TWI765915B - 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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TWI765915B
TWI765915B TW106133615A TW106133615A TWI765915B TW I765915 B TWI765915 B TW I765915B TW 106133615 A TW106133615 A TW 106133615A TW 106133615 A TW106133615 A TW 106133615A TW I765915 B TWI765915 B TW I765915B
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tetracarboxylic dianhydride
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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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    • G02F1/133711—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， 　　及有機溶劑。

Figure 106133615-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, and an organic solvent.
Figure 106133615-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。 [先前技術文獻] [專利文獻] 　　[0004] 　　[專利文獻1]特開2013-167782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, 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. [PRIOR ART DOCUMENT] [PATENT DOCUMENT] [0004] [PATENT DOCUMENT 1] JP-A-2013-167782

[發明所欲解決之問題] 　　[0005] 本發明，以提供一種可製得具有優良再製性的液晶配向膜之液晶配向劑為目的。 [解決問題之方法] 　　[0006] 本發明者們，對於解決上述問題，經過深入研究結果，得知經使用含有特定的芳香族四羧酸二酐之四羧酸二酐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，與含有脂肪族四羧酸二酐之四羧酸二酐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，可製得具有優良再製性的液晶配向膜，因而完成本發明。 　　[0007] 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， 　　及有機溶劑。 　　[0008]

Figure 02_image001
[0009] (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，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的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)。 　　[0010] 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%為前述式(1)所表示之四羧酸二酐。 　　[0011] 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。 　　[0012] 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。 　　[0013] 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。 　　[0014]
Figure 02_image003
[0015] (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、苯環，或熱解離性基，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)。 　　[0016] 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 106133615-A0304-12-0020-4
、吲哚、苯併咪唑、喹啉、異喹啉所成之群所選出之至少1種。 　　[0017] 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。 　　[0018]
Figure 02_image005
[0019] (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)。 　　[0020] 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。 　　[0021] 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。 　　[0022] 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。 　　[0023] 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。 　　[0024] 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] 　　[0025] 由本發明之液晶配向劑所得之液晶配向膜具有優良再製性。 [實施發明之形態] 　　[0026] 本發明之液晶配向劑為含有： 　　(A-1)由使用含有下述式(1)所表示之特定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、 　　(A-2)由使用含有特定之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， 　　及有機溶劑。 　　[0027]
Figure 02_image007
[0028] 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，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的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。 　　[0029] 以下，將詳細敘述各構成要件。 　　[0030] ＜(A-1)成份及(A-2)成份＞ 　　本發明之液晶配向劑所使用的(A-1)成份為由含有上述式(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。 　　[0031] 又，本發明之液晶配向劑所使用的(A-2)成份為由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。 　　[0032] ＜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。 　　[0033]
Figure 02_image009
[0034] (式中，q表示1至20之整數)。 　　[0035] 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。 　　[0036] 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等。 　　[0037]
Figure 02_image011
[0038] 式中，X1 可為下述(X-1)～(X-28)中之任一者。 　　[0039]
Figure 02_image013
[0040]
Figure 02_image015
[0041]
Figure 02_image017
[0042] 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。 　　[0043] 上述之中，(X-1)至(X-20)以不含芳香族部位之觀點而為較佳，以(X-10)特別不易進行熱醯亞胺化之觀點而為最佳。 　　[0044] (A-1)成份中，四羧酸二酐成份全體中的式(1)所表示之四羧酸二酐所佔之量，其量過少時，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，相對於製造(A-1)成份時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%。 　　(A-2)成份中，四羧酸二酐成份全體中之脂肪族酸二酐所佔之量，其量過少時，將無法得到本發明之效果。因此，脂肪族四羧酸二酐之量，相對於製造(A-2)成份時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%。 　　[0045] 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。 　　[0046] 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。 　　[0047]
Figure 02_image019
[0048] 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。 　　[0049]
Figure 02_image021
[0050] ＜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，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的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。 　　[0051] 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。 　　[0052] 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。 　　[0053] 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。 　　[0054] 作為取代基之鹵素基，例如，氟原子、氯原子、溴原子、碘原子等。 　　[0055] 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。 　　[0056] 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。 　　[0057] 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。 　　[0058] 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。 　　[0059] 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。 　　[0060] 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。 　　[0061] 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。 　　[0062] 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。 　　[0063] 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。 　　[0064] 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。 　　[0065] 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。 　　[0066] 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。 　　[0067] 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。 　　[0068] 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。 　　[0069] 式(2)中之Y1 之結構，例如，可具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構，但只要為氮原子上具有被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出之至少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。 　　[0070]
