TWI773689B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

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

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TWI773689B
TWI773689B TW106133267A TW106133267A TWI773689B TW I773689 B TWI773689 B TW I773689B TW 106133267 A TW106133267 A TW 106133267A TW 106133267 A TW106133267 A TW 106133267A TW I773689 B TWI773689 B TW I773689B
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liquid crystal
group
crystal alignment
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diamine
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TW201825555A (en
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萬代淳彦
宮本泰宏
石川和典
李柱永
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日商日產化學工業股份有限公司
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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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • 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
    • 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
    • G02F1/133723—Polyimide, polyamide-imide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

本發明係提供可抑制因配線構造或C/H之影響所產生之配向膜之塗佈不良，可抑制液晶顯示元件之顯示不均的不良，及降低液晶配向劑之黏度，提高樹脂成分比率的液晶配向劑及使用其之液晶配向膜。本發明係有關一種液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及其醯亞胺化物的聚醯亞胺所成群之至少1種，且含有因熱產生脫離之保護基的聚合物，及含有下述A群組的溶劑、B群組的溶劑及二異丁基酮的溶劑成分。在此，A群組的溶劑為選自由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯及1,3-二甲基咪唑啉酮所成群之至少1種的溶劑，B群組的溶劑為選自由丁基溶纖劑、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、二丙二醇二甲醚所成群之至少1種的溶劑。 The present invention provides a method that can suppress the poor coating of the alignment film caused by the wiring structure or the influence of C/H, can suppress the poor display unevenness of the liquid crystal display element, reduce the viscosity of the liquid crystal alignment agent, and improve the resin component ratio. Liquid crystal alignment agent and liquid crystal alignment film using the same. The present invention relates to a liquid crystal alignment agent, which is characterized by containing at least one selected from the group consisting of polyimide precursors and polyimide compounds thereof, and containing a protective group that is detached by heat. A polymer, and a solvent component containing the following group A solvent, B group solvent, and diisobutyl ketone. Here, the solvent of group A is at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and 1,3-dimethylimidazolidinone 1 kind of solvent, the solvent of group B is at least 1 selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, 2-butoxy-1-propanol, and dipropylene glycol dimethyl ether kind of solvent.

Description

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

[0001] 本發明為有關適合噴墨塗佈，維持低黏度，增加樹脂成分比率的液晶配向劑、及由該液晶配向劑所得的液晶配向膜。[0001] The present invention relates to a liquid crystal alignment agent suitable for inkjet coating, maintaining low viscosity, increasing the resin composition ratio, and a liquid crystal alignment film obtained by the liquid crystal alignment agent.

[0002] 液晶配向膜係廣泛地使用塗佈以聚醯胺酸(polyamic acid)等之聚醯亞胺前驅物或可溶性聚醯亞胺溶液為主成分的液晶配向劑，進行燒成之所謂的聚醯亞胺系的液晶配向膜，但是此液晶配向膜的成膜法，一般以旋轉塗佈、浸漬塗佈、凸版印刷等為人所知。實際上，大部分以凸版印刷進行塗佈。 　　[0003] 但是凸版印刷有以下的問題，因液晶面板之品種不同而需要各種的樹脂版，製造步驟中該版更換繁雜，為了使成膜步驟安定，必須在仿真基板(Dummy Substrate)之成膜，版之製作成為液晶顯示面板之製造成本上昇的原因等的問題。 　　[0004] 因此，不使用印刷版之新的液晶配向膜塗佈方法為噴墨法受矚目。噴墨法係將微細的液滴滴下至基板，藉由液滴之潤濕擴散成膜的方法。不僅不使用印刷版，且可自由設定印刷的圖型，故液晶顯示元件之製造步驟簡單化。又，不需要在凸版印刷時必要之在仿真基板之成膜，而有塗佈液浪費較少的優點。可期待藉由噴墨法降低液晶面板的成本、提高生產效率。 　　[0005] 藉由噴墨法形成的液晶配向膜，要求塗佈面內部之膜厚不均小，且塗佈周邊部之成膜精度高。一般而言，藉由噴墨法成膜的液晶配向膜係塗佈面內之膜厚之均勻性與塗佈周邊部之成膜精度為折衷(trade off)的關係。通常，面內均勻性高的材料，其塗佈周邊部之尺寸安定性差，且膜會突出於設定的尺寸。而塗佈周邊部為直線的材料係塗佈面內均勻性變差。 　　[0006] 為了提高上述塗佈周邊部的成膜精度，而提案藉由構造物，將配向膜局限(confine)在特定範圍的方法(專利文獻1、專利文獻2、專利文獻3)。但是此等方法有必須追加構造物的缺點。 [先前技術文獻] [專利文獻] 　　[0007] 　　[專利文獻1] 日本國專利公開公報、特開2004-361623號公報 　　[專利文獻2] 日本國專利公開公報、特開2008-145461號公報 　　[專利文獻3] 日本國專利公開公報、特開2010-281925號公報 [0002] Liquid crystal alignment films widely use liquid crystal alignment agents coated with polyimide precursors such as polyamic acid or soluble polyimide solutions as the main component, and the so-called sintering is carried out. Polyimide-based liquid crystal alignment films are generally known as spin coating, dip coating, letterpress printing, and the like for film-forming methods of the liquid crystal alignment films. In practice, most are applied by letterpress printing. However, letterpress printing has the following problems. Various resin plates are required due to the different types of liquid crystal panels, and the plate is replaced in the manufacturing process. In order to stabilize the film formation process, it is necessary to form a film on a dummy substrate (Dummy Substrate). , the production of the plate has become the cause of the increase in the production cost of the liquid crystal display panel and other problems. [0004] Therefore, a new liquid crystal alignment film coating method that does not use a printing plate is an inkjet method attracting attention. The ink jet method is a method of dropping fine droplets onto a substrate and forming a film by wetting and spreading of the droplets. Not only does not use a printing plate, but also the printing pattern can be freely set, so the manufacturing steps of the liquid crystal display element are simplified. In addition, there is no need to form a film on a dummy substrate, which is necessary in letterpress printing, and there is an advantage that the waste of the coating liquid is less. It can be expected to reduce the cost of the liquid crystal panel and improve the production efficiency by the inkjet method. [0005] The liquid crystal alignment film formed by the inkjet method requires that the film thickness unevenness inside the coating surface is small, and the film forming accuracy of the coating peripheral portion is high. In general, the liquid crystal alignment film formed by the inkjet method has a trade-off relationship between the uniformity of the film thickness in the coating surface and the film forming accuracy of the coating peripheral portion. Generally, for materials with high in-plane uniformity, the dimensional stability of the coating peripheral portion is poor, and the film protrudes beyond the set size. On the other hand, the in-plane uniformity of the coating is deteriorated for a material whose coating peripheral portion is a straight line. [0006] In order to improve the film formation accuracy of the above-mentioned coating peripheral portion, a method of confining the alignment film to a specific range by means of a structure has been proposed (Patent Document 1, Patent Document 2, Patent Document 3). However, these methods have the disadvantage that structures must be added. [PRIOR ART DOCUMENTS] [PATENT DOCUMENTS] [0007] [PATENT DOCUMENTS 1] Japanese Patent Application Laid-Open Publication No. 2004-361623 [Patent Document 2] Japanese Patent Application Laid-Open Publication No. 2008-145461 [Patent Document 2] Document 3] Japanese Patent Laid-Open Gazette, Japanese Unexamined Patent Publication No. 2010-281925

近年，隨著液晶顯示元件之高精細化，多層配線之TFT設計逐漸成為主流。本設計因連接下層的配線與上層的配線，故在TFT基板上形成接觸孔(以下也稱為C/H)。伴隨於此，因配線構造或C/H的影響，在液晶配向劑塗佈時，液之擴散性容易受阻礙。結果有在C/H周邊或其他的部分產生如點(dot)狀不均或條紋狀不均之配向膜之膜厚不均勻，造成液晶顯示元件顯示不均勻的情形。 In recent years, with the high definition of liquid crystal display elements, the TFT design of multilayer wiring has gradually become the mainstream. In this design, a contact hole (hereinafter also referred to as C/H) is formed on the TFT substrate to connect the wiring of the lower layer and the wiring of the upper layer. Along with this, due to the influence of the wiring structure and C/H, the diffusibility of the liquid is likely to be hindered when the liquid crystal aligning agent is applied. As a result, uneven thickness of the alignment film such as dot-like unevenness or stripe-like unevenness occurs around the C/H or other parts, resulting in uneven display of the liquid crystal display element.

又，噴墨法可使用的液晶配向劑，為了由噴墨噴嘴安定地吐出配向劑，而要求低黏度，因此有時將液晶配向劑中之樹脂成分比率設定為較少，另外，為了使配向膜塗佈周邊部之膜厚均勻，抑制寬度時，維持低黏度，增加樹脂成分比率為佳，因而要求這種液晶配向劑。 In addition, the liquid crystal aligning agent that can be used in the inkjet method requires low viscosity in order to stably discharge the aligning agent from the inkjet nozzle. Therefore, the ratio of the resin component in the liquid crystal aligning agent may be set to a small amount. The film thickness of the film coating peripheral portion is uniform, and when the width is suppressed, the viscosity is kept low, and the resin component ratio is preferably increased, so this liquid crystal alignment agent is required.

本發明有鑑於上述課題，而提供可抑制因配線構造或C/H之影響所產生之配向膜之塗佈不良，可抑制液晶顯示元件之顯示不均勻的不良，及降低液晶配向劑之黏度，提高樹脂成分比率的液晶配向劑及使用其之液晶配向膜。 In view of the above-mentioned problems, the present invention provides that the coating defects of the alignment film caused by the wiring structure or the influence of C/H can be suppressed, the display unevenness of the liquid crystal display element can be suppressed, and the viscosity of the liquid crystal alignment agent can be reduced, A liquid crystal aligning agent with improved resin component ratio and a liquid crystal aligning film using the same.

本發明人為了解決上述課題而精心研究的結 果，發現使用具有特定結構之溶劑的液晶配向劑，可有效地解決上述課題，遂完成本發明。 In order to solve the above-mentioned problems, the inventors of the present invention have diligently studied As a result, it was found that using a liquid crystal aligning agent having a solvent having a specific structure can effectively solve the above-mentioned problems, and the present invention was completed.

本發明之技術特徵如下述。 The technical features of the present invention are as follows.

1)一種液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及其醯亞胺化物的聚醯亞胺所成群之至少1種，且含有因熱產生脫離之保護基的聚合物，及含有下述A群組的溶劑、B群組的溶劑及二異丁基酮的溶劑成分， 1) A liquid crystal aligning agent characterized by containing at least one selected from the group consisting of polyimide precursors of polyimide precursors and imide compounds thereof, and containing a polymer of a protective group that is detached by heat , and the solvent composition containing the following A group solvent, B group solvent and diisobutyl ketone,

A群組：選自由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯及1,3-二甲基咪唑啉酮所成群之至少1種的溶劑 Group A: at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and 1,3-dimethylimidazolidinone

B群組：選自由丁基溶纖劑、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、二丙二醇二甲醚所成群之至少1種的溶劑。 Group B: at least one solvent selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, 2-butoxy-1-propanol, and dipropylene glycol dimethyl ether.

依據本發明時，可提供可抑制因配線構造或C/H之影響所產生之配向膜之塗佈不良，可抑制液晶顯示元件之顯示不均勻的不良，且低黏度、高樹脂成分比率之聚醯亞胺系的液晶配向劑、及使用其之液晶配向膜。 According to the present invention, the coating defects of the alignment film caused by the wiring structure and the influence of C/H can be suppressed, the display unevenness of the liquid crystal display element can be suppressed, and the polymerization of low viscosity and high resin component ratio can be provided. An imide-based liquid crystal aligning agent and a liquid crystal aligning film using the same.

[實施發明之形態] [Form of implementing the invention]

本發明之液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及其醯亞胺化物的聚醯亞胺所成群之至少1種，且含有因熱產生脫離之保護基的聚合物，及含有上述A群組的溶劑、B群組的溶劑及二異丁基酮的溶劑成分。 The liquid crystal aligning agent of the present invention is characterized by containing at least one selected from the group consisting of polyimide precursors of polyimide precursors and imide compounds thereof, and a polymer containing a protective group that is detached by heat , and the solvent components containing the above-mentioned A group solvent, B group solvent and diisobutyl ketone.

以下詳述各構成要件。 Each constituent element will be described in detail below.

<特定溶劑> <Specific solvent>

本發明之液晶配向劑所含有的溶劑，含有屬於上述A及B群組的溶劑。 The solvent contained in the liquid crystal aligning agent of the present invention contains the solvent belonging to the above-mentioned groups A and B.

<A群組> <A group>

屬於A群組的溶劑為選自由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯及1,3-二甲基咪唑啉酮所成群之至少1種的溶劑。此等之溶劑係溶解液晶配向劑中之聚合物者。 The solvent belonging to Group A is at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and 1,3-dimethylimidazolidinone solvent. These solvents dissolve the polymer in the liquid crystal alignment agent.

其中，較佳為N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯，更佳為N-甲基-2-吡咯烷酮、γ-丁內酯。 Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone and γ-butyrolactone are more preferred.

本發明之液晶配向劑中，屬於A群組的溶劑的含量係相對於液晶配向劑之全質量，較佳為20質量%~90質量%以下，更佳為30質量%~85質量%以下，又更佳為50質量%~85質量%以下。 In the liquid crystal alignment agent of the present invention, the content of the solvent belonging to the A group is relative to the total mass of the liquid crystal alignment agent, preferably 20% by mass to 90% by mass or less, more preferably 30% by mass to 85% by mass or less, Still more preferably, it is 50 mass % - 85 mass % or less.

<B群組> <Group B>

屬於B群組的溶劑係選自由丁基溶纖劑、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、二丙二醇二甲醚所成群之至少1種的溶劑。此溶劑係提高液晶配向劑之塗佈均勻性與賦予低黏度化的溶劑。 The solvent belonging to Group B is at least one solvent selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, 2-butoxy-1-propanol, and dipropylene glycol dimethyl ether. This solvent is a solvent that improves the coating uniformity of the liquid crystal alignment agent and imparts lower viscosity.

其中，較佳為含有丁基溶纖劑、1-丁氧基-2-丙醇、二丙二醇二甲醚，特佳為含有1-丁氧基-2-丙醇。 Among them, it is preferable to contain butyl cellosolve, 1-butoxy-2-propanol, and dipropylene glycol dimethyl ether, and it is particularly preferable to contain 1-butoxy-2-propanol.

又，市售的1-丁氧基-2-丙醇通常含有作為異構物之2-丁氧基-1-丙醇為首之數種類的異構物，通常以該狀態使用。 In addition, commercially available 1-butoxy-2-propanol usually contains several kinds of isomers including 2-butoxy-1-propanol as an isomer, and is usually used in this state.

本發明之液晶配向劑中，屬於B群組之溶劑的含量係相對於液晶配向劑之全質量，較佳為1質量%~50質量%以下，更佳為10質量%~50質量%以下，又更佳為、10質量%~30質量%以下。 In the liquid crystal alignment agent of the present invention, the content of the solvent belonging to the B group is relative to the total mass of the liquid crystal alignment agent, preferably 1 to 50 mass % or less, more preferably 10 to 50 mass % or less, More preferably, it is 10 mass % - 30 mass % or less.

本發明之液晶配向劑所含有之二異丁基酮的含量係相對於液晶配向劑之全質量，較佳為1質量%~20質量%以下，更佳為5質量%~20質量%以下。 The content of diisobutyl ketone contained in the liquid crystal aligning agent of the present invention is preferably 1 to 20 mass % or less, more preferably 5 to 20 mass %, based on the total mass of the liquid crystal aligning agent.

<特定聚合物> <Specific polymer>

本發明之液晶配向劑所含有之聚合物為選自由四羧酸衍生物成分與二胺成分之反應物的聚醯亞胺前驅物及其醯亞胺化物的聚醯亞胺所成群之至少1種，且含有因熱置換成氫原子之保護基的聚合物。 The polymer contained in the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyimide precursor and a polyimide of an imide compound selected from a reaction product of a tetracarboxylic acid derivative component and a diamine component. One type of polymer containing a protective group that is replaced by a hydrogen atom due to thermal replacement.

以下詳述構成聚合物之原料的各成分。 Each component constituting the raw material of the polymer will be described in detail below.

<結構中含有因熱產生脫離之保護基的二胺> <Diamine containing a protective group that is desorbed by heat in its structure>

本發明之液晶配向劑可使用的二胺成分，包含結構中含有因熱產生脫離之保護基的二胺(以下也稱為特定二胺)。 The diamine component which can be used for the liquid crystal aligning agent of this invention contains the diamine (henceforth a specific diamine) containing the protective group which remove|eliminated by heat in a structure.

[0029] 上述保護基只要是因加熱產生脫離之官能基時，其結構無特別限定。從本發明之液晶配向劑之保存安定性的觀點，此保護基A在室溫下不會脫離者為佳，較佳為80℃以上的熱產生脫離的保護基，又更佳為100℃以上的熱產生脫離的保護基。又，從促進聚醯胺酸酯之熱醯亞胺化的效率及與聚醯亞胺前驅物或聚醯亞胺之交聯反應的觀點，較佳為300℃以下的熱產生脫離的保護基，更佳為250℃以下的熱產生脫離的保護基，又更佳為200℃以下的熱產生脫離的保護基。 　　[0030] 本發明中較適合使用的特定二胺含有以下的結構。 　　[0031]

