TW201920365A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using liquid crystal alignment film - Google Patents

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

Info

Publication number
TW201920365A
TW201920365A TW107128084A TW107128084A TW201920365A TW 201920365 A TW201920365 A TW 201920365A TW 107128084 A TW107128084 A TW 107128084A TW 107128084 A TW107128084 A TW 107128084A TW 201920365 A TW201920365 A TW 201920365A
Authority
TW
Taiwan
Prior art keywords
formula
liquid crystal
group
crystal alignment
polymer
Prior art date
Application number
TW107128084A
Other languages
Chinese (zh)
Other versions
TWI788401B (en
Inventor
岩田隆志
田尻十南
Original Assignee
日商捷恩智股份有限公司
日商捷恩智石油化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商捷恩智股份有限公司, 日商捷恩智石油化學股份有限公司 filed Critical 日商捷恩智股份有限公司
Publication of TW201920365A publication Critical patent/TW201920365A/en
Application granted granted Critical
Publication of TWI788401B publication Critical patent/TWI788401B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

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

Abstract

To provide a liquid crystal alignment agent that makes it possible to form a liquid crystal alignment film that gives a liquid crystal display element that has favorable viewing angle characteristics and afterimage characteristics. A liquid crystal alignment agent that contains a polymer that is the product of reacting starting materials that include a tetracarboxylic acid dianhydride and a diamine. The starting materials used to synthesize the polymer include at least one compound selected from compounds represented by formulas (1)-(3) and also include compounds represented by formulas (A)-(C) and at least one compound selected from compounds represented by formula (D), provided that, when m in formula (1) is 8, no compound represented by formulas (A)-(C) need be included in the diamine, and the tetracarboxylic acid dianhydride need not be a compound represented by formula (D).

Description

液晶配向劑、液晶配向膜及使用其的液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

本發明是有關於一種用於形成液晶配向膜的液晶配向劑、使用該液晶配向劑而形成的液晶配向膜、以及具有該液晶配向膜的液晶顯示元件。The present invention relates to a liquid crystal alignment agent for forming a liquid crystal alignment film, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

作為液晶顯示元件，除了扭轉向列（Twisted Nematic，TN）型、超扭轉向列（Super Twisted Nematic，STN）型、垂直配向（Vertical Alignment，VA）型等縱電場方式的液晶顯示元件以外，已知有共面切換（In-Plane Switching，IPS）型或邊緣場切換（Fringe Field Switching，FFS）型等僅於相向配置的一對基板的單側形成電極且於與基板平行的方向上產生電場的橫電場方式的液晶顯示元件。其中，IPS型或FFS型所代表的橫電場方式的液晶顯示元件的視角特性或顏色再現性優異，並於電視機、平板電腦、智慧型電話等多種液晶顯示元件中使用（專利文獻1）。As liquid crystal display elements, in addition to liquid crystal display elements of longitudinal electric field methods such as Twisted Nematic (TN) type, Super Twisted Nematic (STN) type, and Vertical Alignment (VA) type, Known are In-Plane Switching (IPS) type or Fringe Field Switching (FFS) type, etc. Only an electrode is formed on one side of a pair of substrates facing each other and an electric field is generated in a direction parallel to the substrate. Liquid crystal display element of the horizontal electric field type. Among them, the transverse electric field type liquid crystal display device represented by the IPS type or the FFS type has excellent viewing angle characteristics or color reproducibility, and is used in various liquid crystal display devices such as televisions, tablets, and smart phones (Patent Document 1).

作為液晶顯示元件中所使用的構成構件之一的液晶配向膜為與顯示品質相關的重要的構件。近年來，隨著液晶顯示元件的高品質化，對液晶配向膜要求的性能多樣化、且高度化。尤其是，於橫電場方式的液晶顯示元件中，為了進而提高黑顯示中的視角特性及顏色再現性而要求如下液晶配向膜：除了要求將液晶的預傾角抑制得低以外，進而供給在電壓施加後且將電壓斷開（OFF）後不會產生殘像、即殘留直流（direct current，DC）的積存小、電荷的緩和快的液晶顯示元件（專利文獻2及專利文獻3）。 [現有技術文獻] [專利文獻]A liquid crystal alignment film, which is one of the constituent members used in a liquid crystal display element, is an important member related to display quality. In recent years, with the improvement of the quality of liquid crystal display elements, the performance required for a liquid crystal alignment film has been diversified and advanced. In particular, in the liquid crystal display element of the transverse electric field type, in order to further improve the viewing angle characteristics and color reproducibility in black display, a liquid crystal alignment film is required in addition to suppressing the pretilt angle of the liquid crystal to be low, and further supplying it under voltage application. Liquid crystal display elements (Patent Document 2 and Patent Document 3) in which a residual image, that is, a residual direct current (DC) accumulation is small and the charge is relaxed quickly after the voltage is turned OFF. [Prior Art Literature] [Patent Literature]

[專利文獻1]國際公開第1998/027454號 [專利文獻2]國際公開第2015/080185號 [專利文獻3]國際公開第2015/050135號[Patent Literature 1] International Publication No. 1998/027454 [Patent Literature 2] International Publication No. 2015/080185 [Patent Literature 3] International Publication No. 2015/050135

[發明所欲解決之課題] 如專利文獻2及專利文獻3般，迄今為止，提出有具有各種性能的液晶配向膜，但本發明者瞭解到並未提出形成兼具該些兩種性能的液晶配向膜的液晶配向劑。 因此，本發明的課題在於提供一種可將液晶的預傾角抑制得低、且供給殘留DC的積存小、電荷的緩和快的液晶顯示元件的液晶配向膜、及可形成該液晶配向膜的液晶配向劑。另外，本發明的課題在於提供一種具有該液晶配向膜且視角特性或殘像特性良好的液晶顯示元件。 [解決課題之手段][Problems to be Solved by the Invention] As described in Patent Documents 2 and 3, a liquid crystal alignment film having various properties has been proposed so far, but the present inventors have understood that a liquid crystal having both of these properties has not been proposed. Liquid crystal alignment agent for alignment film. Therefore, an object of the present invention is to provide a liquid crystal alignment film for a liquid crystal display element capable of suppressing a low pretilt angle of a liquid crystal, having a small accumulation of residual DC supply, and a rapid relaxation of charge, and a liquid crystal alignment film capable of forming the liquid crystal alignment film. Agent. Another object of the present invention is to provide a liquid crystal display element having the liquid crystal alignment film and having excellent viewing angle characteristics and afterimage characteristics. [Means for solving problems]

本發明者等人發現：含有聚合物作為用於合成的原料之一的液晶配向劑可形成可將液晶的預傾角抑制得低、且供給殘留DC的積存小、電荷的緩和快的液晶顯示元件的液晶配向膜，所述聚合物包含選自下述式（1）～式（3）所表示的化合物中的至少一種，且包含選自下述式（A）～式（C）所表示的化合物、及下述式（D）所表示的化合物中的至少一種。另外，發現具有該液晶配向膜的液晶顯示元件的視角特性或殘像特性良好，從而達成了本發明。The present inventors have found that a liquid crystal alignment agent containing a polymer as one of the raw materials for synthesis can form a liquid crystal display element that can suppress the pretilt angle of the liquid crystal to be low, has a small accumulation of residual DC supply, and has a rapid charge relaxation. Liquid crystal alignment film, the polymer contains at least one selected from the compounds represented by the following formulae (1) to (3), and contains a compound selected from the following formulae (A) to (C) At least one of a compound and a compound represented by the following formula (D). In addition, the liquid crystal display element including the liquid crystal alignment film was found to have good viewing angle characteristics or afterimage characteristics, and the present invention has been achieved.

[化1] [Chemical 1]

[化2] [Chemical 2]

[化3]式（1）中，m為3～8的整數，式（3）中，n為1～3的整數，式（1）～式（3）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意，式（A）中，A1 為氮、或含有氮的雜環，W1 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z1 為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，a獨立地為0或1，式（B）中，A2 獨立地為氮、或含有氮的雜環，W2 及W3 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z2 獨立地為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，a獨立地為0或1，式（C）中，Z3 為含有二級或三級胺基的至少一種的一價有機基，式（D）中，T為包含1個～2個碳-碳雙鍵或1個～2個碳-碳三鍵的二價的含有不飽和鍵的基，而且，式（1）～式（3）及式（A）～式（C）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非下述式（D）所表示的化合物。 [發明的效果][Chemical 3] In formula (1), m is an integer of 3 to 8, in formula (3), n is an integer of 1 to 3, and in formulas (1) to (3), the bonding position is not fixed to any of the members constituting the ring. A one-carbon atom group indicates that the bonding position in the ring is arbitrary. In formula (A), A 1 is nitrogen or a heterocyclic ring containing nitrogen, W 1 is independently an alkylene group having 1 to 5 carbon atoms, any -CH 2 -may be substituted with -CO-, 1,4-phenylene, or 1,3-phenylene, Z 1 is hydrogen, a protecting group substituted with a hydrogen atom by heat, or carbon number 1 to 5 alkyl groups, a is independently 0 or 1, in formula (B), A 2 is independently nitrogen or a heterocyclic ring containing nitrogen, and W 2 and W 3 are independently 1 to 5 carbon atoms Alkyl, any -CH 2 -may be substituted with -CO-, 1,4-phenylene, or 1,3-phenylene, Z 2 is independently hydrogen, and is substituted by a hydrogen atom by heat A protecting group or an alkyl group having 1 to 5 carbon atoms, a is independently 0 or 1, and in formula (C), Z 3 is a monovalent organic group containing at least one of a secondary or tertiary amine group, and formula (D ), T is a divalent unsaturated bond-containing group containing one or two carbon-carbon double bonds or one or two carbon-carbon triple bonds, and Formulas (1) to (3) In the formulae (A) to (C), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, where m in the formula (1) When it is 8, the diamine may not include any of the compounds represented by the formulae (A) to (C), and the tetracarboxylic dianhydride may not be a compound represented by the following formula (D). [Effect of the invention]

藉由使用本發明的液晶配向劑，可獲得可將液晶的預傾角抑制得低、且供給殘留DC的積存小、電荷的緩和快的液晶顯示元件的液晶配向膜。另外，具有該液晶配向膜的液晶顯示元件的視角特性或殘像特性良好。By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film can be obtained for a liquid crystal display element capable of suppressing a low pretilt angle of liquid crystals, providing a small accumulation of residual DC, and a rapid relaxation of electric charges. In addition, the liquid crystal display element having the liquid crystal alignment film has good viewing angle characteristics or afterimage characteristics.

以下，對本發明的實施形態進行說明。再者，本發明並不僅限定於以下的實施形態。另外，於本說明書中，只要並無特別記述，則操作及物性等的測定是於室溫（20℃以上且25℃以下）/相對濕度40%RH以上且50%RH以下的條件下進行。Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In addition, in this specification, unless otherwise stated, measurement of operation, physical properties, and the like are performed under conditions of room temperature (20 ° C or higher and 25 ° C or lower) / relative humidity of 40% RH or higher and 50% RH or lower.

本發明的液晶配向劑為含有聚合物（以下，存在簡稱為「聚合物」、本發明的「聚合物」的情況）作為用於合成的原料之一的液晶配向劑，所述聚合物包含選自下述式（1）～式（3）所表示的化合物中的至少一種、且包含選自下述式（A）～式（C）所表示的化合物、及下述式（D）所表示的化合物中的至少一種。The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer (hereinafter, simply referred to as "polymer" and the "polymer" of the present invention) as one of the raw materials for synthesis. And at least one selected from the compounds represented by the following formulae (1) to (3), and including a compound selected from the following formulae (A) to (C) and the following formula (D) At least one of the compounds.

[化4] [Chemical 4]

[化5] [Chemical 5]

[化6]式（1）中，m為3～8的整數，式（3）中，n為1～3的整數，式（1）～式（3）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意，式（A）中，A1 為氮、或含有氮的雜環，W1 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z1 為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r為0以上的任意整數，a獨立地為0或1，式（B）中，A2 獨立地為氮、或含有氮的雜環，W2 及W3 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z2 獨立地為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r為0以上的任意的整數，a獨立地為0或1，式（C）中，Z3 為含有二級或三級胺基的至少一種的一價有機基，式（D）中，T為包含1個～2個碳-碳雙鍵或1個～2個碳-碳三鍵的二價的含有不飽和鍵的基，而且，式（1）～式（3）及式（A）～式（C）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非所述式（D）所表示的化合物。藉由具有該構成，可提供一種可將液晶的預傾角抑制得低、且殘留DC的積存小、電荷的緩和快的液晶配向膜。 另外，於本發明的實施形態中，提供一種液晶配向劑，其含有包含源自以下原料的構成單元的聚合物的至少一種，並且所述原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種，且包含選自由所述式（A）、所述式（B）、所述式（C）及所述式（D）所組成的群組中的至少一種，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非所述式（D）所表示的化合物。另外，於該實施形態中，所述聚合物為選自由聚醯胺酸、聚醯亞胺、部分聚醯亞胺、聚醯胺酸酯、聚醯胺酸-聚醯胺共聚物及聚醯胺醯亞胺所組成的群組中的至少一種。其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非所述式（D）所表示的化合物。本說明書中，「作為源自包含…的原料的反應產物的聚合物」亦可為「包含源自原料的構成單元的聚合物」。 再者，於本發明的實施形態中，提供一種製造方法，其製造含有作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物的至少一種的液晶配向劑，並且所述方法包括使作為用於合成所述聚合物的原料的、選自所述式（1）～式（3）所表示的化合物的群組中的至少一種、與選自所述式（A）～式（C）所表示的化合物的群組、及所述式（D）所表示的化合物中的至少一種反應，此處，所述聚合物為選自由聚醯胺酸、聚醯亞胺、部分聚醯亞胺、聚醯胺酸酯、聚醯胺酸-聚醯胺共聚物、及聚醯胺醯亞胺所組成的群組中的至少一種，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非下述式（D）所表示的化合物。 再者，於本發明的實施形態中，亦提供一種本發明的聚合物作為液晶配向劑的使用（應用）。[Chemical 6] In formula (1), m is an integer of 3 to 8, in formula (3), n is an integer of 1 to 3, and in formulas (1) to (3), the bonding position is not fixed to any of the members constituting the ring. A one-carbon atom group indicates that the bonding position in the ring is arbitrary. In formula (A), A 1 is nitrogen or a heterocyclic ring containing nitrogen, W 1 is independently an alkylene group having 1 to 5 carbon atoms, any -CH 2 -may be substituted with -CO-, 1,4-phenylene, or 1,3-phenylene, Z 1 is hydrogen, a protecting group substituted with a hydrogen atom by heat, or carbon number 1 to 5 alkyl groups, r is any integer of 0 or more, a is independently 0 or 1, and in formula (B), A 2 is independently nitrogen or a nitrogen-containing heterocyclic ring, and W 2 and W 3 are independently Is an alkylene group having 1 to 5 carbon atoms, and any -CH 2 -may be substituted by -CO-, 1,4-phenylene, or 1,3-phenylene, and Z 2 is independently hydrogen, A protective group substituted with a hydrogen atom by heat or an alkyl group having 1 to 5 carbon atoms, r is an arbitrary integer of 0 or more, a is independently 0 or 1, and in formula (C), Z 3 contains a secondary group Or a monovalent organic group of at least one of a tertiary amine group, in formula (D), T is a two containing one to two carbon-carbon double bonds or one to two carbon-carbon triple bonds An unsaturated bond-containing group, and in the formulae (1) to (3) and (A) to (C), a group whose bond position is not fixed to any carbon atom constituting the ring represents the ring The bonding position in is arbitrary, and when m is 8 in the formula (1), the diamine may not include any one of the compounds represented by the formulas (A) to (C). The tetracarboxylic dianhydride may not be a compound represented by the formula (D). By having this structure, it is possible to provide a liquid crystal alignment film capable of suppressing the pretilt angle of the liquid crystal to be low, having a small accumulation of residual DC, and having a rapid relaxation of electric charge. In addition, in an embodiment of the present invention, there is provided a liquid crystal alignment agent containing at least one polymer containing a constituent unit derived from the following raw materials, and the raw materials include a formula selected from the formulas (1) to (3) At least one of the group of compounds represented by), and is selected from the group consisting of the formula (A), the formula (B), the formula (C), and the formula (D) At least one of the above, wherein when m in the formula (1) is 8, the diamine may not include any one of the compounds represented by the formulas (A) to (C), and the tetracarboxylic acid The dianhydride may not be a compound represented by the formula (D). In addition, in this embodiment, the polymer is selected from the group consisting of polyamic acid, polyimide, part of polyimide, polyamidate, polyamic acid-polyamidamine copolymer, and polyfluorene. At least one of the group consisting of amine imine. When m is 8 in the formula (1), the diamine may not include any of the compounds represented by the formulas (A) to (C), and the tetracarboxylic dianhydride may not be A compound represented by the formula (D). In this specification, "a polymer which is a reaction product derived from a raw material containing ..." may be "a polymer which contains the structural unit derived from a raw material." Furthermore, in an embodiment of the present invention, there is provided a manufacturing method for manufacturing a liquid crystal alignment agent containing at least one polymer as a reaction product derived from a raw material containing tetracarboxylic dianhydride and diamine, and The method includes, as a raw material for synthesizing the polymer, at least one selected from the group of compounds represented by the formulas (1) to (3), and selected from the group consisting of the formula (A) ~ A group of compounds represented by formula (C) and at least one of the compounds represented by formula (D) is reacted. Here, the polymer is selected from the group consisting of polyamic acid, polyimide, At least one of the group consisting of polyimide, polyimide, polyacid-polyimide copolymer, and polyimide, wherein in the formula (1) When m is 8, the diamine may not include any of the compounds represented by the formulae (A) to (C), and the tetracarboxylic dianhydride may not be a compound represented by the following formula (D) . Furthermore, in an embodiment of the present invention, use (application) of the polymer of the present invention as a liquid crystal alignment agent is also provided.

於本說明書中，將使所述聚合物溶解於有機溶劑中而成的狀態者稱為清漆。清漆的製造方法並無特別限制，可將聚合物與有機溶劑的混合物直接作為清漆而用於液晶配向劑的製造，所述聚合物是使包含四羧酸二酐（包含其衍生物）及二胺（包含二醯肼）的原料的混合物於有機溶劑中反應而成。另外，亦可將自反應混合物回收聚合物並使該聚合物再次溶解於有機溶劑中而成者作為清漆而用於液晶配向劑的製造。本發明的液晶配向劑為以使聚合物溶解於有機溶劑中而成的清漆為主成分的溶液，亦可使用兩種以上的清漆，所述聚合物是選自聚醯胺酸、聚醯亞胺、部分聚醯亞胺、聚醯胺酸酯、聚醯胺酸-聚醯胺共聚物、及聚醯胺醯亞胺等的群組中。本發明的較佳的形態中，於將該液晶配向劑塗佈於基板上後，藉由加熱等手段而成膜並形成聚醯亞胺系液晶配向膜。In the present specification, a state in which the polymer is dissolved in an organic solvent is referred to as a varnish. The method for producing the varnish is not particularly limited, and a mixture of a polymer and an organic solvent can be directly used as a varnish for the manufacture of a liquid crystal alignment agent. The polymer is made of tetracarboxylic dianhydride (including its derivative) and two A mixture of amine (containing dihydrazine) raw materials is reacted in an organic solvent. In addition, a polymer obtained by recovering a polymer from a reaction mixture and re-dissolving the polymer in an organic solvent may be used as a varnish for the production of a liquid crystal alignment agent. The liquid crystal alignment agent of the present invention is a solution mainly composed of a varnish obtained by dissolving a polymer in an organic solvent. Two or more kinds of varnishes may also be used. The polymer is selected from the group consisting of polyamic acid and polyfluorene. Amines, partial polyimides, polyamidates, polyamic acid-polyamidamine copolymers, polyamidoimines, and the like. In a preferred aspect of the present invention, after the liquid crystal alignment agent is coated on a substrate, a film is formed by means such as heating to form a polyfluorene imide liquid crystal alignment film.

進而詳細而言，本發明的液晶配向劑包含使選自式（1）～式（3）所表示的化合物中的至少一種、與選自所述式（A）～式（C）所表示的化合物、及所述式（D）所表示的化合物中的至少一種反應而獲得的聚合物的至少一種作為用於合成的原料，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非所述式（D）所表示的化合物。另外，於本發明的實施形態中，為一種液晶配向劑，其含有作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物的至少一種，並且用於合成所述聚合物的原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種，且包含選自所述式（A）～式（C）所表示的化合物的群組中的至少一種，並且包含選自所述式（D）所表示的化合物中的至少一種。另外，於本發明的實施形態中，液晶配向劑含有一種作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物，更具體而言，本發明的實施形態中的液晶配向劑含有一種使用如下原料的聚合物，所述原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種、且包含選自所述式（A）～式（C）所表示的化合物的群組、及所述式（D）所表示的化合物中的至少一種（於某實施形態中，為於基板上積層1層的形態，因此亦可稱為「單層系」）。即，於本發明的實施形態中，含有一種所述聚合物。另外，於本發明的實施形態中，含有兩種以上的所述聚合物（於某實施形態中，為於基板上積層2層以上的形態，因此亦可稱為「混合（blend）系」）。另外，本發明的實施形態的液晶配向劑包含聚合物（P）及聚合物（Q）作為用於合成的原料。即，於本發明的實施形態中，含有至少兩種所述聚合物，所述至少兩種聚合物包含聚合物（P）及聚合物（Q）；用於合成所述聚合物（P）的原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種；而且，用於合成所述聚合物（Q）的原料包含選自所述式（A）～式（C）所表示的化合物的群組、及所述式（D）所表示的化合物中的至少一種。Furthermore, the liquid crystal aligning agent of this invention contains at least 1 sort (s) chosen from the compound represented by Formula (1)-Formula (3), and the compound chosen from the said Formula (A)-Formula (C) further. As a raw material for synthesis, at least one of a compound and a polymer obtained by reacting at least one of the compounds represented by the formula (D), wherein when m in the formula (1) is 8, the The diamine may not include any of the compounds represented by the formulae (A) to (C), and the tetracarboxylic dianhydride may not be the compound represented by the formula (D). In addition, in an embodiment of the present invention, it is a liquid crystal alignment agent which contains at least one polymer as a reaction product derived from a raw material containing a tetracarboxylic dianhydride and a diamine, and is used for synthesizing the polymerization. The raw material of the substance contains at least one selected from the group of the compounds represented by the formulae (1) to (3), and includes a group selected from the compounds represented by the formulae (A) to (C). And at least one selected from the group consisting of a compound represented by the formula (D). In the embodiment of the present invention, the liquid crystal alignment agent contains a polymer as a reaction product derived from a raw material containing a tetracarboxylic dianhydride and a diamine. More specifically, the liquid crystal in the embodiment of the present invention The alignment agent contains a polymer using a raw material containing at least one selected from the group of the compounds represented by the formulae (1) to (3), and containing a material selected from the formula (A). ~ At least one of a group of compounds represented by the formula (C) and the compound represented by the formula (D) (in a certain embodiment, it is a form in which one layer is laminated on a substrate, so it can also be called "Single layer system"). That is, in one embodiment of the present invention, one kind of the polymer is contained. In addition, in an embodiment of the present invention, two or more of the polymers are contained (in a certain embodiment, the polymer is laminated in a form of two or more layers on the substrate, so it may be referred to as a "blend system") . The liquid crystal alignment agent according to the embodiment of the present invention includes a polymer (P) and a polymer (Q) as raw materials for synthesis. That is, in an embodiment of the present invention, at least two kinds of the polymers are included, and the at least two kinds of polymers include a polymer (P) and a polymer (Q); The raw material contains at least one selected from the group of the compounds represented by the formulae (1) to (3); and the raw material for synthesizing the polymer (Q) contains a material selected from the formula (A). To at least one of the group of compounds represented by formula (C) and the compound represented by formula (D).

於本發明中，所述聚合物為選自由聚醯胺酸、聚醯亞胺、部分聚醯亞胺、聚醯胺酸酯、聚醯胺酸-聚醯胺共聚物、及聚醯胺醯亞胺所組成的群組中的至少一種。另外，於本說明書中，該些包含該些的衍生物。例如，所述聚合物為聚醯胺酸或其衍生物。In the present invention, the polymer is selected from the group consisting of polyamic acid, polyimide, part of polyimide, polyamidate, polyamic acid-polyamidate copolymer, and polyamidofluorene At least one of the group consisting of imines. In addition, in this specification, these include these derivatives. For example, the polymer is polyamic acid or a derivative thereof.

對式（1）～式（3）所表示的化合物進行說明。The compound represented by Formula (1)-Formula (3) is demonstrated.

