TW201823311A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

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

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TW201823311A
TW201823311A TW106133522A TW106133522A TW201823311A TW 201823311 A TW201823311 A TW 201823311A TW 106133522 A TW106133522 A TW 106133522A TW 106133522 A TW106133522 A TW 106133522A TW 201823311 A TW201823311 A TW 201823311A
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crystal alignment
alignment agent
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TWI745441B (en
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相馬早紀
森本佳道
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日商日產化學工業股份有限公司
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    • 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
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    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

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Abstract

Provided are: a liquid crystal alignment agent whereby a liquid crystal alignment film is obtained which has an excellent voltage holding ratio and fast relaxation of stored charge, and in which flickering is not prone to occur during driving thereof; a liquid crystal alignment film; and a liquid crystal display element. A liquid crystal alignment agent characterized by containing an organic solvent and a polymer obtained from a diamine having the structure represented by formula (1). (In the formula, R1 and R2 are hydrogen atoms or monovalent organic groups, any hydrogen atom in a benzene ring may be substituted with an organic group, and * represents a bonding site).

Description

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

[0001] 本發明為有關使用新穎聚合物之液晶配向劑、液晶配向膜及使用其之液晶顯示元件者。[0001] The present invention relates to a liquid crystal alignment agent using a novel polymer, a liquid crystal alignment film, and a liquid crystal display element using the same.

[0002] 液晶顯示元件，被廣泛地使用作為個人電腦、可攜式電話、智慧型手機、電視等的顯示部份。液晶顯示元件，例如，具備有挾夾於元件基板與濾色器基板之間的液晶層、對液晶層施加電場的畫素電極及共通電極、控制液晶層的液晶分子之配向性的配向膜、開閉對畫素電極供應電氣信號的薄膜電晶體(TFT)等。液晶分子之驅動方式，已知可列舉如，TN方式、VA方式等縱向電場方式，或IPS方式、FFS方式等的橫向電場方式等。僅於基板的單側形成電極，而將電場施加於與基板平行之方向的橫向電場方式，相較於以往將電壓施加於形成於上下基板的電極，而驅動液晶的縱向電場方式，已知有具有寬廣的視角特性，且可以高品質顯示的液晶顯示元件。 　　[0003] 因橫向電場方式的液晶晶格為具有優良的視角特性，但因形成於基板內的電極部份較少，故電壓保持率較低時，液晶無法受到充分的電壓時，將會使顯示之對比降低。又，液晶配向之安定性較低時，於長時間驅動液晶之際，液晶將無法回復至初期狀態，此點亦為對比降低或造成殘像之原因，故液晶配向之安定性為極重要之因素。此外，因靜電容易蓄積於液晶晶格內，經驅動所產生的正負非對稱電壓之施加，也會使電荷蓄積於液晶晶格內，該些之蓄積之電荷，會造成液晶配向之紊亂，或以殘像方式影響顯示內容，而使液晶元件的顯示之品質顯著降低。又，驅動後立即使用背光源光線照射液晶晶格時，也會造成電荷蓄積，而會發生即使短時間之驅動也會產生殘像，驅動中閃爍(flicker)的大小發生變化的問題。 　　[0004] 使用該些橫向電場方式的液晶顯示元件之際，對於具有優良電壓保持率，且可降低電荷蓄積的液晶配向劑，專利文獻1中，揭示一種含有特定二胺與脂肪族四羧酸衍生物之液晶配向劑。但，伴隨液晶顯示元件的高性能化，液晶配向膜所要求之特性亦日漸嚴苛，故該些之以往技術要全部滿足所要求的特性上，仍存在著困難性。 [先前技術文獻] [專利文獻] 　　[0005] [專利文獻1] 國際公開公報WO2004／021076號公報[0002] Liquid crystal display elements are widely used as display parts for personal computers, portable phones, smart phones, and televisions. The liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) or the like that supplies electrical signals to the pixel electrodes is opened and closed. As the driving method of the liquid crystal molecules, a vertical electric field method such as a TN method or a VA method or a lateral electric field method such as an IPS method or an FFS method is known. It is known to form an electrode only on one side of a substrate and apply an electric field to a transverse electric field direction parallel to the substrate. Compared with a conventional method of applying a voltage to electrodes formed on upper and lower substrates to drive a liquid crystal, a vertical electric field method is known. A liquid crystal display element with a wide viewing angle and high-quality display. [0003] Since the liquid crystal lattice of the transverse electric field method has excellent viewing angle characteristics, but because there are fewer electrode portions formed in the substrate, when the voltage retention is low and the liquid crystal cannot receive a sufficient voltage, it will cause The contrast of the display is reduced. In addition, when the stability of the liquid crystal alignment is low, when the liquid crystal is driven for a long time, the liquid crystal will not be able to return to the initial state. This is also the reason for the decrease in contrast or the afterimage, so the stability of the liquid crystal alignment is extremely important. factor. In addition, static electricity is easily accumulated in the liquid crystal lattice, and the application of positive and negative asymmetric voltages generated by the driving will also cause charges to be accumulated in the liquid crystal lattice. These accumulated charges will cause the disorder of liquid crystal alignment, or The display content is affected by the afterimage method, and the display quality of the liquid crystal element is significantly reduced. In addition, when the liquid crystal lattice is irradiated with backlight light immediately after driving, charge accumulation may also occur, and even after a short period of driving, an afterimage may occur, and the size of flicker during driving may change. [0004] When these liquid crystal display elements of the lateral electric field method are used, for a liquid crystal alignment agent that has an excellent voltage retention and can reduce charge accumulation, Patent Document 1 discloses a liquid crystal alignment agent containing a specific diamine and an aliphatic tetracarboxylic acid. Derivative liquid crystal alignment agent. However, with the increase in the performance of liquid crystal display elements, the characteristics required for liquid crystal alignment films are becoming increasingly severe. Therefore, it is still difficult for these conventional technologies to fully meet the required characteristics. [Prior Art Documents] [Patent Documents] [0005] [Patent Documents 1] International Publication WO2004 / 021076

[發明所欲解決之問題] 　　[0006] 本發明則以提供一種可製得具有優良電壓保持率、快速緩和蓄積電荷、驅動中不易引起閃爍(flicker)的液晶配向膜之液晶配向劑、液晶配向膜，及液晶顯示元件為目的。 [解決問題之方法] 　　[0007] 本發明者們，對於解決上述問題，經過深入研究結果，發現於液晶配向劑中所含的聚合物中，導入特定之結構時，即可同時改善各種的特性，因而完成本發明。 　　[0008] 本發明，基於上述之瞭解，而提出下述之要點。 　　1. 一種液晶配向劑，其特徵為，含有由具有下述式(1)所表示之結構的二胺所製得之聚合物，與有機溶劑；(式(1)中，R1 、R2 為氫原子，或一價之有機基。苯環中的任意氫原子可被一價之有機基所取代。＊表示鍵結部位)。 　　2. 如前述1記載之液晶配向劑，其中，前述聚合物為由，具有前述式(1)所表示之結構的二胺與四羧酸二酐之聚縮合物的聚醯亞胺前驅體，及其醯亞胺化物的聚醯亞胺所成之群所選出之至少1種的聚合物。 　　3. 如前述1或2記載之液晶配向劑，其中，前述二胺為以下式(2)所表示者；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容，R3 各自獨立表示單鍵或以下式(3)之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)。(式(3)中，R4 表示由單鍵、-O-、-COO-、-OCO-、 -(CH2 )l -、-O(CH2 )m O-、-CONH-，及-NHCO-所選出的2價之有機基(l、m表示1～5之整數)；＊1 表示與式(2)中的苯環鍵結之部位、＊2 表示與式(2)中的胺基鍵結之部位)。 　　4. 如前述1～3記載之液晶配向劑，其中，前述聚醯亞胺前驅體具有下述式(4)所表示之結構：(式(4)中，X1 為由四羧酸衍生物所產生的4價之有機基，Y1 為由前述式(1)所表示的二胺所產生的2價之有機基，R5 為氫原子或碳數1～5之烷基)。 　　5. 如前述4記載之液晶配向劑，其於前述式(6)中，X1 為由下述(A-1)～(A-21)所表示之結構所成之群所選出的至少1種。 　　6. 如前述4或5記載之液晶配向劑，其中，具有前述式(4)所表示之結構單位的聚合物，相對於液晶配向劑所含的全聚合物，為含有10莫耳%以上。 　　7. 如前述1～6中任一項記載之液晶配向劑，其中，前述有機溶劑為含有由4-羥基-4-甲基-2-戊酮及二乙二醇二乙醚所成之群所選出之至少1種。 　　8. 一種液晶配向膜，其特徵為，使用前述1～7中任一項記載之液晶配向劑而製得者。 　　9. 一種液晶顯示元件，其特徵為，具備前述8記載之液晶配向膜。 　　10. 如前述9記載之液晶顯示元件，其中，液晶顯示元件為橫向電場驅動方式者。 　　11. 一種聚合物，其特徵為，由具有下述式(1)所表示之結構的二胺與四羧酸二酐之聚縮合物的聚醯亞胺前驅體及其醯亞胺化物的聚醯亞胺所成之群所選出之至少1種；(式(1)中，R1 ，R2 為氫原子，或一價之有機基。苯環中的任意氫原子可被一價之有機基所取代。＊表示鍵結部位)。 　　12. 如前述11記載之聚合物，其中，上述二胺為以下式(2)所表示者；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容，R3 各自獨立為單鍵，或具有以下式(3)所表示之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)。(式(3)中，R4 表示由單鍵、-O-、-COO-、-OCO-、 -(CH2 )l -、-O(CH2 )m O-、-CONH-，及-NHCO-所選出的2價之有機基(l、m表示1～5之整數)；＊1 表示與式(2)中的苯環鍵結之部位、＊2 表示與式(2)中的胺基鍵結之部位)。(式(4)中，X1 為由四羧酸衍生物所產生的4價之有機基，Y1 為由前述式(1)所表示的二胺所產生的2價之有機基，R5 為氫原子或碳數1～5之烷基)。 　　14. 如前述13記載之聚合物，其中，前述式(6)中，X1 為由下述(A-1)～(A-21)所表示之結構所成之群所選出的至少1種。 　　15. 一種下述式(2)所表示之二胺；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容，R3 各自獨立為單鍵，或具有以下式(3)所表示之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)。 [發明之效果] 　　[0009] 使用本發明之液晶配向劑時，可提供一種具有可快速緩和蓄積電荷、不易於驅動中引起閃爍(flicker)的液晶配向膜及優良顯示特性的液晶顯示元件。 　　本願發明可解決上述問題之理由，雖仍未確定，但推測應為以下機制所得之效果。本發明之液晶配向劑所含有的聚合物中，所具有的上述(1)所表示之二胺，因導電性吡咯環與苯環具有共軛之結構，故由該液晶配向劑所形成的液晶配向膜，可使元件驅動時所施加的電荷之移動更為容易，故推測其為可促進緩和蓄積電荷之理由。 [實施發明之形態] 　　[0010] ＜特定二胺＞ 　　本發明之液晶配向劑為含有，由具有下述式(1)結構的二胺(本發明中，亦稱為特定二胺)所得之聚合物。[0011] 上述式(1)中，R1 、R2 ，係如上述之定義。其中，R1 、R2 又以具有碳數1～3的烷基、烯基、烷氧基、氟烷基、氟烯基，或氟烷氧基為佳，特別是以氫原子，或甲基為佳。又，＊表示與胺基、取代胺基、其他有機基等鍵結之部位。 　　[0012] 特定二胺中，如下述式(1-1)所示般，相對於2個苯環的吡咯環之鍵結位置，就電荷移動之觀點，以其中至少1個鍵結於吡咯環上的氮原子所相鄰的碳原子上為佳。[0013] 上述特定二胺，例如，可以下述式(1-2)表示，特別是以下述式(1-3)所表示之二胺為佳，又以式(1-4)所表示之二胺為較佳。該些之式中，＊表示鍵結部位。 　　[0014][0015] 式(1-2)～式(1-4)中，R1 及R2 之定義與前述式(1)之情形為相同，Q1 、Q2 ，各自獨立為單鍵或2價之有機基，即，Q1 與Q2 可為互相相異的結構。又，式(1-4)中，2個Q2 可為互相相異的結構。又，苯環的任意氫原子，與上述式(1)之情形相同般，可被一價之有機基所取代。 　　[0016] 上述特定二胺之較佳例示，可列舉如，下述式(2)所表示之二胺等，更佳為式(2-1)所表示之二胺。[0017] 式(2)中，R1 及R2 之定義，與上述式(1)為相同內容，R3 各自獨立表示單鍵或以下式(3)之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代。(式(3)中，R4 表示由單鍵、-O-、-COO-、-OCO-、 -(CH2 )l -、-O(CH2 )m O-、-CONH-，及-NHCO-所選出的2價之有機基(l、m表示1～5之整數)；＊1 表示與式(2)中的苯環鍵結之部位、＊2 表示與式(2)中的胺基鍵結之部位)。 　　式(2)及式(2-1)中，n表示1～3之整數；較佳為1或2。 　　[0018] 上述式(2)的二胺之具體例，可列舉如以下之例示，但並非限定於該內容。其中，就緩和蓄積電荷之觀點，以(2-1-1)、(2-1-2)、(2-1-3)、(2-1-4)、(2-1-5)、(2-1-8)、(2-1-9)、(2-1-10)、(2-1-11)或(2-1-12)為佳，以(2-1-1)、(2-1-2)、(2-1-3)、(2-1-4)、(2-1-5)、(2-1-11)或(2-1-12)為特佳。 　　[0019][0020] ＜特定二胺之合成方法＞ 　　本發明之特定二胺之合成方法並未有特別之限定，例如，可先合成下述式(1)所表示之二硝基化合物，再將硝基還原變換為胺基之方法等。(R1 、R2 及R3 表示氫，或一價之有機基)。 　　[0021] 該還原反應所使用的觸媒，以可以市售品方式取得的活性碳擔持金屬為佳，例如，鈀-活性碳、鉑-活性碳、銠-活性碳等。又，該觸媒，亦可為氫氧化鈀、氧化鉑、拉尼鎳等非活性碳擔持型的金屬觸媒亦可。特別是以鈀-活性碳可得到良好的結果，而為較佳。 　　為使還原反應更有效果地進行，亦可於與活性碳共存下實施反應。此時，所使用的活性碳的量並未有特別之限定，對於二硝基化合物，一般以1～30質量%之範圍為佳，以10～20質量%為較佳。基於相同之理由，亦可實施於加壓下進行反應之情形。該情形中，為避免苯核之還原，以於低於20氣壓為止的加壓範圍內進行為佳，以至10氣壓為止的加壓範圍內進行者為較佳。 　　[0022] 溶劑，只要不會與各原料反應之溶劑時，並無任何限制，皆可使用。例如，可使用非質子性極性有機溶劑(DMF、DMSO、DMAc、NMP等)；醚類(Et2 O、i-Pr2 O、TBME、CPME、THF、二噁烷等)；脂肪族烴類(戊烷、己烷、庚烷、石油醚等)；芳香族烴類(苯、甲苯、二甲苯、三甲苯、氯苯、二氯苯、硝基苯、四氫萘等)；鹵素系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等)；低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等)；腈類(乙腈、丙腈、丁腈等)；等。該些溶劑，可於考慮引起反應之容易度等後，作適當的選擇使用，亦可使用2種以上混合而得者。必要時，可使用適當的脫水劑或乾燥劑將溶劑乾燥，作為非水溶劑方式使用。 　　溶劑之使用量(反應濃度)，相對於二硝基化合物，以0.1～10質量倍為佳，以0.5～30質量倍為較佳，以1～10質量倍為特佳。反應溫度並未有特別之限定，通常為-100℃起至所使用的溶劑之沸點為止之範圍，較佳為-50～150℃。反應時間、通常為0.05～350小時，較佳為0.5～100小時。 　　[0023] 另一方面，合成硝基化合物(A-1)之方法並未有特別之限制，於化合物(A-1)的胺基之取代位置為第2位及第4位之情形，例如，可將下述式(A-2)所表示之二胺與具有硝基之鹵化芳基，於鹼存在下，必要時，於添加劑之存在下進行反應而可製得(X表示F、Cl、Br、I，或OTf)。[0024] 上述具有硝基之鹵化芳基中，X為F或Cl，且，NO2 基相對於X為第2位，或第4位時，可於鹼存在下，使鹵化芳基與脂肪族胺化合物進行反應，而可製得化合物(A-1)。所使用之鹼，例如，可使用碳酸氫鈉、碳酸氫鉀、磷酸鉀、碳酸鈉、碳酸鉀、碳酸鋰、碳酸銫等之無機鹼、三甲胺、三乙胺、三丙胺、三異丙胺、三丁胺、二異丙基乙胺、吡啶、喹啉、柯林鹼等之胺類，或氫化鈉、氫化鉀等。反應溶劑、反應溫度則依前述記載為準。生成物，可經由再結晶、蒸餾、二氧化矽凝膠管柱色層分析等純化。 　　[0025] X為Br或I時，NO2 基相對於X，可為第2位或第3位或第4位皆可，可於適當的金屬觸媒、配位基，或鹼存在下，使用C-N交叉耦合反應時，亦可製得二硝基體。金屬觸媒之例，可列舉如，乙酸鈀、氯化鈀、氯化鈀-乙腈錯合物、鈀-活性碳、雙(二亞苄基丙酮)鈀、參(二亞苄基丙酮)二鈀、雙(乙腈)二氯鈀、雙(苯腈)二氯鈀、CuCl、CuBr、CuI、CuCN等，但並不限定於該些內容。配位基之例，可列舉如，三苯基次膦(phosphine)、三-o-甲苯基次膦、二苯基甲基次膦、苯基二甲基次膦、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,1’-雙(二苯基膦基)二茂鐵、三甲基亞磷酸酯、三乙基亞磷酸酯、三苯基亞磷酸酯、三-tert-丁基次膦(phosphine)等，但並不限定於該些內容。鹼之例，例如可使用前述之鹼。反應溶劑、反應溫度，係依前述之記載為準。生成物可經由再結晶、蒸餾、二氧化矽凝膠管柱色層分析等予以純化。 　　[0026] 又，合成化合物(A-2)之方法並未有特別之限制，例如，先合成下述式(A-3)所表示之二胺，再於NH2 基中導入R1 、R3 之方法等。導入R1 、R3 時，只要為可與胺類進行反應之化合物即可，例如，酸鹵化物、酸酐、異氰酸酯類、環氧類、氧環丁烷類、鹵化芳基類、鹵化烷基類等。又，亦可使用醇的羥基被OMs、OTf、OTs等的解離基所取代之醇類等。 　　[0027] 於NH2 基中，導入由R1 、R3 所形成的1價之有機基之方法，並未有特別之限制，例如，於適當的鹼之存在下，使酸鹵化物進行反應之方法等。酸鹵化物之例，可列舉如，氯化乙醯、氯化丙酸、氯甲酸甲酯、氯甲酸乙酯、氯甲酸n-丙酯、氯甲酸i-丙酯、氯甲酸n-丁酯、氯甲酸i-丁酯、氯甲酸t-丁酯、氯甲酸苄酯、氯甲酸-9-茀酯等。鹼之例，例如可前述之鹼。反應溶劑、反應溫度，係依前述之記載為準。 　　[0028] 亦可使NH2 基與酸酐進行反應，導入R1 、R3 。酸酐之例，可列舉如，乙酸酐、丙酸酐、二碳酸二甲酯、二碳酸二乙酯、二碳酸-二-第三丁酯、二碳酸二苄酯等。亦可使用促進反應的觸媒，也可使用吡啶、柯林鹼、N,N-二甲基-4-胺基吡啶等。觸媒量相對於(A-3)之使用量，較佳為0.0001～1莫耳。反應溶劑、反應溫度，係依前述之記載為準。 　　亦可使NH2 基與異氰酸酯類進行反應，導入R1 。異氰酸酯類之例，可列舉如，異氰酸甲酯、異氰酸乙酯、異氰酸n-丙酯、異氰酸苯酯等。反應溶劑及反應溫度，係依前述之記載為準。 　　[0029] 亦可使NH2 基與環氧化合物類或氧環丁烷化合物類進行反應，導入R1 、R3 。環氧類或氧環丁烷類之例，可列舉如，環氧乙烷、環氧丙烷、1,2-環氧丁烷、氧化三甲酯等。反應溶劑、反應溫度，係依前述之記載為準。 　　NH2 基，可於適當的鹼存在下，與醇中的羥基被OMs、OTf、OTs等的解離基所取代的醇類進行反應，導入R1 、R3 。醇類之例，可列舉如，甲醇、乙醇、1-丙醇等，該些之醇類，與氯化甲烷磺醯、氯化三氟甲烷磺醯、氯化對甲苯磺酸等進行反應時，可製得被OMs、OTf、OTs等的解離基所取代之醇。鹼之例，可使用前述之鹼。反應溶劑、反應溫度，係依前述之記載為準。 　　[0030] 亦可使NH2 基於適當的鹼存在下，與鹵化烷基進行反應，而導入R1 、R3 。鹵化烷基類之例，可列舉如，碘化甲基、碘化乙基、碘化n-丙基、溴化甲基、溴化乙基、溴化n-丙基等。鹼之例，除前述之鹼以外，亦可tert-丁氧化鉀、tert-丁氧化鈉等的烷氧金屬類。反應溶劑、反應溫度，係依前述之記載為準。 　　[0031] 又，合成化合物(A-3)之方法並未有特別之限制，可列舉如，先合成下述式(4)所表示之硝基化合物，再使該硝基化合物所具有的硝基還原，變換為胺基之方法等。