TWI750233B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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TWI750233B
TWI750233B TW106133609A TW106133609A TWI750233B TW I750233 B TWI750233 B TW I750233B TW 106133609 A TW106133609 A TW 106133609A TW 106133609 A TW106133609 A TW 106133609A TW I750233 B TWI750233 B TW I750233B
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金爾潤
中原翔一朗
橋本淳
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日商日產化學工業股份有限公司
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    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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Abstract

一種液晶配向劑，其特徵為含有： 　　(A-1)由使用含有下述式(1)所表示之四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(A-2)由使用含有脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(B)由聚醯亞胺前驅體、該聚醯亞胺前驅體之醯亞胺化聚合物及於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物所成之群所選出之至少1種的聚合物， 　　及有機溶劑。

Figure 106133609-A0101-11-0001-1
A liquid crystal aligning agent characterized by containing: (A-1) by using a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (1), and a liquid crystal aligning agent containing the following formula (2) A polyamic acid obtained as a diamine component of a diamine, and a polymer of at least one selected from the imidized polymer of the polyamic acid, (A-2) by using an aliphatic tetracarboxylic acid containing The tetracarboxylic dianhydride component of the acid dianhydride, the polyamic acid obtained by the diamine component containing the diamine represented by the following formula (2), and the imidized polymer of the polyamic acid. At least one selected polymer, (B) a polyimide precursor, an imidized polymer of the polyimide precursor, and a photosensitive side-chain acrylic acid having liquid crystallinity in a specific temperature range At least one polymer selected from the group of polymers, and an organic solvent.
Figure 106133609-A0101-11-0001-1

Description

液晶配向劑、液晶配向膜，及液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

[0001] 本發明為有關液晶顯示元件所使用的液晶配向劑、液晶配向膜，及使用其之液晶顯示元件。[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film used in a liquid crystal display element, and a liquid crystal display element using the same.

[0002] 從以往以來，液晶裝置被廣泛的使用於個人電腦或攜帶式電話、影像接收機等的顯示部位。液晶裝置，例如，具備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，已知例如有，TN方式、VA方式等的縱向電場方式，或IPS方式、廣視角開閉(以下，FFS)方式等的橫向電場方式(例如，專利文獻1)。 　　[0003] 另一方面，近年來，因為液晶顯示元件或有機EL元件於生產步驟上的經濟性也成為極重要之因素，故也開始尋求元件基板的循環使用。即，尋求一種於由液晶配向劑形成液晶配向膜之後，於進行配向性等的檢査中，發現缺陷時，可以簡便地實施將液晶配向膜由基板去除，再回收基板等使其得以重複利用之步驟。但由該些以往提案的液晶配向劑所製得的液晶配向膜，多以使後燒焙後的有機溶劑等形成不溶，以求降低膜消減等為目的者。又，目前為止所研究的具有再製性的液晶配向劑之構成內容，即使將其作為橫向電場用液晶配向劑之構成內容時，也難以達到所期待的目的，因而必須對液晶配向劑重新實際評估其是否具有優良的再製性，必須對是否可達成最佳組成物的構成等內容進行再研究。 　　[0004] 又，液晶顯示元件，目前已被廣泛地使用於顯示裝置。作為液晶顯示元件構成構件的液晶配向膜，為需使液晶形成均勻排列之膜，故不僅需要液晶配向的均勻性，也必須具有其他各種的特性。例如，於液晶配向膜的製作步驟中，一般多需使用布對高分子膜的表面進行擦拭摩擦的配向處理。但，若液晶配向膜的耐摩擦性不足時，會發生膜被消減之損傷或粉塵、膜本身產生剝離等，而造成液晶顯示元件的顯示品質降低。又，液晶顯示元件為以施加電壓方式驅動液晶者。因此，若液晶配向膜的電壓保持率(VHR)過低時，將無法施加充份的電壓，而會造成顯示之對比劣化。又，受到驅動液晶的電壓之影響，而會於液晶配向膜中蓄積電荷，而消除蓄積之電荷的時間過長時，也會發生殘像或顯示之殘影等現象。 　　[0005] 而可同時滿足上述要求之特性者，目前已有各種的提案。例如，專利文獻2等已有提出一種製造具有優良耐摩擦性，且具有更少殘像或殘影的液晶配向膜之方法。又，專利文獻3等也有提出一種製造具有優良的液晶配向性、配向規制力、耐摩擦性、高電壓保持率，且可降低電荷蓄積的液晶配向膜之方法。 [先前技術文獻] [專利文獻] 　　[0006] 　　[專利文獻1] 特開2013-167782號公報 　　[專利文獻2] 國際公開第WO02/33481號公報 　　[專利文獻3] 國際公開第WO2004/053583號公報[0002] Conventionally, liquid crystal devices have been widely used in display parts of personal computers, mobile phones, video receivers, and the like. The liquid crystal device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling the alignment of liquid crystal molecules in the liquid crystal layer, and an opening and closing pair. The pixel electrodes supply thin film transistors (TFTs) and the like for electrical signals. As a driving method of liquid crystal molecules, for example, vertical electric field methods such as TN method and VA method, and lateral electric field methods such as IPS method and wide viewing angle opening and closing (hereinafter, FFS) method are known (for example, Patent Document 1). [0003] On the other hand, in recent years, because the economical efficiency of liquid crystal display elements or organic EL elements in the production steps has also become an extremely important factor, the recycling of element substrates has also been sought. That is, after forming a liquid crystal alignment film from a liquid crystal alignment agent, when a defect is found in the inspection of alignment, etc., the liquid crystal alignment film can be easily removed from the substrate, and the substrate can be recovered and reused. step. However, the liquid crystal alignment films produced from these conventionally proposed liquid crystal alignment agents are often made for the purpose of insolubilizing the organic solvent after post-baking and the like to reduce film shrinkage. In addition, the composition of the reproducible liquid crystal aligning agent studied so far, even if it is used as the composition of the liquid crystal aligning agent for transverse electric field, it is difficult to achieve the expected purpose, so it is necessary to re-evaluate the actual liquid crystal aligning agent. Whether it has excellent reproducibility, it is necessary to re-examine whether the composition of the optimal composition can be achieved. [0004] Furthermore, liquid crystal display elements have been widely used in display devices at present. The liquid crystal alignment film, which is a constituent member of a liquid crystal display element, is required to have not only the uniformity of the liquid crystal alignment but also other various properties in order to form a film in which liquid crystals are uniformly aligned. For example, in the production step of the liquid crystal alignment film, it is generally necessary to use a cloth to rub the surface of the polymer film for alignment treatment. However, if the rubbing resistance of the liquid crystal alignment film is insufficient, damage to the film, dust, and peeling of the film itself may occur, resulting in a decrease in the display quality of the liquid crystal display element. In addition, a liquid crystal display element drives a liquid crystal by applying a voltage. Therefore, if the voltage holding ratio (VHR) of the liquid crystal alignment film is too low, a sufficient voltage cannot be applied, and the contrast of the display will be deteriorated. In addition, under the influence of the voltage for driving the liquid crystal, charges are accumulated in the liquid crystal alignment film, and when the time for eliminating the accumulated charges is too long, afterimages or display afterimages may also occur. [0005] There are various proposals that can meet the characteristics of the above requirements at the same time. For example, Patent Document 2 and the like have proposed a method of producing a liquid crystal alignment film having excellent rubbing resistance and less afterimage or afterimage. In addition, Patent Document 3 and the like also propose a method for producing a liquid crystal alignment film having excellent liquid crystal alignment, alignment regulation force, rubbing resistance, and high voltage retention, and reducing charge accumulation. [Prior Art Document] [Patent Document] [0006] [Patent Document 1] Japanese Patent Laid-Open No. 2013-167782 [Patent Document 2] International Publication No. WO02/33481 [Patent Document 3] International Publication No. WO2004/053583

[發明所欲解決之問題] 　　[0007] 本發明為提供一種可製得滿足液晶配向膜所必需的各種特性的同時，也具有優良再製性的液晶配向膜之液晶配向劑。 [解決問題之方法] 　　[0008] 本發明者們，對於解決上述問題，經過深入研究結果，發現使用由含有特定的芳香族四羧酸二酐與脂肪族四羧酸二酐之四羧酸與具有特定結構的二胺所得的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物時，於滿足液晶配向膜所必需的各種特性的同時，也具有優良再製性的液晶配向膜，因而完成本發明。 　　[0009] 即，本發明為基於上述結果所提出者，其具有下述主要內容。 　　1.一種液晶配向劑，其特徵為含有： 　　(A-1)由使用含有下述式(1)所表示之四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(A-2)由使用含有脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(B)由聚醯亞胺前驅體、該聚醯亞胺前驅體之醯亞胺化聚合物及於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物所成之群所選出之至少1種的聚合物， 　　及有機溶劑。 　　[0010]

Figure 02_image001
[0011] (式(1)中，i為0或1，X為單鍵、醚鍵結、羰基、酯鍵結、伸苯基、碳原子數1至20的直鏈伸烷基、碳原子數2至20的分支伸烷基、碳原子數3至12之環狀伸烷基、磺醯基、醯胺鍵結或由該些組合而形成之基，其中，碳原子數1至20的伸烷基，可被由酯鍵結及醚鍵結所選出的鍵結所中斷，伸苯基及伸烷基的碳原子可被由鹵素原子、氰基、烷基、鹵烷基、烷氧基及鹵烷氧基所選出的1個或複數個相同或相異的取代基所取代。 　　式(2)中，Y1 為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，B1 、B2 各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基。 　　[0012] 2.如1記載之液晶配向劑，其中，前述(A-1)之四羧酸二酐成份中之10～100莫耳%為式(1)之四羧酸二酐。 　　[0013] 3.如1或2記載之液晶配向劑，其中，前述(A-2)之四羧酸二酐成份中之10～100莫耳%為脂肪族四羧酸二酐。 　　[0014] 4.如1至3中任一項記載之液晶配向劑，其中，前述(A-1)及前述(A-2)之二胺成份中之10～100莫耳%，為式(2)之二胺。 　　[0015] 5.如1至4中任一項記載之液晶配向劑，其中，式(2)中之Y1 為由下述式(YD-1)～(YD-5)之結構所選出之至少1種。 　　[0016]
Figure 02_image003
[0017] (式(YD-1)中，A1 為碳數3～15之含氮原子的雜環，Z1 為氫原子，或可具有取代基的碳數1～20的烴基；式(YD-2)中，W1 為碳數1～10的烴基，A2 為具有含氮原子的雜環之碳數3～15之1價之有機基，或被碳數1至6的脂肪族基所取代的二取代胺基；式(YD-3)中，W2 為碳數6～15，且具有1至2個苯環的2價之有機基，W3 為碳數2～5之伸烷基或伸聯苯基，Z2 為氫原子、碳數1～5之烷基，或苯環，a為0～1之整數；式(YD-4)中，A3 為碳數3～15之含氮原子的雜環；式(YD-5)中，A4 為碳數3～15之含氮原子的雜環，W5 為碳數2～5之伸烷基)。 　　[0018] 6.如5記載之液晶配向劑，其中，式(YD-1)、(YD-2)、(YD-4)，及(YD-5)記載之A1 、A2 、A3 ，及A4 ，為由吡咯啶、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌嗪、吡啶、吡
Figure 106133609-A0304
、吲哚、苯併咪唑、喹啉、異喹啉所成之群所選出之至少1種。 　　[0019] 7.如1至6中任一項記載之液晶配向劑，其中，式(2)中之Y1 為由具有下述式(YD-6)～(YD-21)之結構的2價之有機基所成之群所選出之至少1種。 　　[0020]
Figure 02_image005
[0021] (式(YD-17)中，h為1～3之整數，式(YD-14)及(YD-21)中，j為1至3之整數)。 　　[0022] 8.如7記載之液晶配向劑，其中，式(2)中之Y1 為由具有上述式(YD-14)及(YD-18)之結構的2價之有機基所成之群所選出之至少1種。 　　[0023] 9.如1至8中任一項記載之液晶配向劑，其中，前述式(1)所表示之四羧酸二酐為3,3’,4,4’-聯苯四羧酸二酐。 　　[0024] 10.如1至9中任一項記載之液晶配向劑，其中，前述脂肪族四羧酸二酐為雙環[3.3.0]辛烷2,4,6,8-四羧酸2,4：6,8二酐。 　　[0025] 11.一種液晶配向膜，其特徵為將1至10中任一項記載之液晶配向劑經塗佈、燒結而得者。 　　[0026] 12.一種液晶顯示元件，其特徵為，具備11記載之液晶配向膜。 [發明之效果] 　　[0027] 由本發明之液晶配向劑所得之液晶配向膜，於可抑制因交流驅動的非對稱化所造成的電荷蓄積的同時，也具有優良的再製性。 [實施發明之形態] 　　[0028] 本發明之液晶配向劑，為含有： 　　(A-1)由使用含有下述式(1)所表示之四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(A-2)由使用含有脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 　　(B)由聚醯亞胺前驅體、該聚醯亞胺前驅體之醯亞胺化聚合物及於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物所成之群所選出之至少1種的聚合物， 　　及有機溶劑。 　　[0029]
Figure 02_image007
[0030] 式(1)中，i為0或1，X為單鍵、醚鍵結、羰基、酯鍵結、伸苯基、碳原子數1至20的直鏈伸烷基、碳原子數2至20的分支伸烷基、碳原子數3至12之環狀伸烷基、磺醯基、醯胺鍵結或由該些組合而形成之基，其中，碳原子數1至20的伸烷基，可被由酯鍵結及醚鍵結所選出的鍵結所中斷，伸苯基及伸烷基的碳原子可被由鹵素原子、氰基、烷基、鹵烷基、烷氧基及鹵烷氧基所選出的1個或複數個相同或相異的取代基所取代。 　　[0031] 式(2)中，Y1 為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，B1 ～B2 各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基。 　　[0032] 以下，將詳細敘述各構成要件。 　　[0033] ＜(A-1)成份及(A-2)成份＞ 　　本發明之液晶配向劑所使用的(A-1)成份，為含有上述式(1)所表示之四羧酸二酐之四羧酸二酐成份與含有上述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物。 　　[0034] 又，本發明之液晶配向劑所使用的(A-2)成份，為含有脂肪族四羧酸二酐之四羧酸二酐成份與含有上述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物。 　　[0035] ＜四羧酸二酐成份＞ 　　上述式(1)所表示之四羧酸二酐，例如，以下所列舉之化合物，但並不僅限定於該些內容。 　　[0036]
Figure 02_image009
[0037] (式中，q表示1至20之整數)。 　　[0038] 該些式(1)所表示之四羧酸二酐中就具有高度提升再製性效果之觀點，以式(1)中之i為1之四羧酸二酐，即，具有2個以上苯環的四羧酸二酐為佳，上述具體例中，又以(1-2)～(1-11)為佳，就同時含有聯苯結構與具有剛直結構之觀點，又以式(1-5)所表示之3,3’,4,4’-聯苯四羧酸二酐為特佳。 　　[0039] 本發明所使用的特定脂肪族四羧酸二酐，例如，下述式(3)所表示之四羧酸二酐。 　　[0040]
Figure 02_image011
[0041] 式中，X1 可為下述(X-1)～(X-28)中之任一者。 　　[0042]
Figure 02_image013
[0043]
Figure 02_image015
[0044]
Figure 02_image017
[0045] 式(X-1)中，R3 ～R6 ，各自獨立為氫原子、碳數1～6之烷基，或苯基，又以氫原子，或甲基為較佳。 　　[0046] 上述之中，(X-1)至(X-20)以不含芳香族部位之觀點而為較佳，(X-10)特別是不易進行熱醯亞胺化之觀點而為最佳。 　　[0047] (A-1)成份中，於四羧酸二酐成份全體所佔的量中，式(1)所表示之四羧酸二酐之量過少時，將無法得到本發明之效果。因此，式(1)所表示之四羧酸二酐之量，相對於(A-1)成份之製造所使用的全四羧酸二酐1莫耳，以10～100莫耳%為佳，更佳為50～100莫耳%，特佳為80～100莫耳%。 　　[0048] (A-2)成份中，於四羧酸二酐成份全體所佔的量中，脂肪族酸二酐之量過少時，將無法得到本發明之效果。因此，脂肪族四羧酸二酐的量，相對於(A-2)成份之製造所使用的全四羧酸二酐1莫耳，以10～100莫耳%為佳，更佳為50～100莫耳%，特佳為80～100莫耳%。 　　[0049] 式(1)所表示之四羧酸二酐及脂肪族四羧酸二酐，其可分別單獨使用，或將複數個合併使用亦可，該情形中，式(1)所表示之四羧酸二酐及脂肪族四羧酸二酐之合計量，以使用上述較佳之量者為佳。 　　[0050] 本發明之液晶配向劑所含有的聚醯胺酸，除式(1)所表示之四羧酸二酐與脂肪族四羧酸二酐以外，亦可使用下述式(4)所表示之四羧酸二酐。 　　[0051]
Figure 02_image019
[0052] 式(4)中，X為4價之有機基，其結構並未有特別之限定。列舉具體例時，例如，下述式(X-31)～(X-36)之結構等。 　　[0053]
Figure 02_image021
[0054] ＜二胺成份＞ 　　本發明之(A-1)成份或(A-2)成份之製造所使用的二胺成份，為含有上述式(2)之二胺。式(2)中，Y1 為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，B1 ～B2 各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基。 　　[0055] 上述烷基之具體例，例如，甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基等。烯基，例如，上述烷基中所存在的1個以上之CH-CH結構，被C=C結構所取代者，更具體而言，例如，乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-己烯基、環丙烯基、環戊烯基、環己烯基等。炔基，例如，前述之烷基所存在的1個以上之CH2 -CH2 結構被C≡C結構所取代者，更具體而言，例如，乙炔基、1-丙炔基、2-丙炔基等。 　　[0056] 上述之烷基、烯基、炔基，以全體為碳數1～10者時，其可具有取代基，更可經由取代基而形成環結構。又，經由取代基而形成環結構之意，係指取代基相互間或取代基與主骨架的一部份鍵結而形成環結構之意。 　　[0057] 該取代基之例，例如，鹵素基、羥基、硫醇基、硝基、芳基、有機氧基、有機硫基、有機矽烷基、醯基、酯基、硫酯基、磷酸酯基、醯胺基、烷基、烯基、炔基等。 　　[0058] 作為取代基之鹵素基，例如，氟原子、氯原子、溴原子、碘原子等。 　　[0059] 作為取代基之芳基，例如，苯基等。該芳基可再被前述其他取代基所取代。 　　[0060] 作為取代基之有機氧基，例如，O-R所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷氧基之具體例，例如，甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基等。 　　[0061] 作為取代基之有機硫基，例如，-S-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷基硫基之具體例，例如，甲基硫基、乙基硫基、丙基硫基、丁基硫基、戊基硫基、己基硫基、庚基硫基、辛基硫基等。 　　[0062] 作為取代基之有機矽烷基，例如，-Si-(R)3 所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷基矽烷基之具體例，例如，三甲基矽烷基、三乙基矽烷基、三丙基矽烷基、三丁基矽烷基、三戊基矽烷基、三己基矽烷基、戊基二甲基矽烷基、己基二甲基矽烷基等。 　　[0063] 作為取代基之醯基，例如，-C(O)-R所表示之結構。該R，例如，前述之烷基、烯基、芳基等例示。該些之R中，可再被前述取代基所取代。醯基之具體例，例如，甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、苯甲醯基等。 　　[0064] 作為取代基之酯基，例如，-C(O)O-R，或 -OC(O)-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 　　[0065] 作為取代基之硫酯基，例如，具有-C(S)O-R，或-OC(S)-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 　　[0066] 作為取代基之磷酸酯基，例如，-OP(O)-(OR)2 所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 　　[0067] 作為取代基之醯胺基，例如，-C(O)NH2 ，或 -C(O)NHR、-NHC(O)R、-C(O)N(R)2 、-NRC(O)R所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 　　[0068] 作為取代基之芳基，例如，與前述之芳基為相同之內容。該芳基可再被前述其他取代基所取代。 　　[0069] 作為取代基之烷基，例如，與前述之烷基為相同之內容。該烷基中，可再被前述其他取代基所取代。 　　[0070] 作為取代基之烯基，例如，與前述之烯基為相同之內容。該烯基中，可再被前述其他取代基所取代。 　　[0071] 作為取代基之炔基，例如，與前述之炔基為相同之內容。該炔基中，可再被前述其他取代基所取代。 　　[0072] 一般而言，導入巨大結構時，可降低胺基的反應性或液晶配向性，故B1 及B2 ，例如，以氫原子，或可具有取代基的碳數1～5之烷基為較佳，以氫原子、甲基或乙基為特佳。 　　[0073] 式(2)中之Y1 之結構，例如，只要具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構時，其結構並未有特別之限定。因此，該具體例，可列舉如，具有由下述式(YD-1)～(YD-5)所表示之胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基等。 　　[0074]
Figure 02_image023
[0075] 式(YD-1)中，A1 為碳數3～15之含氮原子的雜環，Z1 為氫原子，或可具有取代基之碳數1～20的烴基。 　　[0076] 式(YD-2)中，W1 為碳數1～10的烴基，A2 為具有含氮原子的雜環之碳數3～15之1價之有機基，或被碳數1至6的脂肪族基所取代的二取代胺基。 　　[0077] 式(YD-3)中，W2 為碳數6～15，且具有1至2個苯環的2價之有機基，W3 為碳數2～5之伸烷基或伸聯苯基，Z2 為氫原子、碳數1～5之烷基，或苯環，a為0～1之整數。 　　[0078] 式(YD-4)中，A3 為碳數3～15之含氮原子的雜環。 　　[0079] 式(YD-5)中，A4 為碳數3～15之含氮原子的雜環，W5 為碳數2～5之伸烷基)。 　　[0080] 式(YD-1)、(YD-2)、(YD-4)，及(YD-5)之A1 、A2 、A3 ，及A4 之碳數3～15之含氮原子的雜環，例如，只要為公知之結構時，則未有特別之限定。其中，又可例如，吡咯啶、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌嗪、吡啶、吡
Figure 106133609-A0304
、吲哚、苯併咪唑、喹啉、異喹啉、咔唑等，又以哌嗪、哌啶、吲哚、苯併咪唑、咪唑、咔唑，及吡啶為較佳。 　　[0081] 又，式(2)中之Y2 之具體例，例如，具有下述式(YD-6)～(YD-38)所表示之氮原子的2價之有機基，就可抑制因交流驅動所造成的電荷蓄積之觀點，以式(YD-14)～式(YD-21)為較佳，以(YD-14)及(YD-18)為特佳。 　　[0082]
Figure 02_image025
[0083] 式(YD-14)及(YD-21)中，j為0至3之整數；式(YD-17)中，h為1～3之整數。 　　[0084]
Figure 02_image027
[0085] 式(YD-24)、(YD-25)、(YD-28)及(YD-29)中，j為0至3之整數。 　　[0086]
Figure 02_image029
[0087] 本發明之(A-1)成份或(A-2)成份的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中之式(2)所表示之二胺之比例，相對於製造(A-1)成份或(A-2)成份所使用的全二胺1莫耳，以10～100莫耳%為佳，更佳為30～100莫耳%，特佳為50～100莫耳%。 　　[0088] 本發明之(A-1)成份及(A-2)成份中，製造聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中之式(2)所表示之二胺，可單獨使用亦可，將複數個合併使用亦可，於該情形中，式(2)所表示之二胺，其合計量亦以使用上述較佳之量為佳。又，(A-1)成份與(A-2)成份中，以使用相同的二胺之情形，就更能提高本案發明效果之觀點為較佳者。 　　[0089] 又，本發明中，(A-1)成份及(A-2)成份中，製造聚醯胺酸及聚醯胺酸之醯亞胺化聚合物之際所使用的二胺，以相同者為佳。 　　[0090] 本發明之液晶配向劑所含有的(A-1)成份或(A-2)成份的聚醯胺酸，除上述式(2)所表示之二胺以外，亦可使用下述式(5)所表示之二胺。下述式(5)中之Y2 為2價之有機基，其結構並未有特別限定之內容，亦可將2種類以上混合使用。又，該具體例示，可列舉如，下述(Y-1)～(Y-49)及(Y-57)～(Y-75)等。 　　[0091]
Figure 02_image031
[0092]
Figure 02_image033
[0093]
Figure 02_image035
[0094]
Figure 02_image037
[0095]
Figure 02_image039
[0096]
Figure 02_image041
[0097]
Figure 02_image043
[0098] 本發明之液晶配向劑所含有的(A-1)成份或(A-2)成份的聚醯胺酸中，式(5)所表示之二胺之比例過多時，會有損害本發明效果之可能性，而為不佳。因此，式(5)所表示之二胺之比例，相對於全二胺1莫耳，以0～90莫耳%為佳，更佳為0～50莫耳%，特佳為0～20莫耳%。 　　[0099] ＜聚醯胺酸之製造方法＞ 　　本發明所使用的聚醯亞胺前驅體之聚醯胺酸，可依以下所示方法合成。 　　[0100] 具體而言，將四羧酸二酐與二胺於有機溶劑之存在下，於-20～150℃，較佳為0～70℃之間，進行30分鐘～24小時，較佳為1～12小時反應而合成。 　　[0101] 上述反應所使用的有機溶劑，就單體及聚合物的溶解性之觀點，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯等為佳，該些可使用1種或將2種以上混合使用。 　　[0102] 聚合物之濃度，於考慮不易引起聚合物的析出，且容易得到高分子量體之觀點，以1～30質量%為佳，以5～20質量%為較佳。 　　[0103] 將依上述方法所得之聚醯胺酸，於將反應溶液充份攪拌中，注入貧溶劑時，可使聚合物析出而回收。又，進行數次析出，使用貧溶劑洗淨後，於常溫或加熱下乾燥，即可製得純化之聚醯胺酸粉末。貧溶劑，並未有特別之限定，可列舉如，水、甲醇、乙醇、2-丙醇、己烷、丁基溶纖劑(cellosolve)、丙酮、甲苯等，又以水、甲醇、乙醇、2-丙醇等為佳。 　　[0104] ＜聚醯亞胺之製造方法＞ 　　本發明所使用的聚醯亞胺，可將前述聚醯胺酸進行醯亞胺化反應而製得。 　　[0105] 由聚醯胺酸製造聚醯亞胺之情形，以於二胺成份與四羧酸二酐反應所得之前述聚醯胺酸的溶液中，添加觸媒的化學性醯亞胺化反應為簡便之方法。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，不易造成聚合物的分子量降低，而為較佳。 　　[0106] 化學性醯亞胺化為，將欲進行醯亞胺化之聚合物，於有機溶劑中及鹼性觸媒與酸酐之存在下進行攪拌之方式進行。有機溶劑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，又以吡啶可於反應進行中維持適當的鹼性，而為較佳。又，酸酐可列舉如，乙酸酐、偏苯三甲酸酐、苯均四酸酐等，其中，又以使用乙酸酐時，於反應結束後容易進行純化，而為較佳。 　　[0107] 進行醯亞胺化反應時之溫度，可於-20～140℃，較佳為0～100℃下，反應時間為1～100小時內進行。鹼性觸媒之量為聚醯胺酸基的0.5～30莫耳倍，較佳為2～20莫耳倍，酸酐之量為聚醯胺酸基的1～50莫耳倍，較佳為3～30莫耳倍。所得聚合物之醯亞胺化率，可以調節觸媒量、溫度、反應時間之方式予以控制。 　　[0108] 聚醯胺酸之醯亞胺化反應後之溶液中因殘留有所添加的觸媒等，其又以使用以下所述手段，回收所得的醯亞胺化聚合物，使其再溶解於有機溶劑，作為本發明之液晶配向劑者為佳。 　　[0109] 將依上述方式所得之聚醯亞胺溶液，於充份攪拌中注入貧溶劑中，即可析出聚合物。進行數次析出，使用貧溶劑洗淨後，於常溫或加熱狀態下乾燥，即可製得純化的聚合物粉末。 　　[0110] 前述貧溶劑，並未有特別之限定，可列舉如，甲醇、2-丙醇、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，又以甲醇、乙醇、2-丙醇、丙酮等為佳。 　　[0111] 依該方法所製得之(A-1)成份及(A-2)成份的含有比，相對於上述式(1)所表示之四羧酸二酐與脂肪族四羧酸二酐之含有比例為達10：90至90：10之比例，又較佳為20：80至80：20，更佳為形成40：60至60：40之比例，特佳為形成46：54至54：46之比例，實質上以當量計算者為最佳。 　　[0112] ＜(B)成份＞ 　　本發明之液晶配向劑所含之(B)成份為，由聚醯亞胺前驅體、該聚醯亞胺前驅體之醯亞胺化聚合物及於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物所成之群所選出之至少1種的聚合物。 　　[0113] ＜聚醯亞胺前驅體＞ 　　聚醯亞胺前驅體為，具有下述式(11)所表示之結構單位的聚醯亞胺前驅體。 　　[0114]
Figure 02_image045
[0115] 式(11)中，X11 ，各自獨立為4價之有機基，Y11 各自獨立為2價之有機基；R11 為氫原子，或碳數1～5之烷基，A11 ～A12 各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、碳數2～10之烯基，或碳數2～10的炔基。 　　[0116] R11 中之上述烷基之具體例，例如，甲基、乙基、丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基等。就容易經由加熱而醯亞胺化之觀點，R11 以氫原子，或甲基為佳。 　　[0117] 式(11)中，X11 為由四羧酸衍生物所衍生的4價之有機基，其結構並未有特別之限定。聚醯亞胺前驅體中，X11 可為2種以上之混合。列舉X11 之具體例示時，例如，下述式(X-1)～(X-44)之結構等。 　　[0118]
Figure 02_image047
[0119]
Figure 02_image049
[0120]
Figure 02_image051
[0121]
Figure 02_image053
[0122] 上述式(X-1)中之R8 ～R11 ，各自獨立為氫原子、鹵素原子、碳數1～6之烷基、碳數2～6之烯基、炔基，或苯基；R8 ～R11 為巨大結構時，會有造成液晶配向性降低之可能性，故以氫原子、甲基、乙基為較佳，以氫原子，或甲基為特佳。 　　[0123] 式(11)中，X11 就單體的取得性之觀點，以含有由(X-1)～(X-14)所選出的結構為佳。 　　[0124] 上述(X-1)～(X-14)所選出的結構之較佳比例，例如，為X11 全體的20莫耳%以上，更佳為60莫耳%以上，特佳為80莫耳%以上。 　　[0125] 式(11)中，A11 及A12 各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、可具有取代基的碳數2～10之烯基、可具有取代基的碳數2～10的炔基。 　　[0126] 該些A11 及A12 之具體例或其較佳之例示，與上述(A-1)成份與(A-2)成份的項中之B1 及B2 為相同之內容。 　　[0127] 式(11)中，Y11 為由二胺衍生的2價之有機基，其結構並未有特別之限定。Y11 之結構之具體例示，可列舉如，前述(A)成份的項中所記載的上述(Y-1)～(Y-49)及(Y-57)～(Y-75)或(YD-6)～(YD-38)等。又，此外，又例如下述(Y-76)～(Y-97)，及(YD-39)～(YD-52)等。 　　[0128]
