TWI360680B - Liquid crystal alignment agent and manufacturing m - Google Patents

Liquid crystal alignment agent and manufacturing m Download PDF

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Publication number
TWI360680B
TWI360680B TW094104333A TW94104333A TWI360680B TW I360680 B TWI360680 B TW I360680B TW 094104333 A TW094104333 A TW 094104333A TW 94104333 A TW94104333 A TW 94104333A TW I360680 B TWI360680 B TW I360680B
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liquid crystal
crystal alignment
group
compound
formula
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TW094104333A
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Chinese (zh)
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TW200537180A (en
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Tooru Natsui
Yoshihiko Kuroda
Michinori Nishikawa
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Jsr Corp
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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
    • 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
    • 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

Description

1360680 • 九、發明說明： 【發明所屬之技術領域】 本發明關於液晶配向劑。更詳細地，關於不拘於構成 . 液晶顯示元件的電極種類而燒結特性良好的液晶配向劑。 【先前技術】 過去，人們知道的有具有TN(扭曲向列，Twisted Nematic)型液晶胞的TN型液晶顯示元件，在其TN型液晶 胞中’在2片***透明導電膜並在表面形成液晶配向膜的 φ 基板之間，形成具有正介電異方向性的向列型液晶層而形 成疊層結構的元件’上述液晶分子的長軸從一個基板朝向 另一個基板連續扭轉90度。 另外’也存在通過對掌劑的添加實現該液晶分子的長 軸在基板間連續扭轉1 8 0度或1 8 0度以上的狀態，利用由 此產生的雙折射效果之STN(超扭曲向列，Super Twisted Nematic)型液晶顯示元件。而且最近，也開發了在對向基 板間形成具有負介電異方向性的垂直（homeotropic)配向狀 φ態的向列型液晶層’或螺旋軸與基板法線呈平行狀態的膽 固醇型液晶層，在這些液晶層中添加色素的客（guest)_宿主 (ho st)型反射型液晶顯示元件。這些液晶顯示元件的液晶配 向，通常係通過實施摩擦處理的液晶配向膜來實現。此處， 作爲構成液晶顯示元件的_液晶配向膜材料,已知過去係摩 用聚醯g—g一，和聚雹等^。特別是，醯亞胺_，由於耐 熱性、與液晶的親和性、機械強度等優異，故在多數液晶 顯示元件中使用。 最近’在進行以液晶顯示元件的高精細化爲主的顯示 1360680 品質提局、低耗電量化等的硏究’液晶顯不兀件的利用範 圍也在擴大。特別地，在室外使用時也可以維持高顯示品 質的反射型或半透過型液晶顯示元件由於在攜帶末端使 - 用，爲了能發揮反射外來光的功能而使用各種金屬電極（下 . 面，稱爲反射電極）。但爲，具有反射電極的液晶顯示元件 如果用現有的ITO電極中使用的配向膜則產生燒結的問 題。 【發明內容】 φ 本發明的目的在於提供即使在使用不限於ITO的反射 電極的情況下’可以得到燒結特性優異的液晶配向膜之液 晶顯示元件用液晶配向劑。 本發明的其他目的和優點，可以從以下說明加以明白。 根據本發明’本發明的上述目的和優點係藉由液晶配 向劑而實現’其特徵在於該液晶配向劑含有1〇〇重量份具 有下式（1-1)所示之重複單位和下式（1-2)所示之重複單位、 且式（I- 1 )所示之重複單位的比例以重量計占全部重複單位 鲁元的40%~60%的聚合物，和至少5重量份分子內至少具有 2個環氧基之化合物。 [化1]1360680 • Nine, invention description: [Technical field to which the invention pertains] The present invention relates to a liquid crystal alignment agent. More specifically, the liquid crystal alignment agent having good sintering characteristics regardless of the type of electrode of the liquid crystal display element. [Prior Art] In the past, a TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell has been known, and in its TN type liquid crystal cell, a transparent conductive film is inserted in two sheets and liquid crystal is formed on the surface. Between the φ substrates of the alignment film, a nematic liquid crystal layer having a positive dielectric anisotropy is formed to form a laminated structure. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate. In addition, there is also a state in which the long axis of the liquid crystal molecule is continuously twisted between the substrates by 180 degrees or more than 180 degrees by the addition of the palm powder, and the STN (super twisted nematic) using the birefringence effect thus produced , Super Twisted Nematic) liquid crystal display element. Further, recently, a nematic liquid crystal layer having a homeotropic alignment φ state having a negative dielectric anisotropy or a cholesteric liquid crystal layer having a spiral axis parallel to the substrate normal has been developed. A guest-hoist type reflective liquid crystal display element in which a coloring matter is added to these liquid crystal layers. The liquid crystal alignment of these liquid crystal display elements is usually achieved by a liquid crystal alignment film which is subjected to rubbing treatment. Here, as the material of the liquid crystal alignment film constituting the liquid crystal display element, it has been known to use a polyp-g-g, a polyfluorene or the like. In particular, ruthenium amide is used in many liquid crystal display elements because it is excellent in heat resistance, affinity with liquid crystals, mechanical strength, and the like. Recently, the display of the high-definition liquid crystal display device, the 1360680 quality improvement, and the low power consumption, etc., have been expanded. In particular, a reflective or semi-transmissive liquid crystal display element which can maintain high display quality even when used outdoors is used in a portable terminal, and various metal electrodes are used in order to function as a reflection of external light (lower surface, called For the reflective electrode). However, the liquid crystal display element having the reflective electrode has a problem of sintering if the alignment film used in the conventional ITO electrode is used. [Explanation] φ An object of the present invention is to provide a liquid crystal alignment agent for a liquid crystal display element which can obtain a liquid crystal alignment film having excellent sintering characteristics even when a reflective electrode not limited to ITO is used. Other objects and advantages of the present invention will be apparent from the description. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent, characterized in that the liquid crystal alignment agent contains 1 part by weight of a repeating unit represented by the following formula (1-1) and the following formula ( 1-2) the repeating unit shown, and the ratio of the repeating unit represented by the formula (I-1) is 40% to 60% by weight of the polymer of all repeating units of the luer, and at least 5 parts by weight of the intramolecular weight A compound having at least 2 epoxy groups. [Chemical 1]