該反應所使用的觸媒、溶劑、溫度，係依前述之記載為準。 　　[0032] 又，合成化合物(A-4)之方法並未有特別之限制，其可於酸性條件下，使下述式(5)所表示之1,4-二酮化合物(A-5)與一級胺進行脫水縮合而合成。該反應所使用的酸之例，例如，可使用乙酸、p-甲苯磺酸、p-甲苯磺酸吡啶鎓等，但並不限定於該些內容。反應溶劑、反應溫度，係依前述之記載為準。 　　[0033] 又，合成化合物(A-5)之方法並未有特別之限制，其可將下述式(6)所表示之具有硝基之α-鹵化酮與具有硝基之酮，於鹼之存在下進行反應而可製得。 　　(X表示Br、I或OTf)。[0034] 該反應所使用的鹼之例，例如可使用前述之鹼。反應溶劑、反應溫度，係依前述之記載為準。亦可使用以促進反應速度為目的之添加劑。當該添加劑，可列舉如，氯化鋅、碘化鈉、碘化鉀、碘化四丁基銨等，但並不限定於該些內容。 　　[0035] ＜特定聚合物＞ 　　本發明之聚合物，為使用上述特定二胺所製得之聚合物。其具體例，可列舉如，聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚脲、聚醯胺等。其中，就作為液晶配向劑使用之觀點，以含有由下述式(4)所表示之結構單位的聚醯亞胺前驅體，及其醯亞胺化物的聚醯亞胺所選出之至少1種的聚合物(以下，亦稱為特定聚合物)為較佳。 　　[0036][0037] 上述式(4)中，X1 為由四羧酸衍生物所產生的4價之有機基，Y1 為由特定二胺所衍生的2價之有機基。R5 為氫原子或碳數1～5之烷基。R5 ，就經由加熱而容易醯亞胺化之觀點，以氫原子、甲基或乙基為佳。 　　[0038] 上述X1 ，於考量聚合物對溶劑之溶解性或作為液晶配向劑之塗佈性、作為液晶配向膜時之液晶的配向性、電壓保持率、蓄積電荷等之際，可配合必要特性之程度作適當之選擇，亦可於同一聚合物中存在2種類以上。 　　X1 之具體例示，可列舉如，國際公開公報2015／119168之13頁～14頁所揭示之式(X-1)～(X-46)之結構等。 　　[0039] 以下為X1 較佳例示之(A-1)～(A-21)，但並不限定於該些內容。[0040][0041] 上述之中，(A-1)、(A-2)就使耐摩擦性更向上提升之觀點為特佳，(A-4)就使蓄積電荷之緩和速度更向上提升之觀點為特佳，(A-15)～(A-17)等，就使液晶配向性與蓄積電荷之緩和速度更向上提升之觀點為特佳。 　　[0042] ＜其他結構單位＞ 　　上述聚醯亞胺前驅體，除式(4)所表示之結構單位外，亦可具有下述式(5)所表示之結構單位。[0043] 式(5)中，X2 與前述式(4)中之定義為相同內容。X2 之具體例，可列舉如，包含較佳之例的式(4)之X1 所例示之內容等。R4 中，任一者皆與前述式(4)中之定義為相同內容。2個R4 中之至少一者，以氫原子為佳。 　　[0044] 又，Y2 為由不包含於主鏈方向的上述式(1)所表示之結構二胺所衍生的二價之有機基，其結構並未有特別之限定。Y2 於考量聚合物對溶劑之溶解性或作為液晶配向劑之塗佈性、作為液晶配向膜時之液晶的配向性、電壓保持率、蓄積電荷等之際，可配合必要特性之程度作適當之選擇，於同一聚合物中可混合存在2種類以上。 　　[0045] Y2 之具體例示，可列舉如，國際公開公報2015／119168之4頁所揭示之式(2)之結構，及，8頁～12頁所揭示之式(Y-1)～(Y-97)、(Y-101)～(Y-118)之結構；國際公開公報2013／008906的6頁所揭示之由式(2)去除2個胺基而得的二價之有機基；國際公開公報2015／122413的8頁所揭示之由式(1)去除2個胺基而得的二價之有機基；國際公開公報2015／060360的8頁所揭示之式(3)之結構；日本公開專利公報2012-173514的8頁記載之由式(1)去除2個胺基而得的二價之有機基；國際公開公報2010-050523的9頁所揭示之由式(A)～(F)去除2個胺基而得的二價之有機基等。 　　[0046] 以下為列舉較佳的Y2 之結構，但本發明並不限定於該些內容。[0047][0048][0049][0050] 上述之結構中，(B-28)、(B-29)等，就使耐摩擦性更向上提升之觀點為特佳，(B-1)～(B-3)等，就使液晶配向性更向上提升之觀點為特佳，(B-14)～(B-18)及(B-27)等，就更提高蓄積電荷的緩和速度之觀點為特佳，(B-26)等，就使電壓保持率更向上提升之觀點為更佳。 　　[0051] 上述聚醯亞胺前驅體，除式(4)所表示之結構單位以外，又包含式(5)所表示之結構單位之情形，式(4)所表示之結構單位，相對於式(4)與式(5)之合計，以10莫耳%以上為佳，更佳為20莫耳%以上，特佳為30莫耳%以上。 　　本發明所使用的聚醯亞胺前驅體之分子量，依重量平均分子量以2,000～500,000為佳，更佳為5,000～300,000，特佳為10,000～100,000。 　　[0052] ＜聚醯亞胺＞ 　　特定聚合物中之聚醯亞胺，可使式(4)、式(5)所表示之聚醯亞胺前驅體閉環而製得。該情形之醯亞胺化率，並非必須為100%，而可配合用途或目的作任意之調整。 　　使聚醯亞胺前驅體醯亞胺化之方法，例如可使用已知之方法。又以於聚醯亞胺前驅體之溶液中，添加鹼性觸媒的化學性醯亞胺化為簡便之方法。化學性醯亞胺化，可於較低溫下進行醯亞胺化反應，且於醯亞胺化過程中，不易引起聚合物的分子量下降，而為較佳。 　　[0053] 化學性醯亞胺化，可將聚醯亞胺前驅體，於有機溶劑中、鹼性觸媒存在下進行攪拌之方式進行。有機溶劑，例如，可使用前述聚合反應時所使用的溶劑。鹼性觸媒，可列舉如，吡啶、三乙胺、三甲胺、三丁胺、三辛胺等。其中，又以三乙胺於反應進行中，可維持充分的鹼性，而為較佳。 　　[0054] 進行醯亞胺化反應時之溫度，可為-20～140℃，較佳為0～100℃，較佳為於反應時間1～100小時間進行。鹼性觸媒之量，為醯胺酸酯基之0.5～30莫耳倍，較佳為2～20莫耳倍。所得聚合物之醯亞胺化率，可以調節觸媒量、溫度、反應時間等方式予以控制。 　　[0055] 聚醯亞胺前驅體於醯亞胺化反應後之溶液，因殘存有添加之觸媒等，故可依以下所述之手段，回收所得之醯亞胺化聚合物，使用有機溶劑再溶解，作為本發明之液晶配向劑為佳。 　　即，依上述方法所製得之聚醯亞胺之溶液，可於充分攪拌中注入貧溶劑內，而析出聚合物。於進行數次析出，使用貧溶劑洗淨後，進行常溫或加熱乾燥，即可製得純化後的聚醯亞胺之粉末。 　　貧溶劑，可列舉如下，但並未有特別之限定，例如，甲醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯等。 　　[0056] ＜液晶配向劑＞ 　　本發明之液晶配向劑，為含有特定聚合物之配向劑，但只要可達成本發明記載之效果時，也可含有2種以上具有相異結構的特定聚合物。又，特定聚合物以外，也可含有其他的聚合物。其他聚合物之種類，可列舉如，聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或其衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。又，也可含有上述式(5)所表示之聚醯亞胺前驅體及該聚醯亞胺前驅體經醯亞胺化的聚醯亞胺所選出的聚醯亞胺等。 　　本發明之液晶配向劑含有其他聚合物之情形，相對於全聚合物成份，特定聚合物之比例以5質量%以上為佳，更佳為5～95質量%。 　　[0057] 液晶配向劑，為製作液晶配向膜時所使用者，就可形成均勻薄膜之觀點，一般為使用塗佈液之形態。本發明之液晶配向劑，以含有前述聚合物成份，與可溶解該聚合物成份的有機溶劑之塗佈液為佳。此時，液晶配向劑中的聚合物之濃度，可配合所欲形成的塗膜厚度之設定作適當之變更。就可形成均勻且無缺陷之塗膜的觀點，以1質量%以上為佳，就溶液保存安定性之觀點，以10質量%以下為佳。特佳之聚合物濃度為2～8質量%。 　　[0058] 液晶配向劑所含有的有機溶劑，只要可使聚合物成份均勻溶解時，並未有特別之限定。列舉其具體例時，例如，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-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙酮、環己酮、環戊酮等。其中，又以N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮，或γ-丁內酯為佳。 　　[0059] 又，液晶配向劑所含有的有機溶劑，一般為使用於上述溶劑中加入液晶配向劑進行塗佈之際，可併用提高塗佈性或塗膜的表面平滑性之溶劑而得的混合溶劑，本發明之液晶配向劑中，該些混合溶劑亦為適合使用者。可併用的有機溶劑之具體例，例如下述所列舉之內容，但並不僅限定於該些之例示。 　　[0060] 例如，乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己烷二醇、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙醚、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、丙烯碳酸酯、乙烯碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁醚、乙二醇單異戊醚、乙二醇單己醚、2-(己基氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲醚乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇二甲醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單乙醚、乳酸甲基、乳酸乙基、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙醚、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、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、下述式[D-1]～[D-3]所表示之溶劑等。 　　[0061][0062] 式[D-1]中，D1 表示碳數1～3之烷基，式[D-2]中，D2 表示碳數1～3之烷基，式[D-3]中，D3 表示碳數1～4之烷基。其中，又以1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、丙二醇單丁醚、二乙二醇二乙醚、4-羥基-4-甲基-2-戊酮、乙二醇單丁醚或二丙二醇二甲醚為佳。該些溶劑之種類及含量，可配合液晶配向劑之塗佈裝置、塗佈條件、塗佈環境等作適當之選擇。 　　[0063] 本發明之液晶配向劑，可再追加含有聚合物成份及有機溶劑以外的成份。該些追加成份，可列舉如，提高液晶配向膜與基板密著性，或提高液晶配向膜與密封材之密著性的密著助劑、提高液晶配向膜強度的交聯劑、調整液晶配向膜之介電係數或電氣電阻的介電體或導電物質等。該些追加成份之具體例，例如，揭示於有關液晶配向劑的各種公知文獻中，舉例而言，例如揭示於國際公開公報2015／060357號之53頁[0105]～55頁[0116]中之成份等。 　　[0064] ＜液晶配向膜＞ 　　本發明之液晶配向膜，可由上述本發明之液晶配向劑所製得。舉例說明由液晶配向劑製得液晶配向膜之方法時，例如，將塗佈液形態的液晶配向劑塗佈於基板後，對經乾燥、燒結而得之膜依摩擦處理法或光配向處理法實施配向處理之方法等。 　　塗佈液晶配向劑之基板，例如，只要具有高透明性之基板時，並未有特別之限定，除玻璃基板或氮化矽基板以外，亦可使用丙烯酸基板或聚碳酸酯基板等之塑膠基板等。此時，使用為驅動液晶而使用的形成ITO電極等之基板時，就製程簡易化之觀點為較佳。又，為反射型之液晶顯示元件時，不僅單側的基板，亦可使用矽晶圓等之不透明之物，該情形中之電極，亦可使用鋁等可反射光線的材料。 　　[0065] 液晶配向劑之塗佈方法，並未有特別之限定，於工業上，一般為使用網版印刷、平版印刷、凸版(Flexo)印刷、噴墨法等。其他的塗佈方法，可列舉如，浸漬法、輥式塗佈法、縫狀塗佈法、旋轉塗佈器法、噴霧法等，其可配合目的，使用上述方法皆可。 　　將液晶配向劑塗佈於基板上之後，經使用加熱板、熱循環型烘箱、IR(紅外線)型烘箱等之加熱手段，將溶劑蒸發、燒結。於塗佈液晶配向劑後的乾燥、燒結步驟，可選擇任意的溫度與時間。通常，就可充分去除溶劑時，例如可於50～120℃進行1～10分鐘燒結，隨後，於150～300℃進行5～120分鐘燒結之條件等。 　　[0066] 燒結後的液晶配向膜之厚度，並未有特別之限定，但過薄時，液晶顯示元件之信賴性會有降低之情形，故以5～300nm為佳，以10～200nm為較佳。 　　本發明之液晶配向膜，適合作為IPS方式或FFS方式等橫向電場方式的液晶顯示元件之液晶配向膜，特別是適合作為FFS方式的液晶顯示元件之液晶配向膜。 　　[0067] ＜液晶顯示元件＞ 　　本發明之液晶顯示元件，為製得由上述液晶配向劑所得之附有液晶配向膜之基板後，依已知之方法製作液晶晶格，並使用該液晶晶格而得之元件。 　　液晶晶格之製作方法之一例，將列舉被動元件矩陣結構的液晶顯示元件為例進行說明。又，構成圖像顯示的各畫素部份，亦可為設有TFT(Thin Film Transistor)等開閉元件的主動矩陣結構之液晶顯示元件。 　　[0068] 具體而言為，準備透明玻璃製之基板，於一側之基板上設置共用電極，另一側之基板上設置節段電極。該些之電極，例如可為ITO電極，並可形成可顯示所期待之圖像顯示的圖型。其次，於各基板上，以被覆共用電極與節段電極之方式設置絕緣膜。絕緣膜，例如，可使用溶膠凝膠法而形成由SiO2 -TiO2 所形成的膜。其次，於前述條件下，於各基板上形成液晶配向膜。 　　[0069] 其次，將形成液晶配向膜的2片基板中之一片基板上的特定場所，配置例如紫外線硬化性之密封材，再於液晶配向膜面上，於特定的數處配置液晶之後，以液晶配向膜向對向方式貼合於另一片基板，並進行壓著使液晶向液晶配向膜全面擠壓拓展後，使用紫外線照射基板全面，使密封材硬化而製得液晶晶格。 　　於基板上形成液晶配向膜後之步驟，例如，於一側基板上的特定場所配置密封材之際，設置可由外部填充液晶的開口部，將未配置液晶的基板貼合後，通過設置於密封材的開口部，將液晶材料注入液晶晶格內，其次，將該開口部使用接著劑密封，而製得液晶晶格。液晶材料之注入，可使用真空注入法亦可，或於大氣中利用毛細現象之方法亦可。 　　[0070] 上述任一之方法中，為確保液晶晶格內可填充液晶材料之空間，可於一側基板上設置柱狀突起，或於一側基板上散佈間隔器，或於密封材內混入間隔器，或可使用組合該些方法等之手段為佳。 　　[0071] 上述液晶材料，可列舉如，向列型液晶或層列型液晶等，其中，又以向列型液晶為佳，其可使用正型液晶材料或負型液晶材料中任一種。隨後，進行偏光板之設置。具體而言，為將一對的偏光板貼合於與2片基板的液晶層為相反側之面者為佳。 　　又，本發明之液晶配向膜及液晶顯示元件，只要使用本發明之液晶配向劑時，並不限定為上述記載之內容，亦可使用其他公知之方法製作。由液晶配向劑製得液晶顯示元件之步驟，例如，揭示於日本特開2015-135393號公報之17頁的段落0074～19頁的段落0081等之內容。[Problems to be Solved by the Invention] [0006] The present invention provides a liquid crystal alignment agent and a liquid crystal alignment film capable of producing a liquid crystal alignment film having an excellent voltage holding ratio, quickly alleviating the accumulation of electric charges, and not easily causing flicker during driving. Film, and liquid crystal display elements. [Methods for Solving Problems] [0007] As a result of in-depth research on solving the above problems, the present inventors found that when a specific structure is introduced into a polymer contained in a liquid crystal alignment agent, various characteristics can be simultaneously improved. Thus, the present invention has been completed. [0008] Based on the above-mentioned knowledge, the present invention proposes the following points. 1. A liquid crystal alignment agent, comprising a polymer prepared from a diamine having a structure represented by the following formula (1), and an organic solvent; (In formula (1), R 1 , R 2 It is a hydrogen atom, or a monovalent organic group. Any hydrogen atom in the benzene ring may be substituted by a monovalent organic group. (* Indicates a bonding site). 2. The liquid crystal alignment agent according to the above 1, wherein the polymer is a polyimide precursor of a polycondensation product of a diamine and a tetracarboxylic dianhydride having a structure represented by the formula (1), A polymer of at least one selected from the group consisting of polyamidoimide and its polyimide. 3. The liquid crystal alignment agent according to 1 or 2 above, wherein the diamine is represented by the following formula (2); (In formula (2), R 1 And R 2 The definition is the same as the above formula (1), R 3 Each independently represents a single bond or a structure of the following formula (3); n represents an integer of 1 to 3; any hydrogen atom in the benzene ring may be substituted by a monovalent organic group). (In formula (3), R 4 Represented by a single bond, -O-, -COO-, -OCO-,-(CH 2 ) l -, -O (CH 2 ) m O-, -CONH-, and -NHCO- selected divalent organic groups (l and m represent integers from 1 to 5); * 1 Represents the site bonded to the benzene ring in formula (2), * 2 Represents a site bonded to an amine group in the formula (2)). 4. The liquid crystal alignment agent according to 1 to 3 above, wherein the polyfluorene imide precursor has a structure represented by the following formula (4): (In formula (4), X 1 Is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 Is a divalent organic group derived from the diamine represented by the aforementioned formula (1), R 5 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 5. The liquid crystal alignment agent according to the above 4, wherein in the formula (6), X 1 At least one selected from the group consisting of the structures represented by the following (A-1) to (A-21). 6. The liquid crystal alignment agent according to the above 4 or 5, wherein the polymer having the structural unit represented by the formula (4) contains 10 mol% or more of the total polymer contained in the liquid crystal alignment agent. 7. The liquid crystal alignment agent according to any one of 1 to 6, wherein the organic solvent is a group containing 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether. At least one selected. 8. A liquid crystal alignment film, which is obtained by using the liquid crystal alignment agent according to any one of 1 to 7 above. 9. A liquid crystal display element comprising the liquid crystal alignment film according to the above 8. 10. The liquid crystal display element according to the above 9, wherein the liquid crystal display element is a lateral electric field drive system. A polymer comprising a polyimide precursor of a polycondensation product of a polycondensation product of a diamine and a tetracarboxylic dianhydride having a structure represented by the following formula (1), and a polymer of the polyimide At least one selected from the group of stilbene imines; (In formula (1), R 1 , R 2 It is a hydrogen atom, or a monovalent organic group. Any hydrogen atom in the benzene ring may be substituted by a monovalent organic group. (* Indicates a bonding site). 12. The polymer according to the above 11, wherein the diamine is represented by the following formula (2); (In formula (2), R 1 And R 2 The definition is the same as the above formula (1), R 3 Each is independently a single bond or has a structure represented by the following formula (3); n represents an integer of 1 to 3; any hydrogen atom in the benzene ring may be substituted by a monovalent organic group). (In formula (3), R 4 Represented by a single bond, -O-, -COO-, -OCO-,-(CH 2 ) l -, -O (CH 2 ) m O-, -CONH-, and -NHCO- selected divalent organic groups (l and m represent integers from 1 to 5); * 1 Represents the site bonded to the benzene ring in formula (2), * 2 Represents a site bonded to an amine group in the formula (2)). (In formula (4), X 1 Is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 Is a divalent organic group derived from the diamine represented by the aforementioned formula (1), R 5 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 14. The polymer according to the above 13, wherein X in the formula (6) 1 At least one selected from the group consisting of the structures represented by the following (A-1) to (A-21). 