TWI826353B - Liquid crystal display element having a liquid crystal panel with a curved surface shape and liquid crystal alignment agent used therefor - Google Patents

Liquid crystal display element having a liquid crystal panel with a curved surface shape and liquid crystal alignment agent used therefor Download PDF

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TWI826353B
TWI826353B TW106126202A TW106126202A TWI826353B TW I826353 B TWI826353 B TW I826353B TW 106126202 A TW106126202 A TW 106126202A TW 106126202 A TW106126202 A TW 106126202A TW I826353 B TWI826353 B TW I826353B
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TW201821483A (en
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大田政太郎
芦澤亮一
杉山暁子
三木徳俊
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日商日產化學工業股份有限公司
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    • 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
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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    • 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
    • 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

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  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

提供即使產生間隔件摩擦等之物理摩擦時亦無亮點的具備具有曲面形狀之液晶面板的液晶顯示裝置。 　　一種曲面液晶顯示元件，其具備液晶配向膜，該液晶配向膜含有聚合物，該聚合物含有下述式[1]之結構；(Y1 為單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-、-COO-或OCO-，Y2 為單鍵或(CH2 )b -(b為1~15之整數)，Y3 為單鍵、-(CH2 )c -(c為1~15之整數)、-O-、-CH2 O-、 -COO-或OCO-；Y4 為選自由苯環、環己烷環及雜環所成之群的環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，或由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基；Y5 為選自由苯環、環己烷環及雜環所成之群的2價環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，Y4 為選自由苯環、環己烷環及雜環所成之群的環狀基時，n為2~4之整數，Y4 為由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基時，n為0~4之整數；又，n為複數個時，複數個Y5 係分別獨立地具有上述定義；Y6 為碳數1~18之烷基、碳數1~18之含氟烷基、碳數1~18之烷氧基或碳數1~18之含氟烷氧基)。Provided is a liquid crystal display device having a liquid crystal panel with a curved surface that has no bright spots even when physical friction such as spacer friction occurs. A curved liquid crystal display element, which is provided with a liquid crystal alignment film, the liquid crystal alignment film contains a polymer, and the polymer contains the structure of the following formula [1]; (Y 1 is a single bond, -(CH 2 ) a -(a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-, Y 2 is a single bond or (CH 2 ) b -(b is an integer from 1 to 15), Y 3 is a single bond, -(CH 2 ) c -(c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-; Y 4 is a cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be replaced by an alkyl group with 1 to 3 carbon atoms, Alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or a fluorine atom substituted), or substituted with an alkoxy group with 12 to 25 carbon atoms with a steroid skeleton. A divalent organic group selected from organic groups; Y 5 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be Alkyl group with 1 to 3 carbon atoms, alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom substitution), Y 4 is When a cyclic group is selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, n is an integer from 2 to 4, and Y 4 is 2 selected from an organic group with a carbon number of 12 to 25 having a steroid skeleton. When n is a valent organic group, n is an integer from 0 to 4; when n is a plurality, the plural Y 5s independently have the above definitions; Y 6 is an alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18 Fluorine-containing alkyl group, alkoxy group having 1 to 18 carbon atoms or fluorine-containing alkoxy group having 1 to 18 carbon atoms).

Description

具備具有曲面形狀之液晶面板的液晶顯示元件及用於其之液晶配向劑Liquid crystal display element having a liquid crystal panel with a curved surface shape and liquid crystal alignment agent used therefor

[0001] 本發明係關於具備具有曲面形狀之液晶面板的液晶顯示元件及用於其之液晶配向劑。[0001] The present invention relates to a liquid crystal display element provided with a liquid crystal panel having a curved surface shape and a liquid crystal alignment agent used therefor.

[0002] 近年來，伴隨著薄型化及低消耗電力化，液晶顯示裝置係使用於智慧型手機、行動電話、電視、導航機器、電子手冊、電子書等之各種電子機器。液晶顯示裝置，具備液晶面板與驅動電路，且係依需要安裝有背光、導光板、外殼等之附帶機器而構成。將通常的液晶顯示裝置使用於電子機器時，該液晶顯示裝置之顯示面，係為與電子機器之殼體大致平行地且平面形狀地配置而構成。 　　[0003] 另一方面，近年來，伴隨於液晶顯示裝置在各種領域中被使用，對於電子機器之顯示部，由顯示面積之增大，或寬視野感、没入感、進而設計上的觀點而言，提出有具備具有沿著電子機器之殼體外面的曲面形狀之液晶面板的液晶顯示裝置而被使用(參照專利文獻1) [先前技術文獻] [專利文獻] 　　[0004] 　　[專利文獻1] 日本特開平10-268245號公報 　　[專利文獻2] 日本特開平10-104633號公報 　　[專利文獻3] 日本特開平8-76128號公報[0002] In recent years, along with thinning and low power consumption, liquid crystal display devices are used in various electronic devices such as smartphones, mobile phones, televisions, navigation devices, electronic manuals, and e-books. A liquid crystal display device is composed of a liquid crystal panel and a drive circuit, and is equipped with accessory equipment such as a backlight, a light guide plate, and a casing as necessary. When a normal liquid crystal display device is used in an electronic device, the display surface of the liquid crystal display device is arranged substantially parallel to the casing of the electronic device in a planar shape. [0003] On the other hand, in recent years, as liquid crystal display devices have been used in various fields, the display portion of electronic equipment has become more and more popular from the perspective of the increase in display area, the feeling of wide viewing angle, the feeling of immersion, and further the design. In other words, a liquid crystal display device having a curved surface shape along the outer surface of the casing of an electronic device has been proposed and used (see Patent Document 1) [Prior Art Document] [Patent Document] [0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 10-268245 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-104633 [Patent Document 3] Japanese Patent Application Laid-Open No. 8-76128

[發明所欲解決之課題] 　　[0005] 製造具備曲面形狀之液晶面板的顯示裝置時，係使液晶面板沿著殼體外面而彎曲。藉此，液晶面板之內部所存在的間隔件係於液晶面板內移動，而摩擦液晶配向膜。以間隔件賦予壓力之液晶配向膜無法調節液晶之配向，將液晶面板例如雖進行黑顯示，但會由間隔件周邊部透光，顯示為亮點而成為問題。 　　[0006] 本發明之目的係有鑑於上述實情而為者，而為提供具備即使產生間隔件所致的摩擦等之物理摩擦時亦可使亮點為最少，但仍具有曲面形狀之液晶面板的液晶顯示裝置，及用於其之液晶配向劑。 [用以解決課題之手段] 　　[0007] 本發明者進行努力研究的結果，完成了本發明。亦即本發明為具有以下要旨者。 　　(1) 一種液晶顯示元件，其具備曲面液晶面板，該曲面液晶面板具有由含有具有下述式[1]表示之結構的聚合物之液晶配向劑所得到的液晶配向膜，Y1 為單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-、-COO-或OCO-，Y2 為單鍵或(CH2 )b -(b為1~15之整數)，Y3 為單鍵、-(CH2 )c -(c為1~15之整數)、-O-、-CH2 O-、 -COO-或OCO-。Y4 為選自由苯環、環己烷環及雜環所成之群的環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，或由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基，Y5 為選自由苯環、環己烷環及雜環所成之群的2價環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，Y4 為選自由苯環、環己烷環及雜環所成之群的環狀基時，n為2~4之整數，Y4 為由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基時，n為0~4之整數。又，n為複數個時，複數個Y5 係分別獨立地具有上述定義。Y6 為碳數1~18之烷基、碳數1~18之含氟烷基、碳數1~18之烷氧基或碳數1~18之含氟烷氧基。 　　(2) 一種液晶配向劑，其係用於具備具有曲面形狀之液晶面板的液晶顯示元件之液晶配向劑，且含有具有上述式[1]表示之結構的聚合物。 [發明之效果] 　　[0008] 依照本發明，可提供具備即使產生間隔件所致的摩擦等之物理摩擦時亦可使亮點為最少，但仍具有曲面形狀之液晶面板的液晶顯示裝置，及用於其之液晶配向劑。[Problems to be Solved by the Invention] [0005] When manufacturing a display device having a curved liquid crystal panel, the liquid crystal panel is curved along the outer surface of the casing. Thereby, the spacer existing inside the liquid crystal panel moves within the liquid crystal panel and rubs the liquid crystal alignment film. A liquid crystal alignment film that uses spacers to apply pressure cannot adjust the alignment of liquid crystals. For example, although the liquid crystal panel performs a black display, light will be transmitted from the periphery of the spacers and display as bright spots, which poses a problem. [0006] The object of the present invention is to provide a liquid crystal panel with a curved surface that can minimize bright spots even when physical friction such as friction caused by spacers occurs in view of the above-mentioned circumstances. Display device, and liquid crystal alignment agent used therefor. [Means for Solving the Problems] [0007] As a result of diligent research, the present inventors completed the present invention. That is, the present invention has the following gist. (1) A liquid crystal display element provided with a curved liquid crystal panel having a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer having a structure represented by the following formula [1], Y 1 is a single bond, -(CH 2 ) a - (a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-, Y 2 is a single bond or (CH 2 ) b -(b is an integer from 1 to 15), Y 3 is a single bond, -(CH 2 ) c -(c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO -. Y 4 is a cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be replaced by an alkyl group with 1 to 3 carbon atoms, or an alkyl group with 1 carbon number). ~3 alkoxy group, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom substituted), or by an organic group with 12 to 25 carbon atoms having a steroid skeleton. The selected divalent organic group, Y 5 , is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be replaced by a carbon number of 1 ~3 alkyl group, C1~3 alkoxy group, C1~3 fluorine-containing alkyl group, C1~3 fluorine-containing alkoxy group or fluorine atom substitution), Y 4 is selected from benzene In the case of a cyclic group consisting of a ring, a cyclohexane ring and a heterocyclic ring, n is an integer from 2 to 4, and Y 4 is a divalent organic group selected from organic groups having a steroid skeleton with a carbon number of 12 to 25. When , n is an integer from 0 to 4. In addition, when n is a plurality of Y 5 s, each of the plurality of Y 5 independently has the above definition. Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. (2) A liquid crystal alignment agent used for a liquid crystal display element having a liquid crystal panel having a curved surface shape, and containing a polymer having a structure represented by the above formula [1]. [Effects of the Invention] [0008] According to the present invention, it is possible to provide a liquid crystal display device having a liquid crystal panel with a curved surface shape that minimizes bright spots even when physical friction such as friction caused by spacers occurs, and uses In its liquid crystal alignment agent.