(式中’ P1爲4價有機基，且Q1爲2價有機基） 1360680 i t [化2] Ο Ο(wherein P1 is a tetravalent organic group and Q1 is a divalent organic group) 1360680 i t [Chemical 2] Ο Ο

(式中，Ρ2爲4價有機基，且Q2爲2價有機基） 通過本發明的液晶配向劑而形成的液晶配向膜，即使 φ 在使用不限於ITO的反射電極的情況下，也可以得到燒結(In the formula, Ρ2 is a tetravalent organic group, and Q2 is a divalent organic group.) The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can be obtained even when φ is used without using a reflective electrode of ITO. sintering

I 特性優異的液晶配向膜，可以適宜在爲構成TN型液晶顯 示元件，STN型液晶顯示元件，反射型液晶·顯示元件和半 ' 透過型液晶顯示元件等各種液晶顯示元件中使用。 本發明的液晶顯示元件，可以在各種裝置中有效地使 用。例如，可以適宜作爲桌上型電腦、手錶、計時器、手 機、計數顯示板、文字處理機、個人電腦、液晶電視等顯 示裝置使用。 φ 實施發明之最佳型態 _ 下面，對本發明詳細說明》 本發明的液晶配向劑，含有具有上述式（1-1)所示之重 複單位和上述式（1-2)所表示重複單位的聚合物（以下稱爲 “特定聚合物”）。該聚合物可以爲（1)具有上述式（1-1)所 示之重複單位的聚醯胺酸和具有上述式（1-2)所示之重複單 位的聚醯亞胺的混合物，也可以爲（2)由上述式（1-1)所示之 重複單位和上述式（1-2)所表示重複單位，在同一分子中無 規或嵌段狀鍵合而形成的聚合物（下面，稱爲“部分醯亞胺 1360680 < . 化聚合物”）。 上述聚醯胺酸，可以使四羧酸二酸酐和二胺化合物開 環聚合加成而得到。另外，聚醯亞胺爲通常將聚醯胺酸脫 水閉環而得到。部分醯亞胺化聚合物爲通常可以通過使聚 醯胺酸部分脫水閉環的方法，或將醯胺酸預聚物與醯亞胺 預聚物鍵合合成嵌段共聚物的方法而得到。 <聚醯胺酸> [四羧酸二酸酐] • 作爲四羧酸二酸酐，例如可以列爭丁烷四羧酸二酸 酐，1,2,3,4-環丁烷四羧酸二酸酐，1，2-二甲基-1，2,3,4-環 丁烷四羧酸二酸酐’ 1，3 -二甲基-1，2,3,4-環丁烷四羧酸二酸 酐，1，3-二氯-1，2,3,4-環丁烷四羧酸二酸酐，1，2,3,4-四甲 基-1，2,3,4-環丁烷四羧酸二酸酐，1，2,3,4-環戊烷四羧酸二 酸酐，1，2,4,5-環己烷四羧酸二酸酐，3,3’，4,4’-二環己烷四 羧酸二酸酐，2,3,5-三羧基環戊基乙酸二酸酐，3,5,6-三羧 基降冰片烷-2-乙酸二酸酐’ 2,3,4,5·四氫呋喃四羧酸二酸 φ 酐，1，3,33,4,5,91)-六氫-5-(四氫-2,5-二氧代-3-呋喃基）-萘 並[l，2-c]-呋喃-1，3-二酮，1，3,3&，4,5,915-六氫-5-甲基-5-(四 氫-2,5-二氧代-3-呋喃基）-萘並[1，2-叫-呋喃-1，3-二酮， 1,3,3&，4,5,915-六氫-5-乙基-5-(四氫-2,5-二氧代-3-呋喃基）-萘並[l，2-c]-呋喃-1,3-二酮，l，3,3a，4,5,9b-六氫-7 -甲基 -5-(四氫-2,5-二氧代-3-呋喃基）-萘並[l，2-c] -呋喃-1,3 -二 酮，l，3,3a，4，5,9b-六氫-7·乙基- 5- (四氫-2,5-二氧代-3-呋喃 基）-萘並[l，2-c]-呋喃-1,3-二酮 ’ 1，3,3&，4,5,915-六氫-8-甲基 -5-(四氫-2,5-二氧代-3-呋喃基）-萘並[1,2-c]-呋喃-1,3 -二 1360680 酮，l，3,3a，4,5,9b -六氫_8_乙基·5_(四氫·2,5•二氧代-3-呋喃 基）-萘並[l，2-c]-呋喃·13二酮， 甲基-5-(四氫_2,5-二氧代_3_呋喃基）·萘並pj-c]-呋喃 -1，3-_酮’5-(2,5-二氧代四氫糠基）_3_甲基-3_環己烷-1，2- —殘酸二酸酐’雙環[2,22]_辛·7_烯-2,35,6_四羧酸二酸 野’ 3_氧代雙環[3.2·1]辛烷-2,4-二酮-6-螺-3，-(四氫呋喃 -2’’5’-二嗣）’下式（1)和（11)所示之化合物等脂肪族和脂環 族四羧酸二酸酐；The liquid crystal alignment film having excellent I characteristics can be suitably used for various liquid crystal display elements such as a TN type liquid crystal display element, an STN type liquid crystal display element, a reflective liquid crystal display element, and a semi-transmissive liquid crystal display element. The liquid crystal display element of the present invention can be effectively used in various devices. For example, it can be suitably used as a display device such as a desktop computer, a watch, a timer, a mobile phone, a counting display panel, a word processor, a personal computer, or a liquid crystal television. φ The best mode for carrying out the invention _ Hereinafter, the liquid crystal alignment agent of the present invention