TW201323521A

TW201323521A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: TW201323521A
Application number: TW101132743A
Authority: TW
Inventors: Noritoshi Miki; Masaaki Katayama; Kohei Goto; Kazuyoshi Hosaka
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2011-09-08
Filing date: 2012-09-07
Publication date: 2013-06-16
Also published as: CN106635061A; KR20180072830A; JPWO2013035803A1; CN106635061B; KR102224531B1; KR101951501B1; KR20190124815A; WO2013035803A1; CN103782231B; TWI586757B; JP6011537B2; JP6414145B2; TW201726811A; JP2016194707A; CN103782231A; KR20140059219A; TWI620794B

Abstract

Provided is a liquid crystal aligning agent which has high wettability and spreadability over substrates and is capable of providing a liquid crystal alignment film that has excellent coating film uniformity and excellent coating film properties in the end portions, said liquid crystal alignment film enabling the achievement of pretilt angles that do not change even if left at high temperatures or irradiated with light for a long period of time. A liquid crystal aligning agent which contains N-ethyl-2-pyrrolidone and at least one polymer that is selected from the group consisting of polyimide precursors having a side chain represented by formula [1] and polyimides. (In the formula, each of X1, X2 and X3 independently represents a single bond or the like; each of X4 and X5 independently represents a benzene ring or the like; X6 represents an alkyl group having 1-18 carbon atoms, or the like; and n represents an integer of 0-4.)

Description

液晶配向處理劑、液晶配向膜及液晶顯示元件 Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element

本發明係關於製造液晶配向膜所使用的液晶配向處理劑及使用其之液晶顯示元件。 The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.

現今使用於液晶顯示元件的液晶配向膜中，有多數特性被要求著。作為其中特性之一為，對於基板面的液晶分子之配向傾斜角保持於任意值，所謂可控制液晶之預傾角。已知該預傾角之尺寸為可藉由選擇構成液晶配向膜的聚醯亞胺之結構而變更。藉由聚醯亞胺之結構，控制預傾角之技術中，將具有側鏈之二胺化合物作為聚醯亞胺原料之一部份使用的方法為可配合該二胺化合物之使用比率而控制預傾角。因此，比較容易得到目的之預傾角，作為加大預傾角之手段為有用。作為擴大液晶之預傾角的二胺化合物之側鏈結構，有人提出含有長鏈的烷基或氟烷基(例如參照專利文獻1)、苯基或環己基等環結構者(例如參照專利文獻2、3)。 In the liquid crystal alignment film currently used for liquid crystal display elements, many characteristics are required. One of the characteristics is that the alignment tilt angle of the liquid crystal molecules on the substrate surface is maintained at an arbitrary value, so that the pretilt angle of the liquid crystal can be controlled. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimine which constitutes the liquid crystal alignment film. In the technique of controlling the pretilt angle by the structure of polyimine, the method of using the side chain diamine compound as a part of the polyimine raw material is controlled in accordance with the use ratio of the diamine compound. inclination. Therefore, it is easier to obtain the pretilt angle of the object, and it is useful as means for increasing the pretilt angle. As a side chain structure of the diamine compound which expands the pretilt angle of the liquid crystal, a ring structure including a long-chain alkyl group or a fluoroalkyl group (for example, see Patent Document 1), a phenyl group or a cyclohexyl group has been proposed (for example, refer to Patent Document 2). 3).

近年來，液晶顯示元件隨著大畫面之液晶電視或高精細移動用途(數位照相機或行動電話之顯示部分)上廣泛被實用化，與過去相比所使用的基板之大型化、基板段差之凹凸漸漸地變大。如此狀況下，由顯示特性之觀點來看，對於大型基板或段差，期待可均勻地進行液晶配向膜之成膜。對於該液晶配向膜之製作步驟，將聚醯胺酸或溶劑可溶性聚醯亞胺(亦稱為樹脂)的液晶配向處理劑(亦稱為塗佈溶液)塗佈於基板時，於工業上進行柔版印刷法或噴墨塗佈法等為一般。此時，於塗佈溶液之溶劑中加入樹脂之溶解性優良的溶劑(亦稱為良溶劑)之N-甲基-2-吡咯烷酮或γ-丁內酯等，可提高液晶配向膜之塗膜均勻性，故混合樹脂之溶解性較低的溶劑(亦稱為貧溶劑)之丁基溶纖劑等(例如參照專利文獻4)。 In recent years, liquid crystal display elements have been widely used in liquid crystal televisions for large screens or high-definition mobile applications (display portions of digital cameras or mobile phones), and the size of substrates used in comparison with the past has been increased. Gradually getting bigger. In such a case, from the viewpoint of display characteristics, it is expected that the deposition of the liquid crystal alignment film can be performed uniformly for a large substrate or a step. For the production step of the liquid crystal alignment film, polylysine or solvent When a liquid crystal alignment treatment agent (also referred to as a coating solution) of a soluble polyimine (also referred to as a resin) is applied to a substrate, a flexographic printing method, an inkjet coating method, or the like is industrially performed. In this case, by adding N-methyl-2-pyrrolidone or γ-butyrolactone, which is a solvent having excellent solubility in a resin (also referred to as a good solvent), to the solvent of the coating solution, the coating film of the liquid crystal alignment film can be improved. The butyl cellosolve of a solvent (also referred to as a poor solvent) having a low solubility in a mixed resin (for example, see Patent Document 4).

[先行技術文獻] [Advanced technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平2-282726號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 2-282726

[專利文獻2]日本特開平9-278724號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9-278724

[專利文獻3]國際公開第2004/52962號說明書 [Patent Document 3] International Publication No. 2004/52962

[專利文獻4]日本特開平2-37324號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 2-37324

液晶配向膜亦使用於進行對基板之液晶角度，即液晶之預傾角的控制上，但在使液晶顯示元件高性能化，該使用範圍年年逐漸擴大中，不僅得到所定預傾角，預傾角之安定性漸漸變的重要。 The liquid crystal alignment film is also used to control the liquid crystal angle of the substrate, that is, the pretilt angle of the liquid crystal. However, in order to improve the performance of the liquid crystal display element, the use range is gradually expanded year by year, and not only the predetermined pretilt angle but also the pretilt angle is obtained. The importance of stability is gradually becoming more important.

對於液晶顯示元件之製造步驟中，欲提高液晶之配向均勻性，將液晶封入後進行加熱處理，有著一旦將液晶進行各向同性化之情況。然而，預傾角之安定性較為低時，該各向同性化處理後無法得到作為目的尺寸的預傾角，或有著產生預傾角之偏差的問題。特別為欲得到高亮度時使發熱量變大，在使用光之照射量多的背光的液晶顯示元件，例如有在衛星導航系統或大型電視，於長時間高溫及光照射曝曬之環境下使用或被放置之情況。對於如此過酷條件，預傾角徐徐地變化時，無法得到初期之顯示特性，或顯示上會產生不均等問題。 In the manufacturing process of the liquid crystal display element, in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is sealed and then subjected to heat treatment, and the liquid crystal is isotropically formed. However, when the stability of the pretilt angle is relatively low, the pretilt angle as the target size cannot be obtained after the isotropic treatment, or There is a problem of bias in the pretilt angle. In particular, in order to obtain a high-intensity heat source, a liquid crystal display element using a backlight having a large amount of light irradiation is used, for example, in a satellite navigation system or a large-sized television, in an environment of prolonged high temperature and light exposure. Placement. In such a cool condition, when the pretilt angle changes slowly, the initial display characteristics cannot be obtained, or the display may be uneven.

又，使用具有側鏈之二胺化合物所得之聚醯胺酸或使用溶劑可溶性聚醯亞胺的液晶配向處理劑，具有降低液晶配向膜之塗膜均勻性的傾向。特別無法得到均勻塗膜性時，即產生眼洞或針孔時，使其成為液晶顯示元件時，該部分成為顯示缺陷。因此，必須增加對基板之塗佈溶液的濕潤擴大性高的貧溶劑之混合量，但貧溶劑對於溶解聚醯胺酸或溶劑可溶性聚醯亞胺的能力較為差，故大量混合時會產生樹脂析出問題。 Further, a polyphthalic acid obtained by using a diamine compound having a side chain or a liquid crystal alignment treatment agent using a solvent-soluble polyimine has a tendency to lower the uniformity of the coating film of the liquid crystal alignment film. In particular, when uniform coating property is not obtained, that is, when an eye hole or a pinhole is generated, when it becomes a liquid crystal display element, this part becomes a display defect. Therefore, it is necessary to increase the mixing amount of the poor solvent having a high wettability to the coating solution of the substrate, but the poor solvent has a poor ability to dissolve the polyaminic acid or the solvent-soluble polyimine, so that a resin is produced in a large amount of mixing. Precipitate the problem.

且，近年來，欲使用於智慧型手機或行動電話等移動用途上，使用液晶顯示元件。這些用途在盡可能確保多數顯示面時，使用於接著液晶顯示元件之基板間時所使用的密封劑存在於接近液晶配向膜之端部的位置。因此，液晶配向膜的端部之塗膜性降低時，即液晶配向膜之端部並非直線，或該端部在上升的狀態時，密封劑之基板間接著效果會降低，液晶顯示元件之顯示特性或信頼性亦會降低。 Further, in recent years, liquid crystal display elements have been used for mobile applications such as smart phones and mobile phones. In these applications, when a plurality of display surfaces are ensured as much as possible, a sealant used when the substrate between the liquid crystal display elements is used is present at a position close to the end of the liquid crystal alignment film. Therefore, when the coating property of the end portion of the liquid crystal alignment film is lowered, that is, when the end portion of the liquid crystal alignment film is not straight, or the end portion is in a rising state, the adhesion between the substrates of the sealant is lowered, and the display of the liquid crystal display element is lowered. Characteristics or trustworthiness will also be reduced.

本發明係有鑑於上述情事者。即，欲解決本發明之課題為，即使在長時間高溫及光照射曝曬下，提供一種預傾角無變化之液晶配向膜。又，即使為使用具有側鏈之二胺化合物的聚醯胺酸或使用溶劑可溶性聚醯亞胺的液晶配向處理劑，得到對基板之塗佈溶液的濕潤擴大性高且均勻塗膜性，且提供一種液晶配向膜之端部塗膜性亦優良的液晶配向膜。且，提供一種可提供具有上述液晶配向膜之液晶顯示元件、上述液晶配向膜的液晶配向處理劑。 The present invention is made in view of the above circumstances. That is, the object of the present invention is to provide a liquid crystal alignment film having no pretilt angle change even under a long period of high temperature and light exposure. Also, even if a diamine having a side chain is used The polylysine of the compound or the liquid crystal alignment treatment agent using the solvent-soluble polyimine provides a high wettability and uniform coating property to the coating solution of the substrate, and provides a coating property of the end of the liquid crystal alignment film. Also excellent in liquid crystal alignment film. Further, a liquid crystal alignment treatment agent which can provide a liquid crystal display element having the above liquid crystal alignment film and the above liquid crystal alignment film is provided.

本發明者進行詳細研究結果，發現含有具有特定結構之溶劑及特定結構之側鏈的聚合物之液晶配向處理劑可達成上述目的且極為有效，進而完成本發明。 As a result of detailed investigation, the present inventors have found that a liquid crystal alignment treatment agent containing a polymer having a specific structure of a solvent and a side chain of a specific structure can achieve the above object and is extremely effective, and the present invention has been completed.

即，本發明為具有以下要旨者。 That is, the present invention has the following gist.

(1)一種液晶配向處理劑，其為含有下述成分(A)及成分(B)者。 (1) A liquid crystal alignment treatment agent which comprises the following components (A) and (B).

成分(A)：N-乙基-2-吡咯烷酮。 Ingredient (A): N-ethyl-2-pyrrolidone.

成分(B)：選自將具有下述式〔1〕所示側鏈的聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群的至少1種聚合物。 Component (B): at least one selected from the group consisting of a polyimine precursor having a side chain represented by the following formula [1] and a polyimine which is ruthenium imidized with a polyimine precursor polymer.

(式〔1〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃) CO-。X₂為單鍵或-(CH₂)_b-(b為1~15的整數)。X₃為單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。X₄為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)。X₅為選自苯環、環己基環及雜環之2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)。X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基，n為0~4的整數) (In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) CO-. X ₂ is a single bond or -(CH ₂ ) _b -(b Is an integer from 1 to 15.) X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH- , -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. X ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring Divalent cyclic group (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom. X ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups may be a carbon number) an alkyl group having 1 to 3 carbons, alkoxy having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms or fluorine-containing alkoxy group having 1 to 3 fluoro atoms substituted) .X ₆ It is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and n is 0 to 4 Integer)

(2)前述成分(B)為選自將具有前述式〔1〕所示側鏈的二胺化合物作為原料一部份使用的聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群之至少1種聚合物的上述(1)所記載的液晶配向處理劑。 (2) The component (B) is a polyimine precursor selected from the group consisting of a diamine compound having a side chain represented by the above formula [1] as a raw material, and a polyimine precursor is subjected to a quinone imine. The liquid crystal alignment treatment agent according to the above (1), which is a mixture of at least one polymer of the polyimine.

(3)前述具有式〔1〕所示側鏈的二胺化合物為下述式〔1a〕所示二胺化合物之上述(2)所記載的液晶配向處理劑。 (3) The diamine compound having a side chain represented by the formula [1] is a liquid crystal alignment treatment agent according to the above (2), which is a diamine compound represented by the following formula [1a].

(式〔1a〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。X₂為單鍵或-(CH₂)_b-(b為1~15的整數)。X₃為單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。X₄為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)。X₅為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)。X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基。n為0~4的整數，m為1~4的整數) (In the formula [1a], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. X ₂ is a single bond or -(CH ₂ ) _b -(b Is an integer from 1 to 15.) X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH- , -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. X ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring Divalent cyclic group (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom). X ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be a carbon number an alkyl group having 1 to 3 carbons, alkoxy having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms or fluorine-containing alkoxy group having 1 to 3 fluoro atoms substituted) .X ₆ It is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. n is 0 to 4 Integer, m is an integer from 1 to 4)

(4)將前述式〔1a〕所示二胺使用於原料之二胺成分的5~80莫耳%之上述(2)或(3)所記載的液晶配向處理劑。 (4) The diamine represented by the above formula [1a] is used in the liquid crystal alignment treatment agent according to the above (2) or (3) in an amount of from 5 to 80 mol% of the diamine component of the raw material.

(5)前述成分(B)為使用下述式〔2〕所示四羧酸二酐的聚合物之上述(1)~(4)中任一所記載的液晶配向處理劑。 (5) The liquid crystal alignment treatment agent according to any one of the above (1) to (4), which is a polymer of the tetracarboxylic dianhydride represented by the following formula [2].

(式〔2〕中，Y₁為碳數4~13之4價有機基，且含有碳數4~10的非芳香族環狀烴基)。 (In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms).

(6)前述Y₁為下述式〔2a〕~〔2j〕所示結構之基的上述(5)所記載的液晶配向處理劑。 (6) The liquid crystal alignment treatment agent according to the above (5), wherein the Y ₁ is a group having a structure represented by the following formulas [2a] to [2j].

(式〔2a〕中，Y₂~Y₅為氫原子、甲基、氯原子或苯環，各可相同或相異，式〔2g〕中，Y₆及Y₇為氫原子或甲基，各可相同或相異)。 (In the formula [2a], Y ₂ to Y ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [2g], Y ₆ and Y ₇ are a hydrogen atom or a methyl group. Each can be the same or different).

(7)前述成分(B)之聚合物為聚醯胺酸之上述(1)~(6)中任一所記載的液晶配向處理劑。 (7) The polymer of the component (B) is a liquid crystal alignment treatment agent according to any one of the above (1) to (6).

(8)前述成分(B)之聚合物為將聚醯胺酸經脫水閉環後所得之聚醯亞胺的上述(1)~(6)中任一所記載的液晶配向處理劑。 (8) The polymer of the above-mentioned component (B) is a liquid crystal alignment treatment agent according to any one of the above (1) to (6), which is obtained by dehydration ring-closing of poly-proline.

(9)作為成分(C)，含有N-甲基-2-吡咯烷酮或γ-丁內酯之上述(1)~(8)中任一所記載的液晶配向處理劑。 (9) The liquid crystal alignment treatment agent according to any one of the above (1) to (8), which contains N-methyl-2-pyrrolidone or γ-butyrolactone.

(10)作為(D)成分，含有選自1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚及丙二醇單丁基醚所成群之至少1個的上述(1)~(9)中任一所記載的液晶配向處理劑。 (10) as component (D), containing a selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, and ethylene glycol Ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether And a liquid crystal alignment treatment agent according to any one of the above (1) to (9), which is a mixture of at least one of propylene glycol monobutyl ether.

(11)前述成分(A)為於液晶配向處理劑所含的有機溶劑全體之10~100質量%的上述(1)~(10)中任一所記載的液晶配向處理劑。 (11) The liquid crystal alignment treatment agent according to any one of (1) to (10) above, wherein the component (A) is in an amount of from 10 to 100% by mass based on the total amount of the organic solvent contained in the liquid crystal alignment agent.

(12)前述成分(C)為於液晶配向處理劑所含的有機溶劑全體之0.1~50質量%的上述(9)~(11)中任一所記載的液晶配向處理劑。 (12) The liquid crystal alignment treatment agent according to any one of the above (9) to (11), which is in the range of from 0.1 to 50% by mass of the entire organic solvent contained in the liquid crystal alignment agent.

(13)前述成分(D)為於液晶配向處理劑所含的有機溶劑全體之5~80質量%的上述(10)~(12)中任一所記載的液晶配向處理劑。 (13) The liquid crystal alignment treatment agent according to any one of (10) to (12) above, wherein the component (D) is in an amount of from 5 to 80% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent.

(14)液晶配向處理劑中之前述成分(B)為0.1~15質量%的上述(1)~(13)中任一所記載的液晶配向處理劑。 (14) The liquid crystal alignment treatment agent according to any one of the above (1) to (13), wherein the component (B) in the liquid crystal alignment agent is from 0.1 to 15% by mass.

(15)使用上述(1)~(14)中任一所記載的液晶配向處理劑所得之液晶配向膜。 (15) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (14).

(16)使用上述(1)~(14)中任一所記載的液晶配向處理劑，以噴墨法所得之液晶配向膜。 (16) A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to any one of the above (1) to (14).

(17)具有上述(15)或(16)所記載的液晶配向膜之液晶顯示元件。 (17) A liquid crystal display element comprising the liquid crystal alignment film according to (15) or (16) above.

(18)如上述(15)或(16)所記載的液晶配向膜，其特徵為使用於經由下述步驟而製造的液晶顯示元件者，該步驟為具備電極之一對基板之間具有液晶層而成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性化合物之液晶組成物，於前述電極間輸入電壓，繼續使前述聚合性化合物進行聚合者。 (18) The liquid crystal alignment film according to the above (15) or (16), which is characterized in that it is used in a liquid crystal display element manufactured by the following steps, and the step is to provide a liquid crystal layer between the substrate and the substrate. A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is input between the electrodes to continue polymerization of the polymerizable compound.

(19)具有上述(18)所記載的液晶配向膜為特徵之液晶顯示元件。 (19) A liquid crystal display element characterized by comprising the liquid crystal alignment film according to (18) above.

(20)如上述(19)所記載的液晶顯示元件，其特徵為經由下述步驟所製造者，該步驟為於具備電極與前述液晶配向膜的一對基板之間具有液晶層所成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性化合物之液晶組成物，於前述電極間輸入電壓後，使前述聚合性化合物聚合者。 (20) The liquid crystal display device according to the above (19), which is characterized in that, in the step of producing a liquid crystal layer between a pair of substrates including an electrode and the liquid crystal alignment film, A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable compound is polymerized after a voltage is input between the electrodes.

(21)如上述(15)或(16)所記載的液晶配向膜，其特徵為於具備電極的一對基板之間具有液晶層所成，其為使用於經由下述步驟所製造液晶顯示元件，該步驟為於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性基之液晶配向膜，於前述電極間輸入電壓後使前述聚合性基進行聚合者。 (21) The liquid crystal alignment film according to the above (15) or (16), which is characterized in that a liquid crystal layer is formed between a pair of substrates including electrodes, and is used for a liquid crystal display element produced by the following steps The step of disposing at least one of the pair of substrates including the active energy line and the heat A liquid crystal alignment film of a polymerizable polymer which is polymerized, and a polymerizable group is polymerized after a voltage is input between the electrodes.

(22)具有上述(21)所記載的液晶配向膜為特徵之液晶顯示元件。 (22) A liquid crystal display element characterized by comprising the liquid crystal alignment film according to (21) above.

(23)如上述(22)所記載的液晶顯示元件，其特徵為經由下述步驟所製造，該步驟為於具備電極的一對基板之間具有液晶層所成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性基之液晶配向膜，於前述電極間輸入電壓後，使前述聚合性基進行聚合的步驟者。 (23) The liquid crystal display device according to the above (22), which is characterized in that the step is performed by forming a liquid crystal layer between a pair of substrates having electrodes, between the pair of substrates A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, and a step of polymerizing the polymerizable group after inputting a voltage between the electrodes.