Figure 02_image023
[0071] 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。 　　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、苯環，或熱解離性基，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。 　　[0072] 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 106133615-A0304-12-0020-4
、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。 　　又，熱解離性基，例如，於室溫下不會解離、於燒結配向膜之際會產生解離而可被氫原子所取代的取代基即可，具體而言，可列舉如，tert-丁氧基羰基及9-茀基甲氧基羰基等。 　　[0073] 此外，式(2)中之Y2 之具體例，例如，具有下述式(YD-6)～(YD-52)所表示之氮原子的2價之有機基等，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。 　　[0074]
Figure 02_image025
[0075] 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。 　　[0076]
Figure 02_image027
[0077] 式(YD-24)、(YD-25)、(YD-28)及(YD-29)中，j為0至3之整數。 　　[0078]
Figure 02_image029
[0079]
Figure 02_image031
[0080]
Figure 02_image033
[0081]
Figure 02_image035
[0082] (式(YD-50)中，m、n分別為1至11之整數，m＋n為2至12之整數)。 　　[0083] 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%。 　　[0084] 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。 　　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。 　　[0085] 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-97)等。 　　[0086]
Figure 02_image037
[0087]
Figure 02_image039
[0088]
Figure 02_image041
[0089]
Figure 02_image043
[0090]
Figure 02_image045
[0091]
Figure 02_image047
[0092]
Figure 02_image049
[0093]
Figure 02_image051
[0094]
Figure 02_image053
[0095]
Figure 02_image055
[0096] 本發明之液晶配向劑所含有的(A-1)成份或 (A-2)成份的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中，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%。 　　[0097] ＜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。 　　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。 　　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。 　　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。 　　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。 　　[0098] ＜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。 　　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。 　　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。 　　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。 　　[0099] 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。 　　[0100] 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。 　　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。 　　[0101] 依該方法所製得之(A-1)成份及(A-2)成份的含有比，為可使上述式(1)所表示之特定四羧酸二酐與特定脂肪族酸二酐之含有比例達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。 　　[0102] ＜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。 　　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%。 　　[0103] 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。 　　[0104] 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。 　　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、乙二醇二乙醚、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙醚、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、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、二乙二醇單乙醚、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、二丙二醇單乙醚、二丙二醇二甲醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單乙醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、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。 　　[0105]
Figure 02_image057
[0106] 式[D-1]中，D1 表示碳數1～3之烷基，式[D-2]中，D2 表示碳數1～3之烷基，式[D-3]中，D3 表示碳數1～4之烷基。 　　其中較佳溶劑之組合，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-戊酮與二乙二醇二乙醚、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。 　　[0107] 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。 　　[0108]
Figure 02_image059
[0109]
Figure 02_image061
[0110] 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。 　　[0111] 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。 　　[0112] ＜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。 　　[0113] 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賴性之情形，故通常為5～300nm，較佳為10～200nm。 　　[0114] 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。 　　[0115] 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。 　　[0116] 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。 　　[0117] 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。 　　[0118] 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。 　　[0119] 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、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯，及乙酸環己酯等。該些溶劑亦可將2種以上合併使用。 　　[0120] 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。 　　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。 　　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。 　　[0121] 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。 　　[0122] 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。 　　[0123] 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。 　　[0124] 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。 　　[0125] 再製時所使用的溶劑，可列舉如以下之溶劑：乙二醇單甲醚、乙二醇單乙醚、二乙二醇單甲醚、二乙二醇單乙醚、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、乳酸丁基等的酯類、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。 　　