Figure 02_image055
[0129]
Figure 02_image057
[0130]
Figure 02_image059
[0131]
Figure 02_image061
[0132]
Figure 02_image063
[0133]
Figure 02_image065
[0134]
Figure 02_image067
(式(YD-50)中，m、n分別為1至11之整數，m+n為2至12之整數)。 　　[0135] Y11 之結構，例如，就所得液晶配向膜的液晶配向性或預傾角之觀點，以由下述式(15)及(16)所表示之結構所選出之至少1種為較佳。 　　[0136]
Figure 02_image069
[0137] 式(15)中，R12 為單鍵，或碳數1～30的2價之有機基，R13 為氫原子、鹵素原子或碳數1～30的1價之有機基、a為1～4之整數，a為2以上之情形時，R12 ，R13 可互相為相同或相異皆可，式(16)中之R14 為單鍵、-O-、-S-、 -NR15 -、醯胺鍵結、酯鍵結、尿(urea)鍵結，或碳數1～40的2價之有機基，R15 為氫原子，或甲基。 　　[0138] 式(15)及式(16)之具體例，例如，以下之結構等。 　　因具有高直線性之結構，於作為液晶配向膜時，可提高液晶的配向性，故Y11 ，例如，前述Y-7、Y-21、Y-22、Y-23、Y-25、Y-43、Y-44、Y-45、Y-46、Y-48、Y-63、Y-71、Y-72、Y-73、Y-74、Y-75為更佳。就可提高液晶配向性時，上述結構之比例，例如以Y11 全體的20莫耳%以上為佳，更佳為60莫耳%以上，特佳為80莫耳%以上。 　　[0139] 就提高作為液晶配向膜時的液晶的預傾角之觀點，Y11 以具有側鏈具有長鏈烷基、芳香族環、脂肪族環、膽固醇骨架，或該些組合而得的結構者為佳。該些Y11 ，例如，以Y-76、Y-77、Y-78、Y-79、Y-80、Y-81、Y-82、Y-83、Y-84、Y-85、Y-86、Y-87、Y-88、Y-89、Y-90、Y-91、Y-92、Y-93、Y-94、Y-95、Y-96、Y-97為佳。就提高預傾角時的上述結構之比例，例如，Y11 全體的1～30莫耳%為佳，以1～20莫耳%為較佳。 　　[0140] 又，使用具有光配向性側鏈的聚醯亞胺(前驅體)作為(B)成份的聚合物使用時，以使用具有下述光反應性側鏈的聚醯亞胺(前驅體)為佳。 　　[0141]
Figure 02_image071
[0142] (R16 表示-CH2 -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2 O-、-N(CH3 )-、-CON(CH3 )-、 -N(CH3 )CO-中之任一者，R17 表示環狀、無取代或可被氟原子所取代的碳數1至碳數20的伸烷基，其中，伸烷基中的任意的-CH2 -可被-CF2 -或-C=C-所取代，於以下所列舉的任一之基無互相相鄰的情形，亦可被該些之基所取代；-O-、 -COO-、-OCO-、-NHCO-、-CONH-、-NH-、碳環、雜環。R18 表示-CH2 -、-O-、-COO-、-OCO-、-NHCO-、-NH-、 -N(CH3 )-、-CON(CH3 )-、-N(CH3 )CO-、碳環，或雜環中之任一者，R19 表示乙烯基苯基、-CR20 =CH2 基、-CR20 (OH)-CH3 基、碳環、雜環或以下之群所選出的式所表示之結構，R20 表示可被為氫原子或氟原子所取代之甲基)。 　　[0143]
Figure 02_image073
[0144]
Figure 02_image075
[0145]
Figure 02_image077
[0146]
Figure 02_image079
[0147]
Figure 02_image081
[0148]
Figure 02_image083
[0149]
Figure 02_image085
[0150]
Figure 02_image087
[0151]
Figure 02_image089
[0152]
Figure 02_image091
[0153] 製造該些聚醯亞胺前驅體時，二胺以使用被上述式(b)所表示之側鏈所取代之二胺為簡便之選擇。 　　[0154] 又，亦可使用主鏈具有光配向性基的聚醯亞胺前驅體。該情形中，以使用如下述式(21)所表示般，胺與胺之間具有含光配向性基的鍵結之二胺為簡便之選擇。 　　[0155]
Figure 02_image093
[0156] (式(21)中，X21 為單鍵或碳數1～5之伸烷基，X22 為-OCO-CH=CH-或-CH=CH-COO-，X23 為單鍵、碳數1～10的伸烷基或2價之苯環，X24 為單鍵、-OCO-CH=CH-或-CH=CH-COO-，X25 為單鍵或碳數1～5之伸烷基。但，其具有1個以上的桂皮醯基(cinnamoyl))。 　　[0157] 式(21)所表示之二胺，例如，下述二胺等。 　　[0158]
Figure 02_image095
[0159] (式中，X為獨立之由單鍵或醚(-O-)、酯(-COO-或-OCO-)及醯胺(-CONH-或-NHCO-)所選出之鍵結基，Y為獨立之單鍵或碳數1～5之伸烷基，Z為獨立之碳數1～10的伸烷基或伸苯基。苯環上之胺基的鍵結位置，或相對於中央苯環的鍵結基之位置，並未有特別之限定)。 　　[0160] 式(21)所表示之二胺之具體例，例如，下述二胺等。 　　[0161]
Figure 02_image097
[0162]
Figure 02_image099
[0163] 使用該些上述式(21)所表示之二胺作為原料的含有聚醯胺酸、聚醯胺酸酯等的聚醯亞胺前驅體、聚醯亞胺或聚醯胺的液晶配向劑所形成的液晶配向膜，可降低因AC(交流)驅動所造成的液晶配向性能之變化，例如可降低液晶配向方位的變化。因此，具有該液晶配向膜的液晶顯示元件，可使因AC驅動的液晶配向膜的液晶配向性能安定化，將難以產生因AC驅動所造成的殘像，即，可使AC驅動所造成的殘像特性達到非常良好的效果。又，使用上述式(21)所表示之二胺所形成的液晶配向膜，為液晶配向性能本身為優良，且無實質上的配向缺陷者。 　　[0164] 本發明所使用的聚醯亞胺前驅體，為由二胺成份與四羧酸衍生物進行反應而得者，例如，聚醯胺酸或聚醯胺酸酯等。 　　[0165] ＜聚醯亞胺前驅體-聚醯胺酸之製造＞ 　　依(A-1)成份及(A-2)成份項內所記載的聚醯胺酸之製造方法為準。 　　[0166] ＜聚醯亞胺前驅體-聚醯胺酸酯之製造＞ 　　本發明所使用的聚醯亞胺前驅體之聚醯胺酸酯，可依以下所示之(1)、(2)或(3)的製法而製得。 　　[0167] (1)由聚醯胺酸製造之情形 　　聚醯胺酸酯，可將依前述方法所製得之聚醯胺酸，經酯化而製得。具體而言，將聚醯胺酸與酯化劑於有機溶劑之存在下，於-20℃～150℃，較佳為0℃～50℃間，進行30分鐘～24小時，較佳為1～4小時反應而可製得。 　　[0168] 酯化劑，例如，以可經由純化而容易去除者為佳，以N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三
Figure 106133609-A0304
-2-基)-4-甲基嗎啉鎓氯化物等。酯化劑的添加量，相對於聚醯胺酸的重複單位1莫耳，以2～6莫耳當量為佳。 　　[0169] 有機溶劑，例如，N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸或1,3-二甲基-咪唑啉酮等。又，聚醯亞胺前驅體的溶劑溶解性較高時，可使用甲基乙酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮，或後述式[D-1]～式[D-3]所示溶劑。 　　[0170] 該些溶劑可單獨使用亦可、混合使用亦可。此外，即使為不會使聚醯亞胺前驅體溶解之溶劑時，只要不會使所生成的聚醯亞胺前驅體產生析出之範圍時，亦可與前述溶劑混合使用。又，溶劑中的水份會阻礙聚合反應，且為造成所生成的聚醯亞胺前驅體水解之原因，故以將溶劑脫水乾燥後使用者為佳。 　　[0171] 上述之反應所使用的溶劑，就聚合物之溶解性的觀點，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮，或γ-丁內酯為佳，該些可使用1種或將2種以上混合使用。製造時之濃度，就不易引起聚合物的析出，且容易製得高分子量體之觀點，以1～30質量%為佳，以5～20質量%為較佳。 　　[0172] (2)使用四羧酸二酯二氯化物與二胺進行反應而製造之情形 　　聚醯胺酸酯，可由四羧酸二酯二氯化物與二胺而製得。 　　[0173] 具體而言，將四羧酸二酯二氯化物與二胺，於鹼與有機溶劑之存在下，於-20℃～150℃，較佳為0℃～50℃間，進行30分鐘～24小時，較佳為1～4小時反應而可製得。 　　[0174] 前述鹼中，可使用吡啶、三乙胺、4-二甲胺基吡啶等，但就反應得以穩定進行，又以使用吡啶為佳。鹼的添加量，就可容易去除之量，且容易得到高分子量體之觀點，相對於四羧酸二酯二氯化物，以2～4莫耳倍為佳。 　　[0175] 上述之反應所使用的溶劑，就單體及聚合物之溶解性的觀點，以N-甲基-2-吡咯啶酮，或γ-丁內酯為佳，該些可使用1種或將2種以上混合使用。製造時的聚合物之濃度，就不易析出聚合物，且容易製得高分子量體之觀點，以1～30質量%為佳，以5～20質量%為較佳。又，為防止四羧酸二酯二氯化物的水解，製造聚醯胺酸酯時所使用的溶劑，以盡可能使用脫水者為佳，又以於氮氛圍中，防止外氣混入者為佳。 　　[0176] (3)由四羧酸二酯與二胺而製造之情形 　　聚醯胺酸酯，可經由使四羧酸二酯與二胺進行聚縮合反應而製得。 　　[0177] 具體而言，將四羧酸二酯與二胺，於縮合劑、鹼，及有機溶劑之存在下，於0℃～150℃，較佳為0℃～100℃間，進行30分鐘～24小時，較佳為3～15小時之反應而可製得。 　　[0178] 前述縮合劑，例如可使用三苯基亞磷酸酯、二環己基羰二醯亞胺、1-乙基-3-(3-二甲胺基丙基)羰二醯亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三
Figure 106133609-A0304
基甲基嗎啉鎓、O-(苯併***-1-基)-N,N,N’,N’-四甲基脲四氯硼酸鹽、O-(苯併***-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫氧-3-苯併噁唑基)膦酸(phosphonicacid)二苯基等。縮合劑的添加量，相對於四羧酸二酯，以2～3莫耳倍為佳。 　　[0179] 前述鹼中，可使用吡啶、三乙胺等三級胺。鹼的添加量，就可容易去除之量，且容易得到高分子量體之觀點，相對於二胺成份，以2～4莫耳倍為佳。 　　[0180] 又，上述反應中，添加路易士酸作為添加劑時，可使反應有效率地進行。路易士酸，例如，以氯化鋰、溴化鋰等之鹵化鋰為佳。路易士酸的添加量，相對於二胺成份，以0～1.0莫耳倍為佳。 　　[0181] 上述3個聚醯胺酸酯之製造方法中，就可製得高分子量的聚醯胺酸酯之觀點，以使用上述(1)或上述(2)之製法為特佳。 　　[0182] 將依上述方法所製得之聚醯胺酸酯的溶液，於充份攪拌中注入貧溶劑時，可析出聚合物。進行數次析出，使用貧溶劑洗淨後，於常溫或加熱下乾燥後，可製得純化的聚醯胺酸酯之粉末。貧溶劑，並未有特別之限定，可列舉如，水、甲醇、乙醇、己烷、丁基溶纖劑(cellosolve)、丙酮、甲苯等。 　　[0183] ＜聚醯亞胺＞ 　　本發明所使用的聚醯亞胺，可將前述聚醯胺酸酯或聚醯胺酸經醯亞胺化處理而製得。其係依(A-1)成份及(A-2)成份的項內所記載的聚醯亞胺之製造方法為準。 　　[0184] ＜於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物＞ 　　(B)成份的態樣之一為，於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物。 　　[0185] 該側鏈型丙烯酸聚合物，只要為可與250nm～400nm波長範圍的光線反應，且於100℃～300℃之溫度範圍內具有液晶性者即可。 　　[0186] 該側鏈型丙烯酸聚合物，以具有可與250nm～400nm波長範圍的光線進行反應的感光性側鏈者為佳。 　　[0187] 該側鏈型丙烯酸聚合物，以具有於100℃～300℃之溫度範圍內可顯示液晶性的原液晶性基(mesogenic group)為佳。 　　[0188] 該側鏈型丙烯酸聚合物，因主鏈鍵結具有感光性的側鏈，故可感應光線而引起聯反應、異構化反應，或光弗萊斯重排(Friesrearrangement)反應。具有感光性的側鏈之結構，並未有特別之限定，一般以可感應光線，引起交聯反應，或光弗萊斯重排反應之結構為佳，以可引起交聯反應者為更佳。該情形中，即使曝露於熱等外部壓力時，也可使所實現的配向控制能力長期間保持安定化。可引起液晶性的感光性的側鏈型丙烯酸聚合物膜之結構，只要可滿足該特性者，並未有特別之限定，一般又以於側鏈結構上具有剛直的原液晶性成份者為佳。該情形中，該側鏈型丙烯酸聚合物作為液晶配向膜之際，即可得到安定的液晶配向性。 　　[0189] 該丙烯酸聚合物之結構，例如，具有主鏈與鍵結於主鏈之側鏈，該側鏈為，具有聯苯、聯三苯基、苯基環己基、苯基苯甲酸酯基、偶氮苯基等之原液晶性成份，與鍵結於前端部份之可感應光線而引起交聯反應或異構化反應之感光性基的結構，或具有主鏈與鍵結於主鏈之側鏈，該側鏈為由原液晶性成份所形成，且具有可進行光弗萊斯重排反應的苯基苯甲酸酯基之結構者。 　　[0190] 於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物之結構的更具體的例示，例如，具有由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等的自由基聚合性基所成之群所選出之至少1種所構成的主鏈，與下述式(31)至(35)中至少1種所形成的側鏈之結構為佳。 　　[0191]
Figure 02_image101
[0192] 式中，Ar1 表示由苯環、萘環、吡咯環、呋喃環、噻吩環、吡啶環去除2個氫原子而得的2價之取代基，Ar2 與Ar3 ，各自獨立表示由苯環、萘環、吡咯環、呋喃環、噻吩環、吡啶環去除2個氫原子而得的2價之取代基，q1 與q2 中之一者為1，另一者為0，Ar4 與Ar5 各自獨立表示由苯環、萘環、吡咯環、呋喃環、噻吩環、吡啶環去除2個氫原子而得的2價之取代基，Y1 -Y2 表示CH=CH、CH=N、N=CH或C≡C，S1 至S3 各自獨立表示單鍵、碳原子數1至18之直鏈或分支狀之伸烷基、碳原子數5至8之環伸烷基、伸苯基或伸聯苯基，或表示由單鍵、醚鍵結、酯鍵結、醯胺鍵結、脲(urea)鍵結、胺基甲酸酯鍵結、胺基鍵結、羰基或該些之組合所選出的1種或2種以上之鍵結，或介由該1種或2種以上的鍵結，鍵結於由碳原子數1至18的直鏈或分支狀之伸烷基、碳原子數5至8的環伸烷基、伸苯基、伸聯苯基或該些組合所選出的2以上、10以下之部位所得之結構，或前述取代基為介由前述鍵結而分別連結複數個而得之結構皆可； 　　R31 表示氫原子、羥基、氫硫基、胺基、碳原子數1至10之烷基、碳原子數1至10之烷氧基、碳原子數1至8之烷胺基或碳原子數2至16的二烷胺基，苯環及/或萘環可被由鹵素原子、氰基、硝基、羧基及碳原子數2至11之烷氧基羰基所選出的相同或相異的1個以上之取代基所取代者。此時，碳原子數1至10之烷基可為直鏈狀或分支狀或環狀，或該些組合而得之結構皆可，亦可被鹵素原子所取代。 　　[0193] 本案之(B)成份之於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物，可含有液晶性側鏈。 　　[0194] 具有液晶性側鏈之原液晶性基，可由聯苯或苯基苯甲酸酯等單獨構成原液晶性結構之基，或由如安息香酸等於側鏈相互間形成氫鍵結的原液晶性結構所構成之基皆可。具有側鏈之原液晶性基，又以下述之結構為佳。 　　[0195]
Figure 02_image103
[0196] ＜＜感光性側鏈型高分子之製法＞＞ 　　上述之於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物，可將上述之具有感光性側鏈之光反應性側鏈單體與液晶性側鏈單體進行聚合反應而製得。 　　[0197] [光反應性側鏈單體] 　　光反應性側鏈單體，於形成高分子之情形時，可為形成高分子側鏈部位具有感光性側鏈的高分子之單體。 　　[0198] 具有側鏈之光反應性基，以上述式(31)至(35)所表示之結構為佳。 　　[0199] 光反應性側鏈單體之更具體之例示，例如，以具有由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等的自由基聚合性基所成之群所選出之至少1種所構成的聚合性基，與上述式(31)～(35)中之至少1種所形成的感光性側鏈之結構為佳。 　　[0200] [液晶性側鏈單體] 　　液晶性側鏈單體係指，由該單體生成之高分子具有液晶性，且該高分子於側鏈部位可形成原液晶性基之單體之意。 　　[0201] 液晶性側鏈單體之更具體之例示，例如，以具有由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等的自由基聚合性基所成之群所選出之至少1種所構成的聚合性基，與前述「具有液晶性側鏈之原液晶性基」之至少1種的側鏈之結構為佳。 　　[0202] (B)成份的一態樣之側鏈型丙烯酸聚合物，可由上述可產生液晶性的光反應性側鏈單體進行聚合反應而製得。又，亦可經由不會產生液晶性的光反應性側鏈單體與液晶性側鏈單體進行共聚，或由可產生液晶性的光反應性側鏈單體與液晶性側鏈單體進行共聚而可製得。又，只要無損液晶性產生能力之範圍，亦可與其他之單體進行共聚。 　　[0203] 其他之單體，例如，工業上容易取得之可進行自由基聚合反應之單體等。 　　[0204] 其他之單體之具體例，例如，不飽和羧酸、丙烯酸酯化合物、丙烯酸甲酯化合物、馬來醯亞胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。 　　[0205] 不飽和羧酸之具體例，例如，丙烯酸、甲基丙烯酸、依康酸、馬來酸、富馬酸等。 　　[0206] 丙烯酸酯化合物，例如，丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸苄酯、丙烯酸萘酯、丙烯酸蒽酯、甲基丙烯酸蒽酯、丙烯酸苯酯、2,2,2-三氟丙烯酸乙酯、tert-丁基丙烯酸酯、丙烯酸環己酯、丙烯酸異莰酯、2-甲氧基丙烯酸乙酯、甲氧基丙烯酸三乙二醇酯、2-乙氧基丙烯酸乙酯、丙烯酸四氫糠酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯，及，8-乙基-8-三環癸基丙烯酸酯等。 　　[0207] 丙烯酸甲酯化合物，例如，甲基丙烯酸甲酯、乙基丙烯酸甲酯、異丙基丙烯酸甲酯、苄基丙烯酸甲酯、甲基丙烯酸萘酯、甲基丙烯酸蒽酯、蒽基甲基丙烯酸甲酯、苯基丙烯酸甲酯、2,2,2-三氟乙基丙烯酸甲酯、tert-丁基丙烯酸甲酯、環己基丙烯酸甲酯、異莰基丙烯酸甲酯、2-甲氧基乙基丙烯酸甲酯、甲氧基三乙二醇丙烯酸甲酯、2-乙氧基乙基丙烯酸甲酯、丙烯酸四氫糠甲酯、3-甲氧基丁基丙烯酸甲酯、2-甲基-2-金剛烷基丙烯酸甲酯、2-丙基-2-金剛烷基丙烯酸甲酯、8-甲基-8-三環癸基丙烯酸甲酯，及，8-乙基-8-三環癸基丙烯酸甲酯等。亦可使用縮水甘油(甲基)丙烯酸酯、(3-甲基-3-氧環丁烷基)甲基(甲基)丙烯酸酯，及(3-乙基-3-氧環丁烷基)甲基(甲基)丙烯酸酯等之具有環狀醚基的(甲基)丙烯酸酯化合物。 　　[0208] 乙烯基化合物，例如，乙烯醚、甲基乙烯醚、苄基乙烯醚、2-羥基乙基乙烯醚、苯基乙烯醚，及，丙基乙烯醚等。 　　[0209] 苯乙烯化合物，例如，苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯等。 　　[0210] 馬來醯亞胺化合物，例如，馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺，及N-環己基馬來醯亞胺等。 　　[0211] 本實施形態的側鏈型高分子之製造方法，並未有特別限定之內容，其可使用一般工業處理所廣泛使用的方法。具體而言，例如，可使用液晶性側鏈單體或光反應性側鏈單體的乙烯基之陽離子聚合、自由基聚合，或陰離子聚合反應而可製得。該些之中，又就容易進行反應控制之觀點，以自由基聚合為特佳。 　　[0212] 自由基聚合之聚合起始劑，例如，可使用AIBN(偶氮雙異丁腈)等公知的自由基聚合起始劑，或可逆的附加-開裂型鏈移動(RAFT)聚合試藥等公知的化合物。 　　[0213] 自由基聚合法，並未有特別之限制，其可使用乳化聚合法、懸濁聚合法、分散聚合法、沈澱聚合法、塊狀聚合法、溶液聚合法等。 　　[0214] 於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物之聚合反應所使用的有機溶劑，例如，只要可溶解所生成的聚合物之溶劑時，並未有特別之限定。其具體例，如以下所列舉之內容。 　　[0215] 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、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊酮、甲基壬酮、甲基乙酮、甲基異戊酮、甲基異丙酮、甲基溶纖劑、乙基溶纖劑、甲基溶纖劑(cellosolve)乙酸酯、乙基溶纖劑(cellosolve)乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙醚、乙二醇單丁醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲醚、丙二醇-tert-丁醚、二丙二醇單甲醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲醚、二丙二醇單乙酸酯單甲醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單乙酸酯單***、二丙二醇單丙醚、二丙二醇單乙酸酯單丙醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲醚、3-甲基-3-甲氧基丁醇、二異丙醚、乙基異丁醚、二異丁酯、戊基乙酸酯、丁基丁酸酯、丁醚、二異丁酮、甲基環己烯、丙醚、二己醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二***、環己酮、乙烯碳酸酯、丙烯碳酸酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單***、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二乙二醇二醚(glyme)、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-乙氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺等。 　　[0216] 該些有機溶劑可單獨使用亦可、混合使用亦可。又，即使為不會溶解所生成的高分子之溶劑時，只要為不會析出所生成的高分子之範圍，亦可以與上述有機溶劑混合使用。 　　[0217] 又，自由基聚合中，因有機溶劑中之氧為阻礙聚合反應之原因，故有機溶劑以使用盡可能地脫氣者為佳。 　　[0218] 自由基聚合之際的聚合溫度，可選擇30℃～150℃間的任意之溫度，較佳為50℃～100℃之範圍。又，反應雖可於任意濃度下進行，但濃度過低時，將不易製得高分子量之聚合物，濃度過高時，因會使反應液的黏性過度增高，而不容易進行均勻的攪拌，故單體濃度，較佳為1質量%～50質量%，更佳為5質量%～30質量%。反應初期可先以高濃度進行，隨後，再追加有機溶劑亦可。 　　[0219] 上述之自由基聚合反應中，自由基聚合起始劑之比例相對於單體為過多時，將會降低所得高分子之分子量，過少時將會增大所得高分子之分子量，故自由基起始劑之比例，相對於進行聚合之單體，以0.1莫耳%～10莫耳%為佳。又於聚合時亦可追加各種單體成份或溶劑、起始劑等。 　　[0220] [於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物之回收] 　　由上述之反應所得的可產生液晶性之感光性側鏈型高分子之反應溶液中，回收所生成的高分子的情形，可將反應溶液投入貧溶劑中，使該些聚合物產生沈澱即可。沈澱所使用的貧溶劑，例如，甲醇、丙酮、己烷、庚烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯、二***、甲基***、水等。投入貧溶劑而產生沈澱的聚合物，經過濾回收之後，可於常壓或減壓下，以常溫或加熱狀態進行乾燥處理。又，將沈澱回收之聚合物，重複2次～10次的在溶解於有機溶劑、再沈澱回收之操作時，可降低聚合物中之雜質。此時之貧溶劑，可例如，醇類、酮類、烴等，使用由該些之中所選出的3種類以上的貧溶劑時，以其可再提高純化之效率，而為更佳。 　　[0221] 本發明之(B)成份的一態樣之於特定溫度範圍內具有液晶性的感光性側鏈型丙烯酸聚合物的分子量，於考慮所得塗膜之強度、塗膜形成時之作業性，及塗膜均勻性時，該以GPC(Gel Permeation Chromatography)法所測定的重量平均分子量，以2,000～1,000,000為佳，更佳為5,000～100,000。 　　[0222] 本發明之液晶配向劑中之(A-1)成份與(A-2)成份與(B)成份的含量，以(A-1)成份與(A-2)成份的合計量與(B)成份之質量比達5：95～95：5，10：90～90：10者為更佳。 　　[0223] 本發明之液晶配向劑中之(A-1)成份與(A-2)成份與(B)成份之醯亞胺化率，可配合用途或目的作任意的調整，就溶解性或電荷蓄積特性之觀點，該特定聚合物(A-1)成份與(A-2)成份之醯亞胺化率以0～55%為佳，更佳為0～20%。又，就液晶配向性或配向規制力、電壓保持率之觀點，該特定聚合物(B)之醯亞胺化率以越高者為佳，較佳為40%～95%，更佳為55～90%。 　　[0224] ＜液晶配向劑＞ 　　本發明所使用的液晶配向劑，為具有聚合物成份溶解於有機溶劑中所形成的溶液形態。聚合物之分子量，其重量平均分子量以2,000～500,000為佳，更佳為5,000～300,000，特佳為10,000～100,000。又，數平均分子量，較佳為1,000～250,000，更佳為2,500～150,000，特佳為5,000～50,000。 　　[0225] 本發明所使用的液晶配向劑之聚合物的濃度，可配合欲形成之塗膜的厚度設定作適當之變更，就形成均勻且無缺陷的塗膜之觀點，以1質量%以上為佳，就溶液保存安定性觀點，以10質量%以下為佳。特佳之聚合物濃度為2～8質量%。 　　[0226] 本發明所使用的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者時，並未有特別之限定。其具體例，可列舉如，N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、3-甲氧基-N,N-二甲基丙烷醯胺等。該些可使用1種或將2種以上混合使用皆可。又，即使為單獨無法使聚合物成份均勻溶解之溶劑，只要為不會析出聚合物之範圍，亦可與上述有機溶劑混合使用。 　　[0227] 又，液晶配向劑所含有的有機溶劑，除上述溶劑以外，一般可使用與塗佈液晶配向劑之際可提高塗佈性或提升塗膜表面平滑性的溶劑合併而得的混合溶劑，本發明之液晶配向劑中，亦適合使用該些混合溶劑。可合併使用的有機溶劑之具體例，例如下述內容，但並不僅限定於該些例示。 　　[0228] 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、2,6-二甲基-4-庚醇、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、二異丙醚、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二***、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***、4-羥基-4-甲基-2-戊酮、二乙二醇甲基***、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、2,6-二甲基-4-庚酮、4,6-二甲基-2-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、二乙二醇單***、二乙二醇單甲醚、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***、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***、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單***、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、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。 　　[0229]
Figure 02_image105
[0230] 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。 　　[0231] 其中較佳溶劑之組合，例如，N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚、N-乙基-2-吡咯啶酮與丙二醇單丁醚、N-甲基-2-吡咯啶酮與γ-丁內酯與4-羥基-4-甲基-2-戊酮與二乙二醇二***、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與2,6-二甲基-4-庚酮、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與二異丙醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與2,6-二甲基-4-庚醇、N-甲基-2-吡咯啶酮與γ-丁內酯與二丙二醇二甲醚等。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。 　　[0232] 又，本發明之液晶配向劑中，就提高膜的機械性強度之觀點，可添加以下添加物。 　　[0233]
Figure 02_image107
[0234]
Figure 02_image109
[0235] 該些之添加劑，相對於液晶配向劑所含有的聚合物成份100質量份，以0.1～30質量份為佳。未達0.1質量份時將無法期待其效果，超過30質量份時，會降低液晶配向性，故更佳為0.5～20質量份。 　　[0236] 本發明之液晶配向劑中，除上述以外，於無損本發明效果之範圍，可添加聚合物以外的聚合物、以改變液晶配向膜的介電係數或導電性等之電氣特性為目的之介電體或導電物質、以提升液晶配向膜與基板之密著性為目的之矽烷耦合劑、以提高作為液晶配向膜時的膜硬度或緻密度為目的之交聯性化合物、或以提高塗膜燒結時可使聚醯胺酸有效地進行醯亞胺化反應為目的之醯亞胺化促進劑等。 　　[0237] ＜液晶配向膜＞ ＜液晶配向膜之製造方法＞ 　　本發明之液晶配向膜為，將上述液晶配向劑塗佈於基板，並經乾燥、燒結而製得之膜。塗佈本發明之液晶配向劑的基板，只要為具有高度透明性之基板時，並未有特別之限定，其可使用玻璃基板、氮化矽基板、丙烯酸基板、聚碳酸酯基板等的塑膠基板等，就製成簡易化之觀點，又以使用形成有驅動液晶的ITO電極等的基板為較佳。又，反射型液晶顯示元件，若僅為單側之基板時，亦可使用矽晶圓等的不透明物質，該情形的電極也可使用鋁等可反射光線之材料。 　　[0238] 本發明之液晶配向劑的塗佈方法，例如，旋轉塗佈法、印刷法、噴墨法等。塗佈本發明之液晶配向劑後的乾燥、燒結步驟，可選擇任意的溫度與時間。通常為充份去除所含有的有機溶劑時，可於50℃～120℃之間乾燥1分鐘～10分鐘，隨後於150℃～300℃之間燒結5分鐘～120分鐘。燒結後塗膜之厚度，並未有特別之限定，但過薄時會有降低液晶顯示元件信頼性之情形，故通常為5～300nm，較佳為10～200nm。 　　[0239] 對所得液晶配向膜進行配向處理之方法，例如，摩擦法、光配向處理法等。 　　[0240] 摩擦處理可使用現有的摩擦裝置進行。此時摩擦布之材質，例如，棉製品、尼龍、嫘縈等。摩擦處理之條件，一般而言，為使用迴轉速度300～2000rpm、輸送速度5～100mm/s、擠壓量0.1～1.0mm之條件。隨後，使用純水或醇等去除因超音波洗淨所產生的因摩擦所生成的殘渣。 　　[0241] 光配向處理法之具體例，例如，使用偏向特定方向的輻射線照射前述塗膜表面，依情況差異，可再於150～250℃之溫度進行加熱處理，以賦予液晶配向能力之方法等。輻射線，例如，可使用具有100nm～800nm波長的紫外線及可見光線。其中，又以具有100nm～400nm波長之紫外線為佳，以具有200nm～400nm波長者為特佳。又，為改善液晶配向性之目的，可將塗膜基板於50～250℃加熱中照射輻射線。前述輻射線之照射量以1～10,000mJ/cm2 為佳，以100～5,000mJ/cm2 為特佳。依上述方式所製得之液晶配向膜，可使液晶分子於特定方向安定地配向。 　　[0242] 又，偏光的紫外線之消光比越高時，以其可賦予更高的異向性，而為更佳。具體而言，相對於直線為偏光之紫外線的消光比，以10：1以上為佳，以20：1以上為較佳。 　　[0243] 依上述方式所得之照射偏光的輻射線之膜，隨後可再使用含有由水及有機溶劑所選出之至少1種的溶劑進行接觸處理。 　　[0244] 接觸處理所使用的溶劑，例如，只要可溶解經由光照射而生成的分解物之溶劑時，並未有特別之限定。具體例，例如，水、甲醇、乙醇、2-丙醇、丙酮、甲基乙酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑(cellosolve)、乳酸乙酯、乳酸甲基、二丙酮醇、3-甲氧基丙酸甲基、3-乙氧基丙酸乙基、乙酸丙基、乙酸丁基，及乙酸環己基等。該些溶劑亦可將2種以上合併使用。 　　[0245] 就廣用性或安全性之觀點，以使用由水、2-丙醇、1-甲氧基-2-丙醇及乳酸乙酯所成之群所選出之至少1種為較佳。水、2-丙醇，及水與2-丙醇之混合溶劑為特佳。 　　[0246] 本發明中，照射偏光的輻射線之膜與含有有機溶劑的溶液之接觸處理，為使用浸潤處理、噴霧(Spray)處理等可使膜與液體進行較佳且充份的接觸之處理方式進行。其中，又以對含有有機溶劑的溶液中之膜，實施較佳為10秒～1小時，更佳為1～30分鐘浸潤處理之方法為佳。接觸處理可於常溫或加溫下進行，較佳為於10～80℃，更佳為於20～50℃之間實施。又，必要時，可施以超音波等提高接觸之手段。 　　[0247] 上述接觸處理後，就去除使用後溶液中的有機溶劑之目的，可以水、甲醇、乙醇、2-丙醇、丙酮、甲基乙酮等之低沸點溶劑進行洗滌(Rinse)或乾燥，或兩者同時進行皆可。 　　[0248] 此外，上述使用溶劑進行接觸處理之膜，就乾燥溶劑及使膜中分子鏈進行再配向之目的時，亦可將其加熱至150℃以上。 　　[0249] 加熱之溫度，例如，150～300℃為佳。溫度越高時，雖可促進分子鏈的再配向，但溫度過高時會有伴隨分子鏈分解之疑慮。因此，加熱溫度，例如，180～250℃為較佳，以200～230℃為特佳。 　　[0250] 加熱之時間，過短時會有無法得到分子鏈再配向之效果的可能性，過長時，會有造成分子鏈分解之可能性，故以10秒～30分鐘為佳，以1分鐘～10分鐘為較佳。 　　[0251] 又，所得的液晶配向膜，可容易溶解於再製材料中，為具有優良再製性之膜。 　　[0252] 再製時所使用的溶劑，可列舉如以下之溶劑：乙二醇單甲醚、乙二醇單***、二乙二醇單甲醚、二乙二醇單***、丙二醇單甲醚等的二醇醚類；甲基溶纖劑(cellosolve)乙酸酯、乙基溶纖劑(cellosolve)乙酸酯、丙二醇單甲醚乙酸酯、丙二醇丙醚乙酸酯等的二醇酯類；二乙二醇、丙二醇、丁二醇、己二醇等的二醇類；甲醇、乙醇、2-丙醇、丁醇等的醇類；丙酮、甲基乙酮、環戊酮、環己酮、2-庚酮、γ-丁內酯等的酮類；2-羥基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯等的酯類、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基-2-吡咯啶酮等之醯胺類。 　　[0253] 再製材料，例如，於上述溶劑中含有乙醇胺等的鹼性成份的同時，又含有不會使該鹼性損害電極等的其他構件之抗鏽劑者為佳。可提供該些再製材料之廠商，例如，韓國的會明產業股份有限公司、KPX化學等。 　　[0254] 再製，為將上述所列舉的再製材料於室溫下，或30℃～100℃之間加熱後，將附有液晶配向膜之基板浸漬於其中，維持1秒～1000秒，較佳為30秒～500秒，或將再製材料使用噴灑式噴射之後，使用醇系溶劑或純水洗該液體之方式進行。又，再製時的再製液之溫度，就作業效率等觀點，以低溫者為佳，通常為室溫至60℃，更佳為室溫至40℃。 　　[0255] ＜液晶顯示元件＞ 　　本發明之液晶顯示元件，為使用本發明之液晶配向劑並依前述液晶配向膜之製造方法製得附有液晶配向膜之基板後，使用公知之方法製作液晶單元，並使用其作為液晶顯示元件者。 　　[0256] 液晶單元製作方法之例，將舉被動元件矩陣結構的液晶顯示元件為例進行說明。又，其亦可為具有構成圖像顯示的各畫素部份設有TFT(Thin Film Transistor)等開閉元件的主動矩陣結構之液晶顯示元件。 　　[0257] 首先，準備透明的玻璃製之基板，並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，例如可作為ITO電極，或可形成所期待的圖像顯示之圖型。其次，於各基板上，可設置被覆共用電極與節段電極之絕緣膜。絕緣膜，例如，由溶膠-凝膠法所得之由SiO2 -TiO2 所形成的膜。 　　[0258] 其次，於各基板上，依上述方法形成本發明之液晶配向膜。 　　[0259] 其次，將一側之基板與另一側之基板，以配向膜面互相對向之方式重疊，其周邊使用密封劑接著。密封劑中，為控制基板之間隙等目的，通常為混入間隔器。又，於未設置密封劑之面內部份，亦以散佈控制基板間隙的間隔器為佳。密封劑中之一部份，設置可由外部填充液晶之開口部。 　　[0260] 其次，經由設置於密封劑中之開口部，將液晶材料注入由2片之基板與密封劑所包圍的空間內。隨後，使用接著劑密封該開口部。注入法，可使用真空注入法，或於大氣中利用毛細管現象之方法等皆可。隨後，進行偏光板之設置。具體而言，為將一對的偏光板貼附於與2片基板的液晶層為相反側之面。經以上之步驟，而製得本發明之液晶顯示元件。 　　[0261] 本發明中，密封劑，例如，可使用具有環氧基、丙烯醯基、甲基丙烯醯基、羥基、烯丙基、乙醯基等反應性基的經由紫外線照射或加熱而硬化的樹脂。特別是以使用具有環氧基與(甲基)丙烯醯基二者的反應性基之硬化樹脂系者為佳。 　　[0262] 本發明之密封劑中，就提升接著性、耐濕性等目的時，可添加無機填充劑。所可使用的無機填充劑，並未有特別之限定，具體而言，可列舉如，球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、硝子纖維、碳纖維、二硫化鉬、石棉等，較佳為球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁。前述無機填充劑可將2種以上混合使用。 　　[0263] 該液晶顯示元件中，因液晶配向膜為使用本發明的液晶配向膜之製造方法所得之液晶配向膜，故具有優良再製性者，而適合使用於大畫面且高精細的液晶電視等。[Problems to be Solved by the Invention] [0007] The present invention is to provide a liquid crystal alignment agent for a liquid crystal alignment film that can satisfy various properties required for a liquid crystal alignment film and has excellent reproducibility. [Means for Solving the Problems] [0008] The present inventors, as a result of intensive research to solve the above-mentioned problems, found that the use of tetracarboxylic acids containing specific aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides and When the polyamic acid and the imidized polymer of the polyamic acid obtained from the diamine having a specific structure, satisfy the various properties necessary for the liquid crystal alignment film, and also have the liquid crystal alignment film with excellent reproducibility, so The present invention has been completed. That is, the present invention is proposed based on the above results, and it has the following main contents. 1. A liquid crystal aligning agent characterized by containing: (A-1) by using a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (1), and a liquid crystal aligning agent containing the following formula (2) Polyamic acid obtained from the diamine component of the indicated diamine, and at least one polymer selected from the imidized polymer of the polyamic acid, (A-2) A tetracarboxylic dianhydride component of tetracarboxylic dianhydride, a polyamic acid obtained by a diamine component containing a diamine represented by the following formula (2), and the imidization polymerization of the polyamic acid At least one polymer selected from the group, (B) a polyimide precursor, an imidized polymer of the polyimide precursor, and a photosensitive side chain having liquid crystallinity in a specific temperature range At least one polymer selected from the group consisting of type acrylic polymers, and an organic solvent. [0010]