所謂本發明的液晶配向處理劑為，即使於長時間之高溫或光照射曝曬下，得到預傾角無變化之液晶配向膜，且對基板之溶液的濕潤擴大性高，對於大型基板或段差基板，可得到具有優良塗膜均勻性之液晶配向膜。藉由使用該液晶配向膜，可提供顯示特性優良的信頼性高之液晶顯示元件。 In the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film having no pretilt angle is obtained even under a high temperature for a long period of time or exposure to light, and the wet diffusion property of the solution to the substrate is high. For a large substrate or a step substrate, A liquid crystal alignment film having excellent coating film uniformity can be obtained. By using the liquid crystal alignment film, it is possible to provide a liquid crystal display element having high signal conductivity and excellent display characteristics.

實施發明的形態 Form of implementing the invention

本發明的液晶配向處理劑為含有成分(A)之N-乙基-2-吡咯烷酮(亦稱為特定溶劑)、及成分(B)之將選自具有上述式〔1〕所示側鏈(亦稱為特定側鏈結構)的聚醯亞胺前驅物及聚醯亞胺前驅物經醯亞胺化的聚醯亞胺所成群的至少1種聚合物(亦稱為特定聚合物)。 The liquid crystal alignment treatment agent of the present invention is an N-ethyl-2-pyrrolidone (also referred to as a specific solvent) containing the component (A), and the component (B) is selected from the side chain represented by the above formula [1] ( Polyimine precursors and polybendimimine precursors, also known as specific side chain structures, are ruthenium imidized polyimine A group of at least one polymer (also known as a specific polymer).

本發明中之特定溶劑為對於聚醯胺酸或可溶性聚醯亞胺的溶解性優良的良溶劑。且，與一般使用的N-甲基-2-吡咯烷酮或γ-丁內酯相比較，作為溶劑而言表面張力較低。因此，使用特定溶劑的液晶配向處理劑與未使用此的液晶配向處理劑相比較，對基板的塗佈溶液之濕潤擴大性變高，即使不使用大量的樹脂之溶解性低的貧溶劑，亦可得到塗膜均勻性優良的液晶配向膜。且，因塗佈溶液的濕潤擴大性變高，作為液晶配向膜時的該端部的直線性會變高。 The specific solvent in the present invention is a good solvent excellent in solubility to polylysine or soluble polyimine. Further, the surface tension is low as a solvent as compared with N-methyl-2-pyrrolidone or γ-butyrolactone which is generally used. Therefore, the liquid crystal alignment treatment agent using a specific solvent has higher wettability to the coating solution of the substrate than the liquid crystal alignment treatment agent which does not use the liquid solvent, even if a poor solvent having a low solubility of a large amount of resin is not used. A liquid crystal alignment film excellent in uniformity of a coating film can be obtained. In addition, the wettability of the coating solution is increased, and the linearity of the end portion when the liquid crystal alignment film is used becomes high.

又，該特定溶劑與一般使用的N-甲基-2-吡咯烷酮或γ-丁內酯相比較其沸點較高，故使用特定溶劑的液晶配向劑作為液晶配向膜時，可抑制該端部之***。 Further, since the specific solvent has a higher boiling point than N-methyl-2-pyrrolidone or γ-butyrolactone which is generally used, when a liquid crystal alignment agent of a specific solvent is used as the liquid crystal alignment film, the end portion can be suppressed. Uplift.

本發明中之特定側鏈結構為於側鏈部分具有苯環、環己基環或雜環。這些苯環、環己基環或雜環與過去技術之長鏈烷基相比較，顯示剛直結構。藉此，可得到提高對側鏈部位之熱或紫外線的安定性，對於熱或光之預傾角為安定的液晶配向膜。又，這些苯環、環己基環或雜環即使顯示剛直結構，與由過去技術的類固醇骨架所成之環狀基相比較，聚合物的有機溶劑溶解性高。因此，具有本發明之特定側鏈結構的液晶配向處理劑，與由過去技術的類固醇骨架所成的環狀基之液晶配向處理劑相比較，對基板之塗佈均勻性變高。 The specific side chain structure in the present invention has a benzene ring, a cyclohexyl ring or a heterocyclic ring in the side chain portion. These benzene rings, cyclohexyl rings or heterocycles exhibit a rigid structure as compared to the long chain alkyl groups of the prior art. Thereby, it is possible to obtain a liquid crystal alignment film which is improved in heat or ultraviolet rays to the side chain portion and has a stable pretilt angle for heat or light. Further, even if these benzene rings, cyclohexyl rings or heterocyclic rings exhibit a rigid structure, the organic solvent solubility of the polymer is high as compared with the cyclic group formed by the steroid skeleton of the prior art. Therefore, the liquid crystal alignment treatment agent having the specific side chain structure of the present invention has higher coating uniformity to the substrate than the liquid crystal alignment treatment agent of the cyclic group formed by the steroid skeleton of the prior art.

由以上觀點得知，所謂含有具有本發明之特定溶劑及特定側鏈結構的聚合物之液晶配向處理劑，即使長時間高溫及光的照射下曝曬，不會使預傾角產生變化，且得到塗膜均勻性優良的液晶配向膜，又使用該液晶配向膜時，可得到顯示特性優良的信頼性高之液晶顯示元件。 It is known from the above that the inclusion of the specific solvent having the present invention The liquid crystal alignment treatment agent of the polymer having a specific side chain structure does not cause a change in the pretilt angle even when exposed to high temperature for a long period of time and irradiation with light, and a liquid crystal alignment film having excellent coating film uniformity is obtained, and the liquid crystal alignment film is used. In this case, a liquid crystal display element having high signal conductivity and excellent display characteristics can be obtained.

<特定溶劑> <specific solvent>

本發明的特定溶劑為N-乙基-2-吡咯烷酮。N-乙基-2-吡咯烷酮因具有提高對基板的塗佈溶液之濕潤擴大性的效果，含於液晶配向處理劑的有機溶劑全體之10~100質量%者為佳。其中亦以有機溶劑全體的15~100質量%為佳，較佳為20~100質量%，更佳為25~100質量%。 The specific solvent of the present invention is N-ethyl-2-pyrrolidone. The N-ethyl-2-pyrrolidone has an effect of improving the wettability of the coating solution to the substrate, and it is preferably 10 to 100% by mass of the entire organic solvent contained in the liquid crystal alignment treatment agent. The amount of the organic solvent is preferably from 15 to 100% by mass, preferably from 20 to 100% by mass, more preferably from 25 to 100% by mass.

在液晶配向處理劑中之有機溶劑之全體中，本發明之特定溶劑的量越多，本發明之效果，即對基板之塗佈溶液的濕潤擴大性會變高，可得到塗膜均勻性優良的液晶配向膜。 In the whole of the organic solvent in the liquid crystal alignment agent, the more the amount of the specific solvent of the present invention, the effect of the present invention is that the wettability of the coating solution to the substrate is increased, and the uniformity of the coating film can be obtained. Liquid crystal alignment film.

<特定側鏈結構> <specific side chain structure>

本發明的特定聚合物即為選自將聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群的至少1種為具有下述式〔1〕所示特定側鏈結構。 The specific polymer of the present invention is at least one selected from the group consisting of polyimine which is obtained by imidating a polyimide precursor and a polyimide precursor with the following formula [1]. Show specific side chain structure.

式〔1〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。其中亦以單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-CONH-、-CH₂O-或-COO-因容易合成側鏈結構故較佳。較佳為單鍵、-(CH₂)_a-(a為1~10的整數)、-O-、-CONH-、-CH₂O-或-COO-。更佳為單鍵、-(CH₂)_a-(a為1~10的整數)、-O-、-CH₂O-或-COO-。 In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, - NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CONH-, -CH ₂ O- or -COO- is preferred because it is easy to synthesize a side chain structure. It is preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO-. More preferably a single _{_{bond, - (CH 2) a -}} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

X₂為單鍵或-(CH₂)_b-(b為1~15的整數)。其中亦以單鍵或-(CH₂)_b-(b為1~10的整數)為佳。 X ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

X₃為單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。其中亦以單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-因容易合成而較佳。較佳為單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-CH₂O-、-COO-或-OCO-。 X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is preferred because it is easily synthesized. It is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

X₄為選自苯環、環己基環及雜環的2價環狀基。前述環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代。其中作為2價環狀基以苯環或環己基環。 X ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring. Any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom. Among them, a divalent cyclic group is a benzene ring or a cyclohexyl ring.

X₅為選自苯環、環己基環及雜環的2價環狀基。這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代。其中作為2價環狀基，以苯環或環己烷環為佳。 X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring. Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom. Among them, as the divalent cyclic group, a benzene ring or a cyclohexane ring is preferred.

n為0~4的整數，較佳為0~2的整數。 n is an integer of 0 to 4, preferably an integer of 0 to 2.

X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基。其中以碳數1~18的烷基、碳數1~10的含氟的烷基、碳數1~18的烷氧基或碳數1~10的含氟的烷氧基為佳。較佳為碳數1~12的烷基或碳數1~12的烷氧基。更佳為碳數1~9的烷基或碳數1~9的烷氧基。 X ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

作為式〔1〕中之X₁、X₂、X₃、X₄、X₅、X₆及n的較佳組合，可舉出與國際公開公報WO2011/132751(2011.10.27公開)之第13頁~33頁之表6~45所揭示(2-1)~(2-600)之相同組成。且，在國際公開公報之各表中，本發明中之X₁~X₆雖作為Y1~Y6表示，但其為將Y1~Y6改為X₁~X₆者。 Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1] include the 13th of the International Publication WO2011/132751 (2011.10.27 publication). The same composition of (2-1)~(2-600) is shown in Tables 6~45 on page 33. Further, in each of the tables in the international publication, X ₁ to X ₆ in the present invention are represented by Y1 to Y6, but those in which Y1 to Y6 are changed to X ₁ to X ₆ are used.

<特定側鏈型二胺化合物> <Specific side chain type diamine compound>

本發明的特定聚合物，即作為於選自將聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群之至少1種中導入式〔1〕所示特定側鏈結構的方法，使用具有特定側鏈結構之二胺化合物作為原料的一部份為佳。特別使用下述式(1a〕所示二胺化合物(亦稱為特定側鏈型二胺化合物)為佳。 The specific polymer of the present invention is introduced into the group [1] as at least one selected from the group consisting of polyimine which is obtained by imidating a polyimine precursor and a polyimide precursor. A method of exhibiting a specific side chain structure is preferably carried out using a diamine compound having a specific side chain structure as a part of a raw material. In particular, a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula (1a) is preferably used.

式〔1a〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-。其中以單鍵、-(CH₂)a-(a為1~15的整數)、-O-、-CONH-、-CH₂O-或-COO-因容易合成側鏈結構故較佳。較佳為單鍵、-(CH₂)_a-(a為1~10的整數)、-O-、-CONH-、-CH₂O-或-COO-。更佳為單鍵、-(CH₂)_a-(a為1~10的整數)、-O-、-CH₂O-或-COO-。 In the formula [1a], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, - NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ )a- (a is an integer of 1 to 15), -O-, -CONH-, -CH ₂ O- or -COO- is preferred because it is easy to synthesize a side chain structure. It is preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO-. More preferably a single _{_{bond, - (CH 2) a -}} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

X₄為選自苯環、環己基環或雜環的2價環狀基。前述環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代。其中作為2價環狀基以苯環或環己基環為佳。 X ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a hetero ring. Any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom. Among them, a divalent cyclic group is preferably a benzene ring or a cyclohexyl ring.

X₅為選自苯環、環己基環及雜環的2價環狀基。這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代。其中作為2價環狀基以苯環或環己基環為佳。 X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring. Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom. Among them, a divalent cyclic group is preferably a benzene ring or a cyclohexyl ring.

X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基。其中亦以碳數1~18的烷基、碳數1~10的含氟的烷基、碳數1~18的烷氧基或碳數1~10的含氟的烷氧基為佳。較佳為碳數1~12的烷基或碳數1~12的烷氧基。更佳為碳數1~9的烷基或碳數1~9的烷氧基。 X ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

式〔1a〕中之X₁、X₂、X₃、X₄、X₅、X₆及n的較佳組合與式〔1〕同様。 A preferred combination of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1a] is the same as the formula [1].

式〔1〕中之X₁、X₂、X₃、X₄、X₅、X₆及n的組合中，較佳組合為1-25~1-96、1-145~1-168、1-217~1-240、1-268~1-315、1-364~1-387、1-436~1-483等，特佳為組合為1-49~1-96、1-145~1-168、1-217~1-240等。 In the combination of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1], a preferred combination is 1-25 to 1-96, 1-145 to 1-168, 1 -217~1-240, 1-268~1-315, 1-364~1-387, 1-436~1-483, etc., especially for the combination of 1-49~1-96, 1-145~1 -168, 1-217~1-240, etc.

式［1a〕中，m為1~4的整數，較佳為1。 In the formula [1a], m is an integer of 1 to 4, preferably 1.

作為式〔1a〕，具體為例如下述之式〔1-1〕~〔1-13〕所示結構。 Specific examples of the formula [1a] include the structures shown in the following formulas [1-1] to [1-13].

(式〔1-1］~〔1-3〕中，R₁為-O-、-OCH₂-、-CH₂O-、-COOCH₂-或CH₂OCO-，R₂為直鏈狀或分支狀之碳數1~22的烷基、碳數1~22的烷氧基、碳數1~22的含氟的烷基或碳數1~22的含氟的烷氧基) (In the formula [1-1] to [1-3], R ₁ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ₂ is linear or Branched carbon having 1 to 22 carbon atoms, alkoxy group having 1 to 22 carbon atoms, fluorine-containing alkyl group having 1 to 22 carbon atoms or fluorine-containing alkoxy group having 1 to 22 carbon atoms)

(式〔1-4〕~〔1-6〕中，R₃為-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-或-CH₂-，R₄為直鏈狀或分支狀之碳數1~22的烷基、碳數1~22的烷氧基、碳數1~22的含氟的烷基或碳數1~22的含氟的烷氧基) (In the formula [1-4] to [1-6], R ₃ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O- , -OCH ₂ - or -CH ₂ -, R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a fluorine-containing alkane having 1 to 22 carbon atoms. Base or fluorine-containing alkoxy group having 1 to 22 carbon atoms)

(式〔1-7〕及〔1-8〕中，R₅為-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、-O-或-NH-，R₆為氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基。) (In the formulae [1-7] and [1-8], R ₅ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O- , -OCH ₂ -, -CH ₂ -, -O- or -NH-, R ₆ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, an ethyl group Oxy or hydroxy.)

(式〔1-9〕及〔1-10〕中，R₇為碳數3~12的直鏈狀或分支狀的烷基，1,4-環伸己基之順-反式異構性各為反式異構物。) (In the formulae [1-9] and [1-10], R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of the 1,4-cyclohexyl group Is a trans isomer.)

(式〔1-11〕及〔1-12〕中，R₈為碳數3~12的直鏈狀或分支狀烷基，1,4-環伸己基之順-反式異構性各為反式異構物。) (In the formulae [1-11] and [1-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of the 1,4-cyclohexyl group is Trans isomer.)

(式〔1-13〕中，A₄為可由氟原子取代之碳數3~20的直鏈狀或分支狀的烷基，A₃為1,4-環伸己基或1,4-伸苯基，A₂為氧原子或COO-*(但，附有「*」之結合鍵表示與A₃結合)，A₁為氧原子或COO-*(但，附有「*」之結合鍵表示與(CH₂)a2)結合)。 (In the formula [1-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, and A ₃ is a 1,4-cyclohexyl group or a 1,4-phenylene group. A, A ₂ is an oxygen atom or COO-* (however, a bond with "*" indicates binding to A ₃ ), and A ₁ is an oxygen atom or COO-* (however, a bond with "*" is attached) Combined with (CH ₂ )a2)).

又，a₁為0或1，a₂為2~10的整數，a₃為0或1) Further, a ₁ is 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is 0 or 1)

上述的式〔1-1〕~〔1-13〕中，特佳結構之二胺化合物為式〔1-1〕~〔1-6〕、式〔1-9〕~〔1-13〕等。 In the above formula [1-1] to [1-13], the diamine compound of a particularly preferable structure is of the formula [1-1] to [1-6], the formula [1-9] to [1-13], and the like. .

上述特定側鏈型二胺化合物為，配合作為液晶配向膜時的液晶配向性、電壓保持率、蓄積電荷等特性，可混合1種類或2種類以上而使用。 The specific side chain type diamine compound can be used in combination with one type or two types or more in combination with characteristics such as liquid crystal alignment property, voltage holding ratio, and charge accumulation when the liquid crystal alignment film is used.

<其他二胺化合物> <Other diamine compounds>

本發明中，以不損害本發明之效果下，可將特定側鏈型二胺化合物以外之其他二胺化合物(亦稱為其他二胺化合物)作為原料之二胺成分使用。可具體舉出下述例子。 In the present invention, other diamine compounds other than the specific side chain type diamine compound (also referred to as other diamines) may be used without impairing the effects of the present invention. The compound is used as a raw material diamine component. The following examples can be specifically mentioned.

p-伸苯二胺、2,3,5,6-四甲基-p-伸苯二胺、2,5-二甲基-p-伸苯二胺、m-伸苯二胺、2,4-二甲基-m-伸苯二胺、2,5-二胺基甲苯、2,6-二胺基甲苯、2,5-二胺基酚、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲基醇、2,4-二胺基苯甲基醇、4,6-二胺基間苯二酚、4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二羧基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-聯苯、3,3’-三氟甲基-4,4’-二胺基聯苯、3,4’-二胺基聯苯、3,3’-二胺基聯苯、2,2’-二胺基聯苯、2,3’-二胺基聯苯、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺酸基聯苯胺、3,3’-磺酸基聯苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫聯苯胺、3,3’-硫聯苯胺、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯基甲酮、3,3’-二胺基二苯基甲酮、3,4’-二胺基二苯基甲酮、1,4-二胺基萘、2,2’-二胺基二苯基甲酮、2,3’-二胺基二苯基甲酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6-二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-〔1,4-伸苯雙(伸甲基)〕聯苯胺、4,4’-〔1,3-伸苯雙(伸甲基)〕聯苯胺、3,4’-〔1,4-伸苯雙(伸甲基)〕聯苯胺、3,4’-〔1,3-伸苯雙(伸甲基)〕聯苯胺、3,3’-〔1,4-伸苯雙(伸甲基)〕聯苯胺、3,3’-〔1,3-伸苯雙(伸甲基)〕聯苯胺、1,4-伸苯雙〔(4-胺基苯基)甲酮〕、1,4-伸苯雙〔(3-胺基苯基)甲酮〕、1,3-伸苯雙〔(4-胺基苯基)甲酮〕、1,3-伸苯雙〔(3-胺基苯基)甲酮〕、1,4-伸苯雙(4-胺基苯甲酸酯)、1,4-伸苯雙(3-胺基苯甲酸酯)、1,3-伸苯雙(4-胺基苯甲酸酯)、1,3-伸苯雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)異鄰苯二甲酸酯、雙(3-胺基苯基)異鄰苯二甲酸酯、N,N’-(1,4-伸苯)雙(4-胺基苯甲醯胺)、N,N’- (1,3-伸苯)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)二甲酸對苯醯胺、N,N’-雙(3-胺基苯基)二甲酸對苯醯胺、N,N’-雙(4-胺基苯基)異鄰苯二甲酰胺、N,N’-雙(3-胺基苯基)異鄰苯二甲酰胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙〔4-(4-胺基苯氧基)苯基〕丙烷、2,2’-雙［4-(4-胺基苯氧基)苯基〕六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、3,5-二胺基安息香酸、2,5-二胺基安息香酸、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷等芳香族二胺化合物；雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等脂環式二胺化合物；1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等脂肪族二胺化合物。 P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3 , 5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-di Aminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3' -dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diamine Biphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodi Phenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diamino group Phenyl ether, 4,4'-sulfonic acid benzidine, 3,3'-sulfonic acid benzidine, bis(4-aminophenyl)nonane, bis(3-aminophenyl)decane, dimethyl Base-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiobenzidine, 3,3'-thiobenzidine, 4,4' -diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2, 3'-Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N -Methyl (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diamino Diphenyl)amine, 4,4'-diaminodiphenyl Ketone, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 1,4-diaminonaphthalene, 2,2'-diaminodi Phenyl ketone, 2,3'-diaminodiphenyl ketone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-amine Phenyl) ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl) Propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl) Methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4 '-[1,4-Benzene bis(methyl))benzidine, 4,4'-[1,3-phenylenebis(methyl)]benzidine, 3,4'-[1,4 - Benzene bis(methyl)]benzidine, 3,4'-[1,3-phenylenebis(methyl)]benzidine, 3,3'-[1,4-phenylene bis (extension) Methyl)]benzidine, 3,3'-[1,3-stretch Benzene (methyl)]benzidine, 1,4-benzoic bis[(4-aminophenyl)methanone], 1,4-benzoic acid [(3-aminophenyl)methanone] , 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4) -aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-stretch Benzene (3-aminobenzoic acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-amine Phenylphenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzoic acid) Guanamine), N, N'- (1,3-Benzene) bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'- (1,3-Benzene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)dicarboxylic acid p-benzoguanamine, N,N'-bis(3- Aminophenyl)dicarboxylic acid p-benzoguanamine, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalic acid Dimethylamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4 -aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl) Hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2' - bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3 , 5-diamino benzoic acid, 2,5-diamino benzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane , 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkane, 1,5- (3-Aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7- Bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8- Bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10 -(4-Aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11- Aromatic two (3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane Amine compound An alicyclic diamine compound such as bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane; 1,3-diaminopropane, 1,4-di Aminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-di An aliphatic diamine compound such as an aminodecane, a 1,10-diaminodecane, a 1,11-diaminoundecane or a 1,12-diaminododecane.