Figure 02_image001
[0032] 前述式中，X1 為氧原子或硫原子，A1 ~A3 各自獨立為氫原子或碳數1~3之烴基，碳數之合計為1~9。又，*表示與其他原子的鍵結。 　　[0033] 式(a)中，X1 為氧原子或硫原子，較佳為氧原子。A1 ~A3 各自獨立為氫原子或碳數1~3之烴基，碳數1為佳。又，碳數之合計為1~9，較佳為3~6。又，*表示與其他原子的鍵結。 　　[0034] 結構中具有式(a)的二胺，可列舉例如以下結構的二胺。又，式中的「Boc」為第三丁氧基羰基。 　　[0035]
Figure 02_image003
[0036] 本發明之液晶配向劑可使用之特定二胺的量，較佳為全二胺成分中之10莫耳%~50莫耳%，更佳為10莫耳%~40莫耳%。 　　[0037] ＜其他的二胺＞ 　　本發明之液晶配向劑可使用的二胺成分，除了上述的二胺外，可發揮本發明效果時，可含有其他的二胺。其他之二胺的結構無特別限定，例如有以下通式(2)者。 　　[0038]
Figure 02_image005
[0039] 上述式(2)之A1 及A2 各自獨立為氫原子或、碳數1~5之烷基、碳數2~5之烯基、碳數2~5之炔基。從液晶配向性的觀點，A1 及A2 較佳為氫原子、或甲基。 　　例示Y1 之結構時，如以下所示。 　　[0040]
Figure 02_image007
[0041]
Figure 02_image009
[0042]
Figure 02_image011
[0043]
Figure 02_image013
[0044]
Figure 02_image015
[0045]
Figure 02_image017
[0046]
Figure 02_image019
[0047]
Figure 02_image021
[0048]
Figure 02_image023
[0049]
Figure 02_image025
[0050]
Figure 02_image027
[0051]
Figure 02_image029
[0052] 式中，n為1~6之整數。 　　[0053]
Figure 02_image031
[0054] 式中，n為1~6之整數。 　　[0055] ＜垂直配向性二胺：具有特定側鏈結構的二胺＞ 　　將本發明作為VA方式之液晶配向劑使用時，使用展現垂直配向能之具有特定側鏈結構的二胺調製聚合物為佳。此具有特定側鏈結構的二胺，具有選自由下述式[S1]~[S3]表示之群組之至少1種的側鏈結構。 　　[0056] 以下依式[S1]~[S3]的順序說明此具有特定側鏈結構的二胺。 　　[0057] 具有特定側鏈結構之二胺例，具有下述式[S1]表示之特定側鏈結構的二胺。 　　[0058]
Figure 02_image033
[0059] 上述式[S1]中，X1 及X2 各自獨立表示單鍵、-(CH2 )a -(a係1~15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-COO-、-OCO-或-((CH2 )a1 -A1 )m1 -。其中，複數之a1各自獨立表示1~15之整數，複數之A1 各自獨立表示氧原子或-COO-，m1 為1~2。 　　[0060] 其中，從原料之取得性或合成之容易度的觀點，X1 及X2 各自獨立為單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-或-COO-為佳，更佳為單鍵、-(CH2 )a -(a為1~10之整數)、-O-、-CH2 O-或-COO-。 　　[0061] 又，上述式[S1]中，G1 及G2 各自獨立表示選自碳數6~12之2價芳香族基或碳數3~8之2價脂環式基之2價環狀基。該環狀基上之任意的氫原子，可經碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代。m及n各自獨立為0~3之整數，m及n之合計為1~4。 　　[0062] 又，上述式[S1]中，R1 表示碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基。形成R1 之任意的氫可經氟取代。其中，碳數6~12之2價之芳香族基之例，可列舉伸苯基、亞聯苯基、萘等。又，碳數3~8之2價脂環式基之例，可列舉伸環丙基、伸環己基等。 　　[0063] 因此，上述式[S1]之較佳的具體例，可列舉下述式[S1-x1]~[S1-x7]，但是不限定於此等。 　　[0064]
Figure 02_image035
[0065] 上述式[S1-x1]~[S1-x7]中，R1 係與上述式[S1]的情形相同。Xp 表示-(CH2 )a -(a為1~15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-CH2 O-、-COO-或-OCO-。A1 表示氧原子或-COO-*(附有「*」之鍵結鍵與(CH2 )a2 鍵結)。A2 表示氧原子或*-COO-(附有「*」之鍵結鍵與(CH2 )a2 鍵結)。a1 為0或1之整數，a2 為2~10之整數。Cy表示1,4-伸環己基或1,4-伸苯基。 　　[0066] 又，具有特定側鏈結構之二胺之例，可列舉具有下述式[S2]表示之特定側鏈結構的二胺。 　　[0067]
Figure 02_image037
[0068] 上述式[S2]中，X3 表示單鍵、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-CH2 O-、-COO-或-OCO-。其中，從液晶配向劑之液晶配向性的觀點，X3 係-CONH-、-NHCO-、-O-、-CH2 O-、-COO-或-OCO-為佳。 　　[0069] 又，上述式[S2]中，R2 表示碳數1~20之烷基或碳數2~20之烷氧基烷基。形成R2 之任意的氫，可經氟取代。其中，從液晶配向劑之液晶配向性的觀點，R2 係碳數3~20之烷基或碳數2~20之烷氧基烷基為佳。 　　[0070] 此外，具有特定側鏈結構之二胺之例，可列舉具有下述式[S3]表示之特定側鏈結構的二胺。 　　[0071]
Figure 02_image039
[0072] 上述式[S3]中，X4 表示-CONH-、-NHCO-、-O-、-COO-或-OCO-。R3 表示具有類固醇骨架之結構。在此之類固醇骨架係具有鍵結有3個六員環及1個五員環之以下述式(st)表示的骨架。 　　[0073]
Figure 02_image041
[0074] 上述式[S3]之例，可列舉下述式[S3-x]，但是不限定於此。 　　[0075]
Figure 02_image043
[0076] 上述式[S3-x]中，X表示上述式[X1]或[X2]。又，Col表示選自由上述式[Col1]~[Col4]所成群之至少1種，G表示上述式[G1]或[G2]。*表示與其他之基鍵結的部位。 　　[0077] 上述式[S3-x]中之X、Col及G之較佳的組合例，可列舉例如下述。亦即，[X1]與[Col1]及[G1]之組合、[X1]與[Col1]及[G2]之組合、[X1]與[Col2]及[G1]之組合、[X1]與[Col2]及[G2]之組合、[X1]與[Col3]及[G2]之組合、[X1]與[Col4]及[G2]之組合、[X1]與[Col3]及[G1]之組合、[X1]與[Col4]及[G1]之組合、[X2]與[Col1]及[G2]之組合、[X2]與[Col2]及[G2]之組合、[X2]與[Col2]及[G1]之組合、[X2]與[Col3]及[G2]之組合、[X2]與[Col4]及[G2]之組合、[X2]與[Col1]及[G1]之組合、[X2]與[Col4]及[G1]之組合。 　　[0078] 又，上述式[S3]之具體例，可列舉自日本特開平4-281427號公報之段落[0024]所記載的類固醇化合物，去除羥基(Hydroxyl Group)之構造、自同公報之段落[0030]所記載的類固醇化合物，去除酸氯化物基之構造、自同公報之段落[0038]所記載的類固醇化合物，去除胺基的構造、自同公報之段落[0042]所記載的類固醇化合物，去除鹵基的構造、及日本特開平8-146421之段落[0018]~[0022]所記載的構造等。 　　[0079] 又，類固醇骨架之代表例，可列舉膽固醇(上述式[S3-x]中之[Col1]及[G2]之組合)，但是也可利用不含該膽固醇之類固醇骨架。亦即，具有類固醇骨架之二胺，可列舉例如3,5-二胺基苯甲酸膽甾烷酯(cholestanyl)等，但是也可為不含具有此膽固醇骨架之二胺的二胺成分。又，也可利用作為具有特定側鏈結構之二胺，例如在二胺與側鏈之連結位置不含醯胺者。利用這種二胺，或本實施形態中，利用不含具有膽固醇骨架之二胺的二胺成分，也可提供可得到長期可確保高的電壓保持率的液晶配向膜或液晶顯示元件的液晶配向劑。 　　[0080] 又，具有上述式[S1]~[S3]表示之側鏈結構的二胺，分別為以下述式[1-S1]-[1-S3]的結構表示。 　　[0081]
Figure 02_image045
[0082] 上述式[1-S1]中，X1 、X2 、G1 、G2 、R1 、m及n為與上述式[S1]之的情形相同。上述式[1-S2]中，X3 及R2 係與上述式[S2]的情形相同。上述式[1-S3]中，X4 及R3 係與上述式[S3]的情形相同。 　　[0083] ＜垂直配向性二胺：具有二側鏈型之特性側鏈結構的二胺＞ 　　作為VA方式的液晶配向劑使用時，可使用具有2個垂直配向性之特定側鏈結構之二側鏈型的二胺，調製聚合物。 　　本實施形態中，也可作為二胺成分含有的二側鏈二胺，例如以下述式[1]表示。 　　[0084]
Figure 02_image047
[0085] 上述式[1]中，X表示單鍵、-O-、-C(CH3 )2 -、-NH-、-CO-、-NHCO-、-COO-、-(CH2 )m -、-SO2 -或彼等之任意組合所成的2價有機基。其中，X較佳為單鍵、-O-、-NH-、-O-(CH2 )m -O-。「彼等之任意組合」之例，可列舉-O-(CH2 )m -O-、-O-C(CH3 )2 -、-CO-(CH2 )m -、-NH-(CH2 )m -、-SO2 -(CH2 )m -、-CONH-(CH2 )m -、-CONH-(CH2 )m -NHCO-、-COO-(CH2 )m -OCO-等，但是不限定於此等。m係1~8之整數。 　　又，上述式[1]中，2個Y各自獨立表示下述式[1-1]的結構。 　　[0086]
Figure 02_image049
[0087] 上述式[1-1]中，Y1 及Y3 各自獨立表示單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-、-COO-或-OCO-。Y2 表示單鍵或-(CH2 )b -(b係1~15之整數)。但是Y1 或Y3 為單鍵或-(CH2 )a -時，Y2 為單鍵。又，Y1 為-O-、-CH2 O-、-COO-或-OCO-、及/或Y3 為-O-、-CH2 O-、-COO-或-OCO-時，Y2 為單鍵或-(CH2 )b -。 　　[0088] 又，式[1-1]中，Y4 表示選自由苯環、環己烷環及雜環所成群之至少1種之2價之環狀基或具有類固醇骨架之碳數17~51之2價有機基。形成該環狀基之任意的氫原子，也可經碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代。 　　[0089] 又，上述式[1-1]中，Y5 表示選自由苯環、環己烷環及雜環所成群之至少1種的環狀基。形成該環狀基之任意的氫原子，也可經碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代。 　　[0090] 又，上述式[1-1]中，Y6 表示選自由碳數1~18之烷基、碳數2~18之烯基、碳數1~18之含氟烷基、碳數1~18之烷氧基及碳數1~18之含氟烷氧基所成群之至少1種。n係0~4之整數。 　　[0091] 又，具有上述式[S1]~[S3]表示之側鏈結構的二側鏈二胺。分別以下述式[2-S1]-[2-S3]之結構表示。 　　[0092]
Figure 02_image051
[0093] 又，上述式[1]中，Y係由X的位置起算可為間位，也可為鄰位，但是較佳為鄰位。亦即，上述式[1]較佳為下述式[1’]者。 　　[0094]
Figure 02_image053
[0095] 又，上述式[1]中，2個胺基(-NH2 )的位置，可在苯環上之任一位置，較佳為以下述式[1]-a1~[1]-a3表示的位置，更佳為下述式[1]-a1。下述式中，X係與上述式[1]的情形相同。又，下述式[1]-a1~[1]-a3係說明2個胺基的位置，故省略以上述式[1]中表示之Y的敘述。 　　[0096]
Figure 02_image055
[0097] 因此，依據上述式[1’]及[1]-a1~[1]-a3時，上述式[1]為選自下述式[1]-a1-1~[1]-a3-2之任一結構為佳，更佳為下述式[1]-a1-1表示之結構。下述式中，X及Y分別與式[1]的情形相同。 　　[0098]
Figure 02_image057
[0099] 又，上述式[1-1]之例，可列舉下述式[1-1]-1~[1-1]-22，但是不限定於此等。其中，上述式[1-1]之例，較佳為下述式[1-1]-1~[1-1]-4、[1-1]-8或[1-1]-10。又，下述式中，*表示與上述式[1]、[1’]及[1]-a1~[1]-a3中之苯基的鍵結位置。 　　[0100]
Figure 02_image059
[0101] 二胺成分因含有具有特定結構之二側鏈二胺，因而即使處於過度加熱的情形，也可成為使液晶垂直配向之能力變得不易降低的液晶配向膜。又，二胺成分因含有該二側鏈二胺，因而即使膜接觸任何的異物，受傷時，也可成為使液晶垂直配向之能力變得不易降低的液晶配向膜。亦即，二胺成分因含有該二側鏈二胺，而可提供可得到各種上述特性優異之液晶配向膜的液晶配向劑。 　　[0102] ＜其他的二胺：具有光反應性側鏈之二胺＞ 　　又，本發明作為垂直配向方式之PSA模式之液晶配向劑使用的情形，為了提高液晶中所含有之聚合性化合物的反應性，也可使用具有光反應性側鏈的二胺，調製聚合物。 　　本實施形態之二胺成分，也可含有作為其他之二胺之具有光反應性側鏈的二胺。二胺成分因含有具有光反應性側鏈之二胺，可在特定聚合物或其以外的聚合物中，導入光反應性側鏈。 　　[0103] 具有光反應性側鏈之二胺，可列舉例如下述式[VIII]或[IX]表示者，但是不限定於此等。 　　[0104]
Figure 02_image061
[0105] 上述式[VIII]及[IX]中，2個胺基(-NH2 )的位置，可在苯環上之任一位置，例如相對於側鏈之鍵結基，為苯環上之2,3的位置、2,4的位置、2,5的位置、2,6的位置、3,4的位置或3,5的位置。從合成聚醯胺酸時之反應性的觀點，較佳為2,4的位置、2,5的位置或3,5的位置。另外，從合成二胺時之容易性的觀點，更佳為2,4的位置或3,5的位置。 　　[0106] 又，上述式[VIII]中，R8 表示單鍵、-CH2 -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2 O-、-N(CH3 )-、-CON(CH3 )-或-N(CH3 )CO-。特別是R8 係單鍵、-O-、-COO-、-NHCO-或-CONH-為佳。 　　[0107] 又，上述式[VIII]中，R9 表示單鍵或可被氟原子取代之碳數1~20之伸烷基。在此之伸烷基之-CH2 -可經-CF2 -或-CH=CH-任意取代，以下之任一基未彼此相鄰時，也可經此等之基取代；-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、二價之碳環或雜環。又，此二價之碳環或雜環，具體而言，可列舉下述式(1a)者，但是不限定此。 　　[0108]
Figure 02_image063
[0109] 又，上述式[VIII]中，R9 從可以一般有機合成的手法形成，但是合成之容易性的觀點，較佳為單鍵或碳數1~12之伸烷基。 　　[0110] 又，上述式[VIII]中，R10 表示選自由下述式(1b)所成群之光反應性基。其中，R10 從光反應性的觀點，較佳為甲基丙烯醯基、丙烯醯基(Acryl group)或乙烯基。 　　[0111]
Figure 02_image065
[0112] 又，上述式[IX]中，Y1 表示-CH2 -、-O-、-CONH-、-NHCO-、-COO-、-OCO-、-NH-或-CO-。Y2 表示碳數1~30之伸烷基、二價之碳環或雜環。在此之伸烷基、二價之碳環或雜環中之1個或複數之氫原子，也可經氟原子或有機基取代。Y2 係當以下之基未彼此相鄰時，-CH2 -也可經此等之基取代；-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。 　　[0113] 又，上述式[IX]中，Y3 表示-CH2 -、-O-、-CONH-、-NHCO-、-COO-、-OCO-、-NH-、-CO-或單鍵。Y4 表示桂皮醯基。Y5 表示單鍵、碳數1~30之伸烷基、二價之碳環或雜環。在此之伸烷基、二價之碳環或雜環中之1個或複數之氫原子，也可經氟原子或有機基取代。Y5 係當以下之基未彼此相鄰時，-CH2 -也可經此等之基取代；-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。Y6 表示丙烯醯基或甲基丙烯醯基等的光聚合性基。 　　[0114] 這種上述式[VIII]或[IX]表示之具有光反應性側鏈之二胺的具體例，可列舉下述式(1c)，但是不限定於此。 　　[0115]
Figure 02_image067
[0116] 上述式(1c)中，X9 及X10 各自獨立表示單鍵、-O-、-COO-、-NHCO-或-NH-的鍵結基。Y表示可被氟原子取代之碳數1~20之伸烷基。 　　[0117] 具有光反應性側鏈之二胺，可列舉下述式[VII]的二胺。式[VII]之二胺係在側鏈具有含有自由基產生結構的部位。自由基產生結構為藉由紫外線照射，而分解產生自由基。 　　[0118]
Figure 02_image069
[0119] 上述式[VII]中，Ar表示選自由伸苯基、伸萘基及亞聯苯基所成群之至少1種的芳香族烴基，彼等之環的氫原子可經鹵素原子取代。羰基所鍵結的Ar係涉及紫外線之吸收波長，故長波長化時，如伸萘基或亞聯苯基般之共軛長較長的結構為佳。另外，Ar成為如伸萘基或亞聯苯基般的結構時，有溶解性變差的情形，此時，合成之難易度變高。紫外線之波長為250nm~380nm之範圍時，即使苯基也可得到充分的特性，故Ar最佳為苯基。 　　[0120] 上述Ar中，芳香族烴基上可設置取代基。在此之取代基例，較佳為烷基、羥基、烷氧基、胺基等、供電子性的有機基。 　　[0121] 又，上述式[VII]中，R1 及R2 各自獨立表示碳原子數1~10之烷基、烷氧基、苄基或苯乙基。烷基或烷氧基的情形，藉由R1 及R2 ，也可形成環。 　　[0122] 又，上述式[VII]中，T1 及T2 各自獨立表示單鍵、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2 O-、-N(CH3 )-、-CON(CH3 )-或-N(CH3 )CO-之鍵結基。 　　[0123] 又，式[VII]中，S表示單鍵、非取代或經氟原子取代之碳原子數1~20之伸烷基。在此之伸烷基之-CH2 -或-CF2 -，可經-CH=CH-任意取代，以下例舉之任一基彼此不相鄰時，可經此等之基取代；-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、二價之碳環、二價之雜環。 　　[0124] 又，式[VII]中，Q表示選自下述式(1d)的結構。 　　[0125]
Figure 02_image071
[0126] 上述式(1d)中，R表示氫原子或碳原子數1~4之烷基。R3 表示-CH2 -、-NR-、-O-、或-S-。 　　[0127] 又，上述式[VII]中，Q較佳為供電子性之有機基，較佳為如上述Ar之例所列舉之烷基、羥基、烷氧基、胺基等。Q為胺基衍生物時，聚醯亞胺前驅物之聚醯胺酸之聚合時，可能會產生發生之羧酸基與胺基形成鹽等之不理想狀態，故更佳為羥基或烷氧基。 　　[0128] 又，上述式[VII]中，2個胺基(-NH2 )的位置，可為o-苯二胺、m-苯二胺或p-苯二胺之任一，但是與酸二酐之反應性的觀點，較佳為m-苯二胺或p-苯二胺。 　　[0129] 因此，上述式[VII]之較佳具體例，從合成之容易度、泛用性之高度、特性等的觀點，可列舉下述式。又，下述式中，n為2~8之整數。 　　[0130]
Figure 02_image073
[0131] 此等之上述式[VII]、[VIII]或[IX]表示之具有光反應性側鏈之二胺，可1種單獨或混合2種以上使用。配合作為液晶配向膜時之液晶配向性、預傾角、電壓保持特性、蓄積電荷等之特性、作為液晶顯示元件時之液晶之應答速度等，1種單獨使用或混合2種以上使用，或混合2種以上使用時，其比例等適宜調整即可。 　　[0132] ＜四羧酸衍生物＞ 　　本發明之液晶配向劑所含有之製造具有上述式(1)之結構單位之聚合物用的四羧酸衍生物成分，不僅為四羧酸二酐，也可使用其四羧酸衍生物的四羧酸、四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物。 　　[0133] 四羧酸二酐及其衍生物，使用選自下述式(3)表示之四羧酸二酐及其衍生物之至少1個更佳。 　　[0134]
Figure 02_image075
[0135] 式中，X1 為具有脂環式結構之4價有機基，其結構無特別限定。具體例可列舉下述式(X1-1)~(X1-44)。 　　[0136]
Figure 02_image077
[0137] 式(X1-1)~(X1-4)中，R3 至R23 各自獨立為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之一價有機基、或苯基，可相同或相異。從液晶配向性的觀點，R3 至R23 較佳為氫原子、鹵素原子、甲基、或乙基，更佳為氫原子、或甲基。式(X1-1)之具體的結構，可列舉下述式(X1-1-1)~(X1-1-6)表示之結構。從液晶配向性及光反應之感度的觀點，特佳為(X1-1-1)。 　　[0138]
Figure 02_image079
[0139]
Figure 02_image081
[0140]
Figure 02_image083
[0141] 本發明所記載之聚醯亞胺前驅物及聚醯亞胺之原料的四羧酸二酐及其衍生物係相對於全四羧酸二酐及其衍生物1莫耳，上述式(3)表示之四羧酸二酐及其衍生物含有60~100莫耳%為佳。為了得到具有良好液晶配向性的液晶配向膜，更佳為80莫耳%~100莫耳%，又更佳為90莫耳%~100莫耳%。 　　[0142] ＜聚醯胺酸酯之製造方法＞ 　　本發明可使用之聚醯亞胺前驅物之一個的聚醯胺酸酯可使用以下所示之(1)、(2)或(3)的方法合成。 　　[0143] (1)由聚醯胺酸合成的情形 　　聚醯胺酸酯可藉由將由四羧酸二酐與二胺所得之聚醯胺酸進行酯化來合成。 　　具體而言，在有機溶劑之存在下，可藉由使聚醯胺酸與酯化劑在-20℃~150℃，較佳為0℃~50℃下，反應30分鐘~24小時，較佳為1~4小時來合成。 　　[0144] 酯化劑可藉由純化容易除去者為佳，可列舉N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鹽酸鹽(methylmorpholinium chloride)等。酯化劑之添加量係相對於聚醯胺酸之重複單位1莫耳，較佳為2~6莫耳當量。 　　[0145] 上述反應所使用的溶劑，從聚合物之溶解而言，較佳為N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、或γ-丁內酯，此等也可使用1種或混合2種以上使用。合成時的濃度，從聚合物不易產生析出，且可得到高分子量體的觀點，較佳為1~30質量%，更佳為5~20質量%。 　　[0146] (2)藉由四羧酸二酯二氯化物與二胺之反應合成的情形 　　聚醯胺酸酯可由四羧酸二酯二氯化物與二胺合成。 　　[0147] 具體而言，可藉由在鹼與有機溶劑之存在下，使四羧酸二酯二氯化物與二胺在-20℃~150℃，較佳為0℃~50℃下，反應30分鐘~24小時，較佳為1~4小時來合成。 　　[0148] 前述鹼可使用吡啶、三乙基胺、4-二甲基胺基吡啶等，但是為了安定地進行反應，較佳為吡啶。鹼之添加量，從可容易除去的量，且可容易得到高分子量體的觀點，相對於四羧酸二酯二氯化物，較佳為2~4倍莫耳。 　　[0149] 上述反應所使用的溶劑，從單體及聚合物之溶解性的觀點，較佳為N-甲基-2-吡咯烷酮、或γ-丁內酯，此等可使用1種或混合2種以上使用。合成時的聚合物濃度，從聚合物不易析出，且可得到高分子量體的觀點，較佳為1~30質量%，更佳為5~20質量%。又，為了防止四羧酸二酯二氯化物之水解，聚醯胺酸酯之合成所使用的溶劑，盡可能地經脫水者為佳，氮環境中，防止外面空氣混入為佳。 　　[0150] (3)由四羧酸二酯與二胺合成聚醯胺酸酯的情形 　　聚醯胺酸酯可藉由將四羧酸二酯與二胺進行聚縮合來合成。 　　[0151] 具體而言，在縮合劑、鹼、及有機溶劑之存在下，可藉由將四羧酸二酯與二胺在0℃~150℃，較佳為0℃~100℃下，反應30分鐘~24小時，較佳為3~15小時來合成。 　　[0152] 前述縮合劑可使用三苯基亞磷酸酯、二環己基碳二亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三嗪基甲基嗎啉、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基甲基脲六氟磷酸鹽、(2,3-二氫-2-硫氧-3-苯並噁唑基)膦酸二苯酯等。縮合劑之添加量係相對於四羧酸二酯，較佳為2~3倍莫耳。 　　[0153] 前述鹼可使用吡啶、三乙基胺等之三級胺。鹼之添加量，從可容易除去的量，且可容易得到高分子量體的觀點，相對於二胺成分，較佳為2~4倍莫耳。 　　[0154] 又，上述反應中，作為添加劑添加路易斯酸，可有效率地進行反應。路易斯酸較佳為氯化鋰、溴化鋰等之鹵化鋰。路易斯酸之添加量係相對於二胺成分，較佳為0~1.0倍莫耳。 　　[0155] 上述3個聚醯胺酸酯之合成方法中，為了得到高分子量之聚醯胺酸酯，特佳為上述(1)或上述(2)的合成法。 　　[0156] 如上述所得之聚醯胺酸酯的溶液，可藉由邊充分攪拌邊注入於弱溶劑中，使聚合物析出。進行數次析出，以弱溶劑洗凈後，常溫或加熱乾燥，可得到經純化之聚醯胺酸酯的粉末。弱溶劑，無特別限定，可列舉水、甲醇、乙醇、己烷、丁基溶纖劑、丙酮、甲苯等。 　　[0157] ＜聚醯胺酸之製造方法＞ 　　本發明可使用之聚醯亞胺前驅物的聚醯胺酸，可藉由以下所示之方法來合成。 　　[0158] 具體而言，在有機溶劑之存在下，可藉由將四羧酸二酐與二胺，在-20℃~150℃，較佳為0℃~50℃下，反應30分鐘~24小時，較佳為1~12小時來合成。 　　[0159] 上述反應所使用之有機溶劑，從單體及聚合物之溶解性的觀點，較佳為N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、或γ-丁內酯，此等可使用1種或混合2種以上使用。聚合物的濃度，從聚合物不易析出，且可得到高分子量體的觀點，較佳為1~30質量%，更佳為5~20質量%。 　　[0160] 如上述所得之聚醯胺酸，可藉由邊將反應溶液充分攪拌邊注入於弱溶劑中，使聚合物析出回收。又，進行數次析出，以弱溶劑洗凈後，常溫或加熱乾燥，可得到經純化之聚醯胺酸的粉末。弱溶劑，無特別限定，可列舉水、甲醇、乙醇、己烷、丁基溶纖劑、丙酮、甲苯等。 　　[0161] ＜聚醯亞胺之製造方法＞ 　　本發明可使用之聚醯亞胺，可藉由將前述聚醯胺酸酯或聚醯胺酸進行醯亞胺化來製造。由聚醯胺酸酯製造聚醯亞胺時，在前述聚醯胺酸酯溶液、或將聚醯胺酸酯樹脂粉末溶解於有機溶劑所得的聚醯胺酸溶液中，添加鹼性觸媒之化學性醯亞胺化較簡便。化學性醯亞胺化係在比較低溫下進行醯亞胺化反應，在醯亞胺化之過程，不易產生聚合物之分子量降低，故較佳。 　　[0162] 化學性醯亞胺化可藉由將欲醯亞胺化的聚醯胺酸酯，在有機溶劑中，鹼性觸媒存在下攪拌來進行。有機溶劑可使用前述聚合反應時所使用的溶劑。鹼性觸媒可列舉吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等。其中，三乙基胺具有進行反應所需要之充分的鹼性，故較佳。 　　[0163] 進行醯亞胺化反應時之溫度為-20℃~140℃，較佳為0℃~100℃，可以反應時間為1~100小時進行反應。鹼性觸媒的量為醯胺酸酯基之0.5~30莫耳倍，較佳為2~20莫耳倍。所得之聚合物的醯亞胺化率，可藉由調節觸媒量、溫度、反應時間來控制。醯亞胺化反應後的溶液中，殘存有添加的觸媒等，故藉由以下所述的手段，回收所得之醯亞胺化聚合物，以有機溶劑再溶解，作為本發明之液晶配向劑為佳。 　　[0164] 由聚醯胺酸製造聚醯亞胺的情形，在由二胺成分與四羧酸二酐之反應所得之前述聚醯胺酸的溶液中添加觸媒之化學性醯亞胺化較簡便。化學性醯亞胺化係在比較低溫下進行醯亞胺化反應，在醯亞胺化之過程，不易產生聚合物之分子量降低，故較佳。 　　[0165] 化學性醯亞胺化可藉由將欲醯亞胺化的聚合物，在有機溶劑中，鹼性觸媒與酸酐之存在下攪拌來進行。有機溶劑可使用前述聚合反應時使用的溶劑。鹼性觸媒可列舉吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等。其中，吡啶具有進行反應所需之適度的鹼性，故較佳。又，酸酐可列舉乙酸酐、偏苯三甲酸酐、均苯四甲酸酐等，其中，使用乙酸酐時，在反應結束後之純化變得容易，故較佳。 　　[0166] 進行醯亞胺化反應時之溫度為-20℃~140℃，較佳為0℃~100℃，可以反應時間為1~100小時進行反應。鹼性觸媒的量為醯胺酸基之0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐之量為醯胺酸基之1~50莫耳倍，較佳為3~30莫耳倍。所得之聚合物的醯亞胺化率，可藉由調節觸媒量、溫度、反應時間來控制。 　　[0167] 聚醯胺酸酯或聚醯胺酸之醯亞胺化反應後的溶液中，殘存有添加的觸媒等，故藉由以下所述的手段，回收所得之醯亞胺化聚合物，以有機溶劑再溶解，作為本發明之液晶配向劑為佳。 　　[0168] 如上述所得之聚醯亞胺的溶液，可藉由邊充分攪拌邊注入於弱溶劑中，使聚合物析出。進行數次析出，以弱溶劑洗凈後，常溫或加熱乾燥，可得到經純化之聚醯胺酸酯的粉末。 　　前述弱溶劑，無特別限定，可列舉甲醇、丙酮、己烷、丁基纖維素、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯等。 　　[0169] ＜液晶配向劑＞ 　　本發明可使用之液晶配向劑係具有特定結構之聚合物溶解於有機溶劑中之溶液的形態。本發明所記載之聚醯亞胺前驅物及聚醯亞胺的分子量，其重量平均分子量較佳為2,000~500,000，更佳為5,000~300,000，又更佳為10,000~100,000。又，數平均分子量較佳為1,000~250,000，更佳為2,500~150,000，又更佳為5,000~50,000。 [0029] The structure of the above-mentioned protecting group is not particularly limited as long as it is a functional group that is removed due to heating. From the viewpoint of the storage stability of the liquid crystal aligning agent of the present invention, the protecting group A is preferably one that does not desorb at room temperature, preferably a protecting group that is desorbed by heat of 80°C or higher, and more preferably 100°C or higher. The heat produces detached protecting groups. In addition, from the viewpoint of promoting the efficiency of thermal imidization of the polyimide and the crosslinking reaction with the polyimide precursor or polyimide, it is preferable to use a protecting group that is desorbed by heat at 300°C or lower. , more preferably a protecting group desorbed by heat at 250°C or lower, and still more preferably a protecting group desorbed by heat at 200°C or lower. [0030] The specific diamine preferably used in the present invention has the following structure. [0031]
Figure 02_image001
In the aforementioned formula, X 1 is an oxygen atom or a sulfur atom, and A 1 ～A 3 are each independently a hydrogen atom or the hydrocarbon group of carbon number 1～3, and the sum of carbon number is 1～9. Also, * represents a bond with other atoms. In formula (a), X 1 is oxygen atom or sulfur atom, preferably oxygen atom. A 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably 1 carbon number. Moreover, the total number of carbon atoms is 1 to 9, preferably 3 to 6. Also, * represents a bond with other atoms. [0034] The diamine having the formula (a) in the structure includes, for example, the diamine of the following structure. In addition, "Boc" in the formula is a tertiary butoxycarbonyl group. [0035]
Figure 02_image003
[0036] The amount of the specific diamine that can be used in the liquid crystal alignment agent of the present invention is preferably 10 mol% to 50 mol% in the total diamine component, more preferably 10 mol% to 40 mol%. <Other diamines> The diamine components that can be used in the liquid crystal aligning agent of the present invention may contain other diamines when the effects of the present invention can be exhibited in addition to the above-mentioned diamines. The structure of other diamines is not particularly limited, but there are, for example, those of the following general formula (2). [0038]
Figure 02_image005
A 1 and A 2 of above-mentioned formula (2) are each independently a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, and an alkynyl group with 2 to 5 carbon atoms. From the viewpoint of liquid crystal alignment, A 1 and A 2 are preferably a hydrogen atom or a methyl group. When the structure of Y 1 is exemplified, it is as follows. [0040]
Figure 02_image007
[0041]
Figure 02_image009
[0042]
Figure 02_image011
[0043]
Figure 02_image013
[0044]
Figure 02_image015
[0045]
Figure 02_image017
[0046]
Figure 02_image019
[0047]
Figure 02_image021
[0048]
Figure 02_image023
[0049]
Figure 02_image025
[0050]
Figure 02_image027
[0051]
Figure 02_image029
In formula, n is the integer of 1～6. [0053]
Figure 02_image031
In formula, n is the integer of 1～6. <Vertical alignment diamine: diamine having a specific side chain structure> When the present invention is used as a liquid crystal aligning agent of the VA system, a polymer prepared by using a diamine having a specific side chain structure that exhibits vertical alignment energy is: good. This diamine having a specific side chain structure has at least one side chain structure selected from the group represented by the following formulae [S1] to [S3]. [0056] The following describes the diamine with a specific side chain structure in the order of formula [S1]～[S3]. [0057] An example of a diamine having a specific side chain structure is a diamine having a specific side chain structure represented by the following formula [S1]. [0058]
Figure 02_image033
In the above-mentioned formula [S1], X 1 and X 2 each independently represent single bond, -(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -COO-, -OCO- or -((CH 2 ) a1 -A 1 ) m1 -. Wherein, each of the plural a1 independently represents an integer of 1 to 15, the plural A1 each independently represents an oxygen atom or -COO-, and m 1 is 1 to 2. Wherein, from the viewpoint of the availability of raw materials or the ease of synthesis, X 1 and X 2 are each independently a single bond, -(CH 2 ) a - (a is an integer of 1 to 15), -0-, Preferably -CH 2 O- or -COO- is a single bond, -(CH 2 ) a - (a is an integer of 1 to 10), -O-, -CH 2 O- or -COO-. Also, in the above-mentioned formula [S1], G 1 and G 2 each independently represent a divalent ring selected from a bivalent aromatic group of carbon number 6 to 12 or a bivalent alicyclic group of carbon number 3 to 8 shape base. Any hydrogen atom on the cyclic group may be substituted by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, or a group containing 1 to 3 carbon atoms. Fluoroalkoxy or fluorine atom substitution. m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 4. Also, in the above formula [S1], R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. Any hydrogen forming R1 may be substituted with fluorine. Among them, examples of the divalent aromatic group having 6 to 12 carbon atoms include a phenylene group, a biphenylene group, and a naphthalene. In addition, examples of the divalent alicyclic group having 3 to 8 carbon atoms include a cyclopropylidene group, a cyclohexylene group, and the like. Therefore, the preferable specific example of above-mentioned formula [S1], can enumerate following formula [S1-x1]～[S1-x7], but is not limited to these. [0064]
Figure 02_image035
In above-mentioned formula [S1-x1]～[S1-x7], R 1 is identical with the situation of above-mentioned formula [S1]. X p represents -(CH 2 ) a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-. A 1 represents an oxygen atom or -COO-* (the bond with "*" is bonded to (CH 2 ) a2 ). A 2 represents an oxygen atom or *-COO- (the bond with "*" is bonded to (CH 2 ) a2 ). a 1 is an integer of 0 or 1, and a 2 is an integer of 2 to 10. Cy represents 1,4-cyclohexylene or 1,4-phenylene. [0066] In addition, examples of the diamine having a specific side chain structure include diamines having a specific side chain structure represented by the following formula [S2]. [0067]
Figure 02_image037
In above-mentioned formula [S2], X 3 represents single bond,-CONH-,-NHCO-,-CON(CH ) - ,-NH-,-O-,-CH 2 O-,-COO- or -OCO-. Among them, X 3 series -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO- are preferred from the viewpoint of the liquid crystal alignment of the liquid crystal aligning agent. Also, in the above formula [S2], R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. Any hydrogen forming R2 may be substituted with fluorine. Among them, from the viewpoint of the liquid crystal alignment of the liquid crystal alignment agent, R 2 is preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. [0070] In addition, examples of the diamine having a specific side chain structure include diamines having a specific side chain structure represented by the following formula [S3]. [0071]
Figure 02_image039
In above-mentioned formula [S3], X 4 represents-CONH-,-NHCO-,-O-,-COO- or-OCO-. R 3 represents a structure having a steroid backbone. The steroid skeleton here has a skeleton represented by the following formula (st) to which three six-membered rings and one five-membered ring are bonded. [0073]
Figure 02_image041
[0074] Examples of the above formula [S3] include the following formula [S3-x], but are not limited thereto. [0075]
Figure 02_image043
In above-mentioned formula [S3-x], X represents above-mentioned formula [X1] or [X2]. In addition, Col represents at least one kind selected from the group of the above-mentioned formulas [Col1] to [Col4], and G represents the above-mentioned formula [G1] or [G2]. *Indicates the part that is bonded to other bases. The preferred combination example of X, Col and G in the above-mentioned formula [S3-x], for example, the following can be enumerated. That is, the combination of [X1] and [Col1] and [G1], the combination of [X1] and [Col1] and [G2], the combination of [X1] and [Col2] and [G1], the combination of [X1] and [ Combination of Col2] and [G2], combination of [X1] and [Col3] and [G2], combination of [X1] and [Col4] and [G2], combination of [X1] and [Col3] and [G1] , the combination of [X1] and [Col4] and [G1], the combination of [X2] and [Col1] and [G2], the combination of [X2] and [Col2] and [G2], the combination of [X2] and [Col2] and combination of [G1], combination of [X2] and [Col3] and [G2], combination of [X2] and [Col4] and [G2], combination of [X2] and [Col1] and [G1], [ X2] with the combination of [Col4] and [G1]. In addition, the specific example of above-mentioned formula [S3], can enumerate the steroid compound described in paragraph [0024] of Japanese Patent Laid-Open No. 4-281427 Gazette, remove the structure of hydroxyl (Hydroxyl Group), and the paragraph from the same official gazette. [0030] The steroid compound described in the description, the structure of which the acid chloride group is removed, the steroid compound described in paragraph [0038] of the same publication, the structure of which the amine group is removed, the steroid compound described in the paragraph [0042] of the same publication , the structure of removing the halogen group, and the structure described in paragraphs [0018] to [0022] of Japanese Patent Laid-Open No. 8-146421. [0079] A representative example of the steroid skeleton includes cholesterol (the combination of [Col1] and [G2] in the above formula [S3-x]), but a steroid skeleton that does not contain this cholesterol can also be used. That is, as a diamine which has a steroid skeleton, for example, 3, 5- diaminobenzoic acid cholestanyl (cholestanyl) etc. are mentioned, but the diamine component which does not contain the diamine which has this cholesterol skeleton may be sufficient. Moreover, it can also utilize as a diamine which has a specific side chain structure, for example, what does not contain an amide|amido at the connection position of a diamine and a side chain. Using such a diamine, or in this embodiment, using a diamine component that does not contain a diamine having a cholesterol skeleton, it is possible to provide a liquid crystal alignment film or a liquid crystal display element that can secure a high voltage retention over a long period of time. agent. [0080] Also, the diamines having the side chain structures represented by the above formulae [S1] to [S3] are represented by the structures of the following formulae [1-S1]-[1-S3], respectively. [0081]
Figure 02_image045
In above-mentioned formula [1-S1], X 1 , X 2 , G 1 , G 2 , R 1 , m and n are the same as those of above-mentioned formula [S1]. In the above formula [1-S2], X 3 and R 2 are the same as in the above formula [S2]. In the above formula [1-S3], X 4 and R 3 are the same as in the above formula [S3]. <Vertical alignment diamine: diamine having a characteristic side chain structure of two side chain type> When used as a liquid crystal aligning agent of the VA system, two sides of a specific side chain structure having two vertical alignment properties can be used. Chain-type diamines are used to prepare polymers. In the present embodiment, the diamine which can be contained as a diamine component is represented by the following formula [1], for example. [0084]
Figure 02_image047