Figure 02_image001
(in formula (1), i is 0 or 1, X is single bond, ether bond, carbonyl, ester bond, phenylene, straight-chain alkylene with 1 to 20 carbon atoms, carbon atom A branched alkylene group having 2 to 20 carbon atoms, a cyclic alkylene group having 3 to 12 carbon atoms, a sulfonyl group, an amide bond or a group formed by a combination of these, wherein the carbon atom number 1 to 20 Alkylene, which can be interrupted by a bond selected from ester bonds and ether bonds, and the carbon atoms of phenylene and alkylene can be replaced by halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups is substituted by one or more identical or different substituents selected from the group and haloalkoxy. In formula (2), Y 1 It is a divalent organic group having a structure of at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocycle, B 1 , B 2 Each independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an alkynyl group which may have a substituent. 2. The liquid crystal aligning agent as described in 1, wherein 10-100 mol% in the tetracarboxylic dianhydride component of the aforementioned (A-1) is the tetracarboxylic dianhydride of formula (1). 3. The liquid crystal alignment agent according to 1 or 2, wherein 10-100 mol % of the tetracarboxylic dianhydride component of the aforementioned (A-2) is aliphatic tetracarboxylic dianhydride. 4. the liquid crystal aligning agent as described in any one of 1 to 3, wherein, 10～100 mol% in the diamine composition of aforementioned (A-1) and aforementioned (A-2) is formula ( 2) of the diamine. 5. as the liquid crystal aligning agent of any one record in 1 to 4, wherein, the Y in the formula (2) 1 It is at least one selected from the structures of the following formulae (YD-1) to (YD-5). [0016]
Figure 02_image003
(in formula (YD-1), A 1 is a nitrogen-containing heterocyclic ring with 3 to 15 carbon atoms, Z 1 is a hydrogen atom, or a hydrocarbon group with 1 to 20 carbon atoms that may have a substituent; in formula (YD-2), W 1 is a hydrocarbon group with 1 to 10 carbon atoms, A 2 It is a monovalent organic group with 3 to 15 carbon atoms of a nitrogen-containing heterocyclic ring, or a disubstituted amino group substituted by an aliphatic group with 1 to 6 carbon atoms; in formula (YD-3), W 2 It is a divalent organic group with 6 to 15 carbon atoms and 1 to 2 benzene rings, W 3 It is an alkylene extension or a biphenylene extension with 2 to 5 carbon atoms, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring, and a is an integer of 0 to 1; in formula (YD-4), A 3 It is a nitrogen atom-containing heterocycle with 3 to 15 carbon atoms; in formula (YD-5), A 4 is a nitrogen atom-containing heterocyclic ring with 3 to 15 carbon atoms, W 5 It is an alkylene group with 2 to 5 carbon atoms). 6. as the liquid crystal aligning agent of 5 records, wherein, formula (YD-1), (YD-2), (YD-4), and the A of (YD-5) record 1 , A 2 , A 3 , and A 4 , is composed of pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridine
Figure 106133609-A0304
, at least one selected from the group consisting of indole, benzimidazole, quinoline, and isoquinoline. 7. as the liquid crystal aligning agent of any one record in 1 to 6, wherein, the Y in the formula (2) 1 At least one selected from the group consisting of divalent organic groups having structures of the following formulae (YD-6) to (YD-21). [0020]
Figure 02_image005
(In formula (YD-17), h is an integer of 1 to 3, and in formula (YD-14) and (YD-21), j is an integer of 1 to 3). 8. the liquid crystal aligning agent as recorded in 7, wherein, the Y in the formula (2) 1 At least one selected from the group consisting of divalent organic groups having the structures of the above formulas (YD-14) and (YD-18). 9. The liquid crystal aligning agent as described in any one of 1 to 8, wherein the tetracarboxylic dianhydride represented by the aforementioned formula (1) is 3,3',4,4'-biphenyltetracarboxylic acid Dianhydride. 10. The liquid crystal aligning agent as described in any one of 1 to 9, wherein the aforementioned aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2 ,4:6,8 dianhydride. 11. A liquid crystal alignment film, characterized in that the liquid crystal alignment agent recorded in any one of 1 to 10 is coated and sintered. [0026] 12. A liquid crystal display element comprising the liquid crystal alignment film described in 11. [Effect of the Invention] [0027] The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can suppress the accumulation of electric charges caused by the asymmetry of AC driving, and also has excellent reproducibility. [Mode for Carrying Out the Invention] [0028] The liquid crystal aligning agent of the present invention contains: (A-1) a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (1), and A polyamic acid obtained as a diamine component containing a diamine represented by the following formula (2), and a polymer of at least one selected from the imidized polymer of the polyamic acid, (A- 2) A polyamide acid obtained by using a tetracarboxylic dianhydride component containing aliphatic tetracarboxylic dianhydride and a diamine component containing a diamine represented by the following formula (2), and the polyamide At least one polymer selected from the acid imidization polymer, (B) a polyimide precursor, an imidization polymer of the polyimide precursor, and having a polyimide precursor in a specific temperature range A polymer of at least one selected from the group of liquid-crystalline photosensitive side-chain type acrylic polymers, and an organic solvent. [0029]
Figure 02_image007
In formula (1), i is 0 or 1, and X is single bond, ether bond, carbonyl, ester bond, phenylene, straight-chain alkylene with 1 to 20 carbon atoms, carbon number A branched alkylene group having 2 to 20, a cyclic alkylene having 3 to 12 carbon atoms, a sulfonyl group, an amide bond or a group formed by a combination of these, wherein the alkylene group having 1 to 20 carbon atoms. Alkyl, which can be interrupted by a bond selected from ester bonds and ether bonds, and the carbon atoms of phenylene and alkylene can be replaced by halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups and one or more of the same or different substituents selected from haloalkoxy. In formula (2), Y 1 It is a divalent organic group having a structure of at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocycle, B 1 ~B 2 Each independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an alkynyl group which may have a substituent. [0032] Hereinafter, each constituent element will be described in detail. <component (A-1) and component (A-2)> The component (A-1) used in the liquid crystal aligning agent of the present invention is a compound containing the tetracarboxylic dianhydride represented by the above formula (1). Polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component containing the diamine represented by the above formula (2), and at least one selected from the imidized polymer of the polyamic acid polymer. Also, the component (A-2) used in the liquid crystal aligning agent of the present invention is a tetracarboxylic dianhydride component containing aliphatic tetracarboxylic dianhydride and a diamine containing the above-mentioned formula (2). A polyamic acid obtained as a diamine component, and at least one polymer selected from the imidized polymer of the polyamic acid. <Tetracarboxylic dianhydride component> The tetracarboxylic dianhydride represented by the above formula (1) is, for example, the compounds listed below, but is not limited to these contents. [0036]
Figure 02_image009
(in the formula, q represents the integer of 1 to 20). In the tetracarboxylic dianhydrides represented by these formulas (1), from the viewpoint of having a high reproducibility effect, i in the formula (1) is 1 tetracarboxylic dianhydrides, i.e., there are 2 The tetracarboxylic dianhydride of the above benzene ring is preferred, and in the above-mentioned specific examples, (1-2) to (1-11) are preferred, and from the viewpoint of simultaneously containing a biphenyl structure and having a rigid structure, the formula ( 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by 1-5) is particularly preferred. The specific aliphatic tetracarboxylic dianhydride used in the present invention is, for example, the tetracarboxylic dianhydride represented by the following formula (3). [0040]
Figure 02_image011
In formula, X 1 Any of the following (X-1) to (X-28) may be used. [0042]
Figure 02_image013
[0043]
Figure 02_image015
[0044]
Figure 02_image017
In formula (X-1), R 3 ~R 6 , each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. Among the above, (X-1) to (X-20) are preferred from the viewpoint of not containing an aromatic moiety, and (X-10) is particularly preferred from the viewpoint of being difficult to thermal imidization. good. In the component (A-1), when the amount of the tetracarboxylic dianhydride represented by the formula (1) is too small in the total amount of the tetracarboxylic dianhydride component, the effect of the present invention cannot be obtained. Therefore, the amount of the tetracarboxylic dianhydride represented by the formula (1) is preferably 10-100 mol % relative to 1 mol of the total tetracarboxylic dianhydride used in the production of the component (A-1), More preferably, it is 50 to 100 mol %, and particularly preferably, it is 80 to 100 mol %. In the component (A-2), when the amount of the aliphatic acid dianhydride in the total amount of the tetracarboxylic dianhydride component is too small, the effect of the present invention cannot be obtained. Therefore, the amount of aliphatic tetracarboxylic dianhydride is preferably 10 to 100 mol %, more preferably 50 to 100 mol%, particularly preferably 80-100 mol%. Tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by formula (1), it can be used separately, or can be used in combination with multiple, in this case, the represented by formula (1) The total amount of the tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride is preferably the above-mentioned preferred amount. In addition to the tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by the formula (1), the polyamic acid contained in the liquid crystal aligning agent of the present invention can also be used in the following formula (4). Said tetracarboxylic dianhydride. [0051]
Figure 02_image019
In formula (4), X is the organic group of 4 valences, and its structure is not particularly limited. When a specific example is given, the structure of following formula (X-31) - (X-36) etc. are mentioned, for example. [0053]
Figure 02_image021
<Diamine component> The diamine component used in the production of the (A-1) component or (A-2) component of the present invention is a diamine containing the above formula (2). In formula (2), Y 1 It is a divalent organic group having a structure of at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocycle, B 1 ~B 2 Each independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an alkynyl group which may have a substituent. Specific examples of above-mentioned alkyl, for example, methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl and the like. Alkenyl, for example, one or more of the CH-CH structures present in the above-mentioned alkyl group is substituted by a C=C structure, more specifically, for example, vinyl, allyl, 1-propenyl, isopropenyl Propenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. Alkynyl, for example, one or more CH in the aforementioned alkyl group 2 -CH 2 A structure substituted by a C≡C structure, more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, and the like. When the above-mentioned alkyl group, alkenyl group, and alkynyl group are all carbon number 1-10, they may have substituents, and may form a ring structure through substituents. In addition, the meaning of forming a ring structure through a substituent means that the substituents are bonded to each other or a part of the main skeleton is bonded to form a ring structure. Examples of this substituent, for example, halogen group, hydroxyl group, thiol group, nitro group, aryl group, organic oxygen group, organic sulfur group, organic silyl group, acyl group, ester group, thioester group, phosphate ester group, amide group, alkyl group, alkenyl group, alkynyl group, etc. As the halogen group of the substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. As the aryl group of the substituent, for example, a phenyl group and the like. The aryl group may be further substituted by the aforementioned other substituents. As the organic oxygen group of the substituent, for example, the structure represented by OR. The R may be the same or different, for example, the aforementioned alkyl, alkenyl, alkynyl, aryl, etc. are exemplified. Among these, R may be further substituted by the aforementioned substituents. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. As the organosulfur group of the substituent, for example, the structure represented by -SR. As R, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these, R may be further substituted by the aforementioned substituents. Specific examples of the alkylthio group include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio and the like. As the organosilyl group of substituent, for example, -Si-(R) 3 represented structure. The R may be the same or different, for example, the aforementioned alkyl, alkenyl, alkynyl, aryl, etc. are exemplified. Among these, R may be further substituted by the aforementioned substituents. Specific examples of alkylsilyl groups, for example, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl Silyl, hexyldimethylsilyl, etc. As the aryl group of the substituent, for example, the structure represented by -C(O)-R. The R is exemplified by, for example, the aforementioned alkyl group, alkenyl group, aryl group, and the like. Among these, R may be further substituted by the aforementioned substituents. Specific examples of the acyl group include, for example, carboxyl, acetyl, propionyl, butyryl, isobutyryl, pentamyl, isopentyl, and benzyl. As the ester group of the substituent, for example, the structure represented by -C(O)OR, or -OC(O)-R. As R, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these, R may be further substituted by the aforementioned substituents. [0065] The thioester group as a substituent has, for example, a structure represented by -C(S)OR, or -OC(S)-R. As R, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these, R may be further substituted by the aforementioned substituents. As the phosphate group of substituent, for example, -OP(O)-(OR) 2 represented structure. The R may be the same or different, for example, the aforementioned alkyl, alkenyl, alkynyl, aryl, etc. are exemplified. Among these, R may be further substituted by the aforementioned substituents. As the amide group of substituent, for example, -C(O)NH 2 , or -C(O)NHR, -NHC(O)R, -C(O)N(R) 2 , the structure represented by -NRC(O)R. The R may be the same or different, for example, the aforementioned alkyl, alkenyl, alkynyl, aryl, etc. are exemplified. Among these, R may be further substituted by the aforementioned substituents. As the aryl group of the substituent, for example, it is the same content as the aforementioned aryl group. The aryl group may be further substituted by the aforementioned other substituents. As the alkyl group of the substituent, for example, the same content as the above-mentioned alkyl group. The alkyl group may be further substituted by the other substituents mentioned above. [0070] The alkenyl group as the substituent is, for example, the same as the aforementioned alkenyl group. The alkenyl group may be further substituted by the other substituents mentioned above. As the alkynyl group of the substituent, for example, the same content as the aforementioned alkynyl group. The alkynyl group may be further substituted by the other substituents mentioned above. In general, when introducing a giant structure, the reactivity of the amine group or the liquid crystal alignment can be reduced, so B 1 and B 2 For example, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable. The Y in formula (2) 1 The structure, for example, is not particularly limited as long as it has at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocycle. Therefore, the specific examples include at least one selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring represented by the following formulae (YD-1) to (YD-5), for example. The divalent organic group of the structure of the species, etc. [0074]
Figure 02_image023
In formula (YD-1), A 1 is a nitrogen-containing heterocyclic ring with 3 to 15 carbon atoms, Z 1 It is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In formula (YD-2), W 1 is a hydrocarbon group with 1 to 10 carbon atoms, A 2 It is a monovalent organic group having 3 to 15 carbon atoms, or a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms. In formula (YD-3), W 2 It is a divalent organic group with 6 to 15 carbon atoms and 1 to 2 benzene rings, W 3 It is an alkylene extension or a biphenylene extension with 2 to 5 carbon atoms, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring, and a is an integer of 0 to 1. In formula (YD-4), A 3 It is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms. In formula (YD-5), A 4 is a nitrogen atom-containing heterocyclic ring with 3 to 15 carbon atoms, W 5 It is an alkylene group with 2 to 5 carbon atoms). Formula (YD-1), (YD-2), (YD-4), and the A of (YD-5) 1 , A 2 , A 3 , and A 4 The nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms is not particularly limited as long as it has a known structure, for example. Among them, for example, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridine
Figure 106133609-A0304
, indole, benzimidazole, quinoline, isoquinoline, carbazole, etc., and preferably piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine. Again, the Y in formula (2) 2 As a specific example, for example, a divalent organic group having a nitrogen atom represented by the following formulae (YD-6) to (YD-38) can suppress charge accumulation due to AC drive. YD-14) to formula (YD-21) are preferred, and (YD-14) and (YD-18) are particularly preferred. [0082]
