TWI756256B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same - Google Patents

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

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TWI756256B
TWI756256B TW106129429A TW106129429A TWI756256B TW I756256 B TWI756256 B TW I756256B TW 106129429 A TW106129429 A TW 106129429A TW 106129429 A TW106129429 A TW 106129429A TW I756256 B TWI756256 B TW I756256B
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liquid crystal
group
diamine
crystal alignment
formula
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TW201825659A (en
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鉄谷尚士
相馬早紀
野田尚宏
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • C08G73/1075—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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

Abstract

本發明係提供一種液晶配向劑，其係在累積電荷的遺漏等之方面具有優異之電特性，且可形成無著色並具有透明性之液晶配向膜。 　　一種液晶配向劑，其特徵為含有選自含有具有式[1]表示之構造之二胺的二胺成分與四羧酸二酐成分反應所得之聚醯胺酸、及將該聚醯胺酸醯亞胺化所得之聚醯亞胺所成之群中的至少1個聚合物；

Figure 106129429-A0101-11-0001-1
(式中，A係表示藉由溫度150~300℃之加熱而置換為氫原子之熱解離性基，苯環所具有之氫原子亦可藉由碳數1~5之烷基或是烷氧基或鹵素基取代，*係表示鍵結處)。The present invention provides a liquid crystal aligning agent which has excellent electrical properties in terms of omission of accumulated charges and the like, and which can form a non-colored and transparent liquid crystal aligning film. A liquid crystal aligning agent characterized by containing a diamine component selected from the group consisting of a diamine having a structure represented by the formula [1] and a polyamic acid obtained by reacting a tetracarboxylic dianhydride component, and the polyamic acid At least one polymer in the group of polyimide obtained by imidization;
Figure 106129429-A0101-11-0001-1
(In the formula, A represents a thermally dissociable group that is replaced by a hydrogen atom by heating at a temperature of 150 to 300° C. The hydrogen atom of the benzene ring can also be replaced by an alkyl group having 1 to 5 carbon atoms or an alkoxy group. group or halogen group, * indicates the bond).

Description

液晶配向劑、液晶配向膜及使用其之液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same

[0001] 本發明係關於液晶配向劑、使用其之液晶配向膜及液晶顯示元件。[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film using the same, and a liquid crystal display element.

[0002] 液晶配向膜係為作為顯示裝置廣泛被使用的液晶顯示元件的構成構件，擔任將液晶配向於一定方向的角色。現在使用於工業上的主要液晶配向膜係由聚醯亞胺前驅物之聚醯胺酸(亦稱為polyamic acid)或聚醯亞胺的溶液所成的液晶配向劑所形成。具體而言，於基板塗佈液晶配向劑，經加熱‧燒成後，藉由進行液晶配向處理而得。 　　[0003] 以往，在液晶配向處理時，主要藉由摩擦進行表面處理，但在摩擦處理時通常難以高度地進行均等配向處理，有引起液晶的配向不良或引起液晶配向膜之缺損，藉此產生顯示缺陷，產生塵埃等問題。近年來，藉由使用於面板的基板之大型化、高精度化、低成本化等，有著基板面積擴大、凹凸變大等傾向。於如此基板上形成配向膜時，在摩擦處理時，更進一步，留下改善的餘地。 　　[0004] 另一方面，作為改變為摩擦法之配向處理的方法，有人提出利用光反應的配向處理。具體而言，已知於基板表面上形成具有引起聚乙烯桂皮酸酯等光反應的特定部位之聚合物的膜，藉由照射偏光或非偏光之放射線，賦予液晶配向能之方法(光配向法)。依據該方法，不會產生靜電氣或塵埃，可實現均勻液晶配向，亦可能藉由配向分割而提高視野角等(參照專利文獻1、2)。 　　[0005] 又，對於TN(Twisted Nematic)、STN(Super Twisted Nematic)等液晶晶胞，液晶配向膜為必須具有將液晶分子對基板面以所定角度(預傾角)進行傾斜配向的功能。已知欲表現預傾角，使用具有烷基側鏈、類固醇骨架之側鏈、具有環結構之側鏈等聚醯胺酸或聚醯亞胺等之液晶配向膜(專利文獻3、4、5)。使用光的配向處理中，預傾角一般藉由對基板面之入射方向呈基板法線方向傾斜的放射線之照射而被賦予(參照專利文獻1)。 [先前技術文獻] [專利文獻] 　　[0006] 　　[專利文獻1] 日本特開平6-287453號公報 　　[專利文獻2] 日本特開平9-297313號公報 　　[專利文獻3] 日本特開平05-043687號公報 　　[專利文獻4] 日本特開平04-281427號公報 　　[專利文獻5] 日本特開平02-223916號公報[0002] A liquid crystal alignment film is a constituent member of a liquid crystal display element widely used as a display device, and plays a role of aligning liquid crystal in a certain direction. Currently, the main liquid crystal alignment films used in industry are formed from liquid crystal alignment agents formed from polyimide precursors such as polyamic acid (also known as polyamic acid) or a solution of polyimide. Specifically, a liquid crystal aligning agent is coated on a substrate, and is obtained by performing a liquid crystal alignment treatment after heating and firing. In the past, in the liquid crystal alignment treatment, the surface treatment was mainly performed by rubbing, but it is usually difficult to perform the uniform alignment treatment to a high degree during the rubbing treatment, which may cause poor alignment of the liquid crystal or cause defects in the liquid crystal alignment film. Display defects, generation of dust and other problems. In recent years, due to the increase in size, high precision, and cost reduction of substrates used in panels, there is a tendency that the area of the substrate is enlarged, and the unevenness thereof is increased. When an alignment film is formed on such a substrate, in the rubbing treatment, there is still room for improvement. [0004] On the other hand, as a method of changing the alignment treatment to the rubbing method, an alignment treatment utilizing a photoreaction has been proposed. Specifically, a method of imparting alignment energy to a liquid crystal by irradiating a polarized or unpolarized radiation with a polymer film having a specific site that causes a photoreaction such as polyvinyl cinnamate on the surface of a substrate is known (photoalignment method) ). According to this method, it is possible to realize uniform liquid crystal alignment without generating static gas or dust, and it is also possible to improve the viewing angle and the like by dividing the alignment (see Patent Documents 1 and 2). [0005] Furthermore, for liquid crystal cells such as TN (Twisted Nematic) and STN (Super Twisted Nematic), the liquid crystal alignment film must have the function of tilting the liquid crystal molecules to the substrate surface at a predetermined angle (pretilt angle). It is known that in order to express a pretilt angle, a liquid crystal alignment film having an alkyl side chain, a side chain having a steroid skeleton, or a side chain having a ring structure, such as polyamide or polyimide, is used (Patent Documents 3, 4, and 5). . In the alignment treatment using light, the pretilt angle is generally given by irradiating radiation whose incident direction on the substrate surface is inclined to the substrate normal direction (refer to Patent Document 1). [Prior Art Document] [Patent Document] [0006] [Patent Document 1] Japanese Patent Laid-Open No. 6-287453 [Patent Document 2] Japanese Patent Laid-Open No. 9-297313 [Patent Document 3] Japanese Patent Laid-Open No. 05-043687 Publication [Patent Document 4] Japanese Patent Application Laid-Open No. 04-281427 [Patent Document 5] Japanese Patent Application Laid-Open No. 02-223916

[發明所欲解決之課題] 　　[0007] 如上所述，以往，主要液晶配向膜係藉由自聚醯亞胺前驅物之聚醯胺酸或是聚醯亞胺之溶液所成之液晶配向劑所形成，但近年來，在該液晶配向劑中，由於使用於面板之基板之大型化、高精度化、低成本等問題，存在各種之課題，有改進的空間。為了解決這樣的1個課題，提案將下述之式(DA-3)表示之二胺作為原料，使其與四羧酸二酐成分反應所得之聚醯胺酸及/或是包含將該聚醯胺酸醯亞胺化所得之聚醯亞胺之液晶配向劑。 　　[0008]

