147), a compound represented by the following structural formula E148, and a compound represented by the following structural formula E149.

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、甲基丙烯酸芐酯-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 or N-cyclohexylmaleimide-methyl group. Glycidyl acrylate 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-環氧環己酯以及(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除了所述具有環氧乙烷基的單體以外的其他單體，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)丙烯酸芐酯、(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, other than the monomer having an oxiranyl group, for example, (meth)acrylic acid or methyl (meth)acrylate may be mentioned. , ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid ring Hexyl ester, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (methyl) ) (3-ethyl-3-epoxypropenyl)methyl acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

所述異氰尿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(1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione，下述結構式E150)、1,3-二縮水甘油基-5-烯丙基-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮(下述結構式E151)以及異氰尿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 (1) ,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, the following structural formula E150), 1,3-diglycidyl-5-ene Propyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (structural formula E151 below) and glycidyl isocyanurate 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、以及EPOLEAD PB3600(DAICEL化學工業股份有限公司製造)。Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and EPOLEAD PB3600 (manufactured by DAICEL Chemical Industry Co., Ltd.).

所述環狀脂肪族型環氧化合物例如可以列舉：2-甲基-3,4-環氧環己基甲基-2'-甲基-3',4'-環氧環己基羧酸酯(下述結構式E153)、2,3-環氧環戊烷-2',3'-環氧環戊烷醚(下述結構式E154)、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(1,2:8,9-diepoxy limonene，CELLOXIDE 3000(DAICEL化學工業股份有限公司製造)、3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯(CELLOXIDE 2021P(DAICEL化學工業股份有限公司製造)，下述結構式E155)、以下述結構式E156表示的化合物，CY-175、CY-177、CY-179(均為CIBA-GEIGY公司製造)，EHPD-3150(DAICEL化學工業股份有限公司製造)以及環狀脂肪族型環氧樹脂。The cyclic aliphatic epoxy compound may, for example, be 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate ( The following structural formula E153), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (structure E154 below), ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2:8,9-diepoxylimene (1,2:8,9-diepoxy limonene, CELLOXIDE 3000 (DAICEL Chemical Industry Shares) Manufactured by the company, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (CELLOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), the following structural formula E155 ), a compound represented by the following structural formula E156, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by DAICEL Chemical Industry Co., Ltd.), and a cyclic aliphatic type Epoxy resin.

而且，例如本發明的液晶配向劑可以進一步含有各種添加劑。各種添加劑例如可以列舉聚醯胺酸以及其衍生物以外的高分子化合物和低分子化合物，可以根據各自的目的來選擇並使用。Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to the respective purposes.

例如，所述高分子化合物可以列舉可溶於有機溶劑中的高分子化合物。將這樣的高分子化合物添加到本發明的液晶配向劑中，從對所形成的液晶配向膜的電特性或者配向性進行控制的觀點考慮較好。該高分子化合物例如可以列舉：聚醯胺、聚氨基甲酸乙酯(polyurethane)、聚脲(Polyurea)、聚酯、聚環氧化物(polyepoxide)、聚酯多元醇(polyester polyol)、矽酮改性聚氨基甲酸乙酯以及矽酮改性聚酯。For example, the polymer compound may be a polymer compound which is soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention from the viewpoint of controlling the electrical characteristics or the alignment property of the formed liquid crystal alignment film. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, and oxime. Polyurethane and anthrone modified polyester.

而且，對於所述低分子化合物，例如，l)當希望提高塗布性時可以列舉符合該目的界面活性劑，2)當必須提高抗靜電性時可以列舉抗靜電劑，3)當希望提高與基板的密著性或者耐摩擦(rubbing)性時可以列舉矽烷偶合劑或者鈦系偶合劑，而且，4)當在低溫下進行醯亞胺化時可以列舉醯亞胺化催化劑。Further, for the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be mentioned when it is necessary to improve the antistatic property, and 3) when it is desired to improve the substrate. In the case of adhesion or rubbing resistance, a decane coupling agent or a titanium coupling agent may be mentioned, and 4) a ruthenium imidization catalyst may be mentioned when ruthenium imidization is carried out at a low temperature.

所述矽烷偶合劑例如可以列舉：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、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-(三乙氧基矽烷基)-1-丙胺以及N,N'-雙[3-(三甲氧基矽烷基)丙基]乙二胺。Examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy decane, and N-( 2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminobenzene Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl A Dimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyl Trimethoxydecane, N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, and N,N'-bis[3-(trimethoxydecyl) Propyl] ethylenediamine.

所述醯亞胺化催化劑例如可以列舉：三甲胺、三乙胺、三丙胺、三丁胺等脂肪族胺類；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、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的是，選自N,N-二甲基苯胺、鄰羥基苯胺、間羥基苯胺、對羥基苯胺、鄰羥基吡啶、間羥基吡啶、對羥基吡啶以及異喹啉中的一種或者兩種或兩種以上。Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline a cyclic amine such as a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquinoline. One or two or more.

矽烷偶合劑的添加量通常為聚醯胺酸或者其衍生物的總重量的0重量%～20重量%，優選為0.1重量%～10重量%。The amount of the decane coupling agent to be added is usually from 0% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight based on the total mass of the polyamic acid or the derivative thereof.

醯亞胺化催化劑的添加量通常相對於聚醯胺酸或者其衍生物的羰基，而為0.01當量～5當量，優選為0.05當量～3當量。The amount of the ruthenium imidization catalyst to be added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, per mole of the carbonyl group of the polyglycolic acid or the derivative thereof.

其他添加劑的添加量是根據其用途而有所不同，通常為聚醯胺酸或者其衍生物的總重量的0重量%～100重量%，優選為0.1重量%～50重量%。The amount of the other additives to be added varies depending on the use thereof, and is usually from 0% by weight to 100% by weight, preferably from 0.1% by weight to 50% by weight based on the total mass of the polyamic acid or the derivative thereof.

而且，例如本發明的液晶配向劑可以在不損及本發明效果的範圍(優選為所述聚醯胺酸或者其衍生物的20重量%以內的量)內進一步含有：丙烯酸聚合物，丙烯酸酯聚合物，以及作為四羧酸二酐、二羧酸或者其衍生物與二胺的反應產物的聚醯胺醯亞胺等其他聚合物成分。Further, for example, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer, an acrylate, in a range not detracting from the effects of the present invention (preferably, the amount of the polyamic acid or a derivative thereof within 20% by weight) A polymer, and other polymer components such as polyamidoximine which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and a diamine.

而且，例如從調整液晶配向劑的塗布性以及所述聚醯胺酸或者其衍生物的濃度的觀點考慮，本發明的液晶配向劑可以進一步含有溶劑。所述溶劑只要是具有溶解高分子成分的能力的溶劑則可以使用，並無特別限制。所述溶劑廣泛地包括聚醯胺酸、可溶性聚醯亞胺等高分子成分的製造步驟或者用途方面通常所使用的溶劑，可以根據使用目的而適當選擇。所述溶劑可以是一種溶劑，也可以是兩種或者兩種以上溶劑的混合溶劑。Further, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent and the concentration of the polyamic acid or a derivative thereof, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent can be used as long as it has a solvent capable of dissolving a polymer component, and is not particularly limited. The solvent widely includes a solvent used in a production step or a use of a polymer component such as polyaminic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be a solvent or a mixed solvent of two or more solvents.

所述溶劑可以列舉：所述聚醯胺酸或其衍生物的良溶劑、或者以改善塗布性為目的之其他溶劑。The solvent may, for example, be a good solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

相對於所述聚醯胺酸或者其衍生物而言為良溶劑的非質子性極性有機溶劑，可以列舉：N-甲基-2-吡咯烷酮、二甲基咪唑烷酮(dimethyl imidazolidinone)、N-甲基己內醯胺(N-methyl Caprolactam)、N-甲基丙醯胺(N-methyl 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、二乙基乙醯胺、γ-丁內酯(γ-butyrolactone)等內酯。Examples of the aprotic polar organic solvent which is a good solvent with respect to the polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, dimethyl imidazolidinone, and N- N-methyl Caprolactam, N-methyl propionamide, N,N-dimethylacetamide, dimethyl sulfoxide, N, Lactones such as N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone.