In the above-mentioned formula [1], X represents single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-, -NHCO-, -COO-, -(CH 2 ) m A divalent organic group formed by -, -SO 2 - or any combination thereof. Among them, X is preferably a single bond, -O-, -NH-, -O-(CH 2 ) m -O-. Examples of "arbitrary combinations of them" include -O-(CH 2 ) m -O-, -OC(CH 3 ) 2 -, -CO-(CH 2 ) m -, -NH-(CH 2 ) m- , -SO2- ( CH2 ) m- , -CONH-( CH2 ) m- , -CONH-( CH2 ) m -NHCO-, -COO-( CH2 ) m -OCO-, etc., but It is not limited to these. m is an integer from 1 to 8. In addition, in the above formula [1], each of the two Ys independently represents the structure of the following formula [1-1]. [0086]
Figure 02_image049
In above-mentioned formula [1-1], Y 1 and Y 3 each independently represent single bond,-(CH 2 ) a- (a is an integer of 1～15),-O-,-CH 2 O-, -COO- or -OCO-. Y 2 represents a single bond or -(CH 2 ) b - (b is an integer of 1 to 15). However, when Y 1 or Y 3 is a single bond or -(CH 2 ) a -, Y 2 is a single bond. Also, when Y 1 is -O-, -CH 2 O-, -COO- or -OCO-, and/or Y 3 is -O-, -CH 2 O-, -COO- or -OCO-, Y 2 is a single bond or -(CH 2 ) b -. Also, in formula [1-1], Y 4 represents a bivalent cyclic group selected from at least one of benzene ring, cyclohexane ring and heterocycle grouped or has carbon number 17 of steroid skeleton ~51 Divalent organic group. An arbitrary hydrogen atom forming the cyclic group may also pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Fluorine-containing alkoxy or fluorine atom substitution. Also, in the above formula [1-1], Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. An arbitrary hydrogen atom forming the cyclic group may also pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Fluorine-containing alkoxy or fluorine atom substitution. Also, in above-mentioned formula [1-1], Y 6 represents selected from the alkyl group of carbon number 1～18, the alkenyl group of carbon number 2～18, the fluorine-containing alkyl group of carbon number 1～18, carbon number At least one of the group consisting of an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. n is an integer from 0 to 4. [0091] Also, there are two side chain diamines of the side chain structure represented by the above formulas [S1]～[S3]. They are represented by the structures of the following formulae [2-S1]-[2-S3], respectively. [0092]
Figure 02_image051
Also, in above-mentioned formula [1], Y system can be meta position from the position of X, also can be adjacent position, but is preferably adjacent position. That is, the above-mentioned formula [1] is preferably one of the following formula [1']. [0094]
Figure 02_image053
In addition, in the above-mentioned formula [1], the position of 2 amino groups (-NH 2 ) can be at any position on the benzene ring, preferably with the following formula [1]-a1～[1]- The position represented by a3 is more preferably the following formula [1]-a1. In the following formula, X is the same as in the case of the above-mentioned formula [1]. In addition, since the following formulas [1]-a1 to [1]-a3 illustrate the positions of two amino groups, the description of Y represented by the above formula [1] is omitted. [0096]
Figure 02_image055
Therefore, according to above-mentioned formula [1'] and [1]-a1～[1]-a3, above-mentioned formula [1] is selected from following formula [1]-a1-1～[1]-a3 The structure of any one of -2 is preferable, and the structure represented by the following formula [1]-a1-1 is more preferable. In the following formula, X and Y are the same as in the case of formula [1], respectively. [0098]
Figure 02_image057
[0099] Also, examples of the above-mentioned formula [1-1] include the following formulae [1-1]-1 to [1-1]-22, but are not limited to these. Among them, the examples of the above formula [1-1] are preferably the following formulae [1-1]-1 to [1-1]-4, [1-1]-8 or [1-1]-10. In addition, in the following formula, * represents the bonding position with the phenyl group in the said formula [1], [1'], and [1]-a1 - [1]-a3. [0100]
Figure 02_image059
[0101] Since the diamine component contains two side chain diamines having a specific structure, even in the case of excessive heating, it can be used as a liquid crystal alignment film in which the ability to vertically align the liquid crystal is not easily reduced. In addition, since the diamine component contains the diamine in the side chain, even if the film comes into contact with any foreign matter and is damaged, it can become a liquid crystal alignment film in which the ability to vertically align the liquid crystal is not easily reduced. That is, the diamine component can provide a liquid crystal aligning agent which can obtain a liquid crystal aligning film excellent in various above-mentioned properties by containing the diamine in the side chain. <Other diamines: diamines having photoreactive side chains> In addition, when the present invention is used as a liquid crystal alignment agent in a PSA mode of a vertical alignment system, in order to improve the reaction of the polymerizable compound contained in the liquid crystal It is also possible to prepare polymers using diamines having photoreactive side chains. The diamine component of this embodiment may contain the diamine which has a photoreactive side chain as another diamine. Since a diamine component contains the diamine which has a photoreactive side chain, a photoreactive side chain can be introduce|transduced into a specific polymer or a polymer other than it. [0103] The diamine having a photoreactive side chain includes, but is not limited to, those represented by the following formula [VIII] or [IX], for example. [0104]
Figure 02_image061
In above-mentioned formula [VIII] and [IX], the position of 2 amino groups (-NH 2 ) can be at any position on the benzene ring, for example, relative to the bonding group of the side chain, it is on the benzene ring The position of 2,3, the position of 2,4, the position of 2,5, the position of 2,6, the position of 3,4 or the position of 3,5. From the viewpoint of reactivity at the time of synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. In addition, from the viewpoint of easiness in synthesizing the diamine, the 2,4 position or the 3,5 position is more preferable. Also, in the above formula [VIII], R 8 represents a single bond, -CH 2 -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N( CH3 )-, -CON( CH3 )- or -N( CH3 )CO-. In particular, R 8 is preferably a single bond, -O-, -COO-, -NHCO- or -CONH-. Also, in the above-mentioned formula [VIII], R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms that can be substituted by a fluorine atom. The -CH 2 - in the alkylene group here can be substituted by -CF 2 - or -CH=CH- at will, and when any of the following groups are not adjacent to each other, they can also be substituted by these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocycle or heterocycle. In addition, the divalent carbocyclic ring or heterocyclic ring is specifically, but not limited to, the following formula (1a). [0108]
Figure 02_image063
In addition, in the above-mentioned formula [VIII], R 9 can be formed by a general organic synthesis method, but from the viewpoint of ease of synthesis, it is preferably a single bond or an alkylene group having 1 to 12 carbon atoms. Also, in the above formula [VIII], R 10 represents a photoreactive group selected from the group of the following formula (1b). Among them, R 10 is preferably a methacryloyl group, an acryl group (Acryl group), or a vinyl group from the viewpoint of photoreactivity. [0111]
Figure 02_image065
Also, in the above formula [IX], Y 1 represents -CH 2 -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y 2 represents an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. One or a plurality of hydrogen atoms in the alkylene group, the divalent carbocyclic ring or the heterocyclic ring here may also be substituted by a fluorine atom or an organic group. Y 2 is when the following groups are not adjacent to each other, -CH 2 - can also be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Also, in above-mentioned formula [IX], Y 3 represents-CH 2 -,-O-,-CONH-,-NHCO-,-COO-,-OCO-,-NH-,-CO- or single bond . Y 4 represents a cinnamon base. Y 5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. One or a plurality of hydrogen atoms in the alkylene group, the divalent carbocyclic ring or the heterocyclic ring here may also be substituted by a fluorine atom or an organic group. Y 5 is when the following groups are not adjacent to each other, -CH 2 - can also be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y 6 represents a photopolymerizable group such as an acryl group or a methacryl group. Specific examples of the diamine having a photoreactive side chain represented by the above formula [VIII] or [IX] include the following formula (1c), but are not limited thereto. [0115]
Figure 02_image067
In the above formula (1c), X 9 and X 10 each independently represent a single bond, -O-, -COO-, -NHCO- or -NH- bonding group. Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom. [0117] The diamine having a photoreactive side chain includes the diamine of the following formula [VII]. The diamine of the formula [VII] has a site containing a radical generating structure in the side chain. The free radical generating structure is decomposed to generate free radicals by ultraviolet irradiation. [0118]
Figure 02_image069
In the above-mentioned formula [VII], Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, and the hydrogen atom of their ring may be substituted by halogen atom . The Ar bound to the carbonyl group is related to the absorption wavelength of ultraviolet rays, so when the wavelength is increased, a structure with a longer conjugate length such as a naphthylene group or a biphenylene group is preferable. In addition, when Ar has a structure like a naphthylene group or a biphenylene group, the solubility may be deteriorated, and in this case, the difficulty of synthesis becomes high. When the wavelength of the ultraviolet rays is in the range of 250 nm to 380 nm, sufficient properties can be obtained even with a phenyl group, so Ar is preferably a phenyl group. In the above-mentioned Ar, a substituent can be set on the aromatic hydrocarbon group. Examples of the substituent here are preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group. Also, in the above formula [VII], R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group. In the case of an alkyl group or an alkoxy group, a ring may be formed by R 1 and R 2 . Also, in the above-mentioned formula [VII], T 1 and T 2 each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 A bonding group of O-, -N(CH 3 )-, -CON(CH 3 )- or -N(CH 3 )CO-. Also, in formula [VII], S represents a single bond, an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms. The -CH 2 - or -CF 2 - of the alkylene group here can be substituted by -CH=CH- at will, and when any of the following groups are not adjacent to each other, they can be substituted by these groups; -O -, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocycle, divalent heterocycle. Also, in formula [VII], Q represents a structure selected from the following formula (1d). [0125]
Figure 02_image071
In the above-mentioned formula (1d), R represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. R 3 represents -CH 2 -, -NR-, -O-, or -S-. Also, in the above formula [VII], Q is preferably an electron-donating organic group, preferably an alkyl group, a hydroxyl group, an alkoxy group, an amino group, etc., as exemplified in the above-mentioned Ar example. When Q is an amine group derivative, the carboxylic acid group and the amine group may form an undesired state during the polymerization of the polyimide precursor of the polyamide acid, such as the formation of a salt, so it is more preferably a hydroxyl group or an alkoxy group. base. In addition, in above-mentioned formula [VII], the position of 2 amine groups (-NH 2 ) can be any of o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, but with acid From the viewpoint of the reactivity of the dianhydride, m-phenylenediamine or p-phenylenediamine is preferable. Therefore, the preferred specific examples of the above-mentioned formula [VII], from the viewpoints of the ease of synthesis, the height of versatility, characteristics, etc., can enumerate the following formulas. In addition, in the following formula, n is an integer of 2-8. [0130]
Figure 02_image073
[0131] These diamines having a photoreactive side chain represented by the above formula [VII], [VIII] or [IX] can be used alone or in combination of two or more. It can be used singly or in combination of two or more, or in combination with the characteristics of liquid crystal alignment, pre-tilt angle, voltage retention characteristics, accumulated electric charge, etc. when used as a liquid crystal alignment film, and response speed of liquid crystal when used as a liquid crystal display element. When more than one type is used, the ratio and the like may be appropriately adjusted. <Tetracarboxylic acid derivative> The liquid crystal aligning agent of the present invention contains not only tetracarboxylic dianhydride, but also a tetracarboxylic acid derivative component for producing a polymer having the structural unit of the above formula (1). A tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound, which is a tetracarboxylic acid derivative thereof, can be used. [0133] Tetracarboxylic dianhydride and derivatives thereof, it is more preferable to use at least one selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof represented by the following formula (3). [0134]
Figure 02_image075
In the formula, X 1 is a tetravalent organic group with an alicyclic structure, and its structure is not particularly limited. Specific examples include the following formulae (X1-1) to (X1-44). [0136]
Figure 02_image077
In formula (X1-1)～(X1-4), R 3 to R 23 are each independently hydrogen atom, halogen atom, alkyl of carbon number 1～6, alkenyl of carbon number 2～6, carbon The alkynyl group having 2 to 6 numbers, the monovalent organic group having fluorine atoms having 1 to 6 carbon atoms, or the phenyl group may be the same or different. From the viewpoint of liquid crystal alignment, R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group. Specific structures of the formula (X1-1) include structures represented by the following formulae (X1-1-1) to (X1-1-6). From the viewpoint of liquid crystal alignment and sensitivity to photoreaction, (X1-1-1) is particularly preferred. [0138]
Figure 02_image079
[0139]
Figure 02_image081
[0140]
Figure 02_image083
The tetracarboxylic dianhydride and the derivative thereof of the polyimide precursor of the present invention and the raw material of the polyimide described in the present invention are relative to all tetracarboxylic dianhydride and 1 mol of the derivative thereof, the above formula The tetracarboxylic dianhydride and its derivatives represented by (3) preferably contain 60 to 100 mol%. In order to obtain a liquid crystal alignment film with good liquid crystal alignment, it is more preferably 80 mol % to 100 mol %, and still more preferably 90 mol % to 100 mol %. <The manufacturing method of polyamic acid ester> The polyamic acid ester of one of the polyimide precursors that can be used in the present invention can use (1), (2) or (3) shown below. method synthesis. (1) In the case of synthesis from polyamic acid, polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, in the presence of an organic solvent, the polyamic acid and the esterifying agent can be reacted at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably It takes 1 to 4 hours to synthesize. The esterification agent can be easily removed by purification. Preferably, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4 -(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is 1 mol, preferably 2-6 mol equivalent, with respect to the repeating unit of the polyamide acid. The solvent used in the above-mentioned reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the dissolving of polymer, etc. You may use 1 type or a mixture of 2 or more types. The concentration at the time of synthesis is preferably 1 to 30 mass %, more preferably 5 to 20 mass %, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight body can be obtained. (2) In the case of synthesis by reaction of tetracarboxylic acid diester dichloride and diamine The polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, by making tetracarboxylic acid diester dichloride and diamine react at -20 ℃～150 ℃, preferably 0 ℃～50 ℃ in the presence of alkali and organic solvent 30 minutes to 24 hours, preferably 1 to 4 hours for synthesis. [0148] Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the base, but pyridine is preferred in order to perform the reaction stably. The addition amount of the base is preferably 2 to 4 times mol relative to the tetracarboxylic acid diester dichloride from the viewpoint of an amount that can be easily removed and a high molecular weight body can be easily obtained. The solvent used in above-mentioned reaction, from the viewpoint of the solubility of monomer and polymer, is preferably N-methyl-2-pyrrolidone or γ-butyrolactone, and these can use one kind or mix 2 more than one type of use. The polymer concentration at the time of synthesis is preferably 1 to 30 mass %, more preferably 5 to 20 mass %, from the viewpoint that the polymer is not easily precipitated and a high molecular weight body can be obtained. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is better to prevent the outside air from being mixed in a nitrogen environment. (3) In the case of synthesizing a polyamic acid ester from a tetracarboxylic acid diester and a diamine The polyamic acid ester can be synthesized by polycondensing a tetracarboxylic acid diester and a diamine. Specifically, in the presence of a condensing agent, a base, and an organic solvent, the tetracarboxylic acid diester and the diamine can be reacted at 0°C to 150°C, preferably 0°C to 100°C. 30 minutes to 24 hours, preferably 3 to 15 hours for synthesis. The aforementioned condensing agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N ,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'- Tetramethylurea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylmethylurea hexafluorophosphate, (2,3-dihydrogen -2-thiooxy-3-benzoxazolyl) phosphonic acid diphenyl ester and the like. The addition amount of the condensing agent is preferably 2 to 3 times moles relative to the tetracarboxylic acid diester. As the aforementioned base, tertiary amines such as pyridine, triethylamine and the like can be used. The addition amount of the base is preferably 2 to 4 times mol relative to the diamine component, from the viewpoint of an amount that can be easily removed and that a high molecular weight body can be easily obtained. In addition, in the above-mentioned reaction, the Lewis acid is added as an additive, and the reaction can be carried out efficiently. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The addition amount of the Lewis acid is preferably 0 to 1.0 times mol relative to the diamine component. Among the above-mentioned three methods for synthesizing polyamic acid esters, in order to obtain a high-molecular-weight polyamic acid ester, the above-mentioned (1) or above-mentioned (2) synthesis methods are particularly preferred. [0156] The solution of the polyamic acid ester obtained as described above can be injected into a weak solvent with sufficient stirring to precipitate the polymer. After several times of precipitation, washing with weak solvent, and drying at room temperature or heating, a powder of purified polyamide can be obtained. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene. [0157] <The production method of polyimide> The polyimide precursor of the polyimide which can be used in the present invention can be synthesized by the method shown below. Specifically, in the presence of an organic solvent, tetracarboxylic dianhydride and diamine can be reacted for 30 minutes to 24 minutes at -20°C to 150°C, preferably 0°C to 50°C. hours, preferably 1 to 12 hours for synthesis. The organic solvent used in the above-mentioned reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butane from the viewpoint of the solubility of monomers and polymers Lactones can be used alone or in combination of two or more. The concentration of the polymer is preferably 1 to 30 mass %, more preferably 5 to 20 mass %, from the viewpoint that the polymer is not easily precipitated and a high molecular weight body can be obtained. The polyamide acid obtained as above can be injected into the weak solvent by fully stirring the reaction solution, so that the polymer is precipitated and recovered. In addition, after performing several precipitations, washing with a weak solvent, and drying at room temperature or heating, a powder of purified polyamic acid can be obtained. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene. <The production method of polyimide> The polyimide that can be used in the present invention can be produced by imidizing the above-mentioned polyimide or polyimide. In the production of polyimide from polyamic acid ester, the above-mentioned polyamic acid ester solution or polyamic acid solution obtained by dissolving polyamic acid ester resin powder in an organic solvent is added with an alkaline catalyst. Chemical imidization is relatively simple. The chemical imidization is performed at a relatively low temperature. During the imidization process, the molecular weight of the polymer is not easily reduced, so it is preferred. [0162] The chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of an alkaline catalyst. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferable because it has sufficient basicity required for the reaction to proceed. [0163] The temperature during the imidization reaction is -20°C to 140°C, preferably 0°C to 100°C, and the reaction time is 1 to 100 hours. The amount of the alkaline catalyst is 0.5-30 mol times the amide group, preferably 2-20 mol times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time. In the solution after the imidization reaction, the added catalyst and the like remain, so by the means described below, the obtained imidized polymer is recovered and redissolved in an organic solvent to serve as the liquid crystal alignment agent of the present invention better. In the case of producing polyimide from polyamide, the chemical imidization ratio of adding a catalyst to the solution of the aforementioned polyamide obtained by the reaction of a diamine component and tetracarboxylic dianhydride Simple. The chemical imidization is performed at a relatively low temperature. During the imidization process, the molecular weight of the polymer is not easily reduced, so it is preferred. Chemical imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a moderate basicity required for the reaction. Moreover, acetic anhydride, trimellitic anhydride, pyromellitic anhydride etc. are mentioned as an acid anhydride, Among these, when acetic anhydride is used, purification after completion|finish of reaction becomes easy, and it is preferable. [0166] The temperature during the imidization reaction is -20°C to 140°C, preferably 0°C to 100°C, and the reaction time is 1 to 100 hours. The amount of the alkaline catalyst is 0.5~30 mole times of the amide acid group, preferably 2~20 mole times, and the amount of the acid anhydride is 1~50 mole times of the amide acid group, preferably 3~ 30 mole times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time. In the solution after the imidization reaction of polyamic acid ester or polyamic acid, the added catalyst etc. remained, so by the means described below, the obtained imidized polymer was recovered , which is redissolved in an organic solvent, preferably as the liquid crystal alignment agent of the present invention. [0168] The solution of the polyimide obtained as described above can be injected into a weak solvent by fully stirring, so that the polymer is precipitated. After several times of precipitation, washing with weak solvent, and drying at room temperature or heating, a powder of purified polyamide can be obtained. Although the said weak solvent is not specifically limited, Methanol, acetone, hexane, butyl cellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned. <Liquid crystal alignment agent> The liquid crystal alignment agent that can be used in the present invention is a form of a solution in which a polymer having a specific structure is dissolved in an organic solvent. The molecular weight of the polyimide precursor and polyimide described in the present invention is preferably 2,000-500,000 in weight average molecular weight, more preferably 5,000-300,000, still more preferably 10,000-100,000. Also, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