Figure 02_image003
具備自該液晶配向劑所得之液晶配向膜之液晶顯示元件係在電特性(累積電荷的遺漏等)之方面具有優異之特性。另一方面，使用該液晶配向劑之情況，所得之液晶配向膜著色為黑褐色且失去透明性，結果發現有時具有液晶配向膜的液晶配向元件會受到不好的影響。 　　[0009] 本發明係以提供經由使用上述之二胺化合物作為液晶配向劑中所包含的聚合物之聚醯胺酸之原料，維持優異的特性，另一方面，所得的液晶配向膜不會對著色成黑褐色且失去透明性等之液晶配向元件造成不良影響之液晶配向劑為目的。 [用以解決課題之手段] 　　[0010] 本發明者欲達到上述目的而進行詳細研究之結果，以完成本發明。 　　本發明係以一種液晶配向劑，其特徵為含有：選自含有具有下述式[1]表示之構造之二胺的二胺成分與四羧酸二酐成分反應所得之聚醯胺酸、及將該聚醯胺酸醯亞胺化所得之聚醯亞胺所成之群中的至少1個聚合物為要旨；
Figure 02_image005
(式中，A係表示藉由溫度150~300℃之加熱而置換為氫原子之熱解離性基，苯環所具有之氫原子亦可藉由碳數1~5之烷基、碳數1~5之烷氧基或鹵素基取代，*係表示鍵結處)。 [本發明之效果] 　　[0011] 本發明之液晶配向劑係於將式[1]表示之二胺(以下，亦稱為特定二胺)作為原料之聚醯胺酸及/或是含有將該聚醯胺酸該醯亞胺化所得之聚醯亞胺之方面具有特徵，該聚合物係於N-甲基吡咯烷酮(NMP)等之極性溶劑中之溶解性非常高、聚合時之處理性為良好，且含有該聚合物之液晶配向劑係塗佈･成膜性優異，進而即使經光照射下曝曬，亦可得電壓保持率之降低被抑制之液晶配向膜。 　　此外，本發明之液晶配向劑係將具有特定胺與類似構造之後述之二胺化合物(DA-3)為原料之聚醯胺酸或包含該聚醯亞胺之液晶配向劑相比，所得到的液晶配向膜不著色為黑褐色且具有透明性，故可形成對液晶顯示元件沒不良影響的液晶配向膜。 　　[0012] 對於本發明之液晶配向劑為何可得上述優異效果，大致推測如下所述。即，具有與特定二胺相同之二苯基胺骨架之類似構造之上述式(DA-3)之二胺係於該構造中，存在與1級胺基相較之下，更富含反應性之2級胺基，該2級胺基於與四羧酸二酐成分(其係用於得到聚醯胺酸)之反應過程等中反應，發生不期望的三次元反應。其結果認為所得之反應物產生著色現象同時，液晶配向劑之特性降低。 　　[0013] 另一方面，本發明之特定二胺係於該構造中，具有與上述之式(DA-3)相同之富含反應性之2級胺基，但該2級胺基係以熱解離性基保護，故與四羧酸二酐成分(其係用於得到聚醯胺酸)之反應過程中，不發生不期望的三次元的反應，其結果認為不發生著色現象、液晶配向劑之特性不降低。 　　進而，在本發明之液晶配向劑中，所含有之聚合物之聚醯胺酸或聚醯亞胺具有以熱解離性基保護之胺基，但以該熱解離性基保護之胺基係如後述般，將液晶配向劑塗佈於基板，且燒成後，於形成液晶配向膜之過程中，藉由燒成過程中之加熱，可使其變化為熱解離性基經去保護之胺基。 　　[0014] 經上述去保護之胺基再度回覆反應性，藉由解離產生之胺基藉由於分子內進行反應，從而形成雜環等、生成剛性的側鏈，該側鏈構造作為預傾角良好的誘發部位而發揮作用。再者，熱解離性基脫落後之胺基，該全部不僅使用於上述環化反應，一部分亦使用於分子間反應，由於膜強度之提昇或聚合物之低分子成分交聯，而貢獻於信賴性之提昇。 　　如此般地，使用本發明之特定二胺之聚醯胺酸或聚醯亞胺不易發生磨擦處理時之切削現象，且即使於長時間之高溫、經背光照射等曝光，亦不易產生電壓保持率之降低或離子密度之增加。[Problems to be Solved by the Invention] [0007] As mentioned above, conventionally, the main liquid crystal alignment films are liquid crystal alignment agents formed from polyimide precursors of polyimide or polyimide solutions. However, in recent years, in this liquid crystal aligning agent, there are various problems due to problems such as increase in size, high precision, and low cost of the substrate used for the panel, and there is room for improvement. In order to solve such a problem, a diamine represented by the following formula (DA-3) is proposed as a raw material, and a polyamic acid obtained by reacting it with a tetracarboxylic dianhydride component, and/or a polyamide containing the It is a liquid crystal alignment agent of polyimide obtained by imidization of amide acid. [0008]
Figure 02_image003
The liquid crystal display element provided with the liquid crystal aligning film obtained from this liquid crystal aligning agent has the outstanding characteristic in the point of electric characteristic (the omission of accumulated electric charge, etc.). On the other hand, when this liquid crystal alignment agent is used, the resulting liquid crystal alignment film is colored dark brown and loses transparency. As a result, it has been found that a liquid crystal alignment element having a liquid crystal alignment film may be adversely affected. The present invention is to provide by using the above-mentioned diamine compound as the raw material of the polyamic acid of the polymer contained in the liquid crystal alignment agent, to maintain excellent characteristics, on the other hand, the obtained liquid crystal alignment film will not The purpose is to use a liquid crystal aligning agent that causes adverse effects on liquid crystal aligning elements that are colored dark brown and lose transparency. [MEANS TO SOLVE THE PROBLEM] [0010] The present inventors completed the present invention as a result of detailed research to achieve the above-mentioned object. The present invention is based on a liquid crystal aligning agent characterized by containing: a diamine component selected from the group consisting of a diamine having a structure represented by the following formula [1] and a tetracarboxylic dianhydride component obtained by reacting a polyamic acid; and At least one polymer in the group of polyimides obtained by imidizing the polyimide is the gist;
Figure 02_image005
(In the formula, A represents a thermally dissociable group that is replaced by a hydrogen atom by heating at a temperature of 150 to 300° C. The hydrogen atom of the benzene ring ~5 is substituted by alkoxy or halogen group, * means the bond). [Effects of the Invention] [0011] The liquid crystal aligning agent of the present invention is a polyamic acid containing a diamine (hereinafter, also referred to as a specific diamine) represented by the formula [1] as a raw material and/or containing the The polyimide obtained by the imidization of the polyimide is characterized in that the polymer has a very high solubility in polar solvents such as N-methylpyrrolidone (NMP), and its properties during polymerization are as follows: Good, and the liquid crystal aligning agent containing the polymer is excellent in coating and film-forming properties, and even when exposed to light, a liquid crystal aligning film in which the voltage holding ratio is suppressed can be obtained. In addition, the liquid crystal aligning agent of the present invention is obtained by comparing the liquid crystal aligning agent with a specific amine and a diamine compound (DA-3) described later as a raw material having a specific amine as a raw material or a liquid crystal aligning agent containing the polyimide. The liquid crystal alignment film is not colored dark brown and has transparency, so it can form a liquid crystal alignment film that has no adverse effect on the liquid crystal display element. [0012] The reason why the liquid crystal aligning agent of the present invention can obtain the above-mentioned excellent effects is roughly presumed as follows. That is, the diamine of the above-mentioned formula (DA-3) having a similar structure with the same diphenylamine skeleton as the specific diamine is present in this structure, and is richer in reactivity than the primary amine group The secondary amine group, the secondary amine reacts with the tetracarboxylic dianhydride component (which is used to obtain the polyamide acid) in the reaction process, etc., and an undesired three-dimensional reaction occurs. As a result, it is considered that a coloring phenomenon occurs in the obtained reactant, and the properties of the liquid crystal aligning agent are degraded. On the other hand, the specific diamine of the present invention is in this structure, has the 2-level amino group that is rich in reactivity identical with above-mentioned formula (DA-3), but this 2-level amino group is with heat The dissociative group is protected, so during the reaction with the tetracarboxylic dianhydride component (which is used to obtain polyamide acid), an undesired three-dimensional reaction does not occur, and as a result, it is considered that no coloring phenomenon, liquid crystal aligning agent occurs. The characteristics are not reduced. Furthermore, in the liquid crystal aligning agent of the present invention, the polyamic acid or polyimide of the contained polymer has an amine group protected by a thermally dissociable group, but the amine group protected by the thermally dissociative group is such as As described later, the liquid crystal alignment agent is coated on the substrate, and after firing, in the process of forming the liquid crystal alignment film, by heating during the firing process, it can be changed into an amine group with a thermally dissociable group deprotected . Through the above-mentioned deprotected amine group, the reactivity is returned again, and the amine group generated by dissociation is reacted in the molecule, thereby forming a heterocyclic ring, etc., generating a rigid side chain, and the side chain structure is good as a pretilt angle. act at the inducing site. Furthermore, the amine group after the thermal dissociation group has been removed is not only used in the above-mentioned cyclization reaction, but also partly used in the intermolecular reaction, and contributes to the trust due to the improvement of the membrane strength or the cross-linking of the low molecular components of the polymer. Sexual enhancement. In this way, the polyamide acid or polyimide using the specific diamine of the present invention is not easy to cause cutting phenomenon during friction treatment, and it is not easy to generate voltage retention even under long-term high temperature, exposure to backlight, etc. decrease or increase in ion density.