又，以不損害本發明之效果下，可使用具有二胺側鏈烷基或含氟的烷基之二胺化合物。 Further, a diamine side chain can be used without impairing the effects of the present invention. A diamine compound of an alkyl or fluorine-containing alkyl group.

具體可舉出例如下述式〔DA1〕~〔DA12〕所示二胺化合物之例示。 Specific examples of the diamine compound represented by the following formulas [DA1] to [DA12] are exemplified.

(式〔DA1〕~〔DA5〕中，A₁為碳數1~22的直鏈狀或分支狀的烷基或碳數1~22的直鏈狀或分支狀的含氟的烷基。) (In the formula [DA1] to [DA5], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(式〔DA6〕~〔DA11〕中，A₂表示-COO-、-OCO-、-CONH-、-NHCO-、-CH₂-、-O-、-CO-或-NH-，A₃表示碳數1~22的直鏈狀或分支狀的烷基或碳數1~22的直鏈狀或分支狀的含氟的烷基) (In the formula [DA6]~[DA11], A ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ₃ represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms)

(式〔DA12〕中，p為1~10的整數。) (In the formula [DA12], p is an integer from 1 to 10.)

以不損害本發明之效果下，可使用下述式〔DA13〕~〔DA20〕所示二胺化合物。 The diamine compound represented by the following formulas [DA13] to [DA20] can be used without impairing the effects of the present invention.

(式〔DA17〕中，m為0~3的整數。式〔DA20〕中，n為1~5的整數) (In the formula [DA17], m is an integer of 0 to 3. In the formula [DA20], n is an integer of 1 to 5)

且，以不損害本發明之效果下，可使用下述式〔DA21〕~〔DA24〕所示，於分子內具有羧基之二胺化合物。 Further, a diamine compound having a carboxyl group in the molecule, which is represented by the following formulas [DA21] to [DA24], can be used without impairing the effects of the present invention.

(式〔DA21〕中，m₁為1~4的整數。 (In the formula [DA21], m ₁ is an integer of 1 to 4.

式［DA22〕中，A₄為單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、 -N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-，m₂及m₃各為0~4的整數，且m₂+m₃為1~4的整數。 In the formula [DA22], A ₄ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O- , -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO-, m ₂ and m _{3 are} each an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4.

式〔DA23〕中，m₄及m₅各為1~5的整數。式〔DA24〕中，A₅為碳數1~5的直鏈狀或分支狀的烷基，m₆為1~5的整數。 In the formula [DA23], m ₄ and m _{5 are} each an integer of 1 to 5. In the formula [DA24], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5.

式〔DA25〕中，A₆為單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-，m₇為1~4的整數。) In the formula [DA25], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O- , -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO-, m ₇ is an integer from 1 to 4. )

且，以不損害本發明之效果下，可使用下述式〔DA26〕所示二胺化合物。 Further, the diamine compound represented by the following formula [DA26] can be used without impairing the effects of the present invention.

(式〔DA26〕中，A₁為選自-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-的2價有機基，A₂為單鍵、碳數1~20的脂肪族烴基、非芳香族環式烴基或芳香族烴基。A₃為單鍵、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、-N(CH₃)CO-或-O(CH₂)_m- (m為1~5的整數)，A₄為含氮的芳香族雜環，n為1~4的整數) (In the formula [DA26], A ₁ is selected from the group consisting of -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH) ₃ )- or -N(CH ₃ )CO-divalent organic group, A ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. A ₃ is a single bond , -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5), A ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4)

且，以不損害本發明之效果下，可使用具有下述式〔DA27〕~〔DA46〕所示類固醇骨架的二胺化合物。 Further, a diamine compound having a steroid skeleton represented by the following formula [DA27] to [DA46] can be used without impairing the effects of the present invention.

上述其他二胺化合物可配合作為液晶配向膜時的液晶配向性、電壓保持率、蓄積電荷等特性，可混合1種類或2種類以上使用。 The other diamine compound may be used in combination with a liquid crystal alignment film, a voltage holding ratio, and an accumulated charge when used as a liquid crystal alignment film, and may be used in combination of one type or two types or more.

<特定四羧酸二酐> <Specific tetracarboxylic dianhydride>

欲得到本發明之特定聚合物，可將下述式〔2〕所示四羧酸二酐(亦稱為特定四羧酸二酐)作為原料的一部份使用為佳。 To obtain the specific polymer of the present invention, a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [2] can be preferably used as a part of the raw material.

式〔2〕中，Y₁為碳數4~13之4價有機基，且含有碳數4~10之非芳香族環狀烴基。 In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

式〔2〕中之Y₁，具體例如為下述式〔2a〕~〔2j〕所示4價基。 Y ₁ in the formula [2] is specifically a tetravalent group represented by the following formulas [2a] to [2j].

式〔2a〕中，Y₂~Y₅為氫原子、甲基、氯原子或苯環，各可相同或相異。 In the formula [2a], Y ₂ to Y ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

又，式〔2g〕中，Y₆及Y₇為氫原子或甲基，各可相同或相異。 Further, in the formula [2g], Y ₆ and Y ₇ are each a hydrogen atom or a methyl group, and each may be the same or different.

式〔2〕中，Y₁的特佳結構中，因聚合反應性或合成之容易性，以式〔2a〕、式〔2c〕、式［2d〕、式［2e〕、式〔2f〕或式〔2g〕為佳。其中亦以式［2a〕、式［2e〕、式〔2f〕或式〔2g〕為佳。 Formula [2], the particularly preferred structure of Y _1, the result of the polymerization reaction or synthesis of easiness to formula [2a], formula [2c], formula [2D], formula [2E], formula [2f] or Formula [2g] is preferred. Among them, the formula [2a], the formula [2e], the formula [2f] or the formula [2g] is preferred.

<其他四羧酸二酐> <Other tetracarboxylic dianhydride>

本發明中，以不損害本發明之效果下，可使用特定四羧酸二酐以外的其他四羧酸二酐(亦稱為其他四羧酸二酐)。作為其他四羧酸二酐，可舉出以下所示四羧酸之四羧酸二酐。 In the present invention, other tetracarboxylic dianhydrides (also referred to as other tetracarboxylic dianhydrides) other than the specific tetracarboxylic dianhydride can be used without impairing the effects of the present invention. Examples of the other tetracarboxylic dianhydride include tetracarboxylic dianhydride of the tetracarboxylic acid shown below.

均苯四甲酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、 3,3’,4,4’-聯苯四羧酸、2,3,3’,4-聯苯四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯基甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸。 Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-decanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4 , 4'-diphenyl ketone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-di Carboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)di Methyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane Tetracarboxylic acid.

上述特定四羧酸二酐及其他四羧酸二酐可配合作為液晶配向膜時的液晶配向性、電壓保持率、蓄積電荷等特性，混合1種類或2種類以上後使用。 The specific tetracarboxylic dianhydride and the other tetracarboxylic dianhydride can be used in combination with the liquid crystal alignment property, the voltage holding ratio, and the accumulated charge when the liquid crystal alignment film is used, and one type or two or more types are mixed and used.

<特定聚合物> <specific polymer>

本發明之特定聚合物為選自將具有前述式〔1〕所示側鏈的聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群之至少1種聚合物。 The specific polymer of the present invention is at least 1 selected from the group consisting of a polyamidene precursor having a side chain of the above formula [1] and a polyamidene precursor which is ruthenium imidized. Kind of polymer.

聚醯亞胺前驅物為下述式〔A〕所示結構。 The polyimine precursor is a structure represented by the following formula [A].

(式〔A〕中，R₁為4價有機基，R₂為2價有機基，A₁及A₂ 氫原子或碳數1~8的烷基，各可相同或相異，n表示正的整數。) (In the formula [A], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and A ₁ and A ₂ The hydrogen atom or the alkyl group having 1 to 8 carbon atoms may be the same or different, and n represents a positive integer. )

本發明的特定聚合物為由將下述式〔B〕所示二胺成分與下述式〔C〕所示四羧酸二酐作為原料時比較容易得到之理由來看，將由下述式〔D〕所示重複單位之結構式所成的聚醯胺酸或該聚醯胺酸進行醯亞胺化之聚醯亞胺為佳。 The specific polymer of the present invention is a reason why it is relatively easy to obtain a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C], and will be represented by the following formula [ D] is a polylysine formed by the structural formula of the repeating unit or a polyimine which is ruthenium imidized with the polyamine.

(式〔B〕及〔C〕中，R₁及R₂與式〔A〕所定義者為同義。) (In the formulae [B] and [C], R ₁ and R ₂ are synonymous with those defined by the formula [A].)

(式〔D〕中，R₁及R₂與式〔A〕所定義者同義。) (In the formula [D], R ₁ and R ₂ are synonymous with those defined by the formula [A].)

本發明中，合成特定聚合物之方法並無特別限定。一般將二胺成分與四羧酸成分進行反應而得。一般而言，將選自四羧酸及其衍生物所成群的至少1種四羧酸成分、與由1種或複數種之二胺化合物所成的二胺成分進行反應得到聚醯胺酸。具體為可使用將四羧酸二酐與二胺成分進行聚縮合而得到聚醯胺酸之方法、將四羧酸與二胺成分進行脫水聚縮合反應而得到聚醯胺酸之方法或將四羧酸二鹵化物與二胺成分進行聚縮合而得到聚醯胺酸之方法。 In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is generally obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof, and The diamine component formed from one or a plurality of diamine compounds is reacted to obtain a polyamic acid. Specifically, a method of obtaining poly-proline by polycondensing a tetracarboxylic dianhydride with a diamine component, a method of dehydrating polycondensation of a tetracarboxylic acid and a diamine component, or a method of obtaining a poly-proline may be used. A method in which a carboxylic acid dihalide and a diamine component are polycondensed to obtain a poly-proline.

欲得到聚醯胺酸烷基酯時，使用將使羧酸基進行二烷基酯化的四羧酸與二胺成分進行聚縮合的方法、將使羧酸基進行二烷基酯化之四羧酸二鹵化物與二胺成分進行聚縮合的方法或聚醯胺酸的羧基轉變為酯的方法。 In order to obtain a polyalkyl amide, a method of polycondensing a tetracarboxylic acid and a diamine component which dialkylate a carboxylic acid group, and a dialkyl esterification of a carboxylic acid group are used. A method of polycondensing a carboxylic acid dihalide with a diamine component or a method of converting a carboxyl group of a polylysine to an ester.

欲得到聚醯亞胺，使用將前述聚醯胺酸或聚醯胺酸烷基酯進行閉環作為聚醯亞胺的方法。 In order to obtain a polyimine, a method of ring-closing the polyamic acid or polyalkyl phthalate as a polyimine is used.

使用本發明的特定聚合物所得之液晶配向膜為，上述二胺成分中之前述式〔1〕所示特定側鏈結構的含有比率越多，可作為液晶配向膜時的疏水性與液晶之預傾角變的越高。此時，於二胺成分中使用前述式〔1a〕所示特定側鏈型二胺化合物者為佳。特佳為使用選自前述式〔1-1〕~〔1-6〕及式〔1-9〕~〔1-13〕所示特定側鏈型二胺化合物所成群的至少1種。其中，使用選自式〔1-1〕~〔1-6〕或式〔1-9〕~〔1-12〕所示特定側鏈型二胺化合物所成群的至少1種者為佳。再提高該特性之目的下，二胺成分的5莫耳%以上80莫耳%以下為特定側鏈型二胺化合物者較佳。其中亦由作為液晶配向處理劑之塗佈性或作為液晶配向膜之電氣特性的觀點來看，以二胺成分的5莫耳%以上60莫耳%以下為特定側鏈型二胺化合物者較佳。更佳為二胺成分的10莫耳%以上60莫耳%以下。 In the liquid crystal alignment film obtained by using the specific polymer of the present invention, the more the content ratio of the specific side chain structure represented by the above formula [1] in the diamine component, the more the hydrophobicity and the liquid crystal can be used as the liquid crystal alignment film. The higher the inclination angle becomes. In this case, it is preferred to use the specific side chain type diamine compound represented by the above formula [1a] in the diamine component. It is particularly preferable to use at least one selected from the group consisting of the specific side chain type diamine compounds represented by the above formulas [1-1] to [1-6] and the formulas [1-9] to [1-13]. Among them, at least one selected from the group consisting of the specific side chain type diamine compounds represented by the formulae [1-1] to [1-6] or the formula [1-9] to [1-12] is preferred. Further, in order to further improve the properties, it is preferred that the molybdenum component has a specific side chain type diamine compound in an amount of from 5 mol% to 80 mol%. In addition, from the viewpoint of the coating property of the liquid crystal alignment treatment agent or the electrical characteristics of the liquid crystal alignment film, the specific side chain type diamine compound is 5 mol% or more and 60 mol% or less of the diamine component. good. Better 10 mol% or more and 60 mol% or less of the diamine component.

欲得到本發明之特定聚合物，作為四羧酸成分使用前述式〔2〕所示特定四羧酸二酐為佳。特別以使用式〔2〕中之Y₁為前述式〔2a〕~〔2j〕所示結構的基之四羧酸二酐為佳。此時，四羧酸成分之1莫耳%以上為特定四羧酸二酐者為佳，較佳為5莫耳%以上，更佳為10莫耳%以上。又，四羧酸成分之100莫耳%亦可為特定四羧酸二酐。 In order to obtain the specific polymer of the present invention, it is preferred to use the specific tetracarboxylic dianhydride represented by the above formula [2] as the tetracarboxylic acid component. In particular, the use of formula [2] is the formula [Y _1] - [2a] 2j tetracarboxylic dianhydride represented by the structure of the preferred group. In this case, 1 mol% or more of the tetracarboxylic acid component is preferably a specific tetracarboxylic dianhydride, preferably 5 mol% or more, and more preferably 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.

二胺成分與四羧酸成分之反應，一般在有機溶劑中進行。作為此時所使用的有機溶劑，可為本發明之特定溶劑，僅可溶解所生成之聚醯亞胺前驅物者即可，並無特別限定。以下舉出該具體例。 The reaction of the diamine component with the tetracarboxylic acid component is generally carried out in an organic solvent. The organic solvent to be used in this case may be a specific solvent of the present invention, and it is not particularly limited as long as it can dissolve only the produced polyimide precursor. This specific example is given below.

例如為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑烷酮、甲基乙酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮等。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, γ-butyrolactone, 1,3-two Methyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

這些可單獨下使用，亦可混合後使用。且即使為不溶解聚醯亞胺前驅物之溶劑，在不會析出所生成之聚醯亞胺前驅物的範圍下，可混合上述溶劑後使用。又，有機溶劑中之水分會阻礙聚合反應，且成為水解所生成之聚醯亞胺前驅物的原因，故使用有機溶劑經脫水乾燥者為佳。 These can be used separately or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, the solvent can be mixed and used in the range in which the produced polyimide precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and becomes a cause of the polyimine precursor formed by the hydrolysis, it is preferred to use an organic solvent to be dried by dehydration.

可舉出將二胺成分與四羧酸成分在有機溶劑中進行反應時，將二胺成分分散或溶解於有機溶劑之溶液進行攪拌，將四羧酸成分直接，或分散或溶解於有機溶劑後添加之方法、相反地將四羧酸成分分散或溶解於有機溶劑的溶液添加二胺成分之方法、將四羧酸成分與二胺成分交互添加之方法等，可使用此等任一方法。又，將二胺成分或四羧酸成分使用各複數種進行反應時，可預先混合狀態下進行反應，或各別依順序進行，或亦可將進一步各別進行反應之低分子量體進行混合反應後作為特定聚合物。此時的聚合溫度可選自-20~150℃的任意溫度，較佳為-5~100℃之範圍。又，反應可在任意濃度下進行，但濃度過低時，得到高分子量之特定聚合物變的困難，濃度過高時，反應液之黏性會過高而無法均勻地攪拌。因此，較佳為1~50質量%，更佳為5~30質量%。反應初期在高濃度下進行，其後可追加有機溶劑。 When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly dispersed or dissolved in an organic solvent. a method of adding, or conversely, dispersing or dissolving a tetracarboxylic acid component in an organic solvent Any of these methods can be used as a method of adding a diamine component, a method of adding a tetracarboxylic acid component and a diamine component, and the like. Further, when the diamine component or the tetracarboxylic acid component is reacted with each of plural kinds, the reaction may be carried out in a premixed state, or may be carried out sequentially, or a lower molecular weight body which is further reacted separately may be subjected to a mixing reaction. After that as a specific polymer. The polymerization temperature at this time may be selected from any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a specific polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is too high to be uniformly stirred. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

對於聚醯亞胺前驅物之聚合反應，二胺成分的合計莫耳數與四羧酸成分之合計莫耳數比以0.8~1.2為佳。與一般的聚縮合反應同様地，該莫耳比越接近1.0，所生成之聚醯亞胺前驅物的分子量越大。 In the polymerization reaction of the polyimine precursor, the total molar ratio of the total molar number of the diamine component to the tetracarboxylic acid component is preferably 0.8 to 1.2. In the same manner as a general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

本發明的聚醯亞胺為將前述聚醯亞胺前驅物進行閉環所得之聚醯亞胺，可作為得到液晶配向膜之聚合物使用。 The polyimine of the present invention is a polyimine obtained by ring-closing the polyimine precursor, and can be used as a polymer for obtaining a liquid crystal alignment film.

對於本發明之聚醯亞胺，醯胺酸基之閉環率(亦稱為醯亞胺化率)無必須為100%，配合用途或目的可做任意調整。 For the polyimine of the present invention, the ring closure ratio (also referred to as the oxime imidization ratio) of the valine group is not necessarily 100%, and can be arbitrarily adjusted for use or purpose.

作為將聚醯亞胺前驅物進行醯亞胺化之方法，可舉出將聚醯亞胺前驅物之溶液直接加熱的熱醯亞胺化或於聚醯亞胺前驅物之溶液中添加觸媒的觸媒醯亞胺化。 As a method of ruthenium imidating a polyimide precursor, the heat-imidization of the solution of the polyimide precursor is directly heated or the catalyst is added to the solution of the polyimide precursor. The catalyst is imidized.

將聚醯亞胺前驅物在溶液中使其熱醯亞胺化時的溫度為100~400℃，較佳為120~250℃。 The temperature at which the polybendimimine precursor is thermally imidized in solution It is 100 to 400 ° C, preferably 120 to 250 ° C.

熱醯亞胺化反應為一邊將所生成之水排出於系統外，一邊進行的方法為佳。 The hot hydrazine imidization reaction is preferably carried out while discharging the generated water to the outside of the system.

聚醯亞胺前驅物的觸媒醯亞胺化為，於聚醯亞胺前驅物之溶液中，可添加鹼性觸媒與酸酐，在-20~250℃，較佳為0~180℃下進行攪拌下進行。鹼性觸媒之量為醯胺酸基的0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐的量為醯胺酸基之1~50莫耳倍，較佳為3~30莫耳倍。 The ruthenium imide of the polyimide precursor is imidized into a solution of the polyimide precursor, and a basic catalyst and an acid anhydride may be added at -20 to 250 ° C, preferably 0 to 180 ° C. It is carried out under stirring. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles.

作為鹼性觸媒，可舉出吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等，其中亦以吡啶因在進行反應時可具有適度鹼性而較佳。 Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is also preferably moderately alkaline when it is reacted.

作為酸酐，可舉出乙酸酐、偏苯三酸酐、均苯四甲酸酐等，其中亦以使用乙酸酐時，在反應終了後之純化變的容易故較佳。藉由觸媒醯亞胺化之醯亞胺化率為，可藉由調節觸媒量與反應溫度、反應時間而控制。 Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is preferred, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

回收由聚醯亞胺前驅物或聚醯亞胺之反應溶液所生成之聚醯亞胺前驅物或聚醯亞胺時，僅將反應溶液投入於溶劑中使其沉澱即可。作為使用於沉澱的溶劑，可舉出甲醇、乙醇、異丙基醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、甲苯、苯、水等。投入於溶劑使其沉澱的聚合物經過濾並回收後，在常壓或減壓下，可經常溫或加熱進行乾燥。又，將沉澱回收之聚合物，再溶解於有機溶劑中，將再沉澱與回收之操作重複2~10次，可減少聚合物中之不純物。作為此時的溶劑，例如可舉出醇類、酮類、烴等，使用選自彼等中之3種類以上的溶劑時，可進一步提高純化效率故較佳。 When the polyimine precursor or the polyimine produced by the reaction solution of the polyimine precursor or the polyimine is recovered, only the reaction solution may be placed in a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer which has been subjected to the solvent and precipitated is filtered and recovered, and then dried under normal pressure or reduced pressure at room temperature or under heating. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation and recovery operations are repeated 2 to 10 times to reduce impurities in the polymer. As the solvent at this time, for example, an alcohol can be mentioned When a solvent selected from three or more types selected from the group consisting of a ketone, a hydrocarbon, and the like, the purification efficiency can be further improved, which is preferable.