本發明可使用之液晶配向劑之聚合物的濃度，可藉由設定欲形成之塗膜之厚度，適宜變更，但是從形成均勻且無缺陷之塗膜的觀點，較佳為1重量%以上，從溶液之保存安定性的觀點，較佳為10重量%以下。 The concentration of the polymer of the liquid crystal aligning agent that can be used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by weight or more, From the viewpoint of the storage stability of the solution, it is preferably 10% by weight or less.

<其他的溶劑> <Other solvents>

本發明之液晶配向劑中，在不損及本發明效果的範圍內，也可含有屬於上述A及B群組之溶劑以外的溶劑(以下也稱為其他的溶劑)，例如使本發明所記載的聚醯亞胺前驅物及聚醯亞胺溶解的溶劑(也稱為良溶劑)或提高塗佈有液晶配向劑時之液晶配向膜的塗膜性或表面平滑性的溶劑(也稱為弱溶劑)。 The liquid crystal aligning agent of the present invention may contain solvents other than those belonging to the above-mentioned groups A and B (hereinafter also referred to as other solvents) within the range that does not impair the effects of the present invention, such as those described in the present invention. The polyimide precursor and the solvent in which the polyimide dissolves (also known as a good solvent) or a solvent that improves the coating property or surface smoothness of the liquid crystal alignment film when it is coated with a liquid crystal alignment agent (also known as a weak solvent) solvent).

下述列舉其他溶劑的具體例，但是不限定於此等之例者。 Specific examples of other solvents are listed below, but are not limited to these examples.

良溶劑可列舉，例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、甲基乙基酮、環己酮、環戊酮、3-甲氧基-N,N-二甲基丙醯胺(IPMA或4-羥基-4-甲基-2-戊酮等。 As the good solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3- Methoxy-N,N-dimethylpropionamide (IPMA or 4-hydroxy-4-methyl-2-pentanone, etc.

