TWI648579B - Compound, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Compound, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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TWI648579B
TWI648579B TW104108555A TW104108555A TWI648579B TW I648579 B TWI648579 B TW I648579B TW 104108555 A TW104108555 A TW 104108555A TW 104108555 A TW104108555 A TW 104108555A TW I648579 B TWI648579 B TW I648579B
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alignment agent
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TW201537271A (en
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植阪裕介
菅野尙基
秋池利之
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日商Ｊｓｒ股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

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Abstract

本發明提供一種液晶配向劑，其可形成歷經長期而電壓保持率的下降少、可靠性優異的液晶配向膜。液晶配向劑含有具有式(1)所表示的結構的聚合物。 The present invention provides a liquid crystal alignment agent which can form a liquid crystal alignment film having a small voltage drop retention and excellent reliability over a long period of time. The liquid crystal alignment agent contains a polymer having a structure represented by Formula (1).

*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-* (1) * -X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2- * (1)

式(1)中，X1及X2為單鍵、氧原子、硫原子、羰基或酯鍵，X1及X2兩者不會同時為單鍵，Y是自5員環或6員環的雜芳香族化合物中去除2個氫原子而獲得的基團，雜芳香族化合物在環結構中包含1個或2個選自由氮原子、氧原子及硫原子所組成的組群中的1種以上雜原子，存在多個的R1為氫原子或氟原子，m1及m2為0~20的整數，且「*」分別表示結合鍵。 In formula (1), X 1 and X 2 are a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond. Both X 1 and X 2 are not a single bond at the same time. Y is a 5-membered ring or a 6-membered ring. The heteroaromatic compound is a group obtained by removing two hydrogen atoms. The heteroaromatic compound includes one or two members selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in a ring structure. There are multiple hetero atoms above. R 1 is a hydrogen atom or a fluorine atom, m 1 and m 2 are integers of 0 to 20, and “*” represents a bonding bond, respectively.

Description

化合物、聚合物、液晶配向劑、液晶配向膜以及液晶顯示元件 Compound, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

本發明有關於一種液晶配向劑以及液晶顯示元件。詳細而言，本發明有關於一種可形成即便在嚴酷的使用條件下歷經長期，電壓保持率的下降也少，可靠性優異的液晶配向膜的液晶配向劑；以及歷經長期而顯示品質不會劣化的液晶顯示元件。 The invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film with excellent reliability that reduces the voltage retention even after a long period of use under severe conditions; and that the display quality does not deteriorate over a long period of time. Liquid crystal display element.

液晶顯示元件可根據電極結構以及所使用的液晶分子的物性來分類為各種模式。例如已知有以下模式等的液晶顯示裝置：所謂的扭轉向列(Twisted Nematic，TN)型(專利文獻1)，例如在設置有透明導電膜的基板表面形成液晶配向膜來作為液晶顯示元件用基板，將所述2塊基板對向配置，在其間隙內形成具有正的介電各向異性的向列型液晶的層，製成夾層(sandwich)結構的單元，使液晶分子的長軸自其中一塊基板朝向另一塊基板而連續地扭轉90°；超扭轉向列(Super Twisted Nematic，STN)型(專利文獻2)，能夠實現比TN型液晶顯示元件高的占空比(Duty ratio)； 垂直配向(Vertical Alignment，VA)型(專利文獻3)，在極間隙內注入具有負的介電各向異性的向列型液晶的層，使液晶相對於基板而大致垂直地配向；面內切換(In-Plane Switching，IPS)型(專利文獻4及專利文獻5)，通過將電極對在一塊基板面內配置為梳齒狀，則電場施加時的液晶的驅動方向僅成為基板面內方向；邊緣場切換(Fringe Field Switching，FFS)型(專利文獻6)，將IPS型的電極結構加以變更，提高顯示元件部分的開口率，使亮度上升；光學補償彎曲(Optical Compensated Bend，OCB)型(專利文獻7)，視角依存性少，而且影像畫面的高速回應性優異。 The liquid crystal display element can be classified into various modes according to an electrode structure and physical properties of liquid crystal molecules used. For example, a liquid crystal display device of the following mode is known: a so-called Twisted Nematic (TN) type (Patent Document 1), for example, a liquid crystal alignment film is formed on the surface of a substrate provided with a transparent conductive film as a liquid crystal display element A substrate, the two substrates are arranged to face each other, and a layer of nematic liquid crystal with positive dielectric anisotropy is formed in the gap, and a unit of a sandwich structure is formed, so that the long axis of the liquid crystal molecules is One substrate is continuously twisted 90 ° toward the other substrate; Super Twisted Nematic (STN) type (Patent Document 2) can achieve a higher duty ratio than the TN liquid crystal display element; Vertical alignment (VA) type (Patent Document 3), a layer of nematic liquid crystal with negative dielectric anisotropy is injected into the electrode gap, so that the liquid crystal is aligned approximately perpendicularly to the substrate; in-plane switching (In-Plane Switching, IPS) type (Patent Document 4 and Patent Document 5), by arranging the electrode pairs in a comb-tooth shape on one substrate surface, the driving direction of the liquid crystal when an electric field is applied becomes only the in-plane direction of the substrate; Fringe Field Switching (FFS) type (Patent Document 6), which changes the electrode structure of the IPS type to increase the aperture ratio of the display element part and increase the brightness; Optical Compensated Bend (OCB) type ( Patent Document 7), has a small viewing angle dependency, and is excellent in high-speed responsiveness of a video screen.

作為這些各種液晶顯示元件中的液晶配向膜的材料，已知有聚醯胺酸、聚醯亞胺、聚醯胺、聚酯等樹脂材料，特別是包含聚醯胺酸或者聚醯亞胺的液晶配向膜由於耐熱性、機械強度、與液晶的親和性等優異，故而用於多種液晶顯示元件中(專利文獻8)。 As a material of the liquid crystal alignment film in these various liquid crystal display elements, resin materials such as polyamic acid, polyimide, polyimide, and polyester are known, and especially those containing polyamic acid or polyimide The liquid crystal alignment film is used in various liquid crystal display elements because of its excellent heat resistance, mechanical strength, affinity with liquid crystal, and the like (Patent Document 8).

如上所述的液晶配向劑中，近年來，要求可靠性(對嚴酷環境的長期穩定性)較以前也有提高。所述情況如以下所述。 In the liquid crystal alignment agent as described above, in recent years, reliability (long-term stability against severe environments) has been required to be improved as compared with that in the past. The situation is as follows.

與現有的液晶顯示元件的主用途即個人電腦、監視器用顯示器等相比，近年來普及顯著的液晶電視要求換購週期長，原本就為長壽命。此處，近年來作為家庭影院(home theater)的需要提高的液晶投影儀用途的液晶顯示元件中，由於使用金屬鹵化物燈等照射強度非常高的光源，故而對光及熱的耐受性成為大的問題。另外，手機等移動設備用或車載用汽車導航用的液晶顯示元件為了提高在包含強烈的紫外線的太陽光下的可見性，必須提高 背光源的亮度，因此更擔憂早期的劣化。而且，在使用這些設備作為電視遊戲的顯示器的情況下，會設想在所述的條件下置於極長時間的連續驅動下。 Compared with the main use of existing liquid crystal display elements, namely personal computers, monitors, and the like, in recent years, LCD televisions, which have become popular in recent years, require a long redemption cycle and a long life. Here, in recent years, liquid crystal display elements used as liquid crystal projectors for home theaters need to be improved. Since a light source having a very high irradiation intensity, such as a metal halide lamp, is used, the resistance to light and heat becomes high. Big question. In addition, liquid crystal display elements for mobile devices such as mobile phones or car navigation systems must be improved in order to improve visibility in sunlight containing strong ultraviolet rays. The brightness of the backlight is more worried about early deterioration. Moreover, in the case where these devices are used as a display for a video game, it is envisaged to be placed under continuous driving for an extremely long time under the conditions described.

如上所述，液晶顯示元件中，隨著多用途化等而會暴露於高強度的光照射、長時間驅動等以往所未考慮到的嚴苛環境中，而且要求進一步長壽命化。 As described above, liquid crystal display elements are exposed to severe environments that have not been considered in the past, such as high-intensity light irradiation and long-term driving, as they become multi-purpose, and they are required to have a longer life.

現有已知的液晶配向膜中，已指出對於所述嚴苛環境的耐受性不足。 In the conventionally known liquid crystal alignment films, it has been pointed out that the resistance to the severe environment is insufficient.

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平4-153622號公報 [Patent Document 1] Japanese Patent Laid-Open No. 4-153622

[專利文獻2]日本專利特開昭60-107020號公報 [Patent Document 2] Japanese Patent Laid-Open No. 60-107020

[專利文獻3]日本專利特開平11-258605號公報 [Patent Document 3] Japanese Patent Laid-Open No. 11-258605

[專利文獻4]日本專利特開昭56-91277號公報 [Patent Document 4] Japanese Patent Laid-Open No. 56-91277

[專利文獻5]美國專利第5,928,733號說明書 [Patent Document 5] US Patent No. 5,928,733

[專利文獻6]日本專利特開2002-082357號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2002-082357

[專利文獻7]日本專利特開平9-105957號公報 [Patent Document 7] Japanese Patent Laid-Open No. 9-105957

[專利文獻8]日本專利特開昭62-165628號公報 [Patent Document 8] Japanese Patent Laid-Open No. 62-165628

本發明是鑒於所述情況而形成，其目的在於提供一種液晶配向劑，其可形成歷經長期而電壓保持率的下降少、可靠性優異的液晶配向膜。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a small decrease in voltage retention over a long period of time and excellent reliability.

本發明的另一目的在於提供一種優異的液晶顯示元件，其歷經長期而顯示品質不會劣化。 Another object of the present invention is to provide an excellent liquid crystal display element that does not deteriorate display quality over a long period of time.

依據本發明，第一，本發明的所述目的以及優點是由一種液晶配向劑來達成，其特徵在於：含有具有下述式(1)所表示的結構的聚合物。 According to the present invention, first, the objects and advantages of the present invention are achieved by a liquid crystal alignment agent, which is characterized by containing a polymer having a structure represented by the following formula (1).

*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-* (1) * -X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2- * (1)

(式(1)中，X1及X2分別獨立地為單鍵、氧原子、硫原子、羰基或酯鍵，其中，X1及X2兩者不會同時為單鍵，Y是自5員環或6員環的雜芳香族化合物中去除2個氫原子而獲得的基團，所述雜芳香族化合物在環結構中包含1個或2個選自由氮原子、氧原子及硫原子所組成的組群中的1種以上雜原子，其中，Y的2個結合鍵均直接出自所述5員環或6員環中，存在多個的R1分別獨立地為氫原子或氟原子，m1及m2分別獨立地為0~20的整數，而且「*」分別表示結合鍵) (In the formula (1), X 1 and X 2 are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, wherein X 1 and X 2 are not both single bonds at the same time, and Y is from 5 A group obtained by removing two hydrogen atoms from a six-membered or six-membered heteroaromatic compound. The heteroaromatic compound includes one or two selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in a ring structure. one kind or more heteroatoms of the group consisting of wherein, Y are the two bonds directly from the 5-membered ring or 6-membered ring in the presence of R 1 each independently a hydrogen atom or a fluorine atom more, m1 and m2 are each independently an integer of 0-20, and "*" represents a bonding key, respectively)

第二，本發明的所述目的以及優點是由一種液晶顯示元件來達成，其特徵在於：包括由所述液晶配向劑來形成的液晶配向膜。 Secondly, the object and advantages of the present invention are achieved by a liquid crystal display element, which is characterized by including a liquid crystal alignment film formed by the liquid crystal alignment agent.

通過本發明，提供一種可形成歷經長期而電壓保持率的下降少、可靠性優異的液晶配向膜的液晶配向劑。 According to the present invention, there is provided a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a small decrease in voltage retention over a long period of time and excellent reliability.

包括由所述液晶配向劑形成的液晶配向膜的本發明的液晶顯示元件歷經長期而顯示品質不會劣化。 The liquid crystal display element of the present invention including a liquid crystal alignment film formed of the liquid crystal alignment agent does not deteriorate display quality over a long period of time.

因此，本發明的技術可適合應用於例如液晶電視、液晶投影儀、手機、可擕式遊戲機、資訊用顯示器等用途。 Therefore, the technology of the present invention can be suitably applied to applications such as a liquid crystal television, a liquid crystal projector, a mobile phone, a portable game machine, and an information display.

圖1是表示實施例12以及比較例6及比較例7中製造的液晶單元中的電極圖案的概略圖。 FIG. 1 is a schematic diagram showing an electrode pattern in a liquid crystal cell manufactured in Example 12 and Comparative Examples 6 and 7.

本發明的液晶配向劑含有具有所述式(1)所表示的結構的聚合物。 The liquid crystal alignment agent of the present invention contains a polymer having a structure represented by the formula (1).

所述式(1)中的Y例如可列舉下述式分別所表示的基團。 Examples of Y in the formula (1) include groups represented by the following formulas.

[化1] [Chemical 1]

(所述式中，R為氫原子或者碳數1~6的烷基；X分別獨立地為鹵素原子、碳數1~20的烷基、碳數1~20的氟烷基、碳數2~20的烯基、碳數1~20的烷氧基或者碳數1~20的氟烷氧基；n1及n4分別獨立地為0~2的整數；n2為0或1；n3分別獨立地為0~3的整數；而且「*」分別表示結合鍵) (In the formula, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and 2 carbon atoms; Alkenyl to 20, alkoxy having 1 to 20 carbons or fluoroalkoxy having 1 to 20 carbons; n1 and n4 are each independently an integer of 0 to 2; n2 is 0 or 1; n3 is each independently Is an integer from 0 to 3; and "*" indicates a bonding key respectively)

上式中的R的烷基優選為碳數1~3的烷基，具體而言，例如更優選為甲基、乙基、正丙基或者異丙基。X的鹵素原子例如可列舉氟原子、氯原子、溴原子及碘原子。X的烷基例如可列舉：甲基、乙基、正丙基、異丙基等； 氟烷基例如可列舉：三氟甲基、2,2,2-三氟乙基等；烯基例如可列舉：乙烯基、烯丙基等；烷氧基例如可列舉：甲氧基、乙氧基、正丙氧基等；氟烷氧基例如可列舉：三氟甲氧基、2,2,2-三氟乙氧基等。n1、n4及n5分別獨立地優選為0或1，更優選為0。 The alkyl group of R in the above formula is preferably an alkyl group having 1 to 3 carbon atoms. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable. Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group of X include methyl, ethyl, n-propyl, and isopropyl; Examples of the fluoroalkyl group include trifluoromethyl and 2,2,2-trifluoroethyl. Examples of the alkenyl include vinyl and allyl. Examples of the alkoxy include methoxy and ethyl. Examples of the fluoroalkoxy group include trifluoromethoxy and 2,2,2-trifluoroethoxy. n1, n4, and n5 are each independently preferably 0 or 1, and more preferably 0.

所述式(1)中的Y特別優選為伸吡啶基(pyridinylene)，最優選為2,5-伸吡啶基、2,6-伸吡啶基或者3,5-伸吡啶基。 Y in the formula (1) is particularly preferably pyridinyl, and most preferably 2,5-pyridyl, 2,6-pyridyl, or 3,5-pyridyl.

所述式(1)中的R1優選為氫原子；所述式(1)中的m1及m2分別獨立地優選為0~2的整數。 R 1 in the formula (1) is preferably a hydrogen atom; and m 1 and m 2 in the formula (1) are each independently preferably an integer of 0 to 2.

當所述式(1)中的X1及X2為酯鍵時，其鍵結方向為任意，但優選為該酯鍵的羰基碳位於內側。X1及X2優選為其中一者為氧原子或酯鍵，另一者為單鍵、氧原子或酯鍵。 When X 1 and X 2 in the formula (1) are ester bonds, the bonding direction is arbitrary, but it is preferable that the carbonyl carbon of the ester bond is located inside. X 1 and X 2 are each preferably an oxygen atom or an ester bond, and the other is a single bond, an oxygen atom, or an ester bond.

所述式(1)所表示的結構特別優選為例如下述式分別所表示的結構。 The structures represented by the formula (1) are particularly preferably structures represented by the following formulas, respectively.