所述以改善塗布性等為目的之其他溶劑的例子可以列舉：乳酸烷基酯、3-甲基-3-甲氧基丁醇、萘滿(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、乙二醇單烷基或者苯基乙酸酯、三乙二醇單烷基醚、丙二醇單甲醚及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、它們的乙酸酯類等酯化合物。Examples of the other solvent for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and B. Ethylene glycol monoalkyl ether such as diol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl a propylene glycol monoalkyl ether such as ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether; dialkyl malonate such as dipropyl malonate; dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether; An ester compound such as an analog.

這些化合物中,所述溶劑特別優選N-甲基-2-吡咯烷酮、二甲基咪唑烷酮、γ-丁內酯、乙二醇單丁醚、二乙二醇單***、丙二醇單丁醚、丙二醇單甲醚以及二丙二醇單甲醚。Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

本發明中,液晶配向劑中的包含所述聚醯胺酸或者其衍生物的高分子成分的濃度並無特別限定,優選0.1重量%～40重量%。將該液晶配向劑塗布在基板上時,有時為了調整膜厚而必須進行預先用溶劑來將所含有的高分子成分稀釋的操作。此時,從將液晶配向劑的粘度調整成適合在液晶配向劑中容易地混合溶劑的粘度的觀點考慮,所述高分子成分的濃度優選為40重量%或40重量%以下。In the present invention, the concentration of the polymer component containing the polyamic acid or a derivative thereof in the liquid crystal alignment agent is not particularly limited, but is preferably 0.1% by weight to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, it is necessary to perform an operation of diluting the contained polymer component with a solvent in advance in order to adjust the film thickness. In this case, from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, the concentration of the polymer component is preferably 40% by weight or less.

而且,液晶配向劑中的所述高分子成分的濃度有時也要根據液晶配向劑的塗布方法來調整。當液晶配向劑的塗布方法為旋轉塗布法或者印刷法時，為了良好地保持膜厚，通常大多使所述高分子成分的濃度為10重量%或10重量%以下。對於其他的塗布方法、例如浸漬法(dipping method)或者噴墨法(ink-jet method)來說，有可能要進一步降低濃度。另一方面，如果所述高分子成分的濃度為0.1重量%或者0.1重量%以上，那麼所獲得的液晶配向膜的膜厚容易成為最佳的厚度。因此，在通常的旋轉塗布法或者印刷法等中，所述高分子成分的濃度為0.1重量%或者0.1重量%以上，優選0.5重量%～10重量%。但是，根據液晶配向劑的塗布方法，有時也可以在更低的濃度下使用。Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually 10% by weight or less. For other coating methods, such as a dipping method or an ink-jet method, it is possible to further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film tends to be an optimum thickness. Therefore, in a normal spin coating method, a printing method, or the like, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5% by weight to 10% by weight. However, depending on the method of applying the liquid crystal alignment agent, it may be used at a lower concentration.

另外，將本發明的液晶配向劑用於製作液晶配向膜時，本發明的液晶配向劑的粘度可以根據形成該液晶配向劑膜的機構或者方法來决定。例如，使用印刷機來形成液晶配向劑的膜時，從獲得充分的膜厚的觀點考慮，本發明的液晶配向劑的粘度優選為5mPa‧s或者5mPa‧s以上，而且，從抑制印刷不均的觀點考慮，本發明的液晶配向劑的粘度優選為100mPa‧s或者100 100mPa‧s以下，更加優選為10mPa‧s～80mPa‧s。利用旋轉塗布法來塗布液晶配向劑而形成液晶配向劑的膜時，從同樣的觀點考慮，本發明的液晶配向劑的粘度優選為5mPa‧s～200mPa‧s，更加優選為10mPa‧s～100mPa‧s。液晶配向劑的粘度可以通過溶劑的稀釋或者伴隨著攪拌的熟化而減小。Further, when the liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to a mechanism or method for forming the liquid crystal alignment agent film. For example, when a film of a liquid crystal alignment agent is formed by a printing machine, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa ‧ s or 5 mPa ‧ s or more from the viewpoint of obtaining a sufficient film thickness, and from the viewpoint of suppressing uneven printing From the viewpoint of the liquid crystal alignment agent of the present invention, the viscosity is preferably 100 mPa ‧ s or 100 100 mPa ‧ s or less, and more preferably 10 mPa ‧ to 80 mPa ‧ s. When the liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa ‧ to 200 mPa ‧ s, and more preferably 10 mPa ‧ to 100 mPa from the same viewpoint ‧s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or aging with stirring.

本發明的液晶配向劑可以是含有一種聚醯胺酸或者其衍生物的形態，也可以是混合了兩種或者兩種以上聚醯胺酸或者其衍生物的所謂聚合物摻合物的形態。聚合物摻合物形態的液晶配向劑可以列舉以下的液晶配向劑：其含有聚醯胺酸或者其衍生物A以及B，並且聚醯胺酸或者其衍生物A包含二胺中的所述具有側鏈結構的二胺，且聚醯胺酸或者其衍生物A以及B的二胺中的一方或者兩方包含以所述通式(N)表示的二胺。The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a derivative thereof, or a form of a so-called polymer blend in which two or more kinds of polyaminic acid or a derivative thereof are mixed. The liquid crystal alignment agent in the form of a polymer blend may, for example, be a liquid crystal alignment agent containing polylysine or derivatives A and B thereof, and the polyamine or the derivative A thereof contains the diamine One or both of the diamine of the side chain structure and the polyamine or the derivatives of the derivatives A and B contain a diamine represented by the above formula (N).

聚醯胺酸或者其衍生物A是含有所述具有側鏈結構的二胺的聚醯胺酸或者其衍生物。聚醯胺酸或者其衍生物B是含有除了具有側鏈結構的二胺以外的二胺的聚醯胺酸或者其衍生物。以所述通式(N)表示的二胺，只要包含於在聚合物摻合物中混合的至少一種聚醯胺酸或者其衍生物中即可，可以包含於聚醯胺酸或者其衍生物A以及B兩方中，也可以包含於在聚合物摻合物中混合的所有聚醯胺酸或者其衍生物中。Polyproline or a derivative thereof A is a polyamine or a derivative thereof containing the diamine having a side chain structure. Polylysine or a derivative thereof B is a polyamine or a derivative thereof containing a diamine other than a diamine having a side chain structure. The diamine represented by the above formula (N) may be contained in at least one polyphthalic acid or a derivative thereof mixed in the polymer blend, and may be contained in polylysine or a derivative thereof. Both A and B may also be included in all polyamines or derivatives thereof mixed in the polymer blend.

本發明的液晶配向膜是對所述本發明的液晶配向劑的塗膜進行加熱而形成的膜。本發明的液晶配向膜可以使用由液晶配向劑來製作液晶配向膜的通常方法而獲得，例如，本發明的液晶配向膜可以通過形成本發明液晶配向劑的塗膜的步驟、以及對該塗膜進行加熱並煆燒的步驟而獲得。對於本發明的液晶配向膜而言，視需要可以對所述煆燒步驟中獲得的膜進行摩擦處理。The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method of producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, a step of forming a coating film of the liquid crystal alignment agent of the present invention, and a coating film of the liquid crystal alignment film of the present invention. It is obtained by the step of heating and calcining. For the liquid crystal alignment film of the present invention, the film obtained in the calcination step may be subjected to a rubbing treatment as needed.

與製作通常的液晶配向膜相同，所述塗膜可以通過在液晶顯示元件的基板上塗布本發明的液晶配向劑而形成。所述基板可以列舉：可以設置著氧化銦錫(Indium Tin Oxide，ITO)電極等電極以及彩色濾光片(color filter)等的玻璃制基板。The coating film can be formed by applying the liquid crystal alignment agent of the present invention onto a substrate of a liquid crystal display element, similarly to the production of a usual liquid crystal alignment film. The substrate may be a glass substrate in which an electrode such as an Indium Tin Oxide (ITO) electrode or a color filter may be provided.

將液晶配向劑塗布在基板上的方法，通常已知旋轉器(spinner)法、印刷法、浸漬法、落滴法(falling-drop method)、噴墨法等。這些方法在本發明中也同樣可以應用。A method of applying a liquid crystal alignment agent onto a substrate is generally known as a spinner method, a printing method, a dipping method, a falling-drop method, an inkjet method, or the like. These methods are equally applicable in the present invention.