本發明的特定聚合物之分子量，若考慮到所得之聚合物被膜之強度、聚合物被膜形成時之作業性、聚合物被膜之均勻性時，以GPC(Gel Permeation Chromatography)法所測定之重量平均分子量以5,000~1,000,000為佳，較佳為10,000~150,000。 The molecular weight of the specific polymer of the present invention, in consideration of the strength of the obtained polymer film, the workability when the polymer film is formed, and the uniformity of the polymer film, the weight average measured by the GPC (Gel Permeation Chromatography) method The molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

<液晶配向處理劑> <Liquid alignment treatment agent>

本發明的液晶配向處理劑係為形成液晶配向膜時的塗佈溶液，欲形成含有特定溶劑及特定聚合物之樹脂被膜時的塗佈液。 The liquid crystal alignment treatment agent of the present invention is a coating liquid when a liquid crystal alignment film is formed, and a coating liquid when a resin film containing a specific solvent and a specific polymer is to be formed.

本發明的液晶配向處理劑中之聚合物成分可全為本發明的特定聚合物，於本發明的特定聚合物中可混合此以外的其他聚合物。此時，聚合物成分中之此以外的其他聚合物之含有量為0.5~15質量%，較佳為1~10質量%。 The polymer component in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer of the present invention, and other polymers other than the above may be mixed in the specific polymer of the present invention. In this case, the content of the polymer other than the polymer component is from 0.5 to 15% by mass, preferably from 1 to 10% by mass.

作為此以外的其他聚合物，可舉出選自將由未含特定側鏈型二胺化合物之二胺成分與未含特定四羧酸二酐之四羧酸成分所得之聚醯亞胺前驅物及聚醯亞胺前驅物經醯亞胺化之聚醯亞胺所成群的至少1種聚合物。且，除聚醯亞胺前驅物及聚醯亞胺以外之聚合物，可具體舉出丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯、聚醯胺、矽氧烷系聚合物等。 The other polymer other than this may be selected from a polyimine precursor obtained by a diamine component not containing a specific side chain type diamine compound and a tetracarboxylic acid component not containing a specific tetracarboxylic dianhydride. The polyimine precursor is at least one polymer of a group of ruthenium imidized polyimine. Further, examples of the polymer other than the polyimine precursor and the polyimine are an acrylic polymer, a methacrylic polymer, a polystyrene, a polyamine, a decane-based polymer, or the like.

本發明的液晶配向處理劑中之有機溶劑由可藉由塗佈形成均勻被膜之觀點來看，液晶配向處理劑中，有機溶劑之含有量以70~99質量%為佳。有機溶劑之含有量作為目的可依據液晶配向膜的膜厚做適宜變更。 The organic solvent in the liquid crystal alignment treatment agent of the present invention can be coated by From the viewpoint of forming a uniform film, the content of the organic solvent in the liquid crystal alignment agent is preferably from 70 to 99% by mass. The content of the organic solvent can be appropriately changed depending on the film thickness of the liquid crystal alignment film.

作為有機溶劑，使用本發明的特定溶劑為佳。此時，若為可溶解特定聚合物的有機溶劑即可，於特定溶劑以外亦可使用下述溶劑。具體為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑烷酮、甲基乙酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮。 As the organic solvent, it is preferred to use the specific solvent of the present invention. In this case, the organic solvent which can dissolve a specific polymer may be used, and the following solvent may be used other than a specific solvent. Specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, γ-butyrolactone, 1,3-two Methyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

其中使用N-甲基-2-吡咯烷酮、γ-丁內脂等(這些亦稱為成分(C))為佳。 Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, and the like (these are also referred to as the component (C)) are preferred.

成分(C)的使用量於液晶配向處理劑所含之有機溶劑全體的0.1~70質量%者為佳。其中以1~60質量%為佳。較佳為1~50質量%，更佳為3~40質量%。 The amount of the component (C) to be used is preferably from 0.1 to 70% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent. Among them, 1 to 60% by mass is preferred. It is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass.

本發明的液晶配向處理劑，以不損害本發明之效果下，可使用可提高塗佈液晶配向處理劑時的液晶配向膜之塗膜均勻性或表面平滑性的有機溶劑，即可使用貧溶劑。欲提高液晶配向膜之塗膜均勻性或表面平滑性的貧溶劑之具體例可舉出以下者。 In the liquid crystal alignment treatment agent of the present invention, an organic solvent which can improve the uniformity of the coating film or the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used without impairing the effects of the present invention, and a poor solvent can be used. . Specific examples of the poor solvent for improving the uniformity of the coating film or the surface smoothness of the liquid crystal alignment film include the following.

例如乙醇、異丙基醇、1-丁醇、2-丁醇、異丁基醇、tert-丁基醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊基醇、tert-戊基醇、3-甲基-2-丁醇、戊基醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己烷二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、伸丙基碳酸酯、乙烯碳酸酯、乙二醇單甲基醚、乙二醇單乙基醚、2-(甲氧基甲氧基)乙醇、乙二醇異丙基醚、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠基醇、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等表面張力較低的有機溶劑。 For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, Amyl alcohol, 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-methylcyclohexane Alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butyl Alkanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, Dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxy Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2 -Hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-( Methoxymethoxy)ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, Nonyl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl 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, 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 acetate Ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propyl propionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. Solvent.

其中以使用1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚等(這些亦稱為成分(D))為佳。 Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl are used. Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, etc. Also known as ingredient (D)) is preferred.

貧溶劑(成分(D))之使用量為含於液晶配向處理劑的有機溶劑全體之1~80質量%者為佳。其中亦以5~70質量%為佳，較佳為10~70質量%。 The amount of the poor solvent (component (D)) is preferably from 1 to 80% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent. It is preferably 5 to 70% by mass, preferably 10 to 70% by mass.

本發明的液晶配向處理劑中之有機溶劑的較佳組合為表1~3所示。 Preferred combinations of the organic solvents in the liquid crystal alignment agent of the present invention are shown in Tables 1 to 3.

表1~3中，NEP表示N-乙基-2-吡咯烷酮，NMP表示N-甲基-2-吡咯烷酮，γ-BL表示γ丁內酯，BCS表示乙二醇單丁基醚，ECS表示乙二醇單乙基醚，MC表示二乙二醇單甲基醚，EC表示二乙二醇單乙基醚，PGME表示丙二醇單甲基醚。 In Tables 1 to 3, NEP represents N-ethyl-2-pyrrolidone, NMP represents N-methyl-2-pyrrolidone, γ-BL represents γ-butyrolactone, BCS represents ethylene glycol monobutyl ether, and ECS represents B. Glycol monoethyl ether, MC represents diethylene glycol monomethyl ether, EC represents diethylene glycol monoethyl ether, and PGME represents propylene glycol monomethyl ether.

這些有機溶劑之組合中，以2-1~2-10、2-14~2-17、 2-19~2-25、2-29~2-32、2-34~2-40或2-44~2-46的組合為佳。較佳為2-1~2-10、2-14~2-17、2-19~2-2-25、2-32或2-38-2-40之組合。特佳為2-2、2-8~2-10、2-17、2-23~2-25、2-32或2-38~2-40之組合。 Among these organic solvent combinations, 2-1~2-10, 2-14~2-17, A combination of 2-19~2-25, 2-29~2-32, 2-34~2-40 or 2-44~2-46 is preferred. Preferably, it is a combination of 2-1 to 2-10, 2-14 to 2-17, 2-19 to 2-2-25, 2-32 or 2-38-2-40. Particularly preferred is a combination of 2-2, 2-8~2-10, 2-17, 2-23~2-25, 2-32 or 2-38~2-40.

本發明的液晶配向處理劑中，以不損害本發明之效果下，可導入具有環氧基、異氰酸酯基、氧雜環丁烷基或環碳酸酯基之交聯性化合物、具有選自羥基、羥基烷基及低級烷氧基烷基所成群之至少1種取代基的交聯性化合物、或具有聚合性不飽和鍵之交聯性化合物。這些取代基或聚合性不飽和鍵可於交聯性化合物中具有2個以上為佳。 In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group may be introduced without damaging the effects of the present invention, and has a hydroxyl group selected from the group consisting of A crosslinkable compound having at least one substituent grouped of a hydroxyalkyl group and a lower alkoxyalkyl group, or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds may preferably have two or more of the crosslinkable compounds.

作為具有環氧基或異氰酸酯基之交聯性化合物，例如可舉出雙酚丙酮縮水甘油醚、酚清漆環氧樹脂、甲酚清漆環氧樹脂、三縮水甘油基三聚異氰酸酯、四縮水甘油基胺基二伸苯、四縮水甘油基-m-二甲苯二胺、四縮水甘油基-1,3-雙(胺基乙基)環己烷、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、雙酚六氟乙醯二縮水甘油醚、1,3-雙(1-(2,3-環氧基丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧基丙氧基)八氟聯苯、三縮水甘油基-p-胺基酚、四縮水甘油基間二甲苯二胺、2-(4-(2,3-環氧基丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧基丙氧基)苯基)乙基)苯基)丙烷、1,3-雙(4-(1-(4-(2,3-環氧基丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧基丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol varnish epoxy resin, cresol epoxide epoxy resin, triglycidyl trimer isocyanate, and tetraglycidyl group. Amino diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl Glycidyl etherethane, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2 -trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine 2-(4-(2,3-Epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl) Ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-) (2,3-Epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

作為具有氧雜環丁烷基之交聯性化合物，係為具有至少2個以下述式〔3〕所示氧雜環丁烷基的交聯性化合物。 The crosslinkable compound having an oxetanyl group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [3].

具體為下述式〔3-1〕~〔3-11〕所示交聯性化合物。 Specifically, it is a crosslinkable compound represented by the following formula [3-1] to [3-11].

作為具有環碳酸酯基之交聯性化合物為，具有至少2個以下述式〔4〕所示環碳酸酯基的交聯性化合物。 The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [4].

具體的為下述式〔4-1〕~〔4-37〕所示交聯性化合物。 Specifically, it is a crosslinkable compound represented by the following formula [4-1] to [4-37].

(式〔4-24〕中，n為1~5的整數。式〔4-25〕中，n為1~5的整數。式〔4-36〕中，n為1~100的整數。式〔4-37〕中，n為1~10的整數。) (In the formula [4-24], n is an integer of 1 to 5. In the formula [4-25], n is an integer of 1 to 5. In the formula [4-36], n is an integer of 1 to 100. In [4-37], n is an integer from 1 to 10.)

且，可舉出具有下述式〔4-38〕~〔4-40〕所示至少1種結構的聚矽氧烷。 Further, polyfluorene oxide having at least one structure represented by the following formula [4-38] to [4-40] can be given.

(式〔4-38〕~〔4-40〕中，R₁、R₂、R₃、R₄及R₅各獨立為式〔4〕所示結構、氫原子、羥基、碳數1~10的烷基、烷氧基、脂肪族環或芳香族環，至少1個為式〔4〕所示結構。) (In the formula [4-38] to [4-40], R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} each independently a structure represented by the formula [4], a hydrogen atom, a hydroxyl group, and a carbon number of 1 to 10; At least one of an alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring is a structure represented by the formula [4].

更具體可舉出下述式〔4-41〕及式〔4-42〕之化合物。 More specifically, a compound of the following formula [4-41] and formula [4-42] can be given.

(式〔4-42〕中，n為1~10的整數。) (In the formula [4-42], n is an integer of 1 to 10.)

作為具有選自羥基及烷氧基所成群之至少1種取代基的交聯性化合物，例如可舉出具有羥基或烷氧基之胺基樹脂、例如、三聚氰胺樹脂、尿素樹脂、鳥嘌呤胺樹脂、甘脲-甲醛樹脂、琥珀二醯胺-甲醛樹脂、乙烯尿素-甲醛樹脂等。具體可使用胺基之氫原子為羥甲基及/或烷氧基甲基所取代的三聚氰胺衍生物、苯並鳥嘌呤胺衍生物、或甘脲。三聚氰胺衍生物及苯並鳥嘌呤胺衍生物可以2量體或3量體形式存在。這些在每1個三嗪環中，平均具有3個以上6個以下的羥甲基或烷氧基甲基為佳。 The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a guanamine. Resin, glycoluril-formaldehyde resin, amber diamine-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group and/or an alkoxymethyl group can be used. The melamine derivative and the benzoguanamine derivative may be present in two or three volumes. These are preferably an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per one triazine ring.

作為如此三聚氰胺衍生物或苯並鳥嘌呤胺衍生物之例子，可舉出販賣品之每個三嗪環，甲氧基甲基的平均3.7個被取代之MX-750、每個三嗪環，甲氧基甲基的平均5.8個被取代之MW-30(以上為三和化學製)或CYMEL300、301、303、350、370、771、325、327、703、712等甲氧基甲基化三聚氰胺、CYMEL235、236、238、212、253、254等甲氧基甲基化丁氧基甲基化三聚氰胺、CYMEL506、508等丁氧基甲基化三聚氰胺、如CYMEL1141的含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、如 CYMEL1123的甲氧基甲基化乙氧基甲基化苯並鳥嘌呤胺、如CYMEL1123-10的甲氧基甲基化丁氧基甲基化苯並鳥嘌呤胺、如CYMEL1128的丁氧基甲基化苯並鳥嘌呤胺、如CYMEL1125-80的羧基含有甲氧基甲基化乙氧基甲基化苯並鳥嘌呤胺(以上為三井Cyanamid製)等。又，作為甘脲之例子，可舉出如CYMEL1170之丁氧基甲基化甘脲、如CYMEL1172之羥甲基化甘脲、如Powdering1174之甲氧基羥甲基化甘脲等。 As an example of such a melamine derivative or a benzoguanamine derivative, each triazine ring of a commercial product, an average of 3.7 substituted MX-750 of a methoxymethyl group, and each triazine ring, may be mentioned. The average of 5.8 substituted MW-30 of methoxymethyl group (above is manufactured by Sanwa Chemical) or methoxymethylated by CYMEL300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated butoxymethylated melamine such as melamine, CYMEL235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine such as CYMEL506, 508, carboxy group-containing methoxylated group such as CYMEL1141 Isobutoxymethylated melamine, such as Methoxymethylated ethoxylated benzoguanamine of CYMEL1123, methoxymethylated butoxymethylated benzoguanamine such as CYMEL1123-10, butoxylated as CYMEL1128 The benzoguanamine, such as the carboxyl group of CYMEL1125-80, contains methoxymethylated ethoxymethylated benzoguanamine (manufactured by Mitsui Cyanamid) and the like. Further, examples of the glycoluril include butoxymethylated glycoluril such as CYMEL1170, methylolated glycoluril such as CYMEL1172, methoxymethylolated glycoluril such as Powdering 1174, and the like.

作為具有羥基或烷氧基之苯或酚性化合物，例如可舉出1,3,5-參(甲氧基甲基)苯、1,2,4-參(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯、2,6-二羥基甲基-p-tert-丁基酚等。 Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-glycol(methoxymethyl)benzene and 1,2,4-cis (isopropoxymethyl)benzene. 1,4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

具體可舉出如國際公開公報WO2011/132751(2011.10.27公開)之62頁~66頁所揭示的式〔6-1〕~〔6-48〕所示交聯性化合物。 Specifically, a crosslinkable compound represented by the formula [6-1] to [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (2011.10.27) is mentioned.

作為具有聚合性不飽和鍵之交聯性化合物，例如可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯基氧基乙氧基三羥甲基丙烷、甘油聚縮水甘油醚聚(甲基)丙烯酸酯等聚合性不飽和基於分子內具有3個之交聯性化合物；乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二環氧甘油酯二(甲基)丙烯酸酯、羥基新戊酸新戊二醇二(甲基)丙烯酸酯等聚合性不飽和基於分子內具有2個的交聯性化合物；2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基鄰苯二甲酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯、N-羥甲基(甲基)丙烯醯胺等聚合性不飽和基於分子內具有1個之交聯性化合物等。 Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and three. Polymerizable unsaturated groups such as (meth) acrylonitrile ethoxy ethoxy trimethylolpropane and glycerol polyglycidyl ether poly(meth) acrylate based on three crosslinkable compounds in the molecule; ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)propylene Acid ester, neopentyl glycol di(meth) acrylate, ethylene oxide bisphenol A type di(meth) acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexyl Alkanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diminish Polymeric unsaturation such as glyceryl ether di(meth)acrylate, diglycidyl di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, etc. based on intramolecular 2 crosslinkable compounds; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxime-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate Polymeric unsaturated such as ester, glycerol mono(meth)acrylate, 2-(meth)acryloxyethyl phosphate, or N-hydroxymethyl(meth)acrylamide is one based on one molecule. A crosslinkable compound or the like.

且，可使用下述式〔6〕所示化合物。 Further, a compound represented by the following formula [6] can be used.

式〔6〕中，E₁為選自環己烷環、雙環己烷環、苯環、聯苯環、聯三苯基環、萘環、芴環、蒽環及菲環所成群之基，E₂為選自下述式［6a〕及式〔6b〕的基，n為1~4的整數。 In the formula [6], E ₁ is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring. E ₂ is a group selected from the following formulas [6a] and [6b], and n is an integer of 1 to 4.

上述化合物為交聯性化合物之一例，並未限定於此等。 The above compound is an example of a crosslinkable compound, and is not limited thereto.

又，含於本發明之液晶配向處理劑中的交聯性化合物可為1種類或2種類以上組合。 In addition, the crosslinkable compound to be contained in the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

本發明的液晶配向處理劑中，交聯性化合物的含有量對於所有聚合物成分100質量份而言，以0.1~150質量份為佳。進行交聯反應表現目的效果，且欲不要降低液晶配向性，對於所有聚合物成分100質量份而言，以0.1~100質量份為較佳，以1~50質量份為最佳。 In the liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. The effect of the crosslinking reaction is exhibited, and the liquid crystal alignment property is not required to be lowered. It is preferably 0.1 to 100 parts by mass, and preferably 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components.

作為促進使用本發明的液晶配向處理劑所形成之液晶配向膜中之電荷移動，促進使用該液晶配向膜的液晶胞之電荷除去的化合物，可添加國際公開公報WO2011/132751(2011.10.27公開)之第69頁~第73頁所揭示的式〔M1〕~〔M156〕所示氮含有雜環胺化合物。這些胺化合物可直接添加於特定聚合物之溶液，但在適當溶劑下至濃度0.1~10質量%，較佳為1~7質量%之溶液後再添加為佳。作為該溶劑，可如解上述特定聚合物之有機溶劑即可並無特別限定。 In order to promote the charge transfer in the liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention, a compound which removes the charge of the liquid crystal cell using the liquid crystal alignment film is promoted, and International Publication WO2011/132751 (published 2011.10.27) can be added. The nitrogen represented by the formula [M1] to [M156] disclosed on pages 69 to 73 contains a heterocyclic amine compound. These amine compounds may be directly added to a solution of a specific polymer, but it is preferably added in a suitable solvent to a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent can be, for example, an organic solvent of the specific polymer described above, and is not particularly limited.

本發明的液晶配向處理劑，以不損害本發明之效果下，可使用於塗佈液晶配向處理劑時的聚合物被膜之膜厚均勻性或表面平滑性提高的化合物。且亦可使用提高液晶配向膜與基板的密著性之化合物等。 The liquid crystal alignment treatment agent of the present invention can reduce the film thickness of the polymer film used for coating the liquid crystal alignment treatment agent without impairing the effects of the present invention. A compound with improved homogeneity or surface smoothness. Further, a compound which improves the adhesion between the liquid crystal alignment film and the substrate can be used.

作為提高膜厚均勻性或表面平滑性的化合物，可舉出氟系界面活性劑、矽氧系界面活性劑、非離子系界面活性劑等。 Examples of the compound for improving film thickness uniformity or surface smoothness include a fluorine-based surfactant, a ruthenium-based surfactant, and a nonionic surfactant.

更具體為，例如可舉出FtopEF301、EF303、EF352(Tohkem products公司製)、MegafacF171、F173、R-30(大日本油墨公司製)、FluoradFC430、FC431(住友3M公司製)、AsahiguardAG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。這些界面活性劑之使用比率對於含於液晶配向處理劑之所有聚合物成分100質量份而言，以0.01~2質量份為佳，較佳為0.01~1質量份。 More specifically, for example, FtopEF301, EF303, EF352 (made by Tohkem Products Co., Ltd.), Megafac F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (made by Sumitomo 3M), Asahiguard AG710, Surfon S-382 , SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

作為提高液晶配向膜與基板之密著性的化合物具體例，可舉出以下所示官能性矽烷含有化合物或環氧基含有化合物。 Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the functional decane-containing compound or the epoxy group-containing compound described below.

例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙基三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基- 1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己烷二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己烷二醇、N,N,N’,N’，-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二環氧甘油胺基甲基)環己烷、N,N,N’,N’，-四縮水甘油基-4、4’-二胺基二苯基甲烷等。 Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymercaptopropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxyindenyl- 1,4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazaindole Acetate, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide) --3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2, 2-Dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl -m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4 '-Diaminodiphenylmethane and the like.