(所述式中的「*」分別表示結合鍵) ("*" In the above formula represents a bonding key, respectively)

本發明的液晶配向劑中所含有的聚合物只要是具有所述式 (1)所表示的結構的聚合物，則除此以外，可無任何限定地適當使用。本發明的液晶配向劑中所含有的聚合物優選為在該聚合物的主鏈上具有所述式(1)所表示的結構。 As long as the polymer contained in the liquid crystal alignment agent of the present invention has the formula The polymer having the structure represented by (1) can be suitably used without any limitation other than the polymer. The polymer contained in the liquid crystal alignment agent of the present invention preferably has a structure represented by the formula (1) on the main chain of the polymer.

此處，所謂聚合物的主鏈，是指聚合物中包含最長的原子鏈的「幹」的部分。所謂在主鏈上具有所述式(1)所表示的結構，是指該結構構成主鏈的一部分。該情況下，所述式(1)所表示的結構會存在於主鏈中，但並不禁止該結構重疊地存在於主鏈以外的部分，例如側鏈(自聚合物的「幹」上分支出的部分)。 Here, the main chain of the polymer refers to the "dry" portion of the polymer containing the longest atomic chain. By having the structure represented by the formula (1) on the main chain, it means that the structure constitutes a part of the main chain. In this case, the structure represented by the formula (1) may exist in the main chain, but it is not prohibited that the structure overlaps in a part other than the main chain, such as a side chain (divided from the "dry" of the polymer). Expenditures).

本發明的液晶配向劑中所含有的具有所述式(1)所表示的結構的聚合物例如可列舉：具有所述式(1)所表示的結構的聚醯胺酸、聚醯胺酸的醯亞胺化聚合物、聚醯胺酸酯、聚有機矽氧烷、聚酯、聚醯胺、纖維素衍生物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基順丁烯二醯亞胺)衍生物、聚(甲基)丙烯酸酯等。這些聚合物中，優選為使用選自由聚醯胺酸、聚醯胺酸的醯亞胺化聚合物、聚醯胺酸酯以及聚有機矽氧烷所組成的組群中的1種以上聚合物，更優選為使用選自由聚醯胺酸及其醯亞胺化聚合物所組成的組群中的1種以上聚合物。 Examples of the polymer having a structure represented by the formula (1) contained in the liquid crystal alignment agent of the present invention include polyamic acid having a structure represented by the formula (1), and poly (amino acid) having a structure represented by the formula (1). Perylene imidized polymers, polyamidates, polyorganosiloxanes, polyesters, polyamines, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylcis-butyl Ethylenediimine) derivatives, poly (meth) acrylates, and the like. Among these polymers, it is preferable to use one or more polymers selected from the group consisting of polyamidic acid, polyamidoimidated polymers, polyamidoesters, and polyorganosiloxanes. It is more preferable to use one or more polymers selected from the group consisting of polyamidic acid and its imidized polymers.

所述聚醯胺酸例如可利用以下方法來優選地合成：使包含具有所述式(1)所表示的結構的四羧酸二酐的四羧酸二酐、與二胺進行反應的方法；或者使四羧酸二酐、與包含具有所述式(1)所表示的結構的二胺的二胺進行反應的方法。 The polyamidic acid can be preferably synthesized by, for example, a method of reacting a tetracarboxylic dianhydride containing a tetracarboxylic dianhydride having a structure represented by the formula (1) with a diamine; Alternatively, a method of reacting a tetracarboxylic dianhydride with a diamine containing a diamine having a structure represented by the formula (1).

所述聚醯胺酸的醯亞胺化聚合物可通過將所述聚醯胺酸進行脫水閉環，將醯胺酸結構的全部或者一部分進行醯亞胺化而獲得。 The polyimide-fluorinated imidized polymer can be obtained by subjecting the polyfluorinated acid to dehydration and ring-closing, and performing the imidization of all or a part of the fluorinated acid structure.

本發明的液晶配向劑中所含有的聚合物特別優選為選自由 The polymer contained in the liquid crystal alignment agent of the present invention is particularly preferably selected from the group consisting of

使四羧酸二酐與包含具有所述式(1)所表示的結構的二胺的二胺進行反應而獲得的聚醯胺酸、以及將該聚醯胺酸進行脫水閉環而獲得的醯亞胺化聚合物所組成的組群中的1種以上聚合物。 Polycarboxylic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a diamine having the structure represented by the formula (1), and fluorene obtained by dehydrating and closing the polyamino acid. One or more polymers in the group consisting of aminated polymers.

以下，對本發明的液晶配向劑中特別優選地含有的聚合物的合成方法進行說明。 Hereinafter, a method for synthesizing a polymer particularly preferably contained in the liquid crystal alignment agent of the present invention will be described.

具有所述式(1)所表示的結構的聚醯胺酸的合成中可使用的四羧酸二酐例如可列舉脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作為這些四羧酸二酐的具體例，脂肪族四羧酸二酐例如可列舉：丁烷四羧酸二酐等；脂環式四羧酸二酐例如可列舉：1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺環-3'-(四氫呋喃-2',5'-二酮)、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘並[1,2-c]呋喃-1,3-二酮、3,5,6-三羧基-2-羧基甲基降冰片烷-2：3,5：6-二酐、雙環[3.3.0]辛烷-2,4,6,8-四羧酸2：4,6：8二酐、4,9-二氧雜三環[5.3.1.02,6]十一烷-3,5,8,10-四酮等；芳香族四羧酸二酐例如可列舉：均苯四甲酸二酐等，除此以外，可使用日本專利特願2009-157556號中記載的四羧酸二酐。 Examples of the tetracarboxylic dianhydride that can be used in the synthesis of a polyamic acid having the structure represented by the formula (1) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic acid. Carboxylic dianhydride, etc. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, and the like; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4. -Cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2 , 4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl -3-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c ] Furan-1,3-dione, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2, 4,6,8-tetracarboxylic acid 2: 4,6: 8 dianhydride, 4,9-dioxatricyclo [5.3.1.0 2,6 ] undecane-3,5,8,10-tetraketone Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like. In addition, the tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

所述聚醯胺酸的合成中使用的四羧酸二酐優選為包含所述中的脂環式四羧酸二酐，更優選為包含選自由2,3,5-三羧基環戊 基乙酸二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐以及1,2,3,4-環戊烷四羧酸二酐所組成的組群中的至少1種，尤其優選為相對於全部四羧酸二酐而包含60莫耳%以上的選自這些四羧酸二酐中的至少1種，特別優選為包含80莫耳%以上，極優選為僅使用選自這些四羧酸二酐中的至少1種。 The tetracarboxylic dianhydride used in the synthesis of the polyamic acid is preferably an alicyclic tetracarboxylic dianhydride including the above, and more preferably includes a tetracarboxylic dianhydride selected from the group consisting of 2,3,5-tricarboxycyclopentane. Acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dicarboxylic acid At least one of the group consisting of anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and particularly preferably relative 60 mol% or more of all tetracarboxylic dianhydrides are contained in at least one selected from these tetracarboxylic dianhydrides, it is particularly preferable to contain 80 mol% or more, and it is very preferable to use only those selected from these tetracarboxylic acids. At least one of dianhydride.

具有所述式(1)所表示的結構的聚醯胺酸的合成中優選使用的二胺包含具有所述式(1)所表示的結構的二胺。 The diamine which is preferably used in the synthesis of a polyamic acid having a structure represented by the formula (1) includes a diamine having a structure represented by the formula (1).

所謂具有所述式(1)所表示的結構的二胺，是指在所述式(1)所表示的結構的2個結合鍵上，直接或者經由適當的鍵結基而分別鍵結有胺基的化合物。所述適當的鍵結基例如可列舉：伸苯基、伸萘基、伸聯苯基等。這些基團所具有的芳香環可經鹵素原子、碳數1~20的烷基、碳數1~20的氟烷基、碳數2~20的烯基、碳數1~20的烷氧基或者碳數1~20的氟烷氧基所取代。所述基團中，鍵結基優選為可經取代的伸苯基。即，具有所述式(1)所表示的結構的二胺的優選例可列舉下述式(MDA)所表示的化合物。 The diamine having the structure represented by the formula (1) means that an amine is directly bonded to two bonding bonds of the structure represented by the formula (1), respectively, or via appropriate bonding groups. Compounds. Examples of the appropriate bonding group include phenylene, naphthyl, and phenylene. The aromatic ring of these groups may be through a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Or it may be substituted by a fluoroalkoxy group having 1 to 20 carbon atoms. Among the groups, the bonding group is preferably a phenylene group which may be substituted. That is, as a preferable example of the diamine which has a structure represented by said Formula (1), the compound represented by a following formula (MDA) is mentioned.

H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2...(MDA) H 2 N-Ph-X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2 -Ph-NH 2 ... (MDA)

(式(MDA)中，X1、X2、Y、R1、m1及m2分別為與所述式(1)中的含義相同，存在2個的Ph分別獨立地為可經取代的伸苯基) (In the formula (MDA), X 1 , X 2 , Y, R 1 , m 1 and m 2 have the same meanings as in the formula (1), and two Phs are independently substituted benzene. base)

所述式(MDA)中的Ph特別優選為1,4-伸苯基。 Ph in the formula (MDA) is particularly preferably 1,4-phenylene.

具有所述式(1)所表示的結構的聚醯胺酸的合成中優選使用的二胺可僅使用具有所述式(1)所表示的結構的二胺，也可以並用其以外的其他二胺。 As the diamine preferably used in the synthesis of a polyamic acid having a structure represented by the formula (1), only a diamine having a structure represented by the formula (1) may be used, or a diamine other than the diamine may be used in combination. amine.

此處可使用的其他二胺分類為具有預傾角表現性基的二胺以及不具有預傾角表現性基的二胺。 Other diamines that can be used herein are classified into diamines having a pretilt-angle expressing group and diamines having no pre-tilt-angle expressing group.

具有預傾角表現性基的其他二胺優選為具有預傾角表現性基的芳香族二胺，作為其具體例，例如可列舉：十二烷氧基-2,4-二胺基苯、十四烷氧基-2,4-二胺基苯、十五烷氧基-2,4-二胺基苯、十六烷氧基-2,4-二胺基苯、十八烷氧基-2,4-二胺基苯、十二烷氧基-2,5-二胺基苯、十四烷氧基-2,5-二胺基苯、十五烷氧基-2,5-二胺基苯、十六烷氧基-2,5-二胺基苯、十八烷氧基-2,5-二胺基苯、膽甾烷氧基-3,5-二胺基苯(cholestanyloxy-3,5-diaminobenzene)、膽固醇氧基-3,5-二胺基苯(cholesteryloxy-3,5-diaminobenzene)、膽甾烷氧基-2,4-二胺基苯、膽固醇氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽固醇基酯、3,5-二胺基苯甲酸羊毛甾烷基酯(lanostanyl 3,5-diaminobenzoate)、3,6-雙(4-胺基苯甲醯基氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯氧基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-(4-庚基環己基)環己烷、N-(2,4-二胺基苯基)-4-(4-庚基環己基)苯甲醯胺、下述式(A-1)所表示的化合物等。 The other diamine having a pretilt angle expressive group is preferably an aromatic diamine having a pretilt angle expressive group. Specific examples thereof include dodecyloxy-2,4-diaminobenzene, tetradecyl Alkoxy-2,4-diaminobenzene, pentadecyl-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, stearyloxy-2 , 4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diamine Phenylbenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestanoxy-3,5-diaminobenzene (cholestanyloxy- 3,5-diaminobenzene), cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteroloxy-2, 4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate ( lanostanyl 3,5-diaminobenzoate), 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1 -Bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1, 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) 4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2, 4-diaminophenyl) -4- (4-heptylcyclohexyl) benzamide, a compound represented by the following formula (A-1), and the like.

[化3] [Chemical 3]

(式(A-1)中，XI及XII分別為單鍵、*-O-、*-COO-或*-OOC-(其中，標注有「*」的結合鍵朝向式(A-I)的左方向)；RI為單鍵、亞甲基或者碳數2或3的伸烷基；a為0或1，b為0~2的整數，其中a及b不會同時為0；c為1~20的整數) (In formula (A-1), X I and X II are single bonds, * -O-, * -COO- or * -OOC- (wherein, the bond key marked with "*" is oriented toward the formula (AI) (Left direction); R I is a single bond, methylene, or an alkylene group having 2 or 3 carbon atoms; a is 0 or 1, and b is an integer from 0 to 2, where a and b are not 0 at the same time; c is (1 ~ 20 integer)

所述式(A-1)中的XI-RI-XII-所表示的2價基優選為亞甲基、碳數2或3的伸烷基、*-O-、*-COO-或*-O-CH2CH2-O-(其中，標注有「*」的結合鍵與二胺基苯基鍵結)。基團-CcH2c+1中c為3以上時，該基團優選為直鏈狀。二胺基苯基中的2個胺基優選為相對於其他基團而位於2,4-位或3,5-位。作為所述式(A-1)所表示的化合物的具體例，例如優選為下述式(A-1-1-1)、式(A-1-1-2)以及式(A-1-2)分別所表示的化合物。 The divalent group represented by X I -R I -X II -in the formula (A-1) is preferably a methylene group, an alkylene group having 2 or 3 carbon atoms, * -O-, * -COO- Or * -O-CH 2 CH 2 -O- (wherein the bond marked with "*" is bonded to the diaminophenyl group). When c is 3 or more in the group -C c H 2c + 1 , the group is preferably linear. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups. Specific examples of the compound represented by the formula (A-1) include, for example, the following formula (A-1-1-1), formula (A-1-1-2), and formula (A-1- 2) Compounds shown separately.

[化4] [Chemical 4]

(所述式中，「n-」分別表示直鏈狀) (In the above formula, "n-" each represents a linear shape)

不具有預傾角表現性基的其他二胺可列舉：不具有預傾角表現性基的脂肪族二胺、脂環式二胺、芳香族二胺、二胺基有機矽氧烷等。 Examples of other diamines having no pretilt-angle expressing group include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes that do not have a pretilt-angle expressing group.

不具有預傾角表現性基的其他二胺中，脂肪族二胺例如可列舉：1,1-間苯二甲胺(meta-xylylenediamine)、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等；脂環式二胺例如可列舉：1,4-二胺基環己烷、4,4'-亞甲基雙(環己基胺)、1,3-雙(胺基甲基)環己烷等；芳香族二胺例如可列舉：鄰苯二胺、間苯二胺、對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基硫醚、1,5-二胺基萘、2,2'-二甲基-4,4'-二胺基聯苯、4,4'-二胺基-2,2'-雙(三氟甲基)聯苯、2,7-二胺基芴、4,4'-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、9,9-雙(4-胺基苯基)芴、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、4,4'-(對伸苯基二亞異丙基)雙苯胺、4,4'-(間伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、3,6-二胺基咔唑(3,6-diaminocarbazole)、N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基咔唑、N-苯基-3,6-二胺基咔唑、N,N'-雙(4-胺基苯基)-聯苯胺、N,N'-雙(4-胺基苯基)-N,N'-二甲基聯苯胺、1,4-雙-(4-胺基苯基)-呱嗪、3,5-二胺基苯甲酸、4-(4'-三氟甲氧基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、4-(4'-三氟甲基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、2,4-二胺基-N,N-二烯丙基苯胺、4-胺基苄基胺、3-胺基苄基胺、1-(2,4-二胺基苯基)呱嗪-4-羧酸、4-(嗎啉-4-基)苯-1,3-二胺、1,3-雙(N-(4-胺基苯基)呱啶基)丙烷、α-胺基-ω-胺基苯基伸烷基、4-(2-胺基乙基)苯胺、下述式(N)所表示的化合物等； Among other diamines that do not have a pretilt angle expressing group, examples of the aliphatic diamine include 1,1-meta-xylylenediamine, 1,3-propanediamine, and tetramethylenediamine. , Pentamethylene diamine, hexamethylene diamine, and the like; examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) , 1,3-bis (aminomethyl) cyclohexane, etc .; Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene di Isopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine , 3,4-diaminopyridine, 2, 4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N -Ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N '-Bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -pyrazine, 3,5-diaminobenzoic acid , 4- (4'-trifluoromethoxybenzyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzyloxy) ring Hexyl-3,5-diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) pyrazine-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- (4-amine Phenyl) amidinyl) propane, α-amino-ω-aminophenylalkylene, 4- (2-aminoethyl) aniline, a compound represented by the following formula (N), and the like;

二胺基有機矽氧烷例如可列舉：1,3-雙(3-胺基丙基)-四甲基二矽氧烷等，除此以外，可使用日本專利特開2010-97188號公報中記載的二胺。 Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane, etc. In addition, Japanese Patent Laid-Open No. 2010-97188 can be used. Documented diamine.