[化7]式（1）中，m為3～8的整數，更具體而言，m為3、4、5、6、7或8。此處，若m為8，則尤其就可發揮將預傾角抑制得低的效果的方面而言，亦適宜。另外，若m為3，則尤其就示出良好的液晶配向性的方面而言，亦適宜。 式（3）中，n為1～3的整數。 式（1）～式（3）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意。再者，於本發明的實施形態中，胺基對於環的鍵結位置較佳為間位、對位，以確保下述直線性。[Chemical 7] In Formula (1), m is an integer of 3 to 8, and more specifically, m is 3, 4, 5, 6, 7, or 8. Here, if m is 8, it is suitable especially from the point which can exhibit the effect which suppresses a pretilt angle low. In addition, if m is 3, it is particularly suitable in terms of showing good liquid crystal alignment. In Formula (3), n is an integer of 1-3. In the formulae (1) to (3), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. Furthermore, in the embodiment of the present invention, it is preferable that the bonding position of the amine group to the ring is meta and para to ensure the following linearity.

藉由使用所述式（1）、式（2）及式（3）所表示的化合物的至少一種作為用於合成的原料，所獲得的聚合物的穩定的構型（conformation）非常為直線性，因此認為可將液晶的預傾角抑制得低。By using at least one of the compounds represented by the formulas (1), (2), and (3) as a raw material for synthesis, the stable configuration of the obtained polymer is very linear. Therefore, it is considered that the pretilt angle of the liquid crystal can be suppressed low.

以下示出式（1）～式（3）所表示的化合物的適宜的具體例。Suitable specific examples of the compounds represented by the formulas (1) to (3) are shown below.

[化8] [Chemical 8]

[化9] [Chemical 9]

[化10] [Chemical 10]

其中，式（1-1）、式（1-4）、式（2-1）、及式（3-1）所表示的化合物示出高的液晶配向性，且可進一步將液晶的預傾角抑制得低，因此較佳。尤其是，為式（1-1）及式（1-4）的至少一者的情況因於有機溶媒中的溶解性優異而較佳。如以上所述，於本發明中，亦提供一種二胺，其是由所述式（1-4）所表示。藉由使用所述式（1-4）所表示的二胺作為用於合成液晶配向劑中所使用的聚合物的原料中的二胺原料，可形成一種可特異性地將液晶的預傾角抑制得低、且供給殘留DC的積存小、電荷的緩和快的液晶顯示元件的液晶配向膜。另外，藉由僅使用所述式（1-4）所表示的二胺作為用於合成液晶配向劑中所使用的聚合物的原料中的二胺原料，可特異性地將液晶的預傾角抑制得低。因此，於本發明中，亦提供一種液晶配向劑，其含有作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物的至少一種，並且所述二胺僅包含所述式（1-4）所表示的二胺。再者，於使用所述式（1-4）所表示的二胺作為用於合成液晶配向劑中所使用的聚合物的原料中的二胺原料的情況下，酸二酐並無特別限制。另外，作為所述式（1-4）所表示的二胺的合成方法，可列舉實施例欄中所記載的方法作為一例，但並不限定於此。Among them, the compounds represented by the formulas (1-1), (1-4), (2-1), and (3-1) show high liquid crystal alignment, and can further pre-tilt the liquid crystal. Inhibition is low, so it is better. In particular, the case where it is at least one of the formula (1-1) and the formula (1-4) is preferable because the solubility in the organic solvent is excellent. As described above, in the present invention, a diamine is also provided, which is represented by the formula (1-4). By using the diamine represented by the formula (1-4) as a diamine raw material in a raw material for synthesizing a polymer used in a liquid crystal alignment agent, a pretilt angle of a liquid crystal can be specifically suppressed A liquid crystal alignment film having a low liquid crystal display element with low accumulation of residual DC and fast charge relaxation can be obtained. In addition, by using only the diamine represented by the formula (1-4) as the diamine raw material among the raw materials used to synthesize the polymer used in the liquid crystal alignment agent, the pretilt angle of the liquid crystal can be specifically suppressed. Get low. Therefore, in the present invention, there is also provided a liquid crystal alignment agent containing at least one polymer as a reaction product derived from a raw material containing a tetracarboxylic dianhydride and a diamine, and the diamine includes only the above-mentioned A diamine represented by formula (1-4). When the diamine represented by the formula (1-4) is used as a diamine raw material among the raw materials used to synthesize the polymer used in the liquid crystal alignment agent, the acid dianhydride is not particularly limited. In addition, as a method for synthesizing the diamine represented by the formula (1-4), the method described in the Example column is exemplified, but it is not limited thereto.

繼而，對式（A）～式（D）所表示的化合物進行說明。Next, the compounds represented by formula (A) to formula (D) will be described.

[化11] [Chemical 11]

[化12]式（A）中，A1 為氮、或含有氮的雜環，W1 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z1 為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r為0以上的任意整數，a獨立地為0或1。此處，本說明書中的含有氮的雜環為包含含有氮的雜環、與含有氮的脂肪族環的概念。另外，含有氮的雜環中，除了氮原子以外，亦可包含氧原子、硫原子等雜原子。另外，本說明書中，所謂r的任意整數，為於A1 為含有氮的雜環的情況下藉由縮合的環的數量、或者所含的氮原子、或雜原子的數量而可變化的數，因此無法特別指定，例如可為1～10的整數。本說明書中，所謂「藉由熱而取代為氫原子的保護基」，若為藉由熱而取代為氫原子者，則並無特別限制，可適宜地列舉：Boc（第三丁氧基羰基的簡稱）、苄基氧基羰基、9-茀基甲基氧基羰基、烯丙基氧基羰基等胺基甲酸酯系保護基。 式（B）中，A2 獨立地為氮、或含有氮的雜環，W2 及W3 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z2 獨立地為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r為0以上的任意整數，a獨立地為0或1。 式（C）中，Z3 為含有二級或三級胺基的至少一種的一價有機基。 式（D）中，T為包含1個～2個碳-碳雙鍵或1個～2個碳-碳三鍵的二價的含有不飽和鍵的基。於本發明的實施形態中，T包含碳數6～12的伸芳基。於所述式（1）中m為8時，T可為伸烷基，較佳為該伸烷基的碳數為2～16，更佳為2～8，進而佳為4～8。 另外，式（1）～式（3）及式（A）～式（C）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意。[Chemical 12] In formula (A), A 1 is nitrogen or a heterocyclic ring containing nitrogen, W 1 is independently an alkylene group having 1 to 5 carbon atoms, and any -CH 2 -may be substituted by -CO-, 1,4 -Phenylene or 1,3-phenylene, Z 1 is hydrogen, a protective group substituted with a hydrogen atom by heat, or an alkyl group having 1 to 5 carbon atoms; r is an arbitrary integer of 0 or more, a Independently 0 or 1. Here, the nitrogen-containing heterocyclic ring in the present specification is a concept including a nitrogen-containing heterocyclic ring and a nitrogen-containing aliphatic ring. In addition, the nitrogen-containing heterocyclic ring may include a hetero atom such as an oxygen atom and a sulfur atom in addition to the nitrogen atom. In this specification, an arbitrary integer of "r" is a number that can be changed by the number of condensed rings or the number of nitrogen atoms or heteroatoms contained when A 1 is a heterocyclic ring containing nitrogen. , So it cannot be specified, and it can be an integer from 1 to 10. In the present specification, the "protective group substituted with a hydrogen atom by heat" is not particularly limited as long as it is substituted with a hydrogen atom by heat. Boc (third butoxycarbonyl group) ), Benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl and other urethane-based protecting groups. In formula (B), A 2 is independently nitrogen or a heterocyclic ring containing nitrogen, W 2 and W 3 are independently alkylene groups having 1 to 5 carbon atoms, and any -CH 2 -may be substituted by -CO -, 1,4-phenylene, or 1,3-phenylene, Z 2 is independently hydrogen, a protecting group substituted with a hydrogen atom by heat, or an alkyl group having 1 to 5 carbon atoms, and r is For any integer greater than or equal to 0, a is independently 0 or 1. In the formula (C), Z 3 is a monovalent organic group containing at least one of a secondary or tertiary amine group. In the formula (D), T is a divalent unsaturated bond-containing group containing one to two carbon-carbon double bonds or one to two carbon-carbon triple bonds. In an embodiment of the present invention, T contains an arylene group having 6 to 12 carbon atoms. When m in the formula (1) is 8, T may be an alkylene group, preferably the carbon number of the alkylene group is 2-16, more preferably 2-8, and even more preferably 4-8. Further, in the formulae (1) to (3) and the formulae (A) to (C), a group whose bonding position is not fixed to any carbon atom constituting a ring indicates that the bonding position in the ring is arbitrary.

於本發明的實施形態中，式（A）～式（C）所表示的化合物具有氮（尤其是二級胺基、三級胺基）、或含有氮的雜環。認為該些基作為促進液晶配向膜中的電荷的遷移的基發揮作用，且承擔迅速緩和所蓄積的電荷的職能。另外，式（D）所表示的化合物遍及分子整體而廣布有π電子雲。因此，藉由使式（A）～式（C）所表示的化合物、與式（D）所表示的化合物反應，所獲得的聚合物具有高的共軛性，因此認為於作為液晶配向膜而使用時，降低體積電阻值而減小殘留DC的積存，並有助於電荷的快速緩和。其中，於所述式（1）中m為8時，作為二胺，式（A）～式（D）所表示的化合物並非必需，發揮可驚人地降低預傾角的效果。另外，進行反應的酸二酐亦無特別限制，例如可為式（D）所表示的化合物，亦可為（AN-1）～（AN-18）的任一者所表示者，亦可為其他公知者。In the embodiment of the present invention, the compounds represented by the formulae (A) to (C) have nitrogen (especially a secondary amine group and a tertiary amine group) or a nitrogen-containing heterocyclic ring. It is considered that these groups function as a group that promotes the migration of electric charges in the liquid crystal alignment film, and assume the function of quickly alleviating the accumulated electric charges. In addition, the compound represented by formula (D) has a π-electron cloud spread throughout the entire molecule. Therefore, by reacting the compounds represented by the formulas (A) to (C) with the compounds represented by the formula (D), the obtained polymer has high conjugation properties, and is therefore considered as a liquid crystal alignment film. In use, the volume resistance value is reduced to reduce the accumulation of residual DC, and it is helpful to the rapid relaxation of the charge. However, when m in the formula (1) is 8, the compound represented by the formula (A) to the formula (D) is not necessary as the diamine, and exhibits an effect of surprisingly reducing the pretilt angle. In addition, the acid dianhydride to be reacted is not particularly limited, and may be, for example, a compound represented by formula (D), or any of (AN-1) to (AN-18), or Other well-known.

以下示出式（A）～式（D）所表示的化合物的具體例。Specific examples of the compounds represented by the formulae (A) to (D) are shown below.

[化13] [Chemical 13]

[化14] [Chemical 14]

[化15][化16] [Chemical 15] [Chemical 16]

[化17] [Chemical 17]

[化18]式（A-1）～式（A-11）中，鍵結位置並未固定於構成環的任一碳原子的基表示該環中的鍵結位置為任意。式（B-3）中，k為1～5的整數，更具體而言為1、2、3、4或5。式（B-4）中，n為1～3的整數，更具體而言為1、2或3。[Chemical 18] In the formulae (A-1) to (A-11), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In the formula (B-3), k is an integer of 1 to 5, and more specifically 1, 2, 3, 4 or 5. In formula (B-4), n is an integer of 1 to 3, and more specifically 1, 2 or 3.

其中，較佳為所述式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（A-19）、式（B-3）、式（B-5）、式（C-2）、式（C-3）、式（D-2）、及式（D-3）的至少一種。尤其是，式（B-3）及式（D-2）減小殘留DC的積存且電荷的緩和特別快，因此較佳。另外，式（A-15）不僅減小殘留DC的積存且電荷的緩和快，而且電壓保持率亦良好，因此更佳。此處，式（B-3）中，進而佳為k=2。 根據本發明的實施形態，所述式（1）～式（3）所表示的化合物為選自所述式（1-1）～式（1-4）、式（2-1）、式（2-2）、及式（3-1）～式（3-6）所表示的化合物的群組中的至少一種；所述式（A）～式（C）所表示的化合物為選自所述式（A-1）～式（A-20）、式（B-1）～式（B-8）、及式（C-1）～式（C-3）所表示的化合物的群組中的至少一種；所述式（D）所表示的化合物為選自所述式（D-1）～式（D-4）所表示的化合物的群組中的至少一種。根據該實施形態，可有效率地發揮本發明的所需的效果。 另外，於本發明的實施形態中，所述式（1）～式（3）所表示的化合物為選自所述式（1-1）、式（1-4）、式（2-1）、及式（3-1）所表示的化合物的群組中的至少一種；所述式（A）～式（C）所表示的化合物為選自所述式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（A-19）、式（A-20）、式（B-3）、式（B-5）、式（C-2）、及式（C-3）所表示的化合物的群組中的至少一種；所述式（D）所表示的化合物為選自所述式（D-2）、及式（D-3）所表示的化合物的群組中的至少一種。根據該實施形態，可有效率地發揮本發明的所需的效果。Among them, the formula (A-12), formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (A-19), formula At least one of (B-3), (B-5), (C-2), (C-3), (D-2), and (D-3). In particular, the formulas (B-3) and (D-2) are preferable because they reduce the accumulation of residual DC and reduce the charge particularly quickly. In addition, the formula (A-15) not only reduces the accumulation of residual DC and reduces the charge quickly, but also has a good voltage retention rate, so it is better. Here, k = 2 is more preferable in the formula (B-3). According to an embodiment of the present invention, the compounds represented by the formulae (1) to (3) are selected from the formulae (1-1) to (1-4), the formula (2-1), and the formula ( 2-2) and at least one of the group of compounds represented by formulae (3-1) to (3-6); the compound represented by formula (A) to formula (C) is selected from the group consisting of The group of compounds represented by formula (A-1) to formula (A-20), formula (B-1) to formula (B-8), and formula (C-1) to formula (C-3) At least one of: the compound represented by the formula (D) is at least one selected from the group of compounds represented by the formulas (D-1) to (D-4). According to this embodiment, a desired effect of the present invention can be efficiently exhibited. In addition, in an embodiment of the present invention, the compound represented by the formula (1) to the formula (3) is selected from the group consisting of the formula (1-1), the formula (1-4), and the formula (2-1). And at least one of the group of compounds represented by formula (3-1); the compound represented by formula (A) to formula (C) is selected from the group consisting of formula (A-12) and formula (A) -14), formula (A-15), formula (A-16), formula (A-17), formula (A-19), formula (A-20), formula (B-3), formula (B- 5) at least one of the group of compounds represented by formula (C-2) and formula (C-3); the compound represented by formula (D) is selected from the formula (D-2) And at least one of the group of compounds represented by formula (D-3). According to this embodiment, a desired effect of the present invention can be efficiently exhibited.

於本發明的實施形態中，為了獲得殘留DC的積存小、電荷的緩和快、殘像特性優異的液晶顯示元件，亦較佳為併用式（A）～式（C）所表示的化合物的至少一種、與式（D）所表示的化合物的至少一種。因此，根據本發明的實施形態，用於合成所述聚合物的原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種，且包含選自所述式（A）～式（C）所表示的化合物的群組中的至少一種，並且包含選自所述式（D）所表示的化合物中的至少一種。 本發明中，於包含選自式（1）～式（3）所表示的化合物的群組中的至少一種、與所述式（B）所表示的化合物作為合成所述聚合物的原料的形態中，較佳為有意地減低所述式（C）所表示的化合物相對於二胺總量的含量，相對於所使用的二胺總量，較佳為小於30莫耳%，更佳為小於20莫耳%，進而佳為小於10莫耳%，進而更佳為小於5莫耳%，進而更佳為小於4莫耳%，進而更佳為小於3莫耳%，進而更佳為小於2莫耳%，進而更佳為小於1莫耳%，進而更佳為實質上並不包含。此處，所謂「實質上並不包含」，是指相對於所使用的二胺總量而小於0.1莫耳%。此處，若包含30莫耳%以上，則存在DC殘像的特性惡化的擔憂。 於本發明的實施形態中，在包含一種所述聚合物的情況下，於包含選自式（1）～式（3）所表示的化合物的群組中的至少一種、與所述式（C）所表示的化合物作為合成所述聚合物的原料的形態中，較佳為進而組合所述式（A）所表示的化合物及所述式（B）所表示的化合物的至少一者（尤其是所述式（A）所表示的化合物）。此處，於並不使用所述式（A）所表示的化合物及所述式（B）所表示的化合物的至少一者（尤其是所述式（A）所表示的化合物）的情況下，存在配向性惡化的擔憂。於本發明的實施形態中，在加入所述式（C）所表示的化合物的情況下，藉由亦併用所述式（A）所表示的化合物而存在DC殘像的特性提高的技術效果。 於本發明的實施形態中，在包含一種所述聚合物的情況下，於組合式（1-1）所表示的化合物、與式（B-3）所表示的化合物作為合成所述聚合物的原料的形態中，關於式（1-1）所表示的化合物相對於所使用的二胺總量的含量，為了將液晶的預傾角抑制得低，相對於用於合成聚合物的二胺總量，較佳為使用超過90莫耳%，更佳為使用92莫耳%以上，進而佳為使用95莫耳%以上。於重視一邊維持電壓保持率等電特性一邊減小殘留DC的積存並加快電荷的緩和的情況下，較佳為並不過多，具體而言，較佳為小於90莫耳%，更佳為88莫耳%以下，進而佳為86莫耳%以下，進而佳為84莫耳%以下，進而佳為82莫耳%以下，進而佳為80莫耳%以下，可為78莫耳%以下，亦可為76莫耳%以下，亦可為74莫耳%以下，亦可為72莫耳%以下。 於本發明的實施形態中，在包含一種所述聚合物的情況下，用於合成所述聚合物的原料亦可包含（併用）：選自式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（A-19）、式（B-3）、式（B-5）、式（C-2）、及式（C-3）所表示的化合物的群組中的至少一種；與選自式（D-2）及式（D-3）所表示的化合物的群組中的至少一種。另外，根據本發明的實施形態，用於合成所述聚合物的原料更佳為包含（併用）：選自式（A-15）及式（B-3）所表示的化合物中的至少一種；與式（D-2）所表示的化合物，式（B-3）中，進而佳為k=2。 於本發明的實施形態中，在包含使選自所述式（1）～式（3）所表示的化合物中的至少一種、與選自所述式（A）～式（C）所表示的化合物、及式（D）所表示的化合物中的至少一種進行反應而獲得的聚合物的至少一種作為用於合成的原料的液晶配向劑中，關於用於合成所述聚合物的式（1）～式（3）所表示的化合物的使用量，為了將液晶的預傾角抑制得低，相對於用於合成聚合物的二胺總量（於在所述液晶配向劑中包含兩種以上的聚合物的情況下，為其合計的二胺總量（100莫耳%）），較佳為使用27莫耳%以上，更佳為使用28莫耳%以上，進而佳為使用29莫耳%以上，進而更佳為使用30莫耳%以上，進而更佳為使用31莫耳%以上，進而更佳為使用32莫耳%以上，進而更佳為使用33莫耳%以上，進而更佳為使用34莫耳%以上，進而更佳為使用35莫耳%以上。另外，出於降低體積電阻的目的，較佳為使用99莫耳%以下，可為98莫耳%以下，亦可為96莫耳%以下，亦可為94莫耳%以下，亦可為92莫耳%以下，亦可為90莫耳%以下，亦可為88莫耳%以下，亦可為86莫耳%以下，亦可為84莫耳%以下，亦可為82莫耳%以下。另外，於本發明的實施形態中，關於式（A）～式（C）所表示的化合物的使用量，為了一邊維持電壓保持率等電特性一邊減小殘留DC的積存並加快電荷的緩和，相對於用於合成聚合物的二胺總量（於在所述液晶配向劑中包含兩種以上的聚合物的情況下，為其合計的二胺總量（100莫耳%）），較佳為0莫耳%以上，更佳為超過0莫耳%，進而佳為1莫耳%以上，進而更佳為2莫耳%以上，進而更佳為3莫耳%以上，進而更佳為4莫耳%以上，進而更佳為5莫耳%以上，進而更佳為6莫耳%以上。另外，出於提高液晶配向性的目的，較佳為小於50莫耳%，更佳為46莫耳%以下，進而佳為44莫耳%以下，進而佳為42莫耳%以下，進而更佳為38莫耳%以下，進而更佳為36莫耳%以下，進而更佳為34莫耳%以下，進而更佳為32莫耳%以下，進而更佳為30莫耳%以下，進而更佳為28莫耳%以下，進而更佳為26莫耳%以下，進而更佳為24莫耳%以下，進而更佳為22莫耳%以下。 另外，於本發明的實施形態中，在包含一種所述聚合物的情況下，為了將液晶的預傾角抑制得低，相對於用於合成聚合物的二胺總量，所述式（1）～式（3）所表示的化合物的比例（於包含兩種以上的情況下為其合計）相對於所使用的二胺總量而較佳為超過50莫耳%，更佳為54莫耳%以上，進而佳為60莫耳%以上，進而更佳為超過60莫耳%，進而更佳為65莫耳%以上，進而更佳為66莫耳%以上，進而更佳為67莫耳%以上，進而更佳為68莫耳%以上，進而更佳為69莫耳%以上，進而更佳為70莫耳%以上。另外，較佳為99莫耳%以下，可為98莫耳%以下，亦可為96莫耳%以下，亦可為94莫耳%以下，亦可為90莫耳%以下，亦可為小於90莫耳%。其中，於所述式（1）中m為8時，較佳為100莫耳%，若為100莫耳%，則可驚人地降低預傾角。 另外，於本形態（包含一種所述聚合物的情況）中，所述式（A）～式（C）所表示的化合物的比例（於包含兩種以上的情況下為其合計）相對於所使用的二胺總量，較佳為0.5莫耳%以上，更佳為0.8莫耳%以上，進而佳為1莫耳%以上，可為4莫耳%以上，亦可為6莫耳%以上。另外，於本形態（包含一種所述聚合物的情況）中，出於提高液晶配向性的目的，所述式（A）～式（C）所表示的化合物（於包含兩種以上的情況下為其合計）的比例相對於所使用的二胺總量而較佳為小於50莫耳%，更佳為46莫耳%以下，進而佳為44莫耳%以下，進而更佳為42莫耳%以下，進而更佳為40莫耳%以下，進而更佳為38莫耳%以下，進而更佳為36莫耳%以下，進而更佳為34莫耳%以下，進而更佳為32莫耳%以下，進而更佳為30莫耳%以下，進而更佳為28莫耳%以下，進而更佳為26莫耳%以下，進而更佳為24莫耳%以下，進而更佳為22莫耳%以下。其中，為了降低預傾角，式（B-3）（例如，k=2）、式（B-5）、式（B-8）、式（C-1）～式（C-3）的使用量較佳為40莫耳%以下，更佳為小於40莫耳%，進而佳為30莫耳%以下，進而更佳為小於30莫耳%。尤其是，式（C-1）～式（C-3）的使用量進而佳為10莫耳%以下，進而更佳為小於10莫耳%。 因此，於本形態（包含一種所述聚合物的情況）中，所述式（1）～式（3）所表示的化合物的比例（於包含兩種以上的情況下為其合計）相對於所使用的二胺總量而為70莫耳%以上，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為1莫耳%～30莫耳%。 另外，於本實施形態中，在使用式（D）所表示的化合物的情況下，式（D）所表示的化合物的使用量並無特別限制，為了一邊維持配向電壓保持率等電特性一邊減小殘留DC的積存並進一步加快電荷的緩和，相對於用於合成聚合物的四羧酸二酐總量，可為10莫耳%以上，亦可為20莫耳%以上，亦可為30莫耳%以上。另外，較佳為60莫耳%以下，更佳為50莫耳%以下。In the embodiment of the present invention, in order to obtain a liquid crystal display device with a small accumulation of residual DC, fast charge mitigation, and excellent afterimage characteristics, it is also preferable to use at least the compounds represented by the formulae (A) to (C) in combination. One type and at least one type of compound represented by formula (D). Therefore, according to an embodiment of the present invention, a raw material for synthesizing the polymer includes at least one selected from the group of the compounds represented by the formula (1) to the formula (3), and further includes a member selected from the group consisting of The compound represented by Formula (A) to Formula (C) includes at least one selected from the group consisting of compounds represented by Formula (D). In the present invention, in a form including at least one selected from the group of compounds represented by the formulae (1) to (3) and the compound represented by the formula (B) as a raw material for synthesizing the polymer It is preferable to intentionally reduce the content of the compound represented by the formula (C) with respect to the total amount of diamine, and preferably less than 30 mol%, more preferably less than the total amount of diamine used. 20 mol%, further preferably less than 10 mol%, even more preferably less than 5 mol%, even more preferably less than 4 mol%, even more preferably less than 3 mol%, even more preferably less than 2 Mole%, more preferably less than 1 mole%, and even more preferably, it is substantially not included. Here, "substantially not included" means less than 0.1 mole% with respect to the total amount of the diamine used. Here, if 30 mol% or more is included, there is a concern that the characteristics of the DC afterimage deteriorate. In the embodiment of the present invention, when one kind of the polymer is included, at least one selected from the group consisting of a compound represented by formula (1) to formula (3), and the formula (C In the form of the compound represented by) as a raw material for synthesizing the polymer, it is preferable to further combine at least one of the compound represented by the formula (A) and the compound represented by the formula (B) (especially, A compound represented by the formula (A)). Here, when at least one of the compound represented by the formula (A) and the compound represented by the formula (B) is not used (especially the compound represented by the formula (A)), There is a concern that the alignment deteriorates. In the embodiment of the present invention, when the compound represented by the formula (C) is added, there is a technical effect of improving the characteristics of the DC afterimage by also using the compound represented by the formula (A) in combination. In the embodiment of the present invention, when one kind of the polymer is included, the compound represented by the formula (1-1) and the compound represented by the formula (B-3) are combined as a compound for synthesizing the polymer. In the form of the raw material, the content of the compound represented by the formula (1-1) with respect to the total amount of the diamine used, in order to suppress the pretilt angle of the liquid crystal to be low, with respect to the total amount of the diamine used for the synthesis of the polymer It is preferable to use more than 90 mol%, more preferably to use 92 mol% or more, and even more preferably to use 95 mol% or more. In the case where it is important to reduce the accumulation of residual DC while accelerating the relaxation of electric charges while maintaining electrical characteristics such as voltage retention, it is preferably not too much, and specifically, it is preferably less than 90 mol%, more preferably 88 Molar% or less, and further preferably 86 Molar% or less, further preferably 84 Molar% or less, further preferably 82 Molar% or less, further preferably 80 Molar% or less, and may be 78 Molar% or less. It may be 76 mol% or less, 74 mol% or less, and 72 mol% or less. In the embodiment of the present invention, when one kind of the polymer is included, a raw material for synthesizing the polymer may also include (combined): selected from the formula (A-12), the formula (A-14) , Formula (A-15), formula (A-16), formula (A-17), formula (A-19), formula (B-3), formula (B-5), formula (C-2), And at least one selected from the group of compounds represented by formula (C-3); and at least one selected from the group of compounds represented by formula (D-2) and formula (D-3). In addition, according to an embodiment of the present invention, the raw material for synthesizing the polymer preferably includes (combined): at least one selected from the compounds represented by the formula (A-15) and the formula (B-3); In the compound represented by the formula (D-2), k = 2 is more preferable in the formula (B-3). In an embodiment of the present invention, at least one selected from the compounds represented by the formulae (1) to (3) and a compound selected from the group consisting of the formulae (A) to (C) are included. Among the compounds and at least one polymer obtained by reacting at least one of the compounds represented by the formula (D) as a raw material for synthesis, the liquid crystal alignment agent has formula (1) for synthesizing the polymer. ~ In order to suppress the pretilt angle of the liquid crystal to be low, the amount of the compound represented by the formula (3) is relative to the total amount of diamines used to synthesize the polymer (including two or more kinds of polymerization in the liquid crystal alignment agent). In the case of a product, the total amount of diamines (100 mol%) is preferably 27 mol% or more, more preferably 28 mol% or more, and even more preferably 29 mol% or more. It is more preferable to use 30 mol% or more, even more preferably to use 31 mol% or more, even more preferably to use 32 mol% or more, even more preferably to use 33 mol% or more, and even more preferably to use 34 mol% or more, and more preferably 35 mol% or more. In addition, for the purpose of reducing the volume resistance, it is preferable to use 99 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, or 92 mol%. Molar% or less, 90 Molar% or less, 88 Molar% or less, 86 Molar% or less, 84 Moule% or less, or 82 Moule% or less. In addition, in the embodiment of the present invention, the amount of the compounds represented by the formulae (A) to (C) is used in order to reduce the accumulation of residual DC and accelerate the relaxation of electric charges while maintaining electrical characteristics such as voltage retention rate. Relative to the total amount of diamines used to synthesize the polymer (when two or more polymers are included in the liquid crystal alignment agent, its total amount of diamines (100 mole%) is preferred) 0 mol% or more, more preferably 0 mol% or more, further preferably 1 mol% or more, even more preferably 2 mol% or more, even more preferably 3 mol% or more, and even more preferably 4 Molar% or more, more preferably 5 Molar% or more, even more preferably 6 Molar% or more. In addition, for the purpose of improving liquid crystal alignment, it is preferably less than 50 mol%, more preferably 46 mol% or less, still more preferably 44 mol% or less, still more preferably 42 mol% or less, and even more preferably 38 mol% or less, more preferably 36 mol% or less, even more preferably 34 mol% or less, even more preferably 32 mol% or less, still more preferably 30 mol% or less, and even more preferably It is 28 mol% or less, more preferably 26 mol% or less, still more preferably 24 mol% or less, and still more preferably 22 mol% or less. In addition, in the embodiment of the present invention, when one kind of the polymer is included, in order to suppress the pretilt angle of the liquid crystal to be low, the formula (1) is used relative to the total amount of diamines used to synthesize the polymer. ~ The ratio of the compound represented by formula (3) (total of two or more) is more than 50 mol%, and more preferably 54 mol% relative to the total amount of diamine used. Above, more preferably 60 mol% or more, more preferably more than 60 mol%, still more preferably 65 mol% or more, even more preferably 66 mol% or more, and even more preferably 67 mol% or more Furthermore, it is more preferably 68 mol% or more, even more preferably 69 mol% or more, and even more preferably 70 mol% or more. In addition, it is preferably 99 mol% or less, may be 98 mol% or less, may be 96 mol% or less, may be 94 mol% or less, or may be 90 mol% or less, or may be less than 90 mol%. Wherein, when m is 8 in the formula (1), it is preferably 100 mol%, and if it is 100 mol%, the pretilt angle can be surprisingly reduced. In addition, in this aspect (when one kind of the polymer is included), the ratio of the compounds represented by the formulae (A) to (C) (total of two or more kinds) is relative to The total amount of diamine used is preferably 0.5 mol% or more, more preferably 0.8 mol% or more, further preferably 1 mol% or more, 4 mol% or more, and 6 mol% or more. . In addition, in this aspect (when one kind of the polymer is included), the compound represented by the formula (A) to the formula (C) (when two or more kinds are included) for the purpose of improving the liquid crystal alignment. The ratio thereof is preferably less than 50 mol%, more preferably 46 mol% or less, still more preferably 44 mol% or less, and even more preferably 42 mol% with respect to the total amount of the diamine used. % Or less, and more preferably 40 mol% or less, even more preferably 38 mol% or less, still more preferably 36 mol% or less, still more preferably 34 mol% or less, and even more preferably 32 mol. % Or less, and further preferably 30 mol% or less, further preferably 28 mol% or less, even more preferably 26 mol% or less, still more preferably 24 mol% or less, and even more preferably 22 mol. %the following. Among them, in order to reduce the pretilt angle, the use of formula (B-3) (for example, k = 2), formula (B-5), formula (B-8), formula (C-1) to formula (C-3) The amount is preferably 40 mol% or less, more preferably less than 40 mol%, still more preferably 30 mol% or less, and still more preferably less than 30 mol%. In particular, the use amount of the formulae (C-1) to (C-3) is more preferably 10 mol% or less, and even more preferably less than 10 mol%. Therefore, in this aspect (when one kind of the polymer is included), the ratio of the compounds represented by the formula (1) to the formula (3) (total of two or more kinds) is relative to the ratio The total amount of the diamine used is 70 mol% or more, and the proportion of the compound represented by the formula (A) to the formula (C) is 1 mol% to 30 mol relative to the total amount of the diamine used. %. In addition, in the present embodiment, when the compound represented by the formula (D) is used, the amount of the compound represented by the formula (D) is not particularly limited, and it is reduced in order to maintain electrical characteristics such as the alignment voltage retention rate. Accumulation of small residual DC and further accelerating the easing of the charge can be 10 mol% or more, 20 mol% or more, or 30 mol% relative to the total amount of tetracarboxylic dianhydride used to synthesize the polymer. Ear%. In addition, it is preferably 60 mol% or less, and more preferably 50 mol% or less.