使用於提高與基板之密著性的化合物時，對於含於液晶配向處理劑之所有聚合物成分100質量份而言，以0.1~30質量份為佳，較佳為1~20質量份。未達0.1質量份時，無法期待密著性提高效果，若比30質量份多時，液晶之配向性會有變差的情況。 When the compound is used to improve the adhesion to the substrate, it is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the adhesion improving effect cannot be expected, and when it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

於本發明的液晶配向處理劑中，可添加上述貧溶劑、交聯性化合物、提高膜厚均勻性或表面平滑性之化合物及與基板密著的化合物以外，以不損害本發明之效果的範圍內，以變化液晶配向膜的介電率或導電性等電氣特性為目的，可添加介電體或導電物質。 In the liquid crystal alignment treatment agent of the present invention, the above-mentioned poor solvent, crosslinkable compound, compound having improved film thickness uniformity or surface smoothness, and a compound adhering to the substrate may be added, so as not to impair the effects of the present invention. A dielectric or a conductive material may be added for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film.

<液晶配向膜．液晶顯示元件> <Liquid alignment film. Liquid crystal display element>

本發明的液晶配向處理劑可經由於基板上之塗佈、燒成後，以磨光處理或光照射等進行配向處理後作為液晶配向膜使用。又，垂直配向用途等情況下，即使未進行配向處理，亦可作為液晶配向膜使用。作為此時所使用的基板，僅為透明性高之基板即可，並無特別限定，除玻璃基板以外，亦可使用丙烯酸基板或聚碳酸酯基板等塑質基板等。由製程之簡單化觀點來看，使用形成使用於液晶驅動的ITO電極等的基板為佳。又，在反射型液晶顯示元件中，若僅為單面基板，亦可使用矽晶圓等不透明基板，作為此時的電極，亦可使用反射鋁等光的材料。 The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being subjected to an alignment treatment by a buffing treatment or a light irradiation or the like after application and baking on a substrate. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even if the alignment treatment is not performed. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplification of the process, it is preferred to use a substrate which forms an ITO electrode or the like for liquid crystal driving. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate, and a material that reflects light such as aluminum can be used as the electrode at this time.

液晶配向處理劑之塗佈方法並無特別限制，工業方法、絲網印刷、柯式印刷、柔版印刷、噴墨法等為一般。作為其他塗佈方法，有浸漬法、輥塗佈法、Slit Coater法、轉動子法、噴霧法等，可視必要使用彼等。 The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrial methods, screen printing, offset printing, flexographic printing, and inkjet methods are common. Other coating methods include a dipping method, a roll coating method, a Slit Coater method, a rotor method, a spray method, and the like, and they may be used as necessary.

將液晶配向處理劑塗佈於基板上後，藉由加熱板、熱循環型烤箱或IR(紅外線)型烤箱等加熱手段在50~300℃，較佳為80~250℃下使溶劑蒸發並成為聚合物被膜。燒成後之聚合物被膜厚度，若過厚時，對於液晶顯示元件之消費電力層面上為不利，若過薄時，會降低液晶顯示元件之信頼性，故以5~300nm為佳，較佳為10~100nm。 After the liquid crystal alignment agent is applied onto the substrate, the solvent is evaporated at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. Polymer film. When the thickness of the polymer film after firing is too thick, it is disadvantageous for the power consumption level of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm. It is 10~100nm.

將液晶使其為水平配向或傾斜配向時，將燒成後的聚合物被膜以磨光或偏光紫外線照射等處理。 When the liquid crystal is horizontally aligned or obliquely aligned, the polymer film after firing is treated by buffing or polarized ultraviolet irradiation or the like.

本發明的液晶顯示元件藉由上述手法，由本發明的液晶配向處理劑得到附有液晶配向膜之基板後，以公知方法製造液晶胞，成為液晶顯示元件者。 In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a known method to obtain a liquid crystal display element.

作為液晶胞製作方法，準備液晶配向膜所形成之一對基板，於單面基板的液晶配向膜上散佈間隔物，使液晶配向膜面成為內側，貼合另一單面基板，使液晶減壓注入後封止的方法，於散不間隔物之液晶配向膜面滴入液晶後，貼合基板後進行封止的方法等可例示。 In the liquid crystal cell production method, a pair of substrates formed by the liquid crystal alignment film is prepared, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate, the liquid crystal alignment film surface is formed inside, and the other single-sided substrate is bonded to decompress the liquid crystal. After the method of sealing after the injection, a method in which the liquid crystal is placed on the liquid crystal alignment film surface without the spacer, and the substrate is bonded and sealed is exemplified.

且，本發明的液晶配向處理劑為具備電極的一對基板之間具有液晶層所成，於一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性化合物之液晶組成物，於電極間輸入電壓後，藉由活性能量線之照射及加熱的至少一方，使聚合性化合物進行聚合的步驟所製造的液晶顯示元件亦可使用。其中作為活性能量線，以紫外線為佳。 In the liquid crystal alignment treatment agent of the present invention, a liquid crystal layer is formed between a pair of substrates including electrodes, and a liquid crystal containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates. In the composition, a liquid crystal display element produced by a step of polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray may be used after a voltage is input between the electrodes. Among them, as the active energy ray, ultraviolet rays are preferred.

上述液晶顯示元件為藉由PSA(Polymer Sustained Alignment)方式，控制液晶分子之預傾斜者。在PSA方式中，於液晶材料中混入少量光聚合性化合物，例如光聚合性單體，組裝液晶胞後，於液晶層輸入所定電壓的狀態下於光聚合性化合物以紫外線等進行照射，藉由所生成的聚合物，控制液晶分子的預傾斜。生成聚合物時的液晶分子之配向狀態在除去電壓後亦被記憶者，故藉由控制於液晶層所形成之電場等，可調整液晶分子之預傾斜。又，在PSA方式中，因磨光處理並非必須，故適用於藉由磨光處理難以控制預傾斜的垂直配向型之液晶層形成上。 The liquid crystal display element is a pre-tilt that controls liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, and a liquid crystal cell is assembled, and the photopolymerizable compound is irradiated with ultraviolet rays or the like while a predetermined voltage is applied to the liquid crystal layer. The resulting polymer controls the pretilt of the liquid crystal molecules. The alignment state of the liquid crystal molecules when the polymer is formed is also stored after the voltage is removed. Therefore, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed by the liquid crystal layer or the like. Moreover, in the PSA method, since the buffing process is not necessary, it is suitable for use by the buffing place. It is difficult to control the pre-tilt vertical alignment type liquid crystal layer formation.

即，本發明的液晶顯示元件為，藉由上述手法由本發明之液晶配向處理劑得到附有液晶配向膜之基板後，製作成液晶胞，藉由紫外線的照射及加熱的至少一方，聚合聚合性化合物後控制液晶分子之配向。 In the liquid crystal display device of the present invention, the substrate having the liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and the liquid crystal cell is produced, and at least one of irradiation and heating by ultraviolet rays is used to polymerize and polymerize. The alignment of the liquid crystal molecules is controlled after the compound.

若要舉出PSA方式的液晶胞製作之一例子，可舉出準備液晶配向膜所形成之一對基板，於單面的基板之液晶配向膜上散佈間隔物，使液晶配向膜面成為內側，貼合另一單面之基板，將液晶減壓注入後封止之方法，於散佈間隔物之液晶配向膜面上滴入液晶後，貼合基板進行封止之方法等。 An example of the liquid crystal cell production of the PSA method is a pair of substrates formed by preparing a liquid crystal alignment film, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate to make the liquid crystal alignment film surface inside. A method of bonding a substrate to another single-sided substrate, and injecting the liquid crystal into a post-sealing method, and dropping the liquid crystal on the liquid crystal alignment film surface on which the spacer is dispersed, and sealing the substrate to seal it.

於液晶中，混合藉由熱或紫外線照射進行聚合之聚合性化合物。作為聚合性化合物，可舉出於分子內具有1個丙烯酸酯基或甲基丙烯酸酯基等聚合性不飽和基之化合物。此時，聚合性化合物對於液晶成分的100質量份而言，以0.01~10質量份為佳，較佳為0.1~5質量份。聚合性化合物若未達0.01質量份時，聚合性化合物不會聚合而無法進行液晶之配向控制，若超過10質量份時，未反應之聚合性化合物變多，液晶顯示元件之燒附特性會降低。 In the liquid crystal, a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed. The polymerizable compound may be a compound having a polymerizable unsaturated group such as one acrylate group or methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment control of the liquid crystal cannot be performed. When the amount exceeds 10 parts by mass, the amount of unreacted polymerizable compound increases, and the burning property of the liquid crystal display element decreases. .

製作液晶胞後，於液晶胞一邊輸入交流或直流電壓，一邊照射熱或紫外線，使聚合性化合物聚合。藉此，可控制液晶分子之配向。 After the liquid crystal cell is produced, an alternating current or a direct current voltage is input to the liquid crystal cell, and heat or ultraviolet rays are irradiated to polymerize the polymerizable compound. Thereby, the alignment of the liquid crystal molecules can be controlled.

且，本發明的液晶配向處理劑為適用於經由以下步驟所製造的液晶顯示元件，該步驟為於具備電極之一對基板之間具有液晶層所成，前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性基之液晶配向膜，於電極間輸入電壓的步驟。其中，作為活性能量線以紫外線為佳。 Further, the liquid crystal alignment treatment agent of the present invention is a liquid crystal display element which is suitable for use in the following steps, and the step is to provide one of the electrodes to the substrate A liquid crystal layer is formed between the pair of substrates, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is input between the electrodes. Among them, ultraviolet rays are preferred as the active energy ray.

欲得到含有藉由活性能量線及熱的至少一方進行聚合的聚合性基之液晶配向膜，將含有該聚合性基之化合物添加於液晶配向處理劑中之方法，或使用含有聚合性基之聚合物成分的方法可舉出。本發明之液晶配向處理劑為藉由熱或紫外線之照射，因含有反應之雙鍵部位的特定化合物，故藉由紫外線的照射及加熱的至少一方，可控制液晶分子之配向。 A liquid crystal alignment film containing a polymerizable group which is polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or a polymerization containing a polymerizable group The method of the component is exemplified. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound containing a double bond portion of the reaction by irradiation with heat or ultraviolet rays, the alignment of the liquid crystal molecules can be controlled by at least one of irradiation and heating of ultraviolet rays.

若要舉出液晶胞製作之一例子，準備液晶配向膜所形成之一對基板，於單面基板的液晶配向膜上散佈間隔物，使液晶配向膜面成為內側，貼合另一單面基板，將液晶減壓注入後封止之方法，於散佈間隔物之液晶配向膜面上滴入液晶後貼合基板後進行封止之方法等可舉出。 For example, in the case of liquid crystal cell fabrication, one of the pair of substrates formed by the liquid crystal alignment film is prepared, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate so that the liquid crystal alignment film surface becomes the inner side and the other single-sided substrate is bonded. A method in which a liquid crystal is injected under pressure and then sealed, and a method in which a liquid crystal is dropped onto a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed is exemplified.

製造液晶胞後，一邊於液晶胞輸入交流或直流電壓，一邊照射熱或紫外線，可控制液晶分子之配向。 After the liquid crystal cell is produced, the alignment of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while inputting an alternating current or a direct current voltage to the liquid crystal cell.

如上述，使用本發明之液晶配向處理劑所製作之液晶顯示元件具有優良信頼性，可適用於大畫面且高精細之液晶電視等上。 As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention has excellent signalability and can be applied to a large-screen and high-definition liquid crystal television or the like.

[實施例] [Examples]

以下舉出實施例，對本發明做更詳細說明，但並非解釋為限定於此等。且在實施例及比較例所使用的化合物之簡稱如以下所示。 The present invention will be described in more detail below by way of examples, but not by way of limitation. The abbreviations of the compounds used in the examples and comparative examples are as follows.

(四羧酸二酐) (tetracarboxylic dianhydride)

CBDA：1,2,3,4-環丁烷四羧酸二酐 CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

BODA：雙環〔3,3,0〕辛烷-2,4,6,8-四羧酸二酐 BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

TCA：下述式所示四羧酸二酐 TCA: tetracarboxylic dianhydride represented by the following formula

TDA：下述式所示四羧酸二酐 TDA: tetracarboxylic dianhydride represented by the following formula

(特定側鏈型二胺化合物) (specific side chain type diamine compound)

PCH7DAB：1,3-二胺基-4-〔4-(反-4-n-庚基環己基)苯氧基〕苯 PCH7DAB: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

PBCH5DAB：1,3-二胺基-4-{4-〔反-4-(反-4-n-戊基環己基)環己基〕苯氧基}苯 PBCH5DAB: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

m-PBCH5DABz：1,3-二胺基-5-{4-［4-(反-4-n-戊基環己基)苯基〕苯氧基甲基}苯 m-PBCH5DABz: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)phenyl]phenoxymethyl}benzene

(其他二胺化合物) (other diamine compounds)

p-PDA：p-伸苯二胺 p-PDA: p-phenylenediamine

m-PDA：m-伸苯二胺 m-PDA: m-phenylenediamine

DBA：3,5-二胺基安息香酸 DBA: 3,5-diamino benzoic acid

AP18：1,3-二胺基-4-十八烷氧基苯 AP18: 1,3-diamino-4-octadecyloxybenzene

ColDAB：下述式所示二胺化合物 ColDAB: diamine compound represented by the following formula

(有機溶劑) (Organic solvents)

NEP：N-乙基-2-吡咯烷酮 NEP: N-ethyl-2-pyrrolidone

NMP：N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone

γ-BL：γ丁內酯 γ-BL: γ-butyrolactone

BCS：乙二醇單丁基醚 BCS: ethylene glycol monobutyl ether

ECS：乙二醇單乙基醚 ECS: ethylene glycol monoethyl ether

MC：二乙二醇單甲基醚 MC: diethylene glycol monomethyl ether

EC：二乙二醇單乙基醚 EC: diethylene glycol monoethyl ether

PGME：丙二醇單甲基醚 PGME: propylene glycol monomethyl ether

有關聚醯亞胺前驅物及聚醯亞胺之分子量或醯亞胺化率等物性如以下所示進行測定或評估。 The physical properties such as the molecular weight of the polyimine precursor and the polyimine, or the imidization ratio are measured or evaluated as shown below.

(聚醯亞胺前驅物及聚醯亞胺之分子量測定) (Measurement of molecular weight of polyimine precursors and polyimine)

合成例中之聚醯亞胺的分子量，使用常溫凝膠浸透層析法(GPC)裝置(GPC-101)(昭和電工公司製)、管柱(KD-803、KD-805)(Shodex公司製)，如以下進行測定。 The molecular weight of the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.). ), the measurement was carried out as follows.

管柱溫度：50℃ Column temperature: 50 ° C

溶離液：N,N’-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr．H₂O)為30mmol/L(公升)、磷酸．無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L) Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) is 10ml / L)

流速：1.0ml/分鐘 Flow rate: 1.0ml/min

標準曲線作成用標準樣品：TSK標準聚環氧乙烷(分子量：約900,000、150,000、100,000、及30,000)(Tosoh公司製)及聚乙二醇(分子量：約12,000、4,000、及1,000)(聚合物實驗室公司製)。 Standard curve was prepared using standard samples: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000, and 1,000) (polymerization) Laboratory company).

(醯亞胺化率之測定) (Measurement of sulfhydrylation rate)

合成例中之聚醯亞胺的醯亞胺化率如以下進行測定。將聚醯亞胺粉末20mg放入NMR樣品管(NMR取樣管標準值5(草野科學公司製))，添加氘代二甲基亞碸(DMSO-d6、0.05質量%TMS(四甲基矽烷)混合品)0.53ml，經超音波使其完全溶解。將該溶液使用NMR測定機(JNW-ECA500、日本電子DATUM公司製)測定500MHz之質子NMR。醯亞胺化率係以來自在醯亞胺化前後無變化的結構的質子作為基準質子而決定，使用該質子之波峰積分值、與來自9.5至10.0ppm附近出現的醯胺酸之NH基的質子波峰積分值，藉由以下式子求得。 The oxime imidization ratio of the polyimine in the synthesis example was measured as follows. Put 20mg of polyimine powder into NMR sample tube (NMR sample tube standard value 5 (manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of deuterated dimethyl hydrazine (mixture of DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) was added, and it was completely dissolved by ultrasonic waves. This solution was measured for proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500, manufactured by JEOL Ltd.). The ruthenium imidization ratio is determined by using protons having a structure which does not change before and after imidization as a reference proton, and the peak integral value of the proton and the proton of the NH group derived from 9.5 to 10.0 ppm of proline are present. The peak integral value is obtained by the following formula.

醯亞胺化率(%)=(1-α．x/y)×100 醯 imidization rate (%) = (1-α.x/y) × 100

上述式中，x為來自醯胺酸之NH基的質子波峰積分值，y為基準質子之波峰積分值，α為聚醯胺酸(醯亞胺化率為0%)時的醯胺酸之每個NH基質子之基準質子的個數比率。 In the above formula, x is the integral value of the proton peak derived from the NH group of the proline, y is the peak integral value of the reference proton, and α is the proline acid when the polyproline (the imidization ratio is 0%) The ratio of the number of reference protons per NH matrix.

〔聚醯亞胺及聚醯亞胺酸之合成〕 [Synthesis of Polyimine and Polyimine] <合成例1> <Synthesis Example 1>

將CBDA(5.50g,28.0mmol)、PCH7DAB(3.20g,8.41mmol)、及p-PDA(2.13g,19.7mmol)混合於NEP(32.5g)中，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(1)。該聚醯胺酸的數平均分子量為25,100，重量平均分子量為74,800。 CBDA (5.50 g, 28.0 mmol), PCH7DAB (3.20 g, 8.41 mmol), and p-PDA (2.13 g, 19.7 mmol) were mixed in NEP (32.5 g), and reacted at 40 ° C for 6 hours to obtain a resin. Polylysine solution (1) having a solid concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 74,800.

<合成例2> <Synthesis Example 2>

將BODA(10.2g,40.8mm0l)、PCH7DAB(9.70g,25.5mmol)、及DBA(3.88g,25.5mmol)混合於NEP(42.6g)中，在80℃進行5小時反應。其後，加入CBDA(2.00g,10.2mmol)與NEP(34.8g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(2)。該聚醯胺酸的數平均分子量為24,200，重量平均分子量為64,000。 BODA (10.2 g, 40.8 mmol), PCH7DAB (9.70 g, 25.5 mmol), and DBA (3.88 g, 25.5 mmol) were mixed in NEP (42.6 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (2.00 g, 10.2 mmol) and NEP (34.8 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 64,000.

<合成例3> <Synthesis Example 3>

於在合成例2所得之樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(2)(90.0g)中，加入NEP並稀釋至6質量%後，作為醯亞胺化觸媒加入乙酸酐(11.6g)、及吡啶(8.56g)，在80℃進行4小時反應。將該反應溶液投入甲醇(1800ml)中，將所得之沉澱物經過濾並分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(3)。該聚醯亞胺的醯亞胺化率為57%，數平均分子量為21,300，重量平均分子量為51,500。 In the polyamic acid solution (2) (90.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2, NEP was added and diluted to 6% by mass, and then acetic anhydride was added as a ruthenium catalyst. (11.6 g) and pyridine (8.56 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (1800 ml), and the resulting precipitate was filtered and separated. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (3). The polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 21,300, and a weight average molecular weight of 51,500.

<合成例4> <Synthesis Example 4>

將BODA(6.89g,27.5mmol)、PBCH5DAB(5.21g,12.0mmol)、及DBA(3.42g,22.5mmol)混合於NEP(28.1g)中，在80℃進行5小時反應。其後，加入CBDA( 1.35g,6.88mmol)與NEP(22.4g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 BODA (6.89 g, 27.5 mmol), PBCH5DAB (5.21 g, 12.0 mmol), and DBA (3.42 g, 22.5 mmol) were mixed in NEP (28.1 g), and the reaction was carried out at 80 ° C for 5 hours. Then, join CBDA ( 1.35 g, 6.88 mmol) and NEP (22.4 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(60.0g)中加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(13.5g)、及吡啶(9.80g)，在90℃進行3小時反應。將該反應溶液投入於甲醇(1500ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(4)。該聚醯亞胺的醯亞胺化率為79%，數平均分子量為19,200，重量平均分子量為48,200。 After adding NEP to the obtained polyamic acid solution (60.0 g) and diluting to 6 mass%, acetic anhydride (13.5 g) and pyridine (9.80 g) were added as a ruthenium catalyzed catalyst at 90 ° C. 3 hours reaction. The reaction solution was poured into methanol (1500 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazide conversion ratio of 79%, a number average molecular weight of 19,200, and a weight average molecular weight of 48,200.

<合成例5> <Synthesis Example 5>

將BODA(5.95g,23.8mmol)、m-PBCH5DABz(4.56g,10.2mmol)、及p-PDA(2.57g,23.8mmol)在NEP(25.0g)中混合，在80℃進行5小時反應。其後，加入CBDA(2.00g,10.2mmol)與NEP(20.3g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 BODA (5.95 g, 23.8 mmol), m-PBCH5DABz (4.56 g, 10.2 mmol), and p-PDA (2.57 g, 23.8 mmol) were mixed in NEP (25.0 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (2.00 g, 10.2 mmol) and NEP (20.3 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(55.0g)加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(12.3g)、及吡啶(9.11g)，在90℃進行3小時反應。將該反應溶液投入於甲醇(1500ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(5)。該聚醯亞胺之醯亞胺化率為80%，數平均分子量為21,500，重量平均分子量為53,800。 After the NEPP was added to the obtained polyaminic acid solution (55.0 g) and diluted to 6% by mass, acetic anhydride (12.3 g) and pyridine (9.11 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 90 ° C. Hour response. The reaction solution was poured into methanol (1500 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyamidimide has a ruthenium imidation rate of 80%, and the number is flat. The average molecular weight was 21,500 and the weight average molecular weight was 53,800.