為了合成具有所述式(1)所表示的結構的聚醯胺酸而使用的 二胺優選為相對於全部二胺，而包含1莫耳%以上的具有所述式(1)所表示的結構的二胺，更優選為包含3莫耳%以上，尤其優選為包含5莫耳%以上。 Used to synthesize a polyamidic acid having a structure represented by the formula (1) The diamine is preferably a diamine having a structure represented by the formula (1) in an amount of 1 mol% or more relative to the total diamine, more preferably 3 mol% or more, and particularly preferably 5 mol. %the above.

在將本發明的液晶配向劑應用於VA型等的垂直配向型液晶顯示元件的情況下，優選為相對於全部二胺而包含3莫耳%以上的具有預傾角表現性基的其他二胺，更優選為包含5莫耳%~90莫耳%，尤其優選為包含10莫耳%~80莫耳%。另一方面，在將本發明的液晶配向劑應用於TN型、STN型、IPS型、FFS型等水平配向型液晶顯示元件的情況下，優選為相對於全部二胺，將具有預傾角表現性基的其他二胺的比例設為20莫耳%以下，更優選為設為10莫耳%以下。 When the liquid crystal alignment agent of the present invention is applied to a vertical alignment type liquid crystal display element such as a VA type, it is preferably another diamine having a pretilt expressive group of 3 mol% or more with respect to all the diamines. It is more preferably 5 to 90 mol%, and particularly preferably 10 to 80 mol%. On the other hand, when the liquid crystal alignment agent of the present invention is applied to a horizontal alignment type liquid crystal display element such as a TN type, an STN type, an IPS type, or an FFS type, it is preferable that it has a pretilt angle expression property with respect to all diamines The proportion of other diamines of the group is 20 mol% or less, and more preferably 10 mol% or less.

向聚醯胺酸的合成反應提供的四羧酸二酐與二胺的使用比例優選為相對於二胺化合物中所含的胺基1當量，四羧酸二酐的酸酐基成為0.2當量~2當量的比例，尤其優選為成為0.3當量~1.2當量的比例。 The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of polyamic acid is preferably 1 equivalent to the amine group contained in the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent to 2 The ratio of equivalents is particularly preferably a ratio of 0.3 to 1.2 equivalents.

聚醯胺酸的合成反應優選為在有機溶劑中，優選為在-20℃~150℃、更優選為0℃~100℃的溫度條件下，優選為進行0.5小時~24小時，更優選為進行2小時~10小時。此處，有機溶劑只要是可將所合成的聚醯胺酸溶解的溶劑，則並無特別限制，例如可列舉：N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基咪唑烷酮、N,N,2-三甲基丙醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺(hexamethylphosphortriamide)等非質子系極性溶劑；間甲酚、二甲酚、苯酚、鹵化苯酚等酚系溶劑等。有機溶劑 的使用量(a)為相對於反應溶液的總量(a+b)，四羧酸二酐以及二胺化合物的總量(b)優選為成為0.1重量%~50重量%、更優選為成為5重量%~30重量%的量。 The synthesis reaction of the polyamic acid is preferably performed in an organic solvent, preferably at a temperature of -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, preferably for 0.5 to 24 hours, and more preferably for 2 hours to 10 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyamino acid, and examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazolidinone, N, N, 2-trimethylpropanamide, dimethylsulfenimide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and other aprotic polar solvents; m-cresol, xylenol, phenol, halogenated phenol and other phenolic solvents. Organic solvents The used amount (a) is relative to the total amount (a + b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is preferably 0.1% to 50% by weight, and more preferably 5 to 30% by weight.

如以上所述，獲得將聚醯胺酸溶解而成的反應溶液。該反應溶液可直接提供給液晶配向劑的製備，也可以將反應溶液中所含的聚醯胺酸離析後再提供給液晶配向劑的製備，或者也可以將經離析的聚醯胺酸純化後再提供給液晶配向劑的製備。 As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyfluorinated acid contained in the reaction solution can be isolated and then provided to the preparation of the liquid crystal alignment agent, or the isolated polyfluorinated acid can be purified. It is then provided for the preparation of the liquid crystal alignment agent.

在將聚醯胺酸進行脫水閉環而製成醯亞胺化物的情況下，可將所述反應溶液直接提供給脫水閉環反應，也可以將反應溶液中所含的聚醯胺酸離析後再提供給脫水閉環反應，或者也可以將經離析的聚醯胺酸純化後再提供給脫水閉環反應。 In the case where polyamidic acid is dehydrated and ring-closed to form a sulfonium imide, the reaction solution may be directly provided to the dehydration ring-closed reaction, or the polyphosphonic acid contained in the reaction solution may be isolated and then provided. The dehydration ring-closing reaction may be provided, or the isolated polyamidic acid may be purified and then provided to the dehydration ring-closing reaction.

聚醯胺酸的離析．純化可利用周知的方法來進行。 Isolation of polyamic acid. Purification can be performed by a known method.

具有所述式(1)所表示的結構的聚醯胺酸的醯亞胺化物可通過將以所述方式合成的聚醯胺酸進行脫水閉環，加以醯亞胺化而獲得。此時，可將醯胺酸結構的全部進行脫水閉環而完全地醯亞胺化，或者也可以僅將醯胺酸結構中的一部分進行脫水閉環而製成醯胺酸結構與醯亞胺結構並存的部分醯亞胺化物。聚醯胺酸的醯亞胺化物的醯亞胺化率優選為設為10%以上，更優選為設為30%~95%。 The polyimide of a polyamidic acid having the structure represented by the formula (1) can be obtained by dehydrating and ring-closing the polyamidic acid synthesized in the manner described above, and then performing imidization. At this time, the entire amidine structure can be dehydrated and ring-closed to complete the imidization, or only a part of the amidine structure can be dehydrated and closed to make the amidine structure and the amidine structure coexist. Part of the sulfonium imide. It is preferable that it is 10% or more, and, as for the fluorination rate of the fluorination product of a polyamic acid, 30%-95% is more preferable.

聚醯胺酸的脫水閉環可利用以下方法來進行：(i)對聚醯胺酸進行加熱的方法；或者(ii)將聚醯胺酸溶解於有機溶劑中，在該溶液中添加脫水劑及脫水閉環催化劑，視需要進行加熱的方法。這些方法中，優選為利用(ii)的方法。 The dehydration ring closure of polyamic acid can be performed by the following methods: (i) a method of heating polyamino acid; or (ii) dissolving polyamino acid in an organic solvent, adding a dehydrating agent and A method of dehydrating the closed-loop catalyst and heating if necessary. Among these methods, the method using (ii) is preferred.

另一方面，所述(ii)的方法中，脫水劑例如可使用乙酸 酐、丙酸酐、三氟乙酸酐等酸酐。相對於醯胺酸結構單元的1莫耳，脫水劑的使用量優選為設為0.01莫耳~20莫耳。另外，脫水閉環催化劑例如可使用吡啶(Pyridine)、三甲吡啶(Collidine)、二甲吡啶(Lutidine)、三乙基胺(Triethylamine)等三級胺。但是，並不限定於這些化合物。相對於所使用的脫水劑1莫耳，脫水閉環催化劑的使用量優選為設為0.01莫耳~10莫耳。脫水閉環反應中使用的有機溶劑可列舉作為聚醯胺酸的合成中使用的有機溶劑而例示的有機溶劑。脫水閉環反應的反應溫度優選為0℃~180℃，更優選為10℃~150℃，反應時間優選為0.5小時~20小時，更優選為1小時~8小時。 On the other hand, in the method (ii), the dehydrating agent may be, for example, acetic acid. Anhydrides, such as anhydrides, propionic anhydrides, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.01 to 20 mols with respect to 1 mol of the amino acid structural unit. In addition, as the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these compounds. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol relative to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as the organic solvent used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C, and the reaction time is preferably 0.5 hours to 20 hours, and more preferably 1 hour to 8 hours.

如上所述獲得含有聚醯胺酸的醯亞胺化物的反應溶液。該反應溶液可直接將其提供給液晶配向劑的製備，也可以自反應溶液中去除脫水劑及脫水閉環催化劑後再提供給液晶配向劑的製備，也可以將醯亞胺化物離析．純化後再提供給液晶配向劑的製備。脫水劑及脫水閉環催化劑的去除以及醯亞胺化物的離析．純化可利用周知的方法來進行。 A reaction solution of a polyimide-containing phosphonium imidide was obtained as described above. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then provided to the preparation of the liquid crystal alignment agent, or the sulfonium imide can be isolated. After purification, it is provided to the preparation of the liquid crystal alignment agent. Removal of dehydrating agents and dehydration ring-closing catalysts, and isolation of sulfonium imides. Purification can be performed by a known method.

本發明的液晶配向劑含有具有所述式(1)所表示的結構的聚合物作為必需成分，優選為構成為這些聚合物溶解於後述溶劑中而成的溶液組合物，視需要也可以進而含有其他成分。此處，其他成分例如可列舉：其他聚合物、分子內具有至少一個環氧基的化合物(以下稱為「環氧化合物」)、官能性矽烷化合物等。 The liquid crystal alignment agent of the present invention contains a polymer having a structure represented by the formula (1) as an essential component, and is preferably a solution composition in which these polymers are dissolved in a solvent described later, and may be further contained if necessary. Other ingredients. Here, other components include, for example, other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compounds"), functional silane compounds, and the like.

所述其他聚合物為不具有所述式(1)所表示的結構的聚合物，可用於改善本發明的液晶配向劑的溶液特性(塗布性)以及電特性。 The other polymer is a polymer having no structure represented by the formula (1), and can be used to improve the solution characteristics (coatability) and electrical characteristics of the liquid crystal alignment agent of the present invention.

其他聚合物可列舉：不具有所述式(1)所表示的結構的聚醯胺酸、該聚醯胺酸的醯亞胺化聚合物、聚醯胺酸酯、聚酯、聚醯胺、聚矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基順丁烯二醯亞胺)衍生物、聚(甲基)丙烯酸酯等。 Examples of other polymers include polyamic acid which does not have the structure represented by the formula (1), a polyimidated polymer of the polyamino acid, a polyamic acid ester, a polyester, a polyamino acid, Polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylcis butylene diimide) derivative, poly (meth) acrylate, and the like.

將聚合物的合計(意指具有所述式(1)所表示的結構的聚合物與其他聚合物的合計；以下相同)設為100重量%，其他聚合物的使用比例優選為90重量%以下，更優選為50重量%以下，特別優選為不含有其他聚合物。 The total amount of the polymer (meaning the total amount of the polymer having the structure represented by the formula (1) and other polymers; the same applies hereinafter) is 100% by weight, and the use ratio of the other polymers is preferably 90% by weight or less. , More preferably 50% by weight or less, and particularly preferably not containing other polymers.

所述環氧化合物以及官能性矽烷化合物分別可為了進一步提高所得的液晶配向膜與基板之間的密接性，而含有於本發明的液晶配向劑中。 The epoxy compound and the functional silane compound may be contained in the liquid crystal alignment agent of the present invention in order to further improve the adhesion between the obtained liquid crystal alignment film and the substrate.

所述環氧化合物例如可列舉：乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、N,N,N',N'-四縮水甘油基-間苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、N,N-二縮水甘油基-苄基胺、N,N-二縮水甘油基-胺基甲基環己烷、N,N-二縮水甘油基-環己基胺等，來作為優選者。 Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N '-Tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine and the like are preferred.

相對於聚合物的合計100重量份，這些環氧化合物的調配比例優選為40重量份以下，更優選為0.1重量份~30重量份。 The blending ratio of these epoxy compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total polymer, and more preferably 0.1 to 30 parts by weight.

所述官能性矽烷化合物例如可列舉：3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2- 胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三甲氧基矽烷基-3,6-二氮雜壬酸甲酯、9-三乙氧基矽烷基-3,6-二氮雜壬酸甲酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-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等。 Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrimethoxysilane. Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N- Ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanon Methyl acetate, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl ester, 9-triethoxysilyl-3,6-diazanonanoic acid methyl ester, N-benzyl -3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- 3-aminopropyltriethoxysilane and the like.

相對於聚合物的合計100重量份，這些官能性矽烷化合物的調配比例優選為2重量份以下，更優選為0.02重量份~0.2重量份。 The blending ratio of these functional silane compounds is preferably 2 parts by weight or less with respect to 100 parts by weight of the total polymer, and more preferably 0.02 to 0.2 parts by weight.

本發明的液晶配向劑是將具有所述式(1)所表示的結構的聚合物以及視需要而任意調配的其他成分優選為溶解而含有於溶劑中來構成。 The liquid crystal alignment agent of the present invention is preferably composed of a polymer having a structure represented by the formula (1) and other components arbitrarily blended as necessary, and dissolved in a solvent.

本發明的液晶配向劑中可使用的溶劑優選為使用有機溶劑，例如可列舉：N-甲基-2-吡咯烷酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、乙二醇甲醚、乙二醇***、乙二醇-正丙醚、乙二醇-異丙醚、乙二醇-正丁醚(丁基溶纖劑)、乙二醇二甲醚、乙二醇***乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇單甲 醚、二乙二醇單***、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二異丁基酮、丙酸異戊酯、異丁酸異戊酯、二異戊基醚、碳酸亞乙酯、碳酸亞丙酯等。這些有機溶劑可單獨使用，或者可將2種以上混合使用。 The solvent usable in the liquid crystal alignment agent of the present invention is preferably an organic solvent, and examples thereof include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, and N, N-dimethyl Formamidine, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropyl Acid ester, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve ), Ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diamine Isoamyl ether, ethylene carbonate, propylene carbonate and the like. These organic solvents may be used alone or in combination of two or more.

本發明的液晶配向劑中的固體成分濃度(液晶配向劑的溶劑以外的成分的合計重量在液晶配向劑的總重量中所占的比例)是考慮到黏性、揮發性等來適當選擇，優選為1重量%~10重量%的範圍。即，本發明的液晶配向劑通過以後述方式塗布於基板表面，優選為進行加熱，而形成成為液晶配向膜的塗膜，但在固體成分濃度小於1重量%的情況下，該塗膜的膜厚變得過小，無法獲得良好的液晶配向膜，另一方面，在固體成分濃度超過10重量%的情況下，塗膜的膜厚變得過大，無法獲得良好的液晶配向膜，另外，液晶配向劑的黏性增大，塗布特性劣化。 The solid content concentration (the ratio of the total weight of components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) in the liquid crystal alignment agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. The range is 1% to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of a substrate by a method described later, and is preferably heated to form a coating film that becomes a liquid crystal alignment film, but when the solid content concentration is less than 1% by weight, the film of the coating film When the thickness becomes too small, a good liquid crystal alignment film cannot be obtained. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and a good liquid crystal alignment film cannot be obtained. In addition, the liquid crystal alignment film cannot be obtained. The viscosity of the agent is increased, and the coating characteristics are deteriorated.

特別優選的固體成分濃度的範圍根據在基板上塗布液晶配向劑時所使用的方法而不同。例如在利用旋轉器法的情況下，固體成分濃度特別優選為1.5重量%~4.5重量%的範圍。在利用印刷法的情況下，特別優選為將固體成分濃度設為3重量%~9重量%的範圍，由此將溶液黏度設為12mPa．s~50mPa．s的範圍。在利用噴墨法的情況下，特別優選為將固體成分濃度設為1重量%~5重量%的範圍，由此將溶液黏度設為3mPa．s~15mPa．s的範圍。 A particularly preferred range of the solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when a spinner method is used, the solid content concentration is particularly preferably in a range of 1.5% to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, and thereby set the solution viscosity to 12 mPa. s ~ 50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% to 5% by weight, and thereby set the solution viscosity to 3 mPa. s ~ 15mPa. The range of s.