本發明的液晶配向劑較佳為含有聚合物（P）及聚合物（Q）至少兩種聚合物。因此，含有至少兩種所述聚合物，所述至少兩種聚合物包含聚合物（P）及聚合物（Q）；用於合成所述聚合物（P）的原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種；而且，用於合成所述聚合物（Q）的原料包含選自所述式（A）～式（C）所表示的化合物的群組、及所述式（D）所表示的化合物中的至少一種。 於包含聚合物（P）及聚合物（Q）的液晶配向劑中，關於作為用於合成聚合物（P）的原料的式（1）～式（3）所表示的化合物的使用量（於包含兩種以上的情況下為其合計），為了將液晶的預傾角抑制得低，相對於用於合成聚合物（P）的二胺總量，較佳為超過50莫耳%，更佳為54莫耳%以上，進而佳為56莫耳%以上，進而更佳為60莫耳%以上，進而更佳為使用70莫耳%以上，進而更佳為使用75莫耳%以上，進而更佳為使用80莫耳%以上，進而更佳為使用82莫耳%以上，進而更佳為使用84莫耳%以上，進而更佳為使用85莫耳%以上，進而更佳為使用86莫耳%以上，進而更佳為使用87莫耳%以上，進而更佳為使用88莫耳%以上，進而更佳為使用89莫耳%以上，進而更佳為使用90莫耳%以上。此處，於使用式（1-4）所表示的化合物作為用於合成聚合物（P）的原料，且使用認為是增大表面能量的化合物的式（E-5）所表示的化合物作為用於合成聚合物（Q）的原料的情況下，亦較佳為減低聚合物（P）中使用的式（1-4）所表示的化合物的使用量。另外，上限並無特別限制，可為100莫耳%，亦可為95莫耳%以下，亦可為85莫耳%以下，亦可為75莫耳%以下。另外，關於用於合成聚合物（Q）的式（A）～式（C）所表示的化合物的使用量（於包含兩種以上的情況下為其合計），為了一邊維持電壓保持率等電特性一邊減小殘留DC的積存並進一步加快電荷的緩和，相對於用於合成聚合物的二胺總量，較佳為超過0莫耳%以上，更佳為5莫耳%以上，進而佳為10莫耳%以上，進而更佳為20莫耳%以上，進而更佳為25莫耳%以上，進而更佳為30莫耳%以上。另外，出於維持液晶配向性的目的，較佳為60莫耳%以下，更佳為55莫耳%以下，進而佳為50莫耳%以下。其中，為了降低預傾角，式（B-3）（例如，k=2）、式（B-5）、式（B-8）、式（C-1）～式（C-3）的使用量較佳為30莫耳%以下，更佳為小於30莫耳%。另外，用於合成聚合物（Q）的式（A）～式（C）所表示的化合物的使用量較佳為10莫耳%～50莫耳%，更佳為30莫耳%～50莫耳%。 另外，為了一邊維持電壓保持率等電特性一邊減小殘留DC的積存並進一步加快電荷的緩和，相對於用於合成聚合物（Q）的四羧酸二酐總量，式（D）所表示的化合物的使用量較佳為20莫耳%～50莫耳%，更佳為20莫耳%～30莫耳%。 因此，本發明的實施形態中，於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為70莫耳%以上；於所述聚合物（Q）中，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為10莫耳%～50莫耳%。 另外，於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為90莫耳%以上；於所述聚合物（Q）中，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為30莫耳%～50莫耳%。另外，本發明的實施形態中，於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為70莫耳%以上，較佳為90莫耳%以上；於所述聚合物（Q）中，所述式（D）所表示的化合物的比例相對於所使用的四羧酸二酐總量而為20莫耳%～50莫耳%。The liquid crystal alignment agent of the present invention preferably contains at least two polymers of a polymer (P) and a polymer (Q). Therefore, it contains at least two kinds of the polymers, and the at least two kinds of polymers include a polymer (P) and a polymer (Q); a raw material for synthesizing the polymer (P) includes a member selected from the formula ( 1) to at least one of the group of compounds represented by formula (3); and a raw material for synthesizing the polymer (Q) contains a material selected from the group consisting of the formulas (A) to (C). A group of compounds and at least one of the compounds represented by the formula (D). In the liquid crystal alignment agent containing the polymer (P) and the polymer (Q), the amount of use of the compound represented by formulae (1) to (3) as a raw material for synthesizing the polymer (P) (in In the case where two or more of them are included, they are total.) In order to suppress the pretilt angle of the liquid crystal to be low, it is preferably more than 50 mol%, more preferably 54 mol% or more, further preferably 56 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and even more preferably 75 mol% or more, and more preferably To use 80 mol% or more, more preferably to use 82 mol% or more, even more preferably to use 84 mol% or more, even more preferably to use 85 mol% or more, and even more preferably to use 86 mol%. Above, still more preferably 87 mol% or more, even more preferably 88 mol% or more, even more preferably 89 mol% or more, and even more preferably 90 mol% or more. Here, a compound represented by the formula (1-4) is used as a raw material for synthesizing the polymer (P), and a compound represented by the formula (E-5) which is considered to be a compound that increases surface energy is used. In the case of the raw material of the synthetic polymer (Q), it is also preferable to reduce the amount of the compound represented by the formula (1-4) used in the polymer (P). In addition, the upper limit is not particularly limited, and may be 100 mol%, 95 mol% or less, 85 mol% or less, or 75 mol% or less. In addition, regarding the amount of use of the compound represented by the formula (A) to the formula (C) for synthesizing the polymer (Q) (total of two or more types), in order to maintain the voltage holding ratio and so on, Characteristics While reducing the accumulation of residual DC and further accelerating the relaxation of the charge, it is preferably more than 0 mole%, more preferably 5 mole% or more, and more preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, and even more preferably 30 mol% or more. In addition, for the purpose of maintaining the alignment of the liquid crystal, it is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less. Among them, in order to reduce the pretilt angle, the use of formula (B-3) (for example, k = 2), formula (B-5), formula (B-8), formula (C-1) to formula (C-3) The amount is preferably 30 mol% or less, and more preferably less than 30 mol%. The amount of the compound represented by the formula (A) to the formula (C) used to synthesize the polymer (Q) is preferably 10 mol% to 50 mol%, and more preferably 30 mol% to 50 mol. ear%. In addition, in order to reduce the accumulation of residual DC while maintaining electrical characteristics such as voltage retention, and further accelerate charge relaxation, the formula (D) is expressed with respect to the total amount of tetracarboxylic dianhydride used to synthesize the polymer (Q). The amount of the compound used is preferably 20 mol% to 50 mol%, and more preferably 20 mol% to 30 mol%. Therefore, in the embodiment of the present invention, in the polymer (P), the ratio of the compound represented by the formula (1) to the formula (3) is 70 moles with respect to the total amount of the diamine used. % Or more; in the polymer (Q), the proportion of the compound represented by the formula (A) to the formula (C) is 10 mol% to 50 mol% relative to the total amount of the diamine used. . In addition, in the polymer (P), the proportion of the compound represented by the formula (1) to the formula (3) is 90 mol% or more with respect to the total amount of the diamine used; in the polymerization In the substance (Q), the proportion of the compound represented by the formula (A) to the formula (C) is 30 mol% to 50 mol% with respect to the total amount of the diamine used. In addition, in the embodiment of the present invention, in the polymer (P), the ratio of the compound represented by the formula (1) to the formula (3) is 70 moles with respect to the total amount of the diamine used. % Or more, preferably 90 mol% or more; in the polymer (Q), the proportion of the compound represented by the formula (D) is 20 mol relative to the total amount of tetracarboxylic dianhydride used Ear% to 50 mole%.

於本發明中，作為用於合成聚合物的原料，可進而使用公知的四羧酸二酐（包含其衍生物）、二胺（包含二醯肼）。In the present invention, as a raw material for synthesizing a polymer, a known tetracarboxylic dianhydride (including a derivative thereof) and a diamine (including dihydrazine) can be further used.

本發明中所使用的四羧酸二酐可自公知的四羧酸二酐中無限制地選擇。公知的四羧酸二酐可屬於二羧酸酐直接鍵結於芳香環上而成的芳香族系（包含雜芳香環系）、及二羧酸酐並不直接鍵結於芳香環上的脂肪族系（包含雜環系）的任一群組。例如，可使用日本專利特開2016-029447號公報或日本專利特開2016-041683號公報中所揭示的四羧酸二酐。以下示出較佳例。The tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides. The well-known tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, and an aliphatic system in which a dicarboxylic anhydride is not directly bonded to an aromatic ring. (Including heterocyclic systems). For example, the tetracarboxylic dianhydride disclosed in Japanese Patent Laid-Open No. 2016-029447 or Japanese Patent Laid-Open No. 2016-041683 can be used. A preferred example is shown below.

[化19]式（AN-2）及式（AN-8）中，m獨立地為1～12的整數。[Chemical 19] In Formula (AN-2) and Formula (AN-8), m is an integer of 1-12 independently.

對所述四羧酸二酐中提高各特性的較佳的材料進行敘述。The preferable material which improves each characteristic among the said tetracarboxylic dianhydride is demonstrated.

於重視提高液晶的配向性的情況下，較佳為式（AN-2）、式（AN-7）、及式（AN-8）所表示的化合物。When it is important to improve the alignment of the liquid crystal, compounds represented by the formula (AN-2), (AN-7), and (AN-8) are preferred.

於重視提高液晶顯示元件的透過率的情況下，較佳為式（AN-1）、式（AN-5）、式（AN-4）、式（AN-11）、式（AN-12）、式（AN-13）、式（AN-14）、式（AN-17）、及式（AN-18）。In the case where the transmittance of the liquid crystal display element is emphasized, the formula (AN-1), the formula (AN-5), the formula (AN-4), the formula (AN-11), and the formula (AN-12) are preferred. , Formula (AN-13), formula (AN-14), formula (AN-17), and formula (AN-18).

於重視提高液晶顯示元件的VHR（電壓保持率）的情況下，較佳為式（AN-1）、式（AN-4）、式（AN-5）、式（AN-11）、式（AN-13）、式（AN-14）、式（AN-16）、式（AN-17）、及式（AN-18）。In the case where the VHR (voltage holding ratio) of the liquid crystal display element is emphasized, the formula (AN-1), the formula (AN-4), the formula (AN-5), the formula (AN-11), the formula ( AN-13), formula (AN-14), formula (AN-16), formula (AN-17), and formula (AN-18).

藉由降低液晶配向膜的體積電阻值而提高配向膜中的殘留電荷（殘留DC）的緩和速度作為防止燒印的方法之一而有效。於重視該目的的情況下，較佳為式（AN-3）、式（AN-6）、式（AN-7）、式（AN-9）、式（AN-10）、式（AN-11）、及式（AN-15）。 於本發明中，認為藉由使用具有氮（尤其是二級胺基、三級胺基）、或含有氮的雜環的四羧酸二酐（例如，式（AN-3）或所述式（AN-11））作為用於合成聚合物的原料，可進而減小殘留DC的積存並提高緩和速度。相對於用於合成聚合物的四羧酸二酐總量，較佳為使用1莫耳%～40莫耳%，更佳為使用1莫耳%～15莫耳%，進而佳為使用1莫耳%～10莫耳%。 於本發明的實施形態中，在包含選自式（1）～式（3）所表示的化合物的群組中的至少一種、與選自所述式（A）～式（C）所表示的化合物的群組中的至少一種的形態中，較佳為組合三種以上的四羧酸二酐而使用。於本形態中，若四羧酸二酐為兩種以下的組合，則存在液晶配向性惡化的擔憂。此處，關於三種以上的具體的組合的適宜例，除了本申請案的實施例中所揭示的組合以外，亦可為：（AN-2）、（AN-4）及（AN-6）；（AN-4）、（AN-7）及（AN-9）；（AN-4）、（AN-6）及（AN-11）等。藉由為此種組合，可有效率地發揮本發明的所需的效果。 於本發明的實施形態中，作為酸二酐，較佳為使用式（AN-8）。另外，於將式（1-1）、與式（B）組合的情況下，作為酸二酐，較佳為使用式（AN-8）。根據該實施形態，有如下效果：降低預傾角，減小殘留DC的積存並提高緩和速度，進而提高液晶配向性。於本發明的實施形態中，在為組合式（1-1）所表示的化合物、與式（B）所表示的化合物的情況且式（1-1）所表示的化合物的比例相對於所使用的二胺總量而為90莫耳%以上時，特佳為使用式（AN-8）作為酸二酐。根據該實施形態，有如下效果：降低預傾角，減小殘留DC的積存並提高緩和速度，進而提高液晶配向性。Increasing the relaxation speed of the residual charge (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing burn-in. In the case of paying attention to this purpose, the formula (AN-3), (AN-6), (AN-7), (AN-9), (AN-10), (AN- 11) And sum (AN-15). In the present invention, it is considered that by using a tetracarboxylic dianhydride (for example, formula (AN-3) or the formula (AN-11)) As a raw material for polymer synthesis, it can further reduce the accumulation of residual DC and increase the easing speed. Relative to the total amount of tetracarboxylic dianhydride used to synthesize the polymer, it is preferred to use 1 mol% to 40 mol%, more preferably 1 mol% to 15 mol%, and even more preferably 1 mol. Ear% to 10 mole%. In an embodiment of the present invention, at least one selected from the group consisting of a compound represented by the formula (1) to the formula (3), and one selected from the group represented by the formula (A) to the formula (C) In the form of at least one of the group of compounds, it is preferred to use three or more tetracarboxylic dianhydrides in combination. In this embodiment, if the tetracarboxylic dianhydride is a combination of two or less, there is a concern that the alignment of the liquid crystal is deteriorated. Here, suitable examples of three or more specific combinations may be: (AN-2), (AN-4), and (AN-6) in addition to the combinations disclosed in the examples of the present application; (AN-4), (AN-7) and (AN-9); (AN-4), (AN-6) and (AN-11), etc. By using such a combination, the desired effect of the present invention can be effectively exhibited. In the embodiment of the present invention, it is preferable to use the formula (AN-8) as the acid dianhydride. When formula (1-1) and formula (B) are combined, formula (AN-8) is preferably used as the acid dianhydride. According to this embodiment, there are effects that the pretilt angle is reduced, the accumulation of residual DC is reduced, the relaxation speed is increased, and the liquid crystal alignment is further improved. In the embodiment of the present invention, when the compound represented by the formula (1-1) and the compound represented by the formula (B) are combined, the ratio of the compound represented by the formula (1-1) to the used compound is When the total amount of diamine is 90 mol% or more, it is particularly preferable to use formula (AN-8) as the acid dianhydride. According to this embodiment, there are effects that the pretilt angle is reduced, the accumulation of residual DC is reduced, the relaxation speed is increased, and the liquid crystal alignment is further improved.

於本發明中，在含有聚合物（P）與聚合物（Q）至少兩種聚合物的形態中，作為聚合物（P）中使用的原料，亦可使用選自所述式（D）所表示的化合物中的至少一種。In the present invention, in a form containing at least two polymers of a polymer (P) and a polymer (Q), as a raw material used in the polymer (P), a material selected from the formula (D) may be used. At least one of the compounds represented.

作為聚合物（P）中使用的化合物，較佳為式（AN-1）、式（AN-3）、式（AN-4）、式（AN-6）、式（AN-8）、及式（AN-9），式（AN-8）中，更佳為m=4、或8。為了於液晶配向性或電壓保持率等電特性的各特性中以良好的平衡示出高的特性，較佳為併用式（AN-4）、式（AN-6）、及式（AN-8），式（AN-8）中，更佳為m=4、或8。The compound used in the polymer (P) is preferably a formula (AN-1), a formula (AN-3), a formula (AN-4), a formula (AN-6), a formula (AN-8), and In formula (AN-9) and formula (AN-8), m = 4 or 8 is more preferable. In order to show high characteristics in a good balance among electrical characteristics such as liquid crystal alignment and voltage retention, it is preferable to use the formula (AN-4), (AN-6), and (AN-8) in combination. ), In formula (AN-8), m = 4 or 8 is more preferable.

本發明中所使用的二胺（包含二醯肼）可自公知的二胺及二醯肼中無限制地選擇。例如，可使用日本專利特開2016-029447號公報或日本專利特開2016-041683號公報中所揭示的二胺或二醯肼。以下示出較佳例。The diamine (including dihydrazine) used in the present invention can be selected from known diamines and dihydrazine without limitation. For example, a diamine or dihydrazine disclosed in Japanese Patent Laid-Open No. 2016-029447 or Japanese Patent Laid-Open No. 2016-041683 can be used. A preferred example is shown below.

[化20] [Chemical 20]

[化21]式（DI-3）、式（DI-6）及式（DI-7）中，m為1～12的整數。[Chemical 21] In Formula (DI-3), Formula (DI-6), and Formula (DI-7), m is an integer of 1-12.