[實施發明之最佳形態] 　　[0015] ＜本發明之特定二胺＞ 　　作為本發明之液晶配向劑之原料所使用之二胺係具有下述之式[1]表示之構造之二胺；

Figure 02_image007
式[1]中，A係本發明之液晶配向劑之燒成溫度，藉由溫度150~300℃之加熱而置換為氫之熱解離性基。該熱解離性基係可以較佳為170~300℃、特別佳為180~250℃解離為佳。*係表示鍵結處。 　　[0016] 作為熱解離性基係可舉例苄氧基羰基、9-茀基甲氧基羰基、烯丙氧基羰基、第三級丁氧基羰基(亦稱為Boc基)等代表之胺基甲酸酯系之有機基。由解離之效率為佳，於比較低的溫度且解離之時，為無害之氣體之方面看來，Boc基或是9-茀基甲氧基羰基為特別佳。 　　[0017] 式[1]中之苯環所具有之氫原子係可藉由碳數1~5，較佳為1~3之烷基或是烷氧基，或是氯、溴、氟等之鹵素基任意取代。 　　特定二胺所具有之胺基係第一級胺基為佳。再者，可為例如甲基、乙基、丙基、丁基等之比較分子量小的烷基經取代之第二級胺基。 　　特定之二胺之較佳具體例係可舉例以下者，但不限定於此等。尚，式中之Boc係表示tert-丁氧基羰基。
Figure 02_image009
[0018] ＜四羧酸二酐成分＞ 　　欲得本發明之聚醯亞胺前驅物，將下述式[7]表示之四羧酸二酐(亦稱為特定四羧酸二酐)使用作為四羧酸二酐成分之一部分為佳。 　　[0019]
Figure 02_image011
式[7]中，Z1 係碳數4~13之4價之有機基，且有芳香族環狀烴基。具體而言，下述式[7a]~[7k]之任一者表示之基為較佳。 　　[0020]
Figure 02_image013
[0021] 式[7]中，Z1 之較佳的基係由聚合反應性或合成之容易性看來，為式[7a]或是式[7g]表示之基。其中，式[7a]為最佳。 　　使用式[7a]之構造之四羧酸二酐之時，將其為四羧酸二酐成分全體中之20質量%以上者為佳，更佳為30質量%以上。藉由使用於聚醯亞胺前驅物之製造，四羧酸成分之全部亦可作為式[7a]之構造之四羧酸二酐。 　　[0022] 在本發明中，可使用特定四羧酸二酐以外之脂肪族四羧酸二酐或其他之四羧酸成分。 　　作為脂肪族四羧酸二酐係可舉例1,2,3,4-丁烷四羧酸二酐。再者，作為脂環式四羧酸二酐係可舉例1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二苯基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環已烷四羧酸二酐、1,2,3,4-環庚烷四羧酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、3,4-二羧基-1-環己基琥珀酸二酐、2,3,5-三羧基環正戊基乙酸二酐、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐、聯環[3,3,0]辛烷-2,4,6,8-四羧酸二酐、聯環[4,3,0]壬烷-2,4,7,9-四羧酸二酐、聯環[4,4,0]癸烷-2,4,7,9-四羧酸二酐、聯環[4,4,0]癸烷-2,4,8,10-四羧酸二酐、三環[6.3.0.0＜2,6＞]十一烷-3,5,9,11-四羧酸二酐、4-(2,5-二氧四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸二酐、聯環[2,2,2]辛-7-烯-2,3,5,6-四羧酸二酐、5-(2,5-二氧四氫呋喃)-3-甲基-3-環己烷-1,2-二羧酸二酐、四環[6,2,1,1,0,2,7]十二-4,5,9,10-四羧酸二酐、3,5,6-三羧基降冰片烯-2：3，5：6二羧酸二酐等。 　　作為其他之四羧酸成分係可舉例將四羧酸、四羧酸二鹵化物、四羧酸二酐、四羧酸之羧酸基經二烷基酯化之酯化物、將四羧酸二鹵化物之羧酸基經二烷基酯化之酯化物等。 　　[0023] 考慮上述之其他之四羧酸成分為所形成之液晶配向膜之液晶配向性、電壓保持特性及累積電荷等之特性，可使用1種或是2種以上。 　　[0024] ＜本發明之聚合物＞ 　　本發明中之聚合物係意指將聚醯胺酸及/或是該聚醯胺酸醯亞胺化所得之聚醯亞胺。 　　[0025] ＜聚醯胺酸＞ 　　本發明之聚醯胺酸係藉由含有特定二胺之二胺成分與與四羧酸二酐成分之反應所得。 　　為了得到聚醯胺酸，藉由與上述四羧酸二酐成分之反應之二胺成分中，特定二胺之含有比例不特別限制。二胺成分中之特定二胺之含量係可為100%。然而，液晶配向膜所要求之各種之特性，為了使例如液晶之預傾角變大之特性、液晶之垂直配向性提高等特性被滿足，故可併用各種之二胺。因此，可使用於聚合之二胺成分中之特定二胺之含有比例係1~50mol%為佳、特別佳5~30mol%為佳。 　　[0026] 作為上述二胺成分中倂用於特定二胺為未達為100mol%之時，特定二胺以外之二胺(以下，亦稱為其他之二胺)係可舉例脂環式二胺、芳香族-脂肪族二胺、雜環式二胺、脂肪族二胺等。 　　[0027] 作為脂環式二胺之例子，可舉出1,4-二胺基環己烷、1,3-二胺基環己烷、4,4’-二胺基二環己基甲烷、4,4’-二胺基-3,3’-二甲基二環己基胺、異佛爾酮二胺等。 　　作為芳香族二胺類之例子，可舉出o-伸苯基二胺、m-伸苯基二胺、p-伸苯基二胺、2,4-二胺基甲苯、2,5-二胺基甲苯、3,5-二胺基甲苯、1,4-二胺基-2-甲氧基苯、2,5-二胺基-p-二甲苯、1,3-二胺基-4-氯苯、3,5-二胺基安息香酸、1,4-二胺基-2,5-二氯苯、4,4’-二胺基-1,2-二苯基乙烷、4,4’-二胺基-2,2’-二甲基聯苯甲基、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基-3,3’-二甲基二苯基甲烷、2,2’-二胺基芪、4,4’-二胺基芪、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基硫化物、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、4,4’-二胺基二苯甲酮、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、3,5-雙(4-胺基苯氧基)安息香酸、4,4’-雙(4-胺基苯氧基)聯苯甲基、2,2-雙[(4-胺基苯氧基)甲基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、1,1-雙(4-胺基苯基)環己烷、α、α’-雙(4-胺基苯基)-1,4-二異丙基苯、9,9-雙(4-胺基苯基)芴、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4’-二胺基二苯基胺、2,4-二胺基二苯基胺、1,8-二胺基萘基、1,5-二胺基萘基、1,5-二胺基蒽醌、1,3-二胺基芘、1,6-二胺基芘、1,8-二胺基芘、2,7-二胺基芴、1,3-雙(4-胺基苯基)四甲基二矽氧烷、聯苯胺、2,2’-二甲基聯苯胺、1,2-雙(4-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,4-雙(4-胺基苯基)丁烷、1,5-雙(4-胺基苯基)戊烷、1,6-雙(4-胺基苯基)己烷、1,7-雙(4-胺基苯基)庚烷、1,8-雙(4-胺基苯基)辛烷、1,9-雙(4-胺基苯基)壬烷、1,10-雙(4-胺基苯基)癸烷、1,3-雙(4-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,10-雙(4-胺基苯氧基)癸烷、二(4-胺基苯基)丙烷-1,3-二酸酯、二(4-胺基苯基)丁烷-1,4-二酸酯、二(4-胺基苯基)戊烷-1,5-二酸酯、二(4-胺基苯基)己烷-1,6-二酸酯、二(4-胺基苯基)庚烷-1,7-二酸酯、二(4-胺基苯基)辛烷-1,8-二酸酯、二(4-胺基苯基)壬烷-1,9-二酸酯、二(4-胺基苯基)癸烷-1,10-二酸酯、1,3-雙[4-(4-胺基苯氧基)苯氧基]丙烷、1,4-雙[4-(4-胺基苯氧基)苯氧基]丁烷、1,5-雙[4-(4-胺基苯氧基)苯氧基]戊烷、1,6-雙[4-(4-胺基苯氧基)苯氧基]己烷、1,7-雙[4-(4-胺基苯氧基)苯氧基]庚烷、1,8-雙[4-(4-胺基苯氧基)苯氧基]辛烷、1,9-雙[4-(4-胺基苯氧基)苯氧基]壬烷、1,10-雙[4-(4-胺基苯氧基)苯氧基]癸烷等。 　　[0028] 作為芳香族-脂肪族二胺之例子，可舉出3-胺基苯甲基胺、4-胺基苯甲基胺、3-胺基-N-甲基苯甲基胺、4-胺基-N-甲基苯甲基胺、3-胺基苯乙基胺、4-胺基苯乙基胺、3-胺基-N-甲基苯乙基胺、4-胺基-N-甲基苯乙基胺、3-(3-胺基丙基)苯胺、4-(3-胺基丙基)苯胺、3-(3-甲基胺基丙基)苯胺、4-(3-甲基胺基丙基)苯胺、3-(4-胺基丁基)苯胺、4-(4-胺基丁基)苯胺、3-(4-甲基胺基丁基)苯胺、4-(4-甲基胺基丁基)苯胺、3-(5-胺基戊基)苯胺、4-(5-胺基戊基)苯胺、3-(5-甲基胺基戊基)苯胺、4-(5-甲基胺基戊基)苯胺、2-(6-胺基萘基)甲基胺、3-(6-胺基萘基)甲基胺、2-(6-胺基萘基)乙基胺、3-(6-胺基萘基)乙基胺等。 　　[0029] 作為雜環式二胺之例子，可舉出2,6-二胺基吡啶、2,4-二胺基吡啶、2,4-二胺基-1,3,5-三嗪、2,7-二胺基二苯并呋喃、3,6-二胺基咔唑、2,4-二胺基-6-異丙基-1,3,5-三嗪、2,5-雙(4-胺基苯基)-1,3,4-噁二唑等。 　　作為脂肪族二胺之例子，可舉出1,2-二胺基乙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,3-二胺基-2,2-二甲基丙烷、1,6-二胺基-2,5-二甲基己烷、1,7-二胺基-2,5-二甲基庚烷、1,7-二胺基-4,4-二甲基庚烷、1,7-二胺基-3-甲基庚烷、1,9-二胺基-5-甲基庚烷、1,12-二胺基十二烷、1,18-二胺基十八烷、1,2-雙(3-胺基丙氧基)乙烷等。 　　[0030] 可併用於側鏈具有烷基、含有氟之烷基、芳香環、脂肪族環、雜環或彼等所成的大環狀取代體之二胺化合物。具體可舉出下述式[DA1]~[DA26]所示二胺；
Figure 02_image015
(R6 為具有碳數1~22之烷基或者含有氟之烷基) 　　[0031]
Figure 02_image017
(S5 表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2 -、-O-、-CO-或-NH-，R6 表示具有碳數1~22之烷基或者含有氟之烷基) 　　[0032]
Figure 02_image019
(S6 表示-O-、-OCH2 -、-CH2 O-、-COOCH2 -或-CH2 OCO-，R7 具有碳數1~22之烷基、烷氧基、含有氟之烷基或者含有氟之烷氧基) 　　[0033]
Figure 02_image021
(S7 表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2 -、-CH2 OCO-、-CH2 O-、-OCH2 -或-CH2 -，R8 具有碳數1~22之烷基、烷氧基、含有氟之烷基或者含有氟之烷氧基) 　　[0034]
Figure 02_image023
(S8 表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2 -、-CH2 OCO-、-CH2 O-、-OCH2 -、-CH2 -、-O-或-NH-，R9 係氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基) 　　[0035]
Figure 02_image025
Figure 02_image027
(R10 表示碳數3~12的烷基，1,4-環伸己基順-反異構性各為反式體)。 　　[0036]
Figure 02_image029
[0037]
Figure 02_image031
Figure 02_image033
[0038] 對於藉由光進行配向處理之情況中，藉由併用特定二胺與上述[DA-1]~[DA-26]的二胺，可得到更安定預傾角為佳。作為可併用的較佳二胺，以式[DA-10]~[DA-26]為佳，較佳為[DA-10]~[DA-16]的二胺。此等二胺之較佳含有量雖無特別限定，以二胺成分中之5~50 mol%為佳，由印刷性之觀點來看以5~30 mol%為較佳。 　　又，亦可併用以下二胺。 　　[0039]
Figure 02_image035
(m表示0~3的整數，式[DA-34]中，n係1~5的整數)。 　　藉由含有式[DA-27]、式[DA-28]等二胺，可提高作為液晶配向膜時的電壓保持特性，式[DA-29]~[DA-34]的二胺對於蓄積電化之減低有效果。 　　[0040] 再者，如下述式[DA-35]所示，二胺基矽氧烷等亦可舉出作為其他二胺。
Figure 02_image037
(m為1~10的整數)。 　　其他二胺配合作為液晶配向膜時的液晶配向性、電壓保持特性、累積電荷等特性，可混合1種類或2種類以上後使用。 　　[0041] ＜聚醯胺酸之製造＞ 　　藉由四羧酸二酐成分與二胺成分之反應，得到本發明之聚醯胺酸的方法，可使用已知手法。一般為將四羧酸二酐成分與二胺成分在有機溶劑中進行反應之方法。四羧酸二酐成分與二胺之反應在有機溶劑中比較容易進行，且有著不會產生副產物的優點。 　　[0042] 與為使用於四羧酸二酐成分與二胺之反應的有機溶劑，僅為可溶解所生成之聚醯胺酸者即可，並無特別限定。以下舉出其具體例。 　　可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙酮、甲基異戊基酮、甲基異丙酮、甲基賽路蘇、乙基賽路蘇、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-第三丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸乙二酯、碳酸丙二酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-乙氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺等。此等可單獨使用，亦可混合後使用。且即使為不溶解聚醯胺酸之溶劑，在不析出所生成之聚醯胺酸的範圍內，亦可混合於上述溶劑中使用。 　　[0043] 又，有機溶劑中之水分會阻礙聚合反應，且成為水解所生成之聚醯胺酸的原因，故有機溶劑儘可能使用經過脱水乾燥者為佳。 　　將四羧酸二酐成分與二胺成分在有機溶劑中進行反應時，攪拌將二胺成分分散或溶解於有機溶劑的溶液，將四羧酸二酐成分直接或分散或溶解於有機溶劑後添加之方法、相反地於將四羧酸二酐成分分散或溶解於有機溶劑之溶液中添加二胺成分之方法、交互添加四羧酸二酐成分與二胺成分之方法等，使用此等任一方法皆可。又，四羧酸二酐成分或二胺成分係由複數種化合物所成時，可於預先混合之狀態下進行反應，或亦可各別順序進行反應，且各別反應之低分子量體可經混合反應後作為高分子量體。 　　[0044] 使四羧酸二酐成分與二胺成分反應之溫度可選擇-20~150℃之任意溫度，但較佳為-5~100℃之範圍。又，反應可在任意濃度下進行，但濃度過低時，高分子量之聚合物的獲得變的困難，濃度過高時，反應液之黏性會過高，而難以均勻攪拌，故四羧酸二酐成分與二胺成分之反應溶液中的合計濃度以1~50質量%為佳，較佳為5~30質量%。反應初期在高濃度下進行，其後可追加有機溶劑。 　　對於聚醯胺酸之聚合反應，四羧酸二酐成分之合計莫耳數與二胺成分之合計莫耳數的比以0.8~1.2為佳，以0.9~1.1為較佳。與一般聚縮合反應同樣地，該莫耳比越接近1.0，所生成之聚醯胺酸的分子量越大。 　　[0045] ＜聚醯亞胺之製造＞ 　　本發明的聚醯亞胺係為將前述聚醯胺酸經脱水閉環後所得之聚醯亞胺，可作為欲得到液晶配向膜之聚合物使用。 　　對於本發明之聚醯亞胺，醯胺酸基之脱水閉環率(醯亞胺化率)無須一定要100%，可對應用途或目的做任意調整。 　　作為使聚醯胺酸醯亞胺化之方法，可舉出將聚醯胺酸之溶液直接加熱之熱醯亞胺化法、及於聚醯胺酸之溶液添加觸媒的觸媒醯亞胺化法。 　　將聚醯胺酸在溶液中使其熱醯亞胺化時的溫度為100~400℃，較佳為120~250℃，一邊將藉由醯亞胺化反應所生成之水排除於系統外，一邊進行為佳。 　　[0046] 聚醯胺酸的觸媒醯亞胺化為，可於聚醯胺酸的溶液中添加鹼性觸媒與酸酐，在-20~250℃，較佳為在0~180℃下藉由攪拌而進行。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的1~50莫耳倍，較佳為3~30莫耳倍。作為鹼性觸媒，可舉出吡啶、三乙胺、三甲胺、三丁胺、三辛胺等，其中亦以吡啶因具有適合於進行反應之鹼性故較佳。作為酸酐，可舉出乙酸酐、偏苯三甲酸酐、均苯四甲酸二酐等，其中亦以使用乙酸酐時反應終了後的純化容易進行故較佳。藉由觸媒醯亞胺化之醯亞胺化率可藉由調節觸媒量、反應溫度、反應時間等而控制。 　　[0047] 含於本發明之液晶配向劑的聚合物之分子量，若考慮到所得之塗膜強度、塗膜形成時之作業性、及塗膜之均勻性時，以GPC(Gel Permeation Chromatography)法所測定之重量平均分子量以5,000~1,000,000為佳，較佳為10,000~150,000。 　　[0048] ＜液晶配向劑＞ 　　本發明的液晶配向劑係為形成液晶配向膜時的塗佈液，其為欲形成樹脂被膜時的樹脂成分溶解於有機溶劑之溶液。於此，前述樹脂成分含包含選自上述本發明的聚合物之至少一種聚合物。樹脂成分的液晶配向劑中之含有量以1~20質量%為佳，較佳為3~15質量%，特佳為3~10質量%。 　　樹脂成分可皆為本發明之聚合物，亦可混合除此以外的其他聚合物。此時，樹脂成分中之前述其他聚合物的含有量以0.5~15質量%為佳，較佳為1~10質量%。 　　該其他聚合物，例如作為與四羧酸二酐成分反應之二胺成分，可舉出使用特定二胺化合物以外的二胺化合物所得之聚醯胺酸或聚醯亞胺等。 　　[0049] 使用於本發明的液晶配向劑之有機溶劑僅為可溶解樹脂成分的有機溶劑即可，並無特別限定。以下舉出其具體例。 　　可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯吡咯烷酮、二甲基亞碸、四甲基脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、3-甲氧基-N,N-二甲基丙烷醯胺、3-乙氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺、1,3-二甲基-咪唑烷酮、乙基戊基酮、甲基壬基酮、甲基乙酮、甲基異戊基酮、甲基異丙酮、環己酮、碳酸乙二酯、碳酸丙二酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮等。此等可單獨使用，亦可混合後使用。 　　[0050] 本發明的液晶配向處理劑可含有上述以外之成分。作為該例子有塗佈液晶配向劑時的提高膜厚均勻性或表面平滑性之溶劑多物質等，提高液晶配向膜與基板之密著性之化合物等。 　　作為提高膜厚均勻性或表面平滑性之溶劑(弱溶劑)的具體例，可舉出以下者。 　　[0051] 例如可舉出異丙醇、甲氧基甲基戊醇、甲基賽路蘇乙基賽路蘇、丁基賽路蘇、甲基賽路蘇乙酸酯、乙二醇二乙醚乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-第三丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、二丙二醇二甲基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁酮、甲基環己烯、丙基醚、二己基醚、1-己醇、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、2-丁氧基-1-丙醇、2,6-二甲基-4-庚醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊酯等具有低表面張力之溶劑等。 　　此等弱溶劑可使用1種類亦可使用混合複數種類者。使用上述溶劑時，液晶配向劑所包含之溶劑全體的5~80質量%為佳，較佳為20~60質量%。 　　[0052] 作為提高膜厚的均勻性或表面平滑性之化合物，可舉出氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。 　　更具體例如可舉出Eftop EF301、EF303、EF352 (TOHKEM PRODUCTS CORP製)、Megafac F171、F173、R-30(大日本油墨公司製)、Fluorad FC430、FC431(住友3M公司製)、Asahiguard AG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。此等界面活性劑之使用比率對於液晶配向劑所含之樹脂成分的100質量份而言，較佳為0.01~2質量份，更佳為0.01~1質量份。 　　[0053] 作為提高液晶配向膜與基板之密著性的化合物之具體例，可舉出以下所示官能性矽烷含有化合物、環氧基含有化合物等。 　　例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-醯脲丙基三甲氧基矽烷、3-醯脲丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙基三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二氧化丙烯醚、聚乙二醇二氧化丙烯醚、丙二醇二氧化丙烯醚、三丙二醇二氧化丙烯醚、聚丙二醇二氧化丙烯醚、新戊二醇二氧化丙烯醚、1,6-己二醇二氧化丙烯醚、甘油二氧化丙烯醚、2,2-二溴新戊二醇二氧化丙烯醚、1,3,5,6-四氧化丙烯基-2,4-己二醇、N,N,N’,N’,-四氧化丙烯基-間二甲苯二胺、1,3-雙(N,N-二氧化丙烯基胺基甲基)環己烷、N,N,N’,N’,-四氧化丙烯基-4,4’-二胺基二苯基甲烷等。 　　[0054] 除進一步提高基板與膜之密著性以外，以欲防止因背光所引起的電氣特性降低等為目的，含有如以下之酚醛塑料系的添加劑為佳。具體如以下所示酚醛塑料系添加劑。
Figure 02_image039
[0055] 使用提高與基板之密著性的化合物時，該使用量對於樹脂成分100質量份而言，以0.1~30質量份為佳，較佳為1~20質量份。使用量若未達0.1質量份時，無法期待密著性之提高效果，若比30質量份多時，有時液晶的配向性會變差。 　　本發明的液晶配向劑中，除上述以外，若為不損害本發明的效果的範圍內，以改變液晶配向膜之介電率、導電性等電氣特性為目的，亦可添加提高使其成為介電體、導電物質，進而為液晶配向膜時的膜硬度或緻密度為目的之交聯性化合物等。 　　[0056] ＜液晶配向膜及液晶顯示元件＞ 　　本發明的液晶配向劑塗佈於基板上並燒成後，以摩擦處理或光照射等進行配向處理，或在垂直配向用途等上無經配向處理而作為液晶配向膜使用。此時，作為使用的基板為透明性高的基板即可，並無特別限定，可使用玻璃基板、丙烯基板、聚碳酸酯基板等塑質基板等。又，使用形成有液晶驅動用的ITO電極等之基板，從可使製程簡單化的點來看為佳。又，在反射型液晶顯示元件中若為單面基板，亦可使用矽晶圓等不透明物，此時的電極亦可使用反射鋁等光之材料。 　　液晶配向劑的塗佈方法並無特別限定，但一般在工業上進行網版印刷、柯式印刷、揉版印刷、噴射印刷等方法。作為其他塗佈方法，有浸漬、輥塗佈、縫隙塗佈、旋轉塗佈器等配合目的而進行。 　　[0057] 將液晶配向劑塗佈於基板上後之燒成可藉由加熱板等加熱手段，在50~300℃，較佳為80~250℃下進行，使溶劑蒸發後形成塗膜。燒成後所形成之塗膜厚度若過厚時，由液晶顯示元件的消費電力之層面來看變的不利，過薄時有時液晶顯示元件之信賴性會降低，故較佳為5~300nm，更佳為10~100nm。將液晶呈水平配向或傾斜配向時，將燒成後的塗膜進行摩擦或偏光紫外線照射等處理。 　　本發明的液晶顯示元件係為藉由上述手法由本發明的液晶配向劑得到附有液晶配向膜之基板後，以公知方法製作液晶晶胞，作為液晶顯示元件者。 　　[0058] 若要舉出液晶晶胞製作之一例，準備形成有液晶配向膜之1對基板，於單面基板的液晶配向膜上散布間隔物，使液晶配向膜面成為內側，貼合另一面的基板，將液晶減壓注入後封止之方法，或於散佈間隔物的液晶配向膜面滴入液晶後貼合基板使其封止的方法等可例示。間隔物厚度較佳為1~30μm，更佳為2~10μm。 [實施例] 　　[0059] 以下對於本發明，為了更詳細說明而舉出實施例，但本發明內容並未限定於此等實施例。實施例等使用之縮寫、及特性評估方法如下。 　　[0060]
Figure 02_image041