Figure 02_image025
In formula (YD-14) and (YD-21), j is an integer of 0 to 3; in formula (YD-17), h is an integer of 1 to 3. [0084]
Figure 02_image027
In formula (YD-24), (YD-25), (YD-28) and (YD-29), j is an integer of 0 to 3. [0086]
Figure 02_image029
The ratio of the diamine represented by the formula (2) in the polyamic acid of the (A-1) component or (A-2) component of the present invention and the imidized polymer of the polyamic acid, Relative to 1 mol of all diamine used in the manufacture of component (A-1) or component (A-2), it is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, and particularly preferably 50 mol % ~100 mol%. In the component (A-1) of the present invention and the component (A-2), the diamine represented by the formula (2) in the manufacture of polyamic acid and the imidized polymer of polyamic acid, It may be used alone or in combination. In this case, the total amount of the diamine represented by the formula (2) is preferably the above-mentioned preferred amount. Moreover, in the case where the same diamine is used in the component (A-1) and the component (A-2), it is preferable from the viewpoint that the effect of the present invention can be further improved. Also, in the present invention, in the components (A-1) and (A-2), the diamines used in the manufacture of polyamic acid and the imidized polymer of polyamic acid, with The same is better. The polyamide acid of (A-1) component or (A-2) component contained in the liquid crystal aligning agent of the present invention, in addition to the diamine represented by the above formula (2), can also use the following formula The diamine represented by (5). Y in the following formula (5) 2 It is a divalent organic group, and its structure is not particularly limited, and two or more types may be mixed and used. Moreover, this specific example, the following (Y-1)-(Y-49), (Y-57)-(Y-75), etc. are mentioned, for example. [0091]
Figure 02_image031
[0092]
Figure 02_image033
[0093]
Figure 02_image035
[0094]
Figure 02_image037
[0095]
Figure 02_image039
[0096]
Figure 02_image041
[0097]
Figure 02_image043
In the polyamide acid of (A-1) component or (A-2) component contained in the liquid crystal aligning agent of the present invention, when the ratio of the diamine represented by formula (5) is too large, there will be damage to the present invention. The possibility of the effect of the invention is not good. Therefore, the ratio of the diamine represented by the formula (5) is preferably 0 to 90 mol %, more preferably 0 to 50 mol %, and particularly preferably 0 to 20 mol % relative to 1 mol of total diamine. Ear%. [0099] <The production method of polyimide> The polyimide precursor of the polyimide used in the present invention can be synthesized by the method shown below. Specifically, tetracarboxylic dianhydride and diamine in the presence of organic solvent, at -20～150 ℃, preferably between 0～70 ℃, carry out 30 minutes～24 hours, preferably 1 to 12 hours to react and synthesize. The organic solvent used in the above-mentioned reaction, from the viewpoint of the solubility of monomer and polymer, is N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone Esters and the like are preferable, and these can be used alone or in combination of two or more. [0102] The concentration of the polymer is preferably 1 to 30 mass %, preferably 5 to 20 mass %, from the viewpoint of not easily causing the precipitation of the polymer and easily obtaining a high molecular weight body. [0103] The polyamide acid obtained according to the above-mentioned method, when the reaction solution is fully stirred and injected into the poor solvent, can make the polymer precipitate and be recovered. In addition, after several precipitations, washing with a poor solvent, and drying at room temperature or under heating, purified polyamide powder can be obtained. The poor solvent is not particularly limited, for example, water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene, etc., and water, methanol, ethanol, 2-propanol, etc. Propanol and the like are preferred. <Method for producing polyimide> The polyimide used in the present invention can be obtained by subjecting the aforementioned polyimide to an imidization reaction. In the case of producing polyimide from polyamide, in the solution of the aforementioned polyamide obtained by the reaction of a diamine component and tetracarboxylic dianhydride, a chemical imidization reaction by adding a catalyst for the easy way. The chemical imidization can be carried out at a relatively low temperature, and the molecular weight of the polymer is not easily reduced during the imidization process, which is preferable. The chemical imidization is carried out by stirring the polymer to be imidized in an organic solvent and in the presence of an alkaline catalyst and an acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine can maintain proper basicity during the reaction, which is more preferable. The acid anhydride includes, for example, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, when acetic anhydride is used, purification can be easily performed after completion of the reaction, which is preferable. [0107] The temperature of the imidization reaction can be carried out at -20 to 140°C, preferably at 0 to 100°C, and the reaction time is 1 to 100 hours. The amount of the alkaline catalyst is 0.5-30 mol times the polyamide base, preferably 2-20 mol times, and the amount of the acid anhydride is 1-50 mol times the polyamide base, preferably 3 to 30 mole times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time. In the solution after the imidization reaction of polyamide acid, the catalyst etc. that have been added remain in the solution, and the obtained imidization polymer is recovered and redissolved by using the means described below. Among the organic solvents, those used as the liquid crystal alignment agent of the present invention are preferred. [0109] The polyimide solution obtained in the above-mentioned manner is injected into the poor solvent with sufficient stirring, and the polymer can be precipitated. After several times of precipitation, washing with a poor solvent, and drying at room temperature or under heating, purified polymer powder can be obtained. The above-mentioned poor solvent is not particularly limited, for example, methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, Toluene, benzene, etc., and methanol, ethanol, 2-propanol, acetone, etc. are preferred. According to the content ratio of the (A-1) component and (A-2) component obtained by the method, relative to the tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by the above-mentioned formula (1) The content ratio is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 40:60 to 60:40, particularly preferably 46:54 to 54 : The ratio of 46, in essence, the one calculated by equivalent is the best. <Component (B)> The component (B) contained in the liquid crystal aligning agent of the present invention is composed of a polyimide precursor, an imidized polymer of the polyimide precursor, and a specific temperature. A polymer of at least one selected from the group of photosensitive side chain type acrylic polymers having liquid crystallinity in the range. <Polyimide precursor> The polyimide precursor is a polyimide precursor having a structural unit represented by the following formula (11). [0114]
Figure 02_image045
In formula (11), X 11 , each independently a tetravalent organic group, Y 11 Each independently is a divalent organic group; R 11 is a hydrogen atom, or an alkyl group with 1 to 5 carbon atoms, A 11 ~A 12 Each independently represents a hydrogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. R 11 Specific examples of the above-mentioned alkyl groups, such as methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, etc. . From the viewpoint of easy imidization by heating, R 11 A hydrogen atom or a methyl group is preferred. In formula (11), X 11 It is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In the polyimide precursor, X 11 Two or more kinds can be mixed. List X 11 As a specific example, for example, the structures of the following formulae (X-1) to (X-44) and the like are used. [0118]
Figure 02_image047
[0119]
Figure 02_image049
[0120]
Figure 02_image051
[0121]
Figure 02_image053
R in above-mentioned formula (X-1) 8 ~R 11 , each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group, or a phenyl group; R 8 ~R 11 In the case of a giant structure, there is a possibility that the alignment of the liquid crystal may be lowered, so a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom or a methyl group is particularly preferable. In formula (11), X 11 From the viewpoint of availability of monomers, it is preferable to contain the structures selected from (X-1) to (X-14). The preferred ratio of the structure selected from above-mentioned (X-1)～(X-14), for example, is X 11 It is 20 mol% or more of the whole, more preferably 60 mol% or more, and particularly preferably 80 mol% or more. In formula (11), A 11 and A 12 Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, or an optionally substituted alkynyl group having 2 to 10 carbon atoms. these A 11 and A 12 A specific example or a better example thereof, and B in the items of the above-mentioned (A-1) component and (A-2) component 1 and B 2 for the same content. In formula (11), Y 11 It is a divalent organic group derived from diamine, and its structure is not particularly limited. Y 11 Specific examples of the structure include the above-mentioned (Y-1) to (Y-49) and (Y-57) to (Y-75) or (YD-6) described in the section of component (A) above. ) ~ (YD-38) etc. In addition, there are the following (Y-76) to (Y-97), and (YD-39) to (YD-52), for example. [0128]
Figure 02_image055
[0129]
Figure 02_image057
[0130]
Figure 02_image059
[0131]
Figure 02_image061
[0132]
Figure 02_image063
[0133]
Figure 02_image065
[0134]
Figure 02_image067
(In formula (YD-50), m and n are each an integer of 1 to 11, and m+n is an integer of 2 to 12). Y 11 The structure is preferably at least one selected from the structures represented by the following formulae (15) and (16), for example, from the viewpoint of the liquid crystal alignment property or the pretilt angle of the obtained liquid crystal alignment film. [0136]
Figure 02_image069
In formula (15), R 12 is a single bond, or a divalent organic group with 1 to 30 carbon atoms, R 13 is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, a is an integer of 1 to 4, and when a is 2 or more, R 12 , R 13 can be the same or different from each other, R in formula (16) 14 is a single bond, -O-, -S-, -NR 15 -, amide bond, ester bond, urea bond, or a divalent organic group with 1 to 40 carbon atoms, R 15 is a hydrogen atom, or a methyl group. Specific examples of formula (15) and formula (16), for example, the following structures etc. Due to the structure with high linearity, when used as a liquid crystal alignment film, the alignment of liquid crystal can be improved, so Y 11 , for example, the aforementioned Y-7, Y-21, Y-22, Y-23, Y-25, Y-43, Y-44, Y-45, Y-46, Y-48, Y-63, Y- 71, Y-72, Y-73, Y-74, Y-75 are better. When the alignment of the liquid crystal can be improved, the ratio of the above structures, for example, Y 11 The total content is preferably 20 mol % or more, more preferably 60 mol % or more, and particularly preferably 80 mol % or more. From the viewpoint of improving the pretilt angle of liquid crystal when used as a liquid crystal alignment film, Y 11 It is preferable to have a structure having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a cholesterol skeleton, or a combination of these in the side chain. these Y 11 , for example, in Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y- 87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, Y-97 are preferred. As far as the ratio of the above structure is increased when the pretilt angle is increased, for example, Y 11 1 to 30 mol % of the whole is preferable, and 1 to 20 mol % is more preferable. Also, when using the polyimide (precursor) with the photoalignment side chain as the polymer of the (B) component, to use the polyimide (precursor) with the following photoreactive side chain ) is better. [0141]
Figure 02_image071
(R 16 means -CH 2 -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N (CH 3 )-, -CON(CH 3 )-, -N(CH 3 ) any of CO-, R 17 Represents a cyclic, unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, wherein any -CH in the alkylene group 2 -Can be -CF 2 - or -C=C-, if any of the groups listed below are not adjacent to each other, they can also be substituted by these groups; -O-, -COO-, -OCO-, -NHCO -, -CONH-, -NH-, carbocyclic, heterocyclic. R 18 means -CH 2 -, -O-, -COO-, -OCO-, -NHCO-, -NH-, -N(CH 3 )-, -CON(CH 3 )-, -N(CH 3 ) any one of CO-, carbocycle, or heterocycle, R 19 Represents vinylphenyl, -CR 20 =CH 2 base, -CR 20 (OH)-CH 3 The structure represented by the formula selected from the group of radicals, carbocycles, heterocycles or the following, R 20 represents a methyl group which may be substituted by a hydrogen atom or a fluorine atom). [0143]
Figure 02_image073
[0144]
Figure 02_image075
[0145]
Figure 02_image077
[0146]
Figure 02_image079
[0147]
Figure 02_image081
[0148]
Figure 02_image083
[0149]
Figure 02_image085
[0150]
Figure 02_image087
[0151]
Figure 02_image089
[0152]
Figure 02_image091
When producing these polyimide precursors, it is a convenient choice to use the diamine substituted by the side chain represented by the above formula (b). [0154] Also, a polyimide precursor having a photoalignment group in the main chain can also be used. In this case, as represented by the following formula (21), it is a convenient choice to use a diamine having a photoalignment group-containing bond between an amine and an amine. [0155]
Figure 02_image093
(in formula (21), X twenty one is a single bond or an alkylene group with 1 to 5 carbon atoms, X twenty two For -OCO-CH=CH- or -CH=CH-COO-, X twenty three is a single bond, an alkylene group with 1 to 10 carbon atoms or a divalent benzene ring, X twenty four is a single bond, -OCO-CH=CH- or -CH=CH-COO-, X 25 It is a single bond or an alkylene group with 1 to 5 carbon atoms. However, it has one or more cinnamoyl groups. The diamine represented by formula (21), for example, the following diamine etc. [0158]
Figure 02_image095
(in the formula, X is the independently selected bond group by single bond or ether (-O-), ester (-COO- or -OCO-) and amide (-CONH- or -NHCO-) , Y is an independent single bond or an alkylene group with 1-5 carbon atoms, Z is an independent alkylene group or phenylene group with a carbon number of 1-10. The bonding position of the amine group on the benzene ring, or relative to The position of the bonding group of the central benzene ring is not particularly limited). Specific examples of the diamine represented by the formula (21) include, for example, the following diamines. [0161]
Figure 02_image097
[0162]
Figure 02_image099
Liquid crystal alignment of polyimide precursors, polyimide or polyimide containing polyamic acid, polyamic acid ester, etc., using the diamines represented by the above-mentioned formula (21) as raw materials The liquid crystal alignment film formed by the agent can reduce the change of the liquid crystal alignment performance caused by AC (alternating current) driving, for example, can reduce the change of the liquid crystal alignment orientation. Therefore, the liquid crystal display element having the liquid crystal alignment film can stabilize the liquid crystal alignment performance of the liquid crystal alignment film by AC driving, and it is difficult to generate afterimages caused by AC driving, that is, the afterimage caused by AC driving can be reduced. Image characteristics achieve very good results. In addition, the liquid crystal alignment film formed using the diamine represented by the above formula (21) is excellent in the liquid crystal alignment performance itself and has no substantial alignment defect. [0164] The polyimide precursor used in the present invention is obtained by reacting a diamine component with a tetracarboxylic acid derivative, for example, polyamic acid or polyamic acid ester. <Production of Polyimide Precursor-Polyamic Acid> The method for producing polyamic acid described in the items (A-1) and (A-2) is the criterion. <Production of Polyimide Precursor-Polyurethane> The polyimide precursor used in the present invention may be (1) and (2) shown below. Or prepared by the method of (3). (1) The case of being produced from polyamic acid Polyamic acid ester can be obtained by esterification of the polyamic acid obtained by the aforementioned method. Specifically, in the presence of an organic solvent, the polyamic acid and the esterifying agent are carried out at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 to 100°C. 4 hours reaction can be obtained. Esterification agent, for example, it is better to be able to be easily removed through purification, with N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl Acetal, N,N-Dimethylformamide Dipropyl Acetal, N,N-Dimethylformamide Dineopentyl Butyl Acetal, N,N-Dimethylformamide Di- t-Butyl Acetal, 1-Methyl-3-p-Tolyltriazene, 1-Ethyl-3-p-Tolyltriazene, 1-Propyl-3-p-Tolyltriazene Alkene, 4-(4,6-dimethoxy-1,3,5-tri
Figure 106133609-A0304