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。 　　[0126] 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℃。 　　[0127] ＜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(cell)，並使用其作為液晶顯示元件者。 　　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。 　　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。 　　[0128] 其次，於各基板上，依上述方法形成本發明之液晶配向膜。 　　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。 　　[0129] 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。 　　[0130] 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。 　　[0131] 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。 　　[0132] 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] [0005] The present invention aims to provide a liquid crystal alignment agent capable of producing a liquid crystal alignment film with excellent reproducibility. [Means for Solving the Problems] [0006] The present inventors, as a result of intensive research to solve the above-mentioned problems, found that the use of tetracarboxylic dianhydrides containing a specific aromatic tetracarboxylic dianhydride and a dianhydride having a specific structure Polyamides obtained from amines and imidized polymers of polyamides, and polyamides and polymers obtained from tetracarboxylic dianhydrides containing aliphatic tetracarboxylic dianhydrides and diamines with specific structures A liquid crystal alignment film with excellent reproducibility can be obtained by imidizing a polymer of amide acid, thus completing the present invention. 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 is characterized by containing: (A-1) by using the tetracarboxylic dianhydride composition containing the tetracarboxylic dianhydride represented by the following formula (1), and 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 material, and an organic solvent. [0008]
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 the haloalkoxy group. In formula (2), Y 1 is: has an amino group, an imino group, and a nitrogen-containing heterocyclic ring. A divalent organic group of at least one structure selected from the group, or a divalent organic group selected from an amine group, an imine group and a nitrogen-containing heterocycle substituted by a thermally dissociable group on the nitrogen atom, B 1 and B 2 each independently represent a hydrogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an alkynyl group). 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 represented by the aforementioned formula (1). . 3. The liquid crystal aligning agent as described in 1 or 2, wherein 10-100 mol % of the tetracarboxylic dianhydride component in 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. the liquid crystal aligning agent as described in any one of 1 to 4, wherein, Y in formula (2) is selected from the structure of following formula (YD-1)～(YD-5) At least 1 species. [0014]
Figure 02_image003
(in formula (YD-1), A 1 is the heterocyclic ring containing nitrogen atom of carbon number 3～15, Z 1 is hydrogen atom, or can have the hydrocarbon group of carbon number 1～20 of substituent; Formula ( In YD-2), W 1 is a hydrocarbon group with 1 to 10 carbon atoms, A 2 is a monovalent organic group with 3 to 15 carbon atoms in a heterocyclic ring containing a nitrogen atom, or an aliphatic group with 1 to 6 carbon atoms. A disubstituted amino group substituted by a group; in formula (YD-3), W 2 is a divalent organic group with 6 to 15 carbon atoms and 1 to 2 benzene rings, and W 3 is a carbon number of 2 to 5. Alkylidene or biphenylene group, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, a is an integer of 0 to 1; in formula (YD-4), A 3 is a nitrogen atom-containing heterocycle with 3 to 15 carbon atoms; in formula (YD-5), A 4 is a nitrogen atom-containing heterocycle with 3 to 15 carbon atoms, and W 5 is an alkylene with 2 to 5 carbon atoms base). 6. as the liquid crystal aligning agent of 5 records, wherein, formula (YD-1), (YD-2), (YD-4), and (YD-5) record A 1 , A 2 , A 3 , and A 4 , which is composed of pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridine
Figure 106133615-A0304-12-0020-4
, at least one selected from the group consisting of indole, benzimidazole, quinoline, and isoquinoline. 7. The liquid crystal aligning agent as described in any one of 1 to 6, wherein Y in formula (2) is composed of 2 having the structure of following formula (YD-6)～(YD-21) At least one selected from the group consisting of organic groups of valence. [0018]
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, Y in the formula ( 2 ) is formed by the bivalent organic group having the structure of above-mentioned formula (YD-14) and (YD-18) At least 1 species selected by the group. 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 alignment agent according to 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 obtained by coating and sintering. [0024] 12. A liquid crystal display element comprising the liquid crystal alignment film described in 11. [Effect of the Invention] [0025] The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has excellent reproducibility. [Mode for Carrying Out the Invention] [0026] The liquid crystal aligning agent of the present invention contains: (A-1) by using a tetracarboxylic dianhydride component containing a specific tetracarboxylic dianhydride represented by the following formula (1) and containing Polyamic acid obtained from the diamine component of the diamine represented by the following formula (2), and at least one polymer selected from the imidized polymer of the polyamic acid, (A-2 ) A polyamide acid obtained by using a tetracarboxylic dianhydride component containing a specific 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 imidized polymer of amine acid, and an organic solvent. [0027]