15. A diamine represented by the following formula (2); (In formula (2), R 1 And R 2 The definition is the same as the above formula (1), R 3 Each is independently a single bond or has a structure represented by the following formula (3); n represents an integer of 1 to 3; any hydrogen atom in the benzene ring may be substituted by a monovalent organic group). [Effects of the Invention] [0009] When the liquid crystal alignment agent of the present invention is used, it is possible to provide a liquid crystal alignment film and a liquid crystal display element having excellent display characteristics that can quickly alleviate the accumulated charge and are not easy to cause flicker during driving. Although the reason why the present invention can solve the above-mentioned problems has not yet been determined, it is speculated that the effect should be obtained by the following mechanism. Among the polymers contained in the liquid crystal alignment agent of the present invention, the diamine represented by the above (1) has a structure in which a conductive pyrrole ring and a benzene ring have a conjugated structure, so the liquid crystal formed by the liquid crystal alignment agent The alignment film makes it easier to move the charge applied when the element is driven, so it is presumed to be a reason that can promote the relaxation of the accumulated charge. [Forms of Implementing the Invention] [0010] <Specific Diamine> The liquid crystal alignment agent of the present invention contains a polymer obtained from a diamine (also referred to as a specific diamine in the present invention) having a structure of the following formula (1) Thing. [0011] In the above formula (1), R 1 , R 2 , As defined above. Among them, R 1 , R 2 An alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having a carbon number of 1 to 3 is more preferable, and a hydrogen atom or a methyl group is particularly preferable. In addition, * indicates a site bonded to an amine group, a substituted amine group, or another organic group. [0012] Among the specific diamines, as shown in the following formula (1-1), at least one of them is bonded to the pyrrole ring from the viewpoint of charge transfer with respect to the bonding position of the pyrrole ring of the two benzene rings. The nitrogen atom is preferably adjacent to the carbon atom. [0013] The specific diamine may be represented by, for example, the following formula (1-2), particularly a diamine represented by the following formula (1-3), and further represented by the formula (1-4) Diamine is preferred. In these formulas, * indicates a bonding site. [0014] [0015] In the formulae (1-2) to (1-4), R 1 And R 2 The definition is the same as in the case of the above formula (1), Q 1 , Q 2 , Each independently a single bond or a divalent organic group, ie, Q 1 With Q 2 May be different structures. Moreover, in formula (1-4), two Q 2 May be different structures. In addition, an arbitrary hydrogen atom of a benzene ring may be substituted with a monovalent organic group as in the case of the above formula (1). [0016] Preferable examples of the specific diamine include, for example, a diamine represented by the following formula (2), and more preferably a diamine represented by the formula (2-1). [0017] In the formula (2), R 1 And R 2 The definition is the same as the above formula (1), R 3 Each independently represents a single bond or a structure of the following formula (3); n represents an integer of 1 to 3; any hydrogen atom in the benzene ring may be substituted by a monovalent organic group. (In formula (3), R 4 Represented by a single bond, -O-, -COO-, -OCO-,-(CH 2 ) l -, -O (CH 2 ) m O-, -CONH-, and -NHCO- selected divalent organic groups (l and m represent integers from 1 to 5); * 1 Represents the site bonded to the benzene ring in formula (2), * 2 Represents a site bonded to an amine group in the formula (2)). In formula (2) and formula (2-1), n represents an integer of 1 to 3; preferably 1 or 2. [0018] Specific examples of the diamine of the formula (2) include the following examples, but they are not limited thereto. Among them, from the viewpoint of easing the accumulation of charge, (2-1-1), (2-1-2), (2-1-3), (2-1-4), (2-1-5), (2-1-8), (2-1-9), (2-1-10), (2-1-11) or (2-1-12) is preferred, with (2-1-1) , (2-1-2), (2-1-3), (2-1-4), (2-1-5), (2-1-11) or (2-1-12) are special good. [0019] [0020] <Method for synthesizing specific diamine> The method for synthesizing the specific diamine of the present invention is not particularly limited. For example, a dinitro compound represented by the following formula (1) can be synthesized first, and then the nitro group can be synthesized. Methods for reduction and conversion to amine groups. (R 1 , R 2 And R 3 (Represents hydrogen, or a monovalent organic group). [0021] The catalyst used in the reduction reaction is preferably an activated carbon supporting metal that is commercially available, for example, palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. The catalyst may be an inactive carbon-supporting metal catalyst such as palladium hydroxide, platinum oxide, or Raney nickel. Particularly, a palladium-activated carbon is preferable, because good results can be obtained. In order to make the reduction reaction proceed more effectively, the reaction may be carried out in the presence of activated carbon. At this time, the amount of the activated carbon to be used is not particularly limited, and the dinitro compound is generally preferably in the range of 1 to 30% by mass, and more preferably 10 to 20% by mass. For the same reason, a case where the reaction is carried out under pressure may be carried out. In this case, in order to avoid reduction of the benzene nucleus, it is preferable to perform it in a pressure range up to 20 atmospheres, and it is more preferable to perform it in a pressure range up to 10 atmospheres. [0022] As long as the solvent does not react with each raw material, it can be used without any limitation. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.) can be used; ethers (Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, xylene, chlorobenzene, chlorobenzene, etc.) , Dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogen-based hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate) , Butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); etc. These solvents may be appropriately selected and used in consideration of the easiness of causing a reaction, or may be obtained by mixing two or more kinds. If necessary, the solvent can be dried with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent. The use amount (reaction concentration) of the solvent is preferably 0.1 to 10 mass times, more preferably 0.5 to 30 mass times, and particularly preferably 1 to 10 mass times relative to the dinitro compound. The reaction temperature is not particularly limited, but is usually in the range from -100 ° C to the boiling point of the solvent used, and is preferably -50 to 150 ° C. The reaction time is usually 0.05 to 350 hours, and preferably 0.5 to 100 hours. [0023] On the other hand, the method for synthesizing the nitro compound (A-1) is not particularly limited. In the case where the substitution position of the amine group of the compound (A-1) is in the 2nd and 4th positions, for example It can be prepared by reacting a diamine represented by the following formula (A-2) with a halogenated aryl group having a nitro group in the presence of a base and, if necessary, the presence of an additive (X represents F, Cl , Br, I, or OTf). [0024] In the halogenated aryl group having a nitro group, X is F or Cl, and NO 2 When the group is in the second position or the fourth position with respect to X, a halogenated aryl group and an aliphatic amine compound can be reacted in the presence of a base to obtain a compound (A-1). Examples of the base used include inorganic bases such as sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, and the like. Tributylamine, diisopropylethylamine, pyridine, quinoline, collin base, etc., or sodium hydride, potassium hydride, etc. The reaction solvent and reaction temperature are as described above. The product can be purified by recrystallization, distillation, and silica gel column chromatography. [0025] When X is Br or I, NO 2 Relative to X, the radical can be in the 2nd, 3rd, or 4th position. It can also be prepared by using a CN cross-coupling reaction in the presence of a suitable metal catalyst, ligand, or base. Nitro body. Examples of the metal catalyst include, for example, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis (dibenzylideneacetone) palladium, and (dibenzylideneacetone) diamine. Palladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, CuCl, CuBr, CuI, CuCN, and the like are not limited thereto. Examples of the ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, and 1,2-bis ( Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ) Ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, tri-tert-butylphosphine, etc., but it is not limited to these. Examples of the base include the aforementioned bases. The reaction solvent and reaction temperature are as described above. The product can be purified by recrystallization, distillation, silica gel column chromatography, and the like. [0026] In addition, the method for synthesizing the compound (A-2) is not particularly limited. For example, a diamine represented by the following formula (A-3) is synthesized first, and then NH 2 Import R 1 , R 3 Methods, etc. Import R 1 , R 3 In this case, any compound may be used as long as it is a compound capable of reacting with amines, for example, acid halides, acid anhydrides, isocyanates, epoxy, oxycyclobutanes, halogenated aryls, halogenated alkyls, and the like. In addition, alcohols in which the hydroxyl group of the alcohol is replaced with a dissociating group such as OMs, OTf, OTs, or the like can also be used. NH 2 Base, import by R 1 , R 3 The method of the formed monovalent organic group is not particularly limited, and for example, a method of reacting an acid halide in the presence of a suitable base, and the like. Examples of the acid halide include acetic acid chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, and n-butyl chloroformate. , I-butyl chloroformate, t-butyl chloroformate, benzyl chloroformate, 9-fluorenyl chloroformate, and the like. Examples of the base include the aforementioned bases. The reaction solvent and reaction temperature are as described above. [0028] NH can also be made 2 Group reacts with acid anhydride and introduces R 1 , R 3 . Examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-tertiary-butyl dicarbonate, and dibenzyl dicarbonate. Catalysts that promote the reaction may also be used, and pyridine, collin base, N, N-dimethyl-4-aminopyridine, and the like may also be used. The amount of catalyst is preferably 0.0001 to 1 mole relative to the amount of (A-3) used. The reaction solvent and reaction temperature are as described above. Can also make NH 2 Groups react with isocyanates and introduce R 1 . Examples of the isocyanates include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, and phenyl isocyanate. The reaction solvent and reaction temperature are based on the foregoing description. [0029] NH can also be made 2 Group reacts with epoxy compounds or oxocyclobutane compounds and introduces R 1 , R 3 . Examples of the epoxy-based or oxycyclobutane-based include ethylene oxide, propylene oxide, 1,2-butylene oxide, and trimethyl oxide. The reaction solvent and reaction temperature are as described above. NH 2 In the presence of a suitable base, it can be reacted with an alcohol in which the hydroxyl group in the alcohol is replaced by a dissociating group such as OMs, OTf, OTs, etc., and R is introduced. 