所述塗膜的煆燒可以在所述聚醯胺酸或者其衍生物進行脫水、閉環反應的必要條件下進行。所述塗膜的煆燒通常已知在烘箱(oven)或者紅外爐中進行加熱處理的方法、在熱板(hot plate)上進行加熱處理的方法等。這些方法在本發明中也同樣可以應用。通常優選的是在150℃～300℃左右的溫度下進行1分鐘～3小時。The calcination of the coating film can be carried out under the conditions necessary for the polyhydric acid or a derivative thereof to undergo dehydration and ring closure reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like. These methods are equally applicable in the present invention. It is usually preferred to carry out at a temperature of from about 150 ° C to about 300 ° C for from 1 minute to 3 hours.

所述摩擦處理可以與通常用來對液晶配向膜進行配向處理的摩擦處理同樣地進行，只要是可以使本發明的液晶配向膜獲得充分的延遲(retardation)的條件即可。特別優選的條件是，毛壓入量為0.2mm～0.8mm，平臺移動速度為5mm/sec～250mm/sec，滾筒轉速為500rpm～2,000rpm。液晶配向膜的配向處理方法除摩擦法以外，通常已知光配向法或者轉印法等。在可以獲得本發明效果的範圍內，可以在所述摩擦處理中併用這些其他的配向處理方法。The rubbing treatment can be carried out in the same manner as the rubbing treatment which is usually used for the alignment treatment of the liquid crystal alignment film, as long as the liquid crystal alignment film of the present invention can obtain sufficient retardation. Particularly preferred conditions are a hair injection amount of 0.2 mm to 0.8 mm, a stage moving speed of 5 mm/sec to 250 mm/sec, and a drum rotation speed of 500 rpm to 2,000 rpm. In the alignment treatment method of the liquid crystal alignment film, in addition to the rubbing method, a photoalignment method, a transfer method, or the like is generally known. These other alignment treatment methods may be used in combination in the rubbing treatment within the range in which the effects of the present invention can be obtained.

本發明的液晶配向膜可以利用除了所述步驟以外進一步含有其他步驟的方法而適宜地獲得。這樣的其他步驟可以列舉對所述塗膜進行乾燥的步驟、或者用清洗液對摩擦處理前後的膜進行清洗的步驟等。The liquid crystal alignment film of the present invention can be suitably obtained by a method including further steps other than the above steps. Such a further step may be a step of drying the coating film or a step of washing the film before and after the rubbing treatment with a washing liquid.

與所述煆燒步驟相同，所述乾燥步驟通常已知在烘箱或者紅外爐中進行加熱處理的方法、在熱板上進行加熱處理的方法等。這些方法在所述乾燥步驟中也同樣可以應用。乾燥步驟優選的是在溶劑能够蒸發的範圍內的溫度下實施，更優選的是在與所述煆燒步驟的溫度相比相對較低的溫度下實施。As in the calcining step, the drying step is generally known as a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, or the like. These methods are equally applicable in the drying step. The drying step is preferably carried out at a temperature within a range in which the solvent can evaporate, more preferably at a relatively low temperature compared to the temperature of the calcining step.

用清洗液對配向處理前後的液晶配向膜進行清洗的清洗方法，可以列舉：刷洗(brushing)、噴霧(jet spray)、蒸氣清洗或者超聲波清洗等。這些方法可以單獨進行，也可以併用。清洗液可以使用：純水，或者甲醇、乙醇、異丙醇等各種醇類，苯、甲苯、二甲苯等芳香族烴類，二氯甲烷(methylene chloride)等鹵素系溶劑，丙酮、甲基乙基酮等酮類，但並不限定於這些清洗液。當然，這些清洗液可以使用經充分純化而雜質少的清洗液。這樣的清洗方法在形成本發明的液晶配向膜的所述清洗步驟中也可以應用。The cleaning method for cleaning the liquid crystal alignment film before and after the alignment treatment with a cleaning liquid may, for example, be brushing, jet spraying, steam cleaning or ultrasonic cleaning. These methods can be performed separately or in combination. The cleaning solution can be: pure water, or various alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogen solvents such as methylene chloride; acetone and methyl ethyl Ketones such as ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently purified and has less impurities. Such a cleaning method can also be applied in the cleaning step of forming the liquid crystal alignment film of the present invention.

本發明的液晶配向膜的膜厚並無特別限定，優選為10nm～300nm，更加優選為30nm～150nm。本發明的液晶配向膜的膜厚可以用表面輪廓儀(profilometer)或者橢偏儀(ellipso m eter)等眾所周知的膜厚測定裝置來測定。The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer.

本發明的液晶顯示元件具有：一對基板、含有液晶分子且形成在所述一對基板間的液晶層、對液晶層施加電壓的電極、以及將所述液晶分子配向在預定方向上的液晶配向膜。所述液晶配向膜是使用所述本發明的液晶配向膜。A liquid crystal display device of the present invention has a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment for aligning the liquid crystal molecules in a predetermined direction membrane. The liquid crystal alignment film is a liquid crystal alignment film of the present invention.

所述基板可以使用上文中針對本發明的液晶配向膜所描述的玻璃制基板，所述電極可以使用上文中針對本發明的液晶配向膜所描述的形成在玻璃制基板上的ITO電極。The substrate may use the glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may use the ITO electrode formed on the glass substrate described above for the liquid crystal alignment film of the present invention.

所述液晶層是由被密封在相對向的一對基板間的間隙中的液晶組成物所形成的，該相對向的一對基板是以所述一對基板中的一片基板的形成了液晶配向膜的面朝向另一片基板的方式而對向的。The liquid crystal layer is formed by a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein the pair of opposite substrates form a liquid crystal alignment of one of the pair of substrates The face of the film faces oppositely toward the other substrate.

所述液晶組成物並無特別限制，可以使用介電常數各向異性為正或者負的各種液晶組成物。介電常數各向異性為正的優選液晶組成物可以列舉在以下公報中所揭示的液晶組成物：日本專利第3086228號公報、日本專利第2635435號公報、日本專利特表平5-501735號公報、日本專利特開平8-157826號公報、日本專利特開平8-231960號公報、日本專利特開平9-241644號公報(EP885272A1說明書)、日本專利特開平9-302346號公報(EP806466A1說明書)、日本專利特開平8-199168號公報(EP722998A1說明書)、日本專利特開平9-235552號公報、日本專利特開平9-255956號公報、日本專利特開平9-241643號公報(EP885271A1說明書)、日本專利特開平10-204016號公報(EP844229A1說明書)、日本專利特開平10-204436號公報、日本專利特開平10-231482號公報、日本專利特開2000-087040號公報、日本專利特開2001-48822號公報等。The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A liquid crystal composition which is positive in the dielectric anisotropy is exemplified in the following publications: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735 Japanese Patent Application Laid-Open No. Hei 8-- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), and Japanese Patent No. 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. Wait.

介電常數各向異性為負的液晶組成物可以列舉以下公報中所揭示的液晶組成物：日本專利特開昭57-114532號公報、日本專利特開平2-4725號公報、日本專利特開平4-224885號公報、日本專利特開平8-40953號公報、日本專利特開平8-104869號公報、日本專利特開平10-168076號公報、日本專利特開平10-168453號公報、日本專利特開平10-236989號公報、日本專利特開平10-236990號公報、日本專利特開平10-236992號公報、日本專利特開平10-236993號公報、日本專利特開平10-236994號公報、日本專利特開平10-237000號公報、日本專利特開平10-237004號公報、日本專利特開平10-237024號公報、日本專利特開平10-237035號公報、日本專利特開平10-237075號公報、日本專利特開平10-237076號公報、日本專利特開平10-237448號公報(EP967261Al說明書)、日本專利特開平10-287874號公報、日本專利特開平10-287875號公報、日本專利特開平10-291945號公報、日本專利特開平11-029581號公報、日本專利特開平11-080049號公報、日本專利特開2000-256307公報、日本專利特開2001-019965公報、日本專利特開2001-072626公報、日本專利特開2001-192657公報等。The liquid crystal composition disclosed in the following publications is exemplified by the following Japanese Patent Publication No. Sho 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, and Japanese Patent Laid-Open No. 4 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Hei. No. Hei. Hei. Hei. Hei. Japanese Patent Laid-Open No. Hei 10-236990, Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Application Laid-Open No. Hei No. 10-236993, Japanese Patent Laid-Open No. Hei 10-236994 Japanese Patent Laid-Open No. Hei 10-237004, 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 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 10-287. Japanese Patent Laid-Open No. Hei 10-291945, Japanese Patent Laid-Open No. Hei 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open Publication No. 2000-256307, Japanese Patent Laid-Open Publication No. 2001-019965, Japanese Patent JP-A-2001-072626, JP-A-2001-192657, and the like.