弱溶劑之具體例，可列舉例如乙醇、異丙醇、1-丁醇、2-丁醇、異丁基醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2- 戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸丙烯酯、碳酸乙烯酯、2-(甲氧基甲氧基)乙醇、丁基溶纖劑、乙二醇單異戊醚、乙二醇單己醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、1-(丁氧基乙氧基)丙醇、丙二醇單甲醚乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇單乙醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙醚乙酸酯、二丙酮醇(Diacetone alcohol)、丙二醇二乙酸酯、二異戊醚、二乙二醇單丁醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單乙醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁基、乙酸丙二醇單乙醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲酯乙基、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、乙基卡必醇或以下述式[D-1]~式[D-3]表示之溶劑等。 　　[0174]

Figure 02_image085
[0175] (式[D-1]中，D1 表示碳數1~3之烷基，式[D-2]中，D2 表示碳數1~3之烷基，式[D-3]中，D3 表示碳數1~4之烷基)。 　　[0176] 本發明之液晶配向劑中，也可含有具有環氧基、異氰酸酯基、氧雜環丁烷基或環碳酸酯基之交聯性化合物、具有選自由羥基、羥基烷基及低級烷氧基烷基所成群之至少1種取代基的交聯性化合物、或具有聚合性不飽和鍵之交聯性化合物。此等取代基或聚合性不飽和鍵，在交聯性化合物中必須具有2個以上。 　　[0177] 具有環氧基或異氰酸酯基之交聯性化合物，可列舉例如雙酚丙酮環氧丙醚、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、三環氧丙基異三聚氰酸酯、四環氧丙基胺基二聯苯(diphenylene)、四環氧丙基-m-二甲苯二胺、四環氧丙基-1,3-雙(胺基乙基)環己烷、四苯基環氧丙醚乙烷、三苯基環氧丙醚乙烷、雙酚六氟乙醯二環氧丙醚、1,3-雙(1-(2,3-環氧基丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧基丙氧基)八氟聯苯、三環氧丙基-p-胺基苯酚、四環氧丙基間二甲苯二胺、2-(4-(2,3-環氧基丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧基丙氧基)苯基)乙基)苯基)丙烷或1,3-雙(4-(1-(4-(2,3-環氧基丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧基丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 　　[0178] 具有氧雜環丁烷基( oxetane group) 之交聯性化合物為具有至少2個下述式[4A]表示之氧雜環丁烷基的化合物。 　　[0179]
Figure 02_image087
[0180] 具體而言，可列舉國際公開公報WO2011/ 132751號(2011.10.27公開)之58~59頁所揭示之式[4a]~式[4k]表示的交聯性化合物。 　　[0181] 具有環碳酸酯基之交聯性化合物為具有至少2個下述式[5A]表示之環碳酸酯基的交聯性化合物。 　　[0182]
Figure 02_image089
[0183] 具體而言，可列舉國際公開公報WO2012/014898號(2012.2.2公開)之76~82頁所揭示之式[5-1]~式[5-42]表示的交聯性化合物。 　　[0184] 具有選自由羥基及烷氧基所成群之至少1種取代基的交聯性化合物，可列舉例如具有羥基或烷氧基之胺基樹脂，例如三聚氰胺樹脂、脲樹脂、胍胺樹脂、甘脲-甲醛樹脂、琥珀醯胺(succinyl amide )-甲醛樹脂或乙烯脲-甲醛樹脂等。具體而言，可使用胺基之氫原子經羥甲基或烷氧基甲基或其兩者取代的三聚氰胺衍生物、苯胍胺衍生物、或甘脲。此三聚氰胺衍生物或苯胍胺衍生物，也可以二聚體(Dimer)或三聚體(trimer)的形態存在。此等為1個三嗪環時，平均具有3個以上6個以下之羥甲基或烷氧基甲基者為佳。 　　[0185] 上述三聚氰胺衍生物或苯胍胺衍生物之例，可列舉市售品之1個三嗪環，經平均3.7個甲氧基甲基取代之MX-750、1個三嗪環，經平均5.8個甲氧基甲基取代之MW-30(以上為三和化學公司製)或Cymel 300、301、303、350、370、771、325、327、703、712等之甲氧基甲基化三聚氰胺、Cymel 235、236、238、212、253、254等之甲氧基甲基化丁氧基甲基化三聚氰胺、Cymel506、508等之丁氧基甲基化三聚氰胺、如Cymel 1141之含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、如Cymel 1123之甲氧基甲基化乙氧基甲基化苯胍胺、如Cymel 1123-10之甲氧基甲基化丁氧基甲基化苯胍胺、如Cymel 1128之丁氧基甲基化苯胍胺、如Cymel 1125-80之含有羧基之甲氧基甲基化乙氧基甲基化苯胍胺(以上為三井Cyanamid公司製)。又，甘脲之例，可列舉如Cymel 1170之丁氧基甲基化甘脲、如Cymel 1172之羥甲基化甘脲等、如Powderlink 1174之甲氧基羥甲基化甘脲等。 　　具有羥基或烷氧基之苯或酚性化合物，可列舉例如1,3,5-三(甲氧基甲基)苯、1,2,4-三(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯或2,6-二羥基甲基-p-tert-丁基苯酚。 　　[0186] 更具體而言，可列舉國際公開公報WO2011/ 132751號(2011.10.27公開)之62~66頁所揭示之式[6-1]~式[6-48]的交聯性化合物。 　　[0187] 具有聚合性不飽和鍵之交聯性化合物，可列舉例如三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷或丙三醇聚環氧丙醚聚(甲基)丙烯酸酯等之分子內具有3個聚合性不飽和基之交聯性化合物、及乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二環氧丙醚二(甲基)丙烯酸酯、二乙二醇二環氧丙醚二(甲基)丙烯酸酯、鄰苯二甲酸二環氧丙基酯二(甲基)丙烯酸酯或羥基新戊酸(Pivalic Acid)新戊二醇二(甲基)丙烯酸酯等之分子內具有2個聚合性不飽和基之交聯性化合物、及2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基苯二甲酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、丙三醇單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯或N-羥甲基(甲基)丙烯醯胺等之分子內具有1個聚合性不飽和基之交聯性化合物等。 　　[0188] 此外，也可使用下述式[7A]表示之化合物。 　　[0189]
Figure 02_image091
[0190] (式[7A]中，E1 表示選自由環己烷環、雙環己烷環、苯環、聯苯環、聯三苯環、萘環、茀環、蒽環或菲環所成群之基，E2 表示選自下述式[7a]或式[7b]之基，n表示1~4之整數)。 　　[0191]
Figure 02_image093
[0192] 上述為交聯性化合物之一例，不限定於此等者。又，本發明之液晶配向劑所使用之交聯性化合物，可1種類也可組合2種類以上。 　　本發明之液晶配向劑中之交聯性化合物的含量為相對於全部的聚合物成分100質量份，較佳為0.1~150質量份。其中，進行交聯反應，為了展現目的之效果時，相對於聚合物成分100質量份，較佳為0.1~100質量份。更佳為1~50質量份。 　　[0193] 本發明之液晶配向劑，在不損及本發明效果的範圍內，可使用塗佈於液晶配向劑時之提高液晶配向膜之膜厚的均勻性或表面平滑性的化合物。 　　提高液晶配向膜之膜厚的均勻性或表面平滑性的化合物，可列舉氟系界面活性劑、矽氧系界面活性劑、非離子系界面活性劑等。 　　[0194] 更具體而言，可列舉例如EFTOPEF301、EF303、EF352(以上、TOHKEM PRODUCTS公司製)、MegafacF171、F173、R-30(以上為大日本油墨公司製)、FluoradFC430、FC431(以上為住友3M公司製)、AsahiguardAG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上為旭硝子公司製)等。 　　[0195] 界面活性劑之使用量係相對於液晶配向劑所含有之全部聚合物成分100質量份，較佳為0.01~2質量份，更佳為0.01~1質量份。 　　[0196] 此外，液晶配向劑中可添加促進液晶配向膜中之電荷移動，促進元件之電荷消失的化合物，例如國際公開公報WO2011/132751號(2011.10.27公開)之69~73頁所揭示之式[M1]~式[M156]表示之含氮雜環胺化合物。此胺化合物可直接添加於液晶配向劑中，但是形成濃度0.1~10質量%，較佳為1~7質量%的溶液後添加為佳。此溶劑只要是溶解特定聚合物(A)時，即無特別限定。 　　[0197] 本發明之液晶配向劑中，除了上述弱溶劑、交聯性化合物、提高樹脂被膜或液晶配向膜之膜厚的均勻性或表面平滑性的化合物及促進電荷消失用的化合物外，只要不損及本發明效果的範圍時，也可添加本發明所記載之聚合物以外的聚合物、提高配向膜與基板之密著性之目的之矽烷偶合劑、及塗膜燒成時，有效率地以聚醯亞胺前驅物之加熱進行醯亞胺化之目的之醯亞胺化促進劑等。 　　[0198] ＜液晶配向膜･液晶顯示元件＞ 　　液晶配向膜係將上述液晶配向劑塗佈於基板，經乾燥、燒成所得的膜。塗佈本發明之液晶配向劑的基板，只要是高透明性的基板時，即無特別限定，可使用玻璃基板、氮化矽基板及丙烯酸基板、聚碳酸酯基板等的塑膠基板等。此時，從製程簡單化的觀點，使用形成有液晶驅動用之ITO(Indium Tin Oxide：氧化銦錫)電極等的基板較佳。又，反射型的液晶顯示元件時，僅為單側的基板時，也可使用矽晶圓等之不透明物，此時之電極也可使用鋁等反射光的材料。 　　[0199] 液晶配向劑之塗佈方法，無特別限定，工業上，一般以網版印刷、平版印刷、凸版印刷或噴墨法等進行的方法。其他的塗佈方法，可列舉浸漬法、輥塗佈法、狹縫式塗佈法、旋轉塗佈機法或噴霧法等，配合目的可使用此等。 　　[0200] 於基板上塗佈液晶配向劑後，藉由加熱板、熱循環型烘箱或IR(紅外線)型烤箱等的加熱手段，使溶劑蒸發，可作為液晶配向膜。塗佈本發明之液晶配向劑後的乾燥、燒成步驟可選擇任意之溫度與時間。通常可列舉為了充分地除去所含有的溶劑，在50~120℃下燒成1~10分鐘，然後在150~300℃下燒成5~120分鐘的條件。燒成後之液晶配向膜的厚度，若過薄時，有降低液晶顯示元件之可靠性的情形，故較佳為5~300nm，更佳為10~200nm。 　　[0201] 本發明之液晶配向處理劑係塗佈於基板上，經燒成後，使用以往之裝置、方法進行之摩擦處理或、摩擦處理或光配向處理等進行配向處理，或垂直配向用途等時，可以無配向處理，作為液晶配向膜使用。 　　[0202] 液晶胞之製作方法之一例，以被動矩陣構造之液晶顯示元件作為例來說明。又，也可為在構成畫像顯示的各像素部分，設置有TFT(Thin Film Transistor)等之切換元件之主動矩陣構造的液晶顯示元件。 　　[0203] 具體而言，準備透明玻璃製的基板，在其中一方的基板上設置共用電極( Common Electrode)，另一方的基板上設置片段電極(segment electrode)。此等之電極，例如可作為ITO電極，被圖型化成可顯示所期望的圖像。其次，各基板上，設置絕緣膜以被覆共用電極與片段電極。絕緣膜可為例如藉由溶膠-凝膠法所形成之SiO2 -TiO2 的膜。 　　[0204] 其次，各基板上形成液晶配向膜，其中一方的基板與另一方的基板彼此之液晶配向膜面成為對向予以重疊，將周邊使用密封劑接著。密封劑中，為了控制基板間隙，通常可混入間隔物。又，未設置密封劑的面內部分也散佈基板間隙控制用之間隔物為佳。密封劑之一部分，設置由外部可填充液晶的開口部。其次，通過設置於密封劑的開口部，在被2片之基板與密封劑包圍的空間內注入液晶材料。然後，將此開口部以接著劑密封。注入時，可使用真空注入法，也可使用大氣中，利用毛細管現象的方法。液晶材料可使用正型液晶材料或負型液晶材料之任一，但是較佳為負型液晶材料。其次，設置偏光板。具體而言，與2片基板之液晶層相反側的面，黏貼一對偏光板。 　　[0205] 垂直配向方式(特別是PSA模式(mode))之液晶顯示元件係在單側基板上，形成例如1μm至10μm之線/狹縫(slit)電極圖型，在對向基板未形成縫隙圖型或突起圖型之構造也可作動，藉由此構造的液晶顯示元件，可簡略製造時之製程，得到高的透過率。 　　[0206] 製造IPS型或FFS型之液晶顯示元件的情形，在設置有由圖型化成梳齒型之透明導電膜或金屬膜所成之電極之基板的電極形成面與、未設置電極之對向基板之一面，分別塗佈液晶配向劑，接著藉由將各塗佈面加熱，形成塗膜。金屬膜可使用例如由鉻等之金屬所成的膜。 　　[0207] 構成垂直配向方式之液晶顯示元件之液晶層的液晶材料，無特別限定，可使用以往之垂直配向方式使用的液晶材料，例如Merck公司製之MLC-6608或MLC-6609、MLC-3022等之負型的液晶。又，PSA模式可使用含有聚合性化合物的液晶的MLC-3023等。其他也可使用例如下述式表示之含有聚合性化合物的液晶。 　　[0208]
Figure 02_image095
[0209] 另外，構成IPS或FFS等之水平配向方式之液晶顯示元件之液晶層的液晶材料，無特別限定，可使用以往水平配向方式使用的液晶材料，例如Merck公司製之MLC-2003或MLC-2041等之負型正型之液晶或MLC-6608等之負型的液晶。 　　[0210] 使在2片基板之間挾持液晶層的方法，可列舉習知的方法。例如，準備形成有液晶配向膜之一對基板，於另一之基板的液晶配向膜上散佈珠粒等的間隔物，使形成有液晶配向膜之側的面成為內側，貼合另一基板，以減壓注入液晶，進行封裝的方法。又，準備形成有液晶配向膜之一對基板，於其中之一之基板的液晶配向膜上，散佈珠粒等的間隔物後，滴下液晶後，使形成有液晶配向膜之側的面成為內側，貼合另一基板，進行封裝的方法，也可製作液晶胞。上述間隔物之厚度，較佳為1μm~30μm，更佳為2μm~10μm。 　　[0211] PSA模式方式係藉由使挾持液晶後，邊將電壓外加於液晶配向膜及液晶層，邊照射紫外線，製作液晶胞。此步驟，可列舉例如藉由對設置於基板上之電極間施加電壓，對液晶配向膜及液晶層外加電場，保持此電場的狀態下，照射紫外線的方法。在此，施加於電極間的電壓，例如5~30Vp-p或DC2.5~15V，較佳為10~30Vp-p或DC5~15V。又，照射的光，較佳為包含300~400nm之波長光的紫外線。照射光的光源係如前述。紫外線的照射量，例如1~60J，較佳為40J以下，紫外線照射量較少，可抑制因構成液晶顯示元件之構件之破壞所產生之信賴性降低，且藉由減少紫外線照射時間，可提高製造效率，故較佳。 　　[0212] 如上述，邊對液晶配向膜及液晶層外加電壓，邊照射紫外線時，聚合性化合物反應形成聚合物，藉由此聚合物，記憶液晶分子傾斜的方向，可加速所得之液晶顯示元件之應答速度。又，邊對液晶配向膜及液晶層外加電壓，邊照射紫外線時，選自具有使液晶垂直配向之側鏈與光反應性之側鏈的聚醯亞胺前驅物、及將此聚醯亞胺前驅物進行醯亞胺化所得之聚醯亞胺之至少一種的聚合物所具有之光反應性之側鏈彼此或、聚合物所具有之光反應性之側鏈與聚合性化合物進行反應，故可增加所得之液晶顯示元件的應答速度。 　　[0213] 如上述，藉由使用本發明之液晶配向劑，可得到塗佈面內之膜厚之均勻性或、塗佈周邊部之直線性及尺寸安定性優異之液晶配向膜。Specific examples of the weak solvent include ethanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1- Hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4- Pentylene glycol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether Butyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3 -Pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, butyl cellosolve, ethyl acetate Glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether ethyl Ester, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Esters, Ethylene Glycol Monoacetate, Ethylene Glycol Diacetate, Diethylene Glycol Monoethyl Ether Acetate, Diacetone Alcohol, Propylene Glycol Diacetate, Diisoamyl Ether, Diethylene Diacetate Alcohol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Alcohol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate -Butyl methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, ethyl carbitol or the following formula [D-1]~ The solvent represented by [D-3], etc. [0174]
Figure 02_image085
(in formula [D-1], D 1 represents the alkyl group of carbon number 1～3, in formula [D-2], D 2 represents the alkyl group of carbon number 1～3, formula [D-3] Among them, D 3 represents an alkyl group with 1 to 4 carbon atoms). The liquid crystal aligning agent of the present invention may also contain a crosslinking compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group, a compound having an epoxy group, a hydroxyalkyl group and a lower alkane group selected from the group consisting of: A crosslinkable compound having at least one substituent of an oxyalkyl group, or a crosslinkable compound having a polymerizable unsaturated bond. The crosslinkable compound must have two or more of these substituents or polymerizable unsaturated bonds. The crosslinkable compound with epoxy group or isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isotrimer can be enumerated Cyanate ester, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexyl Alkane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetyl diglycidyl ether, 1,3-bis(1-(2,3-epoxy Propoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triepoxy Propyl-p-aminophenol, tetraglycidyl-m-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1) -Bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxy) Propoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy base)-2-propanol, etc. The crosslinkable compound having an oxetane group ( oxetane group ) is a compound having at least two oxetane groups represented by the following formula [4A]. [0179]
Figure 02_image087
[0180] Specifically, the crosslinkable compounds represented by the formula [4a] to the formula [4k] disclosed in International Publication No. WO2011/132751 (published on October 27, 2011), pages 58 to 59. [0181] The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A]. [0182]
Figure 02_image089
[0183] Specifically, the crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in International Publication No. WO2012/014898 (published on February 2, 2012), pages 76 to 82. The crosslinkable compound having at least one substituent selected from the group consisting of hydroxyl and alkoxy groups, such as amino resins with hydroxyl or alkoxy groups, such as melamine resins, urea resins, guanamine resins , glycoluril-formaldehyde resin, succinyl amide (succinyl amide)-formaldehyde resin or ethylene urea-formaldehyde resin, etc. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amine group is substituted with a methylol group or an alkoxymethyl group or both can be used. This melamine derivative or benzoguanamine derivative may exist in the form of a dimer (Dimer) or a trimer (trimer). When these are one triazine ring, it is preferable to have an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups. Examples of above-mentioned melamine derivative or benzoguanamine derivative can enumerate 1 triazine ring of commercially available product, MX-750 substituted by an average of 3.7 methoxymethyl groups, 1 triazine ring, Average 5.8 methoxymethyl substituted MW-30 (the above are manufactured by Sanwa Chemical Co., Ltd.) or methoxymethyl of Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. melamine, methoxymethylated butoxymethylated melamine of Cymel 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel506, 508, etc., such as Cymel 1141 containing carboxyl group methoxymethylated isobutoxymethylated melamine, such as methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, such as methoxymethylated butoxylated Cymel 1123-10 methoxymethylated benzoguanamine, such as Cymel 1128, butoxymethylated benzoguanamine, such as Cymel 1125-80, methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups (Mitsui above Cyanamid Corporation). Moreover, as an example of glycoluril, the butoxymethylated glycoluril of Cymel 1170, the methylolated glycoluril of Cymel 1172, etc., the methoxymethylolated glycoluril of Powderlink 1174, etc. are mentioned. Benzene or phenolic compounds having a hydroxyl group or an alkoxy group include, for example, 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1 ,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. [0186] More specifically, the crosslinkable compounds of formula [6-1] to formula [6-48] disclosed in pages 62 to 66 of International Publication No. WO2011/132751 (published on October 27, 2011) can be mentioned. The crosslinkable compound having a polymerizable unsaturated bond, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, A crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as tri(meth)acryloyloxyethoxytrimethylolpropane, glycerol polyglycidyl ether poly(meth)acrylate, etc. , and ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate (Meth)acrylate, propylene oxide bisphenol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di( Meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate (Meth)acrylate, hydroxypivalic acid (Pivalic Acid), neopentyl glycol di(meth)acrylate, etc., a crosslinkable compound having two polymerizable unsaturated groups in the molecule, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2 -(Meth)acryloyloxy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl(meth)acrylate, glycerol mono(meth)acrylate, 2- A crosslinkable compound etc. which have one polymerizable unsaturated group in a molecule|numerator, such as (meth)acryloyloxyethyl phosphate and N-methylol (meth)acrylamide. In addition, the compound represented by the following formula [7A] can also be used. [0189]
Figure 02_image091
(in the formula [7A], E represents selected from cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, bi - triphenyl ring, naphthalene ring, perylene ring, anthracene ring or phenanthrene ring. The base of the group, E 2 represents a base selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4). [0191]
Figure 02_image093
The above is an example of the crosslinking compound, and is not limited to these. Moreover, as for the crosslinking compound used for the liquid crystal aligning agent of this invention, 1 type may be sufficient and 2 or more types may be combined. Content of the crosslinking compound in the liquid crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all polymer components. Among them, when the crosslinking reaction is carried out and the intended effect is exhibited, it is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the polymer component. More preferably, it is 1-50 mass parts. [0193] The liquid crystal aligning agent of the present invention can use a compound that improves the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film when it is applied to the liquid crystal aligning agent within the range that does not impair the effect of the present invention. As a compound which improves the uniformity of the film thickness or surface smoothness of a liquid crystal alignment film, a fluorine type surfactant, a silicone type surfactant, a nonionic type surfactant, etc. are mentioned. More specifically, for example, EFTOPEF301, EF303, EF352 (above, manufactured by TOHKEM PRODUCTS), MegafacF171, F173, R-30 (above are manufactured by Dainippon Ink Co., Ltd.), FluoradFC430, FC431 (above are Sumitomo 3M) Company), AsahiguardAG710, SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above are manufactured by Asahi Glass Co., Ltd.), etc. [0195] The usage amount of the surfactant is relative to 100 parts by mass of the total polymer components contained in the liquid crystal alignment agent, preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass. In addition, the liquid crystal alignment agent can be added with a compound that promotes the transfer of charges in the liquid crystal alignment film and promotes the disappearance of the charge of the element, such as disclosed in pages 69 to 73 of International Publication No. WO2011/132751 (published on 2011.10.27). Nitrogen-containing heterocyclic amine compounds represented by formula [M1] to formula [M156]. The amine compound may be directly added to the liquid crystal aligning agent, but it is preferably added after forming a solution with a concentration of 0.1 to 10 mass %, preferably 1 to 7 mass %. The solvent is not particularly limited as long as it dissolves the specific polymer (A). In the liquid crystal aligning agent of the present invention, in addition to the above-mentioned weak solvent, cross-linking compound, the compound that improves the uniformity of the film thickness of the resin film or the liquid crystal aligning film or the surface smoothness and the compound that promotes the disappearance of electric charges, as long as To the extent that the effects of the present invention are not impaired, polymers other than the polymers described in the present invention, silane coupling agents for the purpose of improving the adhesion between the alignment film and the substrate, and coating films can be added efficiently. The imidization accelerator and the like for the purpose of imidization by heating the polyimide precursor. <Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment film is a film obtained by applying the above-mentioned liquid crystal alignment agent to a substrate, drying and firing. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. In this case, it is preferable to use a substrate on which ITO (Indium Tin Oxide: Indium Tin Oxide) electrodes or the like for liquid crystal driving are formed from the viewpoint of process simplification. In addition, in the case of a reflective liquid crystal display element, when only one side of the substrate is used, an opaque material such as a silicon wafer may be used, and a light-reflecting material such as aluminum may be used as the electrode in this case. [0199] The coating method of the liquid crystal aligning agent is not particularly limited. Industrially, it is generally carried out by screen printing, offset printing, letterpress printing, or inkjet method. As another coating method, a dip method, a roll coater method, a slit coater method, a spin coater method, a spray method, etc. can be mentioned, and these can be used according to the purpose. [0200] After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated by heating means such as a hot plate, a thermal cycle oven or an IR (infrared) oven, which can be used as a liquid crystal alignment film. The drying and firing steps after coating the liquid crystal aligning agent of the present invention can select any temperature and time. Usually, in order to fully remove the contained solvent, the conditions of baking at 50-120 degreeC for 1 to 10 minutes, and then baking at 150-300 degreeC for 5-120 minutes are mentioned. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may be reduced, so it is preferably 5 to 300 nm, more preferably 10 to 200 nm. The liquid crystal alignment treatment agent of the present invention is coated on the substrate, and after firing, the rubbing treatment or rubbing treatment or photo-alignment treatment performed by the conventional device and method is used for alignment treatment, or vertical alignment purposes, etc. can be used as a liquid crystal alignment film without alignment treatment. [0202] An example of a method of fabricating a liquid crystal cell will be described by taking a liquid crystal display element having a passive matrix structure as an example. Moreover, the liquid crystal display element of an active matrix structure in which switching elements, such as a TFT (Thin Film Transistor), are provided in each pixel part which comprises an image display may be sufficient. [0203] Specifically, substrates made of transparent glass were prepared, and a common electrode (common electrode) was provided on one of the substrates, and a segment electrode (segment electrode) was provided on the other substrate. These electrodes, such as ITO electrodes, are patterned to display the desired image. Next, on each substrate, an insulating film is provided to cover the common electrode and the segment electrode. The insulating film may be, for example, a film of SiO 2 -TiO 2 formed by a sol-gel method. [0204] Next, a liquid crystal alignment film is formed on each substrate, and the liquid crystal alignment film surfaces of one of the substrates and the other substrate are facing each other to be overlapped, and the periphery is bonded with a sealant. In the encapsulant, a spacer is usually mixed in order to control the gap between the substrates. Moreover, it is preferable to spread the spacer for board|substrate gap control also to the in-plane part in which the sealant is not provided. A part of the sealant is provided with an opening that can be filled with liquid crystal from the outside. Next, the liquid crystal material is injected into the space surrounded by the two sheets of substrates and the sealant through the opening provided in the sealant. Then, this opening is sealed with an adhesive. For injection, a vacuum injection method or a method utilizing capillary phenomenon in the atmosphere may be used. The liquid crystal material can be either a positive type liquid crystal material or a negative type liquid crystal material, but is preferably a negative type liquid crystal material. Second, set the polarizer. Specifically, a pair of polarizers are pasted on the surface opposite to the liquid crystal layer of the two substrates. The liquid crystal display element of the vertical alignment method (especially the PSA mode) is attached to a single-sided substrate, for example, a line/slit electrode pattern of 1 μm to 10 μm is formed, and no slit is formed on the opposite substrate. The structure of the pattern or the protrusion pattern can also be actuated. With the liquid crystal display element of this structure, the manufacturing process can be simplified and high transmittance can be obtained. Manufacture the situation of the liquid crystal display element of IPS type or FFS type, be provided with the electrode formation surface of the substrate of the electrode formed by the transparent conductive film or metal film patterned into comb-tooth type, and the pair of electrodes not provided A liquid crystal aligning agent is respectively applied to one surface of the substrate, and then each applied surface is heated to form a coating film. As the metal film, for example, a film made of a metal such as chromium can be used. The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the vertical alignment method is not particularly limited, and the liquid crystal material used in the vertical alignment method in the past can be used, such as MLC-6608 or MLC-6609, MLC-3022 manufactured by Merck Corporation Equally negative liquid crystal. Moreover, MLC-3023 etc. which contain the liquid crystal of a polymerizable compound can be used for PSA mode. Others, for example, a liquid crystal containing a polymerizable compound represented by the following formula can also be used. [0208]
Figure 02_image095
In addition, the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the horizontal alignment method such as IPS or FFS is not particularly limited, and the liquid crystal material used in the horizontal alignment method in the past can be used, such as MLC-2003 or MLC manufactured by Merck Corporation. -2041 and other negative positive liquid crystals or MLC-6608 and other negative liquid crystals. [0210] As a method of sandwiching the liquid crystal layer between two substrates, a conventional method can be mentioned. For example, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers such as beads on the liquid crystal alignment film of the other substrate, and attach the other substrate so that the surface on which the liquid crystal alignment film is formed is inward. A method of injecting liquid crystal under reduced pressure and encapsulating it. In addition, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film of one of the substrates, and then liquid crystal is dropped, so that the surface on which the liquid crystal alignment film is formed becomes the inner side. , the method of bonding another substrate and encapsulating it can also make a liquid crystal cell. The thickness of the spacer is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. [0211] In the PSA mode, a liquid crystal cell is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer after holding the liquid crystal. In this step, for example, by applying a voltage between electrodes provided on the substrate, an electric field is applied to the liquid crystal alignment film and the liquid crystal layer, and an ultraviolet ray is irradiated while the electric field is maintained. Here, the voltage applied between electrodes is, for example, 5~30Vp-p or DC2.5~15V, preferably 10~30Vp-p or DC5~15V. Moreover, it is preferable that the light to be irradiated is an ultraviolet-ray containing light of a wavelength of 300-400 nm. The light source for irradiating light is as described above. The irradiation dose of ultraviolet rays is, for example, 1 to 60J, preferably 40J or less. The irradiation dose of ultraviolet rays is small, and the reliability reduction caused by the destruction of the components constituting the liquid crystal display element can be suppressed, and the ultraviolet irradiation time can be shortened. Manufacturing efficiency is better. As described above, while applying voltage to the liquid crystal alignment film and the liquid crystal layer, while irradiating ultraviolet rays, the polymerizable compound reacts to form a polymer, and by this polymer, the direction of the tilt of the liquid crystal molecules is memorized, and the resulting liquid crystal display element can be accelerated. response speed. In addition, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, and ultraviolet rays are irradiated, a polyimide precursor having a side chain for vertically aligning the liquid crystal and a photoreactive side chain, and the polyimide precursor are selected from the group consisting of At least one of the polyimide obtained by the imidization of the precursor, the photoreactive side chains possessed by the polymer or the photoreactive side chains possessed by the polymer react with the polymerizable compound, so The response speed of the resulting liquid crystal display element can be increased. [0213] As described above, by using the liquid crystal aligning agent of the present invention, a liquid crystal aligning film having excellent uniformity of the film thickness in the coating surface or the linearity and dimensional stability of the coating peripheral portion can be obtained.