[0061] ＜有機溶劑＞ 　　NMP：N-甲基-2-吡咯啶酮、BCS：丁基溶纖劑 ＜添加劑＞ 　　LS-4668：3-環氧丙氧基丙基三乙氧基矽烷 　　[0062] ＜黏度測定＞ 　　溶液的黏度為使用E型黏度計TVE-22H(東機產業公司製)，於溫度25℃中，測定樣本量1.1mL、錐形轉子TE-1(1°34’、R24)。 　　[0063] ＜液晶顯示元件之製作＞ 　　首先，準備附電極之基板。基板係長30mm×寬35mm之長方形、厚度為0.7mm之玻璃基版。在基板上形成有具備作為第1層之構成對向電極的固體狀的圖型的IZO電極。在第1層之對向電極上形成有以CVD法成膜的SiN(氮化矽)膜作為第2層。第2層的SiN膜之膜厚為500nm，且具有作為層間絕緣膜的機能。第2層的SiN膜上配置將IZO膜圖型化而形成的梳齒狀的像素電極作為第3層，形成第1像素及第2像素的2個像素。各像素的尺寸為長10mm、寬約5mm。此時，第1層的對向電極與第3層的像素電極係以第2層的SiN膜之作用而電絕緣。 　　[0064] 第3層的像素電極具有複數排列中央部分彎曲的「く字」形狀的電極要素所構成的梳齒狀的形狀。各電極要素的寬方向的寬為3μm，且電極要素間之間隔為6μm。形成各像素的像素電極由中央部分彎曲的「く字」形狀電極要素經多個排列而構成，故各像素的形狀不是長方形狀，而具備與電極要素同樣地在中央部分發生彎曲的、類似於粗體的「く字」的形狀。並且，各像素以其中央的彎曲部分為界被上下分割，具有彎曲部分上側的第1區域和下側的第2區域。 　　[0065] 比較各像素的第1區域與第2區域時，構成此等的像素電極的電極要素的形成方向不同。即，將後述液晶配向膜的摩擦方向作為基準時，在像素的第1區域中，以呈現+10°的角度(順時針)的方式形成像素電極的電極要素，在像素的第2區域中，以呈現-10°的角度(順時針)的方式形成像素電極的電極要素。藉由此，各像素的第1區域與第2區域如下構成：透過在像素電極與對向電極之間施加電壓而誘發的液晶的、基板面內的旋轉動作(平面切換)的方向互為相反方向。 　　[0066] 接著，將液晶配向劑以孔徑1.0μm的過濾器進行過濾後，各自旋轉塗佈在經準備之上述附電極之基板與作為對向基板之背面形成有ITO膜且具有高度4μm的柱狀之間隔件之玻璃基板。接著，在80℃的加熱板上進行2分鐘乾燥後、在230℃進行20分鐘燒成，在各基板上得到膜厚60nm的聚醯亞胺膜。於該聚醯亞胺膜上，以特定之磨擦方向，藉由人造絲布實施摩擦(以輥徑120mm、滾筒旋轉數500rpm、移動速度30mm/sec、壓入量0.3mm)處理後，在純水中進行1分鐘超音波照射，在80℃進行10分鐘乾燥，作為液晶配向膜。 　　[0067] 使用所得之附液晶附配向膜的2種類的基板，以各自摩擦方向反向平行之方式組合，留下液晶注入口而將周圍密封，製作液晶晶胞間隙為3.5μm的空液晶晶胞。在該空液晶晶胞使液晶(MLC-3019、默克公司製)在常溫真空注入後，將注入口密封而作成反向平行配向的液晶晶胞。得到的液晶晶胞構成FFS模式液晶顯示元件。之後，使所得到之液晶晶胞在120℃進行1小時加熱，放置一晩後用於各評估。 　　[0068] ＜液晶配向性之評估＞ 　　使用上述製作之液晶晶胞，於60℃之恆溫環境下，以頻率30Hz，施加10VPP之交流電壓168小時。接著，使液晶晶胞之像素電極與對向電極之間為短路的狀態，直接於室溫中放置一天。放置之後，將液晶晶胞設置於以偏光軸垂直的方式配置的兩片偏光板之間，在未施加電壓的狀態下預先點亮背光，調整液晶晶胞的配置角度，以使透射光的亮度達到最小。並且，使液晶晶胞從第1像素的第2區域為最暗的角度旋轉至第1區域為最暗的角度時的旋轉角度作為角度△來算出。第2像素亦同樣地，對第2區域與第1區域進行對比，算出同樣的角度△。然後，將第1像素與第2像素的角度△值的平均值作為液晶晶胞之角度△而算出。 　　液晶晶胞之角度△越小，液晶配向膜的液晶配向性越高。 　　[0069] ＜加德納色度(Gardner Color Scale)＞ 　　將所得到之液晶配向劑於室溫下放置24小時後，測定加德納色度。色調所表示之加德納色度係依據日本工業規格JIS K 0071-2進行測定。意指加德納色度越小，所得到之液晶配向劑之色越淡。 　　[0070] (合成例1) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 0.773g(2.58mmol)、DA-4 2.54g(10.4mmol)，加入NMP46.5g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，在室溫下攪拌2小時後，在50℃下進行攪拌24小時，得到聚醯胺酸溶液(PAA-1、黏度：510.7mPa‧s)。 　　[0071] (合成例2) 　　使附攪拌裝置之50ml的四口燒瓶置成為氮氣氛，量取DA-1 1.55g(5.18mmol)及DA-4為1.90g(7.78mmol)，加入NMP54.6g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-2、黏度：505.4mPa･s)。 　　[0072] (合成例3) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 0.773g(2.58mmol) 、DA-4 2.22g(9.09mmol)及DA-6 0.724g(1.30mmol)，加入NMP46.5g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-3、黏度： 505.4mPa･s)。 　　[0073] (合成例4) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 0.773g(2.58mmol)及DA-5 2.98g(10.4mmol)，加入NMP47.4g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-4、黏度：525.3mPa･s)。 　　[0074] (合成例5) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 1.56g(5.21mmol)及DA-5為2.23g(7.79mmol)，加入NMP47.7g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-5、黏度：510.4mPa･s)。 　　[0075] (合成例6) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 0.778g(2.60mmol)、DA-5 2.60g(9.08mmol)及DA-6 0.724g(1.30mmol)，加入NMP50.0g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-6、黏度：498.1mPa･s)。 　　[0076] (比較合成例1) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-3 2.79g(14.0mmol)，加入NMP47.1g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-1 2.44g(12.4mmol)，於15℃下攪拌2小時後，得到聚醯胺酸溶液(PAA-7、黏度：121.1mPa･s)。 　　[0077] (比較合成例2) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-3 0.518g(2.60mmol)及DA-4 2.51g(10.3mmol)，加入NMP42.3g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-8、黏度：531.5mPa･s)。 　　[0078] (比較合成例3) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-3 1.04g(5.21mmol) 及DA-4 1.91g(7.82mmol)，加入NMP41.4g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-9、黏度：542.2mPa･s)。 　　[0079] (比較合成例4) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-3 0.51g(2.56mmol)及DA-5 2.97g(10.4mmol)，加入NMP47.2g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-10、黏度：547.1mPa･s)。 　　[0080] (比較合成例5) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-3 0.51g(2.56mmol) 及DA-5 2.97g(10.4mmol)，加入NMP47.2g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-2 2.71g(12.4mmol)，於室溫下攪拌2小時後，在50℃下進行24小時攪拌，得到聚醯胺酸溶液(PAA-11、黏度：547.1mPa･s)。 　　[0081] (比較合成例6) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-1 3.29g(11.0mmol)，加入NMP46.1g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加CA-1 1.91g(9.7mmol)，在15℃下進行2小時攪拌後，得到聚醯胺酸溶液(PAA-12、黏度：121.1mPa･s)。 　　[0082] (比較合成例7) 　　使附攪拌裝置之50ml的四口燒瓶成為氮氣氛，量取DA-2 2.77g(13.0mmol)，加入NMP46.1g，一邊送入氮一邊攪拌使其溶解。將該二胺溶液邊攪拌邊添加酸二酐(CA-1) 2.34g(11.9mmol)，在15℃下進行2小時攪拌後，得到聚醯胺酸溶液(PAA-13黏度：110.4mPa･s)。 　　[0083] ＜實施例1~6及比較例1~7＞ 　　各別分取上述之合成例1~6及比較合成例1~7中所得到之10~12%之聚醯胺酸溶液PAA-1~PAA13 24.0g，對於各別，加入NMP5.6g、BCS8.00g及包含LS-4668 1重量%之混合溶液2.4g一邊攪拌，接著，藉由於室溫下攪拌2小時，得到各別之液晶配向劑(AL-1)~(AL-13)。 　　[0084] ＜評估＞ 　　對於上述所得到之實施例1~6及比較例1~7之各自之液晶配向劑(AL-1)~(AL-13)，以上述記載的，進行液晶配向性及加德納色度之評估。結果表示於表1。表1中，加德納色度為「-」係意指未測定。 　　[0085]
Figure 02_image043
[產業上之可利用性] 　　[0086] 本發明之液晶配向劑係可使用於被要求高精度化、低成本化之大型液晶顯示元件或智能手機、手機等之移動用液晶顯示元件等之廣泛的領域。 　　又，2016年8月30日申請的日本專利申請2016-168461號說明書、申請專利範圍、圖面及摘要的全內容引用於此，作為本發明說明書之揭示。[Best Mode for Carrying out the Invention] [0015] <Specific Diamine of the Present Invention> The diamine used as the raw material of the liquid crystal aligning agent of the present invention is a diamine having a structure represented by the following formula [1];
Figure 02_image007
In formula [1], A is the firing temperature of the liquid crystal aligning agent of the present invention, and is substituted with a thermally dissociable group of hydrogen by heating at a temperature of 150 to 300°C. The thermally dissociable base system can be preferably dissociated at 170 to 300°C, particularly preferably at 180 to 250°C. *Denotes a bond. As the thermal dissociation group system, can be exemplified the amino group represented by benzyloxycarbonyl, 9-inylmethoxycarbonyl, allyloxycarbonyl, third-order butoxycarbonyl (also known as Boc group) etc. Formate-based organic group. Since the dissociation efficiency is good, the Boc group or the 9-phenylenylmethoxycarbonyl group is particularly preferable from the viewpoint of being a harmless gas at a relatively low temperature when dissociated. The hydrogen atom system that the benzene ring in the formula [1] has can be by carbon number 1～5, preferably the alkyl group of 1～3 or alkoxy group, or chlorine, bromine, fluorine etc. The halogen group is optionally substituted. The amine group of the specific diamine is preferably the first-order amine group. Furthermore, it can be a second-order amine group substituted by an alkyl group with relatively small molecular weight such as methyl, ethyl, propyl, and butyl. Preferable specific examples of the specific diamine include, but are not limited to, the following. Still, Boc in the formula represents tert-butoxycarbonyl.
Figure 02_image009
<Tetracarboxylic dianhydride component> To obtain the polyimide precursor of the present invention, tetracarboxylic dianhydride (also referred to as specific tetracarboxylic dianhydride) represented by the following formula [7] is used as A part of the tetracarboxylic dianhydride component is preferable. [0019]
Figure 02_image011
In formula [7], Z 1 is a tetravalent organic group having 4 to 13 carbon atoms, and has an aromatic cyclic hydrocarbon group. Specifically, the group represented by any one of the following formulae [7a] to [7k] is preferable. [0020]
Figure 02_image013
[0021] In the formula [7], the preferred group of Z 1 is the group represented by the formula [7a] or the formula [7g] in view of the polymerization reactivity or the ease of synthesis. Among them, formula [7a] is the best. When using the tetracarboxylic dianhydride of the structure of Formula [7a], it is preferable that it is 20 mass % or more in the whole tetracarboxylic dianhydride component, More preferably, it is 30 mass % or more. By using it for manufacture of a polyimide precursor, all the tetracarboxylic acid components can be used as the tetracarboxylic dianhydride of the structure of formula [7a]. In the present invention, aliphatic tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride or other tetracarboxylic acid components can be used. As aliphatic tetracarboxylic dianhydride series, 1,2,3,4- butane tetracarboxylic dianhydride is mentioned. In addition, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3, 1,2,3,4-tetramethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, 4-Cyclobutanetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid di Anhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclo-n-pentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetra Hydro-1-naphthalene succinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2, 4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane- 2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, 4-(2,5 -Dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, bicyclo[2,2,2]oct-7-ene-2,3 ,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo[6,2 ,1,1,0,2,7] Dodec-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornene-2:3,5:6 dicarboxylic acid Dianhydride, etc. Examples of other tetracarboxylic acid components include tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic dianhydride, esterified product of dialkyl-esterified carboxylic acid group of tetracarboxylic acid, tetracarboxylic acid dihalide The carboxylic acid group of the halide is esterified by dialkyl esterification, etc. [0023] Considering that the above-mentioned other tetracarboxylic acid components are the characteristics of the liquid crystal alignment film formed, such as liquid crystal alignment, voltage retention characteristics, and accumulated charge, one or more of them can be used. <Polymer of the present invention> The polymer in the present invention means a polyimide obtained by imidizing a polyamic acid and/or the polyamic acid. <Polyamic acid> The polyamic acid of the present invention is obtained by reacting a diamine component containing a specific diamine and a tetracarboxylic dianhydride component. In order to obtain a polyamic acid, in the diamine component by the reaction with the said tetracarboxylic dianhydride component, the content rate of a specific diamine is not specifically limited. The content of the specific diamine in the diamine component may be 100%. However, in order to satisfy the various properties required for the liquid crystal alignment film, such as the property of increasing the pretilt angle of the liquid crystal and the improvement of the vertical alignment property of the liquid crystal, various diamines can be used in combination. Therefore, the content ratio of the specific diamine in the diamine component that can be used for polymerization is preferably 1 to 50 mol %, particularly preferably 5 to 30 mol %. As the above-mentioned diamine component, when the specific diamine is less than 100 mol%, diamines other than the specific diamine (hereinafter, also referred to as other diamines) can be exemplified by alicyclic diamines , Aromatic-aliphatic diamines, heterocyclic diamines, aliphatic diamines, etc. As