製備本發明的液晶配向劑時的溫度優選為10℃~45℃，更優選為20℃~30℃。 The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 10 ° C to 45 ° C, and more preferably 20 ° C to 30 ° C.

可使用本發明的液晶配向劑來形成液晶配向膜。即，可通過在基板上塗布本發明的液晶配向劑而形成塗膜，優選為經由 對該塗膜實施摩擦處理或者光照射處理的步驟來形成液晶配向膜。 The liquid crystal alignment agent of the present invention can be used to form a liquid crystal alignment film. That is, a coating film can be formed by applying the liquid crystal alignment agent of the present invention on a substrate, and it is preferably via A step of rubbing treatment or light irradiation treatment is performed on the coating film to form a liquid crystal alignment film.

本發明的液晶配向劑可應用於製造具有例如TN型、STN型、IPS型、FFS型、VA型、MVA型等適當的液晶單元的液晶顯示元件。然而，就最大限度的發揮本發明的有利功效的方面而言，優選為應用於具有TN型、STN型、IPS型、FFS型等所謂水平配向型液晶單元的液晶顯示元件。 The liquid crystal alignment agent of the present invention can be applied to the production of a liquid crystal display element having suitable liquid crystal cells such as a TN type, an STN type, an IPS type, an FFS type, a VA type, and an MVA type. However, in terms of maximizing the advantageous effects of the present invention, it is preferably applied to a liquid crystal display element having a so-called horizontal alignment type liquid crystal cell such as a TN type, an STN type, an IPS type, or an FFS type.

在將由本發明的液晶配向劑形成的液晶配向膜應用於TN型或STN型液晶顯示元件的情況下，作為所述基板，將設置有經圖案化的透明導電膜的2塊基板用作一對，所述液晶配向劑塗布於各基板的形成有透明性導電膜的面上。另一方面，在將液晶配向膜應用於IPS型或FFS型液晶顯示元件的情況下，作為所述基板，將在其中一面具有透明導電膜或金屬膜經圖案化為梳齒狀的電極的基板、以及未設置電極的對向基板用作一對，所述液晶配向劑塗布於梳齒狀電極的形成面、以及對向基板的其中一面。 When a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is applied to a TN-type or STN-type liquid crystal display element, as the substrate, two substrates provided with a patterned transparent conductive film are used as a pair The liquid crystal alignment agent is applied on a surface of each substrate on which a transparent conductive film is formed. On the other hand, when a liquid crystal alignment film is applied to an IPS-type or FFS-type liquid crystal display element, as the substrate, a substrate having a transparent conductive film or a metal film patterned into a comb-shaped electrode on one side thereof is used. And a counter substrate without an electrode is used as a pair, and the liquid crystal alignment agent is applied to a formation surface of the comb-shaped electrode and one surface of the counter substrate.

在所述任一種情況下，所述基板均可使用：例如浮法玻璃(float glass)、鈉玻璃之類的玻璃；包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯之類的塑膠的透明基板等。所述透明導電膜例如可使用包含In2O3-SnO2的氧化銦錫．(indium tin oxide，ITO)膜、包含SnO2的奈塞(NESA)(注冊商標)膜等。所述金屬膜可使用例如包含鉻等金屬的膜。透明導電膜以及金屬膜的圖案化中可利用以下方法：例如在形成無圖案的透明導電膜後，利用光蝕刻法(photoetchingmethod)、濺射法等來形成圖案的方法；以及在形成透明導電膜時使用具有所需圖 案的遮罩的方法等。 In either case, the substrate can be used: glass such as float glass, soda glass; containing polyethylene terephthalate, polybutylene terephthalate, Plastic transparent substrates such as polyether fluorene and polycarbonate. The transparent conductive film may be, for example, indium tin oxide containing In 2 O 3 -SnO 2 . (indium tin oxide, ITO) film, Nesa (registered trademark) film containing SnO 2 and the like. As the metal film, for example, a film containing a metal such as chromium can be used. For the patterning of the transparent conductive film and the metal film, the following methods can be used: for example, a method of forming a pattern using a photoetching method, a sputtering method, or the like after forming a patternless transparent conductive film; and forming a transparent conductive film When using a mask with a desired pattern, etc.

將光配向用液晶配向劑塗布於基板上時，為了使基板、以及透明導電膜或金屬膜與塗膜的黏接性更良好，可在基板以及透明導電膜或金屬膜上預先塗布官能性矽烷化合物、鈦酸酯化合物等。 When the liquid crystal alignment agent for photo-alignment is coated on a substrate, in order to make the substrate and the transparent conductive film or the metal film have better adhesion with the coating film, a functional silane may be pre-coated on the substrate and the transparent conductive film or metal film. Compounds, titanate compounds, and the like.

光配向用液晶配向劑在基板上的塗布可優選地利用膠版印刷法(off-set printing)、旋轉塗布法、輥塗布機法、噴墨印刷法等適當的塗布方法來進行，繼而，對塗布面進行預加熱(預烘烤)以及後加熱(後烘烤)，由此形成塗膜。預烘烤條件優選為在40℃~120℃下進行0.1分鐘~5分鐘。後烘烤條件優選為在120℃~300℃、更優選為150℃~250℃下，優選為進行5分鐘~200分鐘、更優選為10分鐘~100分鐘。 The application of the liquid crystal alignment agent for photo-alignment on a substrate can be preferably performed by an appropriate coating method such as an off-set printing method, a spin coating method, a roll coater method, an inkjet printing method, and the like. The surface is pre-heated (pre-baked) and post-heated (post-baked) to form a coating film. The pre-baking conditions are preferably performed at 40 ° C to 120 ° C for 0.1 minute to 5 minutes. The post-baking conditions are preferably 120 ° C to 300 ° C, more preferably 150 ° C to 250 ° C, preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes.

繼而，通過經由對以所述方式形成的塗膜實施摩擦處理或光照射處理的步驟，而對塗膜賦予液晶配向能力來製成液晶配向膜。此處，在所述式(1)中的X1及X2中的至少一者為酯鍵的情況下，優選為進行光照射處理，在其以外的情況下優選為進行摩擦處理。 Then, a liquid crystal alignment film is produced by providing a liquid crystal alignment ability to a coating film by the process of performing a rubbing process or a light irradiation process on the coating film formed as mentioned above. Here, when at least one of X 1 and X 2 in the formula (1) is an ester bond, it is preferable to perform a light irradiation treatment, and it is preferable to perform a rubbing treatment in other cases.

摩擦處理可通過如下方式來進行：利用捲繞有包含例如尼龍、人造絲(Reon)、棉等纖維的布的輥，將形成於基板上的塗膜的面，向一定方向擦拭。 The rubbing treatment can be performed by wiping a surface of a coating film formed on a substrate with a roller wound with a cloth containing fibers such as nylon, rayon (Reon), and cotton in a certain direction.

光照射處理中所照射的光例如可使用包含150nm~800nm波長的光的紫外線、可見光線等。作為所照射的光，優選為使用包含200nm~400nm波長的光的紫外線。所使用的光源例如可使用低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、Hg-Xe燈、準分子鐳射等。所述的優選波長區域的紫外線 可通過將所述光源與例如濾光器、衍射光柵等並用的方法等來獲得。照射光可以是偏光，也可以是非偏光，優選為偏光。照射方向優選為設為相對於基板面而垂直的方向。 As the light to be irradiated in the light irradiation treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. As the light to be irradiated, ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferably used. The light source used may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an Hg-Xe lamp, an excimer laser, or the like. UV in the preferred wavelength range It can be obtained by a method in which the light source is used in combination with, for example, a filter, a diffraction grating, and the like. The irradiation light may be polarized light or non-polarized light, and is preferably polarized light. The irradiation direction is preferably a direction perpendicular to the substrate surface.

光的照射量優選為100J/m2以上，更優選為400J/m2~20,000J/m2，尤其優選為1,000J/m2~10,000J/m2。 Light irradiation amount is preferably 100J / m 2 or more, and more preferably 400J / m 2 ~ 20,000J / m 2, particularly preferably 1,000J / m 2 ~ 10,000J / m 2.

可使用本發明的液晶配向劑，以所述方式在基板上形成液晶配向膜。使用具有該液晶配向膜的基板，能夠以下述方式來製造液晶顯示元件。 The liquid crystal alignment agent of the present invention can be used to form a liquid crystal alignment film on a substrate in the manner described above. Using a substrate having this liquid crystal alignment film, a liquid crystal display element can be manufactured in the following manner.

準備以所述方式形成有液晶配向膜的一對基板，製造在該一對基板間夾持有液晶的構成的液晶單元。為了製造液晶單元，例如可列舉以下的2種方法。 A pair of substrates having a liquid crystal alignment film formed as described above is prepared, and a liquid crystal cell having a structure in which a liquid crystal is sandwiched between the pair of substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

第1方法可列舉如下方法：以各液晶配向膜對向的方式，經由間隙(單元空隙)而將一對基板對向配置，使用密封劑將該一對基板的周邊部貼合，在由基板表面以及適當的密封劑所劃分的單元空隙內注入填充液晶後，將注入孔密封，由此來製造液晶單元。 The first method may be a method in which a pair of substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the pair of substrates are bonded using a sealant, and The liquid crystal cell is manufactured by injecting and filling liquid crystal into the cell gap defined by the surface and an appropriate sealant, and then sealing the injection hole.

第2方法可列舉如下方法(液晶滴注(One Drop Fill，ODF)法)：在形成有液晶配向膜的2塊基板中的其中一塊基板上的既定部位，塗布例如紫外光硬化性的密封劑，進而在液晶配向膜面上的既定的數個部位滴加液晶後，以液晶配向膜對向的方式貼合另一塊基板，並且使液晶在基板整個面上鋪開，繼而對基板的整個面照射紫外光而使密封劑硬化，由此製造液晶單元。 The second method includes a method (One Drop Fill (ODF) method) in which a UV-curable sealant is applied to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed. Then, after the liquid crystal is dropped on predetermined positions on the liquid crystal alignment film surface, another substrate is bonded in a manner that the liquid crystal alignment film faces, and the liquid crystal is spread on the entire surface of the substrate, and then the entire surface of the substrate is spread. Ultraviolet light is irradiated to harden the sealant, thereby manufacturing a liquid crystal cell.

在利用所述任一種方法的情況下，均優選為繼而將液晶單元加熱至所使用的液晶取得各向同性相的溫度為止，然後緩緩 冷卻至室溫，由此去除液晶填充時的流動配向。而且，通過在液晶單元的外側表面以既定的方向貼合偏光板，可獲得本發明的液晶顯示元件。 In the case of using any of the methods, it is preferable to heat the liquid crystal cell to a temperature at which the used liquid crystal acquires an isotropic phase, and then slowly Cooling to room temperature removes the flow alignment during liquid crystal filling. Furthermore, by bonding a polarizing plate in a predetermined direction on the outer surface of the liquid crystal cell, the liquid crystal display element of the present invention can be obtained.

所述液晶例如可使用向列型液晶(nematic liquid crystal)、碟狀液晶(smectic liquid crystal)等。 The liquid crystal may be, for example, a nematic liquid crystal, a smectic liquid crystal, or the like.

在製造水平配向類型的液晶顯示元件的情況下，優選為具有正的介電各向異性的向列型液晶，例如可使用：聯苯基系液晶、苯基環己烷系液晶、酯系液晶、三聯苯系液晶、聯苯基環己烷系液晶、嘧啶系液晶、氟化苯系液晶、二噁烷系液晶、雙環辛烷系液晶、立方烷(cubane)系液晶等。也可以在這些液晶中添加膽甾醇液晶、手性劑、鐵電液晶(ferroelectric liquid crystal)等來使用。另一方面，在製造垂直配向類型的液晶顯示元件的情況下，優選為具有負的介電各向異性的向列型液晶，例如可使用二氰基苯系液晶、噠嗪(pyridazine)系液晶、希夫鹼(Schiff base)系液晶、氧化偶氮系液晶、聯苯系液晶、苯基環己烷系液晶等。 In the case of manufacturing a liquid crystal display element of a horizontal alignment type, a nematic liquid crystal having a positive dielectric anisotropy is preferred. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, and an ester liquid crystal can be used. , Terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, fluorinated benzene liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. A cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, or the like may be added to these liquid crystals and used. On the other hand, in the case of manufacturing a liquid crystal display element of a vertical alignment type, a nematic liquid crystal having a negative dielectric anisotropy is preferred. For example, a dicyanobenzene-based liquid crystal and a pyridazine-based liquid crystal can be used. , Schiff base liquid crystal, azo oxide liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like.

液晶單元的外側所使用的偏光板可列舉：以乙酸纖維素保護膜夾持被稱為「H膜」的偏光膜而成的偏光板、或者包含H膜其本身的偏光板等，所述「H膜」是使聚乙烯醇一邊延伸配向一邊吸收碘而成的膜。 Examples of the polarizing plate used on the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called an “H film” is sandwiched by a cellulose acetate protective film, or a polarizing plate including the H film itself. The "H film" is a film formed by absorbing iodine while extending the orientation of polyvinyl alcohol.

[實施例] [Example]

<具有所述式(1)所表示的結構的二胺的合成> <Synthesis of a diamine having a structure represented by the formula (1)>

合成例MDA-1 Synthesis example MDA-1

依據下述流程1，來合成式(MDA-1)所表示的化合物(化合物(MDA-1))。 A compound represented by the formula (MDA-1) (compound (MDA-1)) was synthesized according to the following scheme 1.

(流程1中，Boc為第三丁氧基羰基) (In Scheme 1, Boc is the third butoxycarbonyl group)

在反應容器中，將3,5-二溴吡啶11.8g(0.050莫耳)、三-鄰甲苯基膦609mg(2.0毫莫耳)以及作為催化劑的乙酸鈀112mg(0.5毫莫耳)進行混合，進行氮氣置換後，添加N,N-二甲基甲醯胺152mL、三乙基胺16.7mL(0.120莫耳)以及丙烯酸第三丁酯17.5mL(0.120莫耳)，在120℃下一邊攪拌一邊進行3小時反應。反應完畢後，向反應混合物中吹入空氣，以使乙酸鈀失活。通過矽藻土過濾來去除催化劑殘渣後，在濾液中添加乙酸乙酯500mL，將所得的有機層利用蒸餾水500mL進行4次提取洗滌。繼而，對於通過減壓自有機層中去除溶劑而獲得的固體，使用乙醇150mL來進行再結晶，獲得黃色的化合物(mda-1-1)13.6g(0.041莫耳，產率為82%)。 In a reaction vessel, 11.8 g (0.050 mol) of 3,5-dibromopyridine, 609 mg (2.0 mmol) of tri-o-tolylphosphine, and 112 mg (0.5 mmol) of palladium acetate as a catalyst were mixed. After nitrogen substitution, 152 mL of N, N-dimethylformamide, 16.7 mL of triethylamine (0.120 mol), and 17.5 mL (0.120 mol) of third butyl acrylate were added, and stirred at 120 ° C The reaction was performed for 3 hours. After completion of the reaction, air was blown into the reaction mixture to deactivate palladium acetate. After removing the catalyst residue by diatomaceous earth filtration, 500 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed 4 times with 500 mL of distilled water. Then, the solid obtained by removing the solvent from the organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 13.6 g (0.041 mole, yield: 82%) of a yellow compound (mda-1-1).