於本發明的實施形態中，作為用於合成所述聚合物的原料，進而包含選自下述式（E）所表示的化合物中的至少一種。 [化22]所述式（E）中，W4 為碳數1～6的伸烷基、1,3-伸苯基、或1,4-伸苯基；而且，W5 獨立地為單鍵、-NHCO-、或-CONH-。尤其是於二層系（混合系）的形態中，藉由包含式（E）所表示的化合物，可有效率地引起相分離。另外，於本發明的實施形態中，包含選自所述式（E）所表示的化合物中的至少一種作為所述聚合物（Q）的合成中所使用的原料。 [化23]式（E）中，W4 為碳數1～6的伸烷基、1,3-伸苯基、或1,4-伸苯基，而且，W5 獨立地為單鍵、-NHCO-、或-CONH-。In the embodiment of the present invention, as a raw material for synthesizing the polymer, it further contains at least one selected from the compounds represented by the following formula (E). [Chemical 22] In the formula (E), W 4 is an alkylene group having 1 to 6 carbon atoms, 1,3-phenylene group, or 1,4-phenylene group; and W 5 is independently a single bond and -NHCO. -, Or -CONH-. In particular, in the form of a two-layer system (mixed system), phase separation can be efficiently caused by including a compound represented by formula (E). In addition, in an embodiment of the present invention, at least one selected from the compounds represented by the formula (E) is included as a raw material used in the synthesis of the polymer (Q). [Chemical 23] In the formula (E), W 4 is an alkylene group having 1 to 6 carbon atoms, 1,3-phenylene group, or 1,4-phenylene group, and W 5 is independently a single bond, -NHCO-, Or -CONH-.

作為式（E）所表示的化合物，可列舉下述式（E-1）～式（E-8）作為具體例。即，所述式（E）所表示的化合物為選自下述式（E-1）～式（E-8）所表示的化合物中的至少一種。Specific examples of the compound represented by the formula (E) include the following formulae (E-1) to (E-8). That is, the compound represented by the formula (E) is at least one selected from the compounds represented by the following formulae (E-1) to (E-8).

[化24]式（E-5）、及式（E-8）中，p分別獨立地為1～6的整數。 另外，於本發明的實施形態中，所述式（1）～式（3）所表示的化合物為選自所述式（1-1）～式（1-4）、式（2-1）、式（2-2）、式（3-1）所表示的化合物的群組中的至少一種；所述式（A）～式（C）所表示的化合物為選自所述式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（B-3）、式（C-2）、及式（C-3）所表示的化合物的群組中的至少一種；所述式（D）所表示的化合物為選自所述式（D-2）、及式（D-3）所表示的化合物的群組中的至少一種；所述式（E）所表示的化合物為選自所述式（E-5）～式（E-7）所表示的化合物的群組中的至少一種。另外，於本發明的實施形態中，所述式（1）～式（3）所表示的化合物為選自所述式（1-1）及式（1-4）中的至少一種；所述式（A）～式（C）所表示的化合物為選自所述式（A-15）及式（B-3）中的至少一種；所述式（D）所表示的化合物為所述式（D-2）所表示的化合物；所述式（E）所表示的化合物為所述式（E-5）所表示的化合物。[Chemical 24] In Formula (E-5) and Formula (E-8), p is each independently an integer of 1-6. In addition, in an embodiment of the present invention, the compound represented by the formulae (1) to (3) is selected from the formulae (1-1) to (1-4) and the formula (2-1) At least one of the group of compounds represented by Formula (2-2) and Formula (3-1); the compound represented by Formula (A) to Formula (C) is selected from the formula (A- 12), formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (B-3), formula (C-2), and formula (C- 3) At least one type of compound represented by the group; the compound represented by the formula (D) is selected from the group of compounds represented by the formula (D-2) and the formula (D-3) At least one of: the compound represented by the formula (E) is at least one selected from the group of compounds represented by the formulas (E-5) to (E-7). In an embodiment of the present invention, the compound represented by the formula (1) to the formula (3) is at least one selected from the group consisting of the formula (1-1) and the formula (1-4); The compound represented by the formula (A) to the formula (C) is at least one selected from the formula (A-15) and the formula (B-3); the compound represented by the formula (D) is the formula A compound represented by (D-2); the compound represented by the formula (E) is a compound represented by the formula (E-5).

對所述二胺（包含二醯肼）中提高各特性的較佳的材料進行敘述。A preferred material for improving the properties of the diamine (including dihydrazine) will be described.

於重視進一步提高液晶的配向性的情況下，所述二胺（包含二醯肼）中，較佳為式（DI-3）、式（DI-6）、式（DI-7）、式（DI-9）、式（DI-10）、式（E-1）、及式（E-8）。更佳為式（DI-3）、式（DI-6）、式（DI-7）、及式（E-1）。式（DI-3）中，較佳為m=1、2、4或6，更佳為m=2、4。式（DI-6）中，較佳為m=2～6，更佳為m=2或5。式（DI-7）中，較佳為m=1、或2，更佳為m=1。所述二胺可單獨使用，亦可將兩種以上組合使用。In the case where the orientation of the liquid crystal is further enhanced, the diamine (including dihydrazine) is preferably Formula (DI-3), Formula (DI-6), Formula (DI-7), Formula ( DI-9), formula (DI-10), formula (E-1), and formula (E-8). More preferred are formula (DI-3), formula (DI-6), formula (DI-7), and formula (E-1). In the formula (DI-3), m = 1, 2, 4, or 6 is preferable, and m = 2, 4 is more preferable. In the formula (DI-6), m = 2 to 6 is preferable, and m = 2 or 5 is more preferable. In the formula (DI-7), m = 1 or 2 is preferable, and m = 1 is more preferable. The diamines may be used alone or in combination of two or more.

於重視提高透過率的情況下，所述二胺（包含二醯肼）中，較佳為式（DI-1）、式（DI-3）、式（DI-8）、及式（E-8），更佳為（DI-1）。式（DI-3）中，較佳為m=1、2、4或6，更佳為m=1或2。In the case of increasing the transmittance, the diamine (including dihydrazine) is preferably the formula (DI-1), the formula (DI-3), the formula (DI-8), and the formula (E- 8), more preferably (DI-1). In the formula (DI-3), m = 1, 2, 4, or 6 is preferable, and m = 1 or 2 is more preferable.

於重視提高液晶顯示元件的VHR的情況下，所述二胺（包含二醯肼）中，較佳為式（DI-1）、式（DI-3）、式（E-1）、及式（E-2），更佳為式（DI-1）、及式（DI-3）。式（DI-3）中，較佳為m=1。In the case where it is important to increase the VHR of a liquid crystal display element, among the diamines (including dihydrazine), Formula (DI-1), Formula (DI-3), Formula (E-1), and Formula (E-2), more preferably Formula (DI-1) and Formula (DI-3). In the formula (DI-3), m = 1 is preferred.

藉由降低液晶配向膜的體積電阻值而提高液晶配向膜中的殘留電荷（殘留DC）的緩和速度作為防止燒印的方法之一而有效。於重視該目的的情況下，所述二胺（包含二醯肼）中，較佳為式（DI-3）、式（DI-6）、式（DI-7）、及式（E-1）～式（E-6），更佳為式（DI-3）、式（DI-7）、式（E-1）、式（E-5）、及式（E-6）。式（DI-3）中，較佳為m=1、2、4或6，更佳為m=1或2。式（DI-6）中，較佳為m=2～6，更佳為m=2或5。式（DI-7）中，較佳為m=1、或2，更佳為m=1。式（E-5）中，較佳為p=4。Increasing the relaxation speed of the residual charge (residual DC) in the liquid crystal alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing burn-in. In consideration of this purpose, among the diamines (including dihydrazine), the formula (DI-3), the formula (DI-6), the formula (DI-7), and the formula (E-1) are preferred. ) To formula (E-6), more preferably formula (DI-3), formula (DI-7), formula (E-1), formula (E-5), and formula (E-6). In the formula (DI-3), m = 1, 2, 4, or 6 is preferable, and m = 1 or 2 is more preferable. In the formula (DI-6), m = 2 to 6 is preferable, and m = 2 or 5 is more preferable. In the formula (DI-7), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (E-5), p = 4 is preferred.

於本發明的實施形態中，在包含聚合物（P）及聚合物（Q）的液晶配向劑中，可使用選自所述式（A）～式（C）所表示的化合物中的至少一種作為聚合物（P）中使用的原料，亦可使用選自式（1）～式（3）所表示的化合物中的至少一種作為聚合物（Q）中使用的原料。於該形態中，在聚合物（P）中使用的原料中，含有氮的雜環較佳為含有氮的環烷烴，例如較佳為式（A-15）、式（A-16）、式（A-17）等。In the embodiment of the present invention, in the liquid crystal alignment agent containing the polymer (P) and the polymer (Q), at least one selected from the compounds represented by the formulae (A) to (C) can be used. As a raw material used in the polymer (P), at least one selected from the compounds represented by the formulas (1) to (3) may be used as a raw material used in the polymer (Q). In this aspect, among the raw materials used in the polymer (P), the nitrogen-containing heterocyclic ring is preferably a nitrogen-containing cycloalkane, and for example, the formula (A-15), the formula (A-16), and the formula (A-17) and so on.

作為聚合物（P）中使用的化合物，較佳為式（DI-3）、式（DI-5）、式（A-15）、及式（C-3）。此處，式（DI-3）中，較佳為m=1或4，更佳為1。另外，作為聚合物（Q）中使用的化合物，較佳為使用選自式（DI-3）、式（DI-5）、式（DI-6）、式（DI-9）、及式（E）所表示的化合物中的至少一種。此處，式（DI-3）中，較佳為m=1、2或4，更佳為1或2。此處，式（DI-6）中，較佳為m=2或5，更佳為2。As a compound used for a polymer (P), Formula (DI-3), Formula (DI-5), Formula (A-15), and Formula (C-3) are preferable. Here, in the formula (DI-3), m = 1 or 4 is preferable, and 1 is more preferable. The compound used in the polymer (Q) is preferably selected from the group consisting of formula (DI-3), formula (DI-5), formula (DI-6), formula (DI-9), and formula (DI). At least one of the compounds represented by E). Here, in the formula (DI-3), m = 1, 2 or 4 is preferable, and 1 or 2 is more preferable. Here, in the formula (DI-6), m = 2 or 5 is preferable, and 2 is more preferable.

於本發明的實施形態中，為了將液晶的預傾角抑制得更低、且減小殘留DC的積存並加快緩和，重要的是使承擔將液晶預傾角抑制得低的作用的聚合物（P）偏析於更上層（液晶層側），使承擔供給殘留DC的積存小且電荷的緩和快的液晶顯示元件的作用的聚合物（Q）偏析於更下層（基板側）。認為藉由在聚合物（Q）中使用增大表面能量的化合物而兩種聚合物更容易偏析。因此，於本發明的實施形態中，用於使液晶層配向的液晶配向膜包含位於基板上的源自液晶配向劑的塗膜，該塗膜包含聚合物（P）及聚合物（Q），該聚合物（P）位於液晶層側，該聚合物（Q）位於基板側。 於本發明的實施形態中，作為聚合物（Q）中使用的原料，較佳為使用認為是增大表面能量的化合物的式（E）所表示的化合物。作為具體的化合物，較佳為式（E-1）～式（E-8），更佳為式（E-1）、式（E-3）、式（E-4）、式（E-5）、式（E-6），進而佳為式（E-3）、式（E-4）、式（E-5）、式（E-6），進而更佳為使用（E-5）、（E-6），進而更佳為（E-5），式（E-5）中，較佳為p=4。另外，於本發明的實施形態中，用於合成所述聚合物（Q）的式（E）所表示的化合物的使用量相對於用於合成所述聚合物（Q）的二胺總量而較佳為50莫耳%～70莫耳%。因此，於所述聚合物（Q）中，所述式（E）所表示的化合物的比例相對於所使用的二胺總量而為50莫耳%～70莫耳%。In the embodiment of the present invention, in order to suppress the pretilt angle of the liquid crystal to be lower, and to reduce the accumulation of residual DC and accelerate the relaxation, it is important to make the polymer (P) that has the effect of suppressing the pretilt angle of the liquid crystal low The polymer (Q) is segregated to the upper layer (liquid crystal layer side), and the polymer (Q), which plays the role of a liquid crystal display element with a small accumulation of residual DC and fast charge relaxation, is segregated to the lower layer (substrate side). It is considered that the two polymers are more likely to segregate by using a compound (Q) that increases the surface energy. Therefore, in the embodiment of the present invention, the liquid crystal alignment film for aligning the liquid crystal layer includes a coating film derived from a liquid crystal alignment agent on a substrate, and the coating film includes a polymer (P) and a polymer (Q). The polymer (P) is located on the liquid crystal layer side, and the polymer (Q) is located on the substrate side. In the embodiment of the present invention, as a raw material used in the polymer (Q), it is preferable to use a compound represented by the formula (E) which is considered to be a compound that increases surface energy. As specific compounds, formulae (E-1) to (E-8) are preferred, and formulae (E-1), (E-3), (E-4), and (E-) are more preferred. 5), formula (E-6), and further preferably formula (E-3), formula (E-4), formula (E-5), formula (E-6), and more preferably use (E-5 ), (E-6), and more preferably (E-5), and in formula (E-5), p = 4 is more preferable. In addition, in the embodiment of the present invention, the amount of the compound represented by the formula (E) used to synthesize the polymer (Q) is used relative to the total amount of diamines used to synthesize the polymer (Q). It is preferably 50 mol% to 70 mol%. Therefore, in the polymer (Q), the proportion of the compound represented by the formula (E) is 50 mol% to 70 mol% with respect to the total amount of the diamine used.

於本發明的實施形態中，在各二胺中，相對於二胺的單胺的比率為40莫耳%以下的範圍，可將二胺的一部分置換為單胺。藉由此種置換，可引起生成聚合物（例如，聚醯胺酸）時的聚合反應的封端（termination），可抑制其以上的聚合反應的進行。而且，可容易控制所獲得的聚合物（例如，聚醯胺酸、聚醯胺酸酯或聚醯亞胺）的重量平均分子量（以下，亦表述為Mw），例如，可無損本發明的效果地改善液晶配向劑的塗佈特性。經置換為單胺的二胺若無損本發明的效果，則可為一種，亦可兩種以上。作為所述單胺，例如可列舉：苯胺、4-羥基苯胺、環己基胺、正丁基胺、正戊基胺、正己基胺、正庚基胺、正辛基胺、正壬基胺、正癸基胺、正十一基胺、正十二基胺、正十三基胺、正十四基胺、正十五基胺、正十六基胺、正十七基胺、正十八基胺、及正二十基胺。In the embodiment of the present invention, in each diamine, the ratio of the monoamine to the diamine is in the range of 40 mol% or less, and a part of the diamine may be replaced with the monoamine. Such substitution can cause termination of the polymerization reaction when a polymer (for example, polyamic acid) is formed, and can inhibit the progress of the polymerization reaction above. In addition, the weight average molecular weight (hereinafter, also referred to as Mw) of the obtained polymer (for example, polyamic acid, polyamic acid ester, or polyimide) can be easily controlled, and for example, the effect of the present invention may not be impaired To improve the coating characteristics of the liquid crystal alignment agent. The diamine substituted with a monoamine may be one kind, or two or more kinds, if the effect of the present invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, N-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine And n-icosylamine.

於本發明的實施形態中，所述聚合物亦可於其原料中進而包含單異氰酸酯化合物。藉由在原料中包含單異氰酸酯化合物，所獲得的聚合物（例如，聚醯胺酸（包含其衍生物））的末端得到修飾，且Mw得到調節。藉由使用該末端修飾型聚合物（例如，聚醯胺酸（包含其衍生物）），例如可無損本發明的效果地改善液晶配向劑的塗佈特性。就所述觀點而言，較佳為原料中的單異氰酸酯化合物的含量相對於原料中的二胺及四羧酸二酐的總量而為1莫耳%～10莫耳%。作為所述單異氰酸酯化合物，例如可列舉：苯基異氰酸酯、及萘基異氰酸酯。In an embodiment of the present invention, the polymer may further include a monoisocyanate compound in a raw material thereof. By including a monoisocyanate compound in the raw material, the terminal of the obtained polymer (for example, polyamic acid (including its derivative)) is modified, and Mw is adjusted. By using the terminal-modified polymer (for example, polyamic acid (including a derivative thereof)), for example, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. From this viewpoint, the content of the monoisocyanate compound in the raw material is preferably 1 mol% to 10 mol% relative to the total amount of the diamine and the tetracarboxylic dianhydride in the raw material. Examples of the monoisocyanate compound include a phenyl isocyanate and a naphthyl isocyanate.

於本發明的實施形態中，所述聚合物可藉由如下方式獲得：使四羧酸二酐與二胺的混合物於有機溶劑中反應。於該合成反應中，除了原料的選擇以外，無需特別的條件，可直接應用通常的聚合物（例如，聚醯胺酸）合成中的條件。關於可使用的溶劑，將於後述。In an embodiment of the present invention, the polymer can be obtained by reacting a mixture of tetracarboxylic dianhydride and diamine in an organic solvent. In this synthesis reaction, in addition to the selection of raw materials, no special conditions are required, and the conditions in the general polymer (for example, polyamic acid) synthesis can be directly applied. The usable solvents will be described later.

於本發明的實施形態中，液晶配向劑亦可進而含有所述聚合物以外的其他成分。其他成分可為一種，亦可為兩種以上。作為其他成分，例如可列舉後述的其他聚合物或化合物等。In the embodiment of the present invention, the liquid crystal alignment agent may further contain components other than the polymer. The other components may be one type or two or more types. Examples of the other components include other polymers and compounds described later.

作為其他聚合物，可列舉：所述聚合物（P）及聚合物（Q）以外的聚醯胺酸、聚醯胺酸酯、或聚醯亞胺（以下，稱為「其他聚醯胺酸或其衍生物」）、聚酯、聚醯胺、聚矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。該些可為一種，亦可為兩種以上。該些中，較佳為其他聚醯胺酸或其衍生物及聚矽氧烷，更佳為其他聚醯胺酸或其衍生物。Examples of other polymers include polyamic acid, polyamic acid ester, or polyimide (hereinafter, referred to as "other polyamic acid") other than the polymer (P) and polymer (Q). Or its derivatives "), polyesters, polyamidoamines, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, Poly (meth) acrylate and the like. These may be one type or two or more types. Among these, other polyamidic acids or their derivatives and polysiloxanes are preferred, and other polyamidic acids or their derivatives are more preferred.

用於合成其他聚醯胺酸或其衍生物的二胺較佳為相對於全部二胺而包含30莫耳%以上的芳香族二胺，更佳為包含50莫耳%以上。The diamine used for synthesizing other polyamic acid or a derivative thereof preferably contains 30 mol% or more of the aromatic diamine relative to the total diamine, and more preferably contains 50 mol% or more.

其他聚醯胺酸或其衍生物分別可依據作為本發明的液晶配向劑的必需成分即聚醯胺酸或其衍生物的合成方法而於下述記載的方法來合成。The other polyamic acid or a derivative thereof can be synthesized by a method described below according to a method for synthesizing polyamino acid or a derivative thereof which is an essential component of the liquid crystal alignment agent of the present invention.

如上所述，本發明的液晶配向劑的較佳的實施形態之一為含有聚合物（P）及聚合物（Q）至少兩種聚合物的液晶配向劑。於使用包含兩種聚合物的液晶配向劑形成塗膜（尤其是薄膜）的過程中，已知有表面能量小的聚合物分離於上層、表面能量大的聚合物分離於下層的現象。於本發明中，藉由使承擔將液晶的預傾角抑制得低的作用的聚合物（P）偏析於上層，使承擔供給殘留DC的積存小且電荷的緩和快的液晶顯示元件的作用的聚合物（Q）偏析於下層，可形成發揮所述兩種特性的液晶配向膜。於本發明的實施形態中，聚合物（P）及聚合物（Q）至少兩種聚合物的表面能量彼此不同，且聚合物（Q）的表面能量大於聚合物（P）的表面能量。As described above, one of the preferred embodiments of the liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing at least two polymers of a polymer (P) and a polymer (Q). In the process of forming a coating film (especially a film) using a liquid crystal alignment agent containing two polymers, a phenomenon in which a polymer having a small surface energy is separated from an upper layer and a polymer having a large surface energy is separated from a lower layer is known. In the present invention, by polymerizing the polymer (P) which acts to suppress the pretilt angle of the liquid crystal to a low level, the polymer (P) is segregated on the upper layer to polymerize the function of the liquid crystal display element, which has a small accumulation of residual DC and a rapid charge relaxation. The substance (Q) is segregated in the lower layer, and a liquid crystal alignment film exhibiting the two characteristics can be formed. In an embodiment of the present invention, the surface energy of at least two polymers of the polymer (P) and the polymer (Q) are different from each other, and the surface energy of the polymer (Q) is greater than the surface energy of the polymer (P).

所述液晶配向膜是否進行層分離的確認例如可對所形成的膜的表面能量進行測定，並藉由為與由僅含有聚合物（P）的液晶配向劑形成的膜的表面能量的值相同、或與其相近的值而確認。The confirmation of whether the liquid crystal alignment film is layer-separated may be, for example, measuring the surface energy of the formed film and setting it to be the same as the value of the surface energy of the film formed of the liquid crystal alignment agent containing only the polymer (P). Or a value close to it.

如以上所述，為了示出良好的液晶配向性及低預傾角特性，本發明的液晶配向劑中的聚合物（P）的含量於將所含的聚合物總量設為100重量%時，較佳為20重量%以上，較佳為30重量%以上。另外，較佳為80重量%以下，更佳為70重量%以下。其中，此處所述的聚合物（P）的較佳的含量為一個指標，有時會根據原料中使用的四羧酸二酐或二胺的組合而變動。As described above, in order to show good liquid crystal alignment and low pretilt angle characteristics, when the content of the polymer (P) in the liquid crystal alignment agent of the present invention is 100% by weight, It is preferably 20% by weight or more, and more preferably 30% by weight or more. In addition, it is preferably 80% by weight or less, and more preferably 70% by weight or less. Among them, the preferable content of the polymer (P) described herein is an index, and it may vary depending on the combination of tetracarboxylic dianhydride or diamine used in the raw material.

本發明中，於含有一種所述聚合物的實施形態中，聚合物的Mw較佳為20,000～160,000，更佳為40,000～80,000，進而佳為45,000～70,000。於聚合物（P）及聚合物（Q）至少兩種聚合物中，Mw亦分別獨立地較佳為20,000～160,000，更佳為40,000～80,000。聚合物的Mw可藉由實施例中所記載的方法進行測定。聚合物的Mw例如可藉由使四羧酸二酐與二胺進行反應的時間來調整。可少量採取聚合反應中的反應液，並藉由利用凝膠滲透層析法（gel permeation chromatography，GPC）的測定求出反應液中所含的聚合物的Mw，且根據該測定值決定反應的終點。另外，亦充分已知有於反應開始時藉由將四羧酸二酐及二胺的相當量置換為單羧酸或單胺而引起聚合反應的封端來對Mw進行控制的方法。In the present invention, in the embodiment containing one of the polymers, the Mw of the polymer is preferably 20,000 to 160,000, more preferably 40,000 to 80,000, and even more preferably 45,000 to 70,000. In at least two polymers of polymer (P) and polymer (Q), Mw is also preferably independently 20,000 to 160,000, more preferably 40,000 to 80,000. The Mw of the polymer can be measured by the method described in the examples. The Mw of the polymer can be adjusted by, for example, the time during which a tetracarboxylic dianhydride and a diamine are reacted. The reaction solution in the polymerization reaction can be taken in small amounts, and the Mw of the polymer contained in the reaction solution can be determined by measurement using gel permeation chromatography (GPC), and the reaction can be determined based on the measured value. end. In addition, a method of controlling Mw by replacing the corresponding amounts of tetracarboxylic dianhydride and diamine with monocarboxylic acids or monoamines at the start of the reaction is well known.

作為所述聚矽氧烷，可進而含有日本專利特開2009-036966號公報、日本專利特開2010-185001號公報、日本專利特開2011-102963號公報、日本專利特開2011-253175號公報、日本專利特開2012-159825號公報、國際公開第2008/044644號公報、國際公開第2009/148099號公報、國際公開第2010/074261號公報、國際公開第2010/074264號公報、國際公開第2010/126108號公報、國際公開第2011/068123號公報、國際公開第2011/068127號公報、國際公開第2011/068128號公報、國際公開第2012/115157號公報、國際公開第2012/165354號公報等中所揭示的聚矽氧烷。 於本發明的實施形態中，進而含有選自包含烯基取代納迪克醯亞胺（nadimide）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、及環氧化合物的化合物群組中的至少一種。The polysiloxane may further include Japanese Patent Laid-Open No. 2009-036966, Japanese Patent Laid-Open No. 2010-185001, Japanese Patent Laid-Open No. 2011-102963, and Japanese Patent Laid-Open No. 2011-253175. Japanese Patent Laid-Open Publication No. 2012-159825, International Publication No. 2008/044644, International Publication No. 2009/148099, International Publication No. 2010/074261, International Publication No. 2010/074264, International Publication No. 2010/126108, International Publication No. 2011/068123, International Publication No. 2011/068127, International Publication No. 2011/068128, International Publication No. 2012/115157, International Publication No. 2012/165354 Et al. In an embodiment of the present invention, it further contains a compound selected from the group consisting of an alkenyl-substituted nadimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy. At least one of a group of compounds of a compound.