contains the repeating unit represented by the above formula (1-1) and the repeating unit represented by the above formula (1-2). Polymer (hereinafter referred to as "specific polymer"). The polymer may be a mixture of (1) a polylysine having a repeating unit represented by the above formula (1-1) and a polyimine having a repeating unit represented by the above formula (1-2), or may be used. (2) a polymer formed by random or block-like bonding in the same molecule by the repeating unit represented by the above formula (1-1) and the repeating unit represented by the above formula (1-2) (hereinafter, It is called "partial quinone imine 1360680 < . Polymer"). The polyamic acid can be obtained by subjecting a tetracarboxylic acid dianhydride and a diamine compound to ring-opening polymerization. Further, polyimine is obtained by subjecting polylysine to dehydration and ring closure. The partially ruthenium iodide polymer is generally obtained by a method of dehydrating a poly (protonic acid) moiety, or a method of bonding a proline prepolymer to a ruthenium imide to form a block copolymer. <Polyamic acid> [Tetracarboxylic acid dianhydride] • As the tetracarboxylic acid dianhydride, for example, butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid Anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride ' 1,3 -dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid Anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane IV Dicarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-di Cyclohexane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5· Tetrahydrofuran tetracarboxylic acid diacid φ anhydride, 1,3,33,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1, 2-c]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furan -Naphtho[1,2-de-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-5-ethyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l,3,3a, 4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3 - Dione, l,3,3a,4,5,9b-hexahydro-7.ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2- c]-furan-1,3-dione' 1,3,3&,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphtho[1,2-c]-furan-1,3 -di 1360680 ketone, l,3,3a,4,5,9b-hexahydro_8_ethyl·5_(tetrahydro·2,5• Dioxo-3-furanyl)-naphtho[l,2-c]-furan·13 diketone, methyl-5-(tetrahydro-2,5-dioxo-3-(furanyl)·naphthalene And pj-c]-furan-1,3-ketone '5-(2,5-dioxotetrahydroindenyl)_3_methyl-3_cyclohexane-1,2--residual acid dianhydride 'Bicyclo[2,22]_octyl-7-ene-2,35,6-tetracarboxylic acid diacid field '3_oxobicyclo[3.2.1]octane-2,4-dione-6-spiro -3,-(tetrahydrofuran-2''5'-dioxime)'s aliphatic and alicyclic tetracarboxylic dianhydrides such as the compounds represented by the following formulas (1) and (11);