-2-yl)-4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 to 6 mol equivalents with respect to 1 mol of the repeating unit of the polyamic acid. Organic solvent, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N -Dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone, etc. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D -1] to a solvent represented by the formula [D-3]. [0170] These solvents may be used alone or in combination. In addition, even in the case of a solvent that does not dissolve the polyimide precursor, it may be used in combination with the above-mentioned solvent as long as it does not cause precipitation of the produced polyimide precursor. In addition, the water in the solvent will hinder the polymerization reaction and cause the hydrolysis of the produced polyimide precursor, so it is better to dehydrate and dry the solvent. The solvent used in the above-mentioned reaction is, from the viewpoint of the solubility of the polymer, with N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone as Preferably, these can be used alone or in combination of two or more. The concentration at the time of production is preferably 1 to 30 mass %, and more preferably 5 to 20 mass %, from the viewpoint of hardly causing precipitation of the polymer and easily obtaining a high molecular weight body. (2) The case where tetracarboxylic acid diester dichloride and diamine are used to react and produce Polyamic acid ester, which can be produced by tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine, in the presence of alkali and organic solvent, at -20 ℃～150 ℃, preferably between 0 ℃～50 ℃, carry out 30 minutes ~ 24 hours, preferably 1 ~ 4 hours of reaction and can be obtained. In the aforementioned base, pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used, but with regard to the reaction being carried out stably, it is better to use pyridine again. The addition amount of the base is an amount that can be easily removed and from the viewpoint of easily obtaining a high-molecular-weight product, it is preferably 2 to 4 mol times relative to the tetracarboxylic acid diester dichloride. The solvent used in the above-mentioned reaction, from the viewpoint of the solubility of monomer and polymer, is preferably with N-methyl-2-pyrrolidone, or γ-butyrolactone, and these can use a kind of Or use a mixture of two or more. The concentration of the polymer at the time of production is preferably 1 to 30 mass %, more preferably 5 to 20 mass %, from the viewpoint that the polymer is not easily precipitated and a high molecular weight body is easily obtained. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the manufacture of the polyamic acid ester is preferably one that is dehydrated as much as possible, and one that is preferably used in a nitrogen atmosphere to prevent the mixing of outside air. . (3) In the case of producing from a tetracarboxylic acid diester and a diamine, the polyamic acid ester can be produced by subjecting a tetracarboxylic acid diester and a diamine to a polycondensation reaction. Specifically, the tetracarboxylic acid diester and the diamine, in the presence of a condensing agent, a base, and an organic solvent, are carried out at 0°C to 150°C, preferably 0°C to 100°C, for 30 minutes. ~ 24 hours, preferably 3 ~ 15 hours of reaction and can be obtained. As the aforementioned condensing agent, for example, triphenyl phosphite, dicyclohexyl carbonodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbonodiimide hydrochloride can be used Salt, N,N'-Carbonyldiimidazole, Dimethoxy-1,3,5-Tris
Figure 106133609-A0304
Methylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea tetrachloroborate, O-(benzotriazol-1-yl )-N,N,N',N'-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-thiooxy-3-benzoxazolyl)phosphonic acid (phosphonicacid)diphenyl Wait. The addition amount of the condensing agent is preferably 2 to 3 mol times with respect to the tetracarboxylic acid diester. Among the aforementioned bases, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is an amount that can be easily removed, and from the viewpoint of easily obtaining a high-molecular-weight compound, it is preferably 2 to 4 mol times relative to the diamine component. Also, in the above reaction, when Lewis acid is added as an additive, the reaction can be efficiently performed. As the Lewis acid, for example, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of Lewis acid is preferably 0-1.0 mol times relative to the diamine component. [0181] Among the above-mentioned three methods for producing polyamic acid esters, from the viewpoint of obtaining high molecular weight polyamic acid esters, it is particularly preferred to use the above-mentioned (1) or above-mentioned (2) production methods. [0182] When the solution of the polyamic acid ester obtained by the above method is injected into the poor solvent in sufficient stirring, the polymer can be precipitated. After several precipitations, washing with a poor solvent, and drying at room temperature or under heating, the purified polyamic acid ester powder can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene. <Polyimide> The polyimide used in the present invention can be obtained by subjecting the aforementioned polyimide or polyimide to an imidization treatment. It is based on the manufacturing method of the polyimide described in the item of (A-1) component and (A-2) component. <Photosensitive side chain type acrylic polymer with liquid crystallinity in a specific temperature range> (B) One of the aspects of the component is a photosensitive side chain type acrylic polymer with liquid crystallinity in a specific temperature range . [0185] The side chain type acrylic polymer can be reacted with light in the wavelength range of 250 nm to 400 nm and has liquid crystallinity in the temperature range of 100 ° C to 300 ° C. [0186] The side chain type acrylic polymer preferably has a photosensitive side chain that can react with light in the wavelength range of 250 nm to 400 nm. [0187] The side chain type acrylic polymer preferably has a mesogenic group capable of exhibiting liquid crystallinity in a temperature range of 100°C to 300°C. [0188] The side chain type acrylic polymer, because the main chain is bonded to a photosensitive side chain, can sense light to cause a coupling reaction, an isomerization reaction, or a photo-Fries rearrangement (Friesrearrangement) reaction. The structure of the side chain with photosensitivity is not particularly limited. Generally, the structure that can sense light, cause a cross-linking reaction, or a photoflash rearrangement reaction is preferred, and the one that can cause a cross-linking reaction is more preferred. . In this case, even when exposed to external pressure such as heat, the achieved alignment control capability can be stabilized for a long period of time. The structure of the photosensitive side chain acrylic polymer film that can induce liquid crystallinity is not particularly limited as long as it can satisfy the characteristics, and generally it is preferable to have a rigid original liquid crystal component on the side chain structure. . In this case, when the side chain type acrylic polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained. The structure of this acrylic polymer, for example, has main chain and the side chain that is bonded to main chain, and this side chain is, has biphenyl, triphenyl, phenylcyclohexyl, phenyl benzoate The original liquid crystal components such as phenyl, azophenyl, etc., and the structure of the photosensitive group bonded to the front part that can sense light to cause cross-linking reaction or isomerization reaction, or have the main chain and the main chain. The side chain of the chain is formed from the original liquid crystal component and has a structure of a phenyl benzoate group that can undergo a photofries rearrangement reaction. A more specific example of the structure of the photosensitive side-chain type acrylic polymer having liquid crystallinity in a specific temperature range, for example, has a structure consisting of hydrocarbon, (meth)acrylate, itaconate, fumarate At least one selected from the group consisting of radical polymerizable groups such as , maleate, α-methylidene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. The constituted main chain preferably has a structure with a side chain formed by at least one of the following formulae (31) to (35). [0191]
Figure 02_image101
In formula, Ar 1 Represents a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, Ar 2 with Ar 3 , each independently represents a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, q 1 with q 2 One of them is 1, the other is 0, Ar 4 with Ar 5 Each independently represents a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, and Y 1 -Y 2 Indicates CH=CH, CH=N, N=CH or C≡C, S 1 to S 3 Each independently represents a single bond, a linear or branched alkylene with 1 to 18 carbon atoms, a cyclic alkylene with 5 to 8 carbon atoms, a phenylene or a biphenylene, or a single bond, Ether bond, ester bond, amide bond, urea bond, urethane bond, amine group bond, carbonyl group or one or more bonds selected from the combination of these or through one or more of these bonds, to a straight-chain or branched alkylene having 1 to 18 carbon atoms, a cyclic alkylene having 5 to 8 carbon atoms, The structure obtained by the phenyl group, the biphenyl group, or the positions selected from the combination of 2 or more and 10 or less, or the structure obtained by connecting a plurality of the above-mentioned substituents through the above-mentioned bonds, respectively; R 31 Represents a hydrogen atom, a hydroxyl group, a hydrogen thiol group, an amine group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. The dialkylamino group of 16, the benzene ring and/or the naphthalene ring may be at least one of the same or different selected from a halogen atom, a cyano group, a nitro group, a carboxyl group and an alkoxycarbonyl group of 2 to 11 carbon atoms substituted by the substituent. In this case, the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, or a structure obtained by combining these, and may be substituted by a halogen atom. [0193] The photosensitive side chain type acrylic polymer of the component (B) of this case having liquid crystallinity in a specific temperature range may contain a liquid crystal side chain. The original liquid crystal group with liquid crystal side chain can be the base of the original liquid crystal structure such as biphenyl or phenyl benzoate alone, or the original liquid crystal structure such as benzoic acid is equal to the hydrogen bonding between the side chains. Any base composed of a liquid crystal structure may be used. The proto-liquid crystalline group having a side chain preferably has the following structure. [0195]
Figure 02_image103
<<Preparation method of photosensitive side chain type polymer>> The above-mentioned photosensitive side chain type acrylic polymer having liquid crystallinity in a specific temperature range, the photoreactive side having the above-mentioned photosensitive side chain can be used. Chain monomer and liquid crystal side chain monomer are polymerized and obtained. [Photoreactive Side Chain Monomer] The photoreactive side chain monomer, when forming a polymer, may be a monomer that forms a polymer having a photosensitive side chain at the side chain portion of the polymer. [0198] The photoreactive group with the side chain is preferably the structure represented by the above-mentioned formulas (31) to (35). More specific illustration of the photoreactive side chain monomer, for example, to have by hydrocarbon, (meth)acrylate, itconate, fumarate, maleate, α-methylidene - A polymerizable group composed of at least one selected from the group of radically polymerizable groups such as γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc., and the above formula ( The structure of the photosensitive side chain formed by at least one of 31) to (35) is preferable. [Liquid crystal side chain monomer] The liquid crystal side chain monomer system means that the polymer generated from the monomer has liquid crystallinity, and the polymer can form the original liquid crystal group at the side chain position of the monomer. meaning. A more specific example of the liquid crystal side chain monomer, for example, to have a compound consisting of hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylidene- The polymerizable group composed of at least one selected from the group of radical polymerizable groups such as γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. The structure of at least one side chain of "the proto-liquid crystal group of the side chain" is preferable. [0202] The side chain acrylic polymer of one aspect of the component (B) can be obtained by polymerizing the above-mentioned photoreactive side chain monomers capable of producing liquid crystallinity. In addition, it is also possible to perform copolymerization via a photoreactive side chain monomer that does not produce liquid crystallinity and a liquid crystal side chain monomer, or a photoreactive side chain monomer that produces liquid crystallinity and a liquid crystal side chain monomer. Copolymerization can be obtained. Moreover, as long as the range which does not impair the liquid crystallinity generating ability, it can also be copolymerized with other monomers. [0203] Other monomers, for example, commercially available monomers that can carry out radical polymerization and the like. Specific examples of other monomers, for example, unsaturated carboxylic acid, acrylate compound, methyl acrylate compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound etc. Specific examples of unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like. Acrylate compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methacrylate, phenyl acrylate, 2,2,2- Ethyl trifluoroacrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, ethyl 2-methoxyacrylate, triethylene glycol methoxyacrylate, ethyl 2-ethoxyacrylate , tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8- Tricyclodecyl acrylate, and, 8-ethyl-8-tricyclodecyl acrylate, and the like. Methyl acrylate compounds, for example, methyl methacrylate, methyl ethacrylate, methyl isopropyl acrylate, methyl benzyl acrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl Methyl methacrylate, methyl phenylacrylate, methyl 2,2,2-trifluoroethyl acrylate, tert-butyl methyl acrylate, methyl cyclohexyl acrylate, methyl isobornyl acrylate, 2-methoxy Ethyl methyl acrylate, methoxytriethylene glycol methyl acrylate, 2-ethoxyethyl methyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl acrylate Methyl-2-adamantyl acrylate, methyl 2-propyl-2-adamantyl acrylate, methyl 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-triacrylate Methyl cyclodecyl acrylate, etc. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (3-ethyl-3-oxetanyl) can also be used A (meth)acrylate compound having a cyclic ether group such as meth (meth)acrylate. Vinyl compounds, for example, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether and the like. Styrene compounds, for example, styrene, methylstyrene, chlorostyrene, bromostyrene and the like. Maleimide compounds, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide and the like. [0211] The production method of the side chain type polymer of the present embodiment is not particularly limited, and a method widely used in general industrial processing can be used. Specifically, for example, it can be obtained by cationic polymerization, radical polymerization, or anionic polymerization of vinyl groups of liquid crystal side chain monomers or photoreactive side chain monomers. Among them, radical polymerization is particularly preferred from the viewpoint of easy reaction control. The polymerization initiator of radical polymerization, for example, can use well-known radical polymerization initiators such as AIBN (azobisisobutyronitrile), or reversible additional-cracking type chain transfer (RAFT) polymerization reagent and other well-known compounds. The radical polymerization method is not particularly limited, and it can use an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, and the like. [0214] The organic solvent used in the polymerization reaction of the photosensitive side-chain acrylic polymer having liquid crystallinity in a specific temperature range is not particularly limited as long as it can dissolve the solvent of the generated polymer, for example. Specific examples thereof are as listed below. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl Ethyl caprolactone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethyl pentanol, dipentane alkene, ethylpentanone, methylnonanone, methyl ethyl ketone, methyl isoamyl ketone, methyl isoacetone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetic acid Esters, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl ether Ethyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutyl ester, pentyl ethyl acid ester, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether Diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate , Methyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 - propyl methoxypropionate, butyl 3-methoxypropionate, diethylene glycol diether (glyme), 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N , N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, etc. [0216] These organic solvents can be used alone or in combination. Moreover, even if it is a solvent which does not dissolve the produced polymer, it can be mixed with the said organic solvent, as long as it is a range which does not precipitate the produced polymer. In addition, in the radical polymerization, since the oxygen in the organic solvent is the reason for inhibiting the polymerization reaction, the organic solvent is preferably used as degassed as possible. [0218] The polymerization temperature at the time of radical polymerization can be selected at any temperature between 30°C and 150°C, preferably in the range of 50°C to 100°C. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it will be difficult to obtain high molecular weight polymers, and if the concentration is too high, the viscosity of the reaction solution will increase excessively, making it difficult to uniformly stir. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction may be carried out at a high concentration, and an organic solvent may be added thereafter. In the above-mentioned free radical polymerization reaction, when the ratio of the free radical polymerization initiator is too much with respect to the monomer, the molecular weight of the obtained macromolecule will be reduced, and the molecular weight of the obtained macromolecule will be increased when too little, so free The ratio of the base initiator is preferably 0.1 mol % to 10 mol % relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during the polymerization. [Recovery of the photosensitive side chain type acrylic polymer with liquid crystallinity in a specific temperature range] In the reaction solution of the photosensitive side chain type polymer with liquid crystallinity obtained by the above reaction, the generated In the case of high polymers, the reaction solution can be put into a poor solvent, and the polymers can be precipitated. Poor solvents used for precipitation, for example, methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water etc. The polymer precipitated by the input of the lean solvent can be dried under normal pressure or reduced pressure at normal temperature or in a heated state after being recovered by filtration. In addition, when the polymer recovered by precipitation is dissolved in an organic solvent and reprecipitated and recovered by repeating 2 to 10 times, impurities in the polymer can be reduced. The poor solvent at this time can be, for example, alcohols, ketones, hydrocarbons, etc. When three or more kinds of poor solvents selected from these are used, the efficiency of purification can be further improved, which is more preferable. One aspect of the component (B) of the present invention is the molecular weight of the photosensitive side-chain type acrylic polymer having liquid crystallinity in a specific temperature range, considering the strength of the obtained coating film and the workability during coating film formation. , and the uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2,000-1,000,000, more preferably 5,000-100,000. The content of (A-1) component and (A-2) component and (B) component in the liquid crystal aligning agent of the present invention, with the total amount of (A-1) component and (A-2) component and (B) The mass ratio of the ingredients is 5:95～95:5, 10:90～90:10 is better. The imidization rate of (A-1) component, (A-2) component and (B) component in the liquid crystal aligning agent of the present invention can be adjusted arbitrarily in conjunction with the purpose or purpose, in terms of solubility or From the viewpoint of charge accumulation characteristics, the imidization ratio of the specific polymer (A-1) component and (A-2) component is preferably 0 to 55%, more preferably 0 to 20%. In addition, from the viewpoint of liquid crystal alignment, alignment regulation force, and voltage retention rate, the imidization rate of the specific polymer (B) is preferably higher, preferably 40% to 95%, more preferably 55%. ~90%. <Liquid crystal alignment agent> The liquid crystal alignment agent used in the present invention is in the form of a solution in which a polymer component is dissolved in an organic solvent. As for the molecular weight of the polymer, the weight average molecular weight is preferably 2,000-500,000, more preferably 5,000-300,000, and particularly preferably 10,000-100,000. Moreover, as for the number average molecular weight, 1,000-250,000 are preferable, 2,500-150,000 are more preferable, 5,000-50,000 are especially preferable. The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed in accordance with the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, more than 1 mass % is It is good, and from the viewpoint of solution storage stability, it is preferably 10 mass % or less. A particularly preferred polymer concentration is 2 to 8 mass %. [0226] The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it can dissolve the polymer component uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidine Ketone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfoxide, γ-Butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropaneamide, etc. These may be used alone or in combination of two or more. Moreover, even if it is a solvent which cannot uniformly dissolve a polymer component by itself, as long as it is a range which does not precipitate a polymer, you may mix and use it with the said organic solvent. In addition, the organic solvent contained in the liquid crystal aligning agent, in addition to the above-mentioned solvent, can generally use a mixed solvent obtained by combining with a solvent that can improve coatability or improve the surface smoothness of the coating film when coating the liquid crystal aligning agent. , these mixed solvents are also suitable for use in the liquid crystal alignment agent of the present invention. Specific examples of the organic solvent that can be used in combination are as follows, but are not limited to these examples. 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, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2- Pentanol, 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, 2,6-dimethyl-4-heptanol, 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, diisopropyl ether, 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, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2- Heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentanone Ethyl acetate, 2-ethylbutyl 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, Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(butoxyethoxy) 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 acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate , Diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene 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, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate ester, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the following formulae [D-1] to [D-3], and the like. [0229]
Figure 02_image105
In formula [D-1], D 1 Represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D 2 Represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms. Wherein the combination of preferred solvent, for example, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butane Lactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl- 2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6- Dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, etc. The type and content of these solvents can be appropriately selected according to the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent. [0232] In addition, in the liquid crystal aligning agent of the present invention, the following additives can be added from the viewpoint of improving the mechanical strength of the film. [0233]
Figure 02_image107
[0234]
Figure 02_image109
[0235] These additives are preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When it is less than 0.1 parts by mass, the effect cannot be expected, and when it exceeds 30 parts by mass, the liquid crystal alignment property is lowered, so it is more preferably 0.5 to 20 parts by mass. In the liquid crystal aligning agent of the present invention, in addition to the above, in the range that does not impair the effect of the present invention, polymers other than polymers can be added to change the electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film for the purpose of A dielectric or conductive substance, a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinking compound for the purpose of improving the film hardness or density when used as a liquid crystal alignment film, or a It is an imidization accelerator and the like for the purpose of efficiently carrying out the imidization reaction of polyamic acid when the coating film is sintered. <Liquid Crystal Alignment Film><Production Method of Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is a film obtained by coating the above-mentioned liquid crystal alignment agent on a substrate, drying and sintering. The substrate to which the liquid crystal alignment agent of the present invention is coated is not particularly limited as long as it is a substrate with high transparency, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. etc., from the viewpoint of simplification of production, it is preferable to use a substrate on which ITO electrodes or the like for driving liquid crystal are formed. In addition, if the reflective liquid crystal display element is only a single-sided substrate, an opaque material such as a silicon wafer can also be used, and a material such as aluminum that can reflect light can also be used as the electrode in this case. The coating method of the liquid crystal aligning agent of the present invention, for example, spin coating method, printing method, ink jet method etc.. For the drying and sintering steps after coating the liquid crystal alignment agent of the present invention, any temperature and time can be selected. Usually, in order to fully remove the organic solvent contained, it can be dried at 50°C to 120°C for 1 minute to 10 minutes, and then sintered at 150°C to 300°C for 5 minutes to 120 minutes. The thickness of the coating film after sintering is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be reduced, so it is usually 5-300 nm, preferably 10-200 nm. [0239] The method for performing an alignment treatment on the obtained liquid crystal alignment film, for example, a rubbing method, a photo-alignment treatment method, and the like. [0240] The rubbing treatment can be performed using an existing rubbing device. At this time, the material of the rubbing cloth, for example, cotton, nylon, rayon, etc. The conditions of the rubbing treatment are, in general, the conditions of a rotation speed of 300 to 2000 rpm, a conveyance speed of 5 to 100 mm/s, and an extrusion amount of 0.1 to 1.0 mm. Then, residues generated by friction generated by ultrasonic cleaning are removed using pure water, alcohol, or the like. A specific example of the photo-alignment treatment method, for example, a method of irradiating the surface of the coating film with radiation that is deviated in a specific direction, and depending on the situation, heat treatment can be performed at a temperature of 150-250 ° C to give the liquid crystal alignment ability. Wait. As the radiation, for example, ultraviolet rays and visible rays having wavelengths of 100 nm to 800 nm can be used. Among them, ultraviolet rays with wavelengths of 100 nm to 400 nm are preferable, and those with wavelengths of 200 nm to 400 nm are particularly preferable. Moreover, for the purpose of improving the liquid crystal alignment, the coated substrate may be irradiated with radiation during heating at 50 to 250°C. The irradiation dose of the aforementioned radiation is 1～10,000mJ/cm 2 Preferably, 100～5,000mJ/cm 2 Excellent. The liquid crystal alignment film prepared in the above manner can stably align liquid crystal molecules in a specific direction. Also, when the extinction ratio of polarized ultraviolet rays is higher, it can give higher anisotropy, which is better. Specifically, the extinction ratio of ultraviolet rays that are polarized in a straight line is preferably 10:1 or more, and more preferably 20:1 or more. [0243] The film of irradiating the polarized radiation obtained in the above-mentioned manner can be contacted with a solvent containing at least one selected from water and an organic solvent subsequently. [0244] The solvent used in the contact treatment, for example, is not particularly limited as long as it can dissolve the solvent of the decomposition product generated by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve Cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate, etc. . These solvents may be used in combination of two or more. From the viewpoint of versatility or safety, it is better to use at least one selected from the group formed by water, 2-propanol, 1-methoxyl group-2-propanol and ethyl lactate . Water, 2-propanol, and mixed solvents of water and 2-propanol are particularly preferred. In the present invention, the contact processing of the film of the radiation irradiating polarized light and the solution containing the organic solvent, for the use of soaking treatment, spray (Spray) treatment, etc., the film and the liquid can be preferably and fully contacted. way to proceed. Among them, the method of dipping the film in the solution containing the organic solvent is preferably performed for 10 seconds to 1 hour, and more preferably for 1 to 30 minutes. The contact treatment can be carried out at normal temperature or under heating, preferably at 10 to 80°C, more preferably at 20 to 50°C. Also, if necessary, means of improving contact such as ultrasound can be applied. After the above-mentioned contact treatment, for the purpose of removing the organic solvent in the solution after use, washing (Rinse) or drying can be carried out with low-boiling solvents such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, etc. , or both at the same time. [0248] In addition, the above-mentioned film subjected to contact treatment with a solvent may also be heated above 150° C. for the purpose of drying the solvent and realigning the molecular chains in the film. [0249] The heating temperature, for example, is preferably 150 to 300°C. When the temperature is higher, the realignment of the molecular chain can be promoted, but when the temperature is too high, the molecular chain may be decomposed. Therefore, the heating temperature is, for example, preferably 180 to 250°C, and particularly preferably 200 to 230°C. When the heating time is too short, the effect of realignment of the molecular chain may not be obtained, and when it is too long, the molecular chain may be decomposed, so 10 seconds to 30 minutes is preferred, and 1 10 minutes to 10 minutes is preferred. [0251] In addition, the obtained liquid crystal alignment film can be easily dissolved in a reproducing material, and is a film with excellent reproducibility. The solvent used when reproducing can enumerate as following solvent: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether etc. glycol ethers; glycol esters of methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc. ; Diethylene glycol, propylene glycol, butanediol, hexanediol and other glycols; methanol, ethanol, 2-propanol, butanol and other alcohols; acetone, methyl ethyl ketone, cyclopentanone, cyclohexane Ketones, 2-heptanone, γ-butyrolactone and other ketones; methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionate Esters of methyl acid, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc., N,N-dimethylformamide, N,N-dimethy Amides such as methylacetamide and N-methyl-2-pyrrolidone. Remanufactured material, for example, while containing the alkaline components of ethanolamine etc. in the above-mentioned solvent, it is better to contain the antirust agent that will not make this alkaline damage other components such as electrode. Manufacturers that can provide these remanufactured materials, such as South Korea's Huiming Industrial Co., Ltd., KPX Chemical, etc. [0254] For remanufacturing, after heating the remanufactured materials listed above at room temperature, or between 30° C. and 100° C., immerse the substrate with the liquid crystal alignment film in it, and keep it for 1 second to 1000 seconds, preferably For 30 seconds to 500 seconds, or after spraying the reproduced material, the liquid is washed with an alcohol-based solvent or pure water. In addition, the temperature of the reconstituted liquid at the time of remanufacturing is preferably low from the viewpoint of work efficiency and the like, and is usually room temperature to 60°C, more preferably room temperature to 40°C. <Liquid crystal display element> The liquid crystal display element of the present invention is to use the liquid crystal alignment agent of the present invention and prepare a substrate with a liquid crystal alignment film according to the above-mentioned manufacturing method of the liquid crystal alignment film, and then use a known method to manufacture a liquid crystal cell , and use it as a liquid crystal display element. [0256] As an example of a liquid crystal cell fabrication method, a liquid crystal display element with a passive element matrix structure will be described as an example. In addition, it may also be a liquid crystal display element having an active matrix structure in which each pixel portion constituting an image display is provided with an opening and closing element such as a TFT (Thin Film Transistor). [0257] First, a transparent glass substrate is prepared, and common electrodes are provided on one side of the substrate, and segment electrodes are provided on the other side of the substrate. These electrodes, for example, can be used as ITO electrodes, or can form a desired image display pattern. Next, an insulating film covering the common electrode and the segment electrode can be provided on each substrate. Insulating film, for example, obtained by the sol-gel method of SiO 2 -TiO 2 formed film. [0258] Next, on each substrate, the liquid crystal alignment film of the present invention is formed according to the above method. [0259] Next, the substrate on one side and the substrate on the other side are overlapped with the alignment film surfaces facing each other, and the periphery thereof is bonded with a sealant. The sealant is usually mixed with spacers for the purpose of controlling the gap between the substrates and the like. In addition, it is also preferable to spread spacers for controlling the gap between the substrates in the in-plane portion where the sealant is not provided. A part of the sealant is provided with an opening that can be filled with liquid crystal from the outside. [0260] Next, through the opening provided in the sealant, the liquid crystal material was injected into the space surrounded by the two sheets of substrates and the sealant. Then, the opening is sealed with an adhesive. As the injection method, a vacuum injection method or a method utilizing capillary phenomenon in the atmosphere may be used. Then, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates is attached to the surface opposite to the liquid crystal layer of the two substrates. Through the above steps, the liquid crystal display element of the present invention is obtained. In the present invention, the sealant, for example, can be cured by ultraviolet irradiation or heating using reactive groups such as epoxy groups, acryl groups, methacryloyl groups, hydroxyl groups, allyl groups, and acetyl groups. of resin. In particular, it is preferable to use a curable resin system having reactive groups of both epoxy groups and (meth)acryloyl groups. [0262] In the sealant of the present invention, an inorganic filler can be added for the purpose of improving adhesion and moisture resistance. The inorganic filler that can be used is not particularly limited, and specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, nitride Silicon, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, Zirconium silicate, barium titanate, nitrocellulose, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, nitrogen Boronide, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate. The aforementioned inorganic fillers may be used in combination of two or more. In this liquid crystal display element, because the liquid crystal alignment film is obtained by using the liquid crystal alignment film of the present invention, it has excellent reproducibility, and is suitable for use in large-screen and high-definition liquid crystal televisions, etc. .