[0010] 本發明之具備具有曲面形狀之液晶面板的曲面液晶顯示元件，具備由含有聚合物的液晶配向劑所得到之液晶配向膜，該聚合物含有下述式[1]表示之結構(亦稱為特定結構)。 ＜特定結構＞[0011] 式[1]中，Y1 為單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-、-COO-或OCO-。其中尤以單鍵、 -(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-或COO-，由於容易合成側鏈結構故較佳。更佳為單鍵、-(CH2 )a -(a為1~10之整數)、-O-、-CH2 O-或COO-。 　　Y2 為單鍵或(CH2 )b -(b為1~15之整數)。其中尤以單鍵或(CH2 )b -(b為1~10之整數)較佳。 　　Y3 為單鍵、-(CH2 )c -(c為1~15之整數)、-O-、-CH2 O-、-COO-或OCO-。其中尤以單鍵、-(CH2 )c -(c為1~15之整數)、-O-、-CH2 O-、-COO-或OCO-，由於合成容易故較佳。更佳為單鍵、-(CH2 )c -(c為1~10之整數)、-O-、-CH2 O-、-COO-或OCO-。 　　[0012] Y4 為選自由苯環、環己烷環及雜環所成之群的2價環狀基，此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代。進一步地，Y4 為具有類固醇骨架之碳數12~25之2價有機基。Y4 較佳為苯環、環己基環或具有類固醇骨架之碳數12~25之有機基。 　　Y5 為選自由苯環、環己基環及雜環所成之群的2價環狀基，此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代。 　　[0013] Y4 為選自由苯環、環己烷環及雜環所成之群的環狀基時，n為2~4之整數，Y4 為由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基時，n為0~4之整數。又，n為複數個時，複數個Y5 係分別獨立地具有上述定義。 　　Y6 為碳數1~18之烷基、碳數1~18之含氟烷基、碳數1~18之烷氧基或碳數1~18之含氟烷氧基。其中尤以碳數1~18之烷基、碳數1~10之含氟烷基、碳數1~18之烷氧基或碳數1~10之含氟烷氧基較佳。更佳為碳數1~12之烷基或碳數1~12之烷氧基。又更佳為碳數1~9之烷基或碳數1~9之烷氧基。 　　[0014] ＜具有特定結構之聚合物＞ 　　本發明所用之具有特定結構之聚合物，並無特殊限定，較佳為選自由丙烯酸聚合物、甲基丙烯酸聚合物、酚醛清漆樹脂、聚羥基苯乙烯、聚醯亞胺前驅體、聚醯亞胺、聚醯胺、聚酯、纖維素及聚矽氧烷所成之群的聚合物。其中尤以聚醯亞胺前驅體、聚醯亞胺或聚矽氧烷為佳；更佳為聚醯亞胺前驅體或聚醯亞胺。 　　本發明所用之聚合物為聚醯亞胺前驅體或聚醯亞胺時，該等可由二胺與四羧酸二酐之反應而得到，由製造上之容易性的觀點，具有特定結構者較佳為二胺。 　　[0015] ＜具有特定結構之二胺＞ 　　上述之具有特定結構之二胺(亦稱為特定二胺)，係以下述式[2]表示。式[2]中之Y1 、Y2 、Y3 、Y4 、Y5 、Y6 、n，包含各自之較佳者，係與式[1]中之上述定義相同。再者，m為1~4之整數，較佳為1。 　　[0016] 具體而言，可列舉下述式[2-1]~[2-23]，但不限定於此等。R7 為碳數3~12之烷基，1,4-伸環己基之順-反異構性，係分別為反式異構物。 　　[0017]R8 為碳數3以上12以下之烷基，1,4-伸環己基之順-反異構性，係分別為反式異構物。 　　[0018][0019] A4 為可經氟原子取代之碳數3~20之烷基，A3 為1,4-伸環己基或1,4-伸苯基，A2 為氧原子或COO-*(惟，標記「*」之鍵結位係與A3 鍵結)，A1 為氧原子或COO-*(惟，標記「*」之鍵結位係與(CH2 )a2 )鍵結)。又，a1 為0或1之整數，a2 為2~10之整數，a3 為1。 　　[0020][0021][0022][0023][0024][0025] ＜其他二胺化合物＞ 　　本發明中，特定二胺以外之其他二胺化合物，可作為二胺成分合併使用。其具體例子列舉如下。 　　p-苯二胺、2,3,5,6-四甲基-p-苯二胺、2,5-二甲基-p-苯二胺、m-苯二胺、2,4-二甲基-m-苯二胺、2,5-二胺基甲苯、2,6-二胺基甲苯、2,5-二胺基酚、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲醇、2,4-二胺基苯甲醇、4,6-二胺基間苯二酚、4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二羧基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-聯苯、3,3’-三氟甲基-4,4’-二胺基聯苯、3,4’-二胺基聯苯、3,3’-二胺基聯苯、2,2’-二胺基聯苯、2,3’-二胺基聯苯、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫代二苯胺、3,3’-硫代二苯胺、4,4’-二胺基二苯胺、3,3’-二胺基二苯胺、3,4’-二胺基二苯胺、2,2’-二胺基二苯胺、2,3’-二胺基二苯胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-[1,4-伸苯基雙(亞甲基)]二苯胺、4,4’-[1,3-伸苯基雙(亞甲基)]二苯胺、3,4’-[1,4-伸苯基雙(亞甲基)]二苯胺、3,4’-[1,3-伸苯基雙(亞甲基)]二苯胺、3,3’-[1,4-伸苯基雙(亞甲基)]二苯胺、3,3’-[1,3-伸苯基雙(亞甲基)]二苯胺、1,4-伸苯基雙[(4-胺基苯基)甲酮]、1,4-伸苯基雙[(3-胺基苯基)甲酮]、1,3-伸苯基雙[(4-胺基苯基)甲酮]、1,3-伸苯基雙[(3-胺基苯基)甲酮]、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)間苯二甲醯胺、N,N’-雙(3-胺基苯基)間苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2’-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷、4-(胺基甲基)苯胺、3-(胺基甲基)苯胺、4-(2-胺基乙基)苯胺、3-(2-胺基乙基苯胺)等之芳香族二胺化合物；雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等之脂環式二胺化合物；1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等之脂肪族二胺化合物。 　　[0026] 又，可合併使用於二胺側鏈具有烷基或含氟烷基之二胺，作為其他二胺。具體而言，可例示下述式[DA1]~[DA12]之二胺。 　　[0027]A5 為碳數1~22之烷基或含氟烷基。 　　[0028]A6 表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2 -、 -O-、-CO-或NH-，A7 表示碳數1~22之烷基或含氟烷基。 　　[0029]p為1~10之整數。 　　[0030] 又，亦可合併使用下述式[DA13]~[DA20]之二胺。 　　[0031]m為0~3之整數，n為1~5之整數。 　　[0032] 進一步地，亦可合併使用下述式[DA21]~ [DA25]表示之分子內具有羧基之二胺。[0033] m1 為1~4之整數，A8 為單鍵、-CH2 -、-C2 H4 -、-C(CH3 )2 -、-CF2 -、-C(CF3 )-、-O-、-CO-、-NH-、 -N(CH3 )-、-CONH-、-NHCO-、-CH2 O-、-OCH2 -、-COO-、-OCO-、-CON(CH3 )-或N(CH3 )CO-，m2 、m3 分別為0~4之整數，且m2 +m3 為1~4之整數。m4 、m5 分別為1~5之整數，A9 為碳數1~5之直鏈或分支烷基，m6 為1~5之整數。A10 為單鍵、-CH2 -、-C2 H4 -、-C(CH3 )2 -、-CF2 -、-C(CF3 )-、-O-、-CO-、-NH-、-N(CH3 )-、-CONH-、-NHCO-、 -CH2 O-、-OCH2 -、-COO-、-OCO-、-CON(CH3 )-或N(CH3 )CO-，m7 為1~4之整數。 　　上述其他二胺化合物，亦可因應作為液晶配向膜時的液晶配向性、電壓保持率、儲存電荷等之特性，以1種或混合2種以上使用。 　　[0034] ＜四羧酸二酐成分＞ 　　為了得到本發明中之特定聚合物，可使用下述式[3]表示之四羧酸二酐(亦稱為特定四羧酸二酐)。式[3]中，Z1 為4價之有機基，其結構並無特殊限定，但較佳為碳數4~13之4價有機基，且含有碳數4~10之非芳香族環狀烴基。 　　[0035] 具體而言，係下述式[3a]~[3j]表示之基。[0036] Z2 ~Z5 ，係分別獨立地為由氫原子、甲基、氯原子或苯環中選出之基。式[3g]中，Z6 、Z7 ，係分別獨立地為氫原子或甲基。Z1 之特佳例子，就聚合反應性或合成之容易性而言，係式[3a]、式[3c]、式[3d]、式[3e]、式[3f]或式[3g]。 　　[0037] ＜其他四羧酸二酐＞ 　　本發明中，可使用特定四羧酸二酐以外之其他四羧酸二酐(其他四羧酸二酐)。其他四羧酸二酐，可列舉以下所示之四羧酸之四羧酸二酐。 　　[0038] 可列舉苯均四酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4-聯苯四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸。 　　上述其他四羧酸二酐亦可因應作為液晶配向膜時的液晶配向性、電壓保持率、儲存電荷等之特性，以1種或混合2種以上使用。 　　[0039] ＜特定聚合物之製造方法＞ 　　合成本發明中之特定聚合物的方法並無特殊限定。通常係使二胺成分與四羧酸二酐成分進行聚縮合反應而得到。一般而言，係使選自由四羧酸及其衍生物所成之群的至少1種四羧酸成分，與由1種或複數種二胺化合物所構成的二胺成分進行反應，而得到聚醯胺酸。欲得到聚醯胺酸烷基酯，可使用將聚醯胺酸之羧基轉換為酯之方法。 　　[0040] 進一步地，欲得到聚醯亞胺，可使用使前述聚醯胺酸或聚醯胺酸烷基酯醯亞胺化而成為聚醯亞胺的方法。 　　使用本發明之特定聚合物所得到之液晶配向膜，上述二胺成分中之特定二胺的含有比例越多，不只初期特性，即使於長時間曝露於背光光後，電壓保持率及因直流電壓所儲存之電荷的緩和越快。又，二胺成分中之特定二胺的含有比例越多，可使液晶之預傾角越大。此時，以提高上述特性為目的時，二胺成分中，特定二胺化合物之含量，相對於特定二胺1莫耳而言，較佳為0.01~99莫耳、更佳為0.1~50莫耳、又更佳為0.5~20莫耳、最佳為0.5~10莫耳。 　　[0041] 又，為了得到本發明之特定聚合物，較佳為於四羧酸二酐成分使用特定四羧酸二酐。此時，較佳為四羧酸二酐成分之1莫耳%以上為特定四羧酸二酐、更佳為5莫耳%以上、又更佳為10莫耳%以上。又，亦可四羧酸二酐成分之100莫耳%為特定四羧酸二酐。 　　二胺成分與四羧酸二酐成分之反應，通常係於有機溶劑中進行。此時所用的有機溶劑，只要係會溶解所生成的聚醯亞胺前驅體者則無特殊限定。其具體例子列舉如下。 　　[0042] 其係N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、雙成烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基賽珞蘇、乙基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、乙酸3-甲基-3-甲氧基丁酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸伸乙酯、碳酸伸丙酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚或4-羥基-4-甲基-2-戊酮等。此等可單獨使用、亦可混合使用。進一步地，即使不溶解聚醯亞胺前驅體之溶劑，亦可於不使所生成之聚醯亞胺前驅體析出的範圍內混合於上述溶劑使用。又，有機溶劑中之水分會阻礙聚合反應，進而成為使所生成之聚醯亞胺前驅體水解的原因，因此有機溶劑較佳為使用經脫水乾燥者。 　　[0043] 使二胺成分與四羧酸二酐成分於有機溶劑中反應時，可列舉攪拌使二胺成分分散或溶解於有機溶劑而得的溶液，將四羧酸二酐成分直接或分散或溶解於有機溶劑予以添加的方法；相反地於使四羧酸二酐分散或溶解於有機溶劑而得的溶液中添加二胺成分的方法；將四羧酸二酐成分與二胺成分交互添加的方法等，此等任意方法均可使用。又，將二胺成分或四羧酸二酐成分分別使用複數種來進行反應時，可於預先混合的狀態下反應、可個別地依次反應、亦可將個別反應後的低分子量體予以混合反應而成為特定聚合物。此時之聚合溫度可選擇-20~150℃之任意溫度，較佳為-5~100℃之範圍。又，反應可於任意濃度進行，但濃度過低時變得不易得到高分子量之特定聚合物，濃度過高時反應液之黏性變得過高，均勻攪拌變得困難。因此，較佳為1~50質量%、更佳為5~30質量%。反應初期以高濃度進行，之後，可追加有機溶劑。 　　[0044] 於得到聚醯亞胺前驅體之聚合反應中，二胺成分之合計莫耳數與四羧酸二酐成分之合計莫耳數的比較佳為0.8~1.2。與通常之聚縮合反應同樣地，該莫耳比越接近1.0，所生成之聚醯亞胺前驅體的分子量越大。 　　本發明之聚醯亞胺為使前述聚醯亞胺前驅體脫水閉環而得到之聚醯亞胺，有用於作為用以得到液晶配向膜之聚合物。 　　本發明之聚醯亞胺中，醯胺酸基之脫水閉環率(醯亞胺化率)，並不一定必須為100%，可因應用途或目的任意調整。 　　使聚醯亞胺前驅體醯亞胺化之方法，可列舉將聚醯亞胺前驅體之溶液直接加熱的熱醯亞胺化或於聚醯亞胺前驅體之溶液中添加觸媒的觸媒醯亞胺化。 　　[0045] 使聚醯亞胺前驅體於溶液中熱醯亞胺化時的溫度，係100~400℃、較佳為120~250℃，較佳為一邊將由醯亞胺化反應所生成之水移除至系外來一邊進行。 　　聚醯亞胺前驅體之觸媒醯亞胺化，可藉由於聚醯亞胺前驅體之溶液中添加鹼性觸媒與酸酐，於-20~250℃、較佳為0~180℃攪拌來進行。鹼性觸媒之量係醯胺酸基之0.5~30莫耳倍、較佳為2~20莫耳倍，酸酐之量係醯胺酸基之1~50莫耳倍、較佳為3~30莫耳倍。鹼性觸媒可列舉吡啶、三乙胺、三甲胺、三丁胺、三辛胺等，其中尤以吡啶，由於具備使反應進行所適度的鹼性故較佳。酸酐可列舉乙酸酐、偏苯三甲酸酐、苯均四酸酐等，其中尤以使用乙酸酐時，由於反應結束後之精製容易，故較佳。觸媒醯亞胺化之醯亞胺化率，可藉由調節觸媒量、反應溫度、反應時間來控制。 　　[0046] 由聚醯亞胺前驅體或聚醯亞胺之反應溶液中回收所生成之聚醯亞胺前驅體或聚醯亞胺時，只要將反應溶液投入溶劑中使其沈澱即可。沈澱所用之溶劑可列舉甲醇、丙酮、己烷、丁基賽珞蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、水等。將投入於溶劑而沈澱的聚合物過濾而回收後，可於常壓或減壓下，常溫或加熱乾燥。又，若重複將沈澱回收之聚合物再溶解於有機溶劑並再沈澱回收的操作2~10次時，可使聚合物中之雜質減少。此時之溶劑，例如可列舉醇類、酮類、烴等，若使用由此等之中選出的3種以上之溶劑，則精製之效率更加上昇故較佳。 　　[0047] 本發明之特定聚合物之分子量，當考慮到由其所得之聚合物被膜的強度、聚合物被膜形成時之作業性、聚合物被膜之均勻性時，以GPC(Gel Permeation Chromatography)法所測定之重量平均分子量較佳為5,000~1,000,000、更佳為10,000~150,000。 　　[0048] ＜液晶配向劑＞ 　　本發明所用之液晶配向劑中，聚合物可全為上述特定聚合物，亦可混合有其以外之其他聚合物。此時，相對於特定聚合物而言，其以外之其他聚合物之含量係0.5~15質量%、較佳為1~10質量%。 　　其以外之其他聚合物，可列舉由不含特定二胺之二胺成分與四羧酸二酐成分所得到的聚醯亞胺前驅體，或由該聚醯亞胺前驅體所得到的聚醯亞胺。進一步地，亦可列舉聚醯亞胺前驅體及聚醯亞胺以外之聚合物，具體而言，可列舉丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯或聚醯胺等。 　　[0049] 本發明所用之液晶配向劑中之有機溶劑，由以塗佈形成均勻的聚合物被膜之觀點而言，有機溶劑之含量較佳為70~99質量%。其含量可依目標之液晶配向膜的膜厚而適當變更。作為有機溶劑，只要係會溶解上述特定聚合物之有機溶劑則無特殊限定。更具體而言，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-乙烯基吡咯啶酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、1,3-二甲基-四氫咪唑酮、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、環己酮、碳酸伸乙酯、碳酸伸丙酯、二甘醇二甲醚及4-羥基-4-甲基-2-戊酮等。此等可單獨使用、亦可混合使用。 　　[0050] ＜添加劑＞ 　　本發明所用之液晶配向劑中，較佳為含有具有環氧基、異氰酸酯基、氧雜環丁烷基或環碳酸酯基之交聯性化合物；具有選自由羥基或烷氧基所成之群的至少1種取代基之交聯性化合物；具有聚合性不飽和鍵之交聯性化合物等(以下亦稱為交聯劑)等。 　　[0051] 具有環氧基或異氰酸酯基之交聯性化合物，例如可列舉雙酚丙酮縮水甘油醚、酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、異三聚氰酸三環氧丙酯、四環氧丙基胺基二亞苯、四環氧丙基-m-二甲苯二胺、四環氧丙基-1,3-雙(胺基乙基)環己烷、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、雙酚六氟乙醯二縮水甘油醚、1,3-雙(1-(2,3-環氧基丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧基丙氧基)八氟聯苯、三環氧丙基-p-胺基酚、四環氧丙基間二甲苯二胺、2-(4-(2,3-環氧基丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧基丙氧基)苯基)乙基)苯基)丙烷、1,3-雙(4-(1-(4-(2,3-環氧基丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧基丙氧基苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 　　[0052] 具有氧雜環丁烷基之交聯性化合物，係具有至少2個下述式[4]所示之氧雜環丁烷基之交聯性化合物。[0053] 具體而言，係下述式[4a]~[4k]表示之交聯性化合物。[0054][0055][0056] 具有環碳酸酯基之交聯性化合物，可列舉具有至少2個下述式[5]表示之環碳酸酯基的交聯性化合物。具體而言，係下述式[5-1]~式[5-37]表示之交聯性化合物。 　　[0057][0058][0059][0060][0061][0062][0063][0064][0065] 式[5-24]中，n為1~5之整數，式[5-25]中，n為1~5之整數，式[5-36]中，n為1~100之整數，式[5-37]中，n為1~10之整數。 　　進一步地，亦可列舉具有下述式[5-38]~式[5-40]所示之至少1種結構的聚矽氧烷。[0066] 式[5-38]~式[5-40]中，R1 、R2 、R3 、R4 及R5 ，係分別獨立地為式[5]表示之結構、氫原子、羥基、碳數1~10之烷基、烷氧基、脂肪族環或芳香族環，至少1者為式[5]表示之結構。 　　具體而言，可列舉下述式[5-41]或式[5-42]之化合物。式[5-42]中，n為1~10之整數。 　　[0067] 具有選自由羥基或烷氧基所成之群的至少1種取代基之交聯性化合物，例如可列舉具有羥基或烷氧基之胺基樹脂，例如三聚氰胺樹脂、尿素樹脂、胍胺樹脂、乙炔脲-甲醛樹脂、琥珀醯胺-甲醛樹脂、乙烯尿素-甲醛樹脂等。具體而言，可使用胺基之氫原子被羥甲基或烷氧基甲基或其兩方所取代之三聚氰胺衍生物、苯并胍胺衍生物或乙炔脲。三聚氰胺衍生物或苯并胍胺衍生物，亦可能存在有2聚體或3聚體。此等較佳係每1個三嗪環，平均具有3~6個羥甲基或烷氧基甲基者。 　　[0068] 如此之三聚氰胺衍生物或苯并胍胺衍生物之例子，可列舉市售品之每1個三嗪環平均取代有3.7個甲氧基甲基之MX-750、每1個三嗪環平均取代有5.8個甲氧基甲基之MW-30(以上，三和Chemical公司製)、Cymel 300、301、303、350、370、771、325、327、703、712等之甲氧基甲基化三聚氰胺；Cymel 235、236、238、212、253、254等之甲氧基甲基化丁氧基甲基化三聚氰胺；Cymel 506、508等之丁氧基甲基化三聚氰胺；Cymel 1141等之含羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺；Cymel 1123等之甲氧基甲基化乙氧基甲基化苯并胍胺；Cymel 1123-10等之甲氧基甲基化丁氧基甲基化苯并胍胺；Cymel 1128等之丁氧基甲基化苯并胍胺；Cymel 1125-80等之含羧基之甲氧基甲基化乙氧基甲基化苯并胍胺(以上，三井Cyanamid公司製)等。又，乙炔脲之例子，可列舉Cymel 1170等之丁氧基甲基化乙炔脲；Cymel 1172等之羥甲基化乙炔脲；Powderlink 1174等之甲氧基羥甲基化乙炔脲等。 　　[0069] 具有羥基或烷氧基之苯，或酚性化合物，亦可例示作為交聯性化合物。例如可列舉1,3,5-參(甲氧基甲基)苯、1,2,4-參(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯或2,6-二羥基甲基-p-tert-丁基酚等。 　　[0070] 更具體而言，係下述式[6-1]~式[6-48]表示之交聯性化合物。[0071][0072][0073][0074][0075] 具有聚合性不飽和鍵之交聯性化合物，例如可列舉三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷或甘油聚縮水甘油醚聚(甲基)丙烯酸酯等之分子內具有3個聚合性不飽和基之交聯性化合物；乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二環氧丙酯二(甲基)丙烯酸酯或羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯等之分子內具有2個聚合性不飽和基之交聯性化合物；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、甘油單(甲基)丙烯酸酯、磷酸2-(甲基)丙烯醯氧基乙酯或N-羥甲基(甲基)丙烯醯胺等之分子內具有1個聚合性不飽和基之交聯性化合物。 　　[0076] 此外，下述式[7]表示之化合物亦可例示作為交聯性化合物。E1 為由環己烷環、雙環己烷環、苯環、聯苯環、三聯苯環、萘環、茀環、蒽環或菲環所構成的1價基，E2 為由下述式[7a]或式[7b]所構成的1價基，n為1~4之整數。 　　[0077]上述化合物係交聯性化合物之一例，並不限定於此等。又，本發明之液晶配向劑中所含有的交聯性化合物，可為1種、亦可組合2種以上。 　　[0078] 本發明之液晶配向劑中，交聯性化合物之含量，相對於聚合物成分100質量份而言，較佳為0.1~150質量份，為了使交聯反應進行而展現目標之效果，且不降低液晶之配向性，更佳為0.1~100質量份、特佳為1~50質量份。 　　較佳為添加下述式[M1]~[M156]表示之含氮之雜環胺化合物，作為促進液晶配向膜中之電荷移動，促進使用該液晶配向膜之液晶晶胞的電荷消去之化合物。該胺化合物，亦可直接添加於特定聚合物之溶液中，但較佳為以適當之溶劑使成為濃度0.1~10質量%、較佳為1~7質量%之溶液後添加。該溶劑只要係會溶解上述特定聚合物之有機溶劑則無特殊限定。 　　[0079][0080][0081][0082][0083][0084][0085] 本發明之液晶配向劑，只要不損及本發明之效果，則可含有會提高塗佈液晶配向劑時之聚合物被膜的膜厚均勻性或表面平滑性之有機溶劑(亦稱為不良溶劑)或化合物。進一步地，亦可含有會提高液晶配向膜與基板之密合性的化合物等。提高膜厚均勻性或表面平滑性之不良溶劑的具體例子可列舉如下者。 　　[0086] 例如，可列舉異丙醇、甲氧基甲基戊醇、甲基賽珞蘇、乙基賽珞蘇、丁基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、二丙二醇二甲基醚、乙酸3-甲基-3-甲氧基丁酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、2,6-二甲基-4-庚醇、二丙酮醇、甲基環己烯、丙基醚、二己基醚、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等之具有低表面張力之有機溶劑。 　　此等不良溶劑可使用1種亦可混合複數種使用。使用如上述之不良溶劑時，較佳為液晶配向劑中所含有的有機溶劑全體之5~80質量%、更佳為20~60質量%。 　　[0087] 提高膜厚均勻性或表面平滑性之化合物，可列舉氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。 　　具體而言，例如可列舉Eftop EF301、EF303、EF352(Tokem Products公司製)；Megafac F171、F173、R-30(大日本油墨公司製)；Fluorad FC430、FC431(住友3M公司製)；Asahiguard AG710；Surflon S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。此等界面活性劑之使用比例，相對於液晶配向劑中所含有的聚合物成分100質量份而言，較佳為0.01~2質量份、更佳為0.01~1質量份。 　　[0088] 提高液晶配向膜與基板之密合性的化合物之具體例子，可列舉以下所示之含官能性矽烷之化合物或含環氧基之化合物。 　　例如，可列舉3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三乙三胺、N-三甲氧基矽烷基丙基三乙三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、乙酸9-三甲氧基矽烷基-3,6-二氮雜壬酯、乙酸9-三乙氧基矽烷基-3,6-二氮雜壬酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N’,N’,-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’,-四縮水甘油基-4、4’-二胺基二苯基甲烷等。 　　[0089] 使用提高與基板之密合性之化合物時，相對於液晶配向劑中所含有的聚合物成分100質量份而言，較佳為0.1~30質量份、更佳為1~20質量份。未達0.1質量份時，無法期待密合性提高之效果，多於30質量份時，可能有液晶配向性變差的情況。 　　本發明之液晶配向劑中，除了上述之交聯性化合物、不良溶劑及提高密合性之化合物以外，只要不損及本發明之效果之範圍，亦可添加以改變液晶配向膜之介電率或導電性等之電特性為目的之介電體或導電物質。 　　[0090] ＜液晶配向膜、液晶顯示元件＞ 　　本發明之液晶配向劑，於基板上塗佈、燒成後，可進行摩擦處理或光照射等之配向處理，作為液晶配向膜使用。又，於垂直配向用途等之情況時，即使不進行配向處理亦可作為液晶配向膜使用。此時所使用的基板，只要係透明性高的基板則無特殊限定，除了玻璃基板以外，亦可使用丙烯酸基板或聚碳酸酯基板等之塑膠基板等。