1 , R 3 . Examples of the alcohols include methanol, ethanol, and 1-propanol. When these alcohols are reacted with methanesulfonium chloride, trifluoromethanesulfonium chloride, and p-toluenesulfonic acid chloride, etc. Alcohols can be prepared by dissociating groups such as OMs, OTf, OTs. Examples of the base include the aforementioned bases. The reaction solvent and reaction temperature are as described above. [0030] NH can also be made 2 Introduction of R based on reaction with a halogenated alkyl group in the presence of a suitable base 1 , R 3 . Examples of the halogenated alkyl group include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, and n-propyl bromide. Examples of the base include, in addition to the aforementioned bases, metal alkoxides such as tert-potassium butoxide and tert-butoxide. The reaction solvent and reaction temperature are as described above. [0031] The method of synthesizing the compound (A-3) is not particularly limited, and examples thereof include firstly synthesizing a nitro compound represented by the following formula (4), and then making the nitrate possessed by the nitro compound Group reduction, conversion to amine groups, etc. The catalyst, solvent, and temperature used in this reaction are as described above. [0032] In addition, the method for synthesizing the compound (A-4) is not particularly limited, and it can make the 1,4-dione compound (A-5) represented by the following formula (5) under acidic conditions. Synthesized by dehydration condensation with primary amine. Examples of the acid used in this reaction include, but are not limited to, acetic acid, p-toluenesulfonic acid, and p-toluenesulfonic acid pyridinium. The reaction solvent and reaction temperature are as described above. [0033] In addition, the method for synthesizing the compound (A-5) is not particularly limited, and an α-halogenated ketone having a nitro group and a ketone having a nitro group can be used in an alkali It can be prepared by carrying out the reaction in the presence. (X represents Br, I or OTf). [0034] Examples of the base used in this reaction include the aforementioned bases. The reaction solvent and reaction temperature are as described above. It is also possible to use additives for the purpose of promoting reaction speed. Examples of the additives include, but are not limited to, zinc chloride, sodium iodide, potassium iodide, and tetrabutylammonium iodide. [Specific Polymer] The polymer of the present invention is a polymer prepared by using the specific diamine described above. Specific examples thereof include polyamidic acid, polyamidate, polyamidoimide, polyurea, polyamido, and the like. Among them, from the viewpoint of use as a liquid crystal alignment agent, at least one selected from the group consisting of a polyimide precursor containing a structural unit represented by the following formula (4), and a polyimide containing a sulfonium imide. A polymer (hereinafter, also referred to as a specific polymer) is preferred. [0036] [0037] In the above formula (4), X 1 Is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 It is a divalent organic group derived from a specific diamine. R 5 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 5 From the viewpoint of easy imidization by heating, a hydrogen atom, a methyl group, or an ethyl group is preferred. The above-mentioned X 1 In consideration of the solubility of the polymer in the solvent or the coating property as a liquid crystal alignment agent, the alignment property of the liquid crystal when it is used as a liquid crystal alignment film, the voltage retention rate, and the accumulated charge, etc., it can be appropriately matched with the degree of necessary characteristics. Alternatively, two or more types may be present in the same polymer. X 1 Specific examples include the structures of formulas (X-1) to (X-46) disclosed in pages 13 to 14 of International Publication Gazette 2015/119168. [0039] The following is X 1 (A-1) to (A-21) are preferably exemplified, but are not limited to these contents. [0040] [0041] Among the above, (A-1) and (A-2) are particularly preferable from the viewpoint of increasing the friction resistance upward, and (A-4) are upward from the viewpoint of increasing the relaxation speed of the accumulated charge as Particularly preferred, (A-15) to (A-17), etc., are particularly advantageous from the viewpoint of increasing the relaxation speed of liquid crystal alignment and accumulated charge. [0042] <Other structural units> In addition to the structural unit represented by the formula (4), the polyfluorene imide precursor may have a structural unit represented by the following formula (5). [0043] In the formula (5), X 2 It is the same as the definition in the aforementioned formula (4). X 2 Specific examples include X in the formula (4) including a preferable example. 1 Exemplified contents, etc. R 4 In either case, it is the same as the definition in the aforementioned formula (4). 2 R 4 At least one of them is preferably a hydrogen atom. [0044] Y 2 It is a divalent organic group derived from the structural diamine represented by the above formula (1) which is not included in the main chain direction, and its structure is not particularly limited. Y 2 When considering the solubility of the polymer in the solvent or the coating property as a liquid crystal alignment agent, the alignment property of the liquid crystal when it is used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge, etc., an appropriate choice can be made in accordance with the degree of necessary characteristics. Two or more types can be mixed in the same polymer. [0045] Y 2 Specific examples include the structure of formula (2) disclosed on page 4 of International Publication Gazette 2015/119168, and the formulas (Y-1) to (Y-97) disclosed on pages 8 to 12. Structures of (Y-101) to (Y-118); Divalent organic groups obtained by removing two amine groups from formula (2) as disclosed on page 6 of International Publication 2013/008906; International Publication 2015 / A bivalent organic group obtained by removing two amine groups from formula (1) disclosed on page 8 of 122413; a structure of formula (3) disclosed on page 8 of International Publication 2015/060360; Japanese Patent Publication 2012 The bivalent organic group obtained by removing two amine groups from formula (1) described on page 8 of -173514; removing two from formulas (A) to (F) disclosed on page 9 of International Publication 2010-050523 Divalent organic groups derived from amine groups. [0046] The following is a list of preferred Y 2 Structure, but the present invention is not limited to these contents. [0047] [0048] [0049] [0050] Among the above-mentioned structures, (B-28), (B-29), etc. are particularly preferable in terms of improving the friction resistance upward, and (B-1) to (B-3), etc. The viewpoint that the alignment of the liquid crystal is further improved is particularly good, (B-14) to (B-18) and (B-27), etc., the viewpoint that the relaxation speed of the accumulated charge is further improved is particularly good, (B-26) It is better to wait for the voltage holding ratio to increase. [0051] In addition to the structural unit represented by formula (4), the above polyfluorene imide precursor also includes the structural unit represented by formula (5). The structural unit represented by formula (4) is The total of (4) and formula (5) is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. The molecular weight of the polyfluorene imide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 100,000 according to the weight average molecular weight. [0052] Polyfluorene imine in a specific polymer can be obtained by closing a polyfluorene imide precursor represented by formula (4) and formula (5). In this case, the imidization rate of fluorene is not necessarily 100%, and can be adjusted arbitrarily according to the purpose or purpose. As a method for imidizing the polyfluorene imide precursor, for example, a known method can be used. It is also a simple method to add a basic catalyst to the chemical imidization of the polyimide precursor solution. The chemical fluorene imidization can be performed at a relatively low temperature, and it is not easy to cause the molecular weight of the polymer to decrease during the fluorene imidization, and it is preferable. [0053] Chemical fluorene imidization can be performed by stirring the polyfluorene imide precursor in an organic solvent in the presence of a basic catalyst. As the organic solvent, for example, a solvent used in the aforementioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is more preferred as it can maintain sufficient basicity during the reaction. The temperature at which the amidine imidization reaction is performed may be -20 to 140 ° C, preferably 0 to 100 ° C, and preferably performed in a reaction time of 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino ester group, preferably 2 to 20 mol times. The hydrazone imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. [0055] The solution of the polyfluorene imine precursor after the fluorene imidization reaction, because the added catalyst and the like remain, so the obtained fluorene imine polymer can be recovered according to the following methods, using an organic solvent Redissolution is preferred as the liquid crystal alignment agent of the present invention. That is, the polyimide solution prepared according to the above method can be poured into a poor solvent while being fully stirred to precipitate a polymer. After carrying out precipitation several times, washing with a poor solvent, drying at room temperature or heating, a purified polyimide powder can be obtained. Examples of the poor solvent include, but are not particularly limited to, for example, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. [0056] <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is an alignment agent containing a specific polymer, but as long as the effect described in the present invention is achieved, it may contain two or more specific polymers having different structures. Further, other polymers may be contained in addition to the specific polymer. Examples of other types of polymers include polyamic acid, polyimide, polyamidate, polyester, polyamine, polyurea, polyorganosiloxane, cellulose derivative, and polyacetal. , Polystyrene or its derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like. Moreover, the polyfluorene imide precursor represented by the said Formula (5), the polyfluorene imide which selected the polyfluorene imidation of this polyfluorene precursor, and the like can also be contained. When the liquid crystal alignment agent of the present invention contains other polymers, the proportion of the specific polymer is preferably 5% by mass or more, more preferably 5 to 95% by mass, relative to the total polymer component. [0057] The liquid crystal alignment agent is generally used in the form of a coating liquid for the viewpoint that a uniform film can be formed by a user when making a liquid crystal alignment film. The liquid crystal alignment agent of the present invention is preferably a coating liquid containing the aforementioned polymer component and an organic solvent capable of dissolving the polymer component. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly preferred polymer concentration is 2 to 8% by mass. [0058] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component can be uniformly dissolved. When specific examples are given, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidine Ketones, dimethyl sulfene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is more preferable. [0059] Generally, the organic solvent contained in the liquid crystal alignment agent is a mixture obtained by adding a liquid crystal alignment agent to the above-mentioned solvent for coating, and using a solvent that improves the coatability or the surface smoothness of the coating film. In the liquid crystal alignment agent of the present invention, these mixed solvents are also suitable for users. Specific examples of the organic solvents that can be used in combination include, for example, those listed below, but are not limited to these examples. [0060] For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2- Amyl alcohol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol Alcohol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl -2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol Diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethyl ether Ethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate , 1-methylpentyl acetate, 2-ethyl Butyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol , Ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butyl (Oxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether ethyl Acid ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethyl ether Glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethyl Diethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate Ester, methyl 3-ethoxypropionate Ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid Methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the following formulas [D-1] to [D-3], and the like. [0061] [0061] In the formula [D-1], D 1 Represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D 2 Represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms. Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl 2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferred. The types and contents of these solvents can be appropriately selected according to the coating device, coating conditions, and coating environment of the liquid crystal alignment agent. [0063] The liquid crystal alignment agent of the present invention may further contain components other than the polymer component and the organic solvent. Examples of such additional components include adhesion promoters that improve the adhesion between the liquid crystal alignment film and the substrate, or adhesion between the liquid crystal alignment film and the sealing material, cross-linking agents that increase the strength of the liquid crystal alignment film, and adjustment of the liquid crystal alignment. The dielectric constant of the film or the dielectric body or conductive substance of the electrical resistance. Specific examples of these additional components are disclosed in various publicly known literatures on liquid crystal alignment agents, for example, disclosed in International Publication Gazette 2015/060357, pages 53 [0105] to 55 [0116]. Ingredients, etc. [0064] <Liquid crystal alignment film> The liquid crystal alignment film of the present invention can be prepared from the liquid crystal alignment agent of the present invention. For example, when a method for preparing a liquid crystal alignment film from a liquid crystal alignment agent is described, for example, after the liquid crystal alignment agent in the form of a coating liquid is coated on a substrate, the film obtained by drying and sintering is subjected to a rubbing treatment method or a photo alignment treatment method. Methods for implementing alignment processing. The substrate on which the liquid crystal alignment agent is applied, for example, is not particularly limited as long as it has a substrate with high transparency. In addition to a glass substrate or a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used. Wait. In this case, when a substrate for forming an ITO electrode or the like used to drive a liquid crystal is used, it is preferable from the viewpoint of simplification of the manufacturing process. In the case of a reflective liquid crystal display device, not only a substrate on one side, but also an opaque object such as a silicon wafer can be used. In this case, the electrode can also use a material that reflects light. [0065] The coating method of the liquid crystal alignment agent is not particularly limited. In industry, generally, screen printing, lithography, flexo printing, inkjet method, and the like are used. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, and a spray method. These methods can be used according to the purpose. After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated and sintered by heating means such as a hot plate, a thermal cycle type oven, and an IR (infrared) type oven. In the drying and sintering steps after applying the liquid crystal alignment agent, an arbitrary temperature and time can be selected. In general, when the solvent can be sufficiently removed, conditions such as sintering at 50 to 120 ° C for 1 to 10 minutes and then sintering at 150 to 300 ° C for 5 to 120 minutes can be performed. [0066] The thickness of the sintered liquid crystal alignment film is not particularly limited, but when it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, 5 to 300 nm is preferred, and 10 to 200 nm is preferred. good. The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a liquid crystal display element with a lateral electric field method such as an IPS method or an FFS method, and is particularly suitable as a liquid crystal alignment film for a liquid crystal display device with an FFS method. [0067] <Liquid crystal display element> The liquid crystal display element of the present invention is to obtain a substrate with a liquid crystal alignment film obtained from the above-mentioned liquid crystal alignment agent, prepare a liquid crystal lattice according to a known method, and use the liquid crystal lattice.得 的 Element. An example of a method for manufacturing a liquid crystal lattice will be described by taking a liquid crystal display element having a passive element matrix structure as an example. In addition, each pixel portion constituting the image display may be a liquid crystal display element having an active matrix structure provided with an opening and closing element such as a TFT (Thin Film Transistor). [0068] Specifically, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes, and can form a pattern that can display a desired image display. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be formed of, for example, SiO using a sol-gel method. 2 -TiO 2 The formed film. Next, a liquid crystal alignment film is formed on each substrate under the aforementioned conditions. [0069] Next, a UV-curable sealing material is arranged at a specific place on one of the two substrates forming the liquid crystal alignment film, and then the liquid crystal alignment film is provided with liquid crystals at a certain number of places. The liquid crystal alignment film is bonded to another substrate in a facing manner, and the liquid crystal is fully squeezed and expanded to the liquid crystal alignment film by pressing. Then, the substrate is irradiated with ultraviolet rays and the sealing material is hardened to obtain a liquid crystal lattice. Steps after forming a liquid crystal alignment film on a substrate, for example, when a sealing material is arranged at a specific place on one substrate, an opening portion can be filled with liquid crystal from the outside, and the substrate without the liquid crystal is bonded, and then the substrate is sealed. A liquid crystal material is injected into the liquid crystal lattice of the opening portion of the material, and then the opening portion is sealed with an adhesive to obtain a liquid crystal lattice. The liquid crystal material can be injected by using a vacuum injection method or a method using a capillary phenomenon in the atmosphere. [0070] In any of the above methods, in order to ensure that the liquid crystal lattice can be filled with liquid crystal material, columnar protrusions may be provided on one side substrate, spacers may be scattered on one side substrate, or mixed in a sealing material. As the spacer, a combination of these methods may be used. [0071] The liquid crystal material includes, for example, a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is more preferable. Any of a positive liquid crystal material and a negative liquid crystal material can be used. Then, the polarizing plate is set. Specifically, it is preferable that a pair of polarizing plates is bonded to a surface opposite to the liquid crystal layer of the two substrates. The liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to those described above as long as the liquid crystal alignment agent of the present invention is used, and they can be produced by other known methods. The steps for producing a liquid crystal display element from a liquid crystal alignment agent are disclosed in, for example, Japanese Patent Application Laid-Open Publication No. 2015-135393, page 17, paragraph 0074 to page 19, paragraph 0081, and the like.

[實施例] 　　[0072] 以下，本發明將列舉實施例等作具體的說明。又，但本發明之解釋並不受該些實施例所限定。 　　以下所述各原材料之簡稱，及特性之評估方法，係如以下所示。[0073][0074] ＜有機溶劑＞ 　　NMP：N-甲基-2-吡咯啶酮、 　　NEP：N-乙基-2-吡咯啶酮 　　GBL：γ-丁內酯、 　　BCS：丁基溶纖劑(cellosolve) 　　PB：丙二醇單丁醚 　　DME：二丙二醇二甲醚 　　DAA：4-羥基-4-甲基-2-戊酮 　　DEDG：二乙二醇二乙醚 　　DIBK：2,6-二甲基-4-庚酮、 　　DIPE：二異丙醚、 　　DIBC：2,6-二甲基-4-庚醇、 　　Pd／C：碳鈀、 　　DMSO：二甲基磺氧化物、 　　THF：四氫呋喃 ＜添加劑＞ 　　LS-4668：3-環氧丙氧基丙基三乙氧基矽烷 　　[0075] ＜交聯劑＞[0076] 又，說明書中，Boc及Fmoc為表示下述所示之基，Me表示甲基。[0077] (1 H-NMR之測定) 　　裝置：Varian NMR system 400NB(400MHz) (Varian公司製)，及JMTC-500／54／SS(500MHz) (JEOL公司製) 　　測定溶劑：CDCl3 (重氫氯仿)，DMSO-d6 (重氫二甲基亞碸) 　　基準物質：TMS(四甲基矽烷) (d：0.0ppm，1 H)及CDCl3 (d：77.0ppm，13 C) 　　[0078] (醯亞胺化率之測定) 　　將聚醯亞胺粉末20mg加入NMR樣品管(NMR標準樣品管，φ5(草野科學公司製))中，重氫二甲基亞碸(DMSO-d6,0.05%TMS(四甲基矽烷)混合品) (0.53ml)，施加超音波使其完全溶解。該溶液使用NMR測定機(JNW-ECA500、日本電子數據公司製)測定500MHz之質子NMR。醯亞胺化率為基於醯亞胺化前後未發生變化的結構所衍生的質子作為基準質子所決定，故可使用該質子的波峰積算值，與出現於9.5ppm～10.0ppm附近的由醯胺酸的NH基所衍生的質子波峰積算值，依以下計算式而可求得。 　　醯亞胺化率(%)＝(1-α・x／y)×100 　　上述式中，x為由醯胺酸之NH基衍生的質子波峰積算值、y為基準質子的波峰積算值、α為聚醯胺酸(醯亞胺化率為0%)之情形中，相對於1個醯胺酸的NH基質子，該基準質子的個數之比例。 　　[0079] ＜二胺化合物(DA-1)之合成＞[0080] 於3L(公升)的四口燒瓶中，加入氯化鋅(120.3g、882 mmol)，升溫至100℃為止，使用油泵進行1小時真空乾燥。隨後，於氮氛圍下、室溫中，依序加入甲苯(460g)、二乙胺(45.0g、615 mmol)、t-丁醇(46.4g、626 mmol)、2-溴-4-硝基苯乙酮(100.0g、410 mmol)，及4-硝基苯乙酮(104.2g、631 mmol)，於室溫下攪拌3日。使用HPLC(高速液體層析儀)確定反應結束後，加入5%硫酸水溶液(400g)，使其中和，再於室溫下攪拌1小時。將析出之結晶減壓過濾，依序使用甲苯(200g)、純水(300g)、甲醇(200g)洗淨後，進行乾燥處理，製得粗結晶。將所得之粗結晶加入於四氫呋喃(1340g)中，於60℃下使其完全溶解後，加入乙醇(1340g)，於5℃下攪拌1小時。將析出之結晶減壓過濾，使用乙醇(200g)洗淨後，進行乾燥處理，得粉末結晶(1) (產量63g，產率45%)。 　　1H-NMR(DMSO-d6 )：8.40-8.36(4H, m), 8.28-8.24(4H, m), 3.53(4H, s) 　　[0081]於2L的四口燒瓶中，加入化合物(1) (65.8g，200 mmol)、乙酸銨(84.5g, 1100 mmol)，及乙酸(855g)，升溫至120℃，於迴流下攪拌3小時。使用HPLC(高速液體層析儀)確認反應結束後，將反應液加入冷水(4000g)中，攪拌1小時。將析出之結晶減壓過濾，使用乙腈(100g)進行再漿化洗淨(Repulping washing)後，進行乾燥處理，而製得粉末結晶(2) (產量53g，產率78%)。 　　1H-NMR(DMSO-d6 )：11.8(1H, br), 8.30-8.26(4H, m), 8.11-8.07(4H, m), 7.04(2H, s) 　　[0082]於1L的四口燒瓶中，加入化合物(2) (41.3g，134 mmol)、碳酸鉀(27.8g，201 mmol)，及二甲基甲醯胺(540g)，於室溫下滴入碘化甲酯(38.1g，268 mmol)，攪拌24小時。使用HPLC(高速液體層析儀)確認反應結束後，將反應液加入冷水(4300g)中，攪拌1小時。將析出之結晶減壓過濾，使用2-丙醇(100g)洗淨後，進行乾燥處理，而得粉末結晶(3) (產量41.1g，產率90%)。 　　1H-NMR(DMSO-d6 )：8.34-8.33(4H, m), 7.86-7.81(4H, m), 6.67(2H, s), 3.73(3H, s) 　　[0083]將化合物(3) (40g、124 mmol)、5質量%Pd／C(50%含水型)、特級白鷺活性碳(4.0g)，及二噁烷(400g)的混合物，在氫加壓條件下，於80℃下攪拌8小時。反應結束後，將觸媒過濾後，進行濃縮處理，加入2-丙醇(400g)，於5℃下攪拌1小時。將析出之結晶減壓過濾，使用2-丙醇(100g)洗淨後，進行乾燥處理，而得粉末結晶(4) (產量17g，產率52%)。 　　1H-NMR(DMSO-d6 )：7.11-7.08(4H, m), 6.63-6.59(4H, m), 5.96(2H, s), 5.15(4H, s), 3.43(3H, s) 　　[0084]於1L的四口燒瓶中，加入化合物(4) (27.4g，104 mmol)及THF(270g)，於冰冷下滴入三氟乙酸酐(46.5g, 220 mmol)，攪拌1小時。使用HPLC(高速液體層析儀)確認反應結束後，進行濃縮乾固處理。於所得之固體中，加入THF(600g)、碳酸鉀(45.1g，326 mmol)，於室溫下滴入碘化甲酯(45.8g，324 mmol)，於40℃下攪拌22小時。使用HPLC(高速液體層析儀)確認反應結束後，將鹽減壓過濾而去除，予以濃縮乾固。 　　[0085] 於所得固體中，加入N-甲基吡咯啶酮(200g)、純水(30g)，及氫氧化鉀(20.8g，315 mmol)，於60℃下攪拌30分鐘。使用HPLC(高速液體層析儀)確認反應結束後，將反應液加入冷水(1200g)中，攪拌1小時。將析出之結晶減壓過濾，使用2-丙醇(100g)洗淨後，進行乾燥處理，而得粉末結晶(5) (產量22.9g，產率76%)。 　　1H-NMR(DMSO-d6 )：7.20-7.17(4H, m), 6.60-6.57(4H, m), 5.99(2H, s), 5.73(2H, q), 3.45(3H, s), 2.70(6H, d) 　　[0086]於1L的四口燒瓶中，加入氫化鈉(19.7g, 494 mmol)及N-甲基吡咯啶酮(20g)，予以冰冷。於氮氣流下，將化合物(5) (22.9g, 78.7 mmol)及N-甲基吡咯啶酮(115g)之溶液緩緩滴入其中之後，其次，滴入4-氟硝基苯(44.4g、315 mmol)及N-甲基吡咯啶酮(44g)之溶液，於室溫下攪拌24小時。 　　[0087] 使用HPLC(高速液體層析儀)確認反應結束後，將反應液加入冷水(1800g)中，攪拌1小時。所得粗結晶使用四氫呋喃(450g)進行再漿化洗淨(Repulping washing)後，進行減壓過濾，使用甲醇(100g)洗淨，進行乾燥處理，而得粉末結晶(6) (產量22.7g，產率54%)。 　　1H-NMR(DMSO-d6 )：8.09(4H, d), 7.64(4H, d), 7.42 (4H, d), 6.87(4H, d), 6.37(2H, s), 3.69(3H, s), 3.44(6H, s) 　　[0088]將化合物(6) (22.7g、42.6 mmol)、5質量%Pd／C(50%含水型)、特性白鷺活性碳(2.0g)，及二噁烷(230g)之混合物，在氫加壓條件下，於80℃下攪拌8小時。反應結束後，將觸媒過濾後，進行濃縮，加入2-丙醇(300g)，於5℃下攪拌1小時。