＜烯基取代納迪克醯亞胺化合物＞ 例如，本發明的液晶配向劑出於使液晶顯示元件的電特性長期穩定的目的，亦可進而含有烯基取代納迪克醯亞胺化合物。烯基取代納迪克醯亞胺化合物可使用一種，亦可併用兩種以上。出於所述目的，烯基取代納迪克醯亞胺化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而較佳為1重量%～100重量%，更佳為1重量%～70重量%，進而佳為1重量%～50重量%。<Alkenyl-substituted Nadicadimide compound> For example, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted Nadicadimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The alkenyl-substituted nadicarium imine compound may be used singly or in combination of two or more kinds. For the purpose described, the content of the alkenyl-substituted nadicarium imine compound is preferably from 1% by weight to 100% by weight, and more preferably relative to the polymer (for example, polyamic acid (including a derivative thereof)). 1 to 70% by weight, more preferably 1 to 50% by weight.

烯基取代納迪克醯亞胺化合物較佳為可溶解於溶解本發明中所使用的聚合物（例如，聚醯胺酸（包含其衍生物））的溶劑中的化合物。作為此種烯基取代納迪克醯亞胺化合物，例如可列舉日本專利特開2013-242526號公報等中所揭示的烯基取代納迪克醯亞胺化合物。作為較佳的烯基取代納迪克醯亞胺化合物，可列舉：雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、N,N'-間伸二甲苯-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)。The alkenyl-substituted nadicarium imine compound is preferably a compound that is soluble in a solvent in which the polymer used in the present invention (for example, polyamidic acid (including a derivative thereof)) is dissolved. Examples of such alkenyl-substituted nadic acid imine compounds include the alkenyl-substituted nadic acid imide compounds disclosed in Japanese Patent Laid-Open No. 2013-242526 and the like. As a preferred alkenyl-substituted nadicariumimine compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine) phenyl} Methane, N, N'-meta-xylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine), N, N'-hexamethylene-bis (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine).

＜具有自由基聚合性不飽和雙鍵的化合物＞ 例如，本發明的液晶配向劑出於使液晶顯示元件的電特性長期穩定的目的，亦可進而含有具有自由基聚合性不飽和雙鍵的化合物。具有自由基聚合性不飽和雙鍵的化合物可為一種化合物，亦可為兩種以上的化合物。再者，具有自由基聚合性不飽和雙鍵的化合物中並不包含烯基取代納迪克醯亞胺化合物。出於所述目的，具有自由基聚合性不飽和雙鍵的化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而較佳為1重量%～100重量%，更佳為1重量%～70重量%，進而佳為1重量%～50重量%。<A compound having a radically polymerizable unsaturated double bond> For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element 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 kinds of compounds. Furthermore, the compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadicarium imine compound. For the purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably 1% to 100% by weight relative to the polymer (for example, polyamic acid (including a derivative thereof)), and more preferably It is preferably 1% to 70% by weight, and further preferably 1% to 50% by weight.

再者，關於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，為了降低液晶顯示元件的離子密度、抑制離子密度的經時性增加、進而抑制殘像的產生，具有自由基聚合性不飽和雙鍵的化合物/烯基取代納迪克醯亞胺化合物以重量比計而較佳為0.1～10，更佳為0.5～5。In addition, regarding the ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadicarium imine compound, in order to reduce the ion density of the liquid crystal display element, suppress the increase of the ion density with time, and further suppress the residual The generation of the image is preferably a compound having a radically polymerizable unsaturated double bond / alkenyl substituted nadicarium imine compound in a weight ratio of preferably 0.1 to 10, more preferably 0.5 to 5.

作為較佳的具有自由基聚合性不飽和雙鍵的化合物，例如可列舉日本專利特開2013-242526號公報等中所揭示的具有自由基聚合性不飽和雙鍵的化合物。Examples of the compound having a radically polymerizable unsaturated double bond include compounds having a radically polymerizable unsaturated double bond disclosed in Japanese Patent Laid-Open No. 2013-242526 and the like.

＜噁嗪化合物＞ 例如，本發明的液晶配向劑出於使液晶顯示元件中的電特性長期穩定的目的，亦可進而含有噁嗪化合物。噁嗪化合物可為一種化合物，亦可為兩種以上的化合物。出於所述目的，噁嗪化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而較佳為0.1重量%～50重量%，更佳為1重量%～40重量%，進而佳為1重量%～20重量%。<Xazine Compound> For example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics in the liquid crystal display element for a long period of time. The oxazine compound may be one kind, or two or more kinds. For the purpose, the content of the oxazine compound is preferably 0.1% to 50% by weight, and more preferably 1% to 40% by weight, relative to the polymer (for example, polyamidic acid (including a derivative thereof)). %, More preferably 1 to 20% by weight.

噁嗪化合物較佳為可溶於溶解聚合物（例如，聚醯胺酸（包含其衍生物））的有機溶媒中、且具有開環聚合性的噁嗪化合物。作為較佳的噁嗪化合物，例如可列舉式（OX-3-1）、式（OX-3-9）所表示的噁嗪化合物、或日本專利特開2013-242526號公報等中所揭示的噁嗪化合物。The oxazine compound is preferably an oxazine compound that is soluble in an organic solvent that dissolves a polymer (for example, polyamic acid (including a derivative thereof)) and has ring-opening polymerizability. Examples of preferred oxazine compounds include oxazine compounds represented by formula (OX-3-1) and formula (OX-3-9), and those disclosed in Japanese Patent Laid-Open No. 2013-242526 Oxazine compounds.

[化25] [Chemical 25]

＜噁唑啉化合物＞ 例如，本發明的液晶配向劑出於使液晶顯示元件中的電特性長期穩定的目的，亦可進而含有噁唑啉化合物。噁唑啉化合物為具有噁唑啉結構的化合物。噁唑啉化合物可為一種化合物，亦可為兩種以上的化合物。出於所述目的，噁唑啉化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而較佳為0.1重量%～50重量%，更佳為1重量%～40重量%，進而佳為1重量%～20重量%。另外，出於所述目的，較佳為於將噁唑啉化合物中的噁唑啉結構換算為噁唑啉時，噁唑啉化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而為0.1重量%～40重量%。<Oxazoline compound> For example, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics in a liquid crystal display element for a long period of time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. For the purpose, the content of the oxazoline compound is preferably 0.1% to 50% by weight, and more preferably 1% to 40% by weight relative to the polymer (for example, polyamidic acid (including a derivative thereof)). % By weight, more preferably 1 to 20% by weight. In addition, for the purpose described above, when the oxazoline structure in the oxazoline compound is converted into an oxazoline, it is preferable that the content of the oxazoline compound with respect to the polymer (for example, polyamino acid (including its Derivative)) and 0.1% to 40% by weight.

作為噁唑啉化合物，例如可列舉日本專利特開2013-242526號公報等中所揭示的噁唑啉化合物。作為較佳的噁唑啉化合物，可列舉1,3-雙(4,5-二氫-2-噁唑基)苯。Examples of the oxazoline compound include oxazoline compounds disclosed in Japanese Patent Laid-Open No. 2013-242526. Preferred oxazoline compounds include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

＜環氧化合物＞ 例如，本發明的液晶配向劑出於使液晶顯示元件中的電特性長期穩定的目的，亦可進而含有環氧化合物。環氧化合物可為一種化合物，亦可為兩種以上的化合物。出於所述目的，環氧化合物的含量相對於聚合物（例如，聚醯胺酸（包含其衍生物））而較佳為0.1重量%～50重量%，更佳為1重量%～40重量%，進而佳為1重量%～20重量%。<Epoxy Compound> For example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics in the liquid crystal display element for a long period of time. The epoxy compound may be one kind of compound or two or more kinds of compounds. For the purpose, the content of the epoxy compound is preferably 0.1% to 50% by weight, and more preferably 1% to 40% by weight relative to the polymer (for example, polyamic acid (including a derivative thereof)). %, More preferably 1 to 20% by weight.

作為環氧化合物，例如可列舉日本專利特開2013-242526號公報等中所揭示的環氧化合物。作為較佳的環氧化合物，可列舉：N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、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、2-(3,4-環氧環己基)乙基三乙氧基矽烷、(3,3',4,4'-二環氧)雙環己基。Examples of the epoxy compound include those disclosed in Japanese Patent Application Laid-Open No. 2013-242526. Preferred epoxy compounds include: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,3 ', 4,4 '-Diepoxy) dicyclohexyl.

另外，例如，本發明的液晶配向劑亦可進而含有各種添加劑。作為各種添加劑，例如可列舉聚合物（例如，聚醯胺酸（包含其衍生物））以外的高分子化合物、及低分子化合物，可根據各種目的而選擇使用。藉由含有添加劑而具有提高膜的硬度的技術效果，尤其提高對於摩擦處理的耐性，進而提高作為配向膜的可靠性。若加入添加劑，則存在預傾角提高的傾向，但於本發明的實施形態中，即便加入此種添加劑，亦具有可有意地減低預傾角的效果。In addition, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include high-molecular compounds other than polymers (for example, polyamic acid (including derivatives thereof)) and low-molecular compounds, and they can be selected and used according to various purposes. The technical effect of increasing the hardness of the film by containing an additive, particularly improving the resistance to the rubbing treatment, and further improving the reliability as an alignment film. If an additive is added, the pretilt angle tends to increase. However, in the embodiment of the present invention, even if such an additive is added, it has the effect of intentionally reducing the pretilt angle.

例如，作為所述高分子化合物，可列舉對於有機溶媒而言為可溶性的高分子化合物。就控制所形成的液晶配向膜的電特性或配向性的觀點而言，較佳為將此種高分子化合物添加至本發明的液晶配向劑中。作為該高分子化合物，例如可列舉：聚醯胺、聚胺基甲酸酯、聚脲、聚酯、聚環氧化物、聚酯多元醇、矽酮改質聚胺基甲酸酯、及矽酮改質聚酯。For example, examples of the polymer compound include polymer compounds that are soluble in organic solvents. From the viewpoint of controlling the electrical characteristics or the alignment properties of the formed liquid crystal alignment film, it is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone modified polyurethane, and silicon. Ketone modified polyester.

另外，作為所述低分子化合物，例如，1）於期望塗佈性的提高時，可列舉符合該目的的界面活性劑；2）於需要抗靜電的提高時，可列舉抗靜電劑；3）於期望與基板的密接性的提高時，可列舉矽烷偶合劑或鈦系偶合劑；另外，4）於在低溫下進行醯亞胺化的情況下，可列舉醯亞胺化觸媒。In addition, as the low-molecular compound, for example, 1) when an improvement in coatability is desired, a surfactant suitable for the purpose may be listed; 2) when an improvement in antistatic is required, an antistatic agent may be listed; 3) When an improvement in the adhesion to the substrate is desired, a silane coupling agent or a titanium-based coupling agent may be mentioned; and 4) when the sulfonium imidization is performed at a low temperature, a sulfonium imidization catalyst may be mentioned.

作為矽烷偶合劑，例如可列舉日本專利特開2013-242526號公報等中所揭示的矽烷偶合劑。作為較佳的矽烷偶合劑，可列舉3-胺基丙基三乙氧基矽烷。另外，作為醯亞胺化觸媒，可列舉日本專利特開2013-242526號公報等中所揭示的醯亞胺化觸媒。Examples of the silane coupling agent include the silane coupling agents disclosed in Japanese Patent Laid-Open No. 2013-242526. As a preferable silane coupling agent, 3-aminopropyltriethoxysilane is mentioned. Examples of the fluorene imidization catalyst include the fluorene imidization catalyst disclosed in Japanese Patent Laid-Open No. 2013-242526 and the like.

矽烷偶合劑的添加量通常為聚合物（例如，聚醯胺酸（包含其衍生物））的總重量的0重量%～20重量%，較佳為0.1重量%～10重量%。The addition amount of the silane coupling agent is usually 0% to 20% by weight, and preferably 0.1% to 10% by weight, based on the total weight of the polymer (for example, polyamic acid (including a derivative thereof)).

醯亞胺化觸媒的添加量通常相對於聚合物（例如，聚醯胺酸（包含其衍生物））的羰基而為0.01當量～5當量，較佳為0.05當量～3當量。The addition amount of the fluorene imidization catalyst is usually 0.01 to 5 equivalents, and preferably 0.05 to 3 equivalents, based on the carbonyl group of the polymer (for example, polyamic acid (including its derivative)).

其他添加劑的添加量根據其用途而不同，通常為聚合物（例如，聚醯胺酸（包含其衍生物））的總重量的0重量%～100重量%，較佳為0.1重量%～50重量%。The amount of other additives to be added varies depending on the application, and is usually 0% to 100% by weight, and preferably 0.1% to 50% by weight, based on the total weight of the polymer (for example, polyamic acid (including its derivative)). %.

另外，例如，就液晶配向劑的塗佈性或所述聚合物（例如，聚醯胺酸（包含其衍生物））的濃度調整的觀點而言，本發明的液晶配向劑亦可進而含有溶劑。所述溶劑若為具有溶解高分子成分的能力的溶劑，則可並無特殊限制地應用。所述溶劑可廣泛包含聚合物（例如，聚醯胺酸、可溶性聚醯亞胺等）的高分子成分的製造步驟或用途方面通常使用的溶劑，可根據使用目的而適宜選擇。所述溶劑可為一種，亦可為兩種以上的混合溶劑。In addition, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent or the concentration of the polymer (for example, polyamic acid (including a derivative thereof)), the liquid crystal alignment agent of the present invention may further contain a solvent. . As long as the solvent is a solvent having the ability to dissolve a polymer component, it can be applied without particular limitation. The solvent may widely include a solvent generally used in the production process or application of a polymer component of a polymer (for example, polyamic acid, soluble polyimide, etc.), and may be appropriately selected according to the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.

作為溶劑，可列舉所述聚合物（例如，聚醯胺酸（包含其衍生物））的親溶劑、或以塗佈性改善為目的的其他溶劑。Examples of the solvent include a lipophilic solvent of the polymer (for example, polyamidic acid (including a derivative thereof)), or another solvent for the purpose of improving coatability.

作為相對於聚合物（例如，聚醯胺酸（包含其衍生物））而為親溶劑的非質子性極性有機溶劑，可列舉：N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲基咪唑啶酮、N-甲基己內醯胺、N-甲基丙醯胺、N,N-二甲基乙醯胺、二甲基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二乙基乙醯胺、γ-丁內酯等內酯。Examples of the aprotic polar organic solvent that is a lipophilic solvent with respect to a polymer (for example, polyamic acid (including a derivative thereof)) include N-methyl-2-pyrrolidone and N-ethyl- 2-pyrrolidone, dimethylimidazolidone, N-methylcaprolactam, N-methylpropanamide, N, N-dimethylacetamidamine, dimethylsulfinamide, N, N -Lactones such as dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, γ-butyrolactone.

作為以塗佈性改善等為目的的其他溶劑的例子，可列舉：乳酸烷基酯、3-甲基-3-甲氧基丁醇、四氫萘、異佛爾酮、苯基乙酸酯、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、三乙二醇單烷基醚、丙二醇單甲醚、丙二醇單丁醚等丙二醇單烷基醚、丙二酸二乙酯等丙二酸二烷基酯、二丙二醇單甲醚等二丙二醇單烷基醚、該些的乙酸酯類等酯化合物、二異丁基酮等酮化合物。Examples of other solvents for the purpose of improving coatability include alkyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, and phenyl acetate. , Ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monoalkyl ethers, propylene glycol monomethyl ether, propylene glycol monobutyl ether Propylene glycol monoalkyl ethers, dialkyl malonates such as diethyl malonate, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, ester compounds such as acetates, and diisobutyl ketone And other ketone compounds.

該些中，所述溶劑特佳為N-甲基-2-吡咯啶酮、二甲基咪唑啶酮、γ-丁內酯、乙二醇單丁醚、二乙二醇單***、乙二醇單甲醚、丙二醇單丁醚、丙二醇單甲醚、二丙二醇單甲醚、及二異丁基酮。Among these, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and ethylene glycol. Alcohol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and diisobutyl ketone.

本發明的液晶配向劑中的聚合物（例如，聚醯胺酸）的濃度較佳為0.1重量%～40重量%，更佳為1重量%～20重量%，進而佳為1.5重量%～8重量%。於將該配向劑塗佈於基板上時，為了調整膜厚，有時需要預先藉由溶劑稀釋所含的聚合物（例如，聚醯胺酸）的操作。The concentration of the polymer (for example, polyamidic acid) in the liquid crystal alignment agent of the present invention is preferably 0.1% to 40% by weight, more preferably 1% to 20% by weight, and even more preferably 1.5% to 8%. weight%. When the alignment agent is applied on a substrate, in order to adjust the film thickness, an operation of diluting a polymer (for example, polyamic acid) contained in the solvent in advance may be required.

本發明的液晶配向劑的黏度的較佳範圍視塗佈的方法、聚合物（例如，聚醯胺酸（包含其衍生物））的濃度、使用的聚合物（例如，聚醯胺酸（包含其衍生物））的種類、溶劑的種類與比例而不同。例如，於利用印刷機的塗佈的情況下，若為5 mPa·s～100 mPa·s的範圍，則可獲得充分的膜厚且可防止印刷不均變大，因此較佳，更佳為10 mPa·s～80 mPa·s。於利用旋塗的塗佈的情況下，適合的是5 mPa·s～200 mPa·s（更佳為10 mPa·s～100 mPa·s）。於使用噴墨塗佈裝置進行塗佈的情況下，適合的是5 mPa·s～50 mPa·s（更佳為5 mPa·s～20 mPa·s）。液晶配向劑的黏度是藉由旋轉黏度測定法測定，例如，使用旋轉黏度計（東機產業製造的TVE-20L型）進行測定（測定溫度：25℃）。再者，本申請案的實施例中為5 mPa·s～15 mPa·s左右。The preferred range of the viscosity of the liquid crystal alignment agent of the present invention depends on the coating method, the concentration of the polymer (for example, polyamic acid (including its derivative)), the polymer used (for example, polyamino acid (including The derivatives)), the types and proportions of solvents vary. For example, in the case of coating by a printing machine, if the thickness is in the range of 5 mPa · s to 100 mPa · s, it is preferable to obtain a sufficient film thickness and prevent large print unevenness. 10 mPa · s to 80 mPa · s. In the case of coating by spin coating, 5 mPa · s to 200 mPa · s (more preferably 10 mPa · s to 100 mPa · s) is suitable. In the case of coating using an inkjet coating device, 5 mPa · s to 50 mPa · s (more preferably 5 mPa · s to 20 mPa · s) is suitable. The viscosity of the liquid crystal alignment agent is measured by a rotational viscosity measurement method. For example, the viscosity is measured using a rotational viscosity meter (TVE-20L type manufactured by Toki Sangyo) (measurement temperature: 25 ° C). In the examples of the present application, it is about 5 mPa · s to 15 mPa · s.

＜液晶配向膜＞ 根據本發明的實施形態，提供一種液晶配向膜，其是由所述液晶配向劑形成。以下，進行詳細說明。於本發明的實施形態中，液晶配向膜是藉由對所述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利用由液晶配向劑製作液晶配向膜的通常的方法而獲得。例如，本發明的液晶配向膜可藉由經過如下步驟而獲得：形成本發明的液晶配向劑的塗膜的步驟、進行加熱乾燥的步驟、以及進行加熱煅燒的步驟。關於本發明的液晶配向膜，亦可視需要而如後所述對經過加熱乾燥步驟、加熱煅燒步驟而獲得的膜進行摩擦處理而賦予各向異性。或者，亦可視需要於塗膜步驟、加熱乾燥步驟後照射光、或於加熱煅燒步驟後照射光而賦予各向異性。<Liquid crystal alignment film> According to an embodiment of the present invention, there is provided a liquid crystal alignment film formed of the liquid crystal alignment agent. The details are described below. In the embodiment of the present invention, the liquid crystal alignment film is a film formed by heating a coating film of the liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be obtained by a general method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by the following steps: a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of heating and drying, and a step of heating and calcining. Regarding the liquid crystal alignment film of the present invention, the film obtained through the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment to impart anisotropy, as necessary, as described later. Alternatively, anisotropy may be imparted by irradiating light after the coating step, the heating and drying step, or irradiating the light after the heating and calcining step as necessary.

塗膜可與通常的液晶配向膜的製作同樣地藉由將本發明的液晶配向劑塗佈於液晶顯示元件中的基板上而形成。基板可列舉：可設置氧化銦錫（Indium Tin Oxide，ITO）、氧化銦鋅（Indium Zinc Oxide，IZO）（In2 O3 -ZnO）、氧化銦鎵鋅（Indium Gallium Zinc Oxide，IGZO）（In-Ga-ZnO4 ）電極等電極或彩色濾光片等的玻璃製、氮化矽製、丙烯酸製、聚碳酸酯製、聚醯亞胺製等基板。再者，本申請案的實施例中使用ITO。The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. Examples of substrates: Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO) (In 2 O 3 -ZnO), Indium Gallium Zinc Oxide (IGZO) (In -Ga-ZnO 4 ) electrodes and other substrates such as glass, silicon nitride, acrylic, polycarbonate, and polyimide substrates such as color filters. Moreover, ITO is used in the Example of this application.

作為將液晶配向劑塗佈於基板上的方法，通常已知有旋轉器法、印刷法、浸漬法、滴加法、噴墨法等。該些方法於本發明中亦可同樣地應用。As a method of applying a liquid crystal alignment agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known. These methods can be similarly applied in the present invention.

所述加熱乾燥步驟（預煅燒步驟）通常已知有於烘箱或紅外爐中進行加熱處理的方法、於加熱板上進行加熱處理的方法等。加熱乾燥步驟較佳為於溶劑可蒸發的範圍內的溫度下實施，更佳為於相對於加熱煅燒步驟中的溫度而言比較低的溫度下實施。具體而言，加熱乾燥溫度較佳為30℃～150℃的範圍，進而佳為50℃～120℃的範圍。另外，時間亦無特別限制，例如適宜為1分鐘～10分鐘，進而適宜為1分鐘～5分鐘。The heat-drying step (pre-calcination step) is generally known as a method of performing a heat treatment in an oven or an infrared oven, a method of performing a heat treatment on a hot plate, and the like. The heat-drying step is preferably performed at a temperature within a range in which the solvent can be evaporated, and more preferably, it is performed at a temperature that is relatively low relative to the temperature in the heat-calcination step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. In addition, the time is not particularly limited. For example, it is preferably 1 minute to 10 minutes, and more preferably 1 minute to 5 minutes.

所述加熱煅燒步驟例如可於所述聚醯胺酸或其衍生物呈現脫水·閉環反應所需的條件下進行。所述塗膜的煅燒通常已知有於烘箱或紅外爐中進行加熱處理的方法、於加熱板上進行加熱處理的方法等。該些方法於本發明中亦可同樣地應用。通常較佳為100℃～300℃左右的溫度，更佳為120℃～280℃，進而佳為150℃～250℃。另外，作為時間，較佳為進行1分鐘～3小時。另外，可於不同的溫度下進行多次加熱煅燒。可使用設定為不同的溫度的多個加熱裝置，亦可使用1台加熱裝置一邊依次變化為不同的溫度一邊進行。於以不同的溫度進行2次加熱煅燒的情況下，較佳為第1次以90℃～180℃、第2次以185℃以上的溫度進行。另外，可使溫度自低溫變化為高溫而進行煅燒。於使溫度變化而進行煅燒的情況下，初始溫度較佳為90℃～180℃。最終溫度較佳為185℃～300℃，更佳為190℃～230℃。The heating and calcining step can be performed, for example, under conditions necessary for the polyamidic acid or a derivative thereof to exhibit a dehydration and ring closure reaction. The firing of the coating film is generally known as a method of performing a heat treatment in an oven or an infrared oven, a method of performing a heat treatment on a hot plate, and the like. These methods can be similarly applied in the present invention. Generally, a temperature of about 100 ° C to 300 ° C is preferable, 120 ° C to 280 ° C is more preferable, and 150 ° C to 250 ° C is more preferable. The time is preferably 1 minute to 3 hours. In addition, multiple calcinations can be performed at different temperatures. A plurality of heating devices set to different temperatures may be used, or one heating device may be used while sequentially changing to different temperatures. When the heating and calcination is performed twice at different temperatures, it is preferably performed at a temperature of 90 ° C. to 180 ° C. for the first time and at a temperature of 185 ° C. or higher for the second time. In addition, the temperature can be changed from a low temperature to a high temperature to perform firing. When the temperature is changed and firing is performed, the initial temperature is preferably 90 ° C to 180 ° C. The final temperature is preferably 185 ° C to 300 ° C, and more preferably 190 ° C to 230 ° C.