an example of alicyclic diamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, isophoronediamine, etc. Examples of aromatic diamines include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 2,4-diaminotoluene, 2,5-diamine Aminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4 -Chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4 ,4'-Diamino-2,2'-dimethylbiphenylmethyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diamino Stilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Diphenyl bismuth, 3,3'-diaminodiphenyl bismuth, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4' -Bis(4-aminophenoxy)biphenylmethyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfanium, Bis[4-(4-Aminophenoxy)phenyl]Tone, 1,1-Bis(4-aminophenyl)cyclohexane, α, α'-Bis(4-aminophenyl)- 1,4-Diisopropylbenzene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4- Aminophenyl) hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthyl, 1,5-diamine Naphthyl, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis(4-aminophenyl)tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane , 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1, 6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9- Bis(4-aminophenyl)nonane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis( 4-Aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis (4-Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy) yl)octane, 1,9-bis(4-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane- 1,3-Diester, bis(4-aminophenyl)butane-1,4-dioate, bis(4-aminophenyl)pentane-1,5-dioate, bis(4-aminophenyl)pentane-1,5-dioate 4-Aminophenyl)hexane-1,6-dioate, bis(4-aminophenyl)heptane-1,7-dioate, bis(4-aminophenyl)octane- 1,8-Diester, bis(4-aminophenyl)nonane-1,9-dioate, bis(4-aminophenyl)decane-1,10-dioate, 1, 3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis [4-(4-Aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4 -(4-Aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-( 4-aminophenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, and the like. Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-aminobenzylamine, -Amino-N-methylphenethylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-aminophenethylamine N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-( 3-Methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4 -(4-Methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline , 4-(5-methylaminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)methylamine naphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, and the like. As the example of heterocyclic diamine, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-Diaminodibenzofuran, 3,6-Diaminocarbazole, 2,4-Diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl)-1,3,4-oxadiazole and the like. Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-Diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethyl Heptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane , 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, etc. [0030] It can be used in combination with a diamine compound having an alkyl group in the side chain, an alkyl group containing fluorine, an aromatic ring, an aliphatic ring, a heterocyclic ring or a macrocyclic substituent formed by them. Specifically, diamines represented by the following formulae [DA1] to [DA26] can be mentioned;
Figure 02_image015
(R 6 is an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine) [0031]
Figure 02_image017
(S 5 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO- or -NH-, R 6 represents an alkyl group with a carbon number of 1 to 22 or Alkyl containing fluorine) [0032]
Figure 02_image019
(S 6 represents -O-, -OCH 2 -, -CH 2 O-, -COOCH 2 - or -CH 2 OCO-, R 7 has an alkyl group with a carbon number of 1 to 22, an alkoxy group, and an alkane containing fluorine group or alkoxy group containing fluorine) [0033]
Figure 02_image021
(S 7 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 - or -CH 2 -, R 8 has C1-22 alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group) [0034]
Figure 02_image023
(S 8 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, -CH 2 -, -O- or -NH-, R 9 is a fluoro group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a methyl group, an acetyl group, an acetoxy group or a hydroxyl group) [0035]
Figure 02_image025
Figure 02_image027
(R 10 represents an alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of 1,4-cyclohexylene is a trans form). [0036]
Figure 02_image029
[0037]
Figure 02_image031
Figure 02_image033
[0038] In the case of performing the alignment treatment by light, it is preferable that a more stable pretilt angle can be obtained by using the specific diamine in combination with the diamines of the above [DA-1] to [DA-26]. As a preferable diamine which can be used together, the diamine of formula [DA-10] - [DA-26] is preferable, and [DA-10] - [DA-16] are preferable. The preferable content of these diamines is not particularly limited, but is preferably 5 to 50 mol % in the diamine component, and more preferably 5 to 30 mol % from the viewpoint of printability. In addition, the following diamines may be used in combination. [0039]
Figure 02_image035
(m represents an integer of 0 to 3, and in formula [DA-34], n represents an integer of 1 to 5). By containing diamines such as formula [DA-27] and formula [DA-28], the voltage retention characteristics when used as a liquid crystal alignment film can be improved, and the diamines of formula [DA-29]~[DA-34] The reduction is effective. [0040] Furthermore, as shown in the following formula [DA-35], diaminosiloxane and the like can also be cited as other diamines.
Figure 02_image037
(m is an integer from 1 to 10). Other diamines can be used by mixing one type or two or more types in combination with properties such as liquid crystal alignment, voltage retention characteristics, and accumulated charge when used as a liquid crystal alignment film. <Production of Polyamic Acid> A known method can be used for the method of obtaining the polyamic acid of the present invention by the reaction of the tetracarboxylic dianhydride component and the diamine component. Generally, it is a method of reacting a tetracarboxylic dianhydride component and a diamine component in an organic solvent. The reaction between the tetracarboxylic dianhydride component and the diamine is relatively easy to carry out in an organic solvent, and there is an advantage that no by-product is produced. [0042] The organic solvent used for the reaction of the tetracarboxylic dianhydride component and the diamine is only one that can dissolve the generated polyamic acid, and is not particularly limited. Specific examples thereof are given below. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone can be mentioned Amine, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfite, hexamethylsene, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl Ketone, Methyl Nonyl Ketone, Methyl Ethyl Ketone, Methyl Isoamyl Ketone, Methyl Isoacetone, Methyl Cyrus, Ethyl Cyrus, Methyl Cyrus Acetate, Ethyl Cyrus acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate mono propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n -Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-Pentanone, 3-Methoxy-N,N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-diol Methylpropanamide, etc. These may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve polyamic acid, in the range which does not precipitate the produced polyamic acid, it can also be mixed with the said solvent and used. In addition, the moisture in the organic solvent can hinder the polymerization reaction, and become the cause of the polyamide acid generated by hydrolysis, so it is better to use the organic solvent as much as possible through dehydration and drying. When the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is added directly or after being dispersed or dissolved in the organic solvent. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, etc., use any of these any method. In addition, when the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of compounds, the reaction may be carried out in a pre-mixed state, or the reaction may be carried out in sequence, and the respectively reacted low-molecular-weight compounds may be subjected to After mixing reaction, it becomes a high molecular weight body. [0044] The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted can be selected at any temperature from -20 to 150 °C, but preferably in the range of -5 to 100 °C. In addition, the reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain high-molecular-weight polymers. The total concentration in the reaction solution of the dianhydride component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and an organic solvent may be added thereafter. In the polymerization reaction of polyamic acid, the ratio of the total molar number of the tetracarboxylic dianhydride component to the total molar number of the diamine component is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. As in a general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. <Production of Polyimide> The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the aforementioned polyimide, and can be used as a polymer for obtaining a liquid crystal alignment film. In the polyimide of the present invention, the dehydration ring closure rate (imidization rate) of the amide acid group does not necessarily have to be 100%, and can be adjusted arbitrarily according to the application or purpose. As a method for imidizing a polyamic acid, a thermal imidization method in which a solution of polyamic acid is directly heated, and a catalytic imidization method in which a catalyst is added to a solution of polyamic acid are mentioned. chemical method. The temperature during thermal imidization of the polyamic acid in the solution is 100 to 400°C, preferably 120 to 250°C, while the water generated by the imidization reaction is excluded from the system, It is better to do it on one side. The catalyst imidization of the polyamic acid is that basic catalyst and acid anhydride can be added in the solution of polyamic acid, at -20 ~ 250 ℃, preferably at 0 ~ 180 ℃. by stirring. The amount of the alkaline catalyst is 0.5-30 mol times the amide acid group, preferably 2-20 mol times, and the amount of the acid anhydride is 1-50 mol times the amide acid group, preferably 3～20 mol times. 