Figure 02_image007
In formula (1), i is 0 or 1, and X is single bond, ether bond, carbonyl group, ester bond, phenylene, straight-chain alkyl extension of carbon number 1 to 20, 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 is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocyclic ring, or a divalent organic group formed by heating on a nitrogen atom. The amine group, imino group and the divalent organic group selected from the nitrogen-containing heterocycle substituted by the dissociative group, B 1 and B 2 each independently represent a hydrogen atom, or an alkane having 1 to 10 carbon atoms which may have a substituent base, alkenyl, alkynyl. [0029] 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 composed of 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. [0033]
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 degree of promoting the effect of reproducibility, 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, tetracarboxylic dianhydride represented by the following formula (3). [0037]
Figure 02_image011
In the formula, X 1 can be any one of the following (X-1)～(X-28). [0039]
Figure 02_image013
[0040]
Figure 02_image015
[0041]
Figure 02_image017
In formula (X-1), R 3 to R 6 are 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 from the viewpoint of (X-10) being particularly difficult to carry out thermal imidization, the most preferred. good. In the component (A-1), the amount of the tetracarboxylic dianhydride represented by the formula (1) in the entire tetracarboxylic dianhydride component is too small, and 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), if the amount of the aliphatic acid dianhydride in the entire tetracarboxylic dianhydride component is too small, the effect of the present invention cannot be obtained. Therefore, the amount of the aliphatic tetracarboxylic dianhydride is preferably 10-100 mol %, more preferably 50- 100 mol%, particularly preferably 80-100 mol%. The tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by formula (1), it can be used separately, or can be combined and used in plural, 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 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. [0047]
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. [0049]
Figure 02_image021
<Diamine component> The diamine component used for 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 is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing heterocyclic ring, or a divalent organic group formed by heating on a nitrogen atom. The amine group, imino group and the divalent organic group selected from the nitrogen-containing heterocycle substituted by the dissociative group, B 1 and B 2 each independently represent a hydrogen atom, or an alkane having 1 to 10 carbon atoms which may have a substituent base, alkenyl, alkynyl. 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 2 -CH 2 structures present in the aforementioned alkyl groups are substituted by C≡C structures, more specifically, for example, ethynyl, 1-propynyl, 2-propynyl Alkynyl etc. [0052] The above-mentioned alkyl group, alkenyl group, and alkynyl group, when the total number of carbon atoms is 1 to 10, may have a substituent, and may form a ring structure through a substituent. 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, phosphoric acid 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. [0058] As the organosilyl group of the substituent, for example, the structure represented by -Si-(R) 3 . 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. [0061] 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 the substituent, for example, the structure represented by -OP(O)-(OR) 2 . 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) NH2 , or -C(O)NHR, -NHC(O)R, -C(O)N(R) 2 , -NRC( O) The structure represented by 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. [0066] The alkenyl group as the substituent, for example, has the same content 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 a giant structure is introduced, the reactivity or liquid crystal alignment of the amine group can be reduced, so B 1 and B 2 are, for example, hydrogen atoms, or alkanes with 1 to 5 carbon atoms that may have substituents The group is preferably a hydrogen atom, a methyl group or an ethyl group. The structure of Y in the formula ( 2 ), for example, can have the structure of at least one selected from the group formed by amino group, imino group, and nitrogen-containing heterocycle, but as long as it is on the nitrogen atom When it has a structure of at least one selected from an amine group, an imino group, and a nitrogen-containing heterocycle substituted by a thermally dissociable group, the structure is not particularly limited. 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. [0070]
Figure 02_image023