於本發明的液晶配向膜的形成方法中，為了使液晶相對於水平及/或垂直方向而於一方向上配向，作為對配向膜賦予各向異性的手段，可適宜使用摩擦法或光配向法等公知的形成方法。作為摩擦布的材質，可列舉：棉、人造絲、尼龍等。In the method for forming a liquid crystal alignment film of the present invention, in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical directions, as a means for imparting anisotropy to the alignment film, a rubbing method or a photo-alignment method may be suitably used. Well-known formation method. Examples of the material of the friction cloth include cotton, rayon, and nylon.

於使用摩擦法的本發明的實施形態中，液晶配向膜可經過如下步驟而形成：將所述液晶配向劑塗佈於基板上的步驟、對塗佈有所述液晶配向劑的基板進行加熱乾燥而製作膜的步驟、對所述膜進行加熱煅燒的步驟、以及對所述加熱煅燒後的膜進行摩擦處理的步驟。In the embodiment of the present invention using the rubbing method, the liquid crystal alignment film may be formed through the following steps: a step of applying the liquid crystal alignment agent on a substrate, and heating and drying the substrate coated with the liquid crystal alignment agent. The step of manufacturing a film, the step of heating and calcining the film, and the step of performing a rubbing treatment on the film after heating and calcining.

摩擦處理可與通常的用於液晶配向膜的配向處理的摩擦處理同樣地進行，於本發明的液晶配向膜中，只要為可獲得充分的延遲（retardation）的條件即可。較佳的條件為毛壓入量為0.2 mm～0.8 mm。另外，平台移動速度為5 mm/sec～250 mm/sec。另外，輥旋轉速度為500 rpm～2,000 rpm。The rubbing treatment can be performed in the same manner as the rubbing treatment used for a general alignment treatment of a liquid crystal alignment film. In the liquid crystal alignment film of the present invention, it is only required to be a condition capable of obtaining sufficient retardation. A preferred condition is that the gross indentation amount is 0.2 mm to 0.8 mm. The moving speed of the platform is 5 mm / sec to 250 mm / sec. The rotation speed of the roller is 500 rpm to 2,000 rpm.

於本發明的實施形態中，液晶配向膜可適宜藉由進而包括所述步驟以外的其他步驟的方法而獲得。例如，於用於製作液晶配向膜的步驟的一部分中亦可設置利用清洗液對所製作的膜進行清洗的步驟。當然，關於本發明的液晶配向膜，利用清洗液對煅燒或放射線照射後的膜進行清洗的步驟並非必需的。另外，其他步驟亦並非必需的，可視需要設置清洗步驟。In the embodiment of the present invention, the liquid crystal alignment film can be suitably obtained by a method further including steps other than the above steps. For example, a part of the step for producing a liquid crystal alignment film may be provided with a step of cleaning the produced film with a cleaning solution. Of course, in the liquid crystal alignment film of the present invention, the step of cleaning the film after calcination or radiation irradiation with a cleaning solution is not necessary. In addition, other steps are not necessary, and cleaning steps can be set as needed.

作為利用清洗液的清洗方法，可列舉：刷洗（brushing）、噴射噴霧（jet spray）、蒸汽清洗或超音波清洗等。該些方法可單獨進行，亦可併用。作為清洗液，可使用純水（較佳為超純水）或、甲基醇、乙基醇、異丙基醇等各種醇類、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，但並不限定於該些。當然，該些清洗液使用經充分精製的雜質少者。此種清洗方法亦可應用於本發明的液晶配向膜的形成中的所述清洗步驟。Examples of the cleaning method using a cleaning solution include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods can be performed individually or in combination. As the cleaning liquid, pure water (preferably ultrapure water), various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, and dichloromethane can be used. Halogen solvents such as (methylene chloride) and ketones such as acetone and methyl ethyl ketone are not limited thereto. As a matter of course, those cleaning liquids are those which have sufficiently refined impurities. This cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

為了提高本發明的液晶配向膜的液晶配向能力，亦可於加熱煅燒步驟前後、摩擦步驟前後使用利用熱或光的退火處理。該退火處理中，退火溫度為30℃～180℃、較佳為50℃～150℃，另外，時間較佳為1分鐘～2小時，更佳為10分鐘～1小時。另外，退火處理中使用的退火光可列舉紫外線（Ultra Violet，UV）燈、螢光燈、發光二極體（Light Emitting Diode，LED）燈等。光的照射量較佳為0.3 J/cm2 ～10 J/cm2 。In order to improve the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, an annealing treatment using heat or light may be used before and after the heating and calcining step and before and after the rubbing step. In this annealing treatment, the annealing temperature is 30 ° C to 180 ° C, preferably 50 ° C to 150 ° C, and the time is preferably 1 minute to 2 hours, and more preferably 10 minutes to 1 hour. Examples of the annealing light used in the annealing process include an ultraviolet (Ultra Violet) lamp, a fluorescent lamp, and a light emitting diode (LED) lamp. The irradiation amount of light is preferably 0.3 J / cm 2 to 10 J / cm 2 .

本發明的液晶配向膜的膜厚並無特別限定，較佳為10 nm～300 nm，更佳為30 nm～150 nm。本發明的液晶配向膜的膜厚可利用階差計或橢圓儀（ellipsometer）等公知的膜厚測定裝置進行測定。The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, 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 step meter or an ellipsometer.

本發明的液晶配向膜的特徵在於具有特別大的配向各向異性。此種各向異性的大小可利用日本專利特開2005-275364號公報等中記載的使用偏光IR的方法進行評價。另外，如以下所示，亦可藉由使用橢圓偏光儀（ellipsometry）的方法來進行評價。詳細而言，可藉由分光橢圓儀測定液晶配向膜的延遲值。膜的延遲值與聚合物主鏈的配向度成比例地變大。即，具有大的延遲值者具有大的配向度。因此，認為於將其作為液晶配向膜而使用的情況下，該液晶配向膜具有更大的各向異性，因此可對液晶組成物大幅度地進行配向限制。The liquid crystal alignment film of the present invention is characterized by having particularly large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in Japanese Patent Laid-Open No. 2005-275364 and the like. In addition, as shown below, evaluation can also be performed by a method using an ellipsometry. Specifically, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film becomes larger in proportion to the degree of alignment of the polymer backbone. That is, a person having a large delay value has a large degree of alignment. Therefore, when it is used as a liquid crystal alignment film, it is considered that this liquid crystal alignment film has greater anisotropy, and therefore, the alignment of the liquid crystal composition can be significantly restricted.

本發明的液晶配向膜可適宜用於橫電場方式的液晶顯示元件。於用於橫電場方式的液晶顯示元件的情況下，預傾（Pt）角越小，另外液晶配向能力越高，暗狀態下的黑顯示位準越變高，對比度越提高。預傾（Pt）角理想的是1.5°以下，更理想的是1.2°以下。因此，根據本發明的實施形態，所述液晶配向劑可用於橫電場型液晶顯示元件的製造。另外，根據本發明的實施形態，提供一種橫電場型液晶顯示元件，其具有所述液晶配向膜。The liquid crystal alignment film of this invention can be used suitably for the liquid crystal display element of a horizontal electric field system. In the case of a liquid crystal display element using a transverse electric field method, the smaller the pretilt (Pt) angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state and the higher the contrast. The pretilt (Pt) angle is preferably 1.5 ° or less, and more preferably 1.2 ° or less. Therefore, according to an embodiment of the present invention, the liquid crystal alignment agent can be used for manufacturing a liquid crystal display element of a transverse electric field type. In addition, according to an embodiment of the present invention, there is provided a lateral electric field type liquid crystal display element including the liquid crystal alignment film.

本發明的液晶配向膜可用於智慧型電話、平板電腦、車載監視器、電視機等液晶顯示器用的液晶組成物的配向控制。除了液晶顯示器用的液晶組成物的配向用途以外，亦可用於光學補償材料或其他所有的液晶材料的配向控制。另外，本發明的配向膜具有大的各向異性，因此可單獨用於光學補償材料用途。另外，根據本發明的實施形態，提供一種液晶顯示元件，其具有所述液晶配向膜。The liquid crystal alignment film of the present invention can be used for alignment control of liquid crystal compositions for liquid crystal displays such as smart phones, tablet computers, car monitors, and televisions. In addition to the alignment application of liquid crystal compositions for liquid crystal displays, it can also be used for alignment control of optical compensation materials or all other liquid crystal materials. In addition, since the alignment film of the present invention has large anisotropy, it can be used alone as an optical compensation material. In addition, according to an embodiment of the present invention, there is provided a liquid crystal display device including the liquid crystal alignment film.

＜液晶顯示元件＞ 對本發明的液晶顯示元件進行詳細說明。本發明提供一種液晶顯示元件，其具有：相向配置的一對基板、形成於所述一對基板的各自的相向的面的一者或兩者上的電極、形成於所述一對基板的各自的相向的面上的液晶配向膜、以及形成於所述一對基板間的液晶層，並且於所述液晶顯示元件中，所述液晶配向膜為本發明的配向膜。<Liquid crystal display element> The liquid crystal display element of this invention is demonstrated in detail. The present invention provides a liquid crystal display element including a pair of substrates disposed opposite to each other, an electrode formed on one or both of the opposing surfaces of the pair of substrates, and a respective one formed on the pair of substrates. The liquid crystal alignment film on the opposite surface and the liquid crystal layer formed between the pair of substrates, and in the liquid crystal display element, the liquid crystal alignment film is the alignment film of the present invention.

所述電極若為形成於基板的一面上的電極，則並無特別限定。此種電極例如可列舉ITO或金屬的蒸鍍膜等。另外，電極可形成於基板的其中一面的整面上，例如亦可形成為經圖案化的所需的形狀。電極的所述所需形狀例如可列舉梳型或鋸齒（zigzag）結構等。電極可形成於一對基板中的其中一基板上，亦可形成於兩基板上。電極的形成形態視液晶顯示元件的種類而不同，例如於IPS型液晶顯示元件的情況下，電極配置於所述一對基板的其中一者上，於其他液晶顯示元件的情況下，電極配置於所述一對基板的兩者上。於所述基板或電極上形成所述液晶配向膜。The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include ITO and a vapor-deposited film of a metal. The electrode may be formed on the entire surface of one surface of the substrate, and may be formed into a desired shape patterned, for example. Examples of the desired shape of the electrode include a comb type or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The formation form of the electrodes varies depending on the type of the liquid crystal display element. For example, in the case of an IPS liquid crystal display element, the electrode is disposed on one of the pair of substrates. In the case of other liquid crystal display elements, the electrode is disposed on On both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

所述液晶層可以如下形態形成：由形成有液晶配向膜的面相向的所述一對基板夾持液晶組成物的形態。液晶層的形成中，可視需要使用微粒子或樹脂片等介隔存在於所述一對基板間並形成適當的間隔的間隔物。The liquid crystal layer may be formed in a form in which a liquid crystal composition is sandwiched between the pair of substrates facing each other on a surface where the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, if necessary, a spacer such as fine particles or a resin sheet is used to form an appropriate interval between the pair of substrates.

作為液晶層的形成方法，例如可使用真空注入法或液晶滴注（One Drop Fill，ODF）法。作為基板的黏合中所使用的密封劑，例如可使用UV硬化型或熱硬化型的密封劑。密封劑的印刷例如可使用網版印刷法。As a method for forming the liquid crystal layer, for example, a vacuum injection method or a liquid crystal drip (ODF) method can be used. As a sealant used for bonding substrates, for example, a UV-curable or thermosetting sealant can be used. The sealant can be printed using, for example, a screen printing method.

液晶組成物並無特別限制，可使用介電各向異性為正或負的各種液晶組成物。介電各向異性為正的較佳的液晶組成物可列舉：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）、日本專利特開平9-302346號公報（EP806466A1）、日本專利特開平8-199168號公報（EP722998A1）、日本專利特開平9-235552號公報、日本專利特開平9-255956號公報、日本專利特開平9-241643號公報（EP885271A1）、日本專利特開平10-204016號公報（EP844229A1）、日本專利特開平10-204436號公報、日本專利特開平10-231482號公報、日本專利特開2000-087040號公報、日本專利特開2001-48822號公報等中所揭示的液晶組成物。The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Examples of preferred liquid crystal compositions having a positive dielectric anisotropy include: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Publication No. 5-501735, and Japanese Patent Publication No. 8-157826. Gazette, Japanese Patent Laid-Open No. 8-231960, Japanese Patent Laid-Open No. 9-241644 (EP885272A1), Japanese Patent Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Laid-Open No. 8-199168 (EP722998A1) Japanese Patent Laid-Open No. 9-235552, Japanese Patent Laid-Open No. 9-255956, Japanese Patent Laid-Open No. 9-241643 (EP885271A1), Japanese Patent Laid-Open No. 10-204016 (EP844229A1), Japanese Patent Laid-Open The liquid crystal compositions disclosed in Kaiping No. 10-204436, Japanese Patent Laid-Open No. 10-231482, Japanese Patent Laid-Open No. 2000-087040, Japanese Patent Laid-Open No. 2001-48822, and the like.

作為所述具有負的介電各向異性的液晶組成物的較佳例，可列舉：日本專利特開昭57-114532號公報、日本專利特開平2-4725號公報、日本專利特開平4-224885號公報、日本專利特開平8-40953號公報、日本專利特開平8-104869號公報、日本專利特開平10-168076號公報、日本專利特開平10-168453號公報、日本專利特開平10-236989號公報、日本專利特開平10-236990號公報、日本專利特開平10-236992號公報、日本專利特開平10-236993號公報、日本專利特開平10-236994號公報、日本專利特開平10-237000號公報、日本專利特開平10-237004號公報、日本專利特開平10-237024號公報、日本專利特開平10-237035號公報、日本專利特開平10-237075號公報、日本專利特開平10-237076號公報、日本專利特開平10-237448號公報（EP967261A1）、日本專利特開平10-287874號公報、日本專利特開平10-287875號公報、日本專利特開平10-291945號公報、日本專利特開平11-029581號公報、日本專利特開平11-080049號公報、日本專利特開2000-256307號公報、日本專利特開2001-019965號公報、日本專利特開2001-072626號公報、日本專利特開2001-192657號公報、日本專利特開2010-037428號公報、國際公開第2011/024666號公報、國際公開第2010/072370號公報、日本專利特表2010-537010號公報、日本專利特開2012-077201號公報、日本專利特開2009-084362號公報等中所揭示的液晶組成物。於介電各向異性為正或負的液晶組成物中添加一種以上的光學活性化合物而使用的情況亦無任何影響。Preferable examples of the liquid crystal composition having negative dielectric anisotropy include Japanese Patent Laid-Open No. 57-114532, Japanese Patent Laid-Open No. 2-4725, and Japanese Patent Laid-Open No. Heisei 4- 224885, Japanese Patent Laid-Open No. 8-40953, Japanese Patent Laid-Open No. 8-104869, Japanese Patent Laid-Open No. 10-168076, Japanese Patent Laid-Open No. 10-168453, Japanese Patent Laid-Open No. 10- 236989, Japanese Patent Laid-Open No. 10-236990, Japanese Patent Laid-Open No. 10-236992, Japanese Patent Laid-Open No. 10-236993, Japanese Patent Laid-Open No. 10-236994, Japanese Patent Laid-Open No. 10- 237000, Japanese Patent Laid-Open No. 10-237004, Japanese Patent Laid-Open No. 10-237024, Japanese Patent Laid-Open No. 10-237035, Japanese Patent Laid-Open No. 10-237075, Japanese Patent Laid-Open No. 10- Japanese Patent Application Publication No. 237076, Japanese Patent Application Publication No. 10-237448 (EP967261A1), Japanese Patent Application Publication No. 10-287874, Japanese Patent Application Publication No. 10-287875, Japanese Patent Application Publication No. 1 0-291945, Japanese Patent Laid-Open No. 11-029581, Japanese Patent Laid-Open No. 11-080049, Japanese Patent Laid-Open No. 2000-256307, Japanese Patent Laid-Open No. 2001-019965, Japanese Patent Laid-Open No. 2001-072626, Japanese Patent Laid-Open Publication No. 2001-192657, Japanese Patent Laid-Open Publication No. 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Patent Publication No. 2010- The liquid crystal composition disclosed in JP 537010, JP 2012-077201, JP 2009-084362, and the like. It does not affect the case where one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy.

另外，例如，就提高例如配向性的觀點而言，本發明的液晶顯示元件中使用的液晶組成物亦可進而添加添加物。此種添加物為光聚合性單體、光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合起始劑、聚合抑制劑等。較佳的光聚合性單體、光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合起始劑、聚合抑制劑可列舉國際公開第2015/146330號公報等中所揭示的化合物。In addition, for example, from the viewpoint of improving the alignment, the liquid crystal composition used in the liquid crystal display element of the present invention may be further added with an additive. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, polymerization inhibitors, and the like. Preferred photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, and polymerization inhibitors include the compounds disclosed in International Publication No. 2015/146330 .

為了適合於聚合物穩定配向（polymer sustained alignment，PSA）模式的液晶顯示元件，可將可聚合的化合物混合至液晶組成物中。可聚合的化合物的較佳例為丙烯酸酯、甲基丙烯酸酯、乙烯基化合物、乙烯基氧基化合物、丙烯基醚、環氧化合物（氧雜環丙烷、氧雜環丁烷）、乙烯基酮等具有可聚合的基的化合物。較佳的化合物可列舉國際公開第2015/146330號公報等中所揭示的化合物。 [實施例]In order to be suitable for a liquid crystal display device in a polymer sustained alignment (PSA) mode, a polymerizable compound may be mixed into the liquid crystal composition. Preferable examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane, oxetane), and vinyl ketone. And other compounds having a polymerizable group. Preferred compounds include those disclosed in International Publication No. 2015/146330 and the like. [Example]

以下，藉由實施例對本發明進行說明，但本發明並不限定於該些實施例。再者，實施例中使用的評價法及化合物如下所述。Hereinafter, the present invention will be described by examples, but the present invention is not limited to these examples. The evaluation methods and compounds used in the examples are as follows.

1. 重量平均分子量（Mw） 聚醯胺酸的重量平均分子量是使用2695分離模組·2414示差折射計（沃特世（Waters）製造）並藉由GPC法測定且進行聚苯乙烯換算而求出。以聚醯胺酸濃度為約2重量%的方式利用磷酸-DMF混合溶液（磷酸/DMF=0.6/100：重量比）對所獲得的聚醯胺酸進行稀釋。管柱是使用HSPgel RT MB-M（沃特世（Waters）製造），並且將所述混合溶液作為展開劑且以管柱溫度50℃、流速0.40 mL/分鐘的條件進行測定。標準聚苯乙烯使用東曹（Tosoh）（股）製造的TSK標準聚苯乙烯。 2. 預傾角（Pt角） 利用中央精機（股）製造的液晶評價裝置（OMS-CA3）於室溫下進行測定。為了獲得廣視角，理想的是1.5°以下，更理想的是1.2°以下。 3. DC殘像評價 施加10分鐘的30 Hz、3 V的矩形波後，重疊20分鐘的0.3 V的直流電壓。將直流電壓設為0 V後，再次施加20分鐘的3 V的矩形波。直流電壓重疊時的電荷的吸收越快，成為非對稱的AC驅動時的殘留DC越小，越難以產生DC殘像，因此將重疊直流電壓後至經過二十分鐘為止閃爍消除電壓成為0.15 V以下的情況定義評價為DC殘像為「○」，將為0.1 V以下的情況定義評價為DC殘像為「◎」。將重疊直流電壓後至經過二十分鐘為止閃爍消除電壓並未成為0.15 V以下的情況定義評價為DC殘像為「×」。 4. 電壓保持率 利用「水嶋他，第14次液晶討論會草稿集 p78(1988)」中記載的方法進行。測定是對單元（cell）施加頻率30 Hz、波高±5 V的矩形波而進行。測定是於60℃下進行。該值是表示所施加的電壓於框週期後以何種程度保持的指標，該值若為100%，則表示保持有所有的電荷。若值為99.5%以上，則為顯示品質良好的液晶顯示元件。1. Weight-average molecular weight (Mw) The weight-average molecular weight of polyamic acid is determined by GPC method using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters) and converting it to polystyrene. Out. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was measured using HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing agent at a column temperature of 50 ° C and a flow rate of 0.40 mL / min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Co., Ltd. was used. 2. Pre-tilt angle (Pt angle) was measured at room temperature using a liquid crystal evaluation device (OMS-CA3) manufactured by Chuo Seiki Co., Ltd. In order to obtain a wide viewing angle, it is preferably 1.5 ° or less, and more preferably 1.2 ° or less. 3. DC residual image evaluation After applying a rectangular wave of 30 Hz and 3 V for 10 minutes, a DC voltage of 0.3 V was superimposed for 20 minutes. After setting the DC voltage to 0 V, a 3 V rectangular wave was applied again for 20 minutes. The faster the charge is absorbed when the DC voltages overlap, the smaller the residual DC during asymmetric AC driving, and the more difficult it is to generate a DC afterimage. Therefore, the flicker elimination voltage will be 0.15 V or less after 20 minutes after the DC voltage is superimposed. In the case definition evaluation, the DC residual image is "○", and when the case is 0.1 V or less, the DC residual image is evaluated as "◎". The case where the flicker elimination voltage did not become 0.15 V or less after the lapse of twenty minutes after the DC voltage was superimposed was defined as a "×" afterimage in DC. 4. Voltage holding ratio It was performed by the method described in "Minamata, Draft Collection of the 14th LCD Symposium p78 (1988)". The measurement was performed by applying a rectangular wave having a frequency of 30 Hz and a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index indicating how much the applied voltage is maintained after the frame period. If the value is 100%, it indicates that all the charges are maintained. If the value is 99.5% or more, it is a liquid crystal display element with good display quality.

＜溶劑＞ NMP：N-甲基-2-吡咯啶酮 BC：丁基溶纖劑（乙二醇單丁醚） GBL：γ-丁內酯。<Solvent> NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether) GBL: γ-butyrolactone.

＜添加劑＞ 添加劑（Ad1）：1,3-雙(4,5-二氫-2-噁唑基)苯 添加劑（Ad2）：3-胺基丙基三乙氧基矽烷 添加劑（Ad3）：2-(3,4-環氧基環己基)乙基三甲氧基矽烷。<Additives> Additive (Ad1): 1,3-bis (4,5-dihydro-2-oxazolyl) benzene additive (Ad2): 3-aminopropyltriethoxysilane additive (Ad3): 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane.

[合成例1a]化合物（1-4）的合成 供於合成的試劑可並不精製地直接使用市售品。[Synthesis Example 1a] Synthesis of Compound (1-4) The reagents used in the synthesis can be used without purification.

＜第1階段＞ 於安裝有滴加漏斗、溫度計的1 L三口燒瓶中加入辛二醯基氯化物50.0 g（236.9 mmol）並添加二氯甲烷（dichloromethane）250 mL。將該溶液冷卻至5℃，並添加氯化鋁（III）75.8 g（568.6 mmol，2.4 eq.）。將溶液保持為5℃並攪拌30分鐘後，滴加添加使苯38.9 g（497.5 mmol，2.1 eq.）溶解於二氯甲烷250 mL中而成的溶液。滴加結束後，停止溶液的冷卻，升溫至室溫，對該溶液進而於室溫下攪拌12小時。該一連串的反應是於氮氣環境下進行。將反應溶液傾倒至3NHCl 1500 mL中，回收有機層並利用純水500 mL對該有機層進行3次清洗。清洗後，利用無水硫酸鎂對有機層進行乾燥，之後將溶媒減壓餾去，獲得粗結晶。使所獲得的粗結晶自甲苯中再結晶，於80℃下對所獲得的結晶進行12小時真空乾燥，獲得1,8-二苯基辛烷-1,8-二酮（產量：61.4 g，產率：88%）。<1st stage> A 1 L three-necked flask equipped with a dropping funnel and a thermometer was charged with 50.0 g (236.9 mmol) of octadecanyl chloride and 250 mL of dichloromethane. The solution was cooled to 5 ° C, and 75.8 g (568.6 mmol, 2.4 eq.) Of aluminum (III) chloride was added. After the solution was kept at 5 ° C and stirred for 30 minutes, a solution prepared by dissolving 38.9 g (497.5 mmol, 2.1 eq.) Of benzene in 250 mL of dichloromethane was added dropwise. After the dropwise addition was completed, the cooling of the solution was stopped, the temperature was raised to room temperature, and the solution was further stirred at room temperature for 12 hours. This series of reactions is performed under a nitrogen atmosphere. The reaction solution was poured into 1500 mL of 3N HCl, the organic layer was recovered, and the organic layer was washed three times with 500 mL of pure water. After washing, the organic layer was dried with anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystals were recrystallized from toluene, and the obtained crystals were vacuum-dried at 80 ° C. for 12 hours to obtain 1,8-diphenyloctane-1,8-dione (yield: 61.4 g, Yield: 88%).