所述介電常數各向異性為正或者負的液晶組成物，即使添加使用一種或者一種以上的光學活性化合物也沒有絲毫影響。The liquid crystal composition in which the dielectric anisotropy is positive or negative does not have any influence even if one or more optically active compounds are added.

本發明的液晶顯示元件是通過下述方式而獲得的：在一對基板中的至少一片基板上形成本發明的液晶配向膜，使液晶配向膜朝內而使所獲得的一對基板隔著間隔物(spacer)相對向，在形成於基板間的間隙中封入液晶組成物而形成液晶層。本發明的液晶顯示元件的製造過程中，視需要可以進一步包含對基板貼附偏光膜等的步驟。The liquid crystal display element of the present invention is obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates such that the liquid crystal alignment film faces inward and the obtained pair of substrates are spaced apart The spacers are opposed to each other, and a liquid crystal composition is sealed in a gap formed between the substrates to form a liquid crystal layer. In the manufacturing process of the liquid crystal display element of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed.

本發明的液晶顯示元件可以形成各種電場方式用的液晶顯示元件。這樣的電場方式用的液晶顯示元件可以列舉：所述電極在相對於所述基板的表面為水平的方向上對所述液晶層施加電壓的橫向電場方式用的液晶顯示元件、或者所述電極在相對於所述基板的表面為垂直的方向上對所述液晶層施加電壓的縱向電場方式用的液晶顯示元件。The liquid crystal display element of the present invention can form liquid crystal display elements for various electric field methods. The liquid crystal display element for the electric field method includes a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction in which the electrode is horizontal with respect to the surface of the substrate, or the electrode is A liquid crystal display element for a vertical electric field method in which a voltage is applied to the liquid crystal layer in a direction perpendicular to the surface of the substrate.

橫向電場方式用的液晶顯示元件即使不表現出較大的預傾角也無妨，因此，由本發明的液晶配向劑所形成的液晶配向膜適用於橫向電場方式用的液晶顯示元件，其中本發明的液晶配向劑含有如由不含具有側鏈結構的二胺之二胺所得的聚醯胺酸或者其衍生物那樣的不具有側鏈結構的聚醯胺酸或者其衍生物。The liquid crystal display element for a lateral electric field method may not exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a transverse electric field mode, wherein the liquid crystal of the present invention The alignment agent contains a poly-proline or a derivative thereof having no side chain structure such as polylysine obtained by a diamine having no diamine having a side chain structure or a derivative thereof.

縱向電場方式用的液晶顯示元件需要表現出較大的預傾角，因此，由本發明的液晶配向劑所形成的液晶配向膜適用於縱向電場方式用的液晶顯示元件，其中本發明的液晶配向劑含有如由包含具有側鏈結構的二胺之二胺所得的聚醯胺酸或者其衍生物那樣的具有側鏈結構的聚醯胺酸或者其衍生物。The liquid crystal display element for the vertical electric field method needs to exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a vertical electric field mode, wherein the liquid crystal alignment agent of the present invention contains A polyamic acid having a side chain structure or a derivative thereof, such as polylysine obtained by a diamine having a diamine having a side chain structure or a derivative thereof.

如上所述，將本發明的液晶配向劑作為原料而製作的液晶配向膜，通過對其原料即聚合物進行適當選擇，可以應用於各種顯示驅動方式的液晶顯示元件中。As described above, the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be suitably applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material.

本發明的液晶顯示元件可以進一步具有所述構成要素以外的要素。對於這樣的其他構成要素，在本發明的液晶顯示元件中可以安裝偏光板(偏光膜)、波長板、光散射膜、驅動電路等液晶顯示元件中通常使用的構成要素。The liquid crystal display element of the present invention may further have elements other than the constituent elements. In such a liquid crystal display element of the present invention, a constituent element which is generally used in a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit can be mounted.

[實施例][Examples]

以下，利用實施例來說明本發明，本發明並不限定於這些實施例。實施例中使用的化合物如下所述。Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The compounds used in the examples are as follows.

＜四羧酸二酐＞<tetracarboxylic dianhydride>

化合物(1)：均苯四甲酸二酐(Pyromellitic Dianhydride)：PMDACompound (1): Pyromellitic Dianhydride: PMDA

化合物(19)：1,2,3,4-環丁烷四甲酸二酐(1,2,3,4-cyclobutane tetracarboxylic dianhydride)：CBDACompound (19): 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA

化合物(23)：1,2,3,4-丁烷四甲酸二酐：BTCompound (23): 1,2,3,4-butanetetracarboxylic dianhydride: BT

化合物(37)：1,3,3a,4,5,9b-六氫-5(四氫-2,5-二氧代-3-呋喃基)萘並[1,2-c]呋喃-1,3-二酮(1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphoto[1,2-c]furan-1,3-dione)：TDACompound (37): 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1 ,3-dione (1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphoto[1,2-c]furan-1,3-dione) :TDA

化合物(49)：2,3,5-三羧基環戊基乙酸二酐(2,3,5-tricarboxy cyclopentyl acetic dianhydride)：TCMPCompound (49): 2,3,5-tricarboxycyclopentyl acetic dianhydride: TCMP

＜二胺＞<Diamine>

化合物：1,4-雙(4-氨基苯基)-1,4-二氮雜環己烷(1,4-bis(4-aminophenyl)-1,4-diazacyclohexane)：DACCompound: 1,4-bis(4-aminophenyl)-1,4-diazacyclohexane (1,4-bis(4-aminophenyl)-1,4-diazacyclohexane): DAC

化合物：4,4'-(呱嗪-1,4-二基)雙(2-甲基苯胺)：3MPDACompound: 4,4'-(pyridazine-1,4-diyl)bis(2-methylaniline): 3MPDA

化合物：1,4-雙(3-氨基丙基)呱嗪：APPCompound: 1,4-bis(3-aminopropyl)pyridazine: APP

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

化合物：1,2-雙(4-氨基苯基)乙烷：DETCompound: 1,2-bis(4-aminophenyl)ethane: DET

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

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

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-aminophenyl)methylphenyl]-4-n-heptylcyclohexane: 7HBZ

化合物：1,3-雙(3-氨基丙基)四甲基二矽氧烷(1,3-bis(3-aminopropyl)tetramethy1disiloxane)：APDSCompound: 1,3-bis(3-aminopropyl)tetramethy1disiloxane: APDS

化合物：雙(4-氨基-2-甲基苯基)甲烷：MDTCompound: bis(4-amino-2-methylphenyl)methane: MDT

化合物：N,N'-雙(4-氨基苯基)-N,N-二甲基乙二胺：NN2DAMeCompound: N,N'-bis(4-aminophenyl)-N,N-dimethylethylenediamine: NN2DAMe

化合物：3,6-二氨基哢唑(3,6-diaminocarbazole)：DACZCompound: 3,6-diaminocarbazole: DACZ

＜添加劑＞<additive>

化合物：雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷：BANI-MCompound: bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane: BANI-M

化合物：N,N'-二羥基亞乙基雙丙烯醯胺：HEACompound: N, N'-dihydroxyethylene bis acrylamide: HEA

化合物：双(3-苯基-3,4-二氢-2H-1,3-苯并恶嗪-6-基)甲烷(bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazine-6-yl)methan e)：PBMCompound: bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)methane (bis(3-phenyl-3,4-dihydro-2H-1,3) -benzoxazine-6-yl)methan e):PBM

化合物：3,4-环氧环己烯基甲基-3',4'-环氧环己烯甲酸酯：EHECompound: 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate: EHE

化合物：2-(3,4-環氧環己基)乙基三甲氧基矽烷：EHSCompound: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane: EHS