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. In formula (YD-2), W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and A 2 is a monovalent organic group having a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. Disubstituted amine groups substituted with aliphatic groups. In formula (YD-3), W 2 is a divalent organic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and W 3 is an alkylene group or a biphenylene group with a carbon number of 2 to 5, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, and a is an integer of 0 to 1. In formula (YD-4), A 3 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 having 3 to 15 carbon atoms, and W 5 is an alkylene group having 2 to 5 carbon atoms. Formula (YD-1), (YD-2), (YD-4), and A 1 , A 2 , A 3 of (YD-5), and the nitrogen of carbon number 3～15 of A 4 The heterocyclic ring of 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 106133615-A0304-12-0020-4
, indole, benzimidazole, quinoline, isoquinoline, carbazole, etc., and preferably piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine. In addition, the thermally dissociable group may be, for example, a substituent that does not dissociate at room temperature, dissociates when the alignment film is sintered, and can be substituted by a hydrogen atom, and specifically, tert-butoxy carbonyl and 9-intenylmethoxycarbonyl, etc. In addition, the specific example of Y in formula ( 2 ), for example, has the divalent organic group etc. of the nitrogen atom represented by following formula (YD-6)～(YD-52), just can suppress From the viewpoint of electric charge accumulation due to AC driving, formulae (YD-14) to (YD-21) are preferred, and (YD-14) and (YD-18) are particularly preferred. [0074]
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. [0076]
Figure 02_image027
In formula (YD-24), (YD-25), (YD-28) and (YD-29), j is an integer of 0 to 3. [0078]
Figure 02_image029
[0079]
Figure 02_image031
[0080]
Figure 02_image033
[0081]
Figure 02_image035
(in formula (YD-50), m, n are respectively the integer of 1 to 11, m+n is the integer of 2 to 12). 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. In addition, in the present invention, among the components (A-1) and (A-2), the diamines used in the production of polyamic acid and the imidized polymer of polyamic acid are the same as the diamines. good. 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 2 in the following formula (5) is a divalent organic group, and its structure is not particularly limited, and two or more types may be used in combination. In addition, the specific examples include the following (Y-1) to (Y-49), (Y-57) to (Y-97), and the like. [0086]
Figure 02_image037
[0087]
Figure 02_image039
[0088]
Figure 02_image041
[0089]
Figure 02_image043
[0090]
Figure 02_image045
[0091]
Figure 02_image047
[0092]
Figure 02_image049
[0093]
Figure 02_image051
[0094]
Figure 02_image053
[0095]
Figure 02_image055
The liquid crystal aligning agent of the present invention contains the (A-1) component or the (A-2) component of the polyamic acid and the imidized polymer of the polyamic acid, the formula (5) is represented. When the ratio of the diamine is too large, the effect of the present invention may be impaired, which is undesirable. 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%. [0097] <The production method of polyamide acid> The polyamide acid of the polyimide precursor used in the present invention can be synthesized according to the method shown below. Specifically, in the presence of an organic solvent, tetracarboxylic dianhydride and diamine are carried out at -20 to 150° C., preferably 0 to 70° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. synthesized in an hour. The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. from the viewpoint of solubility of monomers and polymers. Preferably, these can be used alone or in combination of two or more. The concentration of the polymer is preferably 1 to 30 mass %, and more preferably 5 to 20 mass %, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight body is easily obtained. When the polyamide acid obtained by the above method is fully stirred in the reaction solution and poured into a poor solvent, the polymer can be precipitated and 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. <The manufacturing method of 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 polyimide, the chemical imidization reaction of adding a catalyst to the above-mentioned polyimide solution obtained by the reaction of a diamine component and tetracarboxylic dianhydride is simple. method. 