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has basicity suitable for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, and the like, and among them, when acetic anhydride is used, purification after the completion of the reaction can be easily performed, so it is preferred. The imidization rate of the imidization by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, and the like. The molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention, if considering the obtained coating film strength, the workability during coating film formation, and the uniformity of the coating film, the GPC (Gel Permeation Chromatography) method is used. The measured weight average molecular weight is preferably 5,000-1,000,000, more preferably 10,000-150,000. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and is a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the aforementioned resin component contains at least one polymer selected from the polymers of the present invention described above. The content in the liquid crystal aligning agent of the resin component is preferably 1 to 20 mass %, preferably 3 to 15 mass %, and particularly preferably 3 to 10 mass %. All of the resin components may be the polymers of the present invention, or other polymers may be mixed. In this case, the content of the other polymer in the resin component is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass. As this other polymer, as a diamine component which reacts with a tetracarboxylic dianhydride component, the polyamic acid, polyimide, etc. obtained using the diamine compound other than a specific diamine compound are mentioned, for example. [0049] The organic solvent used in the liquid crystal alignment agent of the present invention is only an organic solvent that can dissolve the resin component, and is not particularly limited. Specific examples thereof are given below. Examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactamide, 2-pyrrolidone, N-ethyl acetate pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfite, hexamethylsulfite, γ-butyrolactone, 3-methoxy-N,N-dimethylene 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, 1,3-dimethyl-imidazolidinone , ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isoacetone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme , 4-hydroxy-4-methyl-2-pentanone, etc. These may be used alone or in combination. [0050] The liquid crystal alignment treatment agent of the present invention may contain components other than those described above. Examples of this include solvent substances that improve the uniformity of film thickness or surface smoothness when applying a liquid crystal aligning agent, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate. As a specific example of the solvent (weak solvent) which improves the uniformity of a film thickness and surface smoothness, the following are mentioned. For example, isopropanol, methoxymethyl amyl alcohol, methyl selosu ethyl sulusu, butyl sulusu, methyl sulusu acetate, ethylene glycol diethyl ether acetic acid can be enumerated Ester, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate, Propylene Glycol Monomethyl Ether, Propylene Glycol-T-butyl Ether, Dipropylene Glycol Monomethyl Ether, Diethylene Glycol, Diethylene Glycol Monoacetate, Diethylene Glycol Diethylene Glycol Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoethyl ether Acetate monopropyl ether, dipropylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether , 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate Ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2 -Propanol, 1-butoxy-2-propanol, 2-butoxy-1-propanol, 2,6-dimethyl-4-heptanol, 1-phenoxy-2-propanol, Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2- Ethoxy propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents with low surface tension, etc. One type of these weak solvents may be used, or a mixture of a plurality of types may be used. When using the said solvent, 5-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, More preferably, it is 20-60 mass %. [0052] As the compound for improving the uniformity of the film thickness or the surface smoothness, fluorine-based surfactants, polysiloxane-based surfactants, nonionic surfactants, etc. can be cited. More specific examples include Eftop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS CORP), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, SurflonS -382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. [0053] As a specific example of the compound for improving the adhesion between the liquid crystal alignment film and the substrate, the following functional silane-containing compounds, epoxy group-containing compounds, etc. can be mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane Ureapropyltrimethoxysilane, 3-Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1, 4,7-Triazadecane, 10-Triethoxysilyl-1,4,7-Triazadecane, 9-Trimethoxysilyl-3,6-diazanonylacetic acid Esters, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-amine Ethylpropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylidene) )-3-aminopropyltrimethoxysilane, N-bis(oxyethylidene)-3-aminopropyltriethoxysilane, ethylene glycol propylene dioxide ether, polyethylene glycol propylene dioxide Ether, propylene glycol propylene dioxide ether, tripropylene glycol propylene dioxide ether, polypropylene glycol propylene dioxide ether, neopentyl glycol propylene dioxide ether, 1,6-hexanediol propylene dioxide ether, glycerol propylene dioxide ether, 2 ,2-dibromoneopentyl glycol propylene dioxide ether, 1,3,5,6-tetraoxypropylene-2,4-hexanediol, N,N,N',N',-tetraoxypropylene -m-xylenediamine, 1,3-bis(N,N-dioxypropenylaminomethyl)cyclohexane, N,N,N',N',-tetraoxypropenyl-4,4' - Diaminodiphenylmethane, etc. [0054] In addition to further improving the adhesion between the substrate and the film, it is preferable to contain the following phenolic plastic additives for the purpose of preventing deterioration of electrical properties due to backlighting. Specifically, the phenolic plastic-based additives are shown below.
Figure 02_image039
[0055] When using a compound that improves adhesion to the substrate, the usage amount is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, for 100 parts by mass of the resin component. When the usage-amount is less than 0.1 mass part, the improvement effect of adhesiveness cannot be anticipated, and when it exceeds 30 mass parts, the orientation of a liquid crystal may worsen. In the liquid crystal aligning agent of the present invention, in addition to the above, within the range that does not impair the effects of the present invention, for the purpose of changing electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, it is also possible to add and improve the dielectric properties. Electrons, conductive substances, and further crosslinkable compounds for the purpose of film hardness or density in liquid crystal alignment films, and the like. <Liquid crystal alignment film and liquid crystal display element> After the liquid crystal alignment agent of the present invention is coated on a substrate and fired, alignment treatment is performed by rubbing treatment or light irradiation, or it is not subjected to alignment treatment in vertical alignment applications, etc. Instead, it is used as a liquid crystal alignment film. In this case, the substrate to be used may be a substrate with high transparency and is not particularly limited, and plastic substrates such as glass substrates, acrylic substrates, and polycarbonate substrates can be used. In addition, it is preferable to use a substrate on which ITO electrodes for liquid crystal driving, etc. are formed, from the viewpoint of simplifying the manufacturing process. In addition, if it is a single-sided substrate in a reflective liquid crystal display element, an opaque material such as a silicon wafer may be used, and a material that reflects light such as aluminum may be used as the electrode in this case. The coating method of the liquid crystal aligning agent is not particularly limited, but methods such as screen printing, offset printing, kneading printing, and jet printing are generally performed industrially. As another coating method, there are dipping, roll coating, slot coating, spin coater, etc., which are performed according to the purpose. [0057] The sintering after coating the liquid crystal alignment agent on the substrate can be performed by heating means such as a hot plate at 50-300° C., preferably 80-250° C., so that the solvent is evaporated to form a coating film. If the thickness of the coating film formed after firing is too thick, it will become unfavorable in terms of the power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5~300 nm. , more preferably 10 to 100 nm. When aligning the liquid crystal horizontally or obliquely, the fired coating film is subjected to treatment such as rubbing or polarized ultraviolet irradiation. The liquid crystal display element of the present invention is a liquid crystal display element prepared by a known method after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent of the present invention by the above-mentioned method. To give an example of the production of liquid crystal cells, prepare a pair of substrates with a liquid crystal alignment film formed, spread spacers on the liquid crystal alignment film of a single-sided substrate, make the liquid crystal alignment film surface become the inner side, and attach the other side A method of sealing after injecting a liquid crystal under reduced pressure, or a method of dropping a liquid crystal on the surface of a liquid crystal alignment film where spacers are scattered, and then bonding a substrate to seal it, etc. can be exemplified. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm. [Examples] [0059] Hereinafter, the present invention will be described in more detail by way of Examples, but the content of the present invention is not limited to these Examples. Abbreviations and characteristic evaluation methods used in Examples and the like are as follows. [0060]
Figure 02_image041