[實施例] 　　[0264] 以下於本發明製造方法之詳細說明中，將列舉研究原料組成或添加比例的實驗方法，及其結果與典型的製造方法的實施例等進行說明。又，本發明並不受該些實施例所限定。 　　本實施例所使用的簡稱之說明 　　(有機溶劑) 　　NMP：N-甲基-2-吡咯啶酮 　　GBL：γ-丁內酯 　　BCS：丁基溶纖劑(cellosolve) 　　酸二酐(A)：下述式(A) 　　酸二酐(B)：下述式(B) 　　酸二酐(C)：下述式(C) 　　酸二酐(D)：下述式(D) 　　酸二酐(E)：下述式(E) 　　DA-1：下述式(DA-1) 　　DA-2：下述式(DA-2) 　　DA-3：下述式(DA-3) 　　DA-4：下述式(DA-4) 　　DA-5：下述式(DA-5) 　　DA-6：下述式(DA-6) 　　DA-7：下述式(DA-7) 　　DA-8：下述式(DA-8) 　　DA-9：下述式(DA-9) 　　DA-10：下述式(DA-10) 　　AD-1：下述式(AD-1) 　　AD-2：下述式(AD-2) 　　[0265]

Figure 02_image111
[0266]
Figure 02_image113
[0267] 以下為記載黏度之測定、醯亞胺化率之測定、再製性之評估、液晶單元(cell)之製作，及電荷緩和特性評估之方法等 　　[0268] [黏度之測定] 　　合成例中，聚醯胺酸酯及聚醯胺酸溶液之黏度，為使用E型黏度計TV-25H(東機產業公司製)，於溫度25℃下，測定樣品量1.1mL、CORD-1(1°34’，R24)而得者。 　　[0269] [醯亞胺化率之測定] 　　將聚醯亞胺粉末20mg置入NMR樣品管(草野科學公司製NMR標準樣品管φ5)，添加重氫二甲基亞碸(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。使用日本電子數據公司製NMR測定器(JNW-ECA500)測定該溶液於500MHz之質子NMR。醯亞胺化率，為使用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方式測定，並將該質子的波峰積算值，與出現於9.5至10.0ppm附近的醯胺酸的NH基所衍生的質子波峰積算值，依以下算式而求得。 　　[0270] 醯亞胺化率(%)=(1-α・x/y)×100 　　上述式中，x為醯胺酸之NH基產生的質子波峰積算值、y為基準質子之波峰積算值、α為相對於聚醯胺酸(醯亞胺化率為0%)之狀態中的醯胺酸之1個NH基質子，該基準質子的個數比例。 　　[0271] [再製性之評估] 　　將本發明之液晶配向劑使用旋轉塗佈機塗佈於ITO基板上。於60℃之加熱板上乾燥1分30秒鐘之後，於230℃之熱風循環式烘箱中進行20分鐘之燒結處理，而形成膜厚100nm之塗膜。隨後，將製得之基板浸漬於加熱的再製材料中300秒鐘，進行顯影後，使用超純水進行20秒鐘的流水洗淨。隨後，進行噴氣處理，並依以下基準進行評估，所得之結果記載如表4所示。 　　○：35℃、5分鐘，無殘膜產生 　　△：40℃、5分鐘，無殘膜產生 　　×：40℃、5分鐘，產生殘膜 　　[0272] [液晶單元之製作] 　　製作具備廣視角開閉(Fringe Field Switching：以下，亦稱為FFS)模式液晶顯示元件之構成內容的液晶單元。 　　[0273] 首先準備附有電極之基板。基板為大小30mm×50mm、厚度0.7mm之玻璃基板。於基板上形成作為第1層的構成對向電極之具備有黏稠狀圖型的ITO電極。第1層的對向電極上的第2層，為形成以CVD法形成膜的SiN(氮化矽)膜。第2層的SiN膜之膜厚為500nm，其具有作為層間絕緣膜之機能。第2層的SiN膜上，配置有作為第3層的將ITO膜經由圖型形成(Patterning)而形成的櫛齒狀的畫素電極，並形成第1畫素及第2畫素等2個的畫素。各畫素之尺寸為縱10mm、橫約5mm。此時，第1層的對向電極與第3層的畫素電極，經由第2層的SiN膜之作用，而形成電氣絕緣。 　　[0274] 第3層之畫素電極，具有由複數配列的中央部份為屈曲之「ㄑ」字形狀的電極要素所構成櫛齒狀之形狀。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，因由複數配列的中央部份為屈曲之「ㄑ」字形狀的電極要素所構成，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之「ㄑ」字的形狀。因此，各畫素經由該中央的屈曲部份為境界而分割為上下部，而具有位於屈曲部份的上側之第1區域與下側之第2區域。 　　[0275] 比較各畫素的第1區域與第2區域時，其差異為構成該畫素的的畫素電極之電極要素具有相異的形成方向。即，以後述液晶配向膜的摩擦方向為基準時，畫素的第1區域為以畫素電極的電極要素為+10°之角度(順時鐘方向)之方式形成，畫素的第2區域為以畫素電極的電極要素為-10°之角度(順時鐘方向)之方式形成。即，各畫素的第1區域與第2區域為具有，畫素電極與對向電極之間，經由施加電壓所引起的液晶於基板面內的迴轉動作(面內・開閉)之方向為互相相反方向之構成。 　　[0276] 其次，將所得液晶配向劑使用1.0μm過濾器過濾後，使用旋轉塗佈機塗佈於所準備的上述附有電極之基板與內面形成ITO膜之具有高4μm的柱狀間隔器之玻璃基板上。於80℃之加熱板上進行5分鐘乾燥後，於230℃之熱風循環式烘箱中進行20分鐘之燒結處理，而形成膜厚100nm之塗膜。對該塗膜面實施摩擦或偏光紫外線照射等配向處理，而得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，另1片基板以面向液晶配向膜面形成配向方向為0°之方式貼合後，使密封劑硬化，而製得空單元。將液晶MLC-2041(莫克股份有限公司製)使用減壓注入法注入該空單元中，將注入口密封，而製得FFS驅動液晶單元。隨後，將所得液晶單元於110℃下加熱1小時，放置一晩後，供各評估使用。 　　[0277] [電荷緩和特性評估] 　　將上述液晶單元置於光源上，測定室溫下之V-T特性(電壓-穿透率特性)後，再測定施加±1.5V/60Hz的矩形波之狀態下，液晶單元之穿透率(Ta)。隨後，重疊直流1V下，於進行30分鐘驅動間，測定液晶單元之穿透率(Tb)，切斷直流電壓後，再測定僅使用±1.5V/60Hz的矩形波、驅動20分鐘時，液晶單元之穿透率(Tc)，由各時間的穿透率(Tb、Tc)與初期的穿透率(Ta)之差(DT)，算出因殘留於液晶顯示元件內的電壓所產生的穿透率之差。該殘留電壓越早緩和時，推測將更不容易發生老化(burn-in)現象。(Tb-Ta)於施加直流電壓開始後5分鐘降至2%以下者標記為○、以上者標記為×，(Tc-Ta)於切斷直流電壓後，5分鐘降至2%以下者標記為○、以上者標記為×。所得之結果記載如表4所示。 　　[0278] (聚合例1) 　　將附有攪拌裝置的1L之四口燒瓶，放置於氮氛圍中，秤取(DA-4)86.0g、(DA-7)53.4g、(DA-10)76.5g，加入NMP 1580g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(E)93.2g，再加入NMP 168g，於氮氛圍、40℃下，攪拌3小時。再添加酸二酐(D)28.2g，再加入NMP 160g，於氮氛圍、23℃下，攪拌4小時，得聚醯胺酸之溶液(PAA-1)。該聚醯胺酸之溶液於溫度25℃之黏度為200mPa・s。 　　於置有攪拌子的300mL三角燒瓶中，濾取該聚醯亞胺粉末20.4g，加入NMP150g，於50℃下攪拌20小時，使其溶解，得聚醯亞胺溶液(SPI-1)。 　　[0279] 於置有攪拌子的300mL三角燒瓶中，濾取該聚醯亞胺粉末20.4g，加入NMP 150g，於50℃下攪拌20小時，使其溶解。又，於置有攪拌子的100mL三角燒瓶中濾取該溶液16.3g，加入NMP3.46g、GBL13.0g、含有3-環氧丙氧基丙基三乙氧基矽烷1質量%的NMP溶液1.95g，及BCS8.69g，使用磁性攪拌子攪拌2小時，得聚醯亞胺溶液(SPI-1)。 　　[0280] (聚合例2) 　　將附有攪拌裝置的100mL四口燒瓶，放置於氮氛圍中，秤取(DA-6)0.58g、(DA-4)1.32g、(DA-5)0.93g、(DA-7)3.01g，加入NMP42.8g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(E)3.91g，再加入NMP 12.4g，於氮氛圍、40℃下，攪拌16小時，得聚醯胺酸溶液(PAA-2)。該聚醯胺酸溶液於溫度25℃之黏度為450cps。 　　[0281] (聚合例3) 　　將附有攪拌裝置的100mL四口燒瓶，放置於氮氛圍中，秤取(DA-9)6.19g、(DA-8)2.14g，加入NMP 61.1g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(B)5.71g，再加入NMP 18.5g，於氮氛圍、50℃下，攪拌16小時，得聚醯胺酸溶液(PAA-3)。該聚醯胺酸溶液於溫度25℃之黏度為351cps。 　　[0282] (聚合例4) 　　將附有攪拌裝置的50mL四口燒瓶，放置於氮氛圍中，秤取(DA-1)2.55g、(DA-4)0.78g，加入NMP24.4g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(B)1.75g，再加入NMP4.3g，於23℃、氮氣氛圍下，攪拌2小時後，添加酸二酐(D)1.41g，再加入NMP8.0g，於23℃、氮氣氛圍下，攪拌2小時。隨後，於50℃下攪拌16小時，聚醯胺酸溶液(PAA-4)。該聚醯胺酸溶液於溫度25℃之黏度為240cps。 　　[0283] (聚合例5) 　　將附有攪拌裝置的50mL四口燒瓶，放置於氮氛圍中，秤取(DA-1)2.55g、(DA-3)0.96g，加入NMP25.7g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，加入酸二酐(C)3.00g，再加入NMP11.2g，於23℃、氮氣氛圍下，攪拌2小時後，添加酸二酐(D)0.77g，再添加NMP4.4g，於23℃、氮氣氛圍下，攪拌2小時。隨後，於50℃下攪拌16小時，得聚醯胺酸溶液(PAA-5)。該聚醯胺酸溶液於溫度25℃之黏度為358cps。 　　[0284] (聚合例6) 　　將附有攪拌裝置的50mL四口燒瓶，放置於氮氛圍中，秤取(DA-1)2.55g、(DA-2)0.46g，加入NMP22.3g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(C)2.00g，再加入NMP6.3g，於23℃、氮氣氛圍下，攪拌2小時後，添加酸二酐(D)1.51g，再加入NMP8.5g，於23℃、氮氣氛圍下，攪拌2小時。隨後，於50℃下攪拌16小時，得聚醯胺酸溶液(PAA-6)。該聚醯胺酸溶液於溫度25℃之黏度為333cps。 　　[0285] (聚合例7) 　　將附有攪拌裝置的50mL四口燒瓶，放置於氮氛圍中，秤取(DA-1)2.55g、(DA-2)0.46g，加入NMP22.3g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，添加酸二酐(A)4.5g，再加入NMP20.5g，於23℃、氮氣氛圍下，攪拌2小時後，於50℃下攪拌16小時，得聚醯胺酸溶液(PAA-7)。該聚醯胺酸溶液於溫度25℃之黏度為350cps。 　　[0286] (聚合例8) 　　將附有攪拌裝置的50mL四口燒瓶，放置於氮氛圍中，秤取(DA-1)2.55g、(DA-2)0.49g，加入NMP22.3g，於23℃、氮氣送入中，攪拌使其溶解。該二胺溶液於攪拌中，加入酸二酐(C)3.00g，再加入NMP12.0g，於23℃、氮氣氛圍下，攪拌2小時後，添加酸二酐(D)0.72g，再加入NMP4.1g，於23℃、氮氣氛圍下，攪拌2小時。隨後，於50℃下攪拌16小時，得聚醯胺酸溶液(PAA-8)。該聚醯胺酸溶液於溫度25℃之黏度為333cps。 　　[0287] (比較例1) 　　於放置有攪拌子的50mL三角燒瓶中，濾取上述所得之聚醯亞胺溶液(SPI-1)7.00g、(PAA-4)10.40g、含有(AD-1)1wt%之NMP溶液2.40g、含有(AD-2)10wt%之NMP溶液0.72g，加入NMP7.48g、BCS12.00g，使用磁性攪拌子攪拌2小時，得液晶配向劑(A-1)。 　　[0288] (比較例2) 　　於放置有攪拌子的50mL三角燒瓶中，濾取比較合成例所得之聚醯胺酸溶液(PAA-2)6.73g、(PAA-5)15.27g、含有(AD-1)1wt%之NMP溶液2.40g、含有(AD-2)10wt%之NMP溶液0.72g，加入NMP2.88g、BCS12.00g，使用磁性攪拌子攪拌2小時，得液晶配向劑(A-2)。 　　[0289] (比較例3) 　　於放置有攪拌子的50mL三角燒瓶中，濾取比較合成例所得之聚醯胺酸溶液(PAA-3)4.00g、(PAA-6)12.80g、含有(AD-1)1wt%之NMP溶液2.40g，加入NMP 8.80g、BCS 12.00g，使用磁性攪拌子攪拌2小時，得液晶配向劑(A-3)。 　　[0290] (實施例1～2) 　　於放置有攪拌子的50mL三角燒瓶中，加入聚醯亞胺溶液(SPI-1)7.00g、如表1所示之由聚合例所得之(PAA-6)與(PAA-7)之克數後，濾取含有(AD-1)1wt%之NMP溶液2.40g、含有(AD-2)10wt%之NMP溶液0.72g，加入NMP 7.48g、BCS12.00g，使用磁性攪拌子攪拌2小時，得如表1所示液晶配向劑(B-1～2)。 　　[0291]
Figure 02_image115
[0292] (實施例3～6) 　　於放置有攪拌子的50mL三角燒瓶中，加入聚醯胺酸溶液(PAA-3)4.00g、依表2所示之由聚合例所得之聚醯胺酸溶液(PAA-6～8)之克數後，濾取含有(AD-1)1wt%之NMP溶液2.40g，加入NMP 4.80g、BCS 12.00g，使用磁性攪拌子攪拌2小時，得如表2所示之液晶配向劑(B-3～6)。 　　[0293]
Figure 02_image117
[0294] (實施例7～8) 　　於放置有攪拌子的50mL三角燒瓶中，加入比較合成例所得之聚醯胺酸溶液(PAA-2)6.73g、依表3所示之由聚合例所得之聚醯胺酸溶液(PAA-5)與(PAA-7)之克數後，濾取含有(AD-1)1wt%之NMP溶液2.40g、含有(AD-2)10wt%之NMP溶液0.72g，加入NMP 2.88g、BCS 12.00g，使用磁性攪拌子攪拌2小時，得液晶配向劑(A-2)。 　　[0295]
Figure 02_image119
[0296]
Figure 02_image121
[產業上利用性] 　　[0297] 由本發明之液晶配向劑所得之液晶配向膜，於IPS驅動方式或FFS驅動方式的液晶顯示元件中，可降低因交流驅動的非對稱化所造成的電荷蓄積，且可快速地緩和因直流電壓所蓄積的殘留電荷，而可製得具有優良殘像特性的IPS驅動方式或FFS驅動方式的液晶顯示元件。因此，其特別適合作為IPS驅動方式或FFS驅動方式的液晶顯示元件或液晶電視的液晶配向膜。[Examples] [0264] In the following detailed description of the production method of the present invention, an experimental method for examining the composition or addition ratio of raw materials, the results thereof, and examples of typical production methods will be described. In addition, this invention is not limited by these Examples. Explanation of abbreviations used in this example (organic solvent) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve Acid dianhydride (A): the following formula (A) Acid dianhydride (B): following formula (B) acid dianhydride (C): following formula (C) acid dianhydride (D): following formula (D) acid dianhydride (E): following Formula (E) DA-1: Following formula (DA-1) DA-2: Following formula (DA-2) DA-3: Following formula (DA-3) DA-4: Following formula (DA-4) -4) DA-5: The following formula (DA-5) DA-6: The following formula (DA-6) DA-7: The following formula (DA-7) DA-8: The following formula (DA-8) ) DA-9: the following formula (DA-9) DA-10: the following formula (DA-10) AD-1: the following formula (AD-1) AD-2: the following formula (AD-2) [ 0265]
Figure 02_image111
[0266]
Figure 02_image113
The following describes the measurement of the viscosity, the measurement of the imidization rate, the evaluation of the reproducibility, the production of the liquid crystal cell (cell), and the method of evaluating the charge relaxation characteristics, etc. [0268] [Measurement of Viscosity] In the synthesis example , the viscosity of polyamide ester and polyamide acid solution, using E-type viscometer TV-25H (manufactured by Toki Sangyo Co., Ltd.), at a temperature of 25 ° C, measure the sample volume of 1.1 mL, CORD-1 (1 ° 34', R24). [Measurement of imidization rate] 20 mg of polyimide powder was placed in an NMR sample tube (NMR standard sample tube φ5 manufactured by Kusano Science Co., Ltd.), and deuterium dimethylsulfite (DMSO-d6, 0.05 %TMS (tetramethylsilane) mixture) 0.53ml, and ultrasonically applied to dissolve it completely. Proton NMR at 500 MHz of this solution was measured using an NMR analyzer (JNW-ECA500) manufactured by Nippon Electronic Data Corporation. The imidization rate is measured by using the proton derived from the structure that does not change before and after imidization as the standard proton method, and the peak value of the proton is calculated as the difference between the protons appearing in the vicinity of 9.5 to 10.0 ppm. The cumulative value of the proton peaks derived from the NH group is obtained by the following equation. Imidization rate (%)=(1-α・x/y)×100 In the above formula, x is the proton peak product value generated by the NH group of the amide acid, and y is the reference proton peak product value , α is the ratio of the number of the reference protons to one NH proton of the aramidic acid in the state of the polyamide acid (the imidization rate is 0%). [Evaluation of Reproducibility] The liquid crystal aligning agent of the present invention was coated on an ITO substrate using a spin coater. After drying on a hot plate at 60° C. for 1 minute and 30 seconds, a sintering process was performed in a hot air circulation oven at 230° C. for 20 minutes to form a coating film with a thickness of 100 nm. Subsequently, the obtained substrate was immersed in the heated rework material for 300 seconds, developed, and then washed with running water for 20 seconds using ultrapure water. Subsequently, air jet treatment was performed, and evaluation was performed according to the following criteria, and the results obtained are described in Table 4. ○: 35℃, 5 minutes, no residual film generation △: 40℃, 5 minutes, no residual film generation ×: 40℃, 5 minutes, residual film generation [0272] [Fabrication of liquid crystal cell] Fringe Field Switching: Hereinafter, it is also referred to as a liquid crystal cell of the structural content of the FFS) mode liquid crystal display element. [0273] First, a substrate with electrodes is prepared. The substrate is a glass substrate with a size of 30mm×50mm and a thickness of 0.7mm. On the substrate, an ITO electrode having a viscous pattern, which constitutes a counter electrode as a first layer, is formed. The second layer on the counter electrode of the first layer is a SiN (silicon nitride) film formed by a CVD method. The thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film as a third layer is arranged, and two elements such as a first pixel and a second pixel are formed. 's pixels. The size of each pixel is 10mm in length and 5mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. [0274] The pixel electrodes of the third layer have a comb-tooth-like shape composed of a plurality of electrode elements arranged in a “ㄑ” shape whose central portion is curved. The width in the short-side direction of each electrode element was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrodes that form each pixel are composed of a plurality of electrode elements with a curved "ㄑ" shape at the center part, so the shape of each pixel is not a rectangular shape, but is the same as the electrode elements. The central part is in the shape of a curved "ㄑ" in approximately bold type. Therefore, each pixel is divided into upper and lower parts with the central curved portion as a boundary, and has a first region located on the upper side of the curved portion and a second region located on the lower side. [0275] When comparing the first area and the second area of each pixel, the difference is that the electrode elements constituting the pixel electrode of the pixel have different forming directions. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the first region of the pixel is formed so that the electrode element of the pixel electrode is at an angle of +10° (clockwise), and the second region of the pixel is It is formed so that the electrode element of the pixel electrode is at an angle of -10° (clockwise). That is, the first area and the second area of each pixel are provided so that the directions of the rotation (in-plane, opening and closing) of the liquid crystal in the substrate plane caused by the application of the voltage between the pixel electrode and the counter electrode are mutually The composition in the opposite direction. Secondly, after gained liquid crystal alignment agent is filtered using 1.0 μm filter, use spin coater to be coated on the prepared above-mentioned substrate with electrode and the inner surface to form the column spacer with high 4 μm of ITO film on the glass substrate. After drying on a hot plate at 80° C. for 5 minutes, a sintering process was performed in a hot air circulation oven at 230° C. for 20 minutes to form a coating film with a thickness of 100 nm. Alignment treatment such as rubbing or polarized ultraviolet irradiation is performed on the coated surface to obtain a substrate with a liquid crystal alignment film. The above-mentioned two substrates were used as a set, the sealant was printed on the substrate, and the other substrate was attached so that the alignment direction was 0° facing the surface of the liquid crystal alignment film, and then the sealant was cured to obtain an empty cell. Liquid crystal MLC-2041 (manufactured by Morco Co., Ltd.) was injected into this empty cell using a reduced pressure injection method, and the injection port was sealed to produce an FFS-driven liquid crystal cell. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and was used for each evaluation after standing overnight. [Evaluation of charge relaxation characteristics] The above-mentioned liquid crystal cell was placed on a light source, and after measuring the VT characteristics (voltage-transmittance characteristics) at room temperature, the state of applying a square wave of ±1.5V/60Hz was measured, The transmittance (Ta) of the liquid crystal cell. Subsequently, the transmittance (Tb) of the liquid crystal cell was measured during driving for 30 minutes under superimposed DC 1V, and after the DC voltage was cut off, the liquid crystal cell was measured when only a square wave of ±1.5V/60Hz was used for 20 minutes of driving. The transmittance (Tc) of the cell is calculated from the difference (DT) between the transmittance (Tb, Tc) at each time and the transmittance (Ta) at the initial stage due to the voltage remaining in the liquid crystal display element. difference in transmittance. It is presumed that the burn-in phenomenon is less likely to occur when the residual voltage is eased earlier. (Tb-Ta) drops below 2% 5 minutes after the start of DC voltage application is marked with ○, above is marked with ×, (Tc-Ta) drops below 2% within 5 minutes after the DC voltage is cut off, mark ○, and the above are marked with ×. The results obtained are described in Table 4. (Polymerization Example 1) A 1 L four-necked flask with a stirring device was placed in a nitrogen atmosphere, and (DA-4) 86.0 g, (DA-7) 53.4 g, (DA-10) 76.5 g were weighed g, 1580 g of NMP was added, and at 23° C., nitrogen gas was introduced, and the mixture was stirred to dissolve. While stirring this diamine solution, 93.2 g of acid dianhydride (E) was added, and 168 g of NMP was further added, and the mixture was stirred at 40° C. for 3 hours in a nitrogen atmosphere. 