在具備旋塞的反應容器中，將所述獲得的化合物(mda-1-1) 13.6g(0.041莫耳)以及5重量%鈀碳(50重量%含水品)1.36g進行混合，進行氮氣置換後，添加四氫呋喃80mL以及乙醇80mL，在旋塞上安裝加入有氫氣的氣球，使容器處於氫氣環境下，在該環境下在50℃下一邊攪拌一邊進行5小時反應。反應完畢後，通過矽藻土過濾而自反應混合物中去除鈀碳後，通過減壓，自所得的濾液中去除溶劑，獲得淡褐色的化合物(mda-1-2)13.1g(0.039莫耳，產率為95%)。 In a reaction vessel provided with a cock, the obtained compound (mda-1-1) 13.6 g (0.041 mole) and 1.36 g of 5 wt% palladium on carbon (50 wt% water-containing product) were mixed. After nitrogen substitution, 80 mL of tetrahydrofuran and 80 mL of ethanol were added. A balloon with hydrogen gas was installed on the cock, and the container was placed Under a hydrogen atmosphere, a reaction was performed for 5 hours under stirring at 50 ° C in this environment. After the reaction was completed, palladium on carbon was removed from the reaction mixture by filtration through diatomaceous earth, and then the solvent was removed from the obtained filtrate under reduced pressure to obtain 13.1 g (0.039 moles) of a light brown compound (mda-1-2). The yield is 95%).

在反應容器中，將所述獲得的化合物(mda-1-2)13.1g(0.039莫耳)、二氯甲烷80mL以及三氟乙酸40mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於通過減壓自反應混合物中去除溶劑而獲得的固體，使用乙醇120mL來進行再結晶，獲得淡褐色的化合物(mda-1-3)7.14g(0.032莫耳，產率為82%)。 In a reaction vessel, 13.1 g (0.039 mole) of the obtained compound (mda-1-2), 80 mL of dichloromethane, and 40 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours while stirring at 20 ° C. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 120 mL of ethanol to obtain 7.14 g (0.032 mol, yield 82) of a light brown compound (mda-1-3). %).

繼而，在反應容器中，將所述獲得的化合物(mda-1-3)7.14g(0.032莫耳)、4-(第三丁氧基羰基胺基)苯酚13.4g(0.064莫耳)以及二氯甲烷128mL進行混合。將容器在冰浴中冷卻，使內溫維持在5℃，並且添加1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽14.7g(0.077莫耳)以及N,N-二甲基-4-胺基吡啶1.56g(0.013莫耳)後，在20℃下一邊攪拌一邊進行2小時反應。反應完畢後，向反應混合物中添加乙酸乙酯300mL，將所得的有機層利用蒸餾水300mL進行3次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇100mL來進行再結晶，獲得淡褐色的化合物(mda-1-4)15.7g(0.026莫耳，產率為81%)。 Next, in a reaction vessel, 7.14 g (0.032 moles) of the obtained compound (mda-1-3), 13.4 g (0.064 moles) of 4- (third butoxycarbonylamino) phenol, and two 128 mL of methyl chloride was mixed. The container was cooled in an ice bath, the internal temperature was maintained at 5 ° C, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 14.7 g (0.077 mol) was added. ) And 1.56 g (0.013 mole) of N, N-dimethyl-4-aminopyridine, and then reacted at 20 ° C for 2 hours while stirring. After completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed three times with 300 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 100 mL of ethanol to obtain 15.7 g (0.026 mole, yield 81%) of a light brown compound (mda-1-4). ).

進而，在反應容器中，將所述獲得的化合物(mda-1-4)15.7 g(0.026莫耳)、二氯甲烷52mL以及三氟乙酸26mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於通過減壓自反應混合物中去除溶劑而獲得的固體，使用乙醇100mL來進行再結晶，由此獲得紫色的化合物(MDA-1)8.86g(0.022莫耳，產率為84%)。 Further, in a reaction vessel, the obtained compound (mda-1-4) was 15.7 g (0.026 mole), 52 mL of dichloromethane, and 26 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours while stirring at 20 ° C. After the reaction was completed, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 100 mL of ethanol to obtain 8.86 g (0.022 mole, yield 84%) of a purple compound (MDA-1). ).

合成例MDA-2 Synthesis example MDA-2

依據下述流程2，來合成式(MDA-2)所表示的化合物(化合物(MDA-2))。 A compound represented by Formula (MDA-2) (Compound (MDA-2)) was synthesized according to the following Scheme 2.

(流程2中，Boc為第三丁氧基羰基) (In Scheme 2, Boc is the third butoxycarbonyl group)

在反應容器中，將3,5-二甲吡啶(lutidine)6.43g(0.060莫耳)、乙腈60mL、N-氯丁二醯亞胺(N-chlorosuccinimide)48.1 g(0.360莫耳)以及2,2'-偶氮雙(異丁腈)2.46g(0.015莫耳)進行混合，在80℃下一邊攪拌一邊進行8小時反應。反應完畢後，對於通過減壓自反應混合物中去除溶劑而獲得的固體，利用管柱色譜法(填充材料：矽膠，展開溶劑：己烷/乙酸乙酯=3/1(體積比))進行純化，由此獲得淡褐色的化合物(mda-2-1)6.65g(0.038莫耳，產率為63%)。 In a reaction vessel, 6.43 g (0.060 mole) of 3,5-lutidine (0.060 mol), 60 mL of acetonitrile, and N-chlorosuccinimide 48.1 g (0.360 mol) and 2,2'-azobis (isobutyronitrile) 2.46 g (0.015 mol) were mixed, and the reaction was carried out for 8 hours while stirring at 80 ° C. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was purified by column chromatography (filling material: silica gel, developing solvent: hexane / ethyl acetate = 3/1 (volume ratio)). Thus, 6.65 g (0.038 moles, yield 63%) of a light brown compound (mda-2-1) was obtained.

繼而，在反應容器中，將所述獲得的化合物(mda-2-1)6.65g(0.038莫耳)、4-(第三丁氧基羰基胺基)苯酚15.9g(0.076莫耳)、N,N-二甲基乙醯胺190mL以及碳酸鉀12.6g(0.091莫耳)進行混合，在90℃下一邊攪拌一邊進行5小時反應。反應完畢後，向反應混合物中添加乙酸乙酯300mL，將所得的有機層利用蒸餾水300mL進行4次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇100mL來進行再結晶，獲得淡褐色的化合物(mda-2-2)16.6g(0.032莫耳，產率為84%)。 Next, in a reaction vessel, 6.65 g (0.038 mole) of the obtained compound (mda-2-1), 15.9 g (0.076 mole) of 4- (third butoxycarbonylamino) phenol, and N 190 mL of N-dimethylacetamide and 12.6 g (0.091 mol) of potassium carbonate were mixed and reacted at 90 ° C for 5 hours while stirring. After the reaction was completed, 300 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed 4 times with 300 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 100 mL of ethanol to obtain 16.6 g (0.032 mol, 84% yield of pale brown compound (mda-2-2)). ).

進而，將所述獲得的化合物(mda-2-2)16.6g(0.032莫耳)、二氯甲烷64mL以及三氟乙酸32mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於通過減壓自反應混合物中去除溶劑而獲得的固體，使用乙醇100mL來進行再結晶，由此獲得紫色的化合物(MDA-2)9.26g(0.029莫耳，產率為90%)。 Furthermore, 16.6 g (0.032 mol) of the obtained compound (mda-2-2), 64 mL of dichloromethane, and 32 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours while stirring at 20 ° C. After the reaction was completed, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 100 mL of ethanol to obtain 9.26 g (0.029 mol, 90% yield of the purple compound (MDA-2)). ).

合成例MDA-3 Synthesis example MDA-3

依據下述流程3，來合成式(MDA-3)所表示的化合物(化合物(MDA-3))。 A compound (compound (MDA-3)) represented by the formula (MDA-3) was synthesized according to the following scheme 3.

[化8] [Chemical 8]

在安裝有迪安-斯塔克(Dean-Stark)管的燒瓶中，將4-胺基苯酚17.9g(0.164莫耳)、二甲基亞碸80mL、甲苯8.0mL以及氫氧化鉀9.88g(0.176莫耳)進行混合，在135℃下攪拌4小時，通過共沸來去除水後，使溫度降低至100℃，添加2,6-二氯吡啶11.8g(0.080莫耳)後，再次使溫度上升至135℃，一邊攪拌一邊進行4小時反應。反應完畢後，在蒸餾水500mL中注入反應混合物，回收所生成的析出物。對於回收的析出物，使用乙醇100mL來進行再結晶，由此獲得紫色的化合物(MDA-3)15.9g(0.054莫耳，產率為68%)。 In a flask equipped with a Dean-Stark tube, 17.9 g (0.164 mol) of 4-aminophenol, 80 mL of dimethyl sulfene, 8.0 mL of toluene, and 9.88 g of potassium hydroxide ( 0.176 mol), and stirred at 135 ° C for 4 hours. After azeotropic removal of water, the temperature was lowered to 100 ° C. After adding 11.8 g (0.080 mol) of 2,6-dichloropyridine, the temperature was increased again. The temperature was raised to 135 ° C, and the reaction was performed for 4 hours while stirring. After completion of the reaction, the reaction mixture was poured into 500 mL of distilled water, and the produced precipitate was recovered. The recovered precipitate was recrystallized using 100 mL of ethanol to obtain 15.9 g (0.054 mole, yield: 68%) of a purple compound (MDA-3).

合成例MDA-4 Synthesis example MDA-4

依據下述流程4，來合成式(MDA-4)所表示的化合物(化合物(MDA-4))。 A compound (compound (MDA-4)) represented by the formula (MDA-4) was synthesized according to the following scheme 4.

[化9] [Chemical 9]

(流程4中，Boc為第三丁氧基羰基) (In Scheme 4, Boc is the third butoxycarbonyl group)

在反應容器中，將4-(第三丁氧基羰基胺基)苯酚20.3g(0.097莫耳)、四氫呋喃300mL以及三乙基胺27.0mL(0.194莫耳)進行混合。將容器在冰浴下進行冷卻，並且滴加將5-溴化菸鹼醯氯(5-bromonicotinoyl chloride)19.4g(0.088毫莫耳)溶解於四氫呋喃50mL中而成的溶液。滴加完畢後，升溫至20℃，在該溫度下一邊攪拌一邊進行4小時反應。反應完畢後，向反應混合物中添加乙酸乙酯750mL，將所得的有機層利用蒸餾水750mL進行4次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇150mL來進行再結晶，獲得淡褐色的化合物(mda-4-1)29.4g(0.075莫耳，產率為85%)。 In a reaction vessel, 20.3 g (0.097 mol) of 4- (third butoxycarbonylamino) phenol, 300 mL of tetrahydrofuran, and 27.0 mL (0.194 mol) of triethylamine were mixed. The container was cooled in an ice bath, and a solution prepared by dissolving 19.4 g (0.088 mmol) of 5-bromonicotinoyl chloride in 50 mL of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the temperature was raised to 20 ° C., and the reaction was performed at this temperature with stirring for 4 hours. After the reaction was completed, 750 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed four times with 750 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 29.4 g (0.075 mol, 85% yield of pale brown compound (mda-4-1)). ).

繼而，在反應容器中，將所述獲得的化合物(mda-4-1)29.4g(0.075莫耳)、N-[4-(4,4,5,5-N-四甲基-1,3,2-二氧硼戊環-2- 基)苯基]胺基甲酸第三丁酯23.9g(0.075莫耳)、碳酸鈉15.9g(0.150莫耳)以及作為催化劑的[1,1'-雙(二苯基膦基)二茂鐵]二氯鈀2.74g(3.75毫莫耳)進行混合，進行氮氣置換後，進而添加甲苯40mL、乙醇40mL以及蒸餾水40mL，在60℃下一邊攪拌一邊進行16小時反應。反應完畢後，向反應混合物中吹入空氣，以使鈀催化劑失活，然後，通過矽藻土過濾來去除催化劑殘渣。向濾液中添加乙酸乙酯500mL，將所得的有機層利用蒸餾水500mL進行4次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇200mL來進行再結晶，獲得淡褐色的化合物(mda-4-2)22.8g(0.045莫耳，產率為60%)。 Next, in a reaction vessel, 29.4 g (0.075 mole) of the obtained compound (mda-4-1), N- [4- (4,4,5,5-N-tetramethyl-1, 3,2-Dioxolane-2- Phenyl) phenyl] 3,3-butylaminocarbamate (0.075 mole), 15.9 g (0.150 mole) of sodium carbonate, and [1,1'-bis (diphenylphosphino) ferrocene as a catalyst ] 2.74 g (3.75 mmol) of dichloropalladium were mixed, and after nitrogen substitution, 40 mL of toluene, 40 mL of ethanol, and 40 mL of distilled water were added, and the reaction was carried out at 60 ° C. for 16 hours while stirring. After completion of the reaction, air was blown into the reaction mixture to deactivate the palladium catalyst, and then the catalyst residue was removed by filtration through celite. 500 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed four times with 500 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 200 mL of ethanol to obtain 22.8 g (0.045 mole, yield 60%) of a light brown compound (mda-4-2). ).

在反應容器中，將所述獲得的化合物(mda-4-2)22.8g(0.045莫耳)、二氯甲烷90mL以及三氟乙酸45mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於通過減壓來去除溶劑而獲得的固體，使用乙酸乙酯30mL以及己烷120mL來進行再結晶，由此獲得褐色的化合物(MDA-4)11.0g(0.036莫耳，產率為80%)。 In a reaction container, 22.8 g (0.045 moles) of the obtained compound (mda-4-2), 90 mL of dichloromethane, and 45 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours while stirring at 20 ° C. After the reaction, the solid obtained by removing the solvent under reduced pressure was recrystallized using 30 mL of ethyl acetate and 120 mL of hexane to obtain 11.0 g (0.036 mole, yield of brown compound (MDA-4)). 80%).

合成例MDA-5 Synthesis example MDA-5

依據下述流程5，來合成式(MDA-5)所表示的化合物(化合物(MDA-5))。 A compound (compound (MDA-5)) represented by the formula (MDA-5) was synthesized according to the following scheme 5.

[化10] [Chemical 10]

(流程5中，Boc為第三丁氧基羰基) (In Scheme 5, Boc is the third butoxycarbonyl group)

在反應容器中，將5-溴-2-碘吡啶42.6g(0.150莫耳)、N-[4-(4,4,5,5-N-四甲基-1,3,2-二氧硼戊環-2-基)苯基]胺基甲酸第 三丁酯47.9g(0.150莫耳)、碳酸鈉47.7g(0.450莫耳)以及作為催化劑的四(三苯基膦)鈀8.67g(7.50毫莫耳)進行混合，進行氮氣置換後，添加四氫呋喃500mL以及蒸餾水250mL，在60℃下一邊攪拌一邊進行20小時反應。反應完畢後，向反應混合物中吹入空氣，以使鈀催化劑失活，然後，進行矽藻土過濾來去除催化劑殘渣。向濾液中添加乙酸乙酯1,000mL，將所得的有機層利用蒸餾水800mL進行4次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇300mL來進行再結晶，獲得淡褐色的化合物(mda-5-1)29.3g(0.084莫耳，產率為56%)。 In a reaction vessel, 42.6 g (0.150 mol) of 5-bromo-2-iodopyridine, N- [4- (4,4,5,5-N-tetramethyl-1,3,2-dioxy Borpentyl-2-yl) phenyl] aminocarboxylic acid 47.9 g (0.150 mol) of tributyl ester, 47.7 g (0.450 mol) of sodium carbonate, and 8.67 g (7.50 mmol) of tetrakis (triphenylphosphine) palladium as a catalyst were mixed. After nitrogen substitution, tetrahydrofuran was added. 500 mL and 250 mL of distilled water were reacted for 20 hours while stirring at 60 ° C. After completion of the reaction, air was blown into the reaction mixture to deactivate the palladium catalyst, and then diatomaceous earth was filtered to remove the catalyst residue. 1,000 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed four times with 800 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 300 mL of ethanol to obtain 29.3 g (0.084 mol, 56% yield of pale brown compound (mda-5-1)). ).