由製程簡化的觀點而言，較佳使用形成有使用於液晶驅動之ITO電極等的基板。又，於反射型之液晶顯示元件中，若僅於單側之基板，則亦可使用矽晶圓等之不透明的基板，此時的電極亦可使用鋁等之會反射光的材料。 　　[0091] 液晶配向劑之塗佈方法，於工業上一般為以網版印刷、平版印刷、柔版印刷、噴墨等所進行的方法。其他塗佈方法，係有浸漬、輥塗佈器、狹縫塗佈器、旋轉器等，可依目的使用此等。 　　將液晶配向劑塗佈於基板上後，可藉由加熱板等之加熱手段於50~300℃、較佳為80~250℃使溶劑蒸發而成為聚合物被膜。燒成後之聚合物被膜的厚度過厚時，於液晶顯示元件之消耗電力方面為不利，過薄時可能有液晶顯示元件之信賴性降低的情況，因此較佳為5~300nm、更佳為10~100nm。將液晶水平配向或傾斜配向時，係將燒成後之聚合物被膜以摩擦或偏光紫外線照射等處理。 　　[0092] 本發明之液晶顯示元件，為由上述液晶配向劑得到附有液晶配向膜之基板後，以公知方法製作液晶晶胞而成為液晶顯示元件者。 　　液晶晶胞之製作方法，可例示準備形成有液晶配向膜之一對基板，於一方之基板的液晶配向膜上散佈間隔件，以液晶配向膜面為內側，貼合另一方之基板，將液晶減壓注入並密封之方法；或於散佈有間隔件之液晶配向膜面滴下液晶後貼合基板並進行密封之方法等。 　　本發明中具特徴性者，係液晶顯示元件中之液晶顯示面板具有曲面形狀。亦即，構成液晶顯示面板之一對基板係具有曲面，該曲面之形狀或程度係有各種者，為任意選擇。特別是本發明中，於沿著一軸方向之截面係具有曲面形狀，對曲面形狀之曲率半徑(R)為1000mm至3000mm的液晶顯示面板具有效果。 　　[0093] 進一步地，本發明之液晶配向劑，為於具備電極之一對基板之間具有液晶層而成，於以下之液晶顯示元件亦可較佳地使用：該液晶顯示元件係經由在一對基板之間配置含有藉著活性能量線及熱之至少一方而聚合的聚合性化合物之液晶組成物，一邊於電極間施加電壓，一邊藉由活性能量線之照射及加熱之至少一方而使得聚合性化合物聚合的步驟所製造。此處，活性能量線係紫外線為適合。 　　上述液晶顯示元件，為藉由PSA(Polymer Sustained Alignment)方式而控制液晶分子之預傾角者。PSA方式中，係於液晶材料中預先混入少量之光聚合性化合物，例如光聚合性單體，組裝液晶晶胞後，於對液晶層施加特定電壓之狀態下對光聚合性化合物照射紫外線等，藉由所生成之聚合物控制液晶分子之預傾角。聚合物生成時之液晶分子的配向狀態在移除電壓後亦被記憶，因此藉由控制形成於液晶層之電場等，可調整液晶分子之預傾角。又，PSA方式中，摩擦處理並非必要，因此適於形成以摩擦處理難以控制預傾角之垂直配向型的液晶層。 　　[0094] 亦即，本發明之液晶顯示元件，藉由上述手法由本發明之液晶配向劑得到附有液晶配向膜之基板後，製作液晶晶胞，藉由以紫外線照射及加熱之至少一方使聚合性化合物聚合，可控制液晶分子之配向。 　　若舉液晶晶胞製作之一例，可列舉準備形成有液晶配向膜之一對基板，於一方之基板的液晶配向膜上散佈間隔件，以液晶配向膜面為內側，貼合另一方之基板，將液晶減壓注入而密封之方法；或於散佈有間隔件之液晶配向膜面滴下液晶後，貼合基板進行密封之方法等。 　　[0095] 液晶中係混合有以熱或紫外線照射而聚合之聚合性化合物。聚合性化合物可列舉分子內具有1個以上之丙烯酸酯基或甲基丙烯酸酯基等之聚合性不飽和基的化合物。此時，相對於液晶成分100質量份而言，聚合性化合物較佳為0.01~10質量份、更佳為0.1~5質量份。聚合性化合物未達0.01質量份時，聚合性化合物未聚合，無法進行液晶之配向控制，多於10質量份時，未反應之聚合性化合物增多，液晶顯示元件之燒印特性會降低。 　　製作液晶晶胞後，係一邊對液晶晶胞施加交流或直流之電壓，一邊照射熱或紫外線使聚合性化合物聚合。藉此，可控制液晶分子之配向。 　　[0096] 此外，本發明之液晶配向劑，為於具備電極之一對基板之間具有液晶層而成，於以下之液晶顯示元件亦可較佳地使用：該液晶顯示元件係經由在前述一對基板之間配置含有以活性能量線及熱之至少一方聚合的聚合性基之液晶配向膜，且於電極間施加電壓的步驟所製造。此處，活性能量線係紫外線為適合。 　　為了得到含有以活性能量線及熱之至少一方聚合的聚合性基之液晶配向膜，可列舉將含有該聚合性基之化合物添加於液晶配向劑中之方法，或使用含有聚合性基之聚合物成分之方法。聚合性基可列舉丙烯酸基、甲基丙烯酸基、乙烯基、馬來醯亞胺基等之聚合性不飽和基。 　　[0097] 本發明之液晶配向劑，由於含有具備以熱或紫外線之照射而反應的雙鍵部位之特定胺化合物，因此可藉由紫外線照射及加熱之至少一方來控制液晶分子之配向。 　　若舉液晶晶胞製作之一例，可列舉準備形成有液晶配向膜之一對基板，於一方之基板的液晶配向膜上散佈間隔件，以液晶配向膜面為內側，貼合另一方之基板，將液晶減壓注入並密封之方法；或於散佈有間隔件之液晶配向膜面滴下液晶後，貼合基板並進行密封之方法等。 　　[0098] 於製作液晶晶胞後，藉由一邊對液晶晶胞施加交流或直流之電壓，一邊照射熱或紫外線，可控制液晶分子之配向。 　　如以上方式，使用本發明之液晶配向劑所製作的液晶顯示元件，為信賴性優良者，可適合地利用於大畫面且高精細之液晶電視等。 [實施例] 　　[0099] 以下列舉實施例以更具體說明本發明，但不限定於此等。再者，以下所使用之略記如以下所述。 (四羧酸二酐) 　　CBDA：1,2,3,4-環丁烷四羧酸二酐 　　BODA：雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐[0100] (二胺) 　　3-AMPDA：3,5-二胺基-N-(吡啶-3-基甲基)苯甲醯胺 　　p-PDA：p-苯二胺 　　PBCH5DAB：1,3-二胺基-4-{4-〔反-4-(反-4-n-戊基環己基)環己基〕苯氧基}苯 　　PCH7DAB：1,3-二胺基-4-〔4-(反-4-n-庚基環己基)苯氧基〕苯 　　[0101][0102] (添加劑)[0103] (矽氧烷) 　　TEOS：四乙氧基矽烷 　　UPS：3-脲基丙基三乙氧基矽烷 　　MPMS：3-甲基丙烯醯氧基丙基三甲氧基矽烷 　　HTMS：十六烷基三甲氧基矽烷 (有機溶劑) 　　NMP：N-甲基-2-吡咯啶酮、NEP：N-乙基-2-吡咯啶酮 　　BCS：丁基賽珞蘇、PB：丙二醇單丁基醚 　　DME：1,2-二甲氧基乙烷、DPM：二丙二醇單甲基醚、DMI：1,3-二甲基-2-四氫咪唑酮、HG：己二醇 　　[0104] ＜聚醯亞胺之分子量測定＞ 　　合成例中之聚醯亞胺之分子量，係使用Senshu Scientific公司製 常溫凝膠滲透層析(GPC)裝置(SSC-7200)、Shodex公司製管柱(KD-803、KD-805)如以下般測定。 　　管柱溫度：50℃ 　　溶離液：N,N’-二甲基甲醯胺(溴化鋰-水合物(LiBr･H2O)30mmol/L、磷酸･無水結晶(o-磷酸)30mmol/L、四氫呋喃(THF)10ml/L作為添加劑)、流速：1.0ml/分， 　　檢量線製成用標準樣品：東曹公司製 TSK 標準聚環氧乙烷(分子量：約9000,000、150,000、100,000、30,000)及Polymer Laboratories公司製 聚乙二醇(分子量：約12,000、4,000、1,000)。 　　[0105] ＜醯亞胺化率之測定＞ 　　聚醯亞胺之醯亞胺化率係如下般測定。將聚醯亞胺粉末20mg置入NMR樣品管(草野科學公司製 NMR標準取樣管φ5)中，添加重氫化二甲基亞碸(DMSO-d6 、0.05%TMS混合品)0.53ml，施加超音波使完全溶解。將該溶液以日本電子datum公司製NMR測定器(JNW-ECA500)測定500MHz之質子NMR。醯亞胺化率係以來自於醯亞胺化前後未變化之結構的質子作為基準質子而決定，使用該質子之波峰積分值，與來自於9.5~10.0ppm附近出現之醯胺酸的NH基之質子波峰積分值，由以下之式求得。 　　醯亞胺化率(%)=(1-α･x/y)×100 　　[0106] ＜分子量測定＞ 　　聚醯亞胺及聚矽氧烷之分子量，係使用Shodex公司製管柱(樣品側KF-803、參照物側KF-800RH)，如以下般測定。 　　管柱溫度：40℃， 　　溶離液：四氫呋喃、流速：1ml/分、檢量線製成用標準樣品：Shodex公司製 聚苯乙烯(分子量：約52,400、19,900、7,200、2,970、580)。 　　[0107] ＜合成例1＞ 　　將BODA(23.64g,94.5mmol)、p-PDA(5.11g,47.3 mmol)、3-AMPDA(16.0g,66.15mmol)及DA-1(32.86g,75.6 mmol)於NMP(216.0g)中混合，於80℃反應5小時後，添加CBDA(18.53g,94.5mmol)與NMP(94.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(62.3g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.02g)及吡啶(1.87g)，於80℃反應3小時。將該反應溶液投入甲醇(601.0g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(A)。該聚醯亞胺之醯亞胺化率為75%，Mn(數平均分子量)為13,200，Mw(重量平均分子量)為40,600。 　　[0108] ＜合成例2＞ 　　將BODA(23.64g,94.5mmol)、p-PDA(5.11g,47.3 mmol)、3-AMPDA(16.0g, 66.15mmol)、DA-1(16.43g,37.8 mmol)及DA-8(14.39g,37.8mmol)於NMP(207.8g)中混合，於80℃反應5小時後，添加CBDA(18.53g,94.5mmol)與NMP(94.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(62.3g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.15g)及吡啶(1.90g)，於80℃反應3小時。將該反應溶液投入甲醇(602.1g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(B)。該聚醯亞胺之醯亞胺化率為75%，Mn為12,900，Mw為40,400。 　　[0109] ＜合成例3＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111 mmol)、DA-2(16.60g,37mmol)及DA-8(16.08g,37mmol)於NMP(170.7g)中混合，於80℃反應5小時後，添加CBDA (17.76g,90.7mmol)與NMP(92.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(C)。該聚醯亞胺之醯亞胺化率為75%，Mn為11,800，Mw為39,600。 　　[0110] ＜合成例4＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111 mmol)、DA-3(17.1g,37mmol)及DA-8(14.08g,37mmol)於NMP(170.7g)中混合，於80℃反應5小時後，添加CBDA (17.78g,90.7mmol)與NMP(92.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(D)。該聚醯亞胺之醯亞胺化率為75%，Mn為11,900，Mw為40,100。 　　[0111] ＜合成例5＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111mmol)及DA-4(34.1g,74mmol)於NMP(170.7g)中混合，於80℃反應5小時後，添加CBDA(17.78g,90.7mmol)與NMP(92.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(E)。該聚醯亞胺之醯亞胺化率為75%，Mn為14,100，Mw為41,000。 　　[0112] ＜合成例6＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111mmol)及DA-5(28.6g,74mmol)於NMP(255g)中混合，於80℃反應5小時後，添加CBDA(17.78g,90.7mmol)與NMP(92.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(F)。該聚醯亞胺之醯亞胺化率為75%，Mn為11,900，Mw為40,000。 　　[0113] ＜合成例7＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111mmol)及DA-6(33.0g,74mmol)於NMP(272.8g)中混合，於80℃反應5小時後，添加CBDA(17.78g,90.7mmol)與NMP(71.1)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(G)。該聚醯亞胺之醯亞胺化率為75%，Mn為11,400，Mw為39,000。 　　[0114] ＜合成例8＞ 　　將BODA(23.14g,88.8mmol)、m-PDA(12.00g,111mmol)及DA-7(33.0g,74mmol)於NMP(272.8g)中混合，於80℃反應5小時後，添加CBDA(17.78g,90.7mmol)與NMP(71.1)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(87.1g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.95g)及吡啶(2.15g)，於80℃反應3小時。將該反應溶液投入甲醇(462.6g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(H)。該聚醯亞胺之醯亞胺化率為75%，Mn為15,700，Mw為41,200。 　　[0115] ＜合成例9＞ 　　於具備有溫度計及回流管之200mL四口反應燒瓶中混合HG 24.9g、BCS 24.9g、TEOS 52.5g及HTMS 11.2g，藉以調製烷氧基矽烷單體之溶液。室溫下花費30分鐘於該溶液中滴下預先混合有HG 8.5g、BCS 8.5g、水16.2g及作為觸媒之草酸0.8g的溶液，進一步於室溫攪拌30分鐘。之後使用油浴加熱回流30分鐘後，預先添加UPS含量92質量%之甲醇溶液0.86g與HG 0.86g、BCS 0.86g之混合液。進一步回流30分鐘後放冷，而得到以SiO2 換算濃度為12重量%之聚矽氧烷溶液(I)。該聚矽氧烷之Mn為5,100，Mw為9,100。 　　[0116] ＜合成例10＞ 　　於具備有溫度計及回流管之200mL四口反應燒瓶中混合HG 21.3g、BCS 21.3g及TEOS 52.5g、18.4g之化合物3，藉以調製烷氧基矽烷單體之溶液。室溫下花費30分鐘於該溶液中滴下預先混合有HG 8.5g、BCS 8.5g、水16.2g及作為觸媒之草酸0.8g的溶液，進一步於室溫攪拌30分鐘。之後使用油浴加熱回流30分鐘後，預先添加UPS含量92質量%之甲醇溶液0.86g與HG 0.86g、BCS 0.86g之混合液。進一步回流30分鐘後放冷，而得到以SiO2 換算濃度為12重量%之聚矽氧烷溶液(J)。該聚矽氧烷之Mn為2,400，Mw為4,800。 　　[0117] ＜比較合成例1＞ 　　將BODA(23.64g,94.5mmol)、p-PDA(5.11g,47.3 mmol)、3-AMPDA(16.0g, 66.15mmol)及DA-8(28.77g,75.6 mmol)於NMP(199.6g)中混合，於80℃反應5小時後，添加CBDA(18.53g,94.5mmol)與NMP(94.6)g，於40℃反應6小時而得到聚醯胺酸溶液。 　　於該聚醯胺酸溶液(30.0g)中添加NMP(62.3g)，稀釋為6質量%後，作為醯亞胺化觸媒而添加乙酸酐(6.29g)及吡啶(1.95g)，於80℃反應3小時。將該反應溶液投入甲醇(603.2g)中，濾離所得到之沈澱物。將該沈澱物以甲醇洗淨，於100℃減壓乾燥而得到聚醯亞胺粉末(D)。該聚醯亞胺之醯亞胺化率為75%，Mn為13,200，Mw為39,300。 　　[0118] ＜實施例1＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[1]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 ＜實施例2＞ 　　對合成例2中得到之聚醯亞胺粉末(B)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[2]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0119] ＜實施例3＞ 　　對合成例3中得到之聚醯亞胺粉末(C)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[3]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0120] ＜實施例4＞ 　　對合成例4中得到之聚醯亞胺粉末(D)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[4]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0121] ＜實施例5＞ 　　對合成例5中得到之聚醯亞胺粉末(E)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[5]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0122] ＜實施例6＞ 　　對合成例6中得到之聚醯亞胺粉末(F)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[7]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0123] ＜實施例7＞ 　　對合成例7中得到之聚醯亞胺粉末(G)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[7]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0124] ＜實施例8＞ 　　對合成例8中得到之聚醯亞胺粉末(H)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時以得到液晶配向劑[8]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0125] ＜實施例9＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加PB(40.0g)，攪拌5小時以得到液晶配向劑[9]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0126] ＜實施例10＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加DME(40.0g)，攪拌5小時以得到液晶配向劑[10]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0127] ＜實施例11＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(30.0g)、DME(10.0g)，攪拌5小時以得到液晶配向劑[11]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0128] ＜實施例12＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(30.0g)、DPM(10.0g)，攪拌5小時以得到液晶配向劑[12]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0129] ＜實施例13＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時後，添加化合物1粉末(0.6g)，攪拌24小時，以得到液晶配向劑[13]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0130] ＜實施例14＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時後，添加化合物2粉末(0.6g)，攪拌24小時，以得到液晶配向劑[14]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0131] ＜實施例15＞ 　　對合成例1中得到之聚醯亞胺粉末(A)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，攪拌5小時後，添加化合物1粉末(0.3g)、化合物2粉末(0.3g)，攪拌24小時，以得到液晶配向劑[15]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 ＜實施例16＞ 　　將合成例9中得到之聚矽氧烷溶液(I)10.0g及HG 15.0g、BCS 15.0g予以混合，以得到液晶配向劑[10]。確認到於該液晶配向劑見不到混濁或析出等之異常。 　　[0132] ＜實施例17＞ 　　將合成例10中得到之聚矽氧烷溶液(J)10.0g及HG 15.0g、BCS 15.0g予以混合，以得到液晶配向劑[17]。確認到於該液晶配向劑見不到混濁或析出等之異常。 　　[0133] ＜比較例1＞ 　　對比較合成例1中得到之聚醯亞胺粉末(K)(6.0g)添加NEP(54.0g)，於70℃攪拌40小時使其溶解。對該溶液添加BCS(40.0g)，於50℃攪拌15小時以得到液晶配向劑[18]。於該液晶配向劑見不到混濁或析出等之異常，確認到樹脂成分均勻溶解。 　　[0134] ＜附聚醯亞胺塗膜之基板之製作＞ 　　將上述實施例1~17及比較例1中分別得到之各液晶配向劑旋轉塗佈於3cm×4cm之附ITO之玻璃基板的ITO面，於70℃下在加熱板燒成1分30秒後，在230℃之紅外線加熱爐中進行30分鐘燒成，製作膜厚100nm之附聚醯亞胺塗膜之基板。 　　再者，實施例16中得到之液晶配向劑的情況時，係將加熱板之燒成於80℃進行3分鐘，以取代於70℃1分30秒，其他相同。 　　[0135] ＜亮點評估＞ 　　將上述實施例1及比較例1中得到之附聚醯亞胺塗膜之基板安裝於Bruker AXS公司製UMT-2(感測器為FVL，裝置尖端安裝有1.6mm藍寶石球)，花費100秒由1mN至20mN於橫軸0.5mm(5mm/秒)、於移動方向2mm進行刮痕試驗後，滴下MLC-3022(Merck Japan公司製)。對於上述中得到之另1枚的附聚醯亞胺塗膜之基板散佈4μm之間隔件，朝向所滴下之MLC-3022側夾入。將經夾入之基板以使偏光顯微鏡(ECLIPSE E600WPOL)(Nikon公司製)為偏光板90°的狀態下觀察進行過刮痕試驗之部位，觀察光是否透過。 　　如圖1般幾乎見不到亮點之狀態評估為「○」，如圖2所示般可見若干亮點之狀態評估為「△」，如圖3所示般經刮痕的部位變成亮點之狀態評估為「×」，該等結果示於表1。 　　[0136]再者，於此係引用於2016年8月3日申請的日本專利申請案第2016-153149號之說明書、申請專利範圍、圖式及摘要的全部內容，併入為本發明之說明書的揭示。The curved liquid crystal display element of the present invention is provided with a liquid crystal panel having a curved surface shape. It is provided with a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer, and the polymer contains a structure represented by the following formula [1] (also called a specific structure). ＜Specific structure＞ In formula [1], Y 1 is a single bond, -(CH 2 ) a - (a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-. Among them, single bonds, -(CH 2 ) a - (a is an integer from 1 to 15), -O-, -CH 2 O- or COO- are preferred because they are easy to synthesize side chain structures. More preferably, it is a single bond, -(CH 2 ) a - (a is an integer from 1 to 10), -O-, -CH 2 O- or COO-. Y 2 is a single bond or (CH 2 ) b - (b is an integer from 1 to 15). Among them, a single bond or (CH 2 ) b - (b is an integer from 1 to 10) is particularly preferred. Y 3 is a single bond, -(CH 2 ) c - (c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-. Among them, single bonds, -(CH 2 ) c - (c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO- are preferred because they are easy to synthesize. More preferably, it is a single bond, -(CH 2 ) c - (c is an integer from 1 to 10), -O-, -CH 2 O-, -COO- or OCO-. Y 4 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring. Any hydrogen atom on these cyclic groups can also be alkane with 1 to 3 carbon atoms. Substituted with a base, an alkoxy group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxy group with 1 to 3 carbon atoms, or a fluorine atom. Furthermore, Y 4 is a divalent organic group having a carbon number of 12 to 25 and having a steroid skeleton. Y 4 is preferably a benzene ring, a cyclohexyl ring or an organic group with 12 to 25 carbon atoms having a steroid skeleton. Y 5 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexyl ring and heterocyclic ring. Any hydrogen atom on these cyclic groups can also be replaced by an alkyl group with a carbon number of 1 to 3, or an alkyl group with a carbon number of 1 to 3. Alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom substitution. When Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, n is an integer of 2 to 4, and Y 4 is a cyclic group having a steroid skeleton having a carbon number of 12 to 25. When a divalent organic group is selected from organic groups, n is an integer from 0 to 4. In addition, when n is a plurality of Y 5 s, each of the plurality of Y 5 independently has the above definition. Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is particularly preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms. <Polymer with specific structure> The polymer with specific structure used in the present invention is not particularly limited, and is preferably selected from acrylic polymers, methacrylic polymers, novolac resins, and polyhydroxystyrenes. , polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane group of polymers. Among them, polyimide precursor, polyimide or polysiloxane is particularly preferred; more preferably, it is polyimide precursor or polyimide. When the polymer used in the present invention is a polyimide precursor or polyimide, these can be obtained by the reaction of diamine and tetracarboxylic dianhydride. From the perspective of ease of production, those with a specific structure are preferred. Preferably it is diamine. <Diamine having a specific structure> The above-mentioned diamine having a specific structure (also referred to as a specific diamine) is represented by the following formula [2]. Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula [2], including the better ones, are the same as the above definitions in the formula [1]. Furthermore, m is an integer from 1 to 4, preferably 1. [0016] Specifically, the following formulas [2-1] to [2-23] can be cited, but are not limited thereto. R 7 is an alkyl group with 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene group is respectively trans isomer. [0017] R 8 is an alkyl group with 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene group is trans isomer respectively. [0018] A 4 is an alkyl group with 3 to 20 carbon atoms that can be substituted by a fluorine atom, A 3 is 1,4-cyclohexylene or 1,4-phenylene, and A 2 is an oxygen atom or COO-*( However, the bonding position marked "*" is bonded with A 3 ), A 1 is an oxygen atom or COO-* (However, the bonding position marked "*" is bonded with (CH 2 )a 2 ) . In addition, a 1 is an integer of 0 or 1, a 2 is an integer of 2 to 10, and a 3 is 1. [0020] [0021] [0022] [0023] [0024] <Other diamine compounds> In the present invention, other diamine compounds other than the specific diamine can be used in combination as the diamine component. Specific examples are listed below. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl Base-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diamine phenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-Dimethyl-4,4'-diaminobiphenyl,3,3'-dimethoxy-4,4'-diaminobiphenyl,3,3'-dihydroxy-4,4'- Diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl -4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'- Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3 '-Sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis (3-Aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine Aniline, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenylamine base)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2 '-Diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diamine benzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobis Benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2 ,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-amine) phenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane Alkane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy) )benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1 ,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methylene) ] diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3' -[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[( 3-Aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone] ketone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis( 4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-amine phenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1 ,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'- (1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N '-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-amino) Phenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4' -Bis(4-aminophenoxy)diphenylsine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4 -Aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-amino) Phenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3- Aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4- Aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3 -Aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4 -Aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis( 3-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4- Aminophenoxy) undecane, 1,11-(3-aminophenoxy) undecane, 1,12-(4-aminophenoxy) dodecane, 1,12-(3 -Aminophenoxy)dodecane, 4-(aminomethyl)aniline, 3-(aminomethyl)aniline, 4-(2-aminoethyl)aniline, 3-(2-amino) Aromatic diamine compounds such as ethylaniline); alicyclic diamine compounds such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane; 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Fats such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. diamine compounds. [0026] In addition, diamines having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used in combination as other diamines. Specifically, diamines of the following formulas [DA1] to [DA12] can be exemplified. [0027] A 5 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group. [0028] A 6 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO- or NH-, A 7 represents an alkyl group with 1 to 22 carbon atoms or a fluorine-containing alkane base. [0029] p is an integer from 1 to 10. [0030] In addition, diamines of the following formulas [DA13] to [DA20] can also be used in combination. [0031] m is an integer from 0 to 3, and n is an integer from 1 to 5. [0032] Furthermore, diamines having carboxyl groups in the molecule represented by the following formulas [DA21] to [DA25] may also be used in combination. m 1 is an integer from 1 to 4, and A 8 is a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 ) -, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, - CON(CH 3 )- or N(CH 3 )CO-, m 2 and m 3 are respectively integers from 0 to 4, and m 2 +m 3 is an integer from 1 to 4. m 4 and m 5 are respectively integers from 1 to 5, A 9 is a linear or branched alkyl group having 1 to 5 carbon atoms, and m 6 is an integer from 1 to 5. A 10 is a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 )-, -O-, -CO-, -NH -, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON(CH 3 )- or N(CH 3 ) CO-, m 7 is an integer from 1 to 4. The above-mentioned other diamine compounds can also be used as one type or in a mixture of two or more types according to the characteristics of liquid crystal alignment, voltage retention, storage charge, etc. when used as a liquid crystal alignment film. <Tetracarboxylic dianhydride component> In order to obtain the specific polymer in the present invention, tetracarboxylic dianhydride (also called specific tetracarboxylic dianhydride) represented by the following formula [3] can be used. In formula [3], Z 1 is a tetravalent organic group, and its structure is not particularly limited, but it is preferably a tetravalent organic group with 4 to 13 carbon atoms, and contains a non-aromatic ring with 4 to 10 carbon atoms. hydrocarbyl. [0035] Specifically, it is a base represented by the following formulas [3a] to [3j]. Z 2 ~ Z 5 are independently selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. In the formula [3g], Z 6 and Z 7 are each independently a hydrogen atom or a methyl group. Particularly preferred examples of Z 1 in terms of polymerization reactivity or ease of synthesis are formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g]. <Other tetracarboxylic dianhydride> In the present invention, other tetracarboxylic dianhydride (other tetracarboxylic dianhydride) other than the specific tetracarboxylic dianhydride can be used. Other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of tetracarboxylic acids shown below. Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2 ,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4- Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)terine, Bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4, 5-Pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenyltetracarboxylic acid, 3,4,9,10- Perylene tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid. The above-mentioned other tetracarboxylic dianhydrides can also be used as one type or in a mixture of two or more types according to the characteristics of liquid crystal alignment, voltage retention, storage charge, etc. when used as a liquid crystal alignment film. [0039] <Production method of specific polymer> The method of synthesizing the specific polymer in the present invention is not particularly limited. Usually, it is obtained by polycondensation reaction of a diamine component and a tetracarboxylic dianhydride component. Generally speaking, a polymer is obtained by reacting at least one tetracarboxylic acid component selected from the group of tetracarboxylic acids and their derivatives with a diamine component consisting of one or a plurality of diamine compounds. Amino acid. To obtain polyamic acid alkyl ester, the method of converting the carboxyl group of polyamic acid into ester can be used. [0040] Furthermore, in order to obtain polyamide imide, a method of imidizing the aforementioned polyamide acid or polyamide alkyl ester to form polyamide imide can be used. The liquid crystal alignment film obtained by using the specific polymer of the present invention, the higher the proportion of the specific diamine in the above-mentioned diamine component, not only the initial characteristics, but also the voltage retention rate and DC voltage change after being exposed to backlight for a long time. The stored charge is relaxed faster. In addition, the greater the content ratio of the specific diamine in the diamine component, the greater the pretilt angle of the liquid crystal. At this time, when the purpose is to improve the above characteristics, the content of the specific diamine compound in the diamine component is preferably 0.01 to 99 moles, more preferably 0.1 to 50 moles per 1 mole of the specific diamine. Ear, preferably 0.5~20 moles, most preferably 0.5~10 moles. [0041] In addition, in order to obtain the specific polymer of the present invention, it is preferred to use specific tetracarboxylic dianhydride as the tetracarboxylic dianhydride component. At this time, it is preferable that 1 mol% or more of the tetracarboxylic dianhydride component is specific tetracarboxylic dianhydride, more preferably 5 mol% or more, and still more preferably 10 mol% or more. Moreover, 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride. The reaction between the diamine component and the tetracarboxylic dianhydride component is usually carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve the generated polyimide precursor. Specific examples are listed below. It is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, N-methyl caprolactam, dimethyl Trisene, tetramethylurea, pyridine, dimethyltrisine, hexamethylteresine, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, bisene, ethyl amyl ketone, methyl Nonyl Ketone, Methyl Ethyl Ketone, Methyl Isoamyl Ketone, Methyl Isopropyl Ketone, Methyl Celluloid, Ethyl Celluloid, Methyl Celluloid Acetate, Ethyl Celluloid Threoacetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol mono Acetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monomethyl ether of monoacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene , amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n- Octane, diethyl ether, cyclohexanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate monoethyl ether , methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme or 4-hydroxy-4-methyl-2-pentanone, etc. . These can be used individually or mixed. Furthermore, even if the solvent does not dissolve the polyimide precursor, it can be mixed with the solvent in a range that does not cause the generated polyimide precursor to precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction and cause hydrolysis of the generated polyimide precursor. Therefore, it is preferable to use an organic solvent that has been dehydrated and dried. When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, a solution obtained by stirring the diamine component to disperse or dissolve it in the organic solvent can be used, and the tetracarboxylic dianhydride component is directly or dispersed or dissolved in the organic solvent. A method of adding it by dissolving it in an organic solvent; a method of adding a diamine component to a solution obtained by dispersing or dissolving tetracarboxylic dianhydride in an organic solvent; and adding a tetracarboxylic dianhydride component and a diamine component alternately Methods, etc. Any of these methods can be used. In addition, when a plurality of diamine components or tetracarboxylic dianhydride components are used for reaction, they can be reacted in a premixed state, they can be reacted individually in sequence, or the low molecular weight components after individual reactions can be mixed and reacted. And become a specific polymer. The polymerization temperature at this time can be selected from any temperature range of -20 to 150°C, preferably -5 to 100°C. In addition, the reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain a specific polymer with a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high, making uniform stirring difficult. Therefore, the content is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%. The reaction is initially carried out at a high concentration, and then an organic solvent can be added. [0044] In the polymerization reaction to obtain the polyimide precursor, the total molar number of the diamine component and the total molar number of the tetracarboxylic dianhydride component are preferably 0.8~1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyimide precursor produced. The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film. In the polyamide imide of the present invention, the dehydration ring-closure rate (imidization rate) of the amide acid group does not necessarily need to be 100%, and can be adjusted arbitrarily according to the use or purpose. Methods for imidizing the polyimide precursor include thermal imidization by directly heating the solution of the polyimide precursor or adding a catalyst to the solution of the polyimide precursor. acyl imidization. The temperature when the polyimide precursor is thermally imidized in the solution is 100~400°C, preferably 120~250°C, preferably the water generated by the imidization reaction on one side Remove it to the outside of the system. The catalytic imidization of the polyimide precursor can be achieved by adding an alkaline catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at -20~250°C, preferably 0~180°C. conduct. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amide acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amide acid group, preferably 3 to 30 molar times. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is particularly preferred because it has a moderate alkalinity that allows the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is particularly preferred because it is easy to purify after the reaction. The imidization rate of catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. [0046] When recovering the generated polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, the reaction solution only needs to be put into a solvent to precipitate. Solvents used for precipitation include methanol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer precipitated by being put into the solvent is filtered and recovered, and then dried under normal pressure or reduced pressure, at normal temperature or by heating. In addition, if the operation of redissolving the polymer recovered by precipitation in an organic solvent and re-precipitating and recovering the polymer is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of solvents in this case include alcohols, ketones, hydrocarbons, and the like. It is preferable to use three or more solvents selected from these solvents because the purification efficiency will further increase. The molecular weight of the specific polymer of the present invention is determined by the GPC (Gel Permeation Chromatography) method when considering the strength of the polymer film obtained therefrom, the workability when forming the polymer film, and the uniformity of the polymer film. The measured weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. [0048] <Liquid crystal alignment agent> In the liquid crystal alignment agent used in the present invention, all polymers may be the above-mentioned specific polymers, or other polymers may be mixed therewith. At this time, the content of polymers other than the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass. Examples of other polymers include a polyimide precursor obtained from a diamine component and a tetracarboxylic dianhydride component that does not contain a specific diamine, or a polyimide precursor obtained from the polyimide precursor. imine. Furthermore, polyimide precursors and polymers other than polyimide can also be cited. Specifically, acrylic polymers, methacrylic polymers, polystyrene, polyamide, etc. can be cited. [0049] The organic solvent in the liquid crystal alignment agent used in the present invention, from the perspective of coating to form a uniform polymer film, the content of the organic solvent is preferably 70 to 99 mass%. Its content can be appropriately changed according to the film thickness of the target liquid crystal alignment film. The organic solvent is not particularly limited as long as it can dissolve the above-mentioned specific polymer. More specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactamide, 2 -pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethylsulfuric acid, tetramethylurea, pyridine, dimethylsulfuric acid, hexamethylsulfuric acid, γ- Butyrolactone, 1,3-dimethyl-tetrahydroimidazolone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, cyclohexyl ketone Hexanone, ethyl carbonate, propyl carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone, etc. These can be used individually or mixed. <Additive> Among the liquid crystal alignment agents used in the present invention, it is preferable to contain a cross-linking compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group; having a compound selected from a hydroxyl group or an alkane group A cross-linking compound having at least one substituent of an oxygen group; a cross-linking compound having a polymerizable unsaturated bond (hereinafter also referred to as a cross-linking agent), etc. Cross-linking compounds with epoxy or isocyanate groups, for example, bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, isocyanuric acid tripoxypropylene Ester, tetraglycidyl aminodiphenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl Glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetyl diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-tri Fluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triepoxypropyl-p-aminophenol , tetraepoxypropyl m-xylylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2, 3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)- 1-(4-(1-(4-(2,3-epoxypropoxyphenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol, etc. The cross-linked compound having an oxetanyl group is a cross-linked compound having at least two oxetanyl groups represented by the following formula [4]. [0053] Specifically, it is a cross-linked compound represented by the following formulas [4a] to [4k]. [0054] [0055] [0056] The cross-linked compound having a cyclic carbonate group includes a cross-linked compound having at least two cyclic carbonate groups represented by the following formula [5]. Specifically, it is a crosslinking compound represented by the following formula [5-1] to formula [5-37]. [0057] [0058] [0059] [0060] [0061] [0062] [0063] [0064] In formula [5-24], n is an integer of 1~5, in formula [5-25], n is an integer of 1~5, in formula [5-36], n is an integer of 1~100 , in formula [5-37], n is an integer from 1 to 10. Furthermore, polysiloxanes having at least one structure represented by the following formulas [5-38] to formulas [5-40] can also be cited. In the formula [5-38] to the formula [5-40], R 1 , R 2 , R 3 , R 4 and R 5 are each independently the structure, hydrogen atom, and hydroxyl group represented by the formula [5]. , an alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring having 1 to 10 carbon atoms, at least one of which has a structure represented by formula [5]. Specific examples include compounds of the following formula [5-41] or formula [5-42]. In formula [5-42], n is an integer from 1 to 10. Cross-linked compounds having at least one substituent selected from the group consisting of hydroxyl or alkoxy groups, for example, amino resins having hydroxyl groups or alkoxy groups, such as melamine resin, urea resin, guanamine Resin, acetylene urea-formaldehyde resin, succinylamine-formaldehyde resin, ethylene urea-formaldehyde resin, etc. Specifically, a melamine derivative, a benzoguanamine derivative, or an acetylene urea in which the hydrogen atom of the amine group is substituted by a hydroxymethyl group, an alkoxymethyl group, or both thereof can be used. Melamine derivatives or benzoguanamine derivatives may also exist as dimers or trimers. Preferably, each triazine ring has an average of 3 to 6 hydroxymethyl or alkoxymethyl groups. Examples of such melamine derivatives or benzoguanamine derivatives include commercially available MX-750, which has an average of 3.7 methoxymethyl groups per triazine ring, and MX-750, which has an average of 3.7 methoxymethyl groups per triazine ring. Methoxy groups of MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., with an average ring substitution of 5.8 methoxymethyl groups Methylated melamine; Cymel 235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine; Cymel 506, 508, etc. butoxymethylated melamine; Cymel 1141, etc. Carboxyl-containing methoxymethylated isobutoxymethylated melamine; Cymel 1123 and other methoxymethylated ethoxymethylated benzoguanamines; Cymel 1123-10 and other methoxymethylated benzoguanamines Butoxymethylated benzoguanamine; Cymel 1128 and other butoxymethylated benzoguanamine; Cymel 1125-80 and other carboxyl-containing methoxymethylated ethoxymethylated benzene Guanamine (the above, manufactured by Mitsui Cyanamid Co., Ltd.), etc. Examples of the acetylene urea include butoxymethylated acetylene urea such as Cymel 1170; hydroxymethylated acetylene urea such as Cymel 1172; and methoxyhydroxymethylated acetylene urea such as Powderlink 1174. [0069] Benzene having a hydroxyl group or an alkoxy group, or a phenolic compound can also be exemplified as the crosslinking compound. Examples include 1,3,5-shen(methoxymethyl)benzene, 1,2,4-shen(isopropoxymethyl)benzene, and 1,4-bis(sec-butoxymethyl) Benzene or 2,6-dihydroxymethyl-p-tert-butylphenol, etc. [0070] More specifically, it is a cross-linked compound represented by the following formula [6-1] to formula [6-48]. [0071] [0072] [0073] [0074] Cross-linked compounds having polymerizable unsaturated bonds include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, Cross-linked compounds with three polymerizable unsaturated groups in the molecule such as tri(meth)acryloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate; ethylene glycol Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate ) Acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate Acrylate, propylene oxide bisphenol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, Ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diepoxypropyl phthalate di(meth)acrylate or hydroxytris Cross-linked compounds with two polymerizable unsaturated groups in the molecule such as neopentyl glycol di(meth)acrylate methylacetate; 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylic acid Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxy phthalate Propyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, glyceryl mono(meth)acrylate, 2-(meth)acryloyloxyethyl phosphate or N-hydroxymethyl (methyl) Cross-linked compounds such as acrylamide and the like having one polymerizable unsaturated group in the molecule. [0076] In addition, the compound represented by the following formula [7] can also be exemplified as the cross-linked compound. E 1 is a univalent group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorine ring, an anthracene ring or a phenanthrene ring, and E 2 is represented by the following formula A univalent base composed of [7a] or formula [7b], n is an integer from 1 to 4. [0077] The above-mentioned compounds are examples of cross-linked compounds and are not limited thereto. In addition, the crosslinking compound contained in the liquid crystal alignment agent of the present invention may be one type, or two or more types may be combined. In the liquid crystal alignment agent of the present invention, the content of the cross-linking compound is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the polymer component. In order to progress the cross-linking reaction and exhibit the target effect, Without reducing the alignment property of the liquid crystal, the amount is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass. It is preferable to add nitrogen-containing heterocyclic amine compounds represented by the following formulas [M1] to [M156] as a compound that promotes charge movement in the liquid crystal alignment film and promotes charge elimination in a liquid crystal cell using the liquid crystal alignment film. The amine compound can also be added directly to a solution of a specific polymer, but it is preferably added to a solution with a concentration of 0.1 to 10 mass %, preferably 1 to 7 mass %, using an appropriate solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve the above-mentioned specific polymer. [0079] [0080] [0081] [0082] [0083] [0084] The liquid crystal alignment agent of the present invention, as long as the effect of the present invention is not impaired, may contain an organic solvent (also known as poor solvent) or compound. Furthermore, compounds that improve the adhesion between the liquid crystal alignment film and the substrate may also be included. Specific examples of poor solvents that improve film thickness uniformity or surface smoothness are as follows. [0086] For example, isopropyl alcohol, methoxymethylpentanol, methylcelloxreo, ethylcelloxreo, butylcelloxreo, methylcellothreate acetate, ethylcelloxane Threacetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, 1-butoxy-2-propanol, 2-butoxy-1-propanol, di Propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol dimethyl ether, 3-methyl-3-methoxy acetate Butyl ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl Ether, diisobutyl ketone, 2,6-dimethyl-4-heptanol, diacetone alcohol, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n - Octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate Propyl propionate, 3-methoxybutyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1 -Phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetic acid Ester, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. have low surface tension of organic solvents. These poor solvents may be used alone or in combination of a plurality of types. When using the above-mentioned poor solvent, it is preferably 5 to 80 mass % of the total organic solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60 mass %. [0087] Compounds that improve film thickness uniformity or surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, nonionic surfactants, and the like. Specific examples include Eftop EF301, EF303, and EF352 (manufactured by Tokem Products Co., Ltd.); Megafac F171, F173, and R-30 (manufactured by Dainippon Ink Co., Ltd.); Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.); Asahiguard AG710; Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. [0088] Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds or epoxy group-containing compounds shown below. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Triethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7- Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-tris acetate Ethoxysilyl-3,6-diazanonyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-phenylmethyl-3-aminopropyltriethoxysilane , N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether Glyceryl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether Ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, etc. When using a compound that improves the adhesion with the substrate, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. . If it is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, liquid crystal alignment may be deteriorated. In the liquid crystal alignment agent of the present invention, in addition to the above-mentioned cross-linking compounds, poor solvents and compounds for improving adhesion, as long as the scope of the effect of the present invention is not impaired, it can also be added to change the dielectric constant of the liquid crystal alignment film. Or a dielectric or conductive substance for the purpose of electrical properties such as conductivity. [0090] <Liquid crystal alignment film, liquid crystal display element> The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film after being coated on a substrate and fired, and then subjected to alignment treatment such as rubbing treatment or light irradiation. In addition, in the case of vertical alignment applications, etc., it can be used as a liquid crystal alignment film without performing alignment treatment. The substrate used in this case is not particularly limited as long as it is highly transparent. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which ITO electrodes for liquid crystal driving are formed. In addition, in a reflective liquid crystal display element, if only one side of the substrate is used, an opaque substrate such as a silicon wafer can also be used. In this case, the electrode can also use a light-reflecting material such as aluminum. [0091] The coating method of liquid crystal alignment agent is generally carried out by screen printing, offset printing, flexographic printing, inkjet, etc. in industry. Other coating methods include dipping, roll coater, slit coater, spinner, etc., which can be used according to the purpose. After the liquid crystal alignment agent is coated on the substrate, the solvent can be evaporated by heating means such as a hot plate at 50 to 300°C, preferably 80 to 250°C to form a polymer film. If the thickness of the polymer film after firing is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, the thickness is preferably 5 to 300 nm, and more preferably 10~100nm. When aligning liquid crystals horizontally or obliquely, the fired polymer film is subjected to rubbing or polarized ultraviolet irradiation. [0092] The liquid crystal display element of the present invention is a liquid crystal display element that is obtained by using the above-mentioned liquid crystal alignment agent to obtain a substrate with a liquid crystal alignment film and then preparing a liquid crystal cell by a known method. An example of a method for manufacturing a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and attach the liquid crystal alignment film surface to the other substrate with the liquid crystal alignment film surface as the inner side. The method of injecting and sealing under reduced pressure; or the method of dropping liquid crystal on the surface of the liquid crystal alignment film with spacers scattered thereon, then bonding it to the substrate and sealing it, etc. A unique feature of the present invention is that the liquid crystal display panel in the liquid crystal display element has a curved surface shape. That is, one of the pair of substrates constituting the liquid crystal display panel has a curved surface, and the shape or degree of the curved surface can be various and can be selected arbitrarily. In particular, in the present invention, the cross section along one axis has a curved surface shape, which is effective for a liquid crystal display panel with a curvature radius (R) of the curved surface shape of 1000 mm to 3000 mm. [0093] Furthermore, the liquid crystal alignment agent of the present invention is formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and can also be preferably used in the following liquid crystal display elements: the liquid crystal display element is formed through a A liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is placed between the substrates, and polymerization is caused by at least one of active energy ray irradiation and heating while applying a voltage between the electrodes. Manufactured by polymerization of chemical compounds. Here, active energy rays such as ultraviolet rays are suitable. The above-mentioned liquid crystal display element controls the pretilt angle of the liquid crystal molecules through the PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of photopolymerizable compounds, such as photopolymerizable monomers, are premixed into the liquid crystal material. After assembling the liquid crystal cell, the photopolymerizable compound is irradiated with ultraviolet rays while applying a specific voltage to the liquid crystal layer. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. The alignment state of the liquid crystal molecules when the polymer is generated is also remembered after the voltage is removed. Therefore, by controlling the electric field formed in the liquid crystal layer, etc., the pretilt angle of the liquid crystal molecules can be adjusted. In addition, in the PSA method, rubbing treatment is not necessary, so it is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt angle by rubbing treatment. That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent of the present invention by the above method, a liquid crystal cell is produced, and polymerization is performed by at least one of ultraviolet irradiation and heating. The polymerization of chemical compounds can control the alignment of liquid crystal molecules. As an example of making a liquid crystal cell, a pair of substrates with a liquid crystal alignment film formed thereon is prepared. Spacers are spread on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is the inner side, and the other substrate is bonded. The method of injecting liquid crystal under reduced pressure and sealing it; or the method of dropping liquid crystal on the surface of the liquid crystal alignment film with spacers scattered thereon, and then bonding it to the substrate for sealing, etc. [0095] The liquid crystal is mixed with a polymerizable compound that is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized and alignment control of the liquid crystal cannot be performed. When it exceeds 10 parts by mass, the unreacted polymerizable compound increases and the printing characteristics of the liquid crystal display element are reduced. After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet light while applying AC or DC voltage to the liquid crystal cell. In this way, the alignment of liquid crystal molecules can be controlled. [0096] In addition, the liquid crystal alignment agent of the present invention is formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and can also be preferably used in the following liquid crystal display elements: the liquid crystal display element is formed through the aforementioned one. It is manufactured by arranging