將析出之結晶減壓過濾，使用2-丙醇(100g)洗淨後，進行乾燥處理，而得粉末結晶(DA-1) (產量17.4g，產率86%)。 　　1H-NMR(DMSO-d6 )：7.20(4H, d), 6.89(4H, d), 6.67-6.59(8H, m), 6.02(2H, s), 5.06(4H, s), 3.46(3H, s), 3.17 (6H, s) 　　[0089] [合成例1] 　　於附有攪拌裝置及氮導入管之100ml的四口燒瓶中，加入DA-1(1.99g，4.2 mmol)之後，加入NMP：GBL＝1：1(質量比)之混合溶劑20.0g，於吹入氮氣間持續攪拌使其溶解。該溶液於攪拌中，加入CA-1(0.61g，2.8 mmol)、CA-2(0.73g，3.7 mmol)，及NMP：GBL＝1：1混合溶劑8.0g之後，再於50℃下攪拌12小時，得聚醯胺酸溶液(PAA-A1)。 　　[0090] [合成例2～6] 　　如表1各別所示內容使用二胺成份、四羧酸成份，及溶劑以外，其他皆依與合成例1相同方法實施，製得聚醯胺酸溶液(PAA-A2)及聚醯胺酸溶液(PAA-B1)～(PAA-B4)。 　　[0091][0092] [合成例7] 　　於附有攪拌裝置及氮導入管之200ml的四口燒瓶中，加入DA-6(4.03g，16.5 mmol)、DA-7(3.59g、9.0 mmol)，及DA-8(2.51g、4.5 mmol)後，加入NMP74.0g，於吹入氮氣間持續攪拌使其溶解。該溶液於攪拌中，加入CA-4(4.37g、19.5 mmol)，及NMP 9.0g，於40℃條件下攪拌3小時。隨後，於25℃條件下，加入CA-2(1.71g，8.7 mmol)，及NMP 9.0g後，再攪拌12小時，而得聚醯胺酸溶液。 　　[0093] 將該聚醯胺酸溶液分餾出80.0g，加入NMP 20.0g後，加入乙酸酐6.8g，及吡啶1.8g，於50℃下反應3小時。將該反應溶液投入於攪拌中的434.4g之甲醇中，將析出之沈澱物濾出。該沈澱物使用甲醇洗淨，於60℃下進行減壓乾燥，得聚醯亞胺之粉末。該聚醯亞胺之醯亞胺化率為75%。於所得聚醯亞胺粉末20.0g中，加入NMP 80.0g，於70℃下攪拌20hr，使其溶解，而製得聚醯亞胺溶液(SPI-B5)。 　　[0094] [合成例8] 　　於附有攪拌裝置及氮導入管之1000mL的四口燒瓶中，量取DA-5(68.5g, 280 mmol)，及DA-8(23.9g, 70 mmol)，加入NMP 586g，於吹入氮氣間持續攪拌使其溶解。該溶液於攪拌中，添加CA-4(74.5g, 332 mmol)，再加入NMP使其固形成份濃度達18質量%，於室溫下攪拌24小時，得聚醯胺酸溶液。 　　量取該聚醯胺酸溶液200g，加入NMP 100g，攪拌30分鐘。於所得聚醯胺酸溶液中，加入乙酸酐21.78g，及吡啶2.81g，於60℃下反應3小時。將所得反應液投入攪拌中的624.2g之甲醇中，將析出之沈澱物濾出。該沈澱物使用甲醇洗淨，於60℃下減壓乾燥，得聚醯亞胺之粉末。該聚醯亞胺之醯亞胺化率為68%。於所得聚醯亞胺粉末32.7g中，加入NMP 239.8g，於70℃下攪拌20小時使其溶解，而得聚醯亞胺溶液(SPI-B6)。 　　[0095] [實施例1～12]及[比較例1～7] 　　將合成例1～6所得之聚醯胺酸溶液，及合成例7、8所得之聚醯亞胺溶液，分別依表2及表3所示組成，於攪拌中，添加溶劑及添加劑，再於室溫下攪拌2小時，而製得實施例1～12及比較例1～7之液晶配向劑。 　　又，表2、3中，※1、※2表示相對於全部聚合物100質量份，所含有(添加)之量(質量份)；※3表示相對於液晶配向劑100質量份，溶劑之使用量(質量份)。 　　[0096][0097][0098] ＜使用摩擦法之液晶顯示元件的製作＞ 　　準備縱30mm×橫35mm大小的厚度為0.7mm之附有電極的玻璃基板。於基板上形成第1層之構成對向電極的具備黏稠狀圖型的IZO電極。第1層的對向電極上的第2層，為形成依CVD法成膜之SiN(氮化矽)膜。第2層的SiN膜之膜厚為500nm，具有作為層間絕緣膜之機能。第2層之SiN膜上，配置有作為第3層的使用圖型形成(Patterning)法形成IZO膜的櫛齒狀之畫素電極，而形成第1畫素及第2畫素等2個畫素。各畫素之尺寸為縱10mm、橫約5mm。此時，第1層之對向電極與第3層之畫素電極，為受到第2層的SiN膜之作用而形成電絕緣。 　　[0099] 第3層之畫素電極，為具有由多數個具有中央部份屈曲為「ㄑ」字形狀的電極要素配列所構成的櫛齒狀形狀(參照日本特開2014-77845號公報之圖3)。各電極要素之短邊方向的寬度為3μm，電極要素間之間隔為6μm。形成各畫素的畫素電極，因具有多數個中央部份為屈曲的「ㄑ」字形狀之電極要素配列之構成，故各畫素的形狀並非長方形之形狀，而與電極要素相同般，為具備中央部份為屈曲狀的近似粗體「ㄑ」字的形狀。因此，各畫素以其中央的屈曲部份作為分界而分割為上下，即，具有屈曲部份的上側之第1區域與下側之第2區域。 　　[0100] 各畫素之第1區域與第2區域比較時，得知構成該些之畫素電極的電極要素為具有不同形成方向者。即，以後述液晶配向膜的摩擦方向作為基準時，畫素的第1區域中之畫素電極的電極要素為以+10°之角度(順時鐘方向)方式形成，畫素的第2區域中之畫素電極的電極要素為以-10°之角度(順時鐘方向)方式形成者。又，各畫素的第1區域與第2區域為具有，對於畫素電極與對向電極之間施加電壓所引發的液晶於基板面內的迴轉動作(面內・開閉)之方向為互相相反的構成。 　　[0101] 其次，將液晶配向劑使用孔徑1.0μm的過濾器過濾後，旋轉塗佈於與上述附有電極的基板的對向基板之內面形成ITO膜，且具有高度4μm的柱狀間隔器的玻璃基板上。其次，於80℃的加熱板上乾燥5分鐘後，於230℃燒結20分鐘，於各基板上製得膜厚60nm之聚醯亞胺膜。將該聚醯亞胺膜面，於滾筒徑120mm、輥迴轉數500rpm、平台移動速度30mm／sec、摩擦布壓入壓0.3mm之條件，使用嫘縈布施以摩擦處理後，於純水中進行1分鐘超音波照射，於80℃乾燥10分鐘。 　　使用上述附有液晶配向膜的2種類之基板，分別將其以摩擦方向為逆平行方式組合，留存液晶注入口後，將周圍密封，製得晶胞間隙(Cell Gap)為3.8μm之空晶格。將液晶(莫克公司製、MLC-3019)於常溫下真空注入該空晶格後，將注入口密封，得逆平行配向之液晶晶格。所得液晶晶格，為構成FFS模式液晶顯示元件者。隨後，將液晶晶格於120℃下加熱1小時，放置一晩後，作為評估用。 　　[0102] ＜殘像消除時間之評估＞ 　　將所製得之液晶晶格設置於偏光軸為垂直交叉配置的2片偏光板之間，於無施加電壓之狀態，將LED背光源點燈放置，將液晶晶格的配置角度調整至穿透光的亮度為最小之角度。其次，使用周波數30Hz的交流電壓施加於該液晶晶格過程中，測定V-T曲度(電壓-穿透率曲線)，算出相對穿透率為23%之交流電壓作為驅動電壓。 　　殘像評估中，為於施加相對穿透率為23%的周波數30Hz的交流電壓驅動液晶晶格過程中，同時施加1V之直流電壓，驅動30分鐘。隨後，將施加直流電壓值調整為0V，僅停止直流電壓之施加狀態下，再驅動15分鐘。 　　[0103] 殘像評估為，由將開始施加直流電壓的時點起，經過30分鐘後，相對穿透率低於30%以下的時間予以數值化。相對穿透率於5分鐘內降低至30%以下時，標記為「○」，於6～30分鐘以內時，則評估為「△」。相對穿透率降低至30%以下的時間需要30分鐘以上時，視為無法消除殘像，則評估為「×」。其中，依上述方法實施的殘像評估，為於液晶晶格的溫度為23℃之狀態的溫度條件下進行。 　　[0104] ＜開始驅動時隨即引起的閃爍變動之評估＞ 　　將所製得的液晶晶格設置於偏光軸為垂直交叉配置的2片偏光板之間，於無施加電壓之狀態下，將LED背光源點燈放置，將液晶晶格的配置角度調整至穿透光的亮度為最小之角度。其次，將周波數30Hz的交流電壓施加於該液晶晶格過程中，測定V-T曲度(電壓-穿透率曲線)，算出相對穿透率為23%時之交流電壓作為驅動電壓。 　　[0105] 閃爍程度之測定，為將點燈後放置的LED背光源於消去燈光後，遮光放置72小時之後，將LED背光源再度點燈，於背光源點燈開始的同時，施加相對穿透率為23%的周波數30Hz之交流電壓，並追蹤液晶晶格驅動60分鐘後的閃爍之振幅。閃爍振幅，為使用介由光二極體及I-V變換幫浦連接的數據收集/數據記錄交換單位34970A (Agilent technologies公司製)讀取通過2片的偏光板及其中間的液晶晶格之LED背光源的穿透光數據而得。閃爍程度可依以下數學式而算出。 　　閃爍程度(%)＝{閃爍振幅／(2×z)}×100 　　[0106] 上述式中，z為使用數據收集/數據記錄交換單位34970A所讀取得相對穿透率為23%的周波數30Hz之交流電壓驅動之際的亮度值。 　　閃爍程度之評估，為由LED背光源之點燈及施加交流電壓開始的時點起，經過60分鐘為止時，閃爍程度維持未達3%之情形，則定義為「○」之方式進行評估。60分鐘後閃爍程度達3%以上之情形，則定義為「×」之方式進行評估。 　　依上述方法所進行的閃爍程度之評估，為於液晶晶格溫度為23℃之狀態的溫度條件下進行者。 　　[0107] ＜評估結果＞ 　　使用上述實施例1、2、4、5及比較例1～4、6、7等各液晶配向劑的液晶顯示元件中，於上述實施的殘像消除時間，及開始驅動時隨即引起的閃爍變動的評估結果係如表4～表6所示。 　　又，表4～6中，※1表示相對於全部聚合物100質量份，各聚合物之含量(質量份)。 　　[0108][0109][0110][0111] 由表4～表6得知，使用實施例1、2、4、5之液晶配向劑的液晶顯示元件，可快速地緩和蓄積電荷，且不易引發開始驅動時隨即引起的閃爍變動。 　　[0112] ＜使用光配向法的液晶顯示元件之製作＞ 　　將液晶配向劑使用孔徑1.0μm之過濾器過濾後，將其分別旋轉塗佈於所準備的上述附有電極之基板與作為對向基板的內面形成ITO膜，且具有高度4μm的柱狀間隔器的玻璃基板上。其次，於80℃之加熱板上乾燥5分鐘後，於230℃燒結30分鐘，於各基板上製得膜厚100nm之塗膜的聚醯亞胺膜。使用消光比26：1的直線偏光之波長254nm的紫外線，以250mJ／cm2 介由偏光板照射塗膜面。 　　[0113] 將該基板浸漬於25℃之EL(乳酸乙酯)溶液5分鐘，其次浸漬於25℃之純水1分鐘後，於230℃之加熱板上加熱30分鐘，製得附有液晶配向膜之基板。將上述2片的基板作為一組，於基板上印刷密封劑，將另1片基板，以液晶配向膜面互相面向的配向方向為0°之方式貼合後，將密封劑硬化而製得空晶格。該空晶格使用減壓注入法，注入負型液晶之MLC-7026-100(莫克公司製)後，將注入口密封，而製得FFS驅動液晶晶格。隨後，將所得液晶晶格於110℃下加熱1小時，放置一晩後，供各評估使用。 　　[0114] ＜殘像消除時間之評估＞ 　　其與使用摩擦法評估液晶顯示元件之情形為相同，使用依上述之光配向法而得之液晶顯示元件的光學系統等進行殘像之評估。 ＜驅動後隨即的閃爍程度之評估＞ 　　其與摩擦法評估液晶顯示元件之情形為相同，使用依上述之光配向法而得之液晶顯示元件的光學系統等進行殘像之評估。 　　[0115] ＜評估結果＞ 　　對使用上述實施例12及比較例7所得之液晶配向劑的液晶顯示元件，依上述內容實施的殘像消除時間之評估，及驅動後隨即的閃爍程度之評估結果係如表7所示。又，表7中，※1表示相對於全部聚合物100質量份，各聚合物之含量(質量份)。 　　[0116][0117] 由表7內容得知，使用實施例12的液晶配向劑之液晶顯示元件，可快速地緩和蓄積之電荷，且不易於開始驅動時隨即發生閃爍變動。 [產業上利用性] 　　[0118] 使用本發明之新穎聚合物的液晶配向劑，可廣泛地使用於TN方式、VA方式等的縱向電場方式，特別是IPS方式、FFS方式等的橫向電場方式之液晶表示元件。 　　又，2016年9月29日所申請的日本專利出願2016-191765號之說明書、申請專利範圍、圖式，及摘要等全部內容皆可引用於此內容，作為本發明之說明書之揭示內容。[Examples] [0072] Hereinafter, the present invention will be specifically described with examples and the like. The explanation of the present invention is not limited to these examples. The abbreviations of the raw materials described below and the evaluation methods of the characteristics are shown below. [0073] [Organic solvents] NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone GBL: γ-butyrolactone, BCS: butyl cellosolve PB: Propylene glycol monobutyl ether DME: dipropylene glycol dimethyl ether DAA: 4-hydroxy-4-methyl-2-pentanone DEDG: diethylene glycol diethyl ether DIBK: 2,6-dimethyl-4-heptanone, DIPE : Diisopropyl ether, DIBC: 2,6-dimethyl-4-heptanol, Pd / C: palladium on carbon, DMSO: dimethylsulfoxide, THF: tetrahydrofuran <additives> LS-4668: 3-ring Oxypropoxypropyltriethoxysilane [0075] <crosslinking agent> [0076] In the description, Boc and Fmoc represent a group shown below, and Me represents a methyl group. [Measurement of 1 H-NMR] Apparatus: Varian NMR system 400NB (400MHz) (manufactured by Varian), and JMTC-500 / 54 / SS (500MHz) (manufactured by JEOL) Measurement solvent: CDCl 3 (deuterium Chloroform), DMSO-d 6 (dihydrodimethylidene) Reference materials: TMS (tetramethylsilane) (d: 0.0 ppm, 1 H) and CDCl 3 (d: 77.0 ppm, 13 C) [0078] (Measurement of hydrazone imidization ratio) 20 mg of polyfluorene imine powder was added to an NMR sample tube (NMR standard sample tube, φ5 (made by Kusano Science Co., Ltd.)), and deuterium dimethylsulfine (DMSO-d6, 0.05%) TMS (tetramethylsilane) mixed product) (0.53ml). This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500, manufactured by Japan Electronics Data Corporation). The fluorene imidization rate is determined based on the protons derived from structures that have not changed before and after fluorimidization as the reference protons. Therefore, the peak value of the proton can be used to compare with the fluorene from 9.5 ppm to 10.0 ppm. The proton peak integrated value derived from the NH group of the acid can be obtained by the following calculation formula.醯 imidization ratio (%) = (1-α · x / y) × 100 In the above formula, x is the integrated value of the proton peak derived from the NH group of the phosphonium acid, y is the integrated value of the peak of the reference proton, α In the case of polyamidic acid (the imidization ratio of fluorene is 0%), the ratio of the number of reference protons to one NH matrix proton of phosphoamic acid. [Synthesis of Diamine Compound (DA-1)> [0080] In a 3 L (liter) four-necked flask, zinc chloride (120.3 g, 882 mmol) was added, the temperature was raised to 100 ° C, and vacuum drying was performed using an oil pump for 1 hour. Subsequently, toluene (460 g), diethylamine (45.0 g, 615 mmol), t-butanol (46.4 g, 626 mmol), and 2-bromo-4-nitro were sequentially added at room temperature under a nitrogen atmosphere. Acetophenone (100.0 g, 410 mmol) and 4-nitroacetophenone (104.2 g, 631 mmol) were stirred at room temperature for 3 days. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), a 5% sulfuric acid aqueous solution (400 g) was added to neutralize the solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with toluene (200 g), pure water (300 g), and methanol (200 g) in that order, and then dried to obtain crude crystals. The obtained crude crystals were added to tetrahydrofuran (1340 g) and completely dissolved at 60 ° C, and then ethanol (1340g) was added, followed by stirring at 5 ° C for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with ethanol (200 g), and then dried to obtain powder crystals (1) (yield 63 g, yield 45%). 1H-NMR (DMSO-d 6 ): 8.40-8.36 (4H, m), 8.28-8.24 (4H, m), 3.53 (4H, s) [0081] In a 2 L four-necked flask, compound (1) (65.8 g, 200 mmol), ammonium acetate (84.5 g, 1100 mmol), and acetic acid (855 g) were added, the temperature was raised to 120 ° C, and the mixture was stirred under reflux for 3 hours. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the reaction solution was added to cold water (4000 g) and stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, and repulping washing was performed using acetonitrile (100 g), followed by drying treatment to obtain powder crystals (2) (yield 53 g, yield 78%). 1H-NMR (DMSO-d 6 ): 11.8 (1H, br), 8.30-8.26 (4H, m), 8.11-8.07 (4H, m), 7.04 (2H, s) [0082] In a 1-liter four-necked flask, compound (2) (41.3 g, 134 mmol), potassium carbonate (27.8 g, 201 mmol), and dimethylformamide (540 g) were added, and iodinated dropwise at room temperature. Methyl ester (38.1 g, 268 mmol), stirred for 24 hours. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the reaction solution was added to cold water (4300 g) and stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (100 g), and then dried to obtain powder crystals (3) (yield 41.1 g, yield 90%). 1H-NMR (DMSO-d 6 ): 8.34-8.33 (4H, m), 7.86-7.81 (4H, m), 6.67 (2H, s), 3.73 (3H, s) [0083] A mixture of compound (3) (40 g, 124 mmol), 5 mass% Pd / C (50% water-containing type), special egret activated carbon (4.0 g), and dioxane (400 g) under hydrogen pressure And stirred at 80 ° C for 8 hours. After the completion of the reaction, the catalyst was filtered, and then concentrated, and 2-propanol (400 g) was added, followed by stirring at 5 ° C for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (100 g), and then dried to obtain powder crystals (4) (yield 17 g, yield 52%). 1H-NMR (DMSO-d 6 ): 7.11-7.08 (4H, m), 6.63-6.59 (4H, m), 5.96 (2H, s), 5.15 (4H, s), 3.43 (3H, s) [0084 ] In a 1 L four-necked flask, compound (4) (27.4 g, 104 mmol) and THF (270 g) were added, and trifluoroacetic anhydride (46.5 g, 220 mmol) was added dropwise under ice cooling, and the mixture was stirred for 1 hour. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the solution was concentrated to dryness. To the obtained solid, THF (600 g) and potassium carbonate (45.1 g, 326 mmol) were added, and methyl iodide (45.8 g, 324 mmol) was added dropwise at room temperature, followed by stirring at 40 ° C for 22 hours. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the salt was filtered off under reduced pressure, and concentrated and dried. [0085] To the obtained solid, N-methylpyrrolidone (200 g), pure water (30 g), and potassium hydroxide (20.8 g, 315 mmol) were added, and stirred at 60 ° C. for 30 minutes. After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the reaction solution was added to cold water (1200 g) and stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (100 g), and then dried to obtain powder crystals (5) (yield 22.9 g, yield 76%). 