<合成例6> <Synthesis Example 6>

將TCA(4.50g,20.1mmol)、PCH7DAB(2.29g,6.02mmol)、及m-PDA(1.52g,14.1mmol)混合於NEP(24.9g)中，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(6)。該聚醯胺酸的數平均分子量為25,100，重量平均分子量為71,900。 TCA (4.50 g, 20.1 mmol), PCH7DAB (2.29 g, 6.02 mmol), and m-PDA (1.52 g, 14.1 mmol) were mixed in NEP (24.9 g), and reacted at 40 ° C for 6 hours to obtain a resin. A polyaminic acid solution (6) having a solid content concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 71,900.

<合成例7> <Synthesis Example 7>

將TCA(7.25g,32.3mmol)、PBCH5DAB(4.20g,9.71mmol)、及DBA(3.44g,22.6mmol)混合於NEP(44.7g)中，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 TCA (7.25 g, 32.3 mmol), PBCH5DAB (4.20 g, 9.71 mmol), and DBA (3.44 g, 22.6 mmol) were mixed in NEP (44.7 g), and reacted at 40 ° C for 6 hours to obtain a resin solid content. A polyaminic acid solution having a concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(50.0g)中加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(6.05g)、及吡啶(4.73g)，在80℃進行4小時反應。將該反應溶液投入於甲醇(900ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(7)。該聚醯亞胺之醯亞胺化率為54%，數平均分子量為21,800，重量平均分子量為56,200。 After adding NEP to the obtained polyaminic acid solution (50.0 g) and diluting to 6 mass%, acetic anhydride (6.05 g) and pyridine (4.73 g) were added as a ruthenium catalyzed catalyst at 80 ° C. 4 hours reaction. The reaction solution was poured into methanol (900 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 54%, a number average molecular weight of 21,800, and a weight average molecular weight of 56,200.

<合成例8> <Synthesis Example 8>

將TDA(2.98g,9.92mmol)、PCH7DAB(3.78g,9.93 mmol)、及DBA(3.53g,23.2mmol)混合於NEP(24.5g)中，在80℃進行5小時反應。其後，加入CBDA(4.55g,23.2mmol)與NEP(20.1g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 TDA (2.98g, 9.92mmol), PCH7DAB (3.78g, 9.93 Methyl) and DBA (3.53 g, 23.2 mmol) were mixed in NEP (24.5 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (4.55 g, 23.2 mmol) and NEP (20.1 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(50.0g)中加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(11.1g)、及吡啶(8.05g)，在90℃進行3小時反應。將該反應溶液投入於甲醇(1500ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，聚醯亞胺粉末(8)。該聚醯亞胺之醯亞胺化率為76%，數平均分子量為20,700，重量平均分子量為52,500。 After adding NEP to the obtained polyamic acid solution (50.0 g) and diluting to 6 mass%, acetic anhydride (11.1 g) and pyridine (8.05 g) were added as a ruthenium amide catalyst, and it was carried out at 90 ° C. 3 hours reaction. The reaction solution was poured into methanol (1500 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a hydrazine imidation ratio of 76%, a number average molecular weight of 20,700, and a weight average molecular weight of 52,500.

<合成例9> <Synthesis Example 9>

將TDA(3.29g,11.0mmol)、PBCH5DAB(4.74g,11.0mmol)、及p-PDA(2.76g,25.5mmol)混合於NEP(26.1g)中，在80℃進行5小時反應。其後，加入CBDA(5.01g,25.5mmol)與NEP(21.3g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 TDA (3.29 g, 11.0 mmol), PBCH5DAB (4.74 g, 11.0 mmol), and p-PDA (2.76 g, 25.5 mmol) were mixed in NEP (26.1 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (5.01 g, 25.5 mmol) and NEP (21.3 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(50.5g)中加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(11.2g)、及吡啶(8.21g)，在90℃進行3小時反應。將該反應溶液投入於甲醇(1500ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(9)。該聚醯亞胺之醯亞胺化率為80%，數平均分子量為20,100，重量平均分子量為50,200。 After adding NEP to the obtained polyaminic acid solution (50.5 g), and diluting to 6 mass%, acetic anhydride (11.2 g) and pyridine (8.21 g) were added as a ruthenium amide catalyst, and it was carried out at 90 ° C. 3 hours reaction. The reaction solution was poured into methanol (1500 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a poly Yttrium imide powder (9). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 20,100, and a weight average molecular weight of 50,200.

<合成例10> <Synthesis Example 10>

將TDA(3.05g,10.2mmol)、m-PBCH5DABz(4.54g,10.2mmol)、及DBA(3.61g,23.7mmol)混合於NEP(26.2g)中，在80℃進行5小時反應。其後，加入CBDA(4.65g,23.7mmol)與NEP(21.4g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液。 TDA (3.05 g, 10.2 mmol), m-PBCH5DABz (4.54 g, 10.2 mmol), and DBA (3.61 g, 23.7 mmol) were mixed in NEP (26.2 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (4.65 g, 23.7 mmol) and NEP (21.4 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

於所得之聚醯胺酸溶液(50.0g)中加入NEP，稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(11.2g)、及吡啶(8.24g)，在90℃進行3小時反應。將該反應溶液投入於甲醇(1500ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(10)。該聚醯亞胺之醯亞胺化率為80%，數平均分子量為20,500，重量平均分子量為52,900。 After adding NEP to the obtained polyaminic acid solution (50.0 g), and diluting to 6 mass%, acetic anhydride (11.2 g) and pyridine (8.24 g) were added as a ruthenium amide catalyst, and it was carried out at 90 ° C. 3 hours reaction. The reaction solution was poured into methanol (1500 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 20,500, and a weight average molecular weight of 52,900.

<合成例11> <Synthesis Example 11>

將BODA(5.21g,20.8mmol)、PCH7DAB(4.95g,13.0mmol)、及DBA(1.98g,13.0mmol)混合於NMP(21.7g)中，在80℃進行5小時反應。其後，加入CBDA(1.02g,5.20mmol)與NMP(17.8g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(11)。該聚醯胺酸的數平均分子量為25,100，重量平均分子量為65,900。 BODA (5.21 g, 20.8 mmol), PCH7DAB (4.95 g, 13.0 mmol), and DBA (1.98 g, 13.0 mmol) were mixed in NMP (21.7 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (1.02 g, 5.20 mmol) and NMP (17.8 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass. Liquid (11). The polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 65,900.

<合成例12> <Synthesis Example 12>

將BODA(6.38g,25.5mmol)、AP18(6.00g,15.9mmol)、及DBA(2.45g,16.1mmol)混合於NMP(26.5g)中，在80℃進行5小時反應。其後，加入CBDA(1.25g,6.37mmol)與NMP(21.7g)，在40℃下進行6小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(12)。該聚醯胺酸的數平均分子量為18,900，重量平均分子量為54,800。 BODA (6.38 g, 25.5 mmol), AP18 (6.00 g, 15.9 mmol), and DBA (2.45 g, 16.1 mmol) were mixed in NMP (26.5 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA (1.25 g, 6.37 mmol) and NMP (21.7 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (12) having a resin solid concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 18,900 and a weight average molecular weight of 54,800.

<合成例13> <Synthesis Example 13>

於在合成例12所得之樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(12)(50.0g)中，加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(6.23g)、及吡啶(4.65g)。在80℃進行4小時反應。將該反應溶液投入於甲醇(1000ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(13)。該聚醯亞胺之醯亞胺化率為58%，數平均分子量為16,900，重量平均分子量為43,800。 In the polyamic acid solution (12) (50.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 12, NMP was added and diluted to 6% by mass, and then added as a ruthenium catalyst. Anhydride (6.23 g) and pyridine (4.65 g). The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (13). The polyimine had a hydrazine imidation ratio of 58%, a number average molecular weight of 16,900, and a weight average molecular weight of 43,800.

<合成例14> <Synthesis Example 14>

將BODA(6.89g,27.5mmol)、ColDAB(5.40g, 10.3mmol)、及DBA(3.68g,24.2mmol)混合於NEP(28.6g)中，在80℃進行5.5小時反應。其後，加入CBDA(1.35g,6.88mmol)與NEP(23.4g)，在40℃進行7小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(14)。該聚醯胺酸的數平均分子量為20,100，重量平均分子量為59,800。 BODA (6.89g, 27.5mmol), ColDAB (5.40g, 10.3 mmol) and DBA (3.68 g, 24.2 mmol) were mixed in NEP (28.6 g), and the reaction was carried out at 80 ° C for 5.5 hours. Thereafter, CBDA (1.35 g, 6.88 mmol) and NEP (23.4 g) were added, and the mixture was reacted at 40 ° C for 7 hours to obtain a polyamic acid solution (14) having a resin solid concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 20,100 and a weight average molecular weight of 59,800.

<合成例15> <Synthesis Example 15>

將BODA(6.74g,26.9mmol)、ColDAB(5.28g,10.1mmol)、及DBA(3.60g,23.7mmol)混合於NMP(27.9g)中，在80℃進行5.5小時反應。其後，加入CBDA(1.32g,6.73mmol)與NMP(22.9g)，在40℃進行7小時反應，得到樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(15)。該聚醯胺酸的數平均分子量為19,900，重量平均分子量為59,100。 BODA (6.74 g, 26.9 mmol), ColDAB (5.28 g, 10.1 mmol), and DBA (3.60 g, 23.7 mmol) were mixed in NMP (27.9 g), and the reaction was carried out at 80 ° C for 5.5 hours. Then, CBDA (1.32 g, 6.73 mmol) and NMP (22.9 g) were added, and the reaction was carried out at 40 ° C for 7 hours to obtain a polyaminic acid solution (15) having a resin solid concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 19,900 and a weight average molecular weight of 59,100.

<合成例16> <Synthesis Example 16>

於在合成例15所得之樹脂固體成分濃度為25.0質量%的聚醯胺酸溶液(15)(55.0g)，加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(6.81g)、及吡啶(5.07g)，在80℃進行4小時反應。將該反應溶液投入甲醇(1100ml)中，將所得之沉澱物經過濾分離。該沉澱物以甲醇洗淨，以100℃進行減壓乾燥，得到聚醯亞胺粉末(16)。該聚醯亞胺的醯亞胺化率為57%，數平均分子量為15,900，重量平均分子量為45,100。 The polyamic acid solution (15) (55.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 15 was added to NMP and diluted to 6% by mass, and then acetic anhydride was added as a ruthenium catalyst. (6.81 g) and pyridine (5.07 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (1100 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (16). The polyamidimide has a ruthenium iodide ratio of 57%, a number average molecule The amount was 15,900 and the weight average molecular weight was 45,100.

將本發明的聚醯胺酸及聚醯亞胺歸納於表4所示。 The polyamic acid and polyimine of the present invention are summarized in Table 4.

〔液晶配向處理劑之調製〕 [Modulation of Liquid Crystal Alignment Treatment Agent]

下述實施例1~34及比較例1~12係為液晶配向處理劑之調製例，皆使用於液晶配向處理劑之評估上。 The following Examples 1 to 34 and Comparative Examples 1 to 12 are examples of preparation of a liquid crystal alignment treatment agent, and are used for evaluation of a liquid crystal alignment treatment agent.

使用實施例及比較例所得之液晶配向處理劑，進行「液晶配向處理劑之印刷性評估」、「液晶配向處理劑之噴墨塗佈性評估」、「液晶胞之製作(一般胞)」、「液晶配向性及預傾角之評估(一般胞)」、「液晶胞之製作(PSA胞)」、及「液晶配向性之評估(PSA胞)」。 Using the liquid crystal alignment treatment agent obtained in the examples and the comparative examples, "the evaluation of the printability of the liquid crystal alignment treatment agent" and the "liquid crystal alignment treatment agent" were carried out. "Ink coating evaluation", "Liquid cell production (general cell)", "Liquid alignment and pretilt evaluation (general cell)", "Liquid cell production (PSA cell)", and "Liquid alignment" Evaluation (PSA cell).

(液晶配向處理劑之印刷性評估) (Printability evaluation of liquid crystal alignment agent)

使用實施例及比較例所得之液晶配向處理劑進行印刷性評估。於印刷機使用簡易印刷機S15型(日本照片印刷公司製)。印刷為於經洗淨的鉻蒸鍍基板上，印刷面積為80mm×80mm，印壓為0.2mm，捨去基板為5片，自印刷至假乾燥的時間為90秒，假乾燥為於加熱板上在70℃，5分鐘之條件下進行。 The printability evaluation was carried out using the liquid crystal alignment treatment agents obtained in the examples and the comparative examples. A simple printing machine S15 type (manufactured by Nippon Photo Printing Co., Ltd.) was used for the printing press. Printing on the washed chrome-vapor-deposited substrate, the printing area is 80mm × 80mm, the printing pressure is 0.2mm, the substrate is 5 pieces, the time from printing to the dummy drying is 90 seconds, and the dummy drying is the heating plate. The reaction was carried out at 70 ° C for 5 minutes.

進行所得之塗膜的針孔評估、液晶配向膜端部的直線性評估、及液晶配向膜端部之***評估。 The evaluation of the pinhole of the obtained coating film, the evaluation of the linearity of the end portion of the liquid crystal alignment film, and the evaluation of the bulging of the end portion of the liquid crystal alignment film were carried out.

針孔之評估為，將塗膜在鈉燈下以目視觀察進行。具體為計算於液晶配向膜上所確認之針孔數，針孔數越少表示塗佈性越優良。 The pinhole was evaluated by visual observation under a sodium lamp. Specifically, the number of pinholes confirmed on the liquid crystal alignment film was calculated, and the smaller the number of pinholes, the more excellent the coatability.

液晶配向膜之端部的直線性之評估為，對於印刷方向，將右側端部的塗膜以光學顯微鏡(Nikon公司製，ECLIPSE E600WPOL)進行觀察而進行。具體為藉由光學顯微鏡，將倍率成為25倍下進行觀察，所得之塗膜影像的圖1中之3與4的差，即測定圖1中之A的長度。所有塗膜影像為同一倍率下得到者。A的長度越短，液晶配向膜之端部的直線性越優良。 The linearity of the end portion of the liquid crystal alignment film was evaluated by observing the coating film on the right end portion with an optical microscope (manufactured by Nikon Corporation, ECLIPSE E600WPOL) for the printing direction. Specifically, the magnification was changed to 25 times by an optical microscope, and the difference between 3 and 4 in FIG. 1 of the obtained film image was measured, that is, the length of A in FIG. 1 was measured. All film images were obtained at the same magnification. The shorter the length of A, the more excellent the linearity of the end portion of the liquid crystal alignment film.

液晶配向膜之端部***的評估為，對於印刷方向，將右側端部之塗膜以光學顯微鏡進行觀察。具體為藉由光學顯微鏡，在倍率25倍下進行觀察，測定所得之塗膜影像(圖2)中的B長度。所有塗膜影像皆為得到同一倍率者。該B之長度越短，液晶配向膜之端部***5越優良。 The evaluation of the end ridge of the liquid crystal alignment film is, for the printing direction, The coating film on the right end was observed with an optical microscope. Specifically, the length of B in the obtained coating film image (Fig. 2) was measured by observing at a magnification of 25 times by an optical microscope. All film images are obtained by the same magnification. The shorter the length of B, the more excellent the end ridge 5 of the liquid crystal alignment film.

於表8~表10表示在實施例及比較例所得之液晶配向膜的針孔數、A的長度及B的長度。 Tables 8 to 10 show the number of pinholes, the length of A, and the length of B in the liquid crystal alignment films obtained in the examples and the comparative examples.

(液晶配向處理劑之噴墨塗佈性評估) (Evaluation of inkjet coating properties of liquid crystal alignment treatment agent)

使用在實施例7所得之液晶配向處理劑(7)及實施例12所得之液晶配向處理劑(12)，進行噴墨塗佈性評估。於噴墨塗佈機，使用HIS-200(Hitachi Plant Technologies公司製)。塗佈為於經洗淨的ITO(氧化銦錫)蒸鍍基板上，塗佈面積為70mm×70mm，噴嘴間隔為0.423mm，掃描間隔為0.5mm，塗佈速度為40mm/秒，自塗佈至假乾燥的時間為60秒、及假乾燥為於加熱板上在70℃，5分鐘之條件下進行。 The liquid crystal alignment treatment agent (7) obtained in Example 7 and the liquid crystal alignment treatment agent (12) obtained in Example 12 were used for evaluation of inkjet coating properties. For the inkjet coater, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was applied to a cleaned ITO (Indium Tin Oxide) vapor-deposited substrate with a coating area of 70 mm × 70 mm, a nozzle interval of 0.423 mm, a scanning interval of 0.5 mm, a coating speed of 40 mm/sec, and self-coating. The time to the dummy drying was 60 seconds, and the dummy drying was carried out on a hot plate at 70 ° C for 5 minutes.

將所得之塗膜的針孔之評估與「液晶配向處理劑之印刷性評估」的相同條件進行。將實施例7、12中之針孔的評估結果如表8所示。 The evaluation of the pinholes of the obtained coating film was carried out under the same conditions as in the "evaluation of the printability of the liquid crystal alignment agent". The evaluation results of the pinholes in Examples 7 and 12 are shown in Table 8.

(液晶胞之製作(一般胞)) (production of liquid crystal cell (general cell))

將實施例及比較例所得之液晶配向處理劑於附有30mm×40mm的ITO電極之基板的ITO面上進行轉動塗佈，於加熱板上在80℃進行5分鐘，在熱循環型無塵烤箱中在 220℃下進行30分鐘加熱處理，得到膜厚為100nm之附有聚醯亞胺液晶配向膜之ITO基板。將該ITO基板的塗膜面，在輥徑為120mm的磨光裝置下使用嫘縈布，在輥轉數為1000rpm、輥進行速度為50mm/sec、及押入量為0.1mm之條件下進行磨光處理。 The liquid crystal alignment treatment agents obtained in the examples and the comparative examples were spin-coated on the ITO surface of a substrate having an ITO electrode of 30 mm × 40 mm, and were subjected to a hot plate at 80 ° C for 5 minutes in a heat cycle type dust-free oven. In The film was heat-treated at 220 ° C for 30 minutes to obtain an ITO substrate having a polyimide film alignment film having a film thickness of 100 nm. The coating film surface of the ITO substrate was ground using a crepe cloth under a polishing apparatus having a roll diameter of 120 mm, and the number of rolls was 1000 rpm, the roll speed was 50 mm/sec, and the amount of pushing was 0.1 mm. Light processing.

準備2片附有液晶配向膜之ITO基板，將液晶配向膜面作為內側，夾著6μm的間隔物之組合，以密封劑接著周圍製作成空胞。於該空胞以減壓注入法，注入MLC-6608(Merck．Japan公司製)，封止注入口後得到液晶胞(一般胞)。 Two ITO substrates with a liquid crystal alignment film were prepared, and a liquid crystal alignment film surface was used as an inner side, and a combination of spacers of 6 μm was interposed therebetween, and a hollow cell was formed around the sealing agent. In this empty cell, MLC-6608 (manufactured by Merck. Japan Co., Ltd.) was injected under a reduced pressure injection method, and a liquid crystal cell (general cell) was obtained after the injection port was sealed.

(液晶配向性及預傾角之評估(一般胞)) (Evaluation of liquid crystal alignment and pretilt angle (general cell))

使用上述所得之液晶胞，進行液晶配向性及預傾角之評估。液晶配向性為，將液晶胞以偏光顯微鏡(Nikon公司製，ECLIPSE E600WPOL)進行觀察，並確認配向缺陷之有無。 The liquid crystal alignment and the pretilt angle were evaluated using the liquid crystal cell obtained above. The alignment property of the liquid crystal was observed by a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation), and the presence or absence of alignment defects was confirmed.

又，預傾角為液晶注入後，在95℃下進行5分鐘加熱處理後。再以120℃下進行5小時加熱處理後進行測定。且對於液晶注入後在95℃以5分鐘加熱處理的液晶胞，照射以365nm換算為10J/cm²的紫外線後，測定預傾角。 Further, after the pretilt angle was liquid crystal injection, heat treatment was performed at 95 ° C for 5 minutes. The measurement was carried out by heating at 120 ° C for 5 hours. Further, the liquid crystal cell which was heat-treated at 95 ° C for 5 minutes after the liquid crystal injection was irradiated with ultraviolet rays of 10 J/cm ² in terms of 365 nm, and then the pretilt angle was measured.

對於在95℃進行5分鐘加熱處理後的預傾角，在120℃進行5小時過熱處理後，或照射紫外線後之預傾角的變化越小，對於熱或紫外線之預傾角的安定性越高。 The pretilt angle after heat treatment at 95 ° C for 5 minutes was carried out after heating at 120 ° C for 5 hours, or the change in the pretilt angle after irradiation with ultraviolet rays was smaller, and the stability with respect to the pretilt angle of heat or ultraviolet rays was higher.