(式中’ R1和R3係表示具有芳香環的2價有機基，R2 和R4係表示氫原子和烷基，存在的多個R2和R4，分別可 以相同也可以不同） 均苯四甲酸二酸酐，3,3’，4,4’-二苯甲酮四羧酸二酸 酐，3,3’，4,4’-二苯基颯四羧酸二酸酐，丨，4,5,8-萘四羧酸二 酸酐’ 2,3,6,7-萘四羧酸二酸酐，3,3，，4,4，-二苯基醚四羧酸 1360680 二酸酐，3,3’，4,4’-二甲基二苯基矽烷四羧酸二酸酐， 3,3’，4,4’-四苯基矽烷四羧酸二酸酐，1，2,3,4-呋喃四羧酸二 酸酐，4,4’-雙（3,4-二羧基苯氧基）二苯基硫醚二酸酐，4,4’-- 雙（3,4-二羧基苯氧基）二苯基楓二酸酐，4,4’-雙（3,4-二羧 基苯氧基）二苯基丙烷二酸酐，3,3’，4,4’-全氟異亞丙基二鄰 苯二甲酸二酸酐，3,3’，4，4’-二苯基四羧酸二酸酐，雙（鄰苯 二甲酸）苯基氧化膦二酸酐，對伸苯基-雙（三苯基鄰苯二甲 酸）二酸酐，間伸苯基-雙（三苯基鄰苯二甲酸）二酸酐，雙（三 φ 苯基鄰苯二甲酸）-4,4’-二苯基醚二酸酐，雙（三苯基鄰苯二 甲酸）-4,4’-二苯基甲烷二酸酐，乙二醇-雙（脫水偏苯三酸 酯），丙二醇-雙（脫水偏苯三酸酯），1,4-丁二醇-雙（脫水偏 _ 苯三酸酯），1,6-己二醇-雙（脫水偏苯三酸酯），1，8-辛二醇-雙（脫水偏苯三酸酯），2,2-雙（4-羥基苯基）丙烷-雙（脫水偏 苯三酸酯），下式（1)〜（4)所示之化合物等芳香族四羧酸二酸 酐化合物。它們可以1種單獨或將至少2種組合使用。 [化4](wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 are a hydrogen atom and an alkyl group, and a plurality of R2 and R4 present may be the same or different) pyromellitic dianhydride ,3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid dianhydride, hydrazine, 4,5,8-naphthalene Tetracarboxylic acid dianhydride '2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3,,4,4,-diphenyl ether tetracarboxylic acid 1360680 dianhydride, 3,3',4,4 '-Dimethyldiphenylnonanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl maple dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3, 3',4,4'-diphenyltetracarboxylic acid dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, Stretching phenyl - Bis(triphenylphthalic acid) dianhydride, bis(tris(phenyl)phthalate)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4, 4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-bis (dehydration partial benzene) Triester), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyl) Phenyl)propane-bis(hydrogen trimellitate), an aromatic tetracarboxylic dianhydride compound such as a compound represented by the following formulas (1) to (4). They may be used singly or in combination of at least two. [Chemical 4]

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(2)(2)