1H-NMR (DMSO-d 6 ): 7.20-7.17 (4H, m), 6.60-6.57 (4H, m), 5.99 (2H, s), 5.73 (2H, q), 3.45 (3H, s), 2.70 (6H, d) [0086] In a 1 L four-necked flask, sodium hydride (19.7 g, 494 mmol) and N-methylpyrrolidone (20 g) were added, and the mixture was ice-cooled. A solution of compound (5) (22.9 g, 78.7 mmol) and N-methylpyrrolidone (115 g) was slowly dropped into the solution under a nitrogen stream, and then 4-fluoronitrobenzene (44.4 g, 315 mmol) and N-methylpyrrolidone (44 g), and stirred at room temperature for 24 hours. [0087] After confirming the completion of the reaction using HPLC (high-speed liquid chromatography), the reaction solution was added to cold water (1800 g) and stirred for 1 hour. The obtained crude crystals were repulping washed with tetrahydrofuran (450g), and then filtered under reduced pressure, washed with methanol (100g), and dried to obtain powder crystals (6) (yield 22.7g, yield Rate 54%). 1H-NMR (DMSO-d 6 ): 8.09 (4H, d), 7.64 (4H, d), 7.42 (4H, d), 6.87 (4H, d), 6.37 (2H, s), 3.69 (3H, s ), 3.44 (6H, s) [0088] A mixture of compound (6) (22.7 g, 42.6 mmol), 5 mass% Pd / C (50% water-containing type), characteristic egret activated carbon (2.0 g), and dioxane (230 g) was subjected to hydrogen pressure. Then, it stirred at 80 degreeC for 8 hours. After the reaction was completed, the catalyst was filtered and concentrated, and 2-propanol (300 g) was added, followed by stirring at 5 ° C for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (100 g), and then dried to obtain powder crystals (DA-1) (yield 17.4 g, yield 86%). 1H-NMR (DMSO-d 6 ): 7.20 (4H, d), 6.89 (4H, d), 6.67-6.59 (8H, m), 6.02 (2H, s), 5.06 (4H, s), 3.46 (3H , s), 3.17 (6H, s) [0089] [Synthesis Example 1] In a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 (1.99 g, 4.2 mmol) was added, and then NMP was added. : 20.0 g of a mixed solvent of GBL = 1: 1 (mass ratio), which was continuously stirred to dissolve while blowing in nitrogen. After the solution was stirred, CA-1 (0.61 g, 2.8 mmol), CA-2 (0.73 g, 3.7 mmol), and 8.0 g of a mixed solvent of NMP: GBL = 1: 1 were added, followed by stirring at 50 ° C for 12 hours. After hours, a polyamic acid solution (PAA-A1) was obtained. [Synthesis Examples 2 to 6] As shown in Table 1, the diamine component, the tetracarboxylic acid component, and the solvent were used in the same manner as in Synthesis Example 1 except that the polyamine solution was prepared. (PAA-A2) and polyamino acid solution (PAA-B1) to (PAA-B4). [0091] [Synthesis Example 7] In a 200-ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-6 (4.03 g, 16.5 mmol), DA-7 (3.59 g, 9.0 mmol), and DA were added. After -8 (2.51 g, 4.5 mmol), 74.0 g of NMP was added, and stirring was continued while blowing nitrogen to dissolve. CA-4 (4.37 g, 19.5 mmol) and 9.0 g of NMP were added to the solution while stirring, and the solution was stirred at 40 ° C for 3 hours. Subsequently, CA-2 (1.71 g, 8.7 mmol) and 9.0 g of NMP were added at 25 ° C, and the mixture was stirred for another 12 hours to obtain a polyamic acid solution. [0093] 80.0 g of this polyphosphonic acid solution was fractionally distilled. After adding 20.0 g of NMP, 6.8 g of acetic anhydride and 1.8 g of pyridine were added, and the reaction was carried out at 50 ° C. for 3 hours. This reaction solution was poured into 434.4 g of methanol under stirring, and the precipitated precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyimide powder. The polyimide has an imidization ratio of 75%. To 20.0 g of the obtained polyfluorene imide powder, 80.0 g of NMP was added, and the mixture was stirred at 70 ° C. for 20 hours to be dissolved to prepare a polyfluorene imide solution (SPI-B5). [Synthesis Example 8] In a 1000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-5 (68.5 g, 280 mmol) and DA-8 (23.9 g, 70 mmol) were measured. 586 g of NMP was added, and stirring was continued while blowing nitrogen gas to dissolve. CA-4 (74.5 g, 332 mmol) was added to the solution while stirring, and then NMP was added to make the solid content concentration reach 18% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution. Measure 200 g of the polyamidic acid solution, add 100 g of NMP, and stir for 30 minutes. To the obtained polyamic acid solution, 21.78 g of acetic anhydride and 2.81 g of pyridine were added, and the mixture was reacted at 60 ° C. for 3 hours. The obtained reaction solution was poured into 624.2 g of methanol under stirring, and the precipitated precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyimide powder. The polyimide has a hydrazone imidization rate of 68%. To 32.7 g of the obtained polyfluorene imide powder, 239.8 g of NMP was added and stirred at 70 ° C. for 20 hours to dissolve, thereby obtaining a polyfluorene imide solution (SPI-B6). [Examples 1 to 12] and [Comparative Examples 1 to 7] The polyamidic acid solution obtained in Synthesis Examples 1 to 6 and the polyamidoimine solution obtained in Synthesis Examples 7 and 8 were respectively according to Table 2 With the composition shown in Table 3, solvents and additives were added to the mixture, and the mixture was stirred at room temperature for 2 hours to prepare liquid crystal alignment agents of Examples 1 to 12 and Comparative Examples 1 to 7. In Tables 2 and 3, ※ 1 and ※ 2 indicate the amount (mass) contained (added) with respect to 100 parts by mass of the entire polymer; ※ 3 indicates the use of solvent with respect to 100 parts by mass of the liquid crystal alignment agent. Amount (parts by mass). [0096] [0097] [Production of Liquid Crystal Display Element Using Friction Method] A glass substrate with an electrode having a thickness of 0.7 mm and a thickness of 30 mm in length and 35 mm in width was prepared. An IZO electrode having a viscous pattern is formed on the substrate as a first layer and constitutes a counter electrode. The second layer on the counter electrode of the first layer is a SiN (silicon nitride) film formed by a CVD method. The SiN film of the second layer has a film thickness of 500 nm and has a function as an interlayer insulating film. On the second layer of the SiN film, as the third layer, a dentate pixel electrode is formed by using a patterning method to form an IZO film, and two pictures such as a first pixel and a second pixel are formed. Vegetarian. The size of each pixel is 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated to receive the action of the SiN film of the second layer. [0099] The pixel electrode of the third layer has a dentate shape composed of a plurality of electrode element arrays having a central portion buckled into a "ㄑ" shape (see Japanese Patent Application Laid-Open No. 2014-77845). 3). The width in the short-side direction of each electrode element is 3 μm, and the interval between the electrode elements is 6 μm. The pixel electrode forming each pixel has a configuration of a plurality of electrode elements arranged in a buckled "ㄑ" shape at the central portion. Therefore, the shape of each pixel is not a rectangular shape, but is the same as the electrode element. It has an approximately bold "粗" shape with a buckled central portion. Therefore, each pixel is divided into an upper part and a lower part using the central buckling portion as a boundary, that is, the upper first region and the lower second region having the buckling portion. [0100] When the first region and the second region of each pixel are compared, it is known that the electrode elements constituting the pixel electrodes have different formation directions. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode in the first region of the pixel is formed at an angle (clockwise) of + 10 °, and the second region of the pixel is formed. The pixel elements of the pixel electrode are formed at an angle (clockwise) of -10 °. The first region and the second region of each pixel have opposite directions in which the liquid crystal rotates in the plane of the substrate (in-plane opening / closing) caused by the voltage applied between the pixel electrode and the counter electrode. Composition. [0101] Next, the liquid crystal alignment agent was filtered using a filter having a pore size of 1.0 μm, and then spin-coated on the inner surface of the opposite substrate with the electrode-attached substrate to form an ITO film, and had a columnar spacer having a height of 4 μm. Glass substrate. Next, after drying on a hot plate at 80 ° C. for 5 minutes, sintering at 230 ° C. for 20 minutes, a polyimide film having a film thickness of 60 nm was prepared on each substrate. The polyimide film surface was subjected to rubbing treatment using pure cloth under the conditions of a roller diameter of 120 mm, roll revolutions of 500 rpm, a platform moving speed of 30 mm / sec, and a friction cloth press pressure of 0.3 mm. Ultrasonic irradiation for 1 minute, and drying at 80 ° C for 10 minutes. The two types of substrates with a liquid crystal alignment film are used, and the rubbing direction is antiparallel. The liquid crystal injection port is retained, and the surroundings are sealed to obtain an empty crystal with a cell gap of 3.8 μm. grid. Liquid crystal (MLC-3019, manufactured by Mok Corporation) was vacuum-injected into the empty lattice at normal temperature, and then the injection port was sealed to obtain a liquid crystal lattice with antiparallel alignment. The obtained liquid crystal lattice is one constituting an FFS mode liquid crystal display element. Subsequently, the liquid crystal lattice was heated at 120 ° C. for 1 hour, and left for a while to serve as an evaluation. [0102] <Evaluation of Afterimage Removal Time> The prepared liquid crystal lattice is set between two polarizing plates whose polarizing axes are vertically crossed, and the LED backlight is turned on in a state where no voltage is applied. The arrangement angle of the liquid crystal lattice is adjusted to an angle at which the brightness of transmitted light is minimized. Next, the VT curvature (voltage-transmittance curve) was measured while an AC voltage of 30 Hz was applied to the liquid crystal lattice, and an AC voltage with a relative transmittance of 23% was calculated as the driving voltage. In the afterimage evaluation, during the driving of the liquid crystal lattice by applying an AC voltage with a frequency of 30% and a relative transmittance of 23%, a DC voltage of 1V was applied for 30 minutes. Subsequently, the value of the applied DC voltage was adjusted to 0V, and only the application of the DC voltage was stopped, and the drive was continued for 15 minutes. [0103] The afterimage was evaluated as the time when the relative transmittance was less than 30% after 30 minutes had elapsed from the time when the DC voltage was applied. When the relative transmittance decreases to 30% or less within 5 minutes, it is marked as "○", and when it is within 6 to 30 minutes, it is evaluated as "△". If it takes more than 30 minutes to reduce the relative transmittance to less than 30%, it is considered that the afterimage cannot be eliminated, and it is evaluated as "×". The afterimage evaluation performed according to the above method was performed under a temperature condition where the temperature of the liquid crystal lattice was 23 ° C. [0104] <Evaluation of Flicker Changes Caused Immediately at the Start of Driving> The obtained liquid crystal lattice was set between two polarizing plates whose polarizing axes were vertically intersected, and the LED was backlit without applying a voltage. Place the source lighting and adjust the arrangement angle of the liquid crystal lattice to an angle where the brightness of the transmitted light is the smallest. Next, the VT curvature (voltage-transmittance curve) was measured while an AC voltage of 30 Hz was applied to the liquid crystal lattice, and the AC voltage at a relative transmittance of 23% was calculated as the driving voltage. [0105] The measurement of the degree of flicker is to place the LED backlight placed after lighting on after eliminating the light, and place it in the light for 72 hours after shading, and then turn on the LED backlight again, and apply relative penetration at the same time as the backlight lighting starts. The AC voltage with a frequency of 23% and a frequency of 30 Hz, and tracked the amplitude of the flicker after the liquid