[實施例] 　　[0214] 以下舉實施例，進一步具體地說明本發明。但是本發明不限定於此等之實施例者。 　　[0215] 以下表示使用之化合物的簡稱。 　　[0216] (溶劑) 　　NMP：N-甲基-2-吡咯烷酮 　　NEP：N-乙基-2-吡咯烷酮 　　GBL：γ-丁內酯 　　BCS：丁基溶纖劑 　　PB：1-丁氧基-2-丙醇 　　DPM：二丙二醇單甲醚 　　DIBK：二異丁基酮 　　[0217] (四羧酸二酐) 　　DC-1：1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐 　　DC-2：1,2,3,4-環丁烷四羧酸二酐 　　DC-3：雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐 　　DC-4：均苯四甲酸酐 　　DC-5：3,3,4,4-聯苯四羧酸二酐 　　[0218] (二胺) 　　DA-1：p-苯二胺 　　DA-2：雙(4-胺基苯氧基)乙烷 　　DA-3：1,3-雙(4-胺基苯氧基)丙烷 　　DA-4：N-甲基-2-(4-胺基苯基)乙基胺 　　DA-5：下述式(DA-5)表示之化合物 　　DA-6：下述式(DA-6)表示之化合物 　　DA-7：下述式(DA-7)表示之化合物 　　DA-8：下述式(DA-8)表示之化合物 　　DA-9：3,5-二胺基苯甲酸 　　DA-10：下述式(DA-10)表示之化合物 　　DA-11：下述式(DA-11)表示之化合物 　　DA-12：下述式(DA-12)表示之化合物 　　DA-13：下述式(DA-13)表示之化合物 　　DA-14：下述式(DA-14)表示之化合物 　　DA-15：下述式(DA-15)表示之化合物 　　DA-16：下述式(DA-16)表示之化合物 　　DA-17：下述式(DA-17)表示之化合物 　　DA-18：下述式(DA-18)表示之化合物 　　DA-19：下述式(DA-19)表示之化合物 　　DA-20：下述式(DA-20)表示之化合物 　　DA-21：下述式(DA-21)表示之化合物 　　[0219] (添加劑) 　　3AMP：3-吡啶甲基胺 　　[0220] 又，以下的化學式中，Me表示甲基、Bu表示n-丁基、Boc表示t-丁氧基。 　　[0221]