化合物：1,3-雙(4,5-二氫-2-噁唑基)苯：BOBCompound: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene: BOB

＜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、原料投入添加口和氮氣導入口的100mL的四口燒瓶中，加入3.651g的化合物DAC和54.0g的脫水NMP，在乾燥氮氣流下進行攪拌溶解。接著，加入1.237g的化合物(1)、1.112g的化合物(19)以及15.0g的脫水GBL，在室溫環境下反應30小時。當反應過程中反應溫度上升時，將反應溫度抑制在約70℃或70℃以下而進行反應。然後在所獲得的溶液中添加25.0g的BC，獲得濃度為6重量%的聚醯胺酸溶液。將該聚醯胺酸作為PA1。PA1的重量平均分子量為34,800。To a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen gas inlet, 3.651 g of a compound DAC and 54.0 g of dehydrated NMP were placed, and stirred and dissolved under a dry nitrogen stream. Next, 1.237 g of the compound (1), 1.112 g of the compound (19), and 15.0 g of dehydrated GBL were added, and the mixture was reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction is carried out by suppressing the reaction temperature to about 70 ° C or lower. Then, 25.0 g of BC was added to the obtained solution to obtain a polyglycine solution having a concentration of 6% by weight. This polyamic acid was used as PA1. PA1 has a weight average molecular weight of 34,800.

聚醯胺酸的重量平均分子量是以如下方式求出的：用磷酸-DMF混合溶液(磷酸/DMF=0.6/100：重量比)來稀釋所獲得的聚醯胺酸，以使聚醯胺酸濃度約為1重量%，然後使用2695分離模塊(separation module)、2414差示折射計(Waters製造)，將所述混合溶液作為展開溶劑並使用GPC法進行測定，再進行聚苯乙烯換算。另外，管柱是使用HSPgel RT MB-M(Waters製造)，在管柱溫度為40℃、流速為0.35mL/min的條件下進行測定。The weight average molecular weight of polylysine is determined in such a manner that the obtained polylysine is diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) to make polylysine The concentration was about 1% by weight, and then the mixed solution was used as a developing solvent and measured by a GPC method using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters), and converted to polystyrene. Further, the column was measured using HSPgel RT MB-M (manufactured by Waters) under the conditions of a column temperature of 40 ° C and a flow rate of 0.35 mL/min.

[合成例2～合成例31][Synthesis Example 2 to Synthesis Example 31]

如表1和表2所示那樣變更四羧酸二酐和二胺，除此以外，依據合成例1來製備聚醯胺酸溶液(PA2)～聚醯胺酸溶液(PA31)。包括合成例1，將結果總結於表1和表2中。合成例24～合成例28中，由於在反應過程中有沉澱物析出，因此無法合成聚醯胺酸。A polyphthalic acid solution (PA2) to a polyaminic acid solution (PA31) was prepared according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Tables 1 and 2. Synthesis Example 1 was included, and the results are summarized in Tables 1 and 2. In Synthesis Example 24 to Synthesis Example 28, since precipitates were precipitated during the reaction, polyamine acid could not be synthesized.

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

[實施例1][Example 1]

在合成例1中所合成的濃度為6重量%的聚醯胺酸溶液(PA1)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。使用所獲得的液晶配向劑，如下述那樣來製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning 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＞<Method of Manufacturing Liquid Crystal Display Element>

用旋轉器將液晶配向劑塗布在兩片附有ITO電極的玻璃基板上，形成膜厚為70nm的膜。塗膜後在80℃下加熱乾燥約5分鐘，然後在210℃下進行20分鐘加熱處理，形成液晶配向膜。接著，用摩擦裝置對形成了液晶配向膜的基板的表面進行摩擦處理而實行配向處理。然後，在超純水中對液晶配向膜進行5分鐘超聲波清洗後，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 by a spinner to form a film having a film thickness of 70 nm. After coating, the film 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. Next, 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. Then, the liquid crystal alignment film was subjected to ultrasonic cleaning for 5 minutes in ultrapure water, and then dried in an oven at 120 ° C for 30 minutes.

在其中一片玻璃基板上散布7μm的間隙材料，以使形成了液晶配向膜的面為內側且摩擦方向成反平行的方式進行對向配置，然後用環氧硬化劑進行密封，製作間隙為7μm的反平行單元(antiparallel cell)。在該單元中注入如下所示的液晶組成物，並使用光固化劑來密封注入口。接著，在110℃下進行30分鐘加熱處理，製作液晶顯示元件。A gap material of 7 μm was spread on one of the glass substrates so that the surface on which the liquid crystal alignment film was formed was inside and the rubbing direction was anti-parallel, and then sealed with an epoxy hardener to make a gap of 7 μm. Antiparallel cell. A liquid crystal composition shown below was injected into the unit, and a light curing agent was used to seal the injection port. Next, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

[實施例2][Embodiment 2]

在合成例2中所合成的濃度為6重量%的聚醯胺酸溶液(PA2)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例3][Example 3]

在合成例3中所合成的濃度為6重量%的聚醯胺酸溶液(PA3)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例4][Example 4]

在合成例4中所合成的濃度為6重量%的聚醯胺酸溶液(PA4)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例5][Example 5]

在合成例5中所合成的濃度為6重量%的聚醯胺酸溶液(PA5)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例6][Embodiment 6]

在合成例6中所合成的濃度為6重量%的聚醯胺酸溶液(PA6)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA6) having a concentration of 6 wt% synthesized in Synthesis Example 6, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例7][Embodiment 7]

在合成例7中所合成的濃度為6重量%的聚醯胺酸溶液(PA7)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA7) having a concentration of 6% by weight synthesized in Synthesis Example 7, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例8][Embodiment 8]

將合成例2中所合成的濃度為6重量%的聚醯胺酸溶液(PA2)與合成例7中所合成的濃度為6重量%的聚醯胺酸溶液(PA7)以8/2的重量比進行混合。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例9][Embodiment 9]

將合成例13中所合成的濃度為6重量%的聚醯胺酸溶液(PA13)與合成例7中所合成的濃度為6重量%的聚醯胺酸溶液(PA7)以8/2的重量比進行混合。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。The polyglycine solution (PA13) having a concentration of 6 wt% synthesized in Synthesis Example 13 and the polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例10][Embodiment 10]

將合成例2中所合成的濃度為6重量%的聚醯胺酸溶液(PA2)與合成例15中所合成的濃度為6重量%的聚醯胺酸溶液(PA15)以8/2的重量比進行混合。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例11][Example 11]

在合成例8中所合成的濃度為6重量%的聚醯胺酸溶液(PA8)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA8) having a concentration of 6 wt% synthesized in Synthesis Example 8, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例12][Embodiment 12]

在合成例9中所合成的濃度為6重量%的聚醯胺酸溶液(PA9)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例13][Example 13]

在合成例10中所合成的濃度為6重量%的聚醯胺酸溶液(PA10)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA10) having a concentration of 6 wt% synthesized in Synthesis Example 10, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例14][Embodiment 14]

在合成例12中所合成的濃度為6重量%的聚醯胺酸溶液(PA12)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA12) having a concentration of 6 wt% synthesized in Synthesis Example 12, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例15][Example 15]

在合成例13中所合成的濃度為6重量%的聚醯胺酸溶液(PA13)中添加NMP.BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP.BC = 1/1 (weight ratio) was added to a polyglycine solution (PA13) having a concentration of 6% by weight synthesized in Synthesis Example 13, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例16][Example 16]

在合成例14中所合成的濃度為6重量%的聚醯胺酸溶液(PA14)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA14) having a concentration of 6 wt% synthesized in Synthesis Example 14, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例17][Example 17]

在合成例15中所合成的濃度為6重量%的聚醯胺酸溶液(PA15)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例18][Embodiment 18]

在合成例16中所合成的濃度為6重量%的聚醯胺酸溶液(PA16)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA16) having a concentration of 6 wt% synthesized in Synthesis Example 16, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例19][Embodiment 19]

在合成例17中所合成的濃度為6重量%的聚醯胺酸溶液(PA17)中添加N MP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of N MP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA17) having a concentration of 6% by weight synthesized in Synthesis Example 17, and the whole was diluted to 4% by weight. Liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例20][Example 20]