繼而，在反應容器中，將所述獲得的化合物(mda-5-1)29.3g(0.084莫耳)、三-鄰甲苯基膦1.02g(3.4毫莫耳)以及作為催化劑的乙酸鈀189mg(0.84毫莫耳)進行混合，進行氮氣置換後，添加N,N-二甲基甲醯胺255mL、三乙基胺14.0mL(0.100莫耳)以及丙烯酸第三丁酯14.6mL(0.100莫耳)，在120℃下一邊攪拌一邊進行4小時反應。反應完畢後，向反應混合物中吹入空氣，以使鈀催化劑失活，通過矽藻土過濾來去除催化劑殘渣。向濾液中添加乙酸乙酯700mL，將所得的有機層利用蒸餾水700mL進行4次提取洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇250mL來進行再結晶，獲得淡褐色的化合物(mda-5-2)26.2g(0.066莫耳，產率為79%)。 Next, in a reaction container, 29.3 g (0.084 mole) of the obtained compound (mda-5-1), 1.02 g (3.4 mmol) of tri-o-tolylphosphine, and 189 mg of palladium acetate as a catalyst ( (0.84 mmol), and after nitrogen substitution, 255 mL of N, N-dimethylformamide, 14.0 mL of triethylamine (0.100 mole), and 14.6 mL (0.100 mole) of third butyl acrylate were added. The reaction was carried out for 4 hours while stirring at 120 ° C. After the reaction was completed, air was blown into the reaction mixture to deactivate the palladium catalyst, and the catalyst residue was removed by filtration through celite. 700 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed four times with 700 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 250 mL of ethanol to obtain 26.2 g (0.066 mol, 79% yield of pale brown compound (mda-5-2)). ).

在具備旋塞的反應容器中，將所述獲得的化合物(mda-5-2)26.2g(0.066莫耳)以及5重量%鈀碳(50重量%含水)2.62g進行混合，進行氮氣置換後，添加四氫呋喃132mL以及乙醇132mL。在反應容器的旋塞上安裝加入有氫氣的氣球，使 容器中處於氫氣環境下，在該環境下在50℃下一邊攪拌一邊進行5小時反應。反應完畢後，通過矽藻土過濾而自反應混合物中去除鈀碳，在減壓下自所得的濾液中去除溶劑，獲得淡褐色的化合物(mda-5-3)24.3g(0.061莫耳，產率為93%)。 In a reaction vessel provided with a cock, 26.2 g (0.066 mole) of the obtained compound (mda-5-2) and 2.62 g of 5% by weight palladium carbon (50% by weight of water) were mixed and replaced with nitrogen. 132 mL of tetrahydrofuran and 132 mL of ethanol were added. Install a balloon filled with hydrogen on the cock of the reaction vessel so that The container was placed under a hydrogen atmosphere, and the reaction was performed for 5 hours under stirring at 50 ° C in this environment. After the reaction was completed, palladium carbon was removed from the reaction mixture by filtration through diatomaceous earth, and the solvent was removed from the obtained filtrate under reduced pressure to obtain 24.3 g (0.061 moles) of light brown compound (mda-5-3). (93%).

在反應容器中，將所述獲得的化合物(mda-5-3)24.3g(0.061莫耳)、二氯甲烷120mL以及三氟乙酸60mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於在減壓下自反應混合物中去除溶劑而獲得的固體，使用乙醇150mL來進行再結晶，獲得淡褐色的化合物(mda-5-4)18.5g(0.054莫耳，產率為89%)。 In a reaction vessel, 24.3 g (0.061 mole) of the obtained compound (mda-5-3), 120 mL of dichloromethane, and 60 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours while stirring at 20 ° C. After the reaction was completed, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 150 mL of ethanol to obtain 18.5 g (0.054 moles) of a pale brown compound (mda-5-4) with a yield of 89%).

繼而在反應容器中，將所述獲得的化合物(mda-5-4)18.5g(0.054莫耳)、4-(第三丁氧基羰基胺基)苯酚11.3g(0.054莫耳)以及二氯甲烷108mL進行混合，在冰浴下冷卻至5℃，並且向其中添加1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽12.4g(0.065莫耳)以及N,N-二甲基-4-胺基吡啶1.32g(0.011莫耳)。然後升溫至20℃，在該溫度下一邊攪拌一邊進行3小時反應。反應完畢後，向反應混合物中添加乙酸乙酯500mL，將所得的有機層利用蒸餾水500mL進行3次洗滌。對於通過減壓自洗滌後的有機層中去除溶劑而獲得的固體，使用乙醇150mL來進行再結晶，獲得淡褐色的化合物(mda-5-5)25.6g(0.048莫耳，產率為89%)。 Then, in a reaction container, 18.5 g (0.054 mole) of the obtained compound (mda-5-4), 11.3 g (0.054 mole) of 4- (third butoxycarbonylamino) phenol, and dichloride were obtained. 108 mL of methane was mixed, cooled to 5 ° C under an ice bath, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 12.4 g (0.065 moles) was added thereto. ) And N, N-dimethyl-4-aminopyridine 1.32 g (0.011 mole). Then, the temperature was raised to 20 ° C, and the reaction was carried out for 3 hours while stirring at this temperature. After completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with 500 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 25.6 g (0.048 mol, 89% yield of pale brown compound (mda-5-5) ).

進而在反應容器中，將所述獲得的化合物(mda-5-5)25.6g(0.048莫耳)、二氯甲烷96mL以及三氟乙酸48mL進行混合，在20℃下一邊攪拌一邊進行3小時反應。反應完畢後，對於通過減壓自反應混合物中去除溶劑而獲得的固體，使用乙醇150mL來 進行再結晶，由此獲得紫色的化合物(MDA-5)12.7g(0.038莫耳，產率為80%)。 Further, 25.6 g (0.048 mole) of the obtained compound (mda-5-5), 96 mL of dichloromethane, and 48 mL of trifluoroacetic acid were mixed in a reaction container, and the reaction was carried out for 3 hours while stirring at 20 ° C. . After the reaction was completed, 150 mL of ethanol was used for the solid obtained by removing the solvent from the reaction mixture under reduced pressure. Recrystallization was performed, whereby 12.7 g (0.038 mol, 80% yield) of a purple compound (MDA-5) was obtained.

合成例MDA-6 Synthesis example MDA-6

依據下述流程6，來合成式(MDA-6)所表示的化合物(化合物MDA-6)。 The compound (compound MDA-6) represented by the formula (MDA-6) was synthesized according to the following scheme 6.

(流程6中，Boc為第三丁氧基羰基) (In Scheme 6, Boc is the third butoxycarbonyl group)

在具備滴液漏斗及氮氣導入管的500mL的三口燒瓶中，加入4-胺基苯酚7.1g以及四氫呋喃350mL。將燒瓶的內溫維持在6℃以下，並且自滴液漏斗中滴加將二碳酸-第三丁酯14.6g溶解於60mL的四氫呋喃中而成的溶液，然後在室溫下進行24小時反應。反應完畢後，將通過減壓自反應混合物中去除溶劑而獲得的固體溶解於乙酸乙酯500mL中，利用蒸餾水500mL進行分液洗滌。將有機層以硫酸鎂進行乾燥後，通過減壓而去除溶劑，獲得作為中間物1的白色結晶12.6g。 A 500 mL three-necked flask equipped with a dropping funnel and a nitrogen introduction tube was charged with 7.1 g of 4-aminophenol and 350 mL of tetrahydrofuran. The internal temperature of the flask was maintained at 6 ° C or lower, and a solution prepared by dissolving 14.6 g of dicarbonate-tertiary-butyl ester in 60 mL of tetrahydrofuran was added dropwise from a dropping funnel, and then reacted at room temperature for 24 hours. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was dissolved in 500 mL of ethyl acetate, and the solution was washed with 500 mL of distilled water. After the organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure to obtain 12.6 g of white crystals as an intermediate 1.

在具備溫度計及氮氣導入管的300mL的三口燒瓶中，加入所述獲得的中間物1 10.14g、2,5-二羧酸吡啶4.05g及二氯甲烷150mL，一邊攪拌一邊製成懸浮液，冷卻至0℃。一邊維持該溫度，一邊向其中加入1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺的氫氯酸鹽12.08g以及N,N-二甲基胺基吡啶2.37g，一邊攪拌一邊進行6小時反應。然後在室溫下進而繼續攪拌6小時。在合計攪拌12小時後的反應混合物中添加乙酸乙酯300mL、四氫呋喃300mL以及蒸餾水300mL來進行分液洗滌，回收有機層。將所得的有機層濃縮至約200mL後，添加乙醇100mL來進行溶劑置換，然後再次濃縮，濾取所析出的白色固體(中間物2)。中間物2的產量為10.0g。 In a 300 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 10.14 g of the obtained intermediate 1, 4.05 g of 2,5-dicarboxylic acid pyridine and 150 mL of dichloromethane were added, and a suspension was prepared while stirring, and cooled. To 0 ° C. While maintaining the temperature, 12.08 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N, N-dimethylaminopyridine were added thereto. 2.37 g, reacted for 6 hours while stirring. Stirring was then continued at room temperature for another 6 hours. To the reaction mixture after stirring for 12 hours in total, 300 mL of ethyl acetate, 300 mL of tetrahydrofuran, and 300 mL of distilled water were added to perform liquid separation washing, and the organic layer was recovered. After the obtained organic layer was concentrated to about 200 mL, 100 mL of ethanol was added to perform solvent replacement, and then concentrated again, and the precipitated white solid (Intermediate 2) was collected by filtration. The yield of Intermediate 2 was 10.0 g.

在具備氮氣導入管的300mL的茄型燒瓶中，使所述獲得的中間物2的8.4g懸浮於二氯甲烷150mL中，向其中添加三氟乙酸30mL，一邊攪拌一邊進行24小時反應。反應完畢後，向反應混合物中添加飽和碳酸鈉水溶液，直至pH值成為7以上，然後， 添加乙酸乙酯200mL以及四氫呋喃200mL進行分液，回收有機層。將該有機層利用蒸餾水300mL進行3次洗滌後，進行濃縮。在濃縮中，溶液變為黑色。濾取所析出的固體，使用包含乙醇及純水的混合溶劑(乙醇：水=4：1(容量比))進行洗滌，由此獲得黃色的化合物(MDA-6)4.2g。 In a 300 mL eggplant-type flask equipped with a nitrogen introduction tube, 8.4 g of the obtained intermediate 2 was suspended in 150 mL of dichloromethane, 30 mL of trifluoroacetic acid was added thereto, and the reaction was performed for 24 hours while stirring. After the reaction is completed, a saturated sodium carbonate aqueous solution is added to the reaction mixture until the pH value becomes 7 or more, and then, 200 mL of ethyl acetate and 200 mL of tetrahydrofuran were added for liquid separation, and the organic layer was recovered. This organic layer was washed three times with 300 mL of distilled water, and then concentrated. Upon concentration, the solution turned black. The precipitated solid was collected by filtration and washed with a mixed solvent (ethanol: water = 4: 1 (volume ratio)) containing ethanol and pure water, thereby obtaining 4.2 g of a yellow compound (MDA-6).

<具有所述式(1)所表示的結構的聚合物的合成> <Synthesis of a polymer having a structure represented by the formula (1)>

合成例PI-1~合成例PI-11 Synthesis example PI-1 ~ Synthesis example PI-11

作為四羧酸二酐及二胺，分別以成為第1表記載的比例(莫耳比)的方式將該表中記載的種類的化合物進行混合，添加N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)，製成單體濃度為20重量%的溶液。對於該溶液，在40℃下一邊攪拌一邊進行4小時反應，由此獲得含有20重量%的聚醯胺酸的溶液。合成例PI-7中，除了四羧酸二酐以及二胺以外，進而以第1表記載的比例(莫耳比)來使用該表記載的單胺。 As the tetracarboxylic dianhydride and diamine, compounds of the types described in this table were mixed so that the ratios (molar ratios) described in Table 1 were obtained, and N-methyl-2-pyrrolidone (N- methyl-2-pyrrolidone (NMP) to make a solution with a monomer concentration of 20% by weight. This solution was reacted for 4 hours while stirring at 40 ° C, thereby obtaining a solution containing 20% by weight of polyamic acid. In Synthesis Example PI-7, in addition to the tetracarboxylic dianhydride and diamine, the monoamines described in the table were used at the ratios (molar ratios) described in the first table.

繼而，在所述獲得的聚醯胺酸溶液中添加NMP，將聚醯胺酸濃度稀釋為10重量%，然後，分別以相對於聚醯胺酸所具有的醯胺酸鍵的量(莫耳數)而言的相對量成為第1表記載的量的方式添加吡啶以及乙酸酐，在110℃下攪拌4小時來進行脫水閉環反應。對於反應完畢後的反應混合物，利用NMP進行溶劑置換，由此獲得分別含有15重量%的醯亞胺化聚合物(PI-1)~醯亞胺化聚合物(PI-9)的溶液。將利用1H-核磁共振(Nuclear Magnetic Resonance，NMR)對所得的醯亞胺化聚合物進行測定而得的醯亞胺化率一併示於第1表中。 Next, NMP was added to the obtained polyamic acid solution, the polyamic acid concentration was diluted to 10% by weight, and then each amount of the polyamic acid bond (mol In terms of relative amounts, pyridine and acetic anhydride were added so that the relative amounts described in the first table, and the mixture was stirred at 110 ° C. for 4 hours to perform a dehydration ring-closure reaction. The reaction mixture after completion of the reaction was subjected to solvent replacement with NMP, thereby obtaining a solution containing 15% by weight of the fluorene imidized polymer (PI-1) to the fluorene imidized polymer (PI-9), respectively. The fluorene imidization rate obtained by measuring the obtained fluorene imidized polymer by 1 H-nuclear magnetic resonance (NMR) is shown in Table 1 together.

<其他聚合物的合成> <Synthesis of other polymers>

合成例rpi-1~合成例rpi-3 Synthesis example rpi-1 ~ Synthesis example rpi-3

作為四羧酸二酐以及二胺，分別以成為第1表記載的比例(莫耳比)的方式來使用該表中記載的種類的化合物，而且將吡啶及乙酸酐的使用量調整為第1表中記載的比例，除此以外，以與所述合成例PI-1相同的方式進行操作，獲得分別含有15重量%的醯亞胺化聚合物(rpi-1)~醯亞胺化聚合物(rpi-3)的溶液。將利用1H-NMR對所得的醯亞胺化聚合物進行測定而得的醯亞胺化率一併示於第1表中。 As the tetracarboxylic dianhydride and diamine, each type of compound described in the table was used so as to have the ratio (mole ratio) described in the first table, and the amount of pyridine and acetic anhydride used was adjusted to the first Except for the ratios listed in the table, the same procedures as in Synthesis Example PI-1 were performed to obtain 15% by weight of fluorene imidized polymer (rpi-1) to fluorene imidized polymer. (rpi-3). The fluorene imidation ratio obtained by measuring the obtained fluorene imidized polymer by 1 H-NMR is shown in Table 1 together.

合成例rpa-1~合成例rpa-4 Synthesis example rpa-1 ~ Synthesis example rpa-4

作為四羧酸二酐以及二胺，分別以成為第1表記載的比例(莫耳比)的方式來使用該表中記載的種類的化合物，除此以外，以與所述合成例PI-1相同的方式進行操作，獲得分別含有20重量%的聚醯胺酸(rpa-1)~聚醯胺酸(rpa-4)的溶液。 As the tetracarboxylic dianhydride and the diamine, the compounds described in the table were used so that the ratios (mole ratios) described in the first table were used, respectively. Operations were performed in the same manner to obtain a solution containing 20% by weight of polyamidic acid (rpa-1) to polyamidic acid (rpa-4), respectively.

在這些合成例中不進行脫水閉環反應，而是將所得的聚醯胺酸溶液直接提供給液晶配向劑的製備。 In these synthesis examples, the dehydration ring-closing reaction is not performed, but the obtained polyamic acid solution is directly provided to the preparation of the liquid crystal alignment agent.

所述第1表的單體欄中的略稱分別為以下含義。 The abbreviations in the single column of the first table have the following meanings.