crystal lattice was driven for 60 minutes. The flicker amplitude is an LED backlight source that reads through two polarizers and the liquid crystal lattice in the middle using a data collection / data recording exchange unit 34970A (manufactured by Agilent Technologies) connected via a photodiode and an IV conversion pump. Derived from the transmitted light data. The degree of flicker can be calculated by the following mathematical formula. Flicker degree (%) = {flicker amplitude / (2 × z)} × 100 [0106] In the above formula, z is a cycle number of 30% with a relative transmission rate of 23%, which is read using a data collection / data recording exchange unit 34970A. The brightness value when the AC voltage is driven. The evaluation of the flicker level is defined as "○" when the flicker level remains below 3% after 60 minutes have elapsed from the time when the LED backlight source was turned on and the AC voltage was applied. When the flicker degree reaches more than 3% after 60 minutes, it is defined as "×" for evaluation. The evaluation of the flicker degree according to the above method was performed under a temperature condition where the liquid crystal lattice temperature was 23 ° C. [0107] <Evaluation Results> In the liquid crystal display elements using the liquid crystal alignment agents of Examples 1, 2, 4, 5 and Comparative Examples 1 to 4, 6, 7, and the like, the afterimage erasing time and the start of Table 4 to Table 6 show the evaluation results of flicker changes caused immediately after driving. In Tables 4 to 6, * 1 indicates the content (parts by mass) of each polymer relative to 100 parts by mass of the entire polymer. [0108] [0109] [0110] [0111] As can be seen from Tables 4 to 6, the liquid crystal display element using the liquid crystal alignment agent of Examples 1, 2, 4, and 5 can quickly alleviate the accumulated charge, and it is not easy to cause flicker changes immediately after the start of driving. [0112] <Production of a liquid crystal display element using a photo-alignment method> After a liquid crystal alignment agent was filtered using a filter having a pore diameter of 1.0 μm, it was spin-coated on the prepared substrate with an electrode and a counter substrate. An ITO film is formed on the inner surface of the substrate, and a glass substrate having a columnar spacer having a height of 4 μm is formed. Next, after drying on a hot plate at 80 ° C. for 5 minutes, sintering at 230 ° C. for 30 minutes, a polyimide film with a film thickness of 100 nm was prepared on each substrate. Ultraviolet rays having a linear extinction ratio of 26: 1 and a wavelength of 254 nm were used, and the coating film surface was irradiated with a polarizing plate at 250 mJ / cm 2 . [0113] The substrate was immersed in an EL (ethyl lactate) solution at 25 ° C for 5 minutes, followed by immersion in pure water at 25 ° C for 1 minute, and then heated on a heating plate at 230 ° C for 30 minutes to obtain a liquid crystal alignment. Film substrate. Using the above two substrates as a set, a sealant was printed on the substrate, and the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surfaces facing each other was 0 °, and the sealant was hardened to make it empty Crystal lattice. This empty lattice was filled with negative liquid crystal MLC-7026-100 (manufactured by Mok) using a reduced pressure injection method, and then the injection port was sealed to obtain an FFS-driven liquid crystal lattice. Subsequently, the obtained liquid crystal lattice was heated at 110 ° C. for 1 hour, and left for a while to be used for each evaluation. [0114] <Evaluation of Afterimage Removal Time> This is the same as the case where the liquid crystal display element is evaluated by the rubbing method, and the afterimage is evaluated using the optical system of the liquid crystal display element obtained by the light alignment method described above. <Evaluation of Flicker Degree Immediately After Driving> This is the same as the case of evaluating the liquid crystal display element by the rubbing method, and the afterimage is evaluated using the optical system of the liquid crystal display element obtained by the light alignment method described above. [0115] <Evaluation Results> For the liquid crystal display device using the liquid crystal alignment agent obtained in the above-mentioned Example 12 and Comparative Example 7, the evaluation of the afterimage erasing time and the evaluation of the flicker degree immediately after the driving were performed. As shown in Table 7. In Table 7, * 1 indicates the content (parts by mass) of each polymer relative to 100 parts by mass of the entire polymer. [0116] [0117] It is known from Table 7 that the liquid crystal display element using the liquid crystal alignment agent of Example 12 can quickly alleviate the accumulated electric charge, and it is not easy to cause flicker changes immediately when driving is started. [Industrial Applicability] [0118] The liquid crystal alignment agent using the novel polymer of the present invention can be widely used in vertical electric field methods such as the TN method and the VA method, especially in the lateral electric field methods such as the IPS method and the FFS method. Liquid crystal display element. In addition, the entire contents of the specification, patent application scope, drawings, and abstract of Japanese Patent Application No. 2016-191765 filed on September 29, 2016 can be incorporated herein as disclosure of the description of the invention.

Claims (15)

一種液晶配向劑，其特徵為，含有由具有下述式(1)所表示之結構的二胺所製得之聚合物，與有機溶劑；(式(1)中，R1 、R2 為氫原子，或一價之有機基；苯環中的任意氫原子可被一價之有機基所取代；＊表示鍵結部位)。A liquid crystal alignment agent, comprising a polymer prepared from a diamine having a structure represented by the following formula (1), and an organic solvent; (In the formula (1), R 1 and R 2 are a hydrogen atom or a monovalent organic group; any hydrogen atom in the benzene ring may be replaced by a monovalent organic group; * represents a bonding site). 如請求項1之液晶配向劑，其中，前述聚合物為，由具有前述式(1)所表示之結構的二胺與四羧酸二酐之聚縮合物的聚醯亞胺前驅體，及其醯亞胺化物之聚醯亞胺所成之群所選出之至少1種的聚合物。The liquid crystal alignment agent according to claim 1, wherein the polymer is a polyimide precursor comprising a polycondensate of a diamine and a tetracarboxylic dianhydride having a structure represented by the formula (1), and A polymer of at least one selected from the group consisting of polyimide of amidine imide. 如請求項1或2之液晶配向劑，其中，前述二胺為以下式(2)所表示者；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容，R3 各自獨立表示單鍵或以下式(3)之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)(式(3)中，R4 表示由單鍵、-O-、-COO-、-OCO-、 -(CH2 )l -、-O(CH2 )m O-、-CONH-，及-NHCO-所選出的2價之有機基(l、m表示1～5之整數)；＊1 表示與式(2)中的苯環鍵結之部位；＊2 表示與式(2)中的胺基鍵結之部位)。The liquid crystal alignment agent according to claim 1 or 2, wherein the aforementioned diamine is represented by the following formula (2); (In the formula (2), the definitions of R 1 and R 2 are the same as those in the above formula (1), and each of R 3 independently represents a single bond or a structure of the following formula (3); n represents an integer of 1 to 3; benzene (Any hydrogen atom in the ring may be replaced by a monovalent organic group) (In the formula (3), R 4 represents a single bond, -O -, - COO -, - OCO-, - (CH 2) l -, - O (CH 2) m O -, - CONH-, and - NHCO- selected divalent organic group (l, m represents integers from 1 to 5); * 1 represents a site bonded to a benzene ring in formula (2); * 2 represents an amine in formula (2) Base bond). 如請求項1～3中任一項之液晶配向劑，其中，前述聚醯亞胺前驅體具有下述式(4)所表示之結構；(式(4)中，X1 為由四羧酸衍生物所產生的4價之有機基，Y1 為由前述式(1)所表示的二胺所產生的2價之有機基，R5 為氫原子或碳數1～5之烷基)。The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polyfluorene imide precursor has a structure represented by the following formula (4); (In formula (4), X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from a diamine represented by the aforementioned formula (1), and R 5 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 如請求項4之液晶配向劑，其中，前述式(4)中，X1 為由下述(A-1)～(A-21)之結構所成之群所選出之至少1種； 。The liquid crystal alignment agent according to claim 4, wherein in the formula (4), X 1 is at least one selected from the group consisting of the following structures (A-1) to (A-21); . 如請求項4或5之液晶配向劑，其中，具有前述式(4)所表示之結構單位的聚合物，相對於液晶配向劑所含的全聚合物，為含有10莫耳%以上。The liquid crystal alignment agent according to claim 4 or 5, wherein the polymer having the structural unit represented by the aforementioned formula (4) contains 10 mol% or more of the total polymer contained in the liquid crystal alignment agent. 如請求項1～6中任一項之液晶配向劑，其中，前述有機溶劑為含有由4-羥基-4-甲基-2-戊酮及二乙二醇二乙醚所成之群所選出之至少1種。The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the organic solvent is selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether. At least one. 一種液晶配向膜，其特徵為，使用請求項1～7中任一項之液晶配向劑而製得者。A liquid crystal alignment film, which is prepared by using the liquid crystal alignment agent according to any one of claims 1 to 7. 一種液晶顯示元件，其特徵為，具備請求項8之液晶配向膜。A liquid crystal display element comprising the liquid crystal alignment film of claim 8. 如請求項9之液晶顯示元件，其中，液晶顯示元件為橫向電場驅動方式者。For example, the liquid crystal display element of claim 9, wherein the liquid crystal display element is a transverse electric field driving method. 一種聚合物，其特徵為，由具有下述式(1)所表示之結構的二胺與四羧酸二酐之聚縮合物的聚醯亞胺前驅體，及其醯亞胺化物的聚醯亞胺所成之群所選出之至少1種；(式(1)中，R1 、R2 為氫原子，或一價之有機基；苯環中的任意氫原子可被一價之有機基所取代；＊表示鍵結部位)。A polymer comprising a polyimide precursor of a polycondensation product of a polycondensation product of a diamine and a tetracarboxylic dianhydride having a structure represented by the following formula (1), and a polyfluorene of an ammonium imide At least one selected from the group of imines; (In the formula (1), R 1 and R 2 are a hydrogen atom or a monovalent organic group; any hydrogen atom in the benzene ring may be replaced by a monovalent organic group; * represents a bonding site). 如請求項11之聚合物，其中，上述之二胺為下式(2)所表示者；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容；R3 各自獨立為單鍵，或具有以下式(3)所表示之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)(式(3)中，R4 表示由單鍵、-O-、-COO-、-OCO-、 -(CH2 )l -、-O(CH2 )m O-、-CONH-，及-NHCO-所選出的2價之有機基(l、m表示1～5之整數)；＊1 表示與式(2)中的苯環鍵結之部位；＊2 表示與式(2)中的胺基鍵結之部位)。The polymer according to claim 11, wherein the above diamine is represented by the following formula (2); (In the formula (2), the definitions of R 1 and R 2 are the same as the above formula (1); each of R 3 is a single bond or has the structure represented by the following formula (3); n represents 1 to 3 Integer; any hydrogen atom in the benzene ring can be replaced by a monovalent organic group) (In the formula (3), R 4 represents a single bond, -O -, - COO -, - OCO-, - (CH 2) l -, - O (CH 2) m O -, - CONH-, and - NHCO- selected divalent organic group (l, m represents integers from 1 to 5); * 1 represents a site bonded to a benzene ring in formula (2); * 2 represents an amine in formula (2) Base bond). 如請求項11或12之聚合物，其中，前述聚醯亞胺前驅體為由下述式(4)所表示者；(式(4)中，X1 為由四羧酸衍生物所產生的4價之有機基，Y1 為由前述式(1)所表示的二胺所產生的2價之有機基，R5 為氫原子或碳數1～5之烷基)。The polymer according to claim 11 or 12, wherein the aforementioned polyimide precursor is represented by the following formula (4); (In formula (4), X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from a diamine represented by the aforementioned formula (1), and R 5 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 如請求項13之聚合物，其中，前述式(6)中，X1 為由下述(A-1)～(A-21)所表示之結構所成之群所選出的至少1種； 。The polymer according to claim 13, wherein in formula (6), X 1 is at least one selected from the group consisting of the structures represented by the following (A-1) to (A-21); . 一種二胺，其特徵為，由下述式(2)所表示者；(式(2)中，R1 及R2 之定義，與上述式(1)為相同內容；R3 各自獨立為單鍵，或具有以下式(3)所表示之結構；n表示1～3之整數；苯環中的任意氫原子可被一價之有機基所取代)。A diamine characterized by the following formula (2): (In the formula (2), the definitions of R 1 and R 2 are the same as the above formula (1); each of R 3 is a single bond or has the structure represented by the following formula (3); n represents 1 to 3 Integer; any hydrogen atom in the benzene ring may be replaced by a monovalent organic group).
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