在合成例18中所合成的濃度為6重量%的聚醯胺酸溶液(PA18)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA18) having a concentration of 6 wt% synthesized in Synthesis Example 18, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例21][Example 21]

在合成例19中所合成的濃度為6重量%的聚醯胺酸溶液(PA19)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA19) having a concentration of 6 wt% synthesized in Synthesis Example 19, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例22][Example 22]

在合成例20中所合成的濃度為6重量%的聚醯胺酸溶液(PA20)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA20) having a concentration of 6 wt% synthesized in Synthesis Example 20, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例23][Example 23]

在合成例21中所合成的濃度為6重量%的聚醯胺酸溶液(PA21)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋戌4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21, and the whole was diluted to 4 wt% to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例24][Example 24]

在合成例22中所合成的濃度為6重量%的聚醯胺酸溶液(PA22)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA22) having a concentration of 6 wt% synthesized in Synthesis Example 22, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例25][Example 25]

在合成例23中所合成的濃度為6重量%的聚醯胺酸溶液(PA23)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA23) having a concentration of 6 wt% synthesized in Synthesis Example 23, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例26][Example 26]

在合成例22中所合成的濃度為6重量%的聚醯胺酸溶液(PA22)中添加相當於聚合物重量的20重量%的BOB。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA22) having a concentration of 6% by weight synthesized in Synthesis Example 22, 20% by weight of BOB equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例27][Example 27]

在合成例11中所合成的濃度為6重量%的聚醯胺酸溶液(PA11)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA11) having a concentration of 6 wt% synthesized in Synthesis Example 11, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例28][Example 28]

在合成例19中所合成的濃度為6重量%的聚醯胺酸溶液(PA19)中添加相當於聚合物重量的20重量%的BANI-M。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19, 20% by weight of BANI-M corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例29][Example 29]

在合成例19中所合成的濃度為6重量%的聚醯胺酸溶液(PA19)中添加相當於聚合物重量的20重量%的HEA。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19, 20% by weight of HEA equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例30][Example 30]

在合成例21中所合成的濃度為6重量%的聚醯胺酸溶液(PA21)中添加相當於聚合物重量的20重量%的PBM。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21, 20% by weight of PBM corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例31][Example 31]

在合成例21中所合成的濃度為6重量%的聚醯胺酸溶液(PA21)中添加相當於聚合物重量的20重量%的BANI-M。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21, 20% by weight of BANI-M corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例32][Example 32]

在合成例21中所合成的濃度為6重量%的聚醯胺酸溶液(PA21)中添加相當於聚合物重量的20重量%的PBM、相當於聚合物重量的10重量%的EHS。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21, 20 wt% of PBM corresponding to the weight of the polymer and EHS equivalent to 10 wt% of the weight of the polymer were added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例33][Example 33]

在合成例9中所合成的濃度為6重量%的聚醯胺酸溶液(PA9)中添加相當於聚合物重量的20重量%的BANI-M、相當於聚合物重量的10重量%的EHS。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA9) having a concentration of 6% by weight synthesized in Synthesis Example 9, 20% by weight of BANI-M, based on the weight of the polymer, and 10% by weight of EHS, based on the weight of the polymer, were added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[實施例34][Example 34]

在合成例11中所合成的濃度為6重量%的聚醯胺酸溶液(PA11)中添加相當於聚合物重量的10重量%的EHE。然後，在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成5重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。To the polyglycine solution (PA11) having a concentration of 6% by weight synthesized in Synthesis Example 11, 10% by weight of EHE equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[比較例1][Comparative Example 1]

在合成例29中所合成的濃度為6重量%的聚醯胺酸溶液(PA29)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[比較例2][Comparative Example 2]

在合成例30中所合成的濃度為6重量%的聚醯胺酸溶液(PA30)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA30) having a concentration of 6 wt% synthesized in Synthesis Example 30, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[比較例3][Comparative Example 3]

在合成例31中所合成的濃度為6重量%的聚醯胺酸溶液(PA31)中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA31) having a concentration of 6 wt% synthesized in Synthesis Example 31, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[比較例4][Comparative Example 4]

將合成例29中所合成的濃度為6重量%的聚醯胺酸溶液(PA29)與合成例30中所合成的濃度為6重量%的聚醯胺酸溶液(PA30)以8/2的重量比進行混合。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。The polyglycine solution (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29 and the polyglycine solution (PA30) having a concentration of 6 wt% synthesized in Synthesis Example 30 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[比較例5][Comparative Example 5]

將合成例29中所合成的濃度為6重量%的聚醯胺酸溶液(PA29)與合成例31中所合成的濃度為6重量%的聚醯胺酸溶液(PA31)以8/2的重量比進行混合。在所獲得的混合物中添加NMP/BC=1/1(重量比)的混合溶劑，將整體稀釋成4重量%，製成液晶配向劑。然後使用所獲得的液晶配向劑，與實施例1同樣地製作液晶顯示元件。A polyglycine solution (PA29) having a concentration of 6% by weight synthesized in Synthesis Example 29 and a polyglycine solution (PA31) having a concentration of 6% by weight synthesized in Synthesis Example 31 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

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

以如下的方式，對實施例1～實施例34、比較例1～比較例5中所製作的液晶顯示元件進行離子密度的測定和長期可靠性的測定。The liquid crystal display elements produced in Examples 1 to 34 and Comparative Examples 1 to 5 were subjected to measurement of ion density and measurement of long-term reliability 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型來進行離子密度的測定。測定條件設定為：波形為三角波，頻率為0.01Hz，電壓為±10V，測定溫度設定為60℃。測定值越小，則可以說電特性越良好。將結果示於表3中。The ion density was measured using a liquid crystal property evaluation device 6254 manufactured by TOYO Technica. The measurement conditions were set such that the waveform was a triangular wave, the frequency was 0.01 Hz, the voltage was ±10 V, and the measurement temperature was set to 60 °C. The smaller the measured value, the better the electrical characteristics can be said. The results are shown in Table 3.

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

對所製作的液晶顯示元件隨時間求出離子密度[pC]，並對其保持特性進行評價。保持特性的試驗方法是采用如下方法：將液晶顯示元件放置在溫度為100℃的環境中，中途隨時間取出而測定離子密度[pC]。離子密度的增加越小(例如增加量小於100：增加量=500小時後的離子密度-初期(0小時)的離子密度)，則可以說離子密度的保持特性越良好，而且可以說電特性的長期可靠性越良好。將300小時後和500小時後的數據示於表3中。The ion density [pC] of the liquid crystal display element produced was determined over time, and the retention characteristics were evaluated. The test method for maintaining the characteristics was to measure the ion density [pC] by placing the liquid crystal display element in an environment at a temperature of 100 ° C and taking it out over time. The smaller the increase in ion density (for example, the amount of increase is less than 100: the amount of increase = the ion density after 500 hours - the ion density of the initial (0 hour)), it can be said that the retention characteristic of the ion density is better, and it can be said that the electrical characteristics are The better the long-term reliability. The data after 300 hours and after 500 hours are shown in Table 3.

如表3所示，使用由含有單體中包含DAC的聚醯胺酸的液晶配向劑所獲得的液晶配向膜的液晶顯示元件，其抑制離子密度隨時間增大的效果得到了明顯改善。As shown in Table 3, the liquid crystal display element using a liquid crystal alignment film obtained by a liquid crystal alignment agent containing a polyamic acid containing a DAC in a monomer has a markedly improved effect of suppressing an increase in ion density with time.