＜第2階段＞ 於安裝有滴加漏斗、溫度計的1 L三口燒瓶中加入第1階段中獲得的1,8-二苯基辛烷-1,8-二酮50.0 g（170.0 mmol）並添加二氯甲烷500 mL。將該溶液冷卻至5℃，並滴加四氯化鈦（IV）70.9 g（374.0 mmol，2.2 eq.）。將該溶液保持為5℃並攪拌1小時後，進而滴加三乙基矽烷59.3 g（510.0 mmol，3.0 eq.）。將該溶液保持為5℃並攪拌6小時。該一連串的反應是於氮氣環境下進行。將反應溶液傾倒至純水1 L中，回收有機層並利用飽和碳酸氫鈉水500 mL對該有機層進行3次清洗，繼而利用純水500 mL進行3次清洗。清洗後，利用無水硫酸鎂對有機層進行乾燥，之後將溶媒減壓餾去，獲得粗體。對所獲得的粗體利用管柱層析儀（填充劑：矽膠，展開溶媒：甲苯：庚烷=2：1）進行分離精製，獲得1,8-二苯基辛烷（產量：42.6 g，產率：94%）。〈Second stage〉 In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 50.0 g (170.0 mmol) of 1,8-diphenyloctane-1,8-dione obtained in the first stage was added and added. 500 mL of dichloromethane. The solution was cooled to 5 ° C, and 70.9 g (374.0 mmol, 2.2 eq.) Of titanium (IV) chloride was added dropwise. After the solution was kept at 5 ° C and stirred for 1 hour, 59.3 g (510.0 mmol, 3.0 eq.) Of triethylsilane was further added dropwise. The solution was kept at 5 ° C and stirred for 6 hours. This series of reactions is performed under a nitrogen atmosphere. The reaction solution was poured into 1 L of pure water, and the organic layer was recovered, and the organic layer was washed 3 times with 500 mL of saturated sodium bicarbonate water, and then washed 3 times with 500 mL of pure water. After washing, the organic layer was dried with anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. The obtained bold was separated and purified using a column chromatography (filler: silica gel, developing solvent: toluene: heptane = 2: 1) to obtain 1,8-diphenyloctane (yield: 42.6 g, Yield: 94%).

＜第3階段＞ [化26]於安裝有滴加漏斗、溫度計的1 L三口燒瓶中加入4-硝基苯甲醯基氯化物50.1 g（270.2 mmol，2.4 eq.）並添加二氯甲烷250 mL。將該溶液冷卻至5℃，並添加氯化鋁（III）45.0 g（337.8 mmol，3.0 eq.）。將溶液保持為5℃並攪拌30分鐘後，滴加添加使第2階段中獲得的1,8-二苯基辛烷30.0 g（112.6 mmol）溶解於二氯甲烷150 mL中而成的溶液。滴加結束後，停止溶液的冷卻，升溫至室溫，對該溶液進而於室溫下攪拌12小時。該一連串的反應是於氮氣環境下進行。將反應溶液傾倒至3NHCl 1500 mL中，回收有機層並利用純水500 mL對該有機層進行3次清洗。清洗後，利用無水硫酸鎂對有機層進行乾燥，之後將溶媒減壓餾去，獲得粗體。對所獲得的粗體利用管柱層析儀（填充劑：矽膠，展開溶媒：二氯甲烷）進行分離精製，獲得化合物（1-4）-NK（產量：52.1 g，產率：82%）。＜ The third stage ＞ [Chem. 26] In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 50.1 g (270.2 mmol, 2.4 eq.) Of 4-nitrobenzyl chloride was added, and 250 mL of dichloromethane was added. The solution was cooled to 5 ° C, and 45.0 g (337.8 mmol, 3.0 eq.) Of aluminum (III) chloride was added. After the solution was kept at 5 ° C and stirred for 30 minutes, a solution prepared by dissolving 30.0 g (112.6 mmol) of 1,8-diphenyloctane obtained in the second stage in 150 mL of dichloromethane was added dropwise. After the dropwise addition was completed, the cooling of the solution was stopped, the temperature was raised to room temperature, and the solution was further stirred at room temperature for 12 hours. This series of reactions is performed under a nitrogen atmosphere. The reaction solution was poured into 1500 mL of 3N HCl, the organic layer was recovered, and the organic layer was washed three times with 500 mL of pure water. After washing, the organic layer was dried with anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. The obtained bold was separated and purified using a column chromatography (filler: silica gel, developing solvent: dichloromethane) to obtain a compound (1-4) -NK (yield: 52.1 g, yield: 82%) .

＜第4階段＞ [化27]於安裝有滴加漏斗、溫度計的1 L三口燒瓶中加入第3階段中獲得的化合物（1-4）-NK 50.0 g（88.6 mmol）並添加二氯甲烷500 mL。將該溶液冷卻至5℃，並於其中滴加四氯化鈦（IV）37.0 g（194.9 mmol，2.2 eq.）。將該溶液保持為5℃並攪拌1小時後，於其中滴加三乙基矽烷30.9 g（265.8 mmol，3.0 eq.）。將該溶液保持為5℃並攪拌4小時。該一連串的反應是於氮氣環境下進行。將反應溶液傾倒至純水1 L中，回收有機層並利用飽和碳酸氫鈉水500 mL對有機層進行3次清洗，繼而利用純水500 mL進行3次清洗。清洗後，利用無水硫酸鎂對有機層進行乾燥，之後將溶媒減壓餾去，獲得粗體。對所獲得的粗體利用管柱層析儀（填充劑：矽膠，展開溶媒：四氫呋喃）進行分離精製，獲得化合物（1-4）-N（產量：41.7 g，產率：88%）。＜ Fourth Stage ＞ [Chem. 27] In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 50.0 g (88.6 mmol) of the compound (1-4) -NK obtained in the third stage was added, and 500 mL of dichloromethane was added. The solution was cooled to 5 ° C, and 37.0 g (194.9 mmol, 2.2 eq.) Of titanium (IV) tetrachloride was added dropwise thereto. After the solution was kept at 5 ° C and stirred for 1 hour, 30.9 g (265.8 mmol, 3.0 eq.) Of triethylsilane was added dropwise thereto. The solution was kept at 5 ° C and stirred for 4 hours. This series of reactions is performed under a nitrogen atmosphere. The reaction solution was poured into 1 L of pure water, the organic layer was recovered, and the organic layer was washed three times with 500 mL of saturated sodium bicarbonate water, and then washed three times with 500 mL of pure water. After washing, the organic layer was dried with anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. The obtained bold was separated and purified by a column chromatography (filler: silica gel, developing solvent: tetrahydrofuran) to obtain a compound (1-4) -N (yield: 41.7 g, yield: 88%).

＜第5階段＞ 於SUS316製的3L 高壓釜反應管中加入第4階段中獲得的化合物（1-4）-N 40.0 g（74.5 mmol）、5%Pd/C粉末（E類型）4.0 g，並添加四氫呋喃800 mL。將該溶液於氫氣環境下（氫氣壓力：0.6 MPa）、60℃下攪拌18小時，放置冷卻後，利用過濾除掉Pd/C粉末後，將溶媒減壓餾去，獲得化合物（1-4）的粗體。對所獲得的粗體利用管柱層析儀（填充劑：矽膠，展開溶媒：四氫呋喃）進行分離精製，繼而，自乙醇：甲苯=2：1（容積比）的混合溶媒中進行再結晶，於80℃下對所獲得的結晶進行12小時真空乾燥，獲得化合物（1-4）（產量：32.0 g，產率：90%）。 所獲得的化合物（1-4）的熔點為113.3℃～114.7℃。熔點是使用梅特勒-托利多（Mettler Toledo）公司製造的自動熔點測定系統MP-70進行測定。<Fifth stage> A 3L autoclave made of SUS316 was charged with the compound (1-4) -N 40.0 g (74.5 mmol) obtained in the fourth stage, 4.0 g of 5% Pd / C powder (type E), And 800 mL of tetrahydrofuran was added. The solution was stirred under a hydrogen environment (hydrogen pressure: 0.6 MPa) at 60 ° C for 18 hours. After being left to cool, the Pd / C powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain compound (1-4). Bold. The obtained bold was separated and purified by a column chromatography (filler: silica gel, developing solvent: tetrahydrofuran), and then recrystallized from a mixed solvent of ethanol: toluene = 2: 1 (volume ratio), and The obtained crystal was vacuum-dried at 80 ° C for 12 hours to obtain a compound (1-4) (yield: 32.0 g, yield: 90%). The melting point of the obtained compound (1-4) is 113.3 ° C to 114.7 ° C. Melting points were measured using an automatic melting point measurement system MP-70 manufactured by Mettler Toledo.

[合成例1]清漆的合成 於安裝有攪拌葉片、氮氣導入管的100 mL三口燒瓶中加入式（1-1）所表示的化合物4.001 g，並添加54.0 g的NMP。對該溶液進行冰浴冷卻而將液溫設為5℃後，添加式（AN-1）所表示的化合物0.390 g、式（AN-4）所表示的化合物0.965 g、式（AN-6）所表示的化合物0.644 g、及NMP 20.0 g，並於室溫下攪拌12小時。於其中添加BC 20.0 g，並於70℃下對該溶液進行加熱攪拌直至溶質的聚合物的重量平均分子量成為所需的重量平均分子量為止，獲得固體成分6 wt%的清漆1。該清漆1中所含的聚合物的重量平均分子量（Mw）為60,000。[Synthesis Example 1] Synthesis of varnish A 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube was charged with 4.001 g of the compound represented by formula (1-1), and 54.0 g of NMP was added. This solution was cooled in an ice bath to set the liquid temperature to 5 ° C, then 0.390 g of a compound represented by Formula (AN-1), 0.965 g of a compound represented by Formula (AN-4), and Formula (AN-6) were added. 0.644 g of the indicated compound and 20.0 g of NMP were stirred at room temperature for 12 hours. 20.0 g of BC was added thereto, and the solution was heated and stirred at 70 ° C. until the weight average molecular weight of the solute polymer became the desired weight average molecular weight, and a varnish 1 having a solid content of 6 wt% was obtained. The weight average molecular weight (Mw) of the polymer contained in this varnish 1 was 60,000.

[合成例2～合成例55] 除了對四羧酸二酐及二胺進行變更以外，依據合成例1，製備聚合物固體成分濃度為6重量%的清漆2～清漆55。將所獲得的清漆的組成、重量平均分子量（Mw）示於表1～表5中。合成例1中亦再次揭示。[]內表示四羧酸化合物群組、二胺化合物群組中的各自的莫耳比。[Synthesis Example 2 to Synthesis Example 55] A varnish 2 to varnish 55 having a polymer solid content concentration of 6% by weight was prepared according to Synthesis Example 1 except that the tetracarboxylic dianhydride and diamine were changed. The composition and weight average molecular weight (Mw) of the obtained varnish are shown in Tables 1 to 5. Synthesis Example 1 is also revealed again. [] Indicates the molar ratios of the tetracarboxylic acid compound group and the diamine compound group.

[表1] 表1 [表 1] Table 1

[表2] 表2 [表 2] Table 2

[表3] 表3 [表4] 表4 [表5] 表5 [表 3] Table 3 [表 4] Table 4 [表 5] Table 5

[實施例1]液晶配向劑的製備、DC殘像及預傾角測定用液晶單元的製作、DC殘像測定、及預傾角測定 於安裝有攪拌葉片、氮氣導入管的50 mL茄形燒瓶中秤取3.0 g的合成例1中合成的清漆1及7.0 g的合成例27中合成的清漆27，於其中添加NMP 4.0 g、GBL 3.0 g及BC 3.0 g，並於室溫下攪拌1小時而獲得樹脂成分濃度3重量%的液晶配向劑1。利用旋轉器法將該液晶配向劑1塗佈於帶FFS電極的玻璃基板及帶管柱間隔物的玻璃基板上（2,000 rpm，15秒）。塗膜後以80℃預煅燒約3分鐘，之後以230℃進行30分鐘煅燒處理，形成膜厚約為100 nm的液晶配向膜。使用飯沼儀錶（iinuma-gauge）製作所股份有限公司製造的摩擦處理裝置，以摩擦布（毛長2.8 mm：棉）的毛壓入量為0.40 mm、平台移動速度為20 mm/sec、輥旋轉速度為1000 rpm的條件對所獲得的液晶配向膜進行摩擦處理。對所獲得的基板利用超純水清洗表面後於烘箱中以120℃乾燥30分鐘。繼而，對於該些形成有液晶配向膜的2片基板，使形成有液晶配向膜的面相向且於相向的液晶配向膜之間設置用於注入液晶組成物的空隙而進行貼合。此時，以各自的液晶配向膜的摩擦方向平行的方式進行。對該些單元真空注入正型液晶組成物A並利用光硬化劑將注入口密封，從而製作單元厚4 μm的液晶單元（液晶顯示元件）。 ＜正型液晶組成物A＞[Example 1] Preparation of liquid crystal alignment agent, production of liquid crystal cell for DC residual image and pretilt angle measurement, DC residual image measurement, and pretilt angle measurement were performed in a 50 mL eggplant-shaped flask equipped with a stirring blade and a nitrogen introduction tube. Take 3.0 g of the varnish 1 synthesized in Synthesis Example 1 and 7.0 g of the varnish 27 synthesized in Synthesis Example 27, add NMP 4.0 g, GBL 3.0 g, and BC 3.0 g, and stir at room temperature for 1 hour to obtain Liquid crystal alignment agent 1 having a resin component concentration of 3% by weight. This liquid crystal alignment agent 1 was coated on a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After coating the film, it was pre-calcined at 80 ° C for about 3 minutes, and then calcined at 230 ° C for 30 minutes to form a liquid crystal alignment film with a film thickness of about 100 nm. A friction treatment device manufactured by Iinuma-gauge Manufacturing Co., Ltd. was used, with a friction cloth (hair length 2.8 mm: cotton) of 0.40 mm, a platform movement speed of 20 mm / sec, and a roller rotation speed. The obtained liquid crystal alignment film was subjected to a rubbing treatment at a condition of 1000 rpm. The surface of the obtained substrate was washed with ultrapure water, and then dried in an oven at 120 ° C. for 30 minutes. Next, for the two substrates on which the liquid crystal alignment film is formed, the surfaces on which the liquid crystal alignment film is formed face each other, and a gap for injecting a liquid crystal composition is provided between the opposing liquid crystal alignment films to be bonded. At this time, the rubbing directions of the respective liquid crystal alignment films were performed in parallel. The positive type liquid crystal composition A was vacuum-injected into these cells, and the injection port was sealed with a light hardener, thereby producing a liquid crystal cell (liquid crystal display element) having a cell thickness of 4 μm. ＜ Positive liquid crystal composition A ＞

[化28]物性值：NI 100.1℃；Δε 5.1；Δn 0.093；η 25.6 mPa･s.[Chemical 28] Physical properties: NI 100.1 ℃; Δε 5.1; Δn 0.093; η 25.6 mPa ･ s.

對液晶單元的DC殘像進行測定，結果為「◎」。另外，對預傾角進行測定，結果值為0.7°。進而，該液晶單元的電壓保持率於5 V-30 Hz下為99.8%。將該單元於經點燈的背光試驗機（富士軟片（股）製造，FujiCOLOR LED Viewer Pro HR-2；亮度2,700 cd/m2 ）上載置500小時，進行可靠性試驗。可靠性試驗後的測定用單元的電壓保持率為99.7%。The DC afterimage of the liquid crystal cell was measured, and the result was "◎". The pretilt angle was measured and found to be 0.7 °. Furthermore, the voltage retention of this liquid crystal cell was 99.8% at 5 V-30 Hz. This unit was placed on an illuminated backlight tester (manufactured by Fujifilm, FujiCOLOR LED Viewer Pro HR-2; brightness 2,700 cd / m 2 ) for 500 hours to perform a reliability test. The voltage retention of the measurement cell after the reliability test was 99.7%.

[實施例2～實施例23及比較例1～比較例3] 除了對使用的清漆進行變更以外，依據實施例1製成液晶單元，測定DC殘像、預傾角及電壓保持率。將所使用的清漆及測定結果與實施例1一併示於表6中。此處，清漆P為使聚合物（P）成分溶解於溶劑中的狀態的清漆組成物。清漆Q為使聚合物（Q）成分溶解於溶劑中的狀態的清漆組成物。[Example 2 to Example 23 and Comparative Example 1 to Comparative Example 3] A liquid crystal cell was prepared according to Example 1 except that the varnish used was changed, and the DC afterimage, pretilt angle, and voltage holding ratio were measured. The varnish used and the measurement results are shown in Table 6 together with Example 1. Here, the varnish P is a varnish composition in a state where the polymer (P) component is dissolved in a solvent. The varnish Q is a varnish composition in which a polymer (Q) component is dissolved in a solvent.

[表6] 表6 [表 6] Table 6

於實施例1～實施例23的全部中，DC殘像為「○」及「◎」。另外，預傾角為1.2°以下，電壓保持率為99.5%以上。比較例1中，DC殘像為「◎」，但預傾角高達2.3°。比較例2中，預傾角為1.5°以下而良好，但DC殘像為「×」。比較例3中，DC殘像為「◎」，但預傾角高達2.2°。In all of Examples 1 to 23, the DC afterimages were "○" and "◎". In addition, the pretilt angle is 1.2 ° or less, and the voltage holding ratio is 99.5% or more. In Comparative Example 1, the DC afterimage was "◎", but the pretilt angle was as high as 2.3 °. In Comparative Example 2, the pretilt angle was 1.5 ° or less, which was good, but the DC afterimage was “×”. In Comparative Example 3, the DC afterimage was "◎", but the pretilt angle was as high as 2.2 °.

[實施例24] 將「3.0 g的合成例1中合成的清漆1及7.0 g的合成例27中合成的清漆27」變更為「10.0 g的合成例3中合成的清漆3」，除此以外，依據實施例1而獲得液晶配向劑27。使用所獲得的液晶配向劑27，並依據實施例1中記載的方法製作液晶單元，測定DC殘像、預傾角及電壓保持率。液晶單元的DC殘像為「○」，預傾角為0.6°。初始電壓保持率為99.8%，可靠性試驗後的測定用單元的電壓保持率為99.7%。[Example 24] Other than "3.0 g of varnish 1 synthesized in Synthesis Example 1 and 7.0 g of varnish 27 synthesized in Synthesis Example 27" was changed to "10.0 g of Varnish 3 synthesized in Synthesis Example 3" According to Example 1, a liquid crystal alignment agent 27 was obtained. Using the obtained liquid crystal alignment agent 27, a liquid crystal cell was produced according to the method described in Example 1, and the DC afterimage, pretilt angle, and voltage retention were measured. The DC afterimage of the liquid crystal cell was "○" and the pretilt angle was 0.6 °. The initial voltage retention was 99.8%, and the voltage retention of the measurement cell after the reliability test was 99.7%.

[實施例25～實施例45、比較例4～比較例6及參考例1～參考例2] 除了對使用的清漆進行變更以外，依據實施例24製成液晶單元，測定DC殘像、預傾角及電壓保持率。將所使用的清漆及測定結果與實施例24一併示於表7中。[Example 25 to Example 45, Comparative Example 4 to Comparative Example 6, and Reference Example 1 to Reference Example 2] Except changing the varnish used, a liquid crystal cell was prepared according to Example 24, and DC afterimage and pretilt angle were measured. And voltage retention. The varnish used and the measurement results are shown in Table 7 together with Example 24.

[表7] 表7 [表 7] Table 7

於實施例24～實施例45的全部中，DC殘像為「○」或「◎」。另外，預傾角為1.5°以下，電壓保持率為99.5%以上。比較例4中，預傾角為1.5°以下而良好，但DC殘像為「×」。比較例5中，DC殘像為「◎」，但預傾角高達2.1°，無法顯現出低預傾角。比較例6中，DC殘像為「◎」，但預傾角高達2.0°，無法顯現出低預傾角。參考例1中，DC殘像為「×」，但預傾角為0.3°，驚人地低。參考例2中，亦是DC殘像為「×」，但預傾角為0.2°，驚人地低。得知於液晶配向劑包含一種聚合物的實施形態中，作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物中的所述二胺僅包含式（1-4）的液晶配向劑發揮可驚人地降低預傾角的效果。In all of Examples 24 to 45, the DC afterimage was "○" or "◎". The pretilt angle is 1.5 ° or less, and the voltage holding ratio is 99.5% or more. In Comparative Example 4, the pretilt angle was 1.5 ° or less, which was good, but the DC afterimage was “×”. In Comparative Example 5, the DC afterimage was "◎", but the pretilt angle was as high as 2.1 °, and a low pretilt angle was not exhibited. In Comparative Example 6, the DC afterimage was "◎", but the pretilt angle was as high as 2.0 °, and a low pretilt angle could not be exhibited. In Reference Example 1, the DC afterimage was “×”, but the pretilt angle was 0.3 °, which was surprisingly low. In Reference Example 2, the DC afterimage was also “×”, but the pretilt angle was 0.2 °, which was surprisingly low. In the embodiment in which the liquid crystal alignment agent contains one polymer, the diamine in the polymer, which is a reaction product derived from a raw material containing tetracarboxylic dianhydride and diamine, contains only formula (1-4). The liquid crystal alignment agent exerts an effect of surprisingly reducing the pretilt angle.

[實施例46] 相對於實施例1的「NMP 4.0 g、GBL 3.0 g及BC 3.0g」，進而添加添加劑（Ad1）6 mg，除此以外，依據實施例1，獲得樹脂成分濃度3重量%、添加劑濃度於樹脂成分每100重量份中為1重量份的液晶配向劑54。使用所獲得的液晶配向劑54，並依據實施例1中記載的方法製作液晶單元，測定DC殘像、預傾角及電壓保持率。液晶單元的DC殘像為「◎」，預傾角為0.9°。初始電壓保持率為99.8%，可靠性試驗後的測定用單元的電壓保持率為99.6%。[Example 46] To the "NMP 4.0 g, GBL 3.0 g, and BC 3.0 g" of Example 1, and further adding 6 mg of an additive (Ad1), in accordance with Example 1, a resin component concentration of 3% by weight was obtained. The liquid crystal alignment agent 54 having an additive concentration of 1 part by weight per 100 parts by weight of the resin component. Using the obtained liquid crystal alignment agent 54, a liquid crystal cell was produced according to the method described in Example 1, and the DC afterimage, the pretilt angle, and the voltage holding ratio were measured. The DC afterimage of the liquid crystal cell was "◎" and the pretilt angle was 0.9 °. The initial voltage retention was 99.8%, and the voltage retention of the measurement cell after the reliability test was 99.6%.

[實施例47～實施例60及比較例7～比較例9] 除了對使用的清漆與添加劑進行變更以外，依據實施例46製作液晶單元，測定DC殘像、預傾角及電壓保持率。將所使用的清漆、添加劑及測定結果與實施例46一併示於表8中。[Example 47 to Example 60 and Comparative Example 7 to Comparative Example 9] A liquid crystal cell was produced in accordance with Example 46 except that the varnish and additives used were changed, and the DC afterimage, pretilt angle, and voltage holding ratio were measured. Table 8 shows the varnish, additives, and measurement results used together with Example 46.

[表8] 表8 [表 8] Table 8

於實施例46～實施例60的全部中，DC殘像為「◎」。另外，預傾角為1.5°以下，電壓保持率為99.5%以上。比較例7中，DC殘像為「◎」，但預傾角高達2.4°。比較例8中，預傾角為1.5°以下而良好，但DC殘像為「×」。比較例9中，DC殘像為「◎」，但預傾角高達2.3°。In all of Examples 46 to 60, the DC afterimage was "◎". The pretilt angle is 1.5 ° or less, and the voltage holding ratio is 99.5% or more. In Comparative Example 7, the DC afterimage was "「 ", but the pretilt angle was as high as 2.4 °. In Comparative Example 8, the pretilt angle was 1.5 ° or less, which was good, but the DC afterimage was “×”. In Comparative Example 9, the DC afterimage was "◎", but the pretilt angle was as high as 2.3 °.

[實施例61] 相對於實施例24中的「NMP 4.0 g、GBL 3.0 g及BC 3.0g」，進而添加添加劑（Ad1）6 mg，除此以外，依據實施例1，獲得樹脂成分濃度3重量%、添加劑濃度於樹脂成分每100重量份中為1重量份的液晶配向劑72。使用所獲得的液晶配向劑72，並依據實施例1中記載的方法製作液晶單元，測定DC殘像、預傾角及電壓保持率。液晶單元的DC殘像為「○」，預傾角為0.8°。初始電壓保持率為99.7%，可靠性試驗後的測定用單元的電壓保持率為99.6%。[Example 61] In addition to "NMP 4.0 g, GBL 3.0 g, and BC 3.0 g" in Example 24, 6 mg of an additive (Ad1) was further added. In addition, according to Example 1, a resin component concentration of 3 weight was obtained. %, The liquid crystal alignment agent 72 having an additive concentration of 1 part by weight per 100 parts by weight of the resin component. Using the obtained liquid crystal alignment agent 72, a liquid crystal cell was produced according to the method described in Example 1, and the DC afterimage, pretilt angle, and voltage retention were measured. The DC afterimage of the liquid crystal cell was "○", and the pretilt angle was 0.8 °. The initial voltage retention was 99.7%, and the voltage retention of the measurement unit after the reliability test was 99.6%.