其中，.從可以發揮良好的液晶配向性的觀點出發，較 佳爲丁烷四羧酸二酸酐，1,2,3,4-環丁烷四羧酸二酸酐，1，2-二甲基-1，2,3,4-環丁烷四羧酸二酸酐，1，3-二甲基-1,2,3,4-環丁烷四羧酸二酸酐，1，3-二氯-1，2,3,4-環丁烷四羧酸二酸 -11- 1360680 酐，1，2,3,4-四甲基- 丁烷四羧酸二酸酐，u，3,4_ 環戊四羧酸二酸酐，丨，2,4,5·環己四羧酸二酸酐，2,3,5-三 狻基環戊基乙酸二酸軒，s 〇 s _铝件四 敗叶，5-(2,5-—氧代四氫糠基）·3甲基 -3 -環己院-1，2 -二殘酸—酿醉，1 7 4 S 〇1_ 一 炫股一酸酐，l，3,3a，4,5,9b-六氫·5_(四氫 -2,5_二氧代·3·呋喃基）·萘並[l，2-c]-呋喃-L3·二酮， Ι3’^，4’5,9^六氯·5·甲基-5-(四氫-2:5-二氧代-3-咲喃基） 萘並[l，2-c]-呋喃十3_二酮，六氫-7甲基 -5-(四氫·2,5·二氧代.3_咲喃基）萘並π，2叫肤喃-u-二 酮，1’3’3&’4,5,91六氫-8-甲基_5_(四氫-2,5_二氧代_3_呋喃 基）-萘並[l，2-c]-呋喃.二酮，1，3,33,4,5，外_六氫_5,8_二 甲基（四氮2,5 - —氧代·3_呋喃基）-萘並[i，2_c]-呋喃 -1，3-二酮，雙環[2,2,2卜辛_7_烯_2,3,5,6_四羧酸二酸酐，％ 氧代又環[3.2.1]辛院_2,4二酮_6螺·3，（四氫呋喃_2，，5，_ 二酮），均苯四甲酸二酸酐，3,3，，4,4，-二苯甲酮四羧酸二酸 野’ 3,3，4,4 苯基珮四羧酸二酸酐，mg·萘四羧酸二 酸酌1 ’ i：述式（I)所表示化合物中的下式（5)〜（7)所示之化合 物和上述式（II)所表示化合物中的下述式（8)所表示化合 物。作爲特別較佳之化合物，可以列舉I，2,3,4-環丁烷四羧 酸二酸酐，1，2 -二甲基-1,2,3,4-環丁烷四羧酸二酸酐，1，3-二甲基-1，2,3,4-環丁烷四羧酸二酸酐，1，3_二氯-1，2,3,4-環 丁烷四羧酸二酸酐，1，2,3,4_四甲基-1，2,3,4-環丁烷四羧酸 二酸酐，1，2,4,5-環己四羧酸二酸酐’ 2,3,5-三羧基環戊基 乙酸二酸酐，l，3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋 喃基）-萘並[12-c]呋喃-1,3-二酮，1，3,3&，4,5,91»-六氫-5-甲 基- 5- (四氫-2,5-二氧代-3-呋喃基）-萘並[l，2-c] -呋喃-1,3- -12- 1360680 二酮，1,3,33,4,5,91?-六氫-7-甲基-5-(四氫-2,5-二氧代-3-呋 喃基）-萘並[l，2-c]-呋喃-1,3-二酮，1，3,33,4,5,91)-六氫-8-甲基-5-(四氫- 2,5-二氧代-3-呋喃基）-萘並[l，2-c]-呋喃 -1,3-二酮，1，3,33,4,5,91?-六氫-5,8-二甲基-5-(四氫-2,5-二 氧代-3-呋喃基）-萘並[1,2-c]-呋喃-1，3-二酮，3-氧代雙環 [3.2.1]辛烷-2,4-二酮-6-螺- 3’-(四氫呋喃-2’，5’-二嗣），均苯 四甲酸二酸酐，均苯四甲酸二酸酐和下述式（5)所表示化合 物。 [化5] Ο ΟAmong them, from the viewpoint of exhibiting good liquid crystal alignment, butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl group is preferred. -1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro- 1,2,3,4-cyclobutanetetracarboxylic acid diacid-11-1360680 anhydride, 1,2,3,4-tetramethyl-butane tetracarboxylic acid dianhydride, u, 3,4_cyclopentatetra Carboxylic acid dianhydride, hydrazine, 2,4,5·cyclohexane tetracarboxylic acid dianhydride, 2,3,5-trimethylcyclopentyl acetic acid diacid sulphate, s 〇s _ aluminum pieces, four leaves, 5- (2,5--oxotetrahydroindenyl)·3 methyl-3-cyclohexanin-1,2-di-residual acid-intoxication, 1 7 4 S 〇1_ a serotonin anhydride, l, 3 ,3a,4,5,9b-hexahydro·5_(tetrahydro-2,5-dioxo-3·furanyl)·naphtho[l,2-c]-furan-L3·dione, Ι3' ^,4'5,9^hexachloro·5·methyl-5-(tetrahydro-2:5-dioxo-3-indolyl)naphtho[l,2-c]-furan-10-3 Diketone, hexahydro-7methyl-5-(tetrahydro-2,5·dioxo.3_indolyl)naphthoquino π, 2 is urethane-u-diketone, 1'3'3& '4,5,91 hexahydro-8-methyl_5_(tetrahydro-2,5-diox _3_furyl)-naphtho[l,2-c]-furan.dione, 1,3,33,4,5, exo-hexahydro-5,8-dimethyl (tetrazine 2,5- —oxo·3—furyl)-naphtho[i,2_c]-furan-1,3-dione, bicyclo[2,2,2-bu-s-7-ene-2,3,5,6_four Carboxylic acid dianhydride, % oxocyclohexane [3.2.1] Xinyuan 2,4 diketone -6 snail · 3, (tetrahydrofuran 2,, 5, _dione), pyromellitic dianhydride, 3 , 3,4,4,-benzophenone tetracarboxylic acid diacid field '3,3,4,4 phenylphosphonium tetracarboxylic acid dianhydride, mg·naphthalene tetracarboxylic acid diacid 1 'i: The compound represented by the following formula (5) to (7) in the compound represented by the formula (I) and the compound represented by the following formula (8) in the compound represented by the above formula (II). As a particularly preferable compound, there may be mentioned 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1 , 2,3,4_tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride ' 2,3,5- Tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[12-c Furan-1,3-dione, 1,3,3&,4,5,91»-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) )-naphtho[l,2-c]-furan-1,3- -12- 1360680 diketone, 1,3,33,4,5,91?-hexahydro-7-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, 1,3,33 ,4,5,91?-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan -1,3-diketone, 3-oxobicyclo[3.2.1]octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2',5'-difluorene), pyromellitic dianhydride, pyromellitic dianhydride, and a compound represented by the following formula (5). [化5] Ο Ο