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 (27)

一種液晶配向劑，其含有作為四羧酸二酐與二胺的反應產物的聚醯胺酸或者其衍生物，該液晶配向劑的特徵在於：所述二胺是選自由以下述結構式(N)-1~結構式(N)-28表示的化合物所組成的族群中的一種或者一種以上： A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent being characterized in that the diamine is selected from the following structural formula (N) -1~ one or more of the groups consisting of the compounds represented by the structural formula (N)-28: 如申請專利範圍第1項所述之液晶配向劑，其特徵在於：所述二胺是選自由以下述結構式(N)-1、結構式(N)-2、結構式(N)-5~結構式(N)-7、結構式(N)-9、結構式(N)-10、結構式(N)-14、結構式(N)-17、結構式(N)-18、結構式(N)-21~結構式(N)-23、結構式(N)-26以及結構式(N)-28表示的化合物所組成的族群中的一種或者一種以上： The liquid crystal alignment agent according to claim 1, wherein the diamine is selected from the group consisting of the following structural formula (N)-1, structural formula (N)-2, and structural formula (N)-5. ~Structure formula (N)-7, structural formula (N)-9, structural formula (N)-10, structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structure One or more of the groups consisting of the compounds represented by the formula (N)-21 to the structural formula (N)-23, the structural formula (N)-26, and the structural formula (N)-28: 如申請專利範圍第2項所述之液晶配向劑，其特徵在於：以通式(N)表示的二胺是以所述結構式(N)-1以及結構式(N)-2表示的化合物中的一方或者兩方。 The liquid crystal alignment agent according to claim 2, wherein the diamine represented by the general formula (N) is a compound represented by the structural formula (N)-1 and the structural formula (N)-2. One or both of them. 如申請專利範圍第1項所述之液晶配向劑，其特徵在於：所述二胺進一步包含以下述通式(VIII)以及通式(X)~通式(XIII)表示的具有側鏈結構的二胺： (通式(VIII)中，A3 表示單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-或者-(CH2 )m -(m表示1~6的整數)，R1 表示具有類固醇骨架的基團、以下述通式(IX)表示的基團，當苯環上所鍵合的兩個氨基的位置關係為對位時，R1 進一步包含碳數為1~30的烷基，當所述位置關係為間位 時，R1 進一步包含碳數為1~30的烷基或者苯基，所述烷基中，任意的-CH2 -可以獨立地經-CF2 -、-CHF-、-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，-CH3 可以經-CH2 F、-CHF2 或者-CF3 所取代，所述苯基的氫可以獨立地被取代為-F、-CH3 、-OCH3 、-OCH2 F、-OCHF2 或者-OCF3 )； (通式(IX)中，A4 以及A5 分別獨立地表示單鍵、-O-(此處為非連續)、-COO-、-OCO-、-CONH-、-CH=CH-或者碳數為1~12的亞烷基，R2 以及R3 分別獨立地表示-F或者-CH3 ，環S獨立地表示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，R4 表示-H、-F、碳數為1~30的烷基、碳數為1~30的氟取代烷基、碳數為1~30的烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ，a以及b分別表示0~4的整數，c、d以及e分別表示0~3的整數，f以及g分別獨立地表示0~2的整數，並且c+d+e≧1)； (通式(X)以及(XI)中，R5 獨立地表示-H或者-CH3 ，R6 表示-H、或者碳數為1~20的烷基或烯基，A6 獨立地表示單鍵、-C(=O)-或者-CH2 -，通式(XI)中，R7 以及R8 分別獨立地表示碳數為1~20的烷基或者苯基)； (通式(XII)以及(XIII)中，A7 獨立地表示-O-或者碳數為1~6的亞烷基，通式(XII)中，R9 表示-H或者碳數為1~30的烷基，該烷基中，碳數為2~30的烷基的任意的-CH2 -可以經-O-(此處為非連續)、-CH=CH-或者-C≡C-所取代，A8 表示單鍵或者碳數為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(XIII)中，R10 表示碳數為6~22的烷基，R11 表示碳數為1~22的烷基)。The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a side chain structure represented by the following general formula (VIII) and general formula (X) to general formula (XIII). Diamine: (In the formula (VIII), A 3 represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH 2 ) m - (m represents an integer of 1 to 6) R 1 represents a group having a steroid skeleton, and a group represented by the following formula (IX). When the positional relationship of two amino groups bonded to the benzene ring is para, R 1 further contains a carbon number of 1 The alkyl group of ~30, when the positional relationship is meta, R 1 further comprises an alkyl group having 1 to 30 carbon atoms or a phenyl group, and any -CH 2 - in the alkyl group may independently pass through - CF 2 -, -CHF-, -O- (here non-continuous), -CH=CH- or -C≡C-, -CH 3 may be via -CH 2 F, -CHF 2 or -CF 3 Substituted, the hydrogen of the phenyl group may be independently substituted with -F, -CH 3 , -OCH 3 , -OCH 2 F, -OCHF 2 or -OCF 3 ); (In the formula (IX), A 4 and A 5 each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon The number is from 1 to 12, and R 2 and R 3 each independently represent -F or -CH 3 , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3 - Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or hydrazine- 9,10-diyl, R 4 represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, CN, -OCH 2 F, -OCHF 2 or -OCF 3 , a and b respectively represent integers of 0 to 4, c, d, and e represent integers of 0 to 3, respectively, and f and g independently represent 0 to 2, respectively. Integer, and c+d+e≧1); (In the general formulae (X) and (XI), R 5 independently represents -H or -CH 3 , R 6 represents -H, or an alkyl group or an alkenyl group having 1 to 20 carbon atoms, and A 6 independently represents a single a bond, -C(=O)- or -CH 2 -, in the formula (XI), R 7 and R 8 each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group; (In the general formulae (XII) and (XIII), A 7 independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and in the formula (XII), R 9 represents -H or the carbon number is 1~. An alkyl group of 30, wherein any -CH 2 - of the alkyl group having 2 to 30 carbon atoms may be -O- (here, discontinuous), -CH=CH- or -C≡C- Substituted, 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, and h represents 0 or 1, and formula (XIII) In the formula, R 10 represents an alkyl group having 6 to 22 carbon atoms, and R 11 represents an alkyl group having 1 to 22 carbon atoms. 如申請專利範圍第4項所述之液晶配向劑，其特徵在於：所述具有側鏈結構的二胺是選自以下述通式(VIII -2)、通式(VIII-4)~通式(VIII-6)、通式(XII-2)、通式(XII-4)以及通式(XII-6)表示的化合物中的至少一種： (所述通式中，R23 、R29 以及R30 分別表示碳數為1~30的烷基、或者碳數為1~30的烷氧基)。The liquid crystal alignment agent according to claim 4, wherein the diamine having a side chain structure is selected from the group consisting of the following formula (VIII-2) and formula (VIII-4). (VIII-6), at least one of the compounds represented by the formula (XII-2), the formula (XII-4), and the formula (XII-6): (In the above formula, R 23 , R 29 and R 30 each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). 如申請專利範圍第1項所述之液晶配向劑，其特徵 在於：所述二胺進一步包含以下述通式(I)~通式(VII)以及通式(XV)表示的不具有側鏈結構的二胺：H2 N-X-NH2 (I) (通式(I)中，X表示-(CH2 )m -(m表示1~6的整數)，通式(III)以及通式(V)~通式(VII)中，Y獨立地表示單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-NH-、-N(CH3 )-(CH2 )m -N(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m -S-(m表示1~6的整數)，通式(V)中，Z表示單鍵或者不存在，通式(XV)中，R33 以及R34 分別獨立地表示碳數為1~3的烷基或者苯基，A3 獨立地表示亞甲基、亞苯基或者經烷基取代的亞苯基；l表示1~6的整數，m表示1~10的整數，通式(II)~通式(VII)中，環己烷環或者苯環上所鍵合的氫可獨立 地被取代為-F、-CH3 、-CF3 、-OH、-COOH、-SO3 H、-PO3 H2 ，通式(IV)中的苯環上所鍵合的氫可經苄基所取代)。The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a side chain structure represented by the following general formula (I) to formula (VII) and formula (XV). Diamine: H 2 NX-NH 2 (I) (In the formula (I), X represents -(CH 2 ) m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents Single bond, -O-, -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH 3 )-(CH 2 ) m -N (CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 ) m -, -O-(CH 2 ) m -O-, -S-(CH 2 m -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R 33 and R 34 each independently represent a carbon number of 1 ~3 alkyl or phenyl, A 3 independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group; l represents an integer of 1 to 6, and m represents an integer of 1 to 10, II)~ In the formula (VII), the hydrogen bonded to the cyclohexane ring or the benzene ring may be independently substituted with -F, -CH 3 , -CF 3 , -OH, -COOH, -SO 3 H , -PO 3 H 2 , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted by a benzyl group). 