a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat between substrates, and applying a voltage between electrodes. Here, active energy rays such as ultraviolet rays are suitable. In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment agent or using a polymer containing a polymerizable group can be used. Ingredients method. Examples of the polymerizable group include polymerizable unsaturated groups such as acrylic acid group, methacrylic acid group, vinyl group, and maleimide group. [0097] Since the liquid crystal alignment agent of the present invention contains a specific amine compound having a double bond site that reacts with heat or ultraviolet irradiation, the alignment of the liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. As an example of making a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed can be prepared. Spacers are spread on the liquid crystal alignment film of one substrate, with the liquid crystal alignment film surface as the inner side, and the other substrate is bonded. The method of injecting liquid crystal under reduced pressure and sealing it; or the method of dropping liquid crystal on the surface of the liquid crystal alignment film with spacers scattered thereon, then laminating the substrate and sealing it, etc. [0098] After the liquid crystal cell is produced, the alignment of the liquid crystal molecules can be controlled by applying AC or DC voltage to the liquid crystal cell while irradiating heat or ultraviolet light. In the above manner, the liquid crystal display element produced using the liquid crystal alignment agent of the present invention has excellent reliability and can be suitably used in large-screen, high-definition LCD televisions and the like. [Examples] [0099] The following examples are given to illustrate the present invention more specifically, but are not limited thereto. Furthermore, the abbreviations used below are as follows. (Tetracarboxylic dianhydride) CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride anhydride (Diamine) 3-AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl) benzamide p-PDA: p-phenylenediamine PBCH5DAB: 1,3-diamine Amino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene PCH7DAB: 1,3-Diamino-4-[4-(trans -4-n-heptylcyclohexyl)phenoxy]benzene [0101] (Additive) (Siloxane) TEOS: tetraethoxysilane UPS: 3-ureidopropyltriethoxysilane MPMS: 3-methacryloxypropyltrimethoxysilane HTMS: hexadecyl Trimethoxysilane (organic solvent) NMP: N-methyl-2-pyrrolidinone, NEP: N-ethyl-2-pyrrolidinone BCS: Butyl cellulose, PB: Propylene glycol monobutyl ether DME: 1,2-dimethoxyethane, DPM: dipropylene glycol monomethyl ether, DMI: 1,3-dimethyl-2-tetrahydroimidazolone, HG: hexanediol [0104] <Polyimide Determination of molecular weight > The molecular weight of the polyimide in the synthesis example was measured using a room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Scientific and a column (KD-803, KD-805) manufactured by Shodex. ) is measured as follows. Column temperature: 50℃ Eluent: N,N'-dimethylformamide (lithium bromide-hydrate (LiBr･H2O) 30mmol/L, phosphoric acid･anhydrous crystal (o-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) )10ml/L as additive), flow rate: 1.0ml/min, standard sample for calibration line preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: approximately 9000,000, 150,000, 100,000, 30,000) and Polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories. <Measurement of the acyl imidization rate> The acyl imidization rate of the polyimide was measured as follows. Place 20 mg of polyimide powder into an NMR sample tube (NMR standard sampling tube φ5 manufactured by Kusano Scientific Co., Ltd.), add 0.53 ml of deuterated dimethylsyanide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic Sonic waves cause complete dissolution. This solution was measured for proton NMR at 500 MHz using an NMR meter (JNW-ECA500) manufactured by JEOL Datum Corporation. The rate of imidization is determined by using the proton from the unchanged structure before and after the imidization as the reference proton, and using the peak integration value of the proton and the NH group from the amide acid appearing around 9.5~10.0ppm. The proton wave peak integral value is obtained by the following formula. Imidization rate (%) = (1-α･x/y)×100 [0106] <Molecular weight measurement> The molecular weight of polyimide and polysiloxane was measured using a column made by Shodex Co., Ltd. (sample side KF -803, reference side KF-800RH), measure as follows. Column temperature: 40°C, eluent: tetrahydrofuran, flow rate: 1 ml/min, standard sample for calibration line preparation: polystyrene manufactured by Shodex (molecular weight: approximately 52,400, 19,900, 7,200, 2,970, 580). <Synthetic Example 1> BODA (23.64g, 94.5mmol), p-PDA (5.11g, 47.3mmol), 3-AMPDA (16.0g, 66.15mmol) and DA-1 (32.86g, 75.6mmol) Mix in NMP (216.0g), react at 80°C for 5 hours, add CBDA (18.53g, 94.5mmol) and NMP (94.6) g, and react at 40°C for 6 hours to obtain a polyamic acid solution. NMP (62.3g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.02g) and pyridine (1.87g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (601.0 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (A). The imidization rate of this polyimide is 75%, Mn (number average molecular weight) is 13,200, and Mw (weight average molecular weight) is 40,600. <Synthesis Example 2> BODA (23.64g, 94.5mmol), p-PDA (5.11g, 47.3mmol), 3-AMPDA (16.0g, 66.15mmol), DA-1 (16.43g, 37.8mmol) and DA-8 (14.39g, 37.8mmol) were mixed in NMP (207.8g), reacted at 80°C for 5 hours, then added CBDA (18.53g, 94.5mmol) and NMP (94.6)g, and reacted at 40°C for 6 hours. A polyamide solution was obtained. NMP (62.3g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.15g) and pyridine (1.90g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (602.1 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (B). The imidization rate of this polyimide is 75%, Mn is 12,900, and Mw is 40,400. <Synthetic Example 3> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol), DA-2 (16.60g, 37mmol) and DA-8 (16.08g, 37mmol) were added to NMP (170.7g), mixed at 80°C for 5 hours, then added CBDA (17.76g, 90.7mmol) and NMP (92.6)g, and reacted at 40°C for 6 hours to obtain a polyamic acid solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (C). The polyimide has an imidization rate of 75%, Mn of 11,800, and Mw of 39,600. <Synthetic Example 4> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol), DA-3 (17.1g, 37mmol) and DA-8 (14.08g, 37mmol) were dissolved in NMP (170.7g), mixed at 80°C for 5 hours, then added CBDA (17.78g, 90.7mmol) and NMP (92.6)g, and reacted at 40°C for 6 hours to obtain a polyamic acid solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (D). The imidization rate of this polyimide is 75%, Mn is 11,900, and Mw is 40,100. <Synthetic Example 5> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol) and DA-4 (34.1g, 74mmol) were mixed in NMP (170.7g) and reacted at 80°C After 5 hours, CBDA (17.78g, 90.7mmol) and NMP (92.6)g were added, and the mixture was reacted at 40° C. for 6 hours to obtain a polyamic acid solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (E). The imidization rate of this polyimide is 75%, Mn is 14,100, and Mw is 41,000. <Synthetic Example 6> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol) and DA-5 (28.6g, 74mmol) were mixed in NMP (255g) and reacted at 80°C for 5 Hours later, CBDA (17.78g, 90.7mmol) and NMP (92.6)g were added, and the mixture was reacted at 40° C. for 6 hours to obtain a polyamide solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (F). The imidization rate of this polyimide is 75%, Mn is 11,900, and Mw is 40,000. <Synthetic Example 7> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol) and DA-6 (33.0g, 74mmol) were mixed in NMP (272.8g) and reacted at 80°C After 5 hours, CBDA (17.78g, 90.7mmol) and NMP (71.1)g were added, and the mixture was reacted at 40° C. for 6 hours to obtain a polyamic acid solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (G). The imidization rate of this polyimide is 75%, Mn is 11,400, and Mw is 39,000. <Synthetic Example 8> BODA (23.14g, 88.8mmol), m-PDA (12.00g, 111mmol) and DA-7 (33.0g, 74mmol) were mixed in NMP (272.8g) and reacted at 80°C After 5 hours, CBDA (17.78g, 90.7mmol) and NMP (71.1)g were added, and the mixture was reacted at 40° C. for 6 hours to obtain a polyamic acid solution. NMP (87.1g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.95g) and pyridine (2.15g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (462.6 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (H). The polyimide has an imidization rate of 75%, Mn of 15,700, and Mw of 41,200. <Synthesis Example 9> In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 24.9 g of HG, 24.9 g of BCS, 52.5 g of TEOS, and 11.2 g of HTMS were mixed to prepare a solution of an alkoxysilane monomer. A solution containing 8.5 g of HG, 8.5 g of BCS, 16.2 g of water, and 0.8 g of oxalic acid as a catalyst was added dropwise to the solution at room temperature for 30 minutes, and the mixture was further stirred at room temperature for 30 minutes. After heating and refluxing in an oil bath for 30 minutes, a mixture of 0.86g of a methanol solution with a UPS content of 92% by mass, 0.86g of HG, and 0.86g of BCS was added in advance. The solution was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (I) with a concentration of 12% by weight in terms of SiO 2 . The polysiloxane has an Mn of 5,100 and an Mw of 9,100. <Synthesis Example 10> In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG 21.3g, BCS 21.3g, TEOS 52.5g, and 18.4g of compound 3 were mixed to prepare an alkoxysilane monomer. solution. A solution containing 8.5 g of HG, 8.5 g of BCS, 16.2 g of water, and 0.8 g of oxalic acid as a catalyst was added dropwise to the solution at room temperature for 30 minutes, and the mixture was further stirred at room temperature for 30 minutes. After heating and refluxing in an oil bath for 30 minutes, a mixture of 0.86g of a methanol solution with a UPS content of 92% by mass, 0.86g of HG, and 0.86g of BCS was added in advance. The solution was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (J) with a concentration of 12% by weight in terms of SiO 2 . The polysiloxane has an Mn of 2,400 and a Mw of 4,800. <Comparative synthesis example 1> BODA (23.64g, 94.5mmol), p-PDA (5.11g, 47.3mmol), 3-AMPDA (16.0g, 66.15mmol) and DA-8 (28.77g, 75.6mmol) ) was mixed with NMP (199.6g), and after reacting at 80°C for 5 hours, CBDA (18.53g, 94.5mmol) and NMP (94.6)g were added, and the mixture was reacted at 40°C for 6 hours to obtain a polyamic acid solution. NMP (62.3g) was added to the polyamide solution (30.0g) and diluted to 6% by mass. Acetic anhydride (6.29g) and pyridine (1.95g) were added as imidization catalysts at 80 ℃ reaction for 3 hours. The reaction solution was poured into methanol (603.2g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder (D). The polyimide has an imidization rate of 75%, Mn of 13,200, and Mw of 39,300. <Example 1> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [1]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 2> NEP (54.0 g) was added to the polyimide powder (B) (6.0 g) obtained in Synthesis Example 2, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [2]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 3> NEP (54.0 g) was added to the polyimide powder (C) (6.0 g) obtained in Synthesis Example 3, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [3]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 4> NEP (54.0 g) was added to the polyimide powder (D) (6.0 g) obtained in Synthesis Example 4, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [4]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 5> NEP (54.0 g) was added to the polyimide powder (E) (6.0 g) obtained in Synthesis Example 5, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [5]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 6> NEP (54.0 g) was added to the polyimide powder (F) (6.0 g) obtained in Synthesis Example 6, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [7]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 7> NEP (54.0 g) was added to the polyimide powder (G) (6.0 g) obtained in Synthesis Example 7, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [7]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 8> NEP (54.0 g) was added to the polyimide powder (H) (6.0 g) obtained in Synthesis Example 8, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [8]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 9> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. PB (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [9]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 10> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. DME (40.0g) was added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [10]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 11> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (30.0g) and DME (10.0g) were added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [11]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 12> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (30.0g) and DPM (10.0g) were added to this solution and stirred for 5 hours to obtain a liquid crystal alignment agent [12]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 13> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to the solution, and after stirring for 5 hours, compound 1 powder (0.6g) was added and stirred for 24 hours to obtain a liquid crystal alignment agent [13]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 14> NEP (54.0g) was added to the polyimide powder (A) (6.0g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to the solution, and after stirring for 5 hours, compound 2 powder (0.6g) was added and stirred for 24 hours to obtain a liquid crystal alignment agent [14]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 15> NEP (54.0 g) was added to the polyimide powder (A) (6.0 g) obtained in Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution, and after stirring for 5 hours, compound 1 powder (0.3g) and compound 2 powder (0.3g) were added, and the mixture was stirred for 24 hours to obtain a liquid crystal alignment agent [15]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Example 16> 10.0 g of the polysiloxane solution (I) obtained in Synthesis Example 9, 15.0 g of HG, and 15.0 g of BCS were mixed to obtain a liquid crystal alignment agent [10]. It was confirmed that no abnormalities such as turbidity or precipitation were observed in the liquid crystal alignment agent. <Example 17> 10.0 g of the polysiloxane solution (J) obtained in Synthesis Example 10, 15.0 g of HG, and 15.0 g of BCS were mixed to obtain a liquid crystal alignment agent [17]. It was confirmed that no abnormalities such as turbidity or precipitation were observed in the liquid crystal alignment agent. <Comparative Example 1> NEP (54.0 g) was added to the polyimide powder (K) (6.0 g) obtained in Comparative Synthesis Example 1, and stirred at 70° C. for 40 hours to dissolve. BCS (40.0g) was added to this solution and stirred at 50°C for 15 hours to obtain a liquid crystal alignment agent [18]. No abnormalities such as turbidity or precipitation were seen in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. <Preparation of a substrate with a polyimide coating> Each liquid crystal alignment agent obtained in the above-mentioned Examples 1 to 17 and Comparative Example 1 was spin-coated on the ITO of a 3 cm × 4 cm ITO-attached glass substrate. The surface was fired on a hot plate at 70°C for 1 minute and 30 seconds, and then fired in an infrared heating furnace at 230°C for 30 minutes to prepare a substrate with a polyimide coating film with a film thickness of 100 nm. Furthermore, in the case of the liquid crystal alignment agent obtained in Example 16, the heating on the hot plate was performed at 80°C for 3 minutes instead of at 70°C for 1 minute and 30 seconds, and the other conditions were the same. <Evaluation of Highlights> The substrate of the agglomerated polyimide coating film obtained in the above-mentioned Example 1 and Comparative Example 1 was mounted on UMT-2 manufactured by Bruker AXS (the sensor was FVL, and the device tip was mounted with a 1.6 mm Sapphire ball), conduct a scratch test from 1mN to 20mN for 100 seconds at a horizontal axis of 0.5mm (5mm/second) and a moving direction of 2mm, and then drop MLC-3022 (Merck Japan). On another substrate of the agglomerated imide coating film obtained above, spacers of 4 μm were spread and sandwiched toward the side where the MLC-3022 was dropped. The sandwiched substrate was observed with the polarizing plate of a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon) at 90°, and the area where the scratch test was performed was observed to see whether light was transmitted. A condition in which few bright spots are visible is evaluated as "○" as shown in Figure 1, a condition in which a few bright spots are visible as in Figure 2 is evaluated as "△", and a condition in which a scratched area becomes a bright spot is evaluated as shown in Figure 3 is "×", and the results are shown in Table 1. [0136] In addition, the entire contents of the specification, patent scope, drawings and abstract of Japanese Patent Application No. 2016-153149 filed on August 3, 2016 are quoted here and incorporated into the disclosure of the specification of the present invention.

[0009] 　　[圖1] 以偏光顯微鏡觀察使用實施過刮痕試驗(於實施例詳述)之附聚醯亞胺塗膜之基板所製作的液晶晶胞之照片。該照片中，於進行過刮痕試驗之部位幾乎未見到亮點。 　　[圖2] 以偏光顯微鏡觀察使用上述實施過刮痕試驗之附聚醯亞胺塗膜之基板所製作的液晶晶胞之照片。該照片中，可知光由進行過刮痕試驗之部位透過，而成為亮點。[Fig. 1] A photograph of a liquid crystal cell produced using a substrate with a polyimide coating film that has been subjected to a scratch test (described in detail in the examples) observed with a polarizing microscope. In this photo, almost no bright spots can be seen in the area where the scratch test was performed. [Figure 2] A photograph of a liquid crystal cell produced using a substrate with a polyimide coating that has been subjected to the scratch test and observed with a polarizing microscope. In this photo, it can be seen that light passes through the area where the scratch test was performed and becomes a bright spot.

Claims (2)

一種液晶顯示元件，其具備具有由含有聚合物之液晶配向劑所得到的液晶配向膜之曲面液晶面板；該聚合物為選自由含有下述式[2]表示之二胺的二胺與含有下述式[3]表示之四羧酸二酐的四羧酸二酐成分之反應物的聚醯亞胺前驅體及聚醯亞胺所成之群的至少1種聚合物；
Figure 106126202-A0305-02-0070-1
 (Y1為單鍵、-(CH2)a-(a為1~15之整數)、-O-、-CH2O-、-COO-或OCO-，Y2為單鍵或(CH2)b-(b為1~15之整數)，Y3為單鍵、-(CH2)c-(c為1~15之整數)、-O-、-CH2O-、-COO-或OCO-；Y4為選自由苯環、環己烷環及雜環所成之群的環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，或由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基，Y5為選自由苯環、環己烷環及雜環所成之群的2價環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，Y4為選自由苯環、環己烷環及雜環所成之群的環狀基時，n為2~4之整數，Y4為由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基時，n為0~4之整數；又，n為複數個時，複數個Y5係分別獨立地具有上述定 義；Y6為碳數1~18之烷基、碳數1~18之含氟烷基、碳數1~18之烷氧基或碳數1~18之含氟烷氧基，m為1~4之整數)；
Figure 106126202-A0305-02-0071-2
 (Z1為由以下結構式中選出的至少1種)；
Figure 106126202-A0305-02-0071-3
 (Z2~Z5，係分別獨立地為由氫原子、甲基、氯原子或苯環中選出之基)。 A liquid crystal display element provided with a curved liquid crystal panel having a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer; the polymer is selected from a diamine containing a diamine represented by the following formula [2] and a diamine containing the following At least one polymer consisting of a polyimide precursor and a polyimide, which is a reactant of the tetracarboxylic dianhydride component of the tetracarboxylic dianhydride represented by the formula [3];
Figure 106126202-A0305-02-0070-1
 (Y 1 is a single bond, -(CH 2 ) a -(a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-, Y 2 is a single bond or (CH 2 ) b -(b is an integer from 1 to 15), Y 3 is a single bond, -(CH 2 ) c -(c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-; Y 4 is a cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be replaced by an alkyl group with 1 to 3 carbon atoms, Alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or a fluorine atom substituted), or substituted with an alkoxy group with 12 to 25 carbon atoms with a steroid skeleton. A divalent organic group selected from organic groups, Y 5 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be Alkyl group with 1 to 3 carbon atoms, alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom substitution), Y 4 is When a cyclic group is selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, n is an integer from 2 to 4, and Y 4 is 2 selected from an organic group with a carbon number of 12 to 25 having a steroid skeleton. When n is a valent organic group, n is an integer from 0 to 4; when n is a plurality, the plural Y 5s independently have the above definitions; Y 6 is an alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18 Fluorine-containing alkyl group, alkoxy group with 1 to 18 carbon atoms or fluorine-containing alkoxy group with 1 to 18 carbon atoms, m is an integer from 1 to 4);
Figure 106126202-A0305-02-0071-2
 (Z 1 is at least one selected from the following structural formulas);
Figure 106126202-A0305-02-0071-3
 (Z 2 ~ Z 5 are independently selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring). 一種液晶配向劑，其係用於具備具有曲面形狀之液晶面板的液晶顯示元件之液晶配向劑，其特徵為含有選自由含有下述式[2]表示之二胺的二胺與含有下述式[3]表示之四羧酸二酐的四羧酸二酐成分之反應物的聚醯亞胺前驅體及聚醯亞胺所成之群的至少1種聚合物；
Figure 106126202-A0305-02-0072-5
 (Y1為單鍵、-(CH2)a-(a為1~15之整數)、-O-、-CH2O-、-COO-或OCO-，Y2為單鍵或(CH2)b-(b為1~15之整數)，Y3為單鍵、-(CH2)c-(c為1~15之整數)、-O-、-CH2O-、-COO-或OCO-；Y4為選自由苯環、環己烷環及雜環所成之群的環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，或由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基，Y5為選自由苯環、環己烷環及雜環所成之群的2價環狀基(此等環狀基上之任意氫原子，亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代)，Y4為選自由苯環、環己烷環及雜環所成之群的環狀基時，n為2~4之整數，Y4為由具有類固醇骨架之碳數12~25之有機基中選出的2價有機基時，n為0~4之整數；又，n為複數個時，複數個Y5係分別獨立地具有上述定義；Y6為碳數1~18之烷基、碳數1~18之含氟烷基、碳數1~18之烷氧基或碳數1~18之含氟烷氧基，m為1~4之整數)；
Figure 106126202-A0305-02-0072-6
 (Z1為由以下結構式中選出的至少1種)；
Figure 106126202-A0305-02-0073-7
 (Z2~Z5，係分別獨立地為由氫原子、甲基、氯原子或苯環中選出之基)。 A liquid crystal alignment agent for use in a liquid crystal display element having a liquid crystal panel having a curved surface shape, characterized by containing a diamine selected from a diamine represented by the following formula [2] and a diamine containing the following formula [3] At least one polymer consisting of a polyimide precursor and a polyimide, which is a reactant of the tetracarboxylic dianhydride component;
Figure 106126202-A0305-02-0072-5
 (Y 1 is a single bond, -(CH 2 ) a -(a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-, Y 2 is a single bond or (CH 2 ) b -(b is an integer from 1 to 15), Y 3 is a single bond, -(CH 2 ) c -(c is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-; Y 4 is a cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be replaced by an alkyl group with 1 to 3 carbon atoms, Alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or a fluorine atom substituted), or substituted with an alkoxy group with 12 to 25 carbon atoms with a steroid skeleton. A divalent organic group selected from organic groups, Y 5 is a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic ring (any hydrogen atom on these cyclic groups can also be Alkyl group with 1 to 3 carbon atoms, alkoxy group with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms or fluorine atom substitution), Y 4 is When a cyclic group is selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, n is an integer from 2 to 4, and Y 4 is 2 selected from an organic group with a carbon number of 12 to 25 having a steroid skeleton. When n is a valent organic group, n is an integer from 0 to 4; when n is a plurality, the plural Y 5s independently have the above definitions; Y 6 is an alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18 Fluorine-containing alkyl group, alkoxy group with 1 to 18 carbon atoms or fluorine-containing alkoxy group with 1 to 18 carbon atoms, m is an integer from 1 to 4);
Figure 106126202-A0305-02-0072-6
 (Z 1 is at least one selected from the following structural formulas);
Figure 106126202-A0305-02-0073-7
 (Z 2 ~ Z 5 are independently selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring).
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