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上述式（1-1)所示之重複單位（醯胺酸單位）中的P1所示 之4價有機基，和上述式（1-2)所示之重複單位（醯亞胺單位） 中的P2所示之4價有機基，均爲由四羧酸二酸酐衍生而來 的基。它們可以相同也可以不同。作爲上述式（1-1)中P1的 較佳實例，可以列舉分別由下述式（i)和（i，）所示之基。作爲 上述式（1-2)中P2的較佳實例，可以列舉具有脂環骨架的 基，特別較佳分別由下述式（Π)和（Π’）所示之基。The tetravalent organic group represented by P1 in the repeating unit (proline acid unit) represented by the above formula (1-1), and the repeating unit (in the imine unit) represented by the above formula (1-2) The tetravalent organic group represented by P2 is a group derived from a tetracarboxylic acid dianhydride. They can be the same or different. Preferred examples of P1 in the above formula (1-1) include those represented by the following formulas (i) and (i,). Preferred examples of P2 in the above formula (1-2) include a group having an alicyclic skeleton, and particularly preferably a group represented by the following formulas (Π) and (Π').

0')0')

(式中，R爲鹵素原子，甲基或乙基，a爲0或丨的整 數，b爲0〜6的整數，c爲0~4的整數，d爲0~5的整數） 作爲各重複單位中較佳的四羧酸二酸酐的具體實例， 作爲構成醯胺酸單位的四羧酸二酸酐，可以列舉1，2,3,4- -14- 1360680 環丁烷四羧酸二酸酐，1，2-二甲基-1，2,3，4-環丁烷四羧酸二 酸酐，1，3-二甲基·1，2,3,4-環丁烷四羧酸二酸酐，1,3-二氯 -1,2,3,4-環丁烷四羧酸二酸酐，1，2,3,4-四甲基-1,2,3,4-環丁 • 烷四羧酸二酸酐，1，2,4,5-環己四羧酸二酸酐，均苯四甲酸 , 二酸酐等，另外，作爲構成醯亞胺單位的四羧酸二酸酐爲 可以列舉脂環族四羧酸二酸酐，特別是可列舉2,3,5-三羧 基環戊基乙酸二酸酐，1，3,3&，4,5,915-六氫-5-(四氫-2,5-二氧 代-3-呋喃基）-萘並[l，2-c]呋喃-1，3-二酮，1，3,33,4,5,91)-六氫 • -5 -甲基-5-(四氫·2,5·二氧代-3-呋喃基）-萘並[l，2-c]-呋喃 . -1,3-二酮，l，3,3a，4,5,9b-六氫-7-甲基-5-(四氫-2,5-二氧代 -3-呋喃基）_萘並[i，2-c]-呋喃-1，3-二酮，1，3,3&,4,5,913-六氫 -8 -甲基- 5-(四氫-2,5-二氧代-3-呋喃基）-萘並[l，2-c]-呋喃 -1，3-二酮 ’ 1，3,3a，4,5,9b-六氫-5，8-二甲基- 5-(四氫-2,5-二氧 代-3-呋喃基）_萘並[u-c]·呋喃- i，3 -二酮等。 [二胺化合物] 作爲上述聚醯胺酸合成中使用的二胺化合物，可以列 #舉例如對苯二胺，間苯二胺，4，4’-二胺基二苯基甲烷，4，4，-, —胺基二苯基乙烷’ 4,4，-二胺基二苯基硫醚，4,4，-二胺基 一苯基颯’ 3,3，-二甲基-4,4，-二胺基聯苯，4,4，-二胺基苯甲 醯苯胺，4,4，-二胺基二苯基醚，ι，5-二胺基萘，2,2，-二甲 基-4,4，·二胺基聯苯，5 -胺基-1-(4，-胺基苯基）-1,3,3-三甲基 節滿’ 6-胺基-1-(4’-胺基苯基）-l，3,3-三甲基茚滿，3,4，-二 胺基二苯基醚’ 3,3，-二胺基二苯甲酮，3,4’-二胺基二苯甲 酮’ 4,4’-二胺基二苯甲酮，2,2-雙[4-(4-胺基苯氧基）苯基] 丙院’ 2,2-雙[4-(4-胺基苯氧基）苯基]六氟丙烷，2,2-雙（4- 1360680 胺基苯基）六氟丙烷，2，2·雙[4-(4-胺基苯氧基）苯基]颯，ι，4-雙（4-胺基苯氧基）苯，1，3·雙（4-胺基苯氧基）苯，l，3-雙（3-胺基苯氧基）苯’ 9,9-雙（4-胺基苯基）-10-氫蒽，2,7-二胺基 . 芴，9,9-雙（4·胺基苯基）芴，4,4’-亞甲基-雙（2-氯苯胺）， • 2,2’，5,5’-四氯-4,4’-二胺基聯苯，2,2，-二氯-4,4’-二胺基 -5,5’ -二甲氧基聯苯，3,3’ -二甲氧基-4,4’ -二胺基聯苯， 1,4,4’-(對伸苯基異·亞丙基）聯苯胺，4,4’-(間伸苯基異亞丙 基）聯苯胺，2,2’·雙[4-(4-胺基-2·三氟甲基苯氧基）苯基]六 • 氟丙烷，4,4’-二胺基-2,2’-雙（三氟甲基）聯苯，4,4’-雙[(4-胺基-2·三氟甲基）苯氧基]-八氟聯苯等芳香族二胺； 1，1-間二甲苯二胺，1,3-丙二胺，丁二胺，戊二胺，己 二胺，庚二胺，辛二胺，壬二胺，4,4-二胺基庚二胺，1，4-二胺基環己烷，異佛爾酮二胺，四氫二環戊二烯二胺，六 氫-4,7-亞甲基茚二亞甲基二胺，三環[6.2.1.02’7]-十一烯二 甲基二胺，4,4’-亞甲基雙（環己基胺）等脂肪族和脂環族二 胺； φ 2，3 -二胺基吡啶，2，6 -二胺基吡啶，3，4 -二胺基吡啶， 2.4- 二胺基吡啶，5,6-二胺基-2,3-二氰基吡阱，5,6-二胺基 -2,4-二羥基嘧啶，2,4-二胺基-6-二甲基胺基-1,3,5-三阱， 1.4- 雙（3-胺基丙基）哌畊，2,4-二胺基-6-異丙氧基-1，3,5-三 畊，2,4-二胺基-6-甲氧基-1，3,5·三畊，2,4-二胺基-6-苯基 -1，3,5-三畊，2,4-二胺基-6-甲基-s-三畊，2,4-二胺基-1，3,5-三阱，4,6·二胺基-2-乙烯基-s-三阱，2,4-二胺基-5-苯基噻 唑，2,6-二胺基嘌呤，5,6·二胺基-1,3-二甲基尿嘧啶，3,5-二胺基-1,2,4-***，6,9-二胺基-2-乙氧基吖啶乳酸酯，3,8- -16 - 1360680 二胺基·6 -苯基菲啶，1,4 -二胺基哌畊，3,6 -二胺基吖啶，雙 (4-胺基苯基）苯胺和下述式（III)~(IV)所示之化合物等的， 分子內具有2個伯胺基和該伯胺基以外的氮原子的二胺；(wherein R is a halogen atom, a methyl group or an ethyl group, a is an integer of 0 or 丨, b is an integer of 0 to 6, c is an integer of 0 to 4, and d is an integer of 0 to 5) Specific examples of the preferred tetracarboxylic dianhydride in the unit, as the tetracarboxylic dianhydride constituting the methionine unit, 1,2,3,4- -14- 1360680 cyclobutane tetracarboxylic acid dianhydride is exemplified. 