28.2 g of acid dianhydride (D) was added, 160 g of NMP was added, and the mixture was stirred under nitrogen atmosphere at 23° C. for 4 hours to obtain a polyamide acid solution (PAA-1). The viscosity of the polyamide acid solution at 25°C is 200mPa·s. In a 300 mL conical flask equipped with a stirring bar, 20.4 g of the polyimide powder was collected by filtration, 150 g of NMP was added, and stirred at 50° C. for 20 hours to dissolve to obtain a polyimide solution (SPI-1). [0279] In a 300 mL conical flask equipped with a stirring bar, 20.4 g of the polyimide powder was collected by filtration, 150 g of NMP was added, and the mixture was stirred at 50° C. for 20 hours to dissolve. Furthermore, 16.3 g of this solution was collected by filtration in a 100 mL conical flask equipped with a stirring bar, and 3.46 g of NMP, 13.0 g of GBL, and 1.95 g of an NMP solution containing 1 mass % of 3-glycidoxypropyltriethoxysilane were added. g, and 8.69 g of BCS, using a magnetic stirring bar to stir for 2 hours to obtain a polyimide solution (SPI-1). (Polymerization example 2) A 100mL four-necked flask with a stirring device was placed in a nitrogen atmosphere, and (DA-6) 0.58g, (DA-4) 1.32g, (DA-5) 0.93g were weighed , (DA-7) 3.01g, NMP42.8g was added, and at 23°C, nitrogen gas was introduced, and the mixture was stirred to dissolve. While stirring the diamine solution, 3.91 g of acid dianhydride (E) was added, and 12.4 g of NMP was added, and the mixture was stirred under nitrogen atmosphere at 40° C. for 16 hours to obtain a polyamide acid solution (PAA-2). The viscosity of the polyamide solution at a temperature of 25° C. was 450 cps. (Polymerization example 3) A 100mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-9) 6.19g, (DA-8) 2.14g were weighed, NMP 61.1g was added, and 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. During stirring, 5.71 g of acid dianhydride (B) was added to the diamine solution, and 18.5 g of NMP was added, and the mixture was stirred for 16 hours under nitrogen atmosphere at 50° C. to obtain a polyamide acid solution (PAA-3). The viscosity of the polyamide solution at a temperature of 25°C was 351 cps. (Polymerization example 4) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55g, (DA-4) 0.78g were weighed, NMP24.4g was added, and in 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. While stirring the diamine solution, 1.75 g of acid dianhydride (B) was added, and then 4.3 g of NMP was added. After stirring for 2 hours at 23°C under nitrogen atmosphere, 1.41 g of acid dianhydride (D) was added, and then NMP8 was added. .0 g, stirred for 2 hours at 23°C under nitrogen atmosphere. Subsequently, the polyamic acid solution (PAA-4) was stirred at 50° C. for 16 hours. The viscosity of the polyamide solution at a temperature of 25°C was 240 cps. (Polymerization example 5) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55g, (DA-3) 0.96g were weighed, NMP25.7g was added, and 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. While stirring the diamine solution, 3.00 g of acid dianhydride (C) was added, and 11.2 g of NMP was added. After stirring for 2 hours at 23°C under nitrogen atmosphere, 0.77 g of acid dianhydride (D) was added, and then NMP4 was added. .4g, stirred for 2 hours at 23°C under nitrogen atmosphere. Subsequently, it was stirred at 50° C. for 16 hours to obtain a polyamic acid solution (PAA-5). The viscosity of the polyamide solution at a temperature of 25° C. was 358 cps. (Polymerization example 6) A 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55g, (DA-2) 0.46g were weighed, NMP22.3g was added, and 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. While stirring the diamine solution, 2.00 g of acid dianhydride (C) was added, and 6.3 g of NMP was added. After stirring for 2 hours at 23°C under nitrogen atmosphere, 1.51 g of acid dianhydride (D) was added, and then NMP8 was added. .5g, stirred for 2 hours at 23°C under nitrogen atmosphere. Subsequently, it was stirred at 50° C. for 16 hours to obtain a polyamic acid solution (PAA-6). The viscosity of the polyamide solution at a temperature of 25°C was 333 cps. (Polymerization example 7) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55g, (DA-2) 0.46g were weighed, NMP22.3g was added, and 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. In this diamine solution, 4.5 g of acid dianhydride (A) was added, and 20.5 g of NMP was added. After stirring for 2 hours at 23° C. under nitrogen atmosphere, the diamine solution was stirred at 50° C. for 16 hours to obtain polyamide acid. solution (PAA-7). The viscosity of the polyamide solution at a temperature of 25° C. was 350 cps. (Polymerization example 8) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55g, (DA-2) 0.49g were weighed, NMP22.3g was added, and 23 ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. During stirring, 3.00 g of acid dianhydride (C) was added to the diamine solution, and then 12.0 g of NMP was added. After stirring for 2 hours at 23° C. under nitrogen atmosphere, 0.72 g of acid dianhydride (D) was added, and then NMP4 was added. .1 g, stirred for 2 hours at 23°C under nitrogen atmosphere. Subsequently, it was stirred at 50° C. for 16 hours to obtain a polyamic acid solution (PAA-8). The viscosity of the polyamide solution at a temperature of 25°C was 333 cps. (Comparative Example 1) In a 50 mL Erlenmeyer flask placed with a stirring bar, 7.00 g of the polyimide solution (SPI-1) obtained above, 10.40 g of (PAA-4), containing (AD-1) were collected by filtration. ) 2.40g of 1wt% NMP solution, 0.72g of NMP solution containing 10wt% of (AD-2), 7.48g of NMP and 12.00g of BCS were added, and a magnetic stirring bar was used to stir for 2 hours to obtain a liquid crystal alignment agent (A-1). (Comparative Example 2) In a 50 mL Erlenmeyer flask placed with a stirring bar, 6.73 g of the polyamide solution (PAA-2), 15.27 g of (PAA-5), 15.27 g of (PAA-5) and (AD) obtained in the Comparative Synthesis Example were collected by filtration. -1) 2.40g of 1wt% NMP solution, 0.72g of NMP solution containing (AD-2) 10wt%, add 2.88g of NMP, 12.00g of BCS, and stir with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-2 ). (Comparative Example 3) In a 50 mL Erlenmeyer flask placed with a stirring bar, 4.00 g of polyamide solution (PAA-3), 12.80 g of (PAA-6), 12.80 g of (PAA-6), and (AD) obtained in Comparative Synthesis Example were collected by filtration. -1) 2.40 g of a 1 wt% NMP solution, add 8.80 g of NMP and 12.00 g of BCS, and stir with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-3). (Examples 1 to 2) In a 50 mL conical flask with a stirring bar, 7.00 g of polyimide solution (SPI-1), and (PAA-6 obtained from the polymerization example shown in Table 1) were added. ) and the grams of (PAA-7), filter 2.40g of NMP solution containing (AD-1) 1wt%, 0.72g of NMP solution containing (AD-2) 10wt%, add NMP 7.48g, BCS12.00g , using a magnetic stirring bar to stir for 2 hours to obtain the liquid crystal aligning agent (B-1~2) shown in Table 1. [0291]
Figure 02_image115
(Examples 3 to 6) In a 50 mL conical flask placed with a stirrer, 4.00 g of a polyamic acid solution (PAA-3), and the polyamic acid obtained from the polymerization examples shown in Table 2 were added. After the grams of the solution (PAA-6～8), filter 2.40g of NMP solution containing (AD-1) 1wt%, add NMP 4.80g, BCS 12.00g, use a magnetic stirring bar to stir for 2 hours, as shown in Table 2 The liquid crystal aligning agents (B-3-6) shown. [0293]
Figure 02_image117
(Examples 7 to 8) In a 50 mL conical flask with a stirring bar, 6.73 g of the polyamide solution (PAA-2) obtained in the comparative synthesis example was added, and 6.73 g obtained by the polymerization example shown in Table 3 were added. After the grams of polyamide solution (PAA-5) and (PAA-7) were obtained, 2.40 g of NMP solution containing (AD-1) 1wt% and 0.72 g of NMP solution containing (AD-2) 10wt% were collected by filtration. g, add 2.88 g of NMP and 12.00 g of BCS, and stir with a magnetic stirring bar for 2 hours to obtain a liquid crystal alignment agent (A-2). [0295]
Figure 02_image119
[0296]
Figure 02_image121
[Industrial Applicability] [0297] The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can reduce the charge accumulation caused by the asymmetry of the AC drive in the liquid crystal display element of the IPS driving method or the FFS driving method, In addition, the residual charge accumulated by the DC voltage can be quickly relieved, and a liquid crystal display element of an IPS driving method or an FFS driving method having excellent afterimage characteristics can be obtained. Therefore, it is particularly suitable as a liquid crystal alignment film of a liquid crystal display element of an IPS driving method or an FFS driving method or a liquid crystal television.

Figure 106133609-A0101-11-0002-2
Figure 106133609-A0101-11-0002-2

Claims (12)

一種液晶配向劑，其特徵為含有：(A-1)由使用含有下述式(1)所表示之四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、(A-2)由使用含有脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、(B)由聚醯亞胺前驅體及該聚醯亞胺前驅體之醯亞胺化聚合物所成之群所選出之至少1種的聚合物(相當於前述(A-1)及前述(A-2)者除外)，及有機溶劑；
Figure 106133609-A0305-02-0089-4
 (式(1)中，i為0或1，X為單鍵、醚鍵結、羰基、酯鍵結、伸苯基、碳原子數1至20的直鏈伸烷基、碳原子數2至20的分支伸烷基、碳原子數3至12之環狀伸烷基、磺醯基、醯胺鍵結或由該些組合而形成之基，其中，碳原子數1至20的伸烷基，可被由酯鍵結及醚鍵結所選出的鍵結所 中斷，伸苯基及伸烷基的碳原子可被由鹵素原子、氰基、烷基、鹵烷基、烷氧基及鹵烷氧基所選出的1個或複數個相同或相異的取代基所取代；式(2)中，Y1為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，B1、B2各自獨立表示氫原子，或可具有取代基的碳數1~10之烷基、烯基、炔基)。 A liquid crystal aligning agent is characterized by containing: (A-1) by using a tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the following formula (1), and containing the following formula (2) A polyamic acid obtained as a diamine component of a diamine, and a polymer of at least one selected from the imidized polymer of the polyamic acid, (A-2) is obtained by using an aliphatic tetracarboxylic acid containing The tetracarboxylic dianhydride component of the acid dianhydride, the polyamic acid obtained by the diamine component containing the diamine represented by the following formula (2), and the imidized polymer of the polyamic acid. At least one polymer selected from the group, (B) at least one polymer selected from the group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor (equivalent to The aforementioned (A-1) and the aforementioned (A-2) are excluded), and organic solvents;
Figure 106133609-A0305-02-0089-4
 (In formula (1), i is 0 or 1, X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenylene group, a straight-chain alkylene group having 1 to 20 carbon atoms, and a carbon group having 2 to 20 carbon atoms. 20 branched alkylene, cyclic alkylene having 3 to 12 carbon atoms, sulfonyl group, amide bond or a group formed by a combination of these, wherein the alkylene having 1 to 20 carbon atoms , can be interrupted by bonds selected from ester linkages and ether linkages, and the carbon atoms of phenylene and alkylene can be interrupted by halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups and halogen substituted by one or more identical or different substituents selected from alkoxy; in formula (2), Y 1 is selected from the group consisting of amino group, imino group, and nitrogen-containing heterocycle In the divalent organic group of at least one of the structures, B 1 and B 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, and an alkynyl group which may have a substituent). 如請求項1之液晶配向劑，其中，前述(A-1)之四羧酸二酐成份中之10~100莫耳%為前述式(1)所表示之四羧酸二酐。 The liquid crystal aligning agent according to claim 1, wherein 10-100 mol% of the tetracarboxylic dianhydride component in (A-1) is the tetracarboxylic dianhydride represented by the aforementioned formula (1). 如請求項1之液晶配向劑，其中，前述(A-2)之四羧酸二酐成份中之10~100莫耳%為脂肪族四羧酸二酐。 The liquid crystal aligning agent according to claim 1, wherein 10-100 mol % of the tetracarboxylic dianhydride component in (A-2) is aliphatic tetracarboxylic dianhydride. 如請求項1之液晶配向劑，其中，前述(A-1)及前述(A-2)之二胺成份中之10~100莫耳%，為式(2)之二胺。 The liquid crystal aligning agent according to claim 1, wherein 10-100 mol% of the diamine components of the aforementioned (A-1) and (A-2) are the diamines of the formula (2). 如請求項1之液晶配向劑，其中，式(2)中之Y1為由下述式(YD-1)~(YD-5)之結構所選出之至少1種；
Figure 106133609-A0305-02-0091-2
 (式(YD-1)中，A1為碳數3~15之含氮原子的雜環，Z1為氫原子，或可具有取代基的碳數1~20的烴基；式(YD-2)中，W1為碳數1~10的烴基，A2為具有含氮原子的雜環之碳數3~15之1價之有機基，或被碳數1至6的脂肪族基所取代的二取代胺基；式(YD-3)中，W2為碳數6~15，且具有1至2個苯環的2價之有機基，W3為碳數2~5之伸烷基或伸聯苯基，Z2為氫原子、碳數1~5之烷基，或苯環，a為0~1之整數；式(YD-4)中，A3為碳數3~15之含氮原子的雜環；式(YD-5)中，A4為碳數3~15之含氮原子的雜環，W5為碳數2~5之伸烷基)。 The liquid crystal alignment agent of claim 1, wherein Y 1 in formula (2) is at least one selected from the structures of the following formulas (YD-1) to (YD-5);
Figure 106133609-A0305-02-0091-2
 (In formula (YD-1), A 1 is a nitrogen atom-containing heterocycle with 3 to 15 carbon atoms, and Z 1 is a hydrogen atom, or a hydrocarbon group with 1 to 20 carbon atoms that may have a substituent; formula (YD-2 ), W 1 is a hydrocarbon group with a carbon number of 1 to 10, A 2 is a monovalent organic group with a nitrogen atom-containing heterocyclic ring with a carbon number of 3 to 15, or is substituted by an aliphatic group with a carbon number of 1 to 6 The disubstituted amine group; in formula (YD-3), W 2 is a 2-valent organic group with 6 to 15 carbon atoms and 1 to 2 benzene rings, and W 3 is an extended alkyl group with 2 to 5 carbon atoms Or a biphenyl group, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring, and a is an integer of 0 to 1; in formula (YD-4), A 3 is a group of 3 to 15 carbon atoms. A nitrogen atom-containing heterocycle; in formula (YD-5), A 4 is a nitrogen atom-containing heterocycle with a carbon number of 3 to 15, and W 5 is an extended alkyl group with a carbon number of 2 to 5). 如請求項5之液晶配向劑，其中，式(YD-1)、(YD-2)、(YD-4)，及(YD-5)記載之A1、A2、A3，及A4，為由吡咯啶、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌嗪、吡啶、吡
Figure 106133609-A0305-02-0091-5
、吲哚、苯併咪唑、喹啉、異喹啉所成之群所選出之至少1種。 The liquid crystal aligning agent of claim 5, wherein A 1 , A 2 , A 3 , and A 4 described in formulas (YD-1), (YD-2), (YD-4), and (YD-5) , is composed of pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridine
Figure 106133609-A0305-02-0091-5
, at least one selected from the group consisting of indole, benzimidazole, quinoline, and isoquinoline. 如請求項1之液晶配向劑，其中，式(2)中之Y1為由具有下述式(YD-6)~(YD-21)之結構的2價之有機基所成之群所選出之至少1種；
Figure 106133609-A0305-02-0092-3
 (式(YD-17)中，h為1~3之整數，式(YD-14)及(YD-21)中，j為1至3之整數)。 The liquid crystal aligning agent of claim 1, wherein Y 1 in the formula (2) is selected from the group consisting of divalent organic groups having the structures of the following formulas (YD-6) to (YD-21) at least one of them;
Figure 106133609-A0305-02-0092-3
 (In formula (YD-17), h is an integer of 1 to 3, and in formula (YD-14) and (YD-21), j is an integer of 1 to 3). 如請求項7之液晶配向劑，其中，式(2)中之Y1為由具有上述式(YD-14)及(YD-18)之結構的2價之有機基所成之群所選出之至少1種。 The liquid crystal aligning agent according to claim 7, wherein Y 1 in formula (2) is selected from the group consisting of divalent organic groups having the structures of the above formulas (YD-14) and (YD-18) At least 1 species. 如請求項1之液晶配向劑，其中，前述式(1)所表示之 四羧酸二酐為3,3’,4,4’-聯苯四羧酸二酐。 The liquid crystal aligning agent according to claim 1, wherein the above formula (1) represents Tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride. 如請求項1之液晶配向劑，其中，前述脂肪族四羧酸二酐為雙環[3.3.0]辛烷2,4,6,8-四羧酸2,4：6,8二酐。 The liquid crystal aligning agent according to claim 1, wherein the aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2,4:6,8 dianhydride. 一種液晶配向膜，其特徵為，將請求項1至請求項10中任一項之液晶配向劑經塗佈、燒結而得者。 A liquid crystal alignment film is characterized by being obtained by coating and sintering the liquid crystal alignment agent of any one of claim 1 to claim 10. 一種液晶顯示元件，其特徵為，具備請求項11之液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film of claim 11.
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