<四羧酸二酐> <Tetracarboxylic dianhydride>

TCA：2,3,5-三羧基環戊基乙酸二酐 TCA: 2,3,5-tricarboxycyclopentylacetic dianhydride

BODA：2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐 BODA: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride

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

MTDA：1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮 MTDA: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c ] Furan-1,3-dione

PMDA：均苯四甲酸二酐 PMDA: pyromellitic dianhydride

TA-1：下述式(TA-1)所表示的化合物 TA-1: Compound represented by the following formula (TA-1)

<二胺> <Diamine>

[具有所述式(1)所表示的結構的二胺] [Diamine having a structure represented by the formula (1)]

MDA-1：所述合成例MDA-1中合成的化合物(MDA-1) MDA-1: Compound (MDA-1) synthesized in said Synthesis Example MDA-1

MDA-2：所述合成例MDA-1中合成的化合物(MDA-2) MDA-2: Compound (MDA-2) synthesized in Synthesis Example MDA-1

MDA-3：所述合成例MDA-1中合成的化合物(MDA-3) MDA-3: Compound (MDA-3) synthesized in Synthesis Example MDA-1

MDA-4：所述合成例MDA-1中合成的化合物(MDA-4) MDA-4: Compound (MDA-4) synthesized in Synthesis Example MDA-1

MDA-5：所述合成例MDA-1中合成的化合物(MDA-5) MDA-5: Compound (MDA-5) synthesized in Synthesis Example MDA-1

[其他二胺] [Other diamines]

PDA：對苯二胺 PDA: p-phenylenediamine

HCDA：3,5-二胺基苯甲酸膽甾烷基酯 HCDA: Cholesteryl 3,5-diaminobenzoate

35DAB：3,5-二胺基苯甲酸 35DAB: 3,5-diaminobenzoic acid

HCODA：膽甾烷氧基-2,4-二胺基苯 HCODA: Cholesteryloxy-2,4-diaminobenzene

LDA：4-{4-[2-(4'-戊基-1,1'-雙環己基)乙基]苯氧基}苯-1,3-二胺 LDA: 4- {4- [2- (4'-pentyl-1,1'-dicyclohexyl) ethyl] phenoxy} benzene-1,3-diamine

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

D-2：1,3-雙(3-胺基丙基)-四甲基二矽氧烷 D-2: 1,3-bis (3-aminopropyl) -tetramethyldisilazane

D-3：3,6-雙(4-胺基苯甲醯基氧基)膽甾烷 D-3: 3,6-bis (4-aminobenzyloxy) cholestane

D-5：2,2'-雙(三氟甲基)-4,4'-二胺基聯苯 D-5: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

D-6：4,4'-二胺基二苯基甲烷 D-6: 4,4'-diaminodiphenylmethane

D-7：2,2'-二甲基-4,4'-二胺基聯苯 D-7: 2,2'-dimethyl-4,4'-diaminobiphenyl

D-8：4,4'-二胺基二苯基醚 D-8: 4,4'-diaminodiphenyl ether

DA-2：下述式(DA-2)所表示的化合物 DA-2: Compound represented by the following formula (DA-2)

DA-3：下述式(DA-3)所表示的化合物 DA-3: Compound represented by the following formula (DA-3)

mda-1：下述式(mda-1)所表示的化合物 mda-1: a compound represented by the following formula (mda-1)

mda-2：下述式(mda-2)所表示的化合物 mda-2: a compound represented by the following formula (mda-2)

[單胺] [Monoamine]

D-4：苯胺 D-4: aniline

合成例rps-1 Synthesis example rps-1

在具備攪拌機、溫度計、滴液漏斗(dropping funnel)以及迴流冷卻管的反應容器中，加入2-(3,4-環氧基環己基)乙基三甲氧基矽烷100.0g、甲基異丁基酮500g以及三乙基胺10.0g，在室溫下混合。繼而，向其中，花30分鐘自滴液漏斗中滴加去離子水100g，然後一邊在迴流下攪拌，一邊在80℃下進行6小時反應。反應完畢後，取出有機層，使用0.2重量%硝酸銨水溶液進行洗滌，直至洗滌後的水成為中性為止，然後在減壓下蒸餾去除溶劑及 水，以黏稠的透明液體的形式獲得具有環氧基的聚有機矽氧烷。對該聚有機矽氧烷進行1H-NMR分析，結果在化學位移(δ)=3.2ppm附近，如理論強度般獲得基於環氧基的峰值，確認在反應中未產生環氧基的副反應。所得的具有環氧基的聚有機矽氧烷的重量平均分子量Mw為3,500，環氧當量為180g/莫耳。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added, and methyl isobutyl 500 g of ketone and 10.0 g of triethylamine were mixed at room temperature. Next, 100 g of deionized water was dropped into the dropping funnel from the dropping funnel over 30 minutes, and then the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy resin in the form of a thick transparent liquid. Polyorganosiloxane. As a result of 1 H-NMR analysis of the polyorganosiloxane, a peak based on epoxy groups was obtained at a chemical shift (δ) = 3.2 ppm as a theoretical intensity, and it was confirmed that no side reaction of epoxy groups occurred in the reaction. . The weight average molecular weight Mw of the obtained polyorganosiloxane having an epoxy group was 3,500, and the epoxy equivalent was 180 g / mole.

繼而，在200mL的三口燒瓶中，加入所述獲得的具有環氧基的聚有機矽氧烷10.0g、作為溶劑的甲基異丁基酮30.28g、作為羧酸的4-十二烷基氧基苯甲酸3.98g以及作為催化劑的UCAT 18X(商品名，三亞普羅(San-Apro)(股)製造)0.10g，在100℃下一邊攪拌一邊進行48小時反應。反應完畢後，向反應混合物中添加乙酸乙酯，將所得的有機層進行3次水洗，利用硫酸鎂進行乾燥後，蒸餾去除溶劑，由此獲得聚有機矽氧烷(rps-1)9.0g。所得的聚有機矽氧烷(rps-1)的重量平均分子量Mw為9,900。 Next, in a 200 mL three-necked flask, 10.0 g of the obtained polyorganosiloxane having an epoxy group, 30.28 g of methyl isobutyl ketone as a solvent, and 4-dodecyloxy as a carboxylic acid were added. 3.98 g of benzoic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro) were used as a catalyst, and the reaction was performed at 100 ° C. for 48 hours while stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture, the obtained organic layer was washed with water three times, and dried with magnesium sulfate, and then the solvent was distilled off to obtain 9.0 g of polyorganosiloxane (rps-1). The weight average molecular weight Mw of the obtained polyorganosiloxane (rps-1) was 9,900.

實施例1 Example 1

1.液晶配向劑的製備 1. Preparation of liquid crystal alignment agent

在含有所述合成例PI-1中獲得的醯亞胺化聚合物(PI-1)的溶液中添加NMP以及丁基溶纖劑(butyl cellosolve，BC)，充分攪拌，製成溶劑組成為NMP：BC=60：40(重量比)、固體成分濃度為2.5質量%的溶液。使用孔徑為1μm的過濾器將該溶液進行過濾，由此製備液晶配向劑。 NMP and butyl cellosolve (BC) were added to the solution containing the fluorene imidized polymer (PI-1) obtained in the synthesis example PI-1, and the mixture was thoroughly stirred to obtain a solvent composition of NMP: BC = 60: 40 (weight ratio), a solid content concentration of 2.5% by mass. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

2.液晶配向劑的評價 2. Evaluation of liquid crystal alignment agent

對於所述製備的液晶配向劑的印刷性以及使用該液晶配向劑來製造的液晶顯示元件的可靠性，利用下述方法來進行評價。 The printability of the prepared liquid crystal alignment agent and the reliability of a liquid crystal display element manufactured using the liquid crystal alignment agent were evaluated by the following methods.

評價結果示於第2表中。 The evaluation results are shown in Table 2.

實施例2~實施例8、實施例10及實施例11以及比較例1~比較例5 Example 2 to Example 8, Example 10 and Example 11 and Comparative Example 1 to Comparative Example 5

1.液晶配向劑的製備 1. Preparation of liquid crystal alignment agent

作為含有聚合物的溶液，分別使用含有第2表中所示的聚合物的溶液，除此以外，以與所述實施例1的「1.液晶配向劑的製備」相同的方式製備液晶配向劑。 A liquid crystal alignment agent was prepared in the same manner as in "1. Preparation of a liquid crystal alignment agent" in Example 1 except that a solution containing the polymer shown in Table 2 was used as the polymer-containing solution. .

此外，實施例7及實施例8中，分別將2種聚合物以第2表中記載的比例進行混合來使用。 In addition, in Example 7 and Example 8, two types of polymers were mixed at the ratios shown in Table 2 and used.

2.液晶配向劑的評價 2. Evaluation of liquid crystal alignment agent

對於所述製備的各液晶配向劑，以與所述實施例1相同的方式進行評價。 Each of the prepared liquid crystal alignment agents was evaluated in the same manner as in Example 1.

評價結果示於第2表中。 The evaluation results are shown in Table 2.

實施例9 Example 9

1.液晶配向劑的製備 1. Preparation of liquid crystal alignment agent

在含有所述合成例PI-9中獲得的醯亞胺化聚合物(PI-9)的溶液中，添加所述合成例rps-1中獲得的聚有機矽氧烷(rps-1)，進而添加NMP以及丁基溶纖劑(BC)，充分攪拌，製成溶劑組成為NMP：BC=60：40(重量比)、固體成分濃度為2.5質量%的溶液。此處，醯亞胺化聚合物(PI-9)與聚有機矽氧烷(rps-1)是以PI-9：rps-1的重量比成為95：5的比例來使用。 The polyorganosiloxane (rps-1) obtained in the synthesis example rps-1 was added to a solution containing the fluorene imidized polymer (PI-9) obtained in the synthesis example PI-9, and further, NMP and butyl cellosolve (BC) were added, and the mixture was sufficiently stirred to prepare a solution having a solvent composition of NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 2.5% by mass. Here, the fluorene imidized polymer (PI-9) and polyorganosiloxane (rps-1) are used at a ratio of PI-9: rps-1 to a weight ratio of 95: 5.

使用孔徑為1μm的過濾器，將該溶液進行過濾，由此製備液晶配向劑。 This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

2.液晶配向劑的評價 2. Evaluation of liquid crystal alignment agent

對於所述製備的液晶配向劑，以與所述實施例1相同的方式 進行評價。 For the prepared liquid crystal alignment agent, in the same manner as in Example 1 Evaluate.

評價結果示於第2表中。 The evaluation results are shown in Table 2.

<液晶配向劑的評價方法(1)> <Evaluation method of liquid crystal alignment agent (1)>

所述實施例1~實施例11以及比較例1~比較例5中製備的液晶配向劑分別利用以下方法進行評價。 The liquid crystal alignment agents prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were evaluated by the following methods, respectively.

1.印刷性的評價 1. Evaluation of printability

關於各實施例或比較例中製備的液晶配向劑，對在基板上連續進行印刷的情況下的印刷性(連續印刷性)進行評價。 About the liquid crystal aligning agent prepared by each Example or a comparative example, the printability (continuous printability) when printing on a board | substrate was evaluated continuously.

首先，使用液晶配向膜印刷機(日本照相印刷(股)製造，品名「埃格斯特瑪(Angstromer)S40L-532」)，以液晶配向劑對網紋輥(anilox roll)的滴加量為往返20滴(約0.2g)的條件，將各液晶配向劑塗布於帶有包含ITO膜的透明電極的玻璃基板的透明電極面上。每隔1分鐘使用新的基板，對基板實施20次塗布。 First, a liquid crystal alignment film printer (manufactured by Nippon Photographic Printing Co., Ltd. under the product name "Angstromer S40L-532") was used. The amount of anilox roll added to the anilox roll was Each liquid crystal alignment agent was applied to the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film under the conditions of 20 drops (about 0.2 g). A new substrate was used every 1 minute, and the substrate was applied 20 times.

繼而，合計進行10次如下的作業(空轉)：每隔1分鐘將液晶配向劑分配(單程)於網紋輥上，屆時，使網紋輥與印刷版接觸。此間，不進行對玻璃基板的印刷。該空轉是為了特意在嚴酷的狀況下實施液晶配向劑的印刷而進行的操作。 Then, a total of 10 operations (idling) were performed: the liquid crystal alignment agent was distributed (one-way) on the anilox roller every 1 minute, and then the anilox roller was brought into contact with the printing plate. During this time, printing on the glass substrate is not performed. This idling is an operation performed to intentionally print the liquid crystal alignment agent under severe conditions.

10次空轉後，繼續使用玻璃基板來進行正式印刷。正式印刷中，在空轉後，每隔30秒的間隔投入5塊基板，將塗布液晶配向劑後的各基板在80℃下加熱(預烘烤)1分鐘而去除溶劑，然後在200℃下加熱(後烘烤)10分鐘，形成膜厚約為80nm的塗膜。利用倍率為20倍的顯微鏡來觀察該塗膜，由此評價印刷性。 After 10 idling cycles, the glass substrate was used for formal printing. In the official printing, after idling, 5 substrates are put in at intervals of 30 seconds. Each substrate after applying the liquid crystal alignment agent is heated (pre-baked) at 80 ° C for 1 minute to remove the solvent, and then heated at 200 ° C. (Post-baking) For 10 minutes, a coating film having a film thickness of about 80 nm was formed. This coating film was observed with a microscope with a magnification of 20 times, thereby evaluating printability.

依據以下基準進行評價。 Evaluation was performed based on the following criteria.

自空轉後的第1次正式印刷起未在塗膜中觀察到聚合物的析 出的情況：A(優良) No polymer separation was observed in the coating film since the first official printing after idling. Situation: A (Excellent)

在空轉後的第1次正式印刷時在塗膜中觀察到聚合物的析出，但在實施5次正式印刷的期間不再觀察到聚合物的析出的情況：B(良好) The polymer was observed in the coating film during the first official printing after idling, but the polymer was no longer observed during the five official printings: B (good)

在反復進行5次正式印刷後，也未在塗膜中觀察到聚合物的析出的情況：C(不良) No polymer precipitation was observed in the coating film even after the official printing was repeated 5 times: C (defective)

對於所述評價中獲得A評價的液晶配向劑，將空轉的次數變更為25次，再次進行同樣的評價。其結果為，自25次空轉後的第1次正式印刷起，未在塗膜中觀察到聚合物的析出的情況被評價為「AA(特別優良)」。 Regarding the liquid crystal alignment agent obtained A evaluation in the evaluation, the number of idling was changed to 25 times, and the same evaluation was performed again. As a result, from the first official printing after 25 idling times, the case where no polymer precipitation was observed in the coating film was evaluated as "AA (particularly excellent)".

2.液晶單元的評價 2. Evaluation of liquid crystal cells

(1)液晶單元的製造 (1) Manufacturing of liquid crystal cells

使用液晶配向膜印刷機(日本照相印刷(股)製造)，將所述實施例及比較例中製備的各液晶配向劑塗布於帶有包含ITO膜的透明電極的玻璃基板的透明電極面上，在80℃的加熱板上加熱(預烘烤)1分鐘而去除溶劑後，在210℃的加熱板上加熱(後烘烤)30分鐘，形成平均膜厚為80nm的塗膜。 Using a liquid crystal alignment film printer (manufactured by Nippon Photographic Printing Co., Ltd.), each liquid crystal alignment agent prepared in the examples and comparative examples was coated on the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film. After heating (pre-baking) on a hot plate at 80 ° C for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 210 ° C for 30 minutes to form a coating film having an average film thickness of 80 nm.

對於該塗膜，利用包括捲繞有人造絲布的輥的摩擦機器，以輥轉速500rpm、平臺移動速度3cm/秒以及毛壓入長度0.4mm來進行摩擦處理，賦予液晶配向能力。然後，在超純水中進行1分鐘超聲波洗滌，繼而在100℃潔淨烘箱中進行10分鐘乾燥，由此獲得具有液晶配向膜的基板。重複進行該操作，獲得具有液晶配向膜的一對(2塊)基板。 This coating film was subjected to a rubbing treatment using a friction machine including a roll wound with a rayon cloth at a roll speed of 500 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.4 mm to give the liquid crystal alignment ability. Then, ultrasonic washing was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two) substrates having a liquid crystal alignment film.

接著，在所述一對基板中的其中一塊的具有液晶配向膜的面 的外緣，在除液晶注入口以外的部位塗布加入有直徑為5.5μm的氧化鋁球的環氧樹脂黏接劑後，以液晶配向膜面相對的方式將一對基板重疊而壓接，使黏接劑硬化。繼而，自液晶注入口向一對基板間填充向列型液晶(默克(Merck)公司製造，品名「MLC-6221」)後，利用丙烯酸系光硬化黏接劑使液晶注入口密封，由此製造液晶單元。 Next, a surface having a liquid crystal alignment film on one of the pair of substrates The outer edge of the substrate is coated with an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm at a position other than the liquid crystal injection port, and a pair of substrates are overlapped and pressure-bonded so that the liquid crystal alignment film faces are opposite to each other, so that The adhesive hardens. Next, a nematic liquid crystal (manufactured by Merck, under the product name "MLC-6221") was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curing adhesive. Manufacturing of liquid crystal cells.

(2)可靠性的評價 (2) Evaluation of reliability

對所述製造的液晶單元進行可靠性的評價。 The manufactured liquid crystal cell was evaluated for reliability.

首先，對於液晶單元，以60微秒的施加時間、167毫秒的跨度施加5V的電壓後，測定自施加解除起167毫秒後的電壓保持率(VHR1)。繼而，將液晶單元在LED燈照射下的80℃烘箱中靜置200小時後，在室溫下靜置，自然冷卻至室溫。對於冷卻後的液晶單元，以60微秒的施加時間、167毫秒的跨度施加5V的電壓後，測定自施加解除起167毫秒後的電壓保持率(VHR2)。 First, a voltage of 5 V was applied to a liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate (VHR1) after 167 milliseconds after the application was released was measured. Then, the liquid crystal cell was allowed to stand for 200 hours in an 80 ° C oven under the irradiation of an LED lamp, and then allowed to stand at room temperature, and then naturally cooled to room temperature. The liquid crystal cell after cooling was applied with a voltage of 5 V for an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate (VHR2) after 167 milliseconds after the application was released was measured.

利用下述數式(1)來算出此時的電壓保持率的變化率(△VHR)，根據所得的△VHR的值，以如下基準來評價可靠性。 The change rate (ΔVHR) of the voltage holding rate at this time was calculated by the following formula (1), and the reliability was evaluated based on the obtained value of ΔVHR on the following basis.

△VHR[%]=(VHR1-VHR2)/(VHR1)×100 (1) △ VHR [%] = (VHR1-VHR2) / (VHR1) × 100 (1)

△VHR小於1%的情況：A(優良) △ VHR is less than 1%: A (Excellent)

△VHR為1%以上且小於2%的情況：B(良好) △ VHR is 1% or more and less than 2%: B (good)

△VHR為2%以上的情況：C(不良) △ When VHR is 2% or more: C (bad)

實施例12 Example 12

1.液晶配向剂的制备 1. Preparation of liquid crystal alignment agent

在含有所述合成例PA-1中獲得的醯亞胺化聚合物(PA-1)的溶液中添加NMP以及丁基溶纖劑(BC)，充分攪拌，製成溶劑組成為NMP：BC=60：40(重量比)、固體成分濃度為2.5質量%的溶液。 NMP and butyl cellosolve (BC) were added to the solution containing the fluorene imidized polymer (PA-1) obtained in Synthesis Example PA-1, and the mixture was stirred thoroughly to make the solvent composition NMP: BC = 60: A solution of 40 (weight ratio) and a solid content concentration of 2.5% by mass.

利用孔徑為1μm的過濾器將該溶液進行過濾，由此製備液晶配向劑。 This solution was filtered through a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

2.液晶配向劑的評價 2. Evaluation of liquid crystal alignment agent

對於所述製備的液晶配向劑的印刷性以及使用該液晶配向劑來製造的液晶單元的可靠性，利用下述方法進行評價。 The printability of the prepared liquid crystal alignment agent and the reliability of a liquid crystal cell manufactured using the liquid crystal alignment agent were evaluated by the following methods.

評價結果示於第3表中。 The evaluation results are shown in Table 3.

比較例6及比較例7 Comparative Example 6 and Comparative Example 7

1.液晶配向劑的製備 1. Preparation of liquid crystal alignment agent

作為含有聚合物的溶液，分別使用含有第3表中所示的聚合物的溶液，除此以外，以與所述實施例12的「1.液晶配向劑的製備」相同的方式製備液晶配向劑。 A liquid crystal alignment agent was prepared in the same manner as in "1. Preparation of a liquid crystal alignment agent" in Example 12 except that a solution containing the polymer shown in Table 3 was used as the polymer-containing solution. .

2.液晶配向劑的評價 2. Evaluation of liquid crystal alignment agent

對於所述製備的各液晶配向劑，以與所述實施例12相同的方式進行評價。 Each of the prepared liquid crystal alignment agents was evaluated in the same manner as in Example 12.

評價結果示於第3表中。 The evaluation results are shown in Table 3.

<液晶配向劑的評價方法(2)> <Evaluation method of liquid crystal alignment agent (2)>

所述實施例12以及比較例6及比較例7中製備的液晶配向劑分別利用以下方法進行評價。 The liquid crystal alignment agents prepared in Example 12 and Comparative Examples 6 and 7 were evaluated by the following methods, respectively.

1.印刷性的評價 1. Evaluation of printability

對於所述實施例以及比較例中製備的各液晶配向劑，利用與所述實施例1~實施例11以及比較例1~比較例5相同的方法來評價對基板的連續印刷性，結果為，實施例12顯示出較比較例6及比較例7更良好的結果。 For each liquid crystal alignment agent prepared in the examples and comparative examples, the same method as in Examples 1 to 11 and Comparative Examples 1 to 5 was used to evaluate the continuous printability to the substrate, and the results were: Example 12 showed better results than Comparative Examples 6 and 7.

2.液晶單元的評價 2. Evaluation of liquid crystal cells

(1)液晶配向性、電壓保持率以及對比度評價用的液晶單元的製造 (1) Manufacturing of liquid crystal cells for evaluation of liquid crystal alignment, voltage retention, and contrast

使用旋轉器，將所述實施例及比較例中製備的各液晶配向劑塗布於帶有包含ITO膜的透明電極的2塊(一對)玻璃基板的各透明電極面上，然後在80℃下加熱(預烘烤)1分鐘，分別形成 塗膜。對於這些塗膜表面，使用Hg-Xe燈，自基板的法線方向以照射量10,000J/m2來照射包含254nm的明線的偏光紫外線後，在230℃的潔淨烘箱中加熱(後烘烤)1小時，在2塊(一對)基板上分別形成液晶配向膜。 Using a spinner, each liquid crystal alignment agent prepared in the examples and comparative examples was coated on each transparent electrode surface of two (pair) glass substrates with a transparent electrode including an ITO film, and then at 80 ° C. Heating (pre-baking) for 1 minute each formed a coating film. For these coating surface, after using Hg-Xe lamp, a direction of the normal of the substrate to irradiation amount 10,000J / m 2 comprising irradiating polarized ultraviolet rays of 254nm open wire, heated in a clean oven of 230 deg.] C (after baking ) For 1 hour, a liquid crystal alignment film is formed on each of the two (pair) substrates.

繼而，對於進行了所述光照射處理的一對基板中的其中一塊，在形成有液晶配向膜的面的外周緣部，在除液晶注入口以外的部位，網版印刷塗布加入有直徑為5.5μm的氧化鋁球的環氧樹脂黏接劑後，以液晶配向膜形成面相對、且光照射時的偏光面在基板面上的投影方向一致的方式，將一對基板重疊而壓接，在150℃下加熱1小時，使黏接劑進行熱硬化。 Next, for one of the pair of substrates subjected to the light irradiation treatment, a screen printing coating having a diameter of 5.5 was added to the outer peripheral portion of the surface on which the liquid crystal alignment film was formed, except for the liquid crystal injection port. After a μm alumina ball epoxy adhesive, a pair of substrates are superimposed and crimped in such a manner that the liquid crystal alignment film formation surfaces face each other and the projection directions of the polarized surfaces on the substrate surface during light irradiation are the same. The adhesive was heated at 150 ° C for 1 hour to thermally harden the adhesive.

繼而，自液晶注入口向一對基板間填充向列型液晶(默克(Merck)公司製造，品名「MLC-7028」)後，利用環氧系黏接劑將液晶注入口密封。進而，為了去除液晶注入時的流動配向，而將其加熱至150℃後，緩緩冷卻至室溫，由此來製造液晶單元。 Next, the liquid crystal injection port was filled with a nematic liquid crystal (manufactured by Merck, product name "MLC-7028") between the pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C. and then slowly cooled to room temperature to manufacture a liquid crystal cell.

(2)液晶配向性的評價 (2) Evaluation of liquid crystal alignment

對於所述製造的液晶單元，利用偏光顯微鏡來觀察當接通．斷開(施加．解除)交流5V的電壓時的異常區域的有無。 For the manufactured liquid crystal cell, a polarizing microscope was used to observe when it was turned on. The presence or absence of an abnormal area when the voltage of 5V AC is turned OFF (applied. Canceled).

將在顯示區域中未觀察到異常區域的情況評價為液晶配向性「A(良好)」，將在顯示區域中觀察到異常區域的情況評價為液晶配向性「C(不良)」，即便所述異常區域僅有1處。 The case where no abnormal region was observed in the display region was evaluated as the liquid crystal alignment "A (good)", and the case where the abnormal region was observed in the display region was evaluated as the liquid crystal alignment "C (poor)", even if the There is only one abnormal area.

(3)電壓保持率的評價 (3) Evaluation of voltage holding ratio

對於所述製造的液晶單元，以60微秒的施加時間、167毫秒的跨度施加5V的電壓後，測定自施加解除起167毫秒後的電壓保持率。 With respect to the manufactured liquid crystal cell, a voltage of 5 V was applied at an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate after 167 milliseconds after the release of the application was measured.

電壓保持率的測定裝置是使用東陽特克尼卡(Toyo Technica)股份有限公司製造的型式名「VHR-1」。 The measurement device of the voltage holding ratio used the model name "VHR-1" manufactured by Toyo Technica Co., Ltd.

依據以下基準進行評價。 Evaluation was performed based on the following criteria.

電壓保持率為98%以上的情況：電壓保持率「A(良好)」 When the voltage retention rate is 98% or more: The voltage retention rate is "A (good)"

電壓保持率小於98%的情況：電壓保持率「C(不良)」 When the voltage holding ratio is less than 98%: The voltage holding ratio "C (defective)"

(4)殘像特性評價用的液晶單元的製造 (4) Manufacturing of liquid crystal cell for evaluation of afterimage characteristics

除了使用以下構成的基板對來作為一對基板以外，以與所述「(1)液晶配向性、電壓保持率以及對比度評價用的液晶單元的製造」相同的方式製造殘像特性評價用的液晶單元(FFS型液晶單元)，進而，在基板的外側兩面貼合偏光板，由此製作液晶顯示元件。 A liquid crystal for evaluation of afterimage characteristics was produced in the same manner as in "(1) Production of liquid crystal cell for evaluation of liquid crystal alignment, voltage holding ratio, and contrast" except that a substrate pair having the following configuration was used as a pair of substrates. Cell (FFS-type liquid crystal cell), and further, polarizing plates were bonded to both outer surfaces of the substrate, thereby producing a liquid crystal display element.

此處，電極基板是使用圖1所示的形成有具有梳齒狀圖案且包含鉻的2系統電極(電極A(101)以及電極B(102))的玻璃基板；對向基板是使用未形成電極的玻璃基板。在電極基板的電極形成面及對向基板的其中一面上塗布液晶配向劑。 Here, the electrode substrate is a glass substrate using two system electrodes (electrode A (101) and electrode B (102)) having a comb-shaped pattern and containing chromium, as shown in FIG. 1; Glass substrate for electrodes. A liquid crystal alignment agent is applied to one of the electrode formation surface of the electrode substrate and one surface of the counter substrate.

(5)殘像特性(燒印(burn-in))的評價 (5) Evaluation of afterimage characteristics (burn-in)

將所述製造的液晶顯示元件放置於25℃、1氣壓的環境下，對電極B不施加電壓，對電極A施加交流電壓3.5V以及直流電壓5V的合成電壓2小時。經過2小時後，立即對電極A及電極B兩者施加交流4V的電壓。而且，測定自對兩電極開始施加交流4V的電壓的時刻起，直至以目視無法再確認到兩電極間的透光性的差為止的時間。 The manufactured liquid crystal display element was placed in an environment of 25 ° C. and 1 atmosphere, no voltage was applied to the electrode B, and a combined voltage of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode A for 2 hours. After 2 hours, a voltage of 4 V AC was applied to both the electrode A and the electrode B immediately. In addition, the time from the time when the voltage of 4V AC was applied to both electrodes was measured until the difference in light transmittance between the two electrodes could no longer be confirmed visually.

依據以下基準進行評價。 Evaluation was performed based on the following criteria.

所述測定的時間小於100秒的情況：殘像特性「A(良好)」 When the measurement time is less than 100 seconds: Afterimage characteristic "A (good)"

100秒以上且小於150秒的情況：殘像特性「B(可)」 For 100 seconds or more and less than 150 seconds: Afterimage characteristic "B (OK)"

超過150秒的情況：殘像特性「C(不良)」 When it exceeds 150 seconds: Afterimage characteristic "C (defective)"

(6)可靠性的評價 (6) Evaluation of reliability

對於所述製造的液晶顯示元件，以與所述實施例1~實施例11以及比較例1~比較例5中相同的方法來評價其可靠性，結果為，實施例12顯示出較比較例6及比較例7更良好的結果。 As for the manufactured liquid crystal display element, the reliability was evaluated by the same method as in Examples 1 to 11 and Comparative Examples 1 to 5. As a result, Example 12 showed that it was more reliable than Comparative Example 6. And Comparative Example 7 had better results.

Claims (7)

一種液晶配向劑，其特徵在於：含有主鏈上具有下述結構的聚合物，所述結構為 或，式中「*」分別表示結合鍵。A liquid crystal alignment agent characterized by containing a polymer having the following structure on a main chain, wherein the structure is or In the formula, "*" indicates a bonding key respectively. 如申請專利範圍第1項所述的液晶配向劑，其中所述聚合物是經過使四羧酸二酐、與包含下述式(MDA)所表示的化合物的二胺進行反應的步驟來合成的聚合物，H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2 (MDA)式(MDA)中，*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-*所表示的結構為 或，式中「*」分別表示結合鍵。The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polymer is synthesized through a step of reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (MDA) polymers, H 2 N-Ph-X 1 - (CR 1 2) m1 -Y- (CR 1 2) in m2 -X 2 -Ph-NH 2 ( MDA) of formula (MDA), * -X 1 - ( CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2- * or In the formula, "*" indicates a bonding key respectively. 如申請專利範圍第2項所述的液晶配向劑，其中所述四羧酸二酐包含選自由2,3,5-三羧基環戊基乙酸二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐以及1,2,3,4-環戊烷四羧酸二酐所組成的組群中的至少一種化合物。The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein the tetracarboxylic dianhydride comprises a compound selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,4,6,8-tetracarboxylic Bicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid At least one compound in the group consisting of acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. 一種液晶配向膜，其特徵在於：由如申請專利範圍第1項至第3項中任一項所述的液晶配向劑來形成。A liquid crystal alignment film is characterized in that it is formed of the liquid crystal alignment agent according to any one of items 1 to 3 of the scope of patent application. 一種液晶顯示元件，其特徵在於：包括如申請專利範圍第4項所述的液晶配向膜。A liquid crystal display element, comprising the liquid crystal alignment film according to item 4 of the scope of patent application. 一種下述式(MDA)所表示的化合物：H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2...(MDA)式(MDA)中，*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-*所表示的結構為 、或，式中「*」分別表示結合鍵。A compound represented by the following formula (MDA): H 2 N-Ph-X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2 -Ph-NH 2 ... (MDA) in the formula (MDA), * -X 1 - (CR 1 2) m1 -Y- (CR 1 2) m2 -X 2 - * as represented by structure , or In the formula, "*" indicates a bonding key respectively. 一種聚合物，其是經過使四羧酸二酐、與包含下述式(MDA)所表示的化合物的二胺進行反應的步驟來合成的聚合物，H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2...(MDA)式(MDA)中，*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-*所表示的結構為 、或，式中「*」分別表示結合鍵。A polymer synthesized by a step of reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (MDA), H 2 N-Ph-X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) m2 -X 2 -Ph-NH 2 ... (MDA) Formula (MDA), * -X 1- (CR 1 2 ) m1 -Y- (CR 1 2 ) The structure represented by m2 -X 2- * is , or In the formula, "*" indicates a bonding key respectively.
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