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 performed by stirring the polymer to be imidized in an organic solvent and in the presence of a basic 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. The temperature during the imidization reaction can be -20 to 140°C, preferably 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 the polyamide acid, the catalyst etc. that have been added remain in the solution, and the resulting 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. [0100] The polyimide solution obtained in the above-mentioned manner is injected into the poor solvent in 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, and examples include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and 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 this method, in order to make the specific tetracarboxylic dianhydride represented by the above formula (1) and the specific aliphatic acid two The anhydride is contained in a ratio of 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. <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 according to the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more. From the viewpoint of solution storage stability, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8 mass %. [0103] 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 the coating property 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 alcohol, 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, 1 -Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propane Diols, 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 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-methylpentylacetic acid ester, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxy methoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, diethylene glycol Alcohol 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 mono Diethyl 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 monoacetate , ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethyl acetate 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, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, solvents represented by the following formulae [D-1] to [D-3], and the like. [0105]
Figure 02_image057
In formula [D-1], D 1 represents an alkyl group with 1 to 3 carbon atoms, in formula [D-2], D 2 represents an alkyl group with 1 to 3 carbon atoms, and in formula [D-3] , D 3 represents an alkyl group with 1 to 4 carbon atoms. The preferred combination of solvents, for example, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone 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-pentane Ketone 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-2 -pyrrolidone with γ-butyrolactone and propylene glycol monobutyl ether with diisopropyl ether, N-methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol monobutyl ether with 2,6-dimethyl ether -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. [0107] Furthermore, 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. [0108]
Figure 02_image059
[0109]
Figure 02_image061
[0110] 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 alignment 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 applying the above-mentioned liquid crystal alignment agent to 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. [0113] The coating method of the liquid crystal alignment agent of the present invention, for example, spin coating method, printing method, inkjet method and the like. 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 lowered, so it is usually 5 to 300 nm, preferably 10 to 200 nm. [0114] The method for performing alignment treatment on the obtained liquid crystal alignment film, for example, a rubbing method, a photo-alignment treatment method, and the like. [0115] 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 is, 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 preferably 1 to 10,000 mJ/cm 2 , and particularly preferably 100 to 5,000 mJ/cm 2 . The liquid crystal alignment film prepared in the above manner can stably align liquid crystal molecules in a specific direction. [0117] Also, when the extinction ratio of polarized ultraviolet rays is higher, it can impart 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. [0118] The film irradiating the polarized radiation obtained in the above-mentioned manner can then be contacted with a solvent containing at least one selected from water and an organic solvent. [0119] The solvent used in the contact treatment is not particularly limited as long as it can dissolve the solvent of the decomposition product generated by light irradiation, for example. 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 Wait. 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 treatment of the film irradiated with polarized radiation and the solution containing the organic solvent is carried out by using a treatment method such as dipping treatment, spray treatment, etc., which enables the film and the liquid to be in better and sufficient contact. 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, it can be washed (Rinse) or dried with a low-boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, etc., or two. Both can be done at the same time. [0121] In addition, the above-mentioned film subjected to contact treatment with a solvent may also be heated to 150° C. or higher for the purpose of drying the solvent and realigning the molecular chains in the film. [0122] The heating temperature, for example, is preferably 150-300°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. If the heating time is too short, the effect of realignment of the molecular chain may not be obtained, and if 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. [0124] 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 remanufacturing can be enumerated as the following solvents: 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. The reconstituted material, for example, preferably contains an alkaline component such as ethanolamine in the above-mentioned solvent, and