<Organic solvent> NMP: N-methyl-2-pyrrolidone, BCS: butyl cellosolve <Additive> LS-4668: 3-glycidoxypropyltriethoxysilane [0062]< Viscosity measurement> The viscosity of the solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25°C, with a sample volume of 1.1 mL, and a conical rotor TE-1 (1°34', R24). [0063] <Production of Liquid Crystal Display Device> First, a substrate with electrodes is prepared. The substrate is a rectangular glass substrate with a length of 30mm×width of 35mm and a thickness of 0.7mm. An IZO electrode having a solid pattern constituting a counter electrode as a first layer was formed on the substrate. On the opposite electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method is formed as a second layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an IZO film is arranged as a third layer, and two pixels of a first pixel and a second pixel are formed. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the function of the SiN film of the second layer. [0064] The pixel electrode of the third layer has a comb-like shape formed by arranging a plurality of electrode elements having a “く” shape with a curved center portion. The width of each electrode element in the width direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode that forms each pixel is composed of a plurality of "く"-shaped electrode elements with a curved center portion arranged in a plurality, so the shape of each pixel is not a rectangular shape, but has a similar electrode element that is curved in the center portion. Bold "く" shape. In addition, each pixel is divided up and down with its central curved portion as a boundary, and has a first area on the upper side of the curved portion and a second area on the lower side. [0065] When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting these pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise), and in the second region of the pixel, The electrode elements of the pixel electrode are formed so as to exhibit an angle of -10° (clockwise). In this way, the first region and the second region of each pixel are configured such that the directions of the rotation operations (plane switching) in the substrate plane of the liquid crystal induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other. direction. Then, after the liquid crystal aligning agent is filtered with the filter of aperture 1.0 μm, each spin-coating is formed on the back side of the prepared above-mentioned electrode-attached substrate and the back side as the opposite substrate with ITO film and a column with a height of 4 μm. The glass substrate of the spacer. Next, after drying on a hot plate at 80° C. for 2 minutes, firing was performed at 230° C. for 20 minutes to obtain a polyimide film having a thickness of 60 nm on each substrate. The polyimide film was rubbed with a rayon cloth in a specific rubbing direction (roller diameter 120mm, drum rotation number 500rpm, moving speed 30mm/sec, pressing amount 0.3mm), and then rubbed in pure rayon. Ultrasonic irradiation was performed in water for 1 minute, and drying was performed at 80° C. for 10 minutes to obtain a liquid crystal alignment film. Using the obtained 2 types of substrates with liquid crystal and alignment film, combined in a way that their respective rubbing directions are anti-parallel, leaving the liquid crystal injection port and sealing the surrounding, making the empty liquid crystal crystal with a liquid crystal cell gap of 3.5 μm cell. After the liquid crystal (MLC-3019, manufactured by Merck & Co., Ltd.) was vacuum-injected at normal temperature in this empty liquid crystal cell, the injection port was sealed to prepare an antiparallel alignment liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Then, the obtained liquid crystal cell was heated at 120 degreeC for 1 hour, and was used for each evaluation after standing overnight. [0068] <Evaluation of Liquid Crystal Alignment> Using the above-produced liquid crystal cell, under a constant temperature environment of 60° C., with a frequency of 30 Hz, an AC voltage of 10 VPP was applied for 168 hours. Next, the liquid crystal cell was left in a short-circuited state between the pixel electrode and the counter electrode, and was left directly at room temperature for one day. After being placed, the liquid crystal cell is placed between two polarizers arranged with the polarization axis vertical, the backlight is lit in advance in the state of no voltage application, and the arrangement angle of the liquid crystal cell is adjusted to make the brightness of the transmitted light. reach the minimum. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is the darkest to the angle at which the first region is the darkest is calculated as the angle Δ. Similarly, for the second pixel, the second area is compared with the first area, and the same angle Δ is calculated. Then, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. The smaller the angle Δ of the liquid crystal cell, the higher the liquid crystal alignment of the liquid crystal alignment film. <Gardner Color Scale> After the obtained liquid crystal aligning agent was left at room temperature for 24 hours, the Gardner color scale was measured. The Gardner chromaticity indicated by the hue was measured in accordance with Japanese Industrial Standard JIS K 0071-2. It means that the smaller the Gardner chromaticity, the lighter the color of the obtained liquid crystal alignment agent. (Synthesis example 1) The four-necked flask of 50ml with stirring device was made into nitrogen atmosphere, DA-1 0.773g (2.58mmol), DA-4 2.54g (10.4mmol) were measured, NMP46.5g was added, while It was dissolved by feeding nitrogen with stirring. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was performed at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-1, viscosity: 510.7mPa·s). (Synthesis example 2) The four-necked flask of the 50ml of the attached stirring device was placed in a nitrogen atmosphere, and DA-1 1.55g (5.18mmol) and DA-4 were measured to be 1.90g (7.78mmol), and NMP54.6g was added. , and stirring to dissolve it while feeding nitrogen. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-2, viscosity: 505.4mPa･s). (Synthesis example 3) The 50ml four-necked flask with stirring device was made into nitrogen atmosphere, and DA-1 0.773g (2.58mmol), DA-4 2.22g (9.09mmol) and DA-6 0.724g ( 1.30 mmol), NMP46.5g was added, and it was made to melt|dissolve with stirring while feeding nitrogen. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-3, viscosity: 505.4mPa･s). (Synthesis example 4) The four-necked flask of 50ml with stirring device was made into nitrogen atmosphere, DA-1 0.773g (2.58mmol) and DA-5 2.98g (10.4mmol) were measured, NMP47.4g was added, while It was dissolved by feeding nitrogen with stirring. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-4, viscosity: 525.3mPa･s). (Synthesis example 5) The four-necked flask of the 50ml with stirring device was made into a nitrogen atmosphere, and DA-1 1.56g (5.21mmol) and DA-5 were measured as 2.23g (7.79mmol), NMP47.7g was added, It was dissolved by stirring while feeding nitrogen. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-5, viscosity: 510.4mPa･s). (Synthesis example 6) The 50ml four-necked flask with stirring device was made into nitrogen atmosphere, and DA-1 0.778g (2.60mmol), DA-5 2.60g (9.08mmol) and DA-6 0.724g ( 1.30 mmol), 50.0 g of NMP was added, and it was dissolved by stirring while feeding nitrogen. 2.71 g (12.4 mmol) of CA-2 was added to this diamine solution while stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-6, viscosity: 498.1mPa･s). (Comparative Synthesis Example 1) The four-necked flask of 50 ml with a stirring device was made into a nitrogen atmosphere, 2.79 g (14.0 mmol) of DA-3 was weighed, 47.1 g of NMP was added, and nitrogen was stirred to dissolve it. 2.44 g (12.4 mmol) of CA-1 was added to this diamine solution with stirring, and after stirring at 15° C. for 2 hours, a polyamic acid solution (PAA-7, viscosity: 121.1 mPa·s) was obtained. (Comparative Synthesis Example 2) The four-necked flask of the 50ml with stirring device was made into nitrogen atmosphere, DA-3 0.518g (2.60mmol) and DA-4 2.51g (10.3mmol) were measured, NMP42.3g was added, It was dissolved by stirring while feeding nitrogen. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-8, viscosity: 531.5mPa･s). (Comparative Synthesis Example 3) The four-necked flask of 50ml of the attached stirring device was made into a nitrogen atmosphere, DA-3 1.04g (5.21mmol) and DA-4 1.91g (7.82mmol) were measured, NMP41.4g was added, It was dissolved by stirring while feeding nitrogen. To this diamine solution, 2.71 g (12.4 mmol) of CA-2 was added with stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-9, viscosity: 542.2mPa･s). (Comparative Synthesis Example 4) The four-necked flask of the 50ml with stirring device was made into nitrogen atmosphere, DA-3 0.51g (2.56mmol) and DA-5 2.97g (10.4mmol) were measured, NMP47.2g was added, It was dissolved by stirring while feeding nitrogen. 2.71 g (12.4 mmol) of CA-2 was added to this diamine solution while stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-10, viscosity: 547.1mPa･s). (Comparative Synthesis Example 5) The four-necked flask of 50ml with stirring device was made into nitrogen atmosphere, DA-3 0.51g (2.56mmol) and DA-5 2.97g (10.4mmol) were measured, NMP47.2g was added, It was dissolved by stirring while feeding nitrogen. 2.71 g (12.4 mmol) of CA-2 was added to this diamine solution while stirring, and after stirring at room temperature for 2 hours, stirring was carried out at 50° C. for 24 hours to obtain a polyamic acid solution (PAA-11, viscosity: 547.1mPa･s). (Comparative Synthesis Example 6) The four-necked flask of 50 ml with a stirring device was made into a nitrogen atmosphere, 3.29 g (11.0 mmol) of DA-1 was weighed, 46.1 g of NMP was added, and nitrogen was stirred to dissolve it. 1.91 g (9.7 mmol) of CA-1 was added to this diamine solution with stirring, and after stirring at 15° C. for 2 hours, a polyamic acid solution (PAA-12, viscosity: 121.1 mPa·s) was obtained. (Comparative Synthesis Example 7) A 50ml four-necked flask with a stirring device was made into a nitrogen atmosphere, 2.77 g (13.0 mmol) of DA-2 was weighed, 46.1 g of NMP was added, and nitrogen was stirred to dissolve it. To this diamine solution, 2.34 g (11.9 mmol) of acid dianhydride (CA-1) was added with stirring, and after stirring at 15° C. for 2 hours, a polyamic acid solution (PAA-13 viscosity: 110.4 mPa･s was obtained) ). <Examples 1 to 6 and Comparative Examples 1 to 7> Take the 10 to 12% polyamide solution PAA- 1 to 24.0 g of PAA13, respectively, add 5.6 g of NMP, 8.00 g of BCS, and 2.4 g of a mixed solution containing 1% by weight of LS-4668 while stirring, and then, by stirring at room temperature for 2 hours, the respective liquid crystals are obtained Alignment agents (AL-1)~(AL-13). <Evaluation> For the liquid crystal alignment agents (AL-1) to (AL-13) of Examples 1 to 6 and Comparative Examples 1 to 7 obtained above, the liquid crystal alignment properties and Evaluation of Gardner Color. The results are shown in Table 1. In Table 1, "-" in the Gardner color means not measured. [0085]
Figure 02_image043
[Industrial Applicability] [0086] The liquid crystal aligning agent of the present invention can be used in a wide range of large-scale liquid crystal display elements requiring high precision and low cost, and mobile liquid crystal display elements such as smart phones and mobile phones. field of. In addition, the entire contents of Japanese Patent Application No. 2016-168461 filed on August 30, 2016, the scope of application, drawings, and abstract are incorporated herein by reference as a disclosure of the present specification.