Figure 02_image097
[0222] 各特性之測量方法如下述。 　　[0223] [黏度] 　　聚醯胺酸酯、聚醯胺酸溶液及聚醯亞胺溶液的黏度係使用E型黏度計TVE-22H(東機產業公司製)，以樣品量1.1mL(毫升)、錐形轉子TE-1(1°34’、R24)，在溫度25℃下測量。 　　[0224] [分子量] 　　聚醯胺酸酯及聚醯胺酸的分子量係藉由GPC(常溫凝膠滲透層析法)裝置進行測量，以聚乙二醇(聚環氧乙烷)換算值算出數平均分子量(以下也稱為Mn)與重量平均分子量(以下也稱為Mw)。 　　[0225] 　　GPC裝置：Shodex公司製(GPC-101) 　　管柱：Shodex公司製(KD803、及KD805之直列) 　　管柱溫度：50℃ 　　溶離液：N,N-二甲基甲醯胺(添加劑為溴化鋰-水合物(LiBr･H2 O)為30mmol/L(公升)、磷酸･無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L) 　　流速：1.0ml/分鐘 　　[0226] 檢量線製作用標準樣品：使用東曹公司製TSK 標準聚環氧乙烷(重量平均分子量(Mw)約900,000、150,000、100,000、及30,000)及Polymer Laboratories製 聚乙二醇(峰頂分子量(peak top molecular weight)(Mp)為約12,000、4,000、及1,000)。測量為了避免波峰重疊，故900,000、100,000、12,000、及1,000之4種類混合的樣品、及150,000、30,000、及4,000之3種類混合之樣品的2樣品分別實施。 　　[0227] ＜合成例1＞ 　　在附攪拌裝置及氮導入管之100mL的四口燒瓶中，秤取二胺DA-1(0.81g(7.5mmol))、DA-2(1.22g(5.0mmol))、DA-3(1.94g(7.5mmol))及二胺DA-6(1.99g(5.0mmol))，添加NMP 74.86g，邊送入氮氣邊攪拌使溶解。邊攪拌此二胺溶液，邊添加四羧酸二酐DC-1(5.38g(24.0mmol))，再添加NMP使固體成分濃度成為12質量%，於40℃下攪拌20小時，得到聚醯胺酸(PAA-1)的溶液。 　　此聚醯胺酸溶液之溫度25℃時之黏度為502mPa･s。又，此聚醯胺酸的分子量為Mn=16,715、Mw=43,662。 　　[0228] ＜合成例2＞ 　　在附攪拌裝置及氮導入管之100mL的四口燒瓶中，秤取二胺DA-5(6.26g(21.0mmol))及二胺DA-4(2.10g (14.0mmol))，添加NMP 76.28g，邊送入氮氣邊攪拌使溶解。邊攪拌此二胺溶液，邊添加四羧酸二酐DC-2(6.58g(33.6mmol))，再添加NMP使固體成分濃度成為15質量%，於室溫下攪拌4小時，得到聚醯胺酸(PAA-2)的溶液。 　　此聚醯胺酸溶液之溫度25℃時之黏度為768mPa･s。又，此聚醯胺酸的分子量為Mn=11,658、Mw=28,328。 ＜合成例3＞ 　　[0229] 在附攪拌裝置及氮導入管之100mL的四口燒瓶中，秤取二胺DA-1(0.84g(7.8mmol))、DA-2(1.27g(5.2 mmol))、DA-3(2.01g(7.8mmol))及二胺DA-5(1.55g(5.2 mmol))，添加NMP 73.26g，邊送入氮氣邊攪拌使溶解。邊攪拌此二胺溶液，邊添加四羧酸二酐DC-1(5.42g(24.2 mmol))，再添加NMP使固體成分濃度成為12質量%，於40℃下攪拌20小時，得到聚醯胺酸(PAA-3)的溶液。 　　此聚醯胺酸溶液之溫度25℃時之黏度為393mPa･s。又，此聚醯胺酸的分子量為Mn=14,654、Mw=39,268。 　　[0230] ＜合成例4＞ 　　在附攪拌裝置及氮導入管之3L的四口燒瓶中，秤取二胺DA-1(17.30g(159.98mmol))、二胺DA-2(58.63g(240.0 mmol))、二胺DA-15(76.89g(240.0mmol))及二胺DA-7 (54.63g(159.99mmol))，添加NMP 2458.13g，邊送入氮氣邊攪拌使溶解。邊攪拌此二胺溶液，邊添加四羧酸二酐DC-1(171.27g(764.02mmol))，再添加NMP使固體成分濃度成為12質量%，於40℃下攪拌20小時，得到聚醯胺酸(PAA-4)的溶液。 　　此聚醯胺酸溶液之溫度25℃時之黏度為426mPa･s。又，此聚醯胺酸的分子量為Mn=12,380、Mw=33,250。 　　[0231] 將此聚醯胺酸溶液分取2250.0g，添加NMP 750.0g後，添加乙酸酐171.1g、及吡啶35.4g，使於55℃下反應3小時。將此反應溶液注入甲醇9619.2g中，將生成的沉澱物過濾取得。以甲醇洗凈此沉澱物，以60℃減壓乾燥得到聚醯亞胺的粉末。此聚醯亞胺的醯亞胺化率為66%。在所得之聚醯亞胺粉末120.0g中，加入NMP880.0g，以70℃攪拌20hr，使溶解得到聚醯亞胺溶液(SPI-1)。 　　此聚醯亞胺溶液之溫度25℃時之黏度為137mPa･s。又，此聚醯亞胺的分子量係Mn=11,035、Mw=27,887。 　　[0232] ＜合成例5＞ 　　在附攪拌裝置及氮導入管之3L的四口燒瓶中，秤取二胺DA-21(130.71g(656.0mmol))及二胺DA-9(24.95g (163.98mmol))，添加NMP 171.60g，邊送入氮氣邊攪拌使溶解。邊攪拌此二胺溶液，邊添加四羧酸二酐DC-5(226.78g(770.8mmol))，再添加NMP使固體成分濃度成為12質量%，於室溫下攪拌4小時，得到聚醯胺酸(PAA-4)的溶液。 　　此聚醯胺酸溶液之溫度25℃時之黏度為234mPa･s。又，此聚醯胺酸的分子量為Mn=9,657、Mw=22,975。 　　[0233] ＜合成例6＞ 　　在附攪拌裝置及氮導入管之200mL的四口燒瓶中，加入二胺DA-2(4.03g(16.5mmol))、二胺DA-6(3.59g(9.0 mmol))、及二胺DA-18(2.50g(4.5mmol))後，添加NMP 102.1g，邊送入氮氣邊攪拌使溶解。邊攪拌此溶液，邊添加四羧酸二酐DC-1(4.37g(19.5mmol))、及NMP 12.8g，40℃條件下攪拌3小時。然後，25℃條件下，添加四羧酸二酐DC-2(1.71g(8.7mmol))、及NMP 12.8g後，再攪拌12小時，得到樹脂固體成分濃度15質量%的聚醯胺酸溶液。 　　此聚醯胺酸溶液的黏度為820mPa･s。又，此聚醯胺酸的分子量為Mn=13,250、Mw=35,459。 　　[0234] 將此聚醯胺酸溶液分取80.0g，添加NMP 70.0g後，添加乙酸酐6.8g、及吡啶1.8g，使於50℃下反應3小時。將此反應溶液注入甲醇555.0g中，將生成的沉澱物過濾取得。以甲醇洗凈此沉澱物，以60℃減壓乾燥得到聚醯亞胺的粉末。此聚醯亞胺的醯亞胺化率為75%。在所得之聚醯亞胺粉末80.0g中，加入NMP 586.7g，以50℃攪拌20hr，使溶解得到聚醯亞胺溶液(SPI-2)。 　　此聚醯亞胺溶液之溫度25℃時之黏度為74.0mPa･s。又，此聚醯亞胺的分子量為Mn=9,848、Mw=23,058。 　　[0235] ＜合成例7＞ 　　在附攪拌裝置及氮導入管之100mL的四口燒瓶中，加入二胺DA-20(1.12g(4.5mmol))、二胺DA-19(0.59g(3.0 mmol))、及二胺DA-21(1.49g(7.5mmol))後，添加NMP：GBL=1：1的混合溶劑31.0g，邊送入氮氣邊攪拌使溶解。邊攪拌此溶液，邊添加四羧酸二酐DC-2(1.15g(5.9 mmol))、及NMP：GBL=1：1的混合溶劑10.0g後，25℃條件下攪拌1小時。然後，添加四羧酸二酐DC-5(2.60g(8.8 mmol))，添加NMP：GBL=1：1的混合溶劑10.0g後，再於50℃條件下攪拌12小時，得到樹脂固體成分濃度12質量%的聚醯胺酸溶液(PAA-5)。 　　此聚醯胺酸溶液之溫度25℃時的黏度為200mPa･s。又，此聚醯胺酸的分子量為Mn=8,026、Mw=18,458。 　　[0236] ＜合成例8＞ 　　在附攪拌裝置及氮導入管之500mL的燒瓶中，投入二胺DA-16(25.20g(0.088mol))、及二胺DA-17(8.72g(0.022 mol))後，添加NMP 334.28g，攪拌使溶解。邊將此溶液在水冷下攪拌，邊添加四羧酸二酐DC-4(23.06g(0.11mol))，再加入NMP 83.57g，於50℃下攪拌12小時，得到聚醯胺酸溶液(PAA-6)。 　　此聚醯胺酸溶液的黏度為545mPa･s。又，此聚醯胺酸的分子量為Mn=17,344、Mw=43,383。 　　[0237] ＜合成例9＞ 　　在附攪拌裝置及氮導入管之500mL的燒瓶中，投入二胺DA-21(23.91g(0.12mol))、及二胺DA-9(4.56g(0.03mol))後，加入NMP 241.76g，進行攪拌使溶解。邊將此溶液在水冷下攪拌，邊添加四羧酸二酐DC-2(13.71g(0.070 mol))，再加入NMP 69.07g後，攪拌2小時。然後，投入四羧酸二酐DC-3(18.77g(0.075mol))後，添加NMP 34.54g，於50℃下攪拌12小時，得到聚醯胺酸溶液(PAA-7)。 　　此聚醯胺酸溶液的黏度為300mPa･s。又，此聚醯胺酸的分子量為Mn=11,333、Mw=24,081。 　　[0238] [液晶配向劑之調製] (實施例1) 　　在置入有攪拌子的40ml樣品管中，秤取以合成例1所得之聚醯胺酸溶液(PAA-1)4.00g、以合成例2所得之聚醯胺酸溶液(PAA-2)4.80g，秤取NMP 23.20g、PB 6.80g及DIBK 1.20g，在室溫下攪拌3小時，得到液晶配向劑A1。 　　[0239] 使用此液晶配向劑A1，測量25℃時的黏度。然後，進行以下的塗佈性評價。 　　[0240] [噴墨塗佈性評價] 　　使用噴墨塗佈裝置(股份公司Hitachi Plant Technologies製)，將上述調製的液晶配向劑A1塗佈於表面蒸鍍有鉻的玻璃基板上。塗佈條件為吐出間距40μm、塗佈速度100mm/sec、射出電壓13.0V、塗佈面積36×80mm下進行。塗膜的膜厚係在80℃的加熱板上，進行2分鐘暫時乾燥後，於230℃、30分鐘的條件下，以IR烤箱燒成時，成為100nm的條件下塗佈。 　　[0241] 針對以80℃暫時乾燥，於230℃下燒成的塗膜，比較因塗佈性不足或液垂流之影響所產生之條紋狀不均的程度，以4階段評價。以目視，可確認全面顯著的不均者，評價為Lv4，以目視可確認部分的不均者，評價為Lv3，以目視無法看見不均者，評價為Lv2，即使以光學顯微鏡也完全無不均者，評價為Lv1。 　　[0242] 將矽氧系撥水膜OA-160R1(日產化學工業製)滴下至10×10cm的玻璃基板上，以2000rpm的旋轉數旋轉塗佈於玻璃基板。然後，將此玻璃基板於200℃、30分鐘的條件下，以IR烤箱進行燒成，得到疏水性玻璃基板。 　　[0243] [點(dot)塗佈評價] 　　關於上述調製的液晶配向劑A1，使用噴墨塗佈裝置(股份公司Hitachi Plant Technologies製)，塗佈於上述準備的疏水性玻璃基板上。塗佈條件為以吐出間距500μm、塗佈速度100mm/sec、射出電壓13.0V、塗佈面積36×80mm的條件進行。以上述條件塗佈液晶配向劑A1後，在80℃的加熱板上，進行2分鐘暫時乾燥後，於230℃30分鐘的條件下，以IR烤箱進行燒成。 　　[0244] [塗膜之評價方法] 　　關於以80℃進行暫時乾燥，230℃下進行燒成之點狀的塗膜，使用顯微鏡測量點的直徑。一般，點的直徑越大，具有越良好之塗膜性的材料。點的直徑為160μm以上，評價為良好，其以下評價為不良。 　　[0245] ＜實施例2~9及比較例1~9＞ 　　將合成例1~3、5、7~9所得之聚醯胺酸溶液及合成例4、6所得之聚醯亞胺溶液，以各種溶劑稀釋成為下述表1表示之特定的摻合比率、固體成分濃度、溶劑比率，得到液晶配向劑A2~A6及液晶配向劑B1~B5、C1、D1、E1、F1、G1、H1、及I1。聚醯胺酸溶液、聚醯亞胺溶液及溶劑的組成比與實施例1一同如表1所示。 　　[0246] 表1中，固體成分組成與重量比係表示各聚合物的混合比率(質量%)。溶液的組成與重量比係表示各有機溶劑相對於聚合物溶液全體的比率(質量%)。 　　[0247]
Figure 02_image099
[0248] 表2表示實施例1~9、及比較例1~9中之各評價結果等。 　　[0249]
Figure 02_image101
[0250] ＜合成例10＞ 　　使四羧酸二酐DC-3(12.51g、50.0mmol)、二胺DA-7(13.66g、40.0mmol)、二胺DA-11(6.61g、20.0mmol)、二胺DA-13(17.39g、40.0mmol)在NMP(179.3g)中溶解，於60℃下使反應5小時後，加入四羧酸二酐DC-2(9.61g、49.0mmol)與NMP(59.8g)，於40℃下使反應10小時，得到聚醯胺酸溶液。 　　[0251] 此聚醯胺酸溶液(100g)中，加入NMP，稀釋成6.5質量%後，添加作為醯亞胺化觸媒之乙酸酐(17.0g)、及吡啶(5.3g)，於70℃下使反應3小時。將此反應溶液投入於甲醇(1700ml)中，將所得之沉澱物過濾取得。以甲醇洗凈此沉澱物，以100℃減壓乾燥得到聚醯亞胺的粉末(J)。此聚醯亞胺的醯亞胺化率為76%，數平均分子量為11000、重量平均分子量為38000。 　　[0252] 在所得之聚醯亞胺粉末(J)(3.0g)中，加入NMP(27.0g)，於70℃下攪拌20小時，使溶解。此溶液中，加入3AMP(1wt%NMP溶液)3.0g、NMP(2.0g)、BCS(50.0 g)，於室溫下攪拌5小時，得到液晶配向劑(J1)。 　　[0253] ＜合成例11＞ 　　將四羧酸二酐DC-3(12.51g、50.0mmol)、二胺DA-8(11.87g、50.0mmol)、二胺DA-11(9.91g、30.0mmol)、二胺DA-14(15.14g、20.0mmol)在NMP(177.1g)中溶解，於60℃下使反應5小時後，加入四羧酸二酐DC-2(9.61g、49.0mmol)與NMP(59.0g)，於40℃下使反應10小時，得到聚醯胺酸溶液。 　　[0254] 此聚醯胺酸溶液(100g)中，加入NMP，稀釋成6.5質量%後，添加作為醯亞胺化觸媒之乙酸酐(17.2g)、及吡啶(5.3g)，於70℃下使反應3小時。將此反應溶液投入於甲醇(1300ml)中，將所得之沉澱物過濾取得。以甲醇洗凈此沉澱物，以100℃減壓乾燥得到聚醯亞胺的粉末(K)。此聚醯亞胺的醯亞胺化率為71%，數平均分子量為9000、重量平均分子量為24000。 　　[0255] 在所得之聚醯亞胺粉末(K)(3.0g)中，加入NMP(27.0g)，於70℃下攪拌20小時，使溶解。此溶液中，加入3AMP(1wt%NMP溶液)3.0g、NMP(2.0g)、BCS (50.0g)，藉由於室溫下攪拌5小時，得到液晶配向劑(K1)。 　　[0256] ＜合成例12＞ 　　將四羧酸二酐DC-3(12.51g、 50.0mmol)、二胺DA-9 (6.10g、40.0mmol)、二胺DA-11(6.61g、20.0mmol)、二胺DA-13(17.39g、40.0mmol)在NMP(156.6g)中溶解，於60℃下使反應5小時後，加入四羧酸二酐DC-2(9.61g、49.0mmol)與NMP(52.2g)，於40℃下使反應10小時，得到聚醯胺酸溶液。 　　[0257] 此聚醯胺酸溶液(100g)中，加入NMP，稀釋成6.5質量%後，添加作為醯亞胺化觸媒之乙酸酐(19.5g)、及吡啶(6.0g)，於70℃下使反應3小時。將此反應溶液投入於甲醇(1300ml)中，將所得之沉澱物過濾取得。以甲醇洗凈此沉澱物，以100℃減壓乾燥得到聚醯亞胺粉末(L)。此聚醯亞胺的醯亞胺化率為75%，數平均分子量為16000、重量平均分子量為43000。 　　[0258] 所得之聚醯亞胺粉末(L)(3.0g)中，加入NEP(27.0g)，於70℃下攪拌20小時，使溶解。此溶液中，加入NEP(20.0g)、BCS(50.0g)，藉由於室溫下攪拌5小時，得到液晶配向劑(L1)。 　　[0259] ＜合成例13＞ 　　將四羧酸二酐DC-3(12.51g、 50.0mmol)、二胺DA-9 (7.61g、50.0mmol)、二胺DA-11(9.91g、30.0mmol)、二胺DA-14(15.14g、20.0mmol)於NMP(164.4g)中溶解，使60℃下反應5小時後，加入四羧酸二酐DC-2(9.61g、49.0mmol)與NMP(54.8g)，於40℃下使反應10小時，得到聚醯胺酸溶液。 　　[0260] 此聚醯胺酸溶液(100g)中，加入NMP，稀釋成6.5質量%後，添加作為醯亞胺化觸媒之乙酸酐(18.6g)、及吡啶(5.8g)，於70℃下使反應3小時。將此反應溶液投入於甲醇(1300ml)中，將所得之沉澱物過濾取得。以甲醇洗凈此沉澱物，以100℃減壓乾燥得到聚醯亞胺粉末(M)。此聚醯亞胺的醯亞胺化率為71%，數平均分子量為12000、重量平均分子量為29000。 　　[0261] 所得之聚醯亞胺粉末(M)(3.0g)中，加入NMP (27.0g)，於70℃下攪拌20小時，使溶解。此溶液中，加入NEP(20.0g)、BCS(50.0g)，藉由於室溫下攪拌5小時，得到液晶配向劑(M1)。 　　[0262] ＜合成例14＞ 　　將四羧酸二酐DC-3(5.00g、20.0mmol)、二胺DA-9 (6.09g、40.0mmol)、二胺DA-10(7.27g、30.0mmol)、二胺DA-12(11.42g、30.0mmol)在NMP(137.1g)中溶解，於60℃下使反應5小時後，加入四羧酸二酐DC-4(4.36g、20.0 mmol)、四羧酸二酐DC-2(11.57g、59.0mmol)與NMP(45.7g)，於40℃下使反應10小時，得到聚醯胺酸溶液。 　　[0263] 此聚醯胺酸溶液(100g)中，加入NMP，稀釋成6.5質量%後，添加作為醯亞胺化觸媒之乙酸酐(22.2g)、及吡啶(6.9g)，於50℃下使反應3小時。將此反應溶液投入於甲醇(1300ml)中，將所得之沉澱物過濾取得。以甲醇洗凈此沉澱物，以100℃減壓乾燥得到聚醯亞胺粉末(N)。此聚醯亞胺的醯亞胺化率為78%，數平均分子量為18000、重量平均分子量為39000。 　　[0264] 所得之聚醯亞胺粉末(N)(3.0g)中，加入NMP(27.0g)，於70℃下攪拌20小時，使溶解。此溶液中，加入3AMP(1wt%NMP溶液)3.0g、NMP(2.0g)、BCS(50.0g)，藉由於室溫下攪拌5小時，得到液晶配向劑(N1)。 　　[0265] 依據如以上的合成例10~14，得到液晶配向劑J1、K1，L1、M1及N1。 　　[0266] 下述表係表示合成例10~14中使用之酸二酐成分與二胺成分的組成比。 　　[0267]
Figure 02_image103
[0268] ＜合成例15~23＞ 　　此外，使用合成例10~14所得之聚醯亞胺粉末(J~N)，藉由與前述合成例3~7同樣的操作，調製下述表4所示之溶劑組成的液晶配向劑。 　　[0269]
Figure 02_image105
[0270] ＜實施例10＞ 　　關於合成例16與合成例20所得之液晶配向劑J2與N3，在室溫下攪拌3小時，使各自所含之樹脂組成物的重量比成為3：7，調製液晶配向劑(JN1)。 　　[0271] ＜實施例11、12、比較例10~14＞ 　　使用與實施例10同樣的操作，調配各液晶配向劑，調製如下述表5所示之各種的液晶配向劑。調製之液晶配向劑的調配比率及、溶劑組成如表5所示。 　　[0272]
Figure 02_image107
[0273] 關於表5的液晶配向劑，與實施例1同樣進行評價。評價結果如表6所示。 　　[0274]
Figure 02_image109
[0275] 由表6的結果可知，將比較例10與比較例11、比較例12與13進行比較時，聚合物中含有因熱產生脫離之保護基的情形時，有塗佈不均或點塗佈性降低的傾向。 　　[0276] 另外，將實施例10與比較例10、實施例11與比較例12、實施例12與比較例14進行比較時，可確認藉由導入二異丁基酮，即使聚合物中含有因熱產生脫離之保護基的情形時，也可改善塗佈性。[Examples] [0214] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these embodiments. The following represents the abbreviation of the compound used. (Solvent) NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve PB: 1-butoxy-2-propanol DPM: dipropylene glycol monomethyl ether DIBK: diisobutyl ketone [0217] (tetracarboxylic dianhydride) DC-1: 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride DC-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride DC-3: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride DC-4: pyromellitic anhydride DC-5: 3,3,4,4-biphenyltetracarboxylic dianhydride [0218] (diamine) DA-1: p-phenylenediamine DA-2: bis( 4-Aminophenoxy)ethane DA-3: 1,3-bis(4-aminophenoxy)propane DA-4: N-methyl-2-(4-aminophenyl)ethyl Amine DA-5: A compound represented by the following formula (DA-5) DA-6: A compound represented by the following formula (DA-6) DA-7: A compound DA-8 represented by the following formula (DA-7): Compound DA-9 represented by the following formula (DA-8): 3,5-diaminobenzoic acid DA-10: Compound represented by the following formula (DA-10) DA-11: The following formula (DA-11) ) represented by the compound DA-12: the compound represented by the following formula (DA-12) DA-13: the compound represented by the following formula (DA-13) DA-14: the compound represented by the following formula (DA-14) DA-14 -15: The compound represented by the following formula (DA-15) DA-16: The compound represented by the following formula (DA-16) DA-17: The compound represented by the following formula (DA-17) DA-18: The following The compound represented by the formula (DA-18) DA-19: The compound represented by the following formula (DA-19) DA-20: The compound represented by the following formula (DA-20) DA-21: The following formula (DA-21) A compound represented by ) [0219] (additive) 3AMP: 3-pyridylmethylamine [0220] In addition, in the following chemical formula, Me represents a methyl group, Bu represents an n-butyl group, and Boc represents a t-butoxy group. [0221]
Figure 02_image097
The measurement method of each characteristic is as follows. [Viscosity] The viscosity of polyamide ester, polyamide acid solution and polyimide solution was measured by using E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL (milliliter) , Conical rotor TE-1 (1°34', R24), measured at a temperature of 25°C. [Molecular weight] The molecular weight of the polyamic acid ester and polyamic acid is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is calculated as a polyethylene glycol (polyethylene oxide) conversion value Number average molecular weight (hereinafter also referred to as Mn) and weight average molecular weight (hereinafter also referred to as Mw). GPC device: manufactured by Shodex (GPC-101) Column: manufactured by Shodex (in-line of KD803 and KD805) Column temperature: 50° C. Eluent: N,N-dimethylformamide (additive: Lithium bromide-hydrate (LiBr･H 2 O): 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid): 30 mmol/L, tetrahydrofuran (THF): 10 ml/L) Flow rate: 1.0 ml/min [0226 ] Standard sample for calibration curve preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation and polyethylene glycol (peak top molecular weight) manufactured by Polymer Laboratories were used (peak top molecular weight (Mp) is about 12,000, 4,000, and 1,000). In order to avoid the overlapping of peaks, the measurement was carried out for 2 samples of 900,000, 100,000, 12,000, and 1,000 mixed samples of 4 types, and 150,000, 30,000, and 4,000 of 3 types of mixed samples, respectively. <Synthesis Example 1> In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, weigh diamines DA-1 (0.81 g (7.5 mmol)) and DA-2 (1.22 g (5.0 mmol) ), DA-3 (1.94 g (7.5 mmol)), and diamine DA-6 (1.99 g (5.0 mmol)), 74.86 g of NMP was added, and the mixture was dissolved by stirring while feeding in nitrogen. While stirring this diamine solution, tetracarboxylic dianhydride DC-1 (5.38 g (24.0 mmol)) was added, and NMP was added to make the solid content concentration 12% by mass, and the mixture was stirred at 40° C. for 20 hours to obtain polyamide. Acid (PAA-1) solution. The viscosity of this polyamide solution at 25°C is 502mPa･s. In addition, the molecular weight of this polyamic acid was Mn=16,715 and Mw=43,662. <Synthesis Example 2> In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, diamine DA-5 (6.26 g (21.0 mmol)) and diamine DA-4 (2.10 g (14.0 g) were weighed. mmol)), 76.28 g of NMP was added, and the mixture was stirred and dissolved while nitrogen gas was introduced. While stirring this diamine solution, tetracarboxylic dianhydride DC-2 (6.58 g (33.6 mmol)) was added, and NMP was added to make the solid content concentration 15% by mass, and the mixture was stirred at room temperature for 4 hours to obtain a polyamide. acid (PAA-2). The viscosity of this polyamide solution at 25°C is 768mPa･s. In addition, the molecular weight of this polyamic acid was Mn=11,658 and Mw=28,328. <Synthesis Example 3> [0229] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, diamines DA-1 (0.84 g (7.8 mmol)) and DA-2 (1.27 g (5.2 mmol) were weighed ), DA-3 (2.01 g (7.8 mmol)), and diamine DA-5 (1.55 g (5.2 mmol)), 73.26 g of NMP was added, and the mixture was dissolved by stirring while feeding in nitrogen. While stirring this diamine solution, tetracarboxylic dianhydride DC-1 (5.42 g (24.2 mmol)) was added, and NMP was further added to make the solid content concentration 12% by mass, and the mixture was stirred at 40° C. for 20 hours to obtain polyamide. acid (PAA-3). The viscosity of this polyamide solution at 25°C is 393mPa･s. In addition, the molecular weight of this polyamic acid was Mn=14,654 and Mw=39,268. <Synthesis Example 4> In a 3-L four-necked flask with a stirring device and a nitrogen introduction tube, diamine DA-1 (17.30 g (159.98 mmol)) and diamine DA-2 (58.63 g (240.00 mmol) were weighed. mmol)), diamine DA-15 (76.89 g (240.0 mmol)), and diamine DA-7 (54.63 g (159.99 mmol)), NMP 2458.13 g was added, and it was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, tetracarboxylic dianhydride DC-1 (171.27 g (764.02 mmol)) was added, and NMP was added to make the solid content concentration 12% by mass, and the mixture was stirred at 40° C. for 20 hours to obtain polyamide. acid (PAA-4). The viscosity of this polyamide solution at 25°C is 426mPa･s. In addition, the molecular weight of this polyamic acid was Mn=12,380 and Mw=33,250. [0231] After 2250.0 g of this polyamic acid solution was fractionated, 750.0 g of NMP was added, 171.1 g of acetic anhydride and 35.4 g of pyridine were added, and the reaction was carried out at 55° C. for 3 hours. This reaction solution was poured into 9619.2 g of methanol, and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a powder of polyimide. The imidization rate of this polyimide was 66%. To 120.0 g of the obtained polyimide powder, 880.0 g of NMP was added, and the mixture was stirred at 70° C. for 20 hr to dissolve to obtain a polyimide solution (SPI-1). The viscosity of this polyimide solution at 25°C is 137mPa･s. In addition, the molecular weight of this polyimide is Mn=11,035 and Mw=27,887. <Synthesis Example 5> In a 3L four-necked flask with a stirring device and a nitrogen introduction tube, diamine DA-21 (130.71 g (656.0 mmol)) and diamine DA-9 (24.95 g (163.98 g) were weighed mmol)), 171.60 g of NMP was added, and the mixture was stirred and dissolved while nitrogen gas was introduced. While stirring this diamine solution, tetracarboxylic dianhydride DC-5 (226.78 g (770.8 mmol)) was added, and NMP was added to make the solid content concentration 12% by mass, and the mixture was stirred at room temperature for 4 hours to obtain polyamide acid (PAA-4). The viscosity of this polyamide solution at 25°C is 234mPa･s. In addition, the molecular weight of this polyamic acid was Mn=9,657 and Mw=22,975. <Synthesis Example 6> In a 200 mL four-necked flask with a stirring device and a nitrogen introduction tube, diamine DA-2 (4.03 g (16.5 mmol)) and diamine DA-6 (3.59 g (9.0 mmol) were added. )) and diamine DA-18 (2.50 g (4.5 mmol)), 102.1 g of NMP was added, and the mixture was stirred and dissolved while nitrogen gas was introduced. While stirring this solution, tetracarboxylic dianhydride DC-1 (4.37 g (19.5 mmol)) and 12.8 g of NMP were added, and the mixture was stirred at 40°C for 3 hours. Then, tetracarboxylic dianhydride DC-2 (1.71 g (8.7 mmol)) and 12.8 g of NMP were added at 25°C, followed by stirring for 12 hours to obtain a polyamic acid solution with a resin solid content concentration of 15 mass % . The viscosity of this polyamide solution is 820mPa･s. In addition, the molecular weight of this polyamic acid was Mn=13,250 and Mw=35,459. [0234] After 80.0 g of this polyamic acid solution was divided, 70.0 g of NMP was added, 6.8 g of acetic anhydride and 1.8 g of pyridine were added, and the reaction was carried out at 50° C. for 3 hours. This reaction solution was poured into 555.0 g of methanol, and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a powder of polyimide. The imidization rate of this polyimide was 75%. To 80.0 g of the obtained polyimide powder, 586.7 g of NMP was added, and the mixture was stirred at 50° C. for 20 hr to dissolve to obtain a polyimide solution (SPI-2). The viscosity of this polyimide solution at 25°C is 74.0mPa･s. In addition, the molecular weight of this polyimide was Mn=9,848 and Mw=23,058. <Synthesis Example 7> In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, diamine DA-20 (1.12 g (4.5 mmol)) and diamine DA-19 (0.59 g (3.0 mmol) were added. )) and diamine DA-21 (1.49 g (7.5 mmol)), 31.0 g of a mixed solvent of NMP:GBL=1:1 was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this solution, tetracarboxylic dianhydride DC-2 (1.15 g (5.9 mmol)) and 10.0 g of a mixed solvent of NMP:GBL=1:1 were added, followed by stirring at 25°C for 1 hour. Then, tetracarboxylic dianhydride DC-5 (2.60 g (8.8 mmol)) was added, and 10.0 g of a mixed solvent of NMP:GBL=1:1 was added, followed by stirring at 50°C for 12 hours to obtain a resin solid content concentration 12 mass % polyamic acid solution (PAA-5). The viscosity of this polyamide solution at a temperature of 25°C is 200mPa･s. In addition, the molecular weight of this polyamic acid was Mn=8,026 and Mw=18,458. <Synthesis Example 8> In a 500 mL flask with a stirring device and a nitrogen introduction tube, diamine DA-16 (25.20 g (0.088 mol)) and diamine DA-17 (8.72 g (0.022 mol) were charged ), 334.28 g of NMP was added, and the mixture was stirred and dissolved. While stirring this solution under water cooling, tetracarboxylic dianhydride DC-4 (23.06 g (0.11 mol)) was added, and NMP 83.57 g was added, and the solution was stirred at 50° C. for 12 hours to obtain a polyamide acid solution (PAA -6). The viscosity of this polyamide solution is 545mPa･s. In addition, the molecular weight of this polyamic acid was Mn=17,344 and Mw=43,383. <Synthesis Example 9> Diamine DA-21 (23.91 g (0.12 mol)) and diamine DA-9 (4.56 g (0.03 mol) were put into a 500 mL flask with a stirring device and a nitrogen introduction tube. ), 241.76 g of NMP was added, and the mixture was stirred and dissolved. While stirring this solution under water cooling, tetracarboxylic dianhydride DC-2 (13.71 g (0.070 mol)) was added, and 69.07 g of NMP was added, followed by stirring for 2 hours. Then, after adding tetracarboxylic dianhydride DC-3 (18.77g (0.075mol)), NMP 34.54g was added, and it stirred at 50 degreeC for 12 hours, and obtained the polyamic acid solution (PAA-7). The viscosity of this polyamide solution is 300mPa･s. In addition, the molecular weight of this polyamic acid was Mn=11,333 and Mw=24,081. [Preparation of Liquid Crystal Alignment Agent] (Example 1) In a 40 ml sample tube with a stirrer placed, 4.00 g of the polyamide acid solution (PAA-1) obtained in Synthesis Example 1 was weighed to synthesize 4.00 g. 4.80 g of the polyamic acid solution (PAA-2) obtained in Example 2, 23.20 g of NMP, 6.80 g of PB and 1.20 g of DIBK were weighed and stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent A1. [0239] Using this liquid crystal alignment agent A1, the viscosity at 25°C was measured. Then, the following coatability evaluation was performed. [Evaluation of Inkjet Coatability] Using an inkjet coater (manufactured by Hitachi Plant Technologies Co., Ltd.), the liquid crystal aligning agent A1 prepared above was applied on a glass substrate on which chromium was vapor-deposited. The coating conditions were performed at a discharge pitch of 40 μm, a coating speed of 100 mm/sec, an injection voltage of 13.0 V, and a coating area of 36×80 mm. The film thickness of the coating film was applied under the condition of 100 nm when baked in an IR oven under the conditions of 230° C. and 30 minutes after temporary drying for 2 minutes on a hot plate at 80° C. [0241] For the coating film that was temporarily dried at 80°C and fired at 230°C, the degree of streak-like unevenness due to insufficient coatability or the influence of sag flow was compared and evaluated in four stages. If the unevenness can be confirmed visually, the evaluation is Lv4, if the unevenness can be partially recognized by the eye, the evaluation is Lv3, and the unevenness cannot be seen visually, the evaluation is Lv2, even with an optical microscope. Average, the evaluation is Lv1. [0242] The silicon-oxygen-based water repellent film OA-160R1 (manufactured by Nissan Chemical Industries) was dropped onto a 10×10 cm glass substrate, and spin-coated on the glass substrate at a rotation speed of 2000 rpm. Then, this glass substrate was fired in an IR oven under the conditions of 200° C. and 30 minutes to obtain a hydrophobic glass substrate. [Evaluation of dot coating] The liquid crystal aligning agent A1 prepared above was coated on the hydrophobic glass substrate prepared above using an ink jet coating apparatus (manufactured by Hitachi Plant Technologies Co., Ltd.). The coating conditions were performed under the conditions of a discharge pitch of 500 μm, a coating speed of 100 mm/sec, an injection voltage of 13.0 V, and a coating area of 36×80 mm. After applying the liquid crystal aligning agent A1 under the above conditions, it was temporarily dried on a hot plate at 80° C. for 2 minutes, and then fired in an IR oven under the conditions of 230° C. for 30 minutes. [Evaluation method of coating film] About the dot-shaped coating film that was temporarily dried at 80°C and fired at 230°C, the diameter of the dots was measured using a microscope. In general, the larger the diameter of the dots, the better the coating properties of the material. When the diameter of the dot was 160 μm or more, the evaluation was good, and the following evaluation was poor. <Examples 2 to 9 and Comparative Examples 1 to 9> The polyimide solutions obtained in Synthesis Examples 1 to 3, 5, and 7 to 9 and the polyimide solutions obtained in Synthesis Examples 4 and 6 were prepared as Various solvents were diluted into specific blending ratios, solid content concentrations, and solvent ratios shown in Table 1 below to obtain liquid crystal alignment agents A2 to A6 and liquid crystal alignment agents B1 to B5, C1, D1, E1, F1, G1, H1, and I1. The composition ratios of the polyimide solution, the polyimide solution and the solvent are shown in Table 1 together with Example 1. In Table 1, the solid content composition and weight ratio represent the mixing ratio (mass %) of each polymer. The composition and weight ratio of the solution represent the ratio (mass %) of each organic solvent with respect to the entire polymer solution. [0247]
Figure 02_image099
Table 2 shows the evaluation results and the like in Examples 1 to 9 and Comparative Examples 1 to 9. [0249]
Figure 02_image101
<Synthesis Example 10> Tetracarboxylic dianhydride DC-3 (12.51 g, 50.0 mmol), diamine DA-7 (13.66 g, 40.0 mmol), and diamine DA-11 (6.61 g, 20.0 mmol) were prepared , diamine DA-13 (17.39 g, 40.0 mmol) was dissolved in NMP (179.3 g), and the reaction was carried out at 60° C. for 5 hours, then tetracarboxylic dianhydride DC-2 (9.61 g, 49.0 mmol) and NMP were added. (59.8 g), it was made to react at 40 degreeC for 10 hours, and the polyamic acid solution was obtained. To this polyamic acid solution (100 g), NMP was added, and after diluting to 6.5 mass %, acetic anhydride (17.0 g) and pyridine (5.3 g) as imidization catalysts were added, and the mixture was heated at 70° C. The reaction was allowed to proceed for 3 hours. This reaction solution was put into methanol (1700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (J). This polyimide had an imidization rate of 76%, a number average molecular weight of 11,000, and a weight average molecular weight of 38,000. [0252] To the obtained polyimide powder (J) (3.0 g), NMP (27.0 g) was added, and the mixture was stirred at 70° C. for 20 hours to dissolve. To this solution, 3.0 g of 3AMP (1 wt % NMP solution), NMP (2.0 g), and BCS (50.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (J1). <Synthesis Example 11> Tetracarboxylic dianhydride DC-3 (12.51 g, 50.0 mmol), diamine DA-8 (11.87 g, 50.0 mmol), and diamine DA-11 (9.91 g, 30.0 mmol) , diamine DA-14 (15.14 g, 20.0 mmol) was dissolved in NMP (177.1 g), and the reaction was carried out at 60° C. for 5 hours, then tetracarboxylic dianhydride DC-2 (9.61 g, 49.0 mmol) and NMP were added. (59.0 g), it was made to react at 40 degreeC for 10 hours, and the polyamic acid solution was obtained. To this polyamic acid solution (100 g), NMP was added, and after diluting to 6.5 mass %, acetic anhydride (17.2 g) and pyridine (5.3 g) as imidization catalysts were added, and the mixture was heated at 70° C. The reaction was allowed to proceed for 3 hours. This reaction solution was put into methanol (1300 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (K). This polyimide had an imidization rate of 71%, a number average molecular weight of 9,000, and a weight average molecular weight of 24,000. [0255] To the obtained polyimide powder (K) (3.0 g), NMP (27.0 g) was added, and the mixture was stirred at 70° C. for 20 hours to dissolve. To this solution, 3.0 g of 3AMP (1 wt % NMP solution), NMP (2.0 g), and BCS (50.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (K1). <Synthesis Example 12> Tetracarboxylic dianhydride DC-3 (12.51 g, 50.0 mmol), diamine DA-9 (6.10 g, 40.0 mmol), and diamine DA-11 (6.61 g, 20.0 mmol) , diamine DA-13 (17.39 g, 40.0 mmol) was dissolved in NMP (156.6 g), and the reaction was carried out at 60° C. for 5 hours. Tetracarboxylic dianhydride DC-2 (9.61 g, 49.0 mmol) and NMP were added. (52.2 g), it was made to react at 40 degreeC for 10 hours, and the polyamic acid solution was obtained. To this polyamic acid solution (100 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (19.5 g) and pyridine (6.0 g) as imidization catalysts were added, and the mixture was heated at 70° C. The reaction was allowed to proceed for 3 hours. This reaction solution was put into methanol (1300 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (L). The imidization rate of this polyimide was 75%, the number average molecular weight was 16,000, and the weight average molecular weight was 43,000. [0258] To the obtained polyimide powder (L) (3.0 g), NEP (27.0 g) was added, and the mixture was stirred at 70° C. for 20 hours to dissolve. To this solution, NEP (20.0 g) and BCS (50.0 g) were added, and the liquid crystal aligning agent (L1) was obtained by stirring at room temperature for 5 hours. <Synthesis Example 13> Tetracarboxylic dianhydride DC-3 (12.51 g, 50.0 mmol), diamine DA-9 (7.61 g, 50.0 mmol), and diamine DA-11 (9.91 g, 30.0 mmol) , diamine DA-14 (15.14g, 20.0mmol) was dissolved in NMP (164.4g), and after 5 hours of reaction at 60°C, tetracarboxylic dianhydride DC-2 (9.61g, 49.0mmol) and NMP ( 54.8 g) and reacted at 40° C. for 10 hours to obtain a polyamic acid solution. To this polyamic acid solution (100 g), NMP was added, and after diluting to 6.5 mass %, acetic anhydride (18.6 g) and pyridine (5.8 g) as imidization catalysts were added, and the mixture was heated at 70° C. The reaction was allowed to proceed for 3 hours. This reaction solution was put into methanol (1300 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (M). This polyimide had an imidization rate of 71%, a number average molecular weight of 12,000, and a weight average molecular weight of 29,000. [0261] To the obtained polyimide powder (M) (3.0 g), NMP (27.0 g) was added, and the mixture was stirred at 70° C. for 20 hours to dissolve. To this solution, NEP (20.0 g) and BCS (50.0 g) were added, and the liquid crystal aligning agent (M1) was obtained by stirring at room temperature for 5 hours. <Synthesis Example 14> Tetracarboxylic dianhydride DC-3 (5.00 g, 20.0 mmol), diamine DA-9 (6.09 g, 40.0 mmol), and diamine DA-10 (7.27 g, 30.0 mmol) , diamine DA-12 (11.42 g, 30.0 mmol) was dissolved in NMP (137.1 g), and the reaction was carried out at 60° C. for 5 hours. Tetracarboxylic dianhydride DC-4 (4.36 g, 20.0 mmol), Carboxylic dianhydride DC-2 (11.57 g, 59.0 mmol) and NMP (45.7 g) were reacted at 40° C. for 10 hours to obtain a polyamic acid solution. To this polyamic acid solution (100 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (22.2 g) and pyridine (6.9 g) were added as imidization catalysts, and the mixture was heated to 50° C. The reaction was allowed to proceed for 3 hours. This reaction solution was put into methanol (1300 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (N). The imidization rate of this polyimide was 78%, the number average molecular weight was 18,000, and the weight average molecular weight was 39,000. [0264] To the obtained polyimide powder (N) (3.0 g), NMP (27.0 g) was added, and the mixture was stirred at 70° C. for 20 hours to dissolve. To this solution, 3.0 g of 3AMP (1 wt % NMP solution), NMP (2.0 g), and BCS (50.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (N1). [0265] According to the above synthesis examples 10 to 14, liquid crystal alignment agents J1, K1, L1, M1 and N1 were obtained. The following table shows the composition ratio of the acid dianhydride component and the diamine component used in Synthesis Examples 10 to 14. [0267]
Figure 02_image103
<Synthesis Examples 15 to 23> In addition, using the polyimide powders (J to N) obtained in Synthesis Examples 10 to 14, by the same operation as the aforementioned Synthesis Examples 3 to 7, the following Table 4 was prepared. The liquid crystal aligning agent composed of the solvent shown. [0269]
Figure 02_image105
<Example 10> The liquid crystal alignment agents J2 and N3 obtained in Synthesis Example 16 and Synthesis Example 20 were stirred at room temperature for 3 hours so that the weight ratio of the resin compositions contained in each was 3:7, and prepared Liquid crystal alignment agent (JN1). <Examples 11, 12, Comparative Examples 10 to 14> Using the same operation as Example 10, each liquid crystal aligning agent was prepared, and various liquid crystal aligning agents shown in Table 5 below were prepared. Table 5 shows the preparation ratio and solvent composition of the prepared liquid crystal aligning agent. [0272]
Figure 02_image107
About the liquid crystal aligning agent of Table 5, carry out evaluation similarly to Example 1. The evaluation results are shown in Table 6. [0274]
Figure 02_image109
As can be seen from the results in Table 6, when comparing Comparative Example 10 with Comparative Example 11, Comparative Example 12 and 13, when the polymer contained the protective group that was removed due to heat, there was uneven coating or spotting. There is a tendency for coatability to decrease. In addition, when comparing Example 10 with Comparative Example 10, Example 11 with Comparative Example 12, Example 12 with Comparative Example 14, it can be confirmed that by introducing diisobutyl ketone, even if the polymer contains Coatability can also be improved in the case of thermally generating a protecting group that is released.