如申請專利範圍第6項所述之液晶配向劑，其特徵在於：所述不具有側鏈結構的二胺是選自以下述結構式(IV-1)、結構式(IV-2)、結構式(IV-15)~結構式(IV-17)、結構式(V-1)~結構式(V-12)、結構式(V-33)、結構式(V-35)~結構式(V-37)、結構式(VII-2)以及結構式(XV-1)表示的化合物中的至少一種： The liquid crystal alignment agent according to claim 6, wherein the diamine having no side chain structure is selected from the following structural formula (IV-1), structural formula (IV-2), and structure. Formula (IV-15)~Structure Formula (IV-17), Structural Formula (V-1)~Structure Formula (V-12), Structural Formula (V-33), Structural Formula (V-35)~Structure Formula ( At least one of a compound represented by V-37), structural formula (VII-2), and structural formula (XV-1): 如申請專利範圍第1項所述之液晶配向劑，其特徵在於：所述四羧酸二酐包含芳香族四羧酸二酐。 The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride. 如申請專利範圍第8項所述之液晶配向劑，其特徵在於：所述芳香族四羧酸二酐是以下述結構式(1)、結構式(2)、結構式(5)~結構式(7)以及結構式(14)表示的化合物中的至少一種： The liquid crystal alignment agent according to claim 8, wherein the aromatic tetracarboxylic dianhydride is a structural formula (1), a structural formula (2), and a structural formula (5) to a structural formula. (7) and at least one of the compounds represented by the structural formula (14): 如申請專利範圍第9項所述之液晶配向劑，其特徵在於：所述芳香族四羧酸二酐是以所述結構式(1)表示的化合物。 The liquid crystal alignment agent according to claim 9, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the structural formula (1). 如申請專利範圍第1項所述之液晶配向劑，其特徵在於：所述四羧酸二酐包含脂環式四羧酸二酐以及脂肪族四羧酸二酐中的一方或者兩方。 The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride comprises one or both of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. 如申請專利範圍第11項所述之液晶配向劑，其特徵在於：所述脂環式四羧酸二酐以及脂肪族四羧酸二酐是以下述結構式(19)、結構式(23)、結構式(25)、結構式(35)~結構式(39)、結構式(44)以及結構式(49)表示的化合物中的至少一種： The liquid crystal alignment agent according to claim 11, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are represented by the following structural formula (19) and structural formula (23). At least one of the compounds represented by the structural formula (25), the structural formula (35) to the structural formula (39), the structural formula (44), and the structural formula (49): 如申請專利範圍第12項所述之液晶配向劑，其特徵在於：所述脂環式四羧酸二酐以及脂肪族四羧酸二酐是以所述結構式(19)、結構式(23)、結構式(37)以及結構式(49)表示的化合物中的至少一種。 The liquid crystal alignment agent according to claim 12, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the structural formula (19) and the structural formula (23). At least one of the compounds represented by the structural formula (37) and the structural formula (49). 如申請專利範圍第4項至第13項中任一項所述之 液晶配向劑，其特徵在於：該液晶配向劑含有所述聚醯胺酸或者其衍生物A以及B，並且所述聚醯胺酸或者其衍生物A包含所述二胺中的所述具有側鏈結構的二胺，且所述聚醯胺酸或者其衍生物A以及B的二胺中的一方或者兩方包含以通式(N)表示的二胺。 As described in any one of claims 4 to 13 a liquid crystal alignment agent, characterized in that the liquid crystal alignment agent contains the polyamic acid or derivatives A and B thereof, and the polyamic acid or derivative A thereof comprises the side having the diamine One or both of the polyamine of the chain structure and the polyamine of the polyamine or the derivatives A and B thereof contain a diamine represented by the formula (N). 如申請專利範圍第1項所述之液晶配向劑，其特徵在於：該液晶配向劑進一步含有選自烯基取代納迪克醯亞胺化合物、具有自由基聚合性不飽和雙鍵的化合物、噁嗪化合物、噁唑啉化合物以及環氧化合物中的一種或者一種以上。 The liquid crystal alignment agent according to claim 1, wherein the liquid crystal alignment agent further contains a compound selected from an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and an oxazine. One or more of a compound, an oxazoline compound, and an epoxy compound. 如申請專利範圍第15項所述之液晶配向劑，其特徵在於：所述烯基取代納迪克醯亞胺化合物是選自由雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)以及N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)所組成的族群中的一種或者一種以上。 The liquid crystal alignment agent according to claim 15, wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine)phenyl}methane, N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl One of a group consisting of quinone imine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) or More than one. 如申請專利範圍第16項所述之液晶配向劑，其特徵在於：所述烯基取代納迪克醯亞胺化合物是雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷。 The liquid crystal alignment agent according to claim 16, wherein the alkenyl-substituted nadicilide compound is bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)phenyl}methane. 如申請專利範圍第15項所述之液晶配向劑，其特徵在於：所述具有自由基聚合性不飽和雙鍵的化合物是選自由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-二羥基亞乙基丙烯酸酯苯胺)所組成的族群中的一種或者一種以上。 The liquid crystal alignment agent according to claim 15, wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-methylenebis propylene amide, N, N '-Dihydroxyethylidene bispropene One or more of a group consisting of guanamine, ethylene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline). 如申請專利範圍第18項所述之液晶配向劑，其特徵在於：所述具有自由基聚合性不飽和雙鍵的化合物為N,N'-二羥基亞乙基雙丙烯醯胺。 The liquid crystal alignment agent according to claim 18, wherein the compound having a radical polymerizable unsaturated double bond is N,N'-dihydroxyethylenebisacrylamide. 如申請專利範圍第15項所述之液晶配向劑，其特徵在於：所述噁嗪化合物是選自由以下述式(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)以及式(f-2)~式(f-4)表示的化合物所組成的族群中的一種或者一種以上： The liquid crystal alignment agent according to claim 15, wherein the oxazine compound is selected from the group consisting of the following formula (b-1), formula (c-1), formula (c-3), and (c-5), formula (c-7), formula (c-9), formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula ( F-2) One or more of the groups consisting of the compounds represented by the formula (f-4): 如申請專利範圍第20項所述之液晶配向劑，其特徵在於：所述噁嗪化合物是以所述式(c-1)表示的化合物。 The liquid crystal alignment agent according to claim 20, wherein the oxazine compound is a compound represented by the formula (c-1). 如申請專利範圍第15項所述之液晶配向劑，其特徵在於：所述噁唑啉化合物是2,2'-雙(2-噁唑啉)以及1,3- 雙(4,5-二氫-2-噁唑基)苯中的一方或者兩方。 The liquid crystal alignment agent according to claim 15, wherein the oxazoline compound is 2,2'-bis(2-oxazoline) and 1,3- One or both of bis(4,5-dihydro-2-oxazolyl)benzene. 如申請專利範圍第22項所述之液晶配向劑，其特徵在於：所述噁唑啉化合物為1,3-雙(4,5-二氫-2-噁唑基)苯。 The liquid crystal alignment agent according to claim 22, wherein the oxazoline compound is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene. 如申請專利範圍第15項所述之液晶配向劑，其特徵在於：所述環氧化合物是選自由N,N,N',N'-四縮水甘油基-間苯二甲胺、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-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯、N-苯基馬來醯亞胺-甲基丙烯酸縮水甘油酯共聚物以及2-(3,4-環氧環己基)乙基三甲氧基矽烷所組成的族群中的一種或者一種以上。 The liquid crystal alignment agent according to claim 15, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine, 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]benzene Propane, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer And one or more of the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane. 如申請專利範圍第24項所述之液晶配向劑，其特徵在於：所述環氧化合物為3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯或者2-(3,4-環氧環己基)乙基三甲氧基矽烷。 The liquid crystal alignment agent according to claim 24, wherein the epoxy compound is 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid. Ester or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. 一種液晶配向膜，其特徵在於：該液晶配向膜是對如申請專利範圍第1項至第25項中任一項所述的液晶配向劑的塗膜進行加熱而形成的。 A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of claims 1 to 25. 一種液晶顯示元件，其具有一對基板、含有液晶分子且形成在所述一對基板間的液晶層、對液晶層施加電壓的電極、以及將所述液晶分子配向於預定方向上的液晶配向膜，此液晶顯示元件的特徵在於： 所述液晶配向膜為如申請專利範圍第26項所述的液晶配向膜。 A liquid crystal display element having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction The liquid crystal display element is characterized by: The liquid crystal alignment film is a liquid crystal alignment film according to claim 26 of the patent application.
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