且，預傾角為使用PAS-301(ELSICON公司製)，在室溫進行測定。且紫外線之照射為使用卓上型UV硬化裝置(HCT3B28HEX-1)(Senraito製)進行。 Moreover, the pretilt angle is PAS-301 (manufactured by ELSICON), The measurement was carried out at room temperature. Further, the irradiation of ultraviolet rays was carried out using a top-type UV curing device (HCT3B28HEX-1) (manufactured by Senraito).

實施例及比較例所得之液晶胞的液晶配向性及預傾角之結果如表11~表13所示。 The liquid crystal alignment properties and pretilt angles of the liquid crystal cells obtained in the examples and the comparative examples are shown in Tables 11 to 13.

(液晶胞之製作(PSA胞)) (Production of liquid crystal cell (PSA cell))

將實施例5所得之液晶配向處理劑(5)、實施例6所得之液晶配向處理劑(6)、實施例11所得之液晶配向處理劑(11)、實施例17所得之液晶配向處理劑(17)及實施例30所得之液晶配向處理劑(30)，於中心10mm×10mm的圖型間隔20μm之附有ITO電極的基板、與於中心10mm×40mm的附有ITO電極之基板之ITO面上進行轉動塗佈，在加熱板上於80℃進行5分鐘，在熱循環型無塵烤箱中於220℃進行30分鐘加熱處理，得到膜厚100nm之聚醯亞胺塗膜。將塗膜面以純水洗淨，其後在熱循環型無塵烤箱中以100℃進行15分鐘加熱處理，得到附有液晶配向膜之基板。 The liquid crystal alignment treatment agent (5) obtained in Example 5, the liquid crystal alignment treatment agent (6) obtained in Example 6, the liquid crystal alignment treatment agent (11) obtained in Example 11, and the liquid crystal alignment treatment agent obtained in Example 17 ( 17) and the liquid crystal alignment treatment agent (30) obtained in Example 30, a substrate having an ITO electrode with a pattern of 10 mm × 10 mm at a center of 10 mm × 10 mm, and an ITO surface of a substrate having an ITO electrode of 10 mm × 40 mm at the center The coating was applied by spin coating on a hot plate at 80 ° C for 5 minutes, and heat-treated in a heat cycle type dust-free oven at 220 ° C for 30 minutes to obtain a polyimide film having a thickness of 100 nm. The coating film surface was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a substrate with a liquid crystal alignment film.

將該附有液晶配向膜之基板，將液晶配向膜面成為內側，夾著6μm之間隔物之組合，以密封劑接著周圍後製作出空胞。於該空胞藉由減壓注入法，於MLC-6608(Merck．Japan公司製)，將下述式所示聚合性化合物(1)，注入對於MLC-6608之100質量%而言，混合聚合性化合物為0.3質量%之液晶，封止注入口後得到液晶胞。 The substrate on which the liquid crystal alignment film was attached was placed on the inside of the liquid crystal alignment film surface, and a combination of spacers of 6 μm was interposed therebetween, and a sealing agent was applied to the periphery to prepare a cell. In the empty cell, the polymerizable compound (1) represented by the following formula was injected into the MLC-6608 (manufactured by Merck. Japan Co., Ltd.) by a vacuum injection method, and 100% by mass of the MLC-6608 was mixed and polymerized. The compound was 0.3% by mass of liquid crystal, and the liquid crystal cell was obtained after sealing the injection port.

於所得之液晶胞中，一邊輸入交流5V之電壓，使用照度60mW之金屬鹵素燈，阻斷350nm以下之波長，進行以365nm換算為20J/cm²的紫外線照射，得到液晶之配向方向受到控制的液晶胞(PSA胞)。於液晶胞照射紫外線時的照射裝置內之溫度為50℃。 In the obtained liquid crystal cell, a voltage of 5 V was input, and a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was blocked, and ultraviolet irradiation was performed at 20 J/cm ² in terms of 365 nm, whereby the alignment direction of the liquid crystal was controlled. Liquid crystal cell (PSA cell). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

(液晶配向性之評估(PSA胞)) (Evaluation of liquid crystal alignment (PSA cell))

測定所得之液晶胞的紫外線照射前與紫外線照射後的液晶之應答速度。應答速度為測定透過率90%至透過率10%為止的T90→T10。實施例及比較例所得之PSA胞與紫外線照射前之液晶胞相比較，紫外線照射後之液晶胞的應答速度較快，故液晶之配向方向的控制受到確認。 The response speed of the obtained liquid crystal cell before the ultraviolet irradiation and the liquid crystal after the ultraviolet irradiation was measured. The response speed is T90 → T10 from the measurement of the transmittance of 90% to the transmittance of 10%. The PSA cells obtained in the examples and the comparative examples were compared with the liquid crystal cells before the ultraviolet irradiation, and the response speed of the liquid crystal cells after the ultraviolet irradiation was faster, so that the control of the alignment direction of the liquid crystals was confirmed.

又，對於所有液晶胞，藉由偏光顯微鏡觀察，確認液晶呈現均勻配向。 Further, for all the liquid crystal cells, it was confirmed by a polarizing microscope that the liquid crystal exhibited uniform alignment.

以下對於實施例1~34及比較例1~12做詳細說明，對於各例中之液晶配向處理劑的調製條件歸納於表5~7。 Hereinafter, Examples 1 to 34 and Comparative Examples 1 to 12 will be described in detail. The preparation conditions of the liquid crystal alignment treatment agent in each example are summarized in Tables 5 to 7.

又，使用實施例1~34及比較例1~12所得之液晶配向處理劑，進行「液晶配向處理劑之印刷性評估」、「液晶配向處理劑之噴墨塗佈性評估」、「液晶胞之製作(一般胞)」、「液晶配向性及預傾角之評估(一般胞)」、「液晶胞之製作(PSA胞)」、「液晶配向性之評估(PSA胞)」等。其結果歸納於表8~13所示。 In addition, the liquid crystal alignment treatment agents obtained in Examples 1 to 34 and Comparative Examples 1 to 12 were used to perform "evaluation of printability of liquid crystal alignment treatment agent", "evaluation of inkjet coating property of liquid crystal alignment treatment agent", and "liquid crystal cell". Production (general Cell"), "Evaluation of liquid crystal alignment and pretilt angle (general cell)", "production of liquid crystal cell (PSA cell)", "evaluation of liquid crystal alignment (PSA cell)", etc. The results are summarized in Tables 8-13.

<實施例1> <Example 1>

於合成例1所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(1)(10.1g)加入NEP(32.0g)，於25℃進行2小時攪拌後得到液晶配向處理劑(1)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyamic acid solution (1) (10.1 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 was added to NEP (32.0 g), and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(1)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (1), the production or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例2> <Example 2>

於合成例1所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(1)(10.0g)加入NEP(12.1g)、BCS(11.8g)及EC(7.84g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(2)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 was added to NEP (12.1 g), BCS (11.8 g), and EC (7.84 g) at 25 ° C. After stirring for 2 hours, a liquid crystal alignment treatment agent (2) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(2)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (2), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例3> <Example 3>

於合成例2所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(2)(10.0g)中加入NEP(31.7g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(3)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyamic acid solution (2) (10.0 g) of the resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2, NEP (31.7 g) was added at 25 ° C. After stirring for 2 hours, the liquid crystal alignment treatment agent (3) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(3)，依據上述條件下，進行晶胞之製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (3), the fabrication or various evaluation of the unit cell was carried out under the above conditions.

<實施例4> <Example 4>

於合成例2所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(2)(10.0g)加入NEP(14.0g)及BCS(17.6g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(4)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2 was added to NEP (14.0 g) and BCS (17.6 g), and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal. Orientation treatment agent (4). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(4)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (4), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例5> <Example 5>

於合成例3所得之聚醯亞胺粉末(3)(2.55g)加入NEP(40.0g)，在70℃進行24小時攪拌後得到液晶配向處理劑(5)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyimine powder (3) (2.55 g) obtained in Synthesis Example 3 was added to NEP (40.0 g), and the mixture was stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (5). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(5)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (5), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例6> <Example 6>

於合成例3所得之聚醯亞胺粉末(3)(2.54g)加入NEP(14.6g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(7.30g)及BCS(17.9g)，在50℃進行10小時攪拌，得到液晶配向處理劑(6)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyimine powder (3) (2.54 g) obtained in Synthesis Example 3, NEP (14.6 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (7.30 g) and BCS (17.9 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (6). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(6)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (6), the production or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例7> <Example 7>

於合成例3所得之聚醯亞胺粉末(3)(2.50g)中加入NEP(29.7g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(14.8g)及BCS(36.4g)，在50℃進行10小時攪拌，得到液晶配向處理劑(7)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (29.7 g) was added to the polyimine powder (3) (2.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (14.8 g) and BCS (36.4 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (7). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(7)，依據上述條件下，進行「液晶配向處理劑之噴墨塗佈性評估」。 Using the obtained liquid crystal alignment treatment agent (7), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<實施例8> <Example 8>

於合成例3所得之聚醯亞胺粉末(3)(2.55g)加入NEP(17.3g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(8.71g)、BCS(8.01g)及MC(6.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(8)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyimine powder (3) (2.55 g) obtained in Synthesis Example 3, NEP (17.3 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (8.71 g), BCS (8.01 g), and MC (6.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (8). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(8)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (8), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例9> <Example 9>

於合成例3所得之聚醯亞胺粉末(3)(2.56g)中加入NEP(18.7g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(9.40g)、BCS(6.00g)及EC(6.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(9)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (18.7 g) was added to the polyimine powder (3) (2.56 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (9.40 g), BCS (6.00 g), and EC (6.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(9)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (9), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例10> <Example 10>

於合成例3所得之聚醯亞胺粉末(3)(2.55g)加入NEP(17.3g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(8.70g)及PGME(14.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(10)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyimine powder (3) (2.55 g) obtained in Synthesis Example 3, NEP (17.3 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (8.70 g) and PGME (14.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (10). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(10)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (10), the production or various evaluation of the unit cell was carried out under the above conditions.

<實施例11> <Example 11>

於合成例3所得之聚醯亞胺粉末(3)(2.55g)中加入NEP(16.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(6.02g)及BCS(18.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(11)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 Addition of the polyimine powder (3) (2.55 g) obtained in Synthesis Example 3 NEP (16.0 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. NMP (6.02 g) and BCS (18.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (11). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(11)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (11), the production or various evaluation of the unit cell was carried out under the above conditions.

<實施例12> <Example 12>

於合成例3所得之聚醯亞胺粉末(3)(2.50g)中加入NEP(27.6g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(10.3g)及BCS(31.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(12)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (27.6 g) was added to the polyimine powder (3) (2.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (10.3 g) and BCS (31.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (12). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之.液晶配向處理劑(12)，依據上述條件下，進行「液晶配向處理劑的噴墨塗佈性評估」。 Using the obtained liquid crystal alignment treatment agent (12), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<實施例13> <Example 13>

於合成例3所得之聚醯亞胺粉末(3)(2.55g)中加入NEP(16.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(4.02g)及BCS(20.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(13)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.0 g) was added to the polyimine powder (3) (2.55 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (4.02 g) and BCS (20.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (13). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(13)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (13), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例14> <Example 14>

於合成例4所得之聚醯亞胺粉末(4)(2.55g)加入NEP(12.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(6.02g)及BCS(22.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(14)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyimine powder (4) (2.55 g) obtained in Synthesis Example 4 was added to NEP (12.0 g), and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (6.02 g) and BCS (22.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (14). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(14)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (14), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例15> <Example 15>

於合成例4所得之聚醯亞胺粉末(4)(2.57g)中加入NEP(16.1g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(8.10g)及ECS(16.1g)，在50℃進行10小時攪拌，得到液晶配向處理劑(15)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.1 g) was added to the polyimine powder (4) (2.57 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (8.10 g) and ECS (16.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(15)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (15), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例16> <Example 16>

於合成例4所得之聚醯亞胺粉末(4)(2.53g)中加入NEP(18.5g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(9.20g)、BCS(7.93g)及MC(3.97g)，在50℃進行10小時攪拌，得到液晶配向處理劑(16)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液， NEP (18.5 g) was added to the polyimine powder (4) (2.53 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (9.20 g), BCS (7.93 g), and MC (3.97 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (16). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(16)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (16), the production or various evaluation of the unit cell was carried out under the above conditions.

<實施例17> <Example 17>

於合成例4所得之聚醯亞胺粉末(4)(2.55g)中加入NEP(16.0g)在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(10.0g)及BCS(14.1g)，在50℃進行10小時攪拌，得到液晶配向處理劑(17)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.0 g) was added to the polyimine powder (4) (2.55 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (10.0 g) and BCS (14.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (17). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(17)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (17), preparation or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例18> <Example 18>

於合成例4所得之聚醯亞胺粉末(4)(2.55g)中加入NEP(20.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(4.00g)及BCS(16.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(18)該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (20.0 g) was added to the polyimine powder (4) (2.55 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (4.00 g) and BCS (16.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (18). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed. Immediately, it was confirmed to be a homogeneous solution.

使用所得之液晶配向處理劑(18)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (18), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例19> <Example 19>

於合成例5所得之聚醯亞胺粉末(5)(2.55g)加入NEP(12.5g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(3.54g)及BCS(24.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(19)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyimine powder (5) (2.55 g) obtained in Synthesis Example 5, NEP (12.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (3.54 g) and BCS (24.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (19). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(19)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (19), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例20> <Example 20>

於合成例5所得之聚醯亞胺粉末(5)(2.56g)中加入NEP(13.4g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(6.70g)、BCS(16.1g)及MC(4.02g)，在50℃進行10小時攪拌，得到液晶配向處理劑(20)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (13.4 g) was added to the polyimine powder (5) (2.56 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (6.70 g), BCS (16.1 g), and MC (4.02 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (20). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(20)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (20), preparation or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例21> <Example 21>

於合成例5所得之聚醯亞胺粉末(5)(2.55g)加入NEP(12.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(10.0g)及BCS(18.1g)，在50℃進行10小時攪拌，得到液晶配向處理劑(21)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 To the polyimine powder (5) (2.55 g) obtained in Synthesis Example 5, NEP (12.0 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (10.0 g) and BCS (18.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (21). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(21)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (21), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例22> <Example 22>

於合成例5所得之聚醯亞胺粉末(5)(2.55g)中加入NEP(17.8g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(2.00g)及BCS(20.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(22)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (17.8 g) was added to the polyimine powder (5) (2.55 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (2.00 g) and BCS (20.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (22). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(22)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (22), preparation or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例23> <Example 23>

於合成例6所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(6)(10.0g)加入NEP(6.21g)及BCS(25.5g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(23)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 The polyamic acid solution (6) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6 was added to NEP (6.21 g) and BCS (25.5 g), and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal. Orientation treatment agent (23). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(23)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (23), preparation or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例24> <Example 24>

於合成例6所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(6)(10.0g)中加入NEP(16.0g)、BCS( 7.87g)及PGME(7.84g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(24)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.0 g) and BCS were added to the polyaminic acid solution (6) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6. 7.87 g) and PGME (7.84 g) were stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (24). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(24)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (24), the production or various evaluation of the unit cell was carried out under the above conditions.

<實施例25> <Example 25>

於合成例7所得之聚醯亞胺粉末(7)(2.54g)中加入NEP(15.9g)。在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(8.00g)及ECS(15.9g)，在50℃進行10小時攪拌，得到液晶配向處理劑(25)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (15.9 g) was added to the polyimine powder (7) (2.54 g) obtained in Synthesis Example 7. The mixture was stirred at 70 ° C for 24 hours to dissolve. NEP (8.00 g) and ECS (15.9 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (25). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(25)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (25), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例26> <Example 26>

於合成例7所得之聚醯亞胺粉末(7)(2.55g)中加入NEP(17.3g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(8.71g)、BCS(8.01g)及PGME(6.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(26)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (17.3 g) was added to the polyimine powder (7) (2.55 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (8.71 g), BCS (8.01 g), and PGME (6.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (26). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(26)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (26), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例27> <Example 27>

於合成例7所得之聚醯亞胺粉末(7)(2.55g)中加入NEP(20.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(8.00g)、BCS(10.1g)及EC(2.02g)，在50℃進行10小時攪拌，得到液晶配向處理劑(27)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (20.0 g) was added to the polyimine powder (7) (2.55 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (8.00 g), BCS (10.1 g) and EC (2.02 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (27). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(27)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (27), the production or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例28> <Example 28>

於合成例7所得之聚醯亞胺粉末(7)(2.55g)中加入NEP(18.1g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(2.00g)、BCS(12.0g)及ECS(8.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(28)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (18.1 g) was added to the polyimine powder (7) (2.55 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (2.00 g), BCS (12.0 g) and ECS (8.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (28). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(28)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (28), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例29> <Example 29>

於合成例8所得之聚醯亞胺粉末(8)(2.55g)中加入NEP(21.3g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(10.7g)及BCS(8.01g)，在50℃進行10小時攪拌，得到液晶配向處理劑(29)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (21.3 g) was added to the polyimine powder (8) (2.55 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. In this NEP (10.7 g) and BCS (8.01 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (29). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(29)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (29), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例30> <Example 30>

於合成例8所得之聚醯亞胺粉末(8)(2.56g)中加入NEP(26.1g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(8.00g)、BCS(4.00g)及MC(2.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(30)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (26.1 g) was added to the polyimine powder (8) (2.56 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (8.00 g), BCS (4.00 g), and MC (2.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (30). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(30)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (30), cell production or various evaluations were carried out in accordance with the above conditions.

<實施例31> <Example 31>

於合成例9所得之聚醯亞胺粉末(9)(2.55g)中加入NEP(16.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(12.0g)及BCS(12.1g)，在50℃進行10小時攪拌，得到液晶配向處理劑(31)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.0 g) was added to the polyimine powder (9) (2.55 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (12.0 g) and BCS (12.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (31). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(31)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (31), preparation of the unit cell or various evaluations were carried out in accordance with the above conditions.

<實施例32> <Example 32>

合成例9所得之聚醯亞胺粉末(9)(2.55g)中加入NEP(20.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(4.00g)及BCS(15.8g)，在50℃進行10小時攪拌，得到液晶配向處理劑(32)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (20.0 g) was added to the polyimine powder (9) (2.55 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (4.00 g) and BCS (15.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (32). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(32)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (32), the production or various evaluation of the unit cell was carried out in accordance with the above conditions.

<實施例33> <Example 33>

於合成例10所得之聚醯亞胺粉末(10)(2.55g)中加入NEP(32.2g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(4.00g)、BCS(2.00g)及EC(2.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(33)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (32.2 g) was added to the polyimine powder (10) (2.55 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (4.00 g), BCS (2.00 g) and EC (2.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (33). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(33)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (33), cell production or various evaluations were carried out under the above conditions.

<實施例34> <Example 34>

於合成例10所得之聚醯亞胺粉末(10)(2.55g)中加入NEP(16.0g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入γ-BL(2.01g)、BCS(16.0g)及MC( 6.00g)，在50℃進行10小時攪拌，得到液晶配向處理劑(34)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (16.0 g) was added to the polyimine powder (10) (2.55 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. γ-BL (2.01g), BCS (16.0g) and MC were added to the solution. 6.00 g) was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (34). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(34)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (34), cell production or various evaluations were carried out in accordance with the above conditions.

<比較例1> <Comparative Example 1>

於合成例3所得之聚醯亞胺粉末(3)(2.52g)中加入NMP(14.5g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(7.21g)及BCS(17.8g)，在50℃進行10小時攪拌，得到液晶配向處理劑(35)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.5 g) was added to the polyimine powder (3) (2.52 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (7.21 g) and BCS (17.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (35). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(35)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (35), the preparation or various evaluation of the unit cell was carried out under the above conditions.

<比較例2> <Comparative Example 2>

於合成例11所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(11)(10.1g)中加入NMP(32.0g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(36)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (32.0 g) was added to the polyamic acid solution (11) (10.1 g) of the resin solid content concentration of 25.0% by mass obtained in Synthesis Example 11, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (36). ). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(36)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (36), cell production or various evaluations were carried out in accordance with the above conditions.

<比較例3> <Comparative Example 3>

於合成例11所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(11)(10.0g)中加入NMP(14.0g)及BCS(17.6g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(37)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.0 g) and BCS (17.6 g) were added to a polyaminic acid solution (11) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 11 and stirred at 25 ° C for 2 hours. Liquid crystal alignment treatment agent (37). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(37)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (37), the preparation or various evaluation of the unit cell was carried out under the above conditions.

<比較例4> <Comparative Example 4>

於合成例12所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(12)(10.0g)中加入NMP(14.0g)及BCS(17.4g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(38)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.0 g) and BCS (17.4 g) were added to the polyamic acid solution (12) (10.0 g) of the resin solid content concentration of 25.0% by mass obtained in Synthesis Example 12, and the mixture was stirred at 25 ° C for 2 hours. Liquid crystal alignment treatment agent (38). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(38)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (38), cell fabrication or various evaluations were carried out in accordance with the above conditions.