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-Dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane-tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, pyromellitic acid, dianhydride, etc., and tetracarboxylic acid dianhydride which is a unit of quinone imine, alicyclic four The carboxylic acid dianhydride, particularly, may be exemplified by 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,33,4,5,91)-hexahydro--5-methyl-5- (tetrahydro-2,5·dioxo-3-furanyl)-naphtho[l,2-c]-furan. -1,3- Ketone, l,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[i,2-c ]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphtho[l,2-c]-furan-1,3-dione' 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[c]·furan-i,3-dione and the like. [Diamine compound] As the diamine compound used in the synthesis of the above polylysine, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4 may be mentioned. ,-,-aminodiphenylethane '4,4,-diaminodiphenyl sulfide, 4,4,-diamino-phenyl-phenyl- 3,3,-dimethyl-4, 4,-Diaminobiphenyl, 4,4,-diaminobenzilide, 4,4,-diaminodiphenyl ether, iota, 5-diaminonaphthalene, 2,2,-di Methyl-4,4,diaminobiphenyl, 5-amino-1-(4,-aminophenyl)-1,3,3-trimethyl-p- 6-amino-1- (4'-Aminophenyl)-l,3,3-trimethylindan, 3,4,-diaminodiphenyl ether '3,3,-diaminobenzophenone, 3, 4'-diaminobenzophenone '4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl] propyl compound 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4- 1360680 aminophenyl)hexafluoropropane, 2,2·bis[4-(4- Aminophenoxy)phenyl]indole, iota, 4-bis(4-aminophenoxy)benzene, 1,3 bis(4-aminophenoxy)benzene, l,3-dual (3 -aminophenoxy Benzene '9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diamino. 芴,9,9-bis(4.aminophenyl)anthracene, 4,4' -methylene-bis(2-chloroaniline), • 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2,-dichloro-4,4' -diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylene) Isopropylidene)benzidine, 4,4'-(meta-phenylisopropylene)benzidine, 2,2'·bis[4-(4-amino-2-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2·3 An aromatic diamine such as fluoromethyl)phenoxy]-octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, glycol Diamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, Hexahydro-4,7-methyleneindole dimethylene diamine, tricyclo[6.2.1.02'7]-undecenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine) ) aliphatic and cycloaliphatic φ 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyridine, 5,6-diamino-2,3-dicyanide Kipipir, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-trisole, 1.4-bis (3 -aminopropyl) piped, 2,4-diamino-6-isopropoxy-1,3,5-trin, 2,4-diamino-6-methoxy-1,3 ,5·three tillage, 2,4-diamino-6-phenyl-1,3,5-three tillage, 2,4-diamino-6-methyl-s-three tillage, 2,4- Diamino-1,3,5-tri-trap, 4,6-diamino-2-vinyl-s-triad, 2,4-diamino-5-phenylthiazole, 2,6-di Aminoguanidine, 5,6.diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethyl Oxyloacyl lactate, 3,8--16 - 1360680 diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, bis (4 -aminophenyl)aniline and a diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule, such as a compound represented by the following formulas (III) to (IV);