Claims (10)

一種液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及其醯亞胺化物的聚醯亞胺所成群之至少1種，且含有因熱產生脫離之保護基的聚合物，及含有下述A群組的溶劑、B群組的溶劑及二異丁基酮的溶劑成分，A群組：選自由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯及1,3-二甲基咪唑啉酮所成群之至少1種的溶劑B群組：選自由丁基溶纖劑、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、二丙二醇二甲醚所成群之至少1種的溶劑。 A liquid crystal aligning agent, which is characterized by containing at least one polymer selected from the group consisting of polyimide precursors and polyimide compounds thereof, and containing a protective group that is detached by heat, and Contains the following solvent components of group A, group B, and diisobutyl ketone, group A: selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ- At least one solvent group B of the group consisting of butyrolactone and 1,3-dimethylimidazolidinone: selected from butyl cellosolve, 1-butoxy-2-propanol, 2-butoxy- A solvent for at least one of the group consisting of 1-propanol and dipropylene glycol dimethyl ether. 如請求項1之液晶配向劑，其中相對於液晶配向劑之全質量，屬於前述A群組之溶劑的含量為20質量%~90質量%以下。 The liquid crystal alignment agent according to claim 1, wherein the content of the solvent belonging to the aforementioned Group A is 20% by mass to 90% by mass or less relative to the total mass of the liquid crystal alignment agent. 如請求項1之液晶配向劑，其中相對於液晶配向劑之全質量，屬於前述B群組之溶劑的含量為1質量%~50質量%以下。 The liquid crystal alignment agent of claim 1, wherein the content of the solvent belonging to the aforementioned Group B is 1 mass % to 50 mass % or less relative to the total mass of the liquid crystal alignment agent. 如請求項1~3中任一項之液晶配向劑，其中相對於液晶配向劑之全質量，前述二異丁基酮的含量為1質量%~20 質量%以下。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the content of the aforementioned diisobutyl ketone is 1% by mass to 20% by mass relative to the total mass of the liquid crystal alignment agent. mass % or less. 如請求項1~3中任一項之液晶配向劑，其中前述聚合物含有以下的結構，
Figure 106133267-A0305-02-0084-1
 式中，X1為氧原子或硫原子，A1~A3各自獨立為氫原子或碳數1~3之烴基，碳數之合計為1~9，又，*表示與其他原子的鍵結。 The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the aforementioned polymer has the following structure,
Figure 106133267-A0305-02-0084-1
 In the formula, X 1 is an oxygen atom or a sulfur atom, A 1 to A 3 are each independently a hydrogen atom or a hydrocarbon group with 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9, and * represents a bond with other atoms. . 如請求項1~3中任一項之液晶配向劑，其中前述聚合物為選自由含有包含上述式(a)之結構之二胺的二胺成分與四羧酸衍生物之反應物的聚醯亞胺前驅物及其醯亞胺化物所成群之至少1種的聚合物。 The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polymer is a polyamide selected from the group consisting of a reactant of a diamine component containing a diamine having the structure of the formula (a) and a tetracarboxylic acid derivative A polymer of at least one of an imine precursor and an imide group thereof. 如請求項6之液晶配向劑，其中含有上述式(a)之結構的二胺為選自以下之二胺的至少1種，
Figure 106133267-A0305-02-0085-2
 The liquid crystal aligning agent according to claim 6, wherein the diamine containing the structure of the above formula (a) is at least one selected from the following diamines,
Figure 106133267-A0305-02-0085-2
 如請求項6之液晶配向劑，其中含有上述式(a)之結構的二胺為全二胺成分中之10莫耳%~50莫耳%。 The liquid crystal alignment agent according to claim 6, wherein the diamine containing the structure of the above formula (a) is 10 mol % to 50 mol % of the total diamine component. 一種液晶配向膜，其係由如請求項1~8中任一項之液晶配向劑而得。 A liquid crystal alignment film, which is obtained from the liquid crystal alignment agent according to any one of claims 1 to 8. 一種液晶顯示元件，其係具備如請求項9之液晶配向膜。A liquid crystal display element comprising the liquid crystal alignment film of claim 9.
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