<比較例5> <Comparative Example 5>

於合成例13所得之聚醯亞胺粉末(13)(2.55g)中加入NMP(14.7g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(7.28g)及BCS(18.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(39)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.7 g) was added to the polyimine powder (13) (2.55 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NMP (7.28 g) and BCS (18.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (39). The liquid crystal No abnormality such as turbidity or precipitation was observed in the treatment agent, and it was confirmed to be a homogeneous solution.

使用所得之液晶配向處理劑(39)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (39), cell production or various evaluations were carried out in accordance with the above conditions.

<比較例6> <Comparative Example 6>

於合成例13所得之聚醯亞胺粉末(13)(2.55g)中加入NEP(14.7g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(7.30g)及BCS(18.0g)，在50℃進行10小時攪拌，得到液晶配向處理劑(40)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (14.7 g) was added to the polyimine powder (13) (2.55 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. NEP (7.30 g) and BCS (18.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (40). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(40)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (40), cell production or various evaluations were carried out in accordance with the above conditions.

<比較例7> <Comparative Example 7>

於合成例14所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(14)(10.0g)中加入NEP(31.7g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(41)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (31.7 g) was added to the polyamic acid solution (14) (10.0 g) of the resin solid content concentration of 25.0% by mass obtained in Synthesis Example 14, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (41). ). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(41)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (41), the preparation or various evaluation of the unit cell was carried out under the above conditions.

<比較例8> <Comparative Example 8>

於合成例14所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(14)(10.0g)中加入NEP(14.1g)及BCS(17.6g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(42)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (14.1 g) and BCS (17.6 g) were added to a polyamic acid solution (14) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 14, and stirred at 25 ° C for 2 hours. Liquid crystal alignment treatment agent (42). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(42)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (42), the production of the unit cell or various evaluations were carried out in accordance with the above conditions.

<比較例9> <Comparative Example 9>

於合成例15所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(15)(10.0g)中加入NMP(31.7g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(43)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (31.7 g) was added to the polyamic acid solution (15) (10.0 g) of the resin solid content concentration of 25.0% by mass obtained in Synthesis Example 15, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (43). ). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(43)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (43), the preparation or various evaluation of the unit cell was carried out in accordance with the above conditions.

<比較例10> <Comparative Example 10>

於合成例15所得之樹脂固體成分濃度25.0質量%的聚醯胺酸溶液(15)(10.0g)中加入NMP(14.0g)及BCS(17.6g)，在25℃下進行2小時攪拌後得到液晶配向處理劑(44)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.0 g) and BCS (17.6 g) were added to a polyamic acid solution (15) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 15 and stirred at 25 ° C for 2 hours. Liquid crystal alignment treatment agent (44). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(44)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (44) under the above conditions , making cell or making various evaluations.

<比較例11> <Comparative Example 11>

於合成例16所得之聚醯亞胺粉末(16)(2.55g)中加入NMP(14.7g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NMP(7.30g)及BCS(18.2g)，在50℃進行10小時攪拌，得到液晶配向處理劑(45)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NMP (14.7 g) was added to the polyimine powder (16) (2.55 g) obtained in Synthesis Example 16 and stirred at 70 ° C for 24 hours to dissolve. NMP (7.30 g) and BCS (18.2 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (45). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(45)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (45), the production or various evaluation of the unit cell was carried out in accordance with the above conditions.

<比較例12> <Comparative Example 12>

於合成例16所得之聚醯亞胺粉末(16)(2.52g)中加入NEP(14.5g)，在70℃進行24小時攪拌使其溶解。於該溶液中加入NEP(7.21g)及BCS(17.8g)，在50℃進行10小時攪拌，得到液晶配向處理劑(46)。該液晶配向處理劑中，未見到混濁或析出等異常現像，確認為均勻溶液。 NEP (14.5 g) was added to the polyimine powder (16) (2.52 g) obtained in Synthesis Example 16 and stirred at 70 ° C for 24 hours to dissolve. NEP (7.21 g) and BCS (17.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment treatment agent (46). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed as a uniform solution.

使用所得之液晶配向處理劑(46)，依據上述條件下，進行晶胞的製作或各種評估。 Using the obtained liquid crystal alignment treatment agent (46), the preparation or various evaluation of the unit cell was carried out under the above conditions.

由上述結果得知，由實施例之液晶配向處理劑所得之液晶配向膜，與由比較例的液晶配向處理劑所得之液晶配向膜相比較，即使經長時間高溫及光照射下曝曬，可得到預傾角變化小之液晶配向膜。 From the above results, it was found that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example can be obtained by exposure to a liquid crystal alignment film obtained by a liquid crystal alignment treatment agent of a comparative example even after exposure to a high temperature for a long period of time and light irradiation. A liquid crystal alignment film having a small pretilt angle change.

且，實施例之液晶配向處理劑為得到上述預傾角變化小之液晶配向膜之同時，亦可得到均勻塗膜性。 Further, in the liquid crystal alignment treatment agent of the example, a liquid crystal alignment film having a small change in the pretilt angle can be obtained, and uniform coating property can be obtained.

又，在同一聚醯胺酸或聚醯亞胺，對於含有本發明之特定溶劑的實施例與未含有特定溶劑之比較例相比較下，未含有特定溶劑之比較例中，上述預傾角之變化較小，但產生多數針孔，液晶配向膜端部之塗膜均勻性較差。具體而言，可由實施例3與比較例2之比較、實施例4與比較例3之比較、及實施例6與比較例1之比較結果得到確認。 Further, in the same polyglycine or polyimine, the above pretilt angle change in the comparative example containing no specific solvent for the example containing the specific solvent of the present invention and the comparative example not containing the specific solvent It is small, but it produces a lot of pinholes, and the uniformity of the coating film at the end of the liquid crystal alignment film is poor. Specifically, comparison between Example 3 and Comparative Example 2, comparison between Example 4 and Comparative Example 3, and comparison between Example 6 and Comparative Example 1 were confirmed.

且，使用含有本發明之特定側鏈結構的二胺化合物之實施例、與使用未含有特定側鏈結構的二胺化合物的比較例之比較下，使用未含有特定側鏈結構之二胺化合物的比較例中，上述預傾角之變化較大，產生多數針孔，液晶配向膜端部之塗膜均勻性較差。具體而言，由實施例4與比較例4之比較、實施例4與比較例5之比較、及實施例4與比較例6之比較可得到確認。特別為在比較例6中，即使使用特定溶劑，亦產生多數針孔，使的液晶配向膜端部之塗膜均勻性變差。 And, an example using a diamine compound containing a specific side chain structure of the present invention, and a comparison with a diamine compound not containing a specific side chain structure In the comparative example using a diamine compound not containing a specific side chain structure, the change in the pretilt angle was large, and a large number of pinholes were generated, and the uniformity of the coating film at the end of the liquid crystal alignment film was poor. Specifically, comparison between Example 4 and Comparative Example 4, comparison between Example 4 and Comparative Example 5, and comparison between Example 4 and Comparative Example 6 were confirmed. In particular, in Comparative Example 6, even when a specific solvent was used, a large number of pinholes were generated, and the uniformity of the coating film at the end portion of the liquid crystal alignment film was deteriorated.

又，使用含有本發明之特定側鏈結構的二胺化合物之實施例與使用未含有特定側鏈結構之二胺化合物的比較例的比較下，使用未含有特定側鏈結構之二胺化合物的比較例中，上述預傾角之變化較小，但產生多數針孔，液晶配向膜端部之塗膜均勻性變差。具體為由實施例3與比較例7之比較、實施例3與比較例9之比較、實施例4與比較例8之比較、實施例4與比較例10之比較、實施例4與比較例11之比較、及實施例4與比較例12之比較得到確認。 Further, a comparison using an example of a diamine compound containing a specific side chain structure of the present invention with a comparative example using a diamine compound not containing a specific side chain structure, using a diamine compound not containing a specific side chain structure In the example, the change in the pretilt angle is small, but a large number of pinholes are generated, and the uniformity of the coating film at the end portion of the liquid crystal alignment film is deteriorated. Specifically, it is a comparison between Example 3 and Comparative Example 7, a comparison between Example 3 and Comparative Example 9, a comparison between Example 4 and Comparative Example 8, a comparison between Example 4 and Comparative Example 10, and Example 4 and Comparative Example 11. The comparison and comparison between Example 4 and Comparative Example 12 were confirmed.

特別為在比較例7、比較例8及比較例12中，即使使用特定溶劑，亦產生多數針孔，使得液晶配向膜端部之塗膜均勻性變差。 In particular, in Comparative Example 7, Comparative Example 8, and Comparative Example 12, even when a specific solvent was used, a large number of pinholes were generated, and the uniformity of the coating film at the end portion of the liquid crystal alignment film was deteriorated.

[產業上可利用性] [Industrial availability]

本發明的液晶配向處理劑為對基板之塗佈溶液的濕潤擴大性高，具有均勻塗膜性，即使在長時間的高溫及光照射下曝曬，亦不會使預傾角產生變化，可提供端部之塗膜性亦優良的液晶配向膜，具有如此液晶配向膜之液晶顯示元件可適用於信頼性優良，大畫面下高精細的液晶電視等上，對於TN元件、STN元件、TFT液晶元件等，特別為垂直配向型之液晶顯示元件上為有用。 The liquid crystal alignment treatment agent of the present invention has high wettability to the coating solution of the substrate, and has uniform coating property, and does not cause a change in the pretilt angle even when exposed to high temperature for a long period of time and light irradiation, and the end can be provided. Liquid crystal alignment film excellent in film coating property, liquid crystal display having such a liquid crystal alignment film The device can be applied to a liquid crystal television or the like which is excellent in signal quality, high-definition on a large screen, and is particularly useful for a vertical alignment type liquid crystal display element for a TN element, an STN element, a TFT liquid crystal element, or the like.

且於2011年9月8日申請之日本專利申請案2011-196320號之說明書、申請專利範圍、圖式及摘要的所有內容皆被引用於此，作為本發明之說明書的揭示內容。 All of the contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2011-196320, filed on Sep. 8, 2011, are hereby incorporated by reference.

1‧‧‧液晶配向膜 1‧‧‧Liquid alignment film

2‧‧‧鉻蒸鍍基板 2‧‧‧Chromium evaporation substrate

3‧‧‧液晶配向膜之端部 3‧‧‧End of liquid crystal alignment film

4‧‧‧液晶配向膜之端部 4‧‧‧End of liquid crystal alignment film

5‧‧‧液晶配向膜之端部*** 5‧‧‧End of the liquid crystal alignment film

[圖1]使用於評估液晶配向膜之端部的直線性的光學顯微鏡之塗膜影像例子。 [Fig. 1] An example of a coating film image of an optical microscope used for evaluating the linearity of the end portion of a liquid crystal alignment film.

[圖2]使用於評估液晶配向膜之端部的***的光學顯微鏡之塗膜影像例子。 [Fig. 2] An example of a coating film image of an optical microscope used for evaluating the bulging of the end portion of the liquid crystal alignment film.

Claims

一種液晶配向處理劑，其特徵為含有下述成分(A)及成分(B)者；成分(A)：N-乙基-2-吡咯烷酮。成分(B)：選自將具有下述式〔1〕所示側鏈的聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群之至少1種聚合物； (式〔1〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；X₂為單鍵或(CH₂)_b-(b為1~15的整數)；X₃為單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；X₄為選自苯環、環己基環及雜環之2價環狀基(這些環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)；X₅為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)；X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基，n為0~4的整數)。 A liquid crystal alignment treatment agent comprising the following components (A) and (B); and component (A): N-ethyl-2-pyrrolidone. Component (B): at least one selected from the group consisting of a polyamidene precursor having a side chain represented by the following formula [1] and a polyimine imide obtained by ruthenium imidization of a polyimide precursor polymer; (In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₂ is a single bond or (CH ₂ ) _b - (b is An integer from 1 to 15; X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. a divalent cyclic group (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carbon number of 1 ~3 is substituted by a fluorine-containing alkoxy group or a fluorine atom; X ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be 1 carbon number) ~3 alkyl group, carbon number 1 to 3 alkoxy group, carbon number 1 to 3 fluorine-containing alkyl group, carbon number 1 to 3 fluorine-containing alkoxy group or fluorine atom); X ₆ is An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and n is 0 to 4 Integer).

如申請專利範圍第1項之液晶配向處理劑，其中前述成分(B)為選自將使用於具有前述式〔1〕所示側鏈的二胺作為原料的二胺成分之一部份的聚醯亞胺前驅物及聚醯亞胺前驅物進行醯亞胺化的聚醯亞胺所成群的至少1種聚合物。 The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the component (B) is a part of a diamine component selected from the group consisting of a diamine having a side chain represented by the above formula [1] as a raw material. The quinone imine precursor and the polyimine precursor are at least one polymer of a group of quinone imidized polyimine.

如申請專利範圍第2項之液晶配向處理劑，其中前述具有式〔1〕所示側鏈之二胺為下述式〔1a〕所示二胺化合物； (式〔1a〕中，X₁為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；X₂為單鍵或(CH₂)_b-(b為1~15的整數)；X₃為單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；X₄為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)；X₅為選自苯環、環己基環及雜環的2價環狀基(這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟的烷基、碳數1~3的含氟的烷氧基或氟原子所取代)；X₆為碳數1~18的烷基、碳數1~18的含氟的烷基、碳數1~18的烷氧基或碳數1~18的含氟的烷氧基；n為0~4的整數，m為1~4的整數)。 The liquid crystal alignment treatment agent of the second aspect of the invention, wherein the diamine having the side chain represented by the formula [1] is a diamine compound represented by the following formula [1a]; (In the formula [1a], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₂ is a single bond or (CH ₂ ) _b - (b is An integer from 1 to 15; X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. a divalent cyclic group (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carbon number of 1) ~3 is substituted by a fluorine-containing alkoxy group or a fluorine atom; X ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be 1 carbon number) ~3 alkyl group, carbon number 1 to 3 alkoxy group, carbon number 1 to 3 fluorine-containing alkyl group, carbon number 1 to 3 fluorine-containing alkoxy group or fluorine atom); X ₆ is An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms; n being 0 to 4 Integer, m is an integer from 1 to 4.)

如申請專利範圍第3項之液晶配向處理劑，其中前述式〔1a〕所示二胺使用於原料之二胺成分的5~80莫耳%。 The liquid crystal alignment treatment agent according to the third aspect of the invention, wherein the diamine represented by the above formula [1a] is used in an amount of from 5 to 80 mol% of the diamine component of the raw material.

如申請專利範圍第1項至第4項中任一項之液晶配向處理劑，其中前述成分(B)為使用下述式〔2〕所示四羧酸二酐的聚合物； (式〔2〕中，Y₁為碳數4~13的4價有機基，且含有碳數4~10的非芳香族環狀烴基)。 The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein the component (B) is a polymer using a tetracarboxylic dianhydride represented by the following formula [2]; (In the formula [2], Y ₁ is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms).

如申請專利範圍第5項之液晶配向處理劑，其中前述Y₁為下述式〔2a〕~〔2j〕所示結構的基； (式〔2a〕中，Y₂~Y₅為氫原子、甲基、氯原子或苯環，各可相同或相異；式〔2g〕中，Y₆及Y₇為氫原子或甲基，各可相同或相異)。 The liquid crystal alignment treatment agent according to claim 5, wherein the Y ₁ is a group having a structure represented by the following formulas [2a] to [2j]; (In the formula [2a], Y ₂ to Y ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different; in the formula [2g], Y ₆ and Y ₇ are a hydrogen atom or a methyl group. Each can be the same or different).

如申請專利範圍第1項至第6項中任一項之液晶配向處理劑，其中前述成分(B)之聚合物為聚醯胺酸。 The liquid crystal alignment treatment agent according to any one of claims 1 to 6, wherein the polymer of the component (B) is polyamic acid.

如申請專利範圍第1項至第6項中任一項之液晶配向處理劑，其中前述成分(B)之聚合物為將聚醯胺酸經脫水閉環所得之聚醯亞胺。 The liquid crystal alignment treatment agent according to any one of claims 1 to 6, wherein the polymer of the component (B) is a polyimine obtained by subjecting polylysine to dehydration ring closure.

如申請專利範圍第1項至第8項中任一項之液晶配向處理劑，其中作為成分(C)，含有N-甲基-2-吡咯烷酮或γ-丁內酯。 The liquid crystal alignment treatment agent according to any one of claims 1 to 8, wherein the component (C) contains N-methyl-2-pyrrolidone or γ-butyrolactone.

如申請專利範圍第1項至第9項中任一項之液晶配向處理劑，其中作為成分(D)，含有選自1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚及丙二醇單丁基醚所成群之至少1種者。 The liquid crystal alignment treatment agent according to any one of claims 1 to 9, wherein as component (D), it is selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, and 1 , 2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Ethylene glycol monobutyl ether, propylene glycol monomethyl At least one of a group of ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

如申請專利範圍第1項至第10項中任一項之液晶配向處理劑，其中前述成分(A)為於液晶配向處理劑所含之有機溶劑全體的10~100質量%者。 The liquid crystal alignment treatment agent according to any one of the first to tenth aspects of the invention, wherein the component (A) is in an amount of from 10 to 100% by mass based on the total of the organic solvent contained in the liquid crystal alignment treatment agent.

如申請專利範圍第9項至第11項中任一項之液晶配向處理劑，其中前述成分(C)為於液晶配向處理劑所含之有機溶劑全體的0.1~70質量%。 The liquid crystal alignment treatment agent according to any one of the items of the present invention, wherein the component (C) is 0.1 to 70% by mass based on the total of the organic solvent contained in the liquid crystal alignment treatment agent.

如申請專利範圍第10項至第12項中任一項之液晶配向處理劑，其中前述成分(D)為於液晶配向處理劑所含之有機溶劑全體的5~80質量%。 The liquid crystal alignment treatment agent according to any one of the items 10 to 12, wherein the component (D) is 5 to 80% by mass based on the total of the organic solvent contained in the liquid crystal alignment treatment agent.

如申請專利範圍第1項至第13項中任一項之液晶配向處理劑，其中液晶配向處理劑中之前述成分(B)為0.1~15質量%。 The liquid crystal alignment treatment agent according to any one of claims 1 to 13, wherein the component (B) in the liquid crystal alignment treatment agent is 0.1 to 15% by mass.

一種液晶配向膜，其特徵為使用如申請專利範圍第1項至第14項中任一向之液晶配向處理劑所得者。 A liquid crystal alignment film which is obtained by using a liquid crystal alignment treatment agent according to any one of claims 1 to 14.

一種液晶配向膜，其特徵為使用如申請專利範圍第1項至第14項中任一向之液晶配向處理劑，以噴墨法而得者。 A liquid crystal alignment film which is obtained by an inkjet method using a liquid crystal alignment treatment agent according to any one of claims 1 to 14.

一種液晶顯示元件，其特徵為具有如申請專利範圍第15項或第16項之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to item 15 or item 16 of the patent application.

如申請專利範圍第15項或第16項之液晶配向膜，其為使用於經由以下步驟所製造的液晶顯示元件者，該步驟為於具備電極的一對基板之間具有液晶層所成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性化合物之液晶組成物，於前述電極間輸入電壓後，聚合前述聚合性化合物之步驟。 The liquid crystal alignment film of claim 15 or 16, which is used for a liquid crystal display element manufactured by the following steps, wherein the step is to form a liquid crystal layer between a pair of substrates having electrodes; A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a step of polymerizing the polymerizable compound is performed after a voltage is input between the electrodes.

一種液晶顯示元件，其特徵為具有如申請專利範圍第18項之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to item 18 of the patent application.

如申請專利範圍第19項之液晶顯示元件，其為經由下述步驟所製造者，該步驟為於具備電極與前述液晶配向膜之一對基板之間具有液晶層所成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性化合物之液晶組成物，於前述電極間輸入電壓後，聚合前述聚合性化合物之步驟。 The liquid crystal display device of claim 19, which is manufactured by the step of providing a liquid crystal layer between the pair of substrates and the liquid crystal alignment film, and the pair of substrates A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat, and a step of polymerizing the polymerizable compound after inputting a voltage between the electrodes.

如申請專利範圍第15項或第16項中任一項之液晶配向膜，其為使用於經由下述步驟所製造的液晶顯示元件者，該步驟為於具備電極的一對基板之間具有液晶層所成，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合之聚合性基的液晶配向膜，於前述電極間輸入電壓後，聚合前述聚合性基之步驟。 The liquid crystal alignment film according to any one of claim 15 or 16, which is used for a liquid crystal display element manufactured by the following steps, wherein the step is to have a liquid crystal between a pair of substrates having electrodes In the layer, a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is input between the electrodes to polymerize the polymerizable group.

一種液晶顯示元件，其特徵為具有如申請專利範圍第21項之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 21 of the patent application.

如申請專利範圍第22項之液晶顯示元件，其為經由下述步驟所製造者，該步驟為於具備電極之一對基板之間具有液晶層，於前述一對基板之間配置含有藉由活性能量線及熱的至少一方進行聚合的聚合性基的液晶配向膜，於前述電極間輸入電壓後，聚合前述聚合性基者。 The liquid crystal display device of claim 22, which is manufactured by the step of providing a liquid crystal layer between the pair of substrates and having the active layer disposed between the pair of substrates A polymerizable group liquid crystal alignment film in which at least one of an energy ray and a heat is polymerized, and a polymerizable matrix is polymerized after a voltage is input between the electrodes.