an anti-rust agent that does not damage other components such as the electrode by the alkalinity. Manufacturers that can provide these remanufactured materials, such as South Korea's Huiming Industrial Co., Ltd., KPX Chemical, etc. [0126] Reproduction, in order to heat the reproducing materials listed above at room temperature, or between 30°C and 100°C, and then immerse the substrate with the liquid crystal alignment film in 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 method for producing a liquid crystal alignment film, and then use a known method to produce a liquid crystal cell. (cell) and use it as a liquid crystal display element. As an example of a method of fabricating a liquid crystal cell, a liquid crystal display element having 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). First, a transparent glass substrate is prepared, and common electrodes are provided on one substrate, and segment electrodes are provided on the other 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. The insulating film is, for example, a film formed of SiO 2 -TiO 2 obtained by a sol-gel method. [0128] Next, on each substrate, the liquid crystal alignment film of the present invention is formed according to the above method. 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 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. [0129] Next, through the opening provided in the sealant, the liquid crystal material was injected into the space surrounded by the two 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. [0131] In the sealant of the present invention, an inorganic filler may 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] 　　[0133] 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) 　　[0134]

Figure 02_image063
[0135] 以下為記載黏度之測定、醯亞胺化率之測定、再製性之評估、液晶單元之製作，及電荷緩和特性評估之方法。 　　[0136] [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。 　　[0137] [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(HM-R20)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3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 　　[0138] (聚合例1) 　　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)0.96g，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-1)。該聚醯胺酸溶液於溫度25℃之黏度為358cps。 　　[0139] (聚合例2) 　　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-2)。該聚醯胺酸溶液於溫度25℃之黏度為333cps。 　　[0140] (聚合例3) 　　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-3)。該聚醯胺酸溶液於溫度25℃之黏度為350cps。 　　[0141] (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-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-4)。該聚醯胺酸溶液於溫度25℃之黏度為333cps。 　　[0142] (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)2.87g、(DA-3)0.71g，加入NMP 26.3g，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(D)2.82g，再加入NMP 10.0g，於23℃、氮氣氛圍下，攪拌2小時後，添加酸二酐(E)0.92g，再添加NMP 5.00g，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322cps。 　　[0143] (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-4)2.15g、(DA-6)1.62g，加入NMP 27.7g，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(D)3.42g，再加入NMP 13.1g，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-6)。該聚醯胺酸溶液於溫度25℃之黏度為348cps。 　　[0144] (比較例1～4) 　　於放置有攪拌子的50mL三角燒瓶中，濾取比較聚合例所得之聚醯胺酸溶液15.0g，加入NMP 11.25g、BCS 11.25g，使用磁性攪拌子攪拌2小時，得表1之液晶配向劑(A-1)～(A-4)。 　　[0145]
Figure 02_image065
[0146] (實施例1～6) 　　於放置有攪拌子的50mL三角燒瓶中，加入聚合例所得之聚醯胺酸溶液與NMP11.25g、BCS11.25g，使用磁性攪拌子攪拌2小時，得表2之液晶配向劑(B-1)～(B-8)。 　　[0147]
Figure 02_image067
[0148]
Figure 02_image069
[產業上利用性] 　　[0149] 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] [0133] 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, and examples of the results and 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: following formula (DA-5) DA-6: following formula (DA-6) [0134]
Figure 02_image063
The following describes the measurement of viscosity, measurement of imidization rate, evaluation of reproducibility, fabrication of liquid crystal cells, and evaluation of charge relaxation properties. [Measurement of Viscosity] In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution was measured at a temperature of 25° C. using an E-type viscometer TV-25H (manufactured by Toki Sangyo Co., Ltd.). The sample volume was 1.1mL, and it was obtained from CORD-1 (1°34', R24). [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 a heated rework material (HM-R20) 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 3. ○: 35°C, 5 minutes, no residual film generation △: 40°C, 5 minutes, no residual film generation ×: 40°C, 5 minutes, residual film generation [0138] (Polymerization Example 1) 50 mL with a stirring device The four-necked flask was placed in a nitrogen atmosphere, and 2.55 g of (DA-1) and 0.96 g of (DA-4) were weighed, and 25.7 g of NMP was added. 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-1). The viscosity of the polyamide solution at a temperature of 25° C. was 358 cps. (Polymerization example 2) The 50mL four-necked flask with stirring device was placed in nitrogen atmosphere, weighed (DA-1) 2.55g, (DA-2) 0.46g, added NMP22.3g, in 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-2). The viscosity of the polyamide solution at a temperature of 25°C was 333 cps. (Polymerization example 3) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, weighed (DA-1) 2.55g, (DA-2) 0.46g, added NMP22.3g, in 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-3). The viscosity of the polyamide solution at a temperature of 25° C. was 350 cps. (Polymerization example 4) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, weighed (DA-1) 2.55g, (DA-2) 0.49g, added NMP22.3g, in 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-4). The viscosity of the polyamide solution at a temperature of 25°C was 333 cps. (Polymerization example 5) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.87g, (DA-3) 0.71g were weighed, NMP 26.3g was added, and 23 g was added. ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. While stirring the diamine solution, 2.82 g of acid dianhydride (D) was added, and 10.0 g of NMP was added. After stirring for 2 hours at 23° C. under nitrogen atmosphere, 0.92 g of acid dianhydride (E) was added, and then NMP was added. 5.00 g was stirred at 23°C under nitrogen atmosphere for 2 hours. 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 322 cps. (Polymerization example 6) The 50mL four-necked flask with stirring device was placed in a nitrogen atmosphere, and (DA-4) 2.15g, (DA-6) 1.62g were weighed, NMP 27.7g was added, and 23 g was added. ℃, nitrogen gas was fed into it, and the mixture was stirred to dissolve. While stirring this diamine solution, 3.42 g of acid dianhydride (D) was added, and 13.1 g of NMP was further added, and the mixture was stirred at 23°C under nitrogen atmosphere for 2 hours. Subsequently, it was stirred at 50° C. for 16 hours to obtain a polyamic acid solution (PAA-6). The viscosity of the polyamic acid solution at a temperature of 25°C was 348 cps. (Comparative Examples 1 to 4) In a 50mL conical flask placed with a stirring bar, 15.0 g of the polyamide acid solution obtained in the comparative polymerization example was collected by filtration, 11.25 g of NMP and 11.25 g of BCS were added, and a magnetic stirring bar was used to stir After 2 hours, the liquid crystal aligning agents (A-1) to (A-4) of Table 1 were obtained. [0145]
Figure 02_image065
(Example 1～6) In the 50mL conical flask that is placed with stirring bar, add the polyamide acid solution of polymerization example gained and NMP11.25g, BCS11.25g, use magnetic stirring bar to stir for 2 hours, get table 2 Liquid crystal alignment agents (B-1) to (B-8). [0147]
Figure 02_image067
[0148]
Figure 02_image069
[Industrial Applicability] [0149] 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 106133615-A0101-11-0002-2
Figure 106133615-A0101-11-0002-2

Claims (11)

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，及有機溶劑；並且前述式(1)所表示之四羧酸二酐為3,3’,4,4’-聯苯四羧酸二酐；
Figure 106133615-A0305-02-0054-1
 (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，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的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 selected polymer, and an organic solvent; and the tetracarboxylic dianhydride represented by the aforementioned formula (1) is 3,3',4,4'-biphenyltetracarboxylic dianhydride;
Figure 106133615-A0305-02-0054-1
 (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 , which 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 atoms. substituted by one or more identical or different substituents selected by the alkoxy group; in formula (2), Y 1 is: has an amino group, an imino group, and a nitrogen-containing heterocyclic ring. A divalent organic group of at least one selected structure, or a divalent organic group selected from an amine group, an imino group and a nitrogen-containing heterocycle substituted by a thermally dissociable group on the nitrogen atom, B 1 , B 2 each independently represents 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 106133615-A0305-02-0056-2
 (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、苯環，或熱解離性基，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 aligning agent of claim 1, wherein Y 1 in the formula (2) is at least one selected from the structures of the following formulas (YD-1) to (YD-5);
Figure 106133615-A0305-02-0056-2
 (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 replaced by an aliphatic group with a carbon number of 1 to 6 The disubstituted amine group; in the 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 a carbon number of 2 to 5 Or a biphenyl group, Z 2 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, a is an integer of 0 to 1; in formula (YD-4), A 3 is a carbon A nitrogen atom-containing heterocycle with 3 to 15 carbon atoms; 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 106133615-A0305-02-0056-4
、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 106133615-A0305-02-0056-4
, 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 106133615-A0305-02-0057-3
 (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 106133615-A0305-02-0057-3
 (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 of claim 7, wherein Y 1 in the 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，前述脂肪族酸二酐 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 of claim 1, wherein the aliphatic acid dianhydride For the 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9中任一項之液晶配向劑經塗佈、燒結而得者。 A liquid crystal alignment film, which is obtained by coating and sintering the liquid crystal alignment agent of any one of claim 1 to claim 9. 一種液晶顯示元件，其特徵為，具備請求項10之液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film of claim 10.
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