Figure 106129429-A0101-11-0002-2
Figure 106129429-A0101-11-0002-2

Claims (7)

一種液晶配向劑，其特徵為含有：選自含有具有下述式[1]表示之構造之二胺的二胺成分與四羧酸二酐成分反應所得之聚醯胺酸、及將該聚醯胺酸醯亞胺化所得之聚醯亞胺所成之群中的至少1個聚合物，前述二胺成分中之具有式[1]表示之構造之二胺之含量為5~95mol%；
Figure 106129429-A0305-02-0042-1
 (式中，A係表示藉由溫度150~300℃之加熱而置換為氫原子之熱解離性基，苯環所具有之氫原子亦可藉由碳數1~5之烷基或是烷氧基或鹵素基取代，*係表示鍵結處)。 A liquid crystal aligning agent characterized by comprising: a diamine component selected from the group consisting of a diamine component having a structure represented by the following formula [1] and a tetracarboxylic dianhydride component obtained by reacting a polyamide acid, and the polyamide At least one polymer in the group of polyimide obtained by imidization of amine acid, the content of the diamine having the structure represented by formula [1] in the diamine component is 5~95mol%;
Figure 106129429-A0305-02-0042-1
 (In the formula, A represents a thermally dissociable group that is replaced by a hydrogen atom by heating at a temperature of 150 to 300° C. The hydrogen atom of the benzene ring can also be replaced by an alkyl group having 1 to 5 carbon atoms or an alkoxy group. group or halogen group, * indicates the bond). 如請求項1之液晶配向劑，其中前述熱解離性基為tert-丁氧基羰基或是9-茀基甲氧基羰基。 The liquid crystal aligning agent according to claim 1, wherein the thermally dissociable group is a tert-butoxycarbonyl group or a 9-phenylenylmethoxycarbonyl group. 如請求項1或2之液晶配向劑，其中，具有前述式[1]表示之構造之二胺為以下述之任一者之式表示之二胺，式中之Boc係表示tert-丁氧基羰基，
Figure 106129429-A0305-02-0043-2
 The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine having the structure represented by the aforementioned formula [1] is a diamine represented by any one of the following formulas, and Boc in the formula represents a tert-butoxy group carbonyl,
Figure 106129429-A0305-02-0043-2
 如請求項1或2之液晶配向劑，其中前述四羧酸二酐成分為下述式[7]表示之化合物，
Figure 106129429-A0305-02-0043-3
 (式中，Z1係碳數4~13之4價之有機基，且具有芳香族環狀烴基)。 The liquid crystal aligning agent according to claim 1 or 2, wherein the aforementioned tetracarboxylic dianhydride component is a compound represented by the following formula [7],
Figure 106129429-A0305-02-0043-3
 (In the formula, Z 1 is a tetravalent organic group having 4 to 13 carbon atoms, and has an aromatic cyclic hydrocarbon group). 如請求項4之液晶配向劑，其中Z1為下述式[7a]~[7k] 表示之構造中之任一者，
Figure 106129429-A0305-02-0044-4
 The liquid crystal aligning agent of claim 4, wherein Z 1 is any one of the structures represented by the following formulae [7a]~[7k],
Figure 106129429-A0305-02-0044-4
 一種液晶配向膜，其特徵為由如請求項1~5中之任一項之液晶配向劑所得。 A liquid crystal alignment film is characterized by being obtained from the liquid crystal alignment agent according to any one of claims 1 to 5. 一種液晶顯示元件，其特徵為具備如請求項6之液晶配向膜。 A liquid crystal display element is characterized by having the liquid crystal alignment film according to claim 6.
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