[實施例62～實施例82、比較例10～比較例12及參考例3～參考例4] 除了對使用的清漆與添加劑進行變更以外，依據實施例61製作液晶單元，測定DC殘像、預傾角及電壓保持率。將所使用的清漆、添加劑及測定結果與實施例61一併示於表9中。[Examples 62 to 82, Comparative Example 10 to Comparative Example 12, and Reference Example 3 to Reference Example 4] Except changing the varnish and additives used, a liquid crystal cell was prepared according to Example 61, and DC afterimages and preimages were measured. Inclination and voltage retention. Table 9 shows the varnish, additives, and measurement results used together with Example 61.

[表9] 表9 [表 9] Table 9

於實施例61～實施例82的全部中，DC殘像為「○」或「◎」。另外，預傾角為1.5°以下，電壓保持率為99.5%以上。比較例10中，預傾角為1.5°以下而良好，但DC殘像為「×」。比較例11中，DC殘像為「◎」，但預傾角高達2.2°，無法顯現出低預傾角。比較例12中，DC殘像為「◎」，但預傾角高達2.2°，無法顯現出低預傾角。參考例3中，DC殘像為「×」，但預傾角為0.4°，驚人地低。參考例4中，亦是DC殘像為「×」，但預傾角為0.3°，驚人地低。得知於液晶配向劑包含一種聚合物的實施形態中，作為源自包含四羧酸二酐及二胺的原料的反應產物的、聚合物中的所述二胺僅包含式（1-4）的液晶配向劑即便加入添加劑亦發揮可有意地減低預傾角的效果。 [產業上之可利用性]In all of Examples 61 to 82, the DC afterimage was "○" or "◎". The pretilt angle is 1.5 ° or less, and the voltage holding ratio is 99.5% or more. In Comparative Example 10, the pretilt angle was 1.5 ° or less, which was good, but the DC afterimage was “×”. In Comparative Example 11, the DC afterimage was "「 ", but the pretilt angle was as high as 2.2 °, and a low pretilt angle was not exhibited. In Comparative Example 12, the DC afterimage was "◎", but the pretilt angle was as high as 2.2 °, and a low pretilt angle could not be exhibited. In Reference Example 3, the DC afterimage was “×”, but the pretilt angle was 0.4 °, which was surprisingly low. In Reference Example 4, the DC afterimage was also “×”, but the pretilt angle was 0.3 °, which was surprisingly low. In the embodiment in which the liquid crystal alignment agent contains one polymer, the diamine in the polymer, which is a reaction product derived from a raw material containing tetracarboxylic dianhydride and diamine, contains only formula (1-4). The liquid crystal alignment agent exhibits the effect of intentionally reducing the pretilt angle even if an additive is added. [Industrial availability]

若使用本發明的液晶配向劑，可形成可將液晶的預傾角抑制得低、且供給殘留DC的積存小、電荷的緩和快的液晶顯示元件的液晶配向膜。本發明的液晶配向劑可適宜應用於橫電場型液晶顯示元件中。By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film can be formed for a liquid crystal display element that can suppress the pretilt angle of liquid crystals to be low, has a small accumulation of residual DC supply, and has a rapid charge relaxation. The liquid crystal alignment agent of the present invention can be suitably used in a transverse electric field type liquid crystal display element.

Claims (23)

一種液晶配向劑，其含有聚合物的至少一種，所述聚合物為源自包含四羧酸二酐及二胺的原料的反應產物，並且 用於合成所述聚合物的原料包含選自下述式（1）～式（3）所表示的化合物的群組中的至少一種，且包含 選自下述式（A）～式（C）所表示的化合物的群組、及下述式（D）所表示的化合物中的至少一種， 此處，所述聚合物為選自由聚醯胺酸、聚醯亞胺、部分聚醯亞胺、聚醯胺酸酯、聚醯胺酸-聚醯胺共聚物、及聚醯胺醯亞胺所組成的群組中的至少一種； 式（1）中，m為3～8的整數； 式（3）中，n為1～3的整數； 式（1）～式（3）中，鍵結位置並未固定於構成環的任一碳原子的基表示所述環中的鍵結位置為任意；而且 式（A）中，A1 為氮、或含有氮的雜環，W1 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z1 為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r為0以上的任意整數，a獨立地為0或1； 式（B）中，A2 獨立地為氮、或含有氮的雜環，W2 及W3 獨立地為碳數1～5的伸烷基，任意的-CH2 -可經取代為-CO-、1,4-伸苯基、或1,3-伸苯基，Z2 獨立地為氫、藉由熱而取代為氫原子的保護基、或碳數1～5的烷基，r獨立地為0以上的任意整數，a獨立地為0或1； 式（C）中，Z3 為含有二級或三級胺基的至少一種的一價有機基； 式（D）中，T為包含1個～2個碳-碳雙鍵或1個～2個碳-碳三鍵的二價的含有不飽和鍵的基； 式（1）～式（3）及式（A）～式（C）中，鍵結位置並未固定於構成環的任一碳原子的基表示所述環中的鍵結位置為任意，其中，於所述式（1）中m為8時，所述二胺亦可不包含所述式（A）～式（C）所表示的化合物的任一種，所述四羧酸二酐可並非所述式（D）所表示的化合物。A liquid crystal alignment agent containing at least one polymer that is a reaction product derived from a raw material including a tetracarboxylic dianhydride and a diamine, and a raw material for synthesizing the polymer includes a member selected from the following: At least one selected from the group of compounds represented by the formulas (1) to (3), and includes a group selected from the group of compounds represented by the following formulas (A) to (C), and the following formula (D) At least one of the compounds represented by). Here, the polymer is selected from the group consisting of polyamic acid, polyimide, part of polyimide, polyamic acid ester, polyamic acid-polyamidamine. At least one of the group consisting of a copolymer and polyimide / imine; In formula (1), m is an integer of 3 to 8; in formula (3), n is an integer of 1 to 3; in formulas (1) to (3), the bonding position is not fixed to any of the members constituting the ring. A one-carbon atom group indicates that the bonding position in the ring is arbitrary; and in formula (A), A 1 is nitrogen or a heterocyclic ring containing nitrogen, and W 1 is independently an alkylene group having 1 to 5 carbon atoms. , Any -CH 2 -may be substituted with -CO-, 1,4-phenylene, or 1,3-phenylene, Z 1 is hydrogen, a protecting group substituted with a hydrogen atom by heat, or An alkyl group having 1 to 5 carbon atoms, r is any integer greater than or equal to 0, and a is independently 0 or 1; In formula (B), A 2 is independently nitrogen or a heterocyclic ring containing nitrogen, W 2 and W 3 Independently is an alkylene group having 1 to 5 carbon atoms, and any -CH 2 -may be substituted with -CO-, 1,4-phenylene, or 1,3-phenylene, and Z 2 is independently hydrogen , A protective group substituted with a hydrogen atom by heat, or an alkyl group having 1 to 5 carbon atoms, r is independently any integer of 0 or more, and a is independently 0 or 1; in the formula (C), Z 3 is A monovalent organic group containing at least one of a secondary or tertiary amine group; in formula (D), T is one or two carbon-carbon double bonds or one or two -A divalent unsaturated bond-containing group having a carbon triple bond; in the formulae (1) to (3) and (A) to (C), the bonding position is not fixed to any carbon atom constituting the ring The base represents that the bonding position in the ring is arbitrary, and when m is 8 in the formula (1), the diamine may not include those represented by the formulas (A) to (C). In any one of the compounds, the tetracarboxylic dianhydride may not be a compound represented by the formula (D). 如申請專利範圍第1項所述的液晶配向劑，其含有一種所述聚合物。The liquid crystal alignment agent according to item 1 of the patent application scope, which contains one of the polymers. 如申請專利範圍第2項所述的液晶配向劑，其中所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為70莫耳%以上，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為1莫耳%～30莫耳%。The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein the proportion of the compound represented by the formula (1) to the formula (3) is 70 mol% or more with respect to the total amount of the diamine used. The proportion of the compound represented by the formula (A) to the formula (C) is 1 mol% to 30 mol% with respect to the total amount of the diamine used. 如申請專利範圍第1項所述的液晶配向劑，其含有至少兩種所述聚合物， 所述至少兩種聚合物包含聚合物（P）及聚合物（Q）； 用於合成所述聚合物（P）的原料包含選自所述式（1）～式（3）所表示的化合物的群組中的至少一種；而且 用於合成所述聚合物（Q）的原料包含選自所述式（A）～式（C）所表示的化合物的群組、及所述式（D）所表示的化合物中的至少一種。The liquid crystal alignment agent according to item 1 of the patent application scope, which contains at least two kinds of the polymers, the at least two kinds of polymers include a polymer (P) and a polymer (Q); and is used for synthesizing the polymer The raw material of the substance (P) contains at least one selected from the group of the compounds represented by the formulae (1) to (3); and the raw material for synthesizing the polymer (Q) contains the material selected from the group consisting of A group of compounds represented by formulas (A) to (C) and at least one of the compounds represented by formula (D). 如申請專利範圍第1項至第4項中任一項所述的液晶配向劑，其中所述式（1）～式（3）所表示的化合物為選自下述式（1-1）～式（1-4）、式（2-1）、式（2-2）、及式（3-1）～式（3-6）所表示的化合物的群組中的至少一種； 所述式（A）～式（C）所表示的化合物為選自下述式（A-1）～式（A-20）、式（B-1）～式（B-8）、及式（C-1）～式（C-3）所表示的化合物的群組中的至少一種； 所述式（D）所表示的化合物為選自下述式（D-1）～式（D-4）所表示的化合物的群組中的至少一種； 式（A-1）～式（A-11）中，鍵結位置並未固定於構成環的任一碳原子的基表示所述環中的鍵結位置為任意； 式（B-3）中，k為1～5的整數；而且， 式（B-4）中，n為1～3的整數。The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the compound represented by the formula (1) to formula (3) is selected from the following formulas (1-1) to At least one of the group of compounds represented by formula (1-4), formula (2-1), formula (2-2), and formula (3-1) to formula (3-6); the formula The compounds represented by (A) to formula (C) are selected from the following formulae (A-1) to (A-20), (B-1) to (B-8), and (C- 1) to at least one group of compounds represented by the formula (C-3); the compound represented by the formula (D) is selected from the group consisting of the following formulae (D-1) to (D-4) At least one of the group of compounds represented; In the formulae (A-1) to (A-11), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; in the formula (B-3) K is an integer of 1 to 5; n is an integer of 1 to 3 in formula (B-4). 如申請專利範圍第5項所述的液晶配向劑，其中所述式（1）～式（3）所表示的化合物為選自所述式（1-1）、式（1-4）、式（2-1）、及式（3-1）所表示的化合物的群組中的至少一種； 所述式（A）～式（C）所表示的化合物為選自所述式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（A-19）、式（A-20）、式（B-3）、式（B-5）、式（C-2）、及式（C-3）所表示的化合物的群組中的至少一種； 所述式（D）所表示的化合物為選自所述式（D-2）、及式（D-3）所表示的化合物的群組中的至少一種。The liquid crystal alignment agent according to item 5 of the scope of patent application, wherein the compound represented by the formula (1) to the formula (3) is selected from the formula (1-1), the formula (1-4), and the formula (2-1) and at least one of the group of compounds represented by formula (3-1); the compound represented by formula (A) to formula (C) is selected from the formula (A-12) ), Formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (A-19), formula (A-20), formula (B-3) At least one of the group of compounds represented by Formula (B-5), Formula (C-2), and Formula (C-3); the compound represented by Formula (D) is selected from the formula (D-2) and at least one of the group of compounds represented by formula (D-3). 如申請專利範圍第1項至第6項中任一項所述的液晶配向劑，其進而包含選自下述式（E）所表示的化合物中的至少一種作為用於合成所述聚合物的原料；所述式（E）中，W4 為碳數1～6的伸烷基、1,3-伸苯基、或1,4-伸苯基；而且， W5 獨立地為單鍵、-NHCO-、或-CONH-。The liquid crystal alignment agent according to any one of claims 1 to 6 of the patent application scope, which further contains at least one selected from the compounds represented by the following formula (E) as a compound for synthesizing the polymer. raw material; In the formula (E), W 4 is an alkylene group having 1 to 6 carbon atoms, 1,3-phenylene group, or 1,4-phenylene group; and W 5 is independently a single bond or -NHCO. -, Or -CONH-. 如申請專利範圍第7項所述的液晶配向劑，其中所述式（E）所表示的化合物為選自下述式（E-1）～式（E-8）所表示的化合物中的至少一種；式（E-5）及式（E-8）中，p分別獨立地為1～6的整數。The liquid crystal alignment agent according to item 7 of the scope of patent application, wherein the compound represented by the formula (E) is at least one selected from the compounds represented by the following formulae (E-1) to (E-8) One kind In Formula (E-5) and Formula (E-8), p is an integer of 1-6 each independently. 如申請專利範圍第7項或第8項所述的液晶配向劑，其包含選自所述式（E）所表示的化合物中的至少一種作為所述聚合物（Q）的合成中使用的原料。The liquid crystal alignment agent according to item 7 or item 8 of the patent application scope, which contains at least one selected from the compounds represented by the formula (E) as a raw material used in the synthesis of the polymer (Q). . 如申請專利範圍第1項至第9項中任一項所述的液晶配向劑，其中所述式（1）～式（3）所表示的化合物為選自所述式（1-1）～式（1-4）、式（2-1）、式（2-2）、式（3-1）所表示的化合物的群組中的至少一種； 所述式（A）～式（C）所表示的化合物為選自所述式（A-12）、式（A-14）、式（A-15）、式（A-16）、式（A-17）、式（B-3）、式（C-2）、及式（C-3）所表示的化合物的群組中的至少一種； 所述式（D）所表示的化合物為選自所述式（D-2）、及式（D-3）所表示的化合物的群組中的至少一種； 所述式（E）所表示的化合物為選自所述式（E-5）～式（E-7）所表示的化合物的群組中的至少一種。The liquid crystal alignment agent according to any one of claims 1 to 9, in which the compound represented by the formula (1) to the formula (3) is selected from the formulas (1-1) to At least one of the group of compounds represented by formula (1-4), formula (2-1), formula (2-2), and formula (3-1); the formula (A) to formula (C) The compound represented by the formula is selected from the formula (A-12), formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (B-3) At least one of the group of compounds represented by Formula (C-2) and Formula (C-3); the compound represented by Formula (D) is selected from the formula (D-2), and At least one of the group of compounds represented by the formula (D-3); the compound represented by the formula (E) is a compound selected from the compounds represented by the formulas (E-5) to (E-7) At least one of the group. 如申請專利範圍第10項所述的液晶配向劑，其中所述式（1）～式（3）所表示的化合物為選自所述式（1-1）及式（1-4）中的至少一種； 所述式（A）～式（C）所表示的化合物為選自所述式（A-15）及式（B-3）中的至少一種； 所述式（D）所表示的化合物為所述式（D-2）所表示的化合物； 所述式（E）所表示的化合物為所述式（E-5）所表示的化合物。The liquid crystal alignment agent according to item 10 of the scope of patent application, wherein the compound represented by the formula (1) to the formula (3) is selected from the group consisting of the formulas (1-1) and (1-4) At least one; the compound represented by the formula (A) to the formula (C) is at least one selected from the formula (A-15) and the formula (B-3); The compound is a compound represented by the formula (D-2); the compound represented by the formula (E) is a compound represented by the formula (E-5). 如申請專利範圍第4項至第11項中任一項所述的液晶配向劑，其中於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為70莫耳%以上； 於所述聚合物（Q）中，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為10莫耳%～50莫耳%。The liquid crystal alignment agent according to any one of claims 4 to 11 in the scope of patent application, wherein in the polymer (P), the proportion of the compound represented by the formula (1) to the formula (3) It is 70 mol% or more with respect to the total amount of the diamine used; In the polymer (Q), the proportion of the compound represented by the formula (A) to the formula (C) with respect to the used diamine The total amount of amine is 10 mol% to 50 mol%. 如申請專利範圍第4項至第11項中任一項所述的液晶配向劑，其中於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為70莫耳%以上； 於所述聚合物（Q）中，所述式（D）所表示的化合物的比例相對於所使用的四羧酸二酐總量而為20莫耳%～50莫耳%。The liquid crystal alignment agent according to any one of claims 4 to 11 in the scope of patent application, wherein in the polymer (P), the proportion of the compound represented by the formula (1) to the formula (3) 70 mol% or more with respect to the total amount of the diamine used; in the polymer (Q), the proportion of the compound represented by the formula (D) with respect to the total tetracarboxylic dianhydride used The amount is 20 mol% to 50 mol%. 如申請專利範圍第12項所述的液晶配向劑，其中於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為90莫耳%以上； 於所述聚合物（Q）中，所述式（A）～式（C）所表示的化合物的比例相對於所使用的二胺總量而為30莫耳%～50莫耳%。The liquid crystal alignment agent according to item 12 of the scope of patent application, wherein in the polymer (P), the proportion of the compound represented by the formula (1) to the formula (3) with respect to the total diamine used In the polymer (Q), the proportion of the compound represented by the formula (A) to the formula (C) is 30 mol relative to the total amount of the diamine used. % To 50 mole%. 如申請專利範圍第13項所述的液晶配向劑，其中於所述聚合物（P）中，所述式（1）～式（3）所表示的化合物的比例相對於所使用的二胺總量而為90莫耳%以上。The liquid crystal alignment agent according to item 13 of the scope of patent application, wherein in the polymer (P), the proportion of the compound represented by the formula (1) to the formula (3) with respect to the total diamine used The amount is more than 90 mol%. 如申請專利範圍第7項至第15項中任一項所述的液晶配向劑，其中於所述聚合物（Q）中，所述式（E）所表示的化合物的比例相對於所使用的二胺總量而為50莫耳%～70莫耳%。The liquid crystal alignment agent according to any one of items 7 to 15 of the scope of patent application, wherein in the polymer (Q), the proportion of the compound represented by the formula (E) with respect to the used compound The total amount of diamine is 50 mol% to 70 mol%. 如申請專利範圍第1項至第16項中任一項所述的液晶配向劑，其進而含有選自包含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、及環氧化合物的化合物群組中的至少一種。The liquid crystal alignment agent according to any one of claims 1 to 16, further comprising a compound selected from the group consisting of an alkenyl substituted nadicarium imine compound, a compound having a radical polymerizable unsaturated double bond, At least one of a compound group of an oxazine compound, an oxazoline compound, and an epoxy compound. 如申請專利範圍第1項至第17項中任一項所述的液晶配向劑，其用於橫電場型液晶顯示元件的製造。The liquid crystal alignment agent according to any one of claims 1 to 17 of the scope of application for a patent, which is used for manufacturing a liquid crystal display element of a transverse electric field type. 一種二胺，其是由所述式（1-4）所表示。A diamine represented by the formula (1-4). 一種液晶配向劑，其含有聚合物的至少一種，所述聚合物為源自包含四羧酸二酐及二胺的原料的反應產物，並且 所述二胺僅包含如申請專利範圍第19項所述的所述式（1-4）所表示的二胺。A liquid crystal alignment agent containing at least one polymer that is a reaction product derived from a raw material containing a tetracarboxylic dianhydride and a diamine, and the diamine contains only The diamine represented by the formula (1-4). 一種液晶配向膜，其是由如申請專利範圍第1項至第20項中任一項所述的液晶配向劑形成。A liquid crystal alignment film is formed by the liquid crystal alignment agent as described in any one of the first to the twenty-first patent application scope. 一種液晶顯示元件，其具有如申請專利範圍第21項所述的液晶配向膜。A liquid crystal display element having the liquid crystal alignment film according to item 21 of the scope of patent application. 一種橫電場型液晶顯示元件，其具有如申請專利範圍第21項所述的液晶配向膜。A transverse electric field type liquid crystal display element includes the liquid crystal alignment film according to item 21 of the patent application scope.
TW107128084A 2017-08-10 2018-08-10 Liquid crystal alignment agent, diamine, liquid crystal alignment film and liquid crystal display element using same TWI788401B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-155628 2017-08-10
JP2017155628 2017-08-10

Publications (2)

Publication Number Publication Date
TW201920365A true TW201920365A (en) 2019-06-01
TWI788401B TWI788401B (en) 2023-01-01

Family

ID=65272303

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107128084A TWI788401B (en) 2017-08-10 2018-08-10 Liquid crystal alignment agent, diamine, liquid crystal alignment film and liquid crystal display element using same

Country Status (5)

Country Link
JP (1) JP7255482B2 (en)
KR (1) KR20200039671A (en)
CN (1) CN110998424B (en)
TW (1) TWI788401B (en)
WO (1) WO2019031604A1 (en)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027454A1 (en) 1996-12-18 1998-06-25 Hitachi, Ltd. Transverse electric field system liquid crystal display device suitable for improving aperture ratio
JP2012155311A (en) * 2011-01-05 2012-08-16 Jnc Corp Liquid crystal aligning agent for forming photo-aligning liquid crystal alignment layer, liquid crystal alignment layer and liquid crystal display element using the same
JP6213281B2 (en) * 2013-03-19 2017-10-18 Jnc株式会社 Photosensitive diamine, liquid crystal aligning agent, and liquid crystal display element
JP6350852B2 (en) * 2013-03-21 2018-07-04 Jnc株式会社 Liquid crystal aligning agent, liquid crystal display element, and tetracarboxylic dianhydride
JP6558245B2 (en) 2013-10-01 2019-08-14 日産化学株式会社 LIQUID CRYSTAL ORIENTING LIQUID CRYSTAL Alignment Agent, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME
KR102278973B1 (en) 2013-11-28 2021-07-16 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent and liquid crystal display element using same
JP6398480B2 (en) * 2014-07-15 2018-10-03 Jnc株式会社 Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JP6421545B2 (en) * 2014-10-21 2018-11-14 Jnc株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element containing polyamic acid or derivative thereof
CN105694912B (en) * 2014-12-11 2019-11-19 捷恩智株式会社 Light orientation aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display element using it
JP6627595B2 (en) * 2015-06-11 2020-01-08 Jnc株式会社 Liquid crystal alignment agent for forming liquid crystal alignment film for photo alignment, liquid crystal alignment film, and liquid crystal display device using the same
JP6520657B2 (en) * 2015-11-16 2019-05-29 Jnc株式会社 Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device

Also Published As

Publication number Publication date
JP7255482B2 (en) 2023-04-11
KR20200039671A (en) 2020-04-16
CN110998424A (en) 2020-04-10
CN110998424B (en) 2023-08-15
JPWO2019031604A1 (en) 2020-09-03
WO2019031604A1 (en) 2019-02-14
TWI788401B (en) 2023-01-01

Similar Documents

Publication Publication Date Title
TWI481587B (en) Diamine
JP5967094B2 (en) Manufacturing method of liquid crystal display element
TWI494292B (en) Diamine, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device
TWI503371B (en) Liquid crystal alignment agent and liquid crystalline polyimide used therein
CN109971494B (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
TW201602694A (en) Liquid crystal aligning agent containing urea compound having alkoxysilyl group
TW201416777A (en) Liquid crystal alignment agent and liquid crystal alignment film for PSA-mode liquid crystal display device, liquid crystal display device and method for manufacturing the same
JP2017138575A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and diamine
JP2020060755A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, tetracarboxylic dianhydride, polyamic acid and derivative thereof
TWI787341B (en) Liquid crystal photo-aligning agents, liquid crystal photo-alignment layers, and liquid crystal displays using the same
TWI788401B (en) Liquid crystal alignment agent, diamine, liquid crystal alignment film and liquid crystal display element using same
WO2014092170A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP2019014837A (en) Tetracarboxylic acid dianhydride, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element prepared therewith
JP2018180227A (en) Liquid crystal aligning agent for photo-alignment to be used for photo-aligning method, and photo-alignment film and liquid crystal display element using the same
JP7102991B2 (en) A liquid crystal alignment film and its manufacturing method, and a liquid crystal display element using the liquid crystal alignment film.
JP7494537B2 (en) Liquid crystal alignment agent for photoalignment, liquid crystal alignment film, and liquid crystal display element
JP7120032B2 (en) Liquid crystal aligning agent for photo-alignment, liquid crystal alignment film, and liquid crystal display element
CN117126676A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element
JP2023033139A (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
JP2023032586A (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device using the same
CN117946697A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element and method for manufacturing liquid crystal alignment film
JP2023131109A (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer, and compound
CN114574222A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element and polymer
TW202340328A (en) Liquid crystal alignment agent, liquid crystal alignment film, manufacturing method thereof and liquid crystal element wherein the liquid crystal alignment agent includes a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid derivative with a diamine
TW201823305A (en) Photo-aligning liquid crystal aligning agents for photo-alignment method, photo-aligning film, liquid crystal display devices, and transverse electric field type liquid crystal display devices using the same using a reaction product containing tetracarboxylic dianhydride and diamine to achieve high adhesion strength with a sealant