R5 (III)R5 (III)

(式中，R5表示具有選自吡啶，嘧啶，三阱，哌啶和哌 哄的含有氮原子的環結構的1價有機基，X表示2價有機 基）(wherein R5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple trap, piperidine and piperazine, and X represents a divalent organic group)

(式中，X表示具有選自吡啶，嘧啶，三畊，哌啶和嘁 畊的含有氮原子的環結構的2價有機基，R6表示2價有機 基，複數存在的X可以相同也可以不同） 下述式（V)所示之單取代苯二胺類；下述式（VI)所示之(wherein, X represents a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-farming, piperidine and hydrazine, and R6 represents a divalent organic group, and X in the plural may be the same or different a monosubstituted phenylenediamine represented by the following formula (V); represented by the following formula (VI)

(式中，117表示選自-0-’-(：00-，-0(：0-，-^11(：0-，-(：(^1{-和- CO-的2價有機基，R8表示具有選自類固醇骨架，三氟 甲基和氟基的1價有機基或碳原子數6~30的烷基） -17- 1360680 [化 ίο](wherein, 117 represents a divalent organic group selected from -0-'-(:00-,-0(:0-, -^11(:0-, -(:(^1{- and -CO-) R8 represents a monovalent organic group selected from a steroid skeleton, a trifluoromethyl group and a fluorine group or an alkyl group having 6 to 30 carbon atoms) -17-1360680 [Chemical]

H2N-fCHH2N-fCH

CH2tNH2 (VI) (式中，R9表示碳原子數12的烴基，複數存在的R9 分別可以相同也可以不同，p爲卜3的整數，q爲1~20的 整數） 下述式（9)〜（13)所示之化合物等。這些二胺化合物，可 φ 以單獨也可以至少2種組合使用。CH2tNH2 (VI) (wherein R9 represents a hydrocarbon group having 12 carbon atoms, and R9 in a plural number may be the same or different, p is an integer of 3, and q is an integer of 1 to 20) The following formula (9)~ (13) A compound or the like as shown. These diamine compounds may be used singly or in combination of at least two.

-18 * 1360680-18 * 1360680

(式中，丫爲2~12的整數’ z爲1〜5的整數） 其中，較佳對苯二胺，4,4’-二胺基二苯基甲烷，4，4’-二胺基二苯基硫醚’ 1，5*二胺基萘’ 2,7·二胺基苟’ 4,4’-二 胺基二苯基醚，2,2 -雙[4-(4 -胺基苯氧基）苯基]丙院’ 9,9-雙（4-胺基苯基）芴，2,2-雙[4-(4-胺基苯氧基）苯基]六氟丙 烷，2,2-雙（4-胺基苯基）六氟丙烷’ 4,4’·（對苯二異亞丙基） φ聯苯胺，4,4，-(間苯二異亞丙基）聯苯胺’丨，4_環己二胺’4,4、 亞甲基雙（環己胺），1，4-雙（4-胺基苯氧基）苯’ 4,4’-雙（4-胺 基苯氧基）聯苯，上述式（9)~(13)所示之化合物，2,6-二胺基 吡Π定，3，4 -二胺基吡D定’ 2,4 -二胺基嘧陡，3，6 -二胺基吖D定’ 上述式（III)所示之化合物中的下述式（14)所示之化合物，上 述式（IV)所示之化合物中的下述式（15)所示之化合物和上 述式（V)所示之化合物中的下述式（16)~(21)所示之化合物。 1360680 [化 12](wherein 丫 is an integer of 2 to 12 'z is an integer of 1 to 5) wherein, preferably, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino group Diphenyl sulfide ' 1,5* diamino naphthalene ' 2,7 · diamino fluorene ' 4,4 '-diaminodiphenyl ether, 2,2-bis[4-(4-amino group) Phenoxy)phenyl]propyl]9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis(4-aminophenyl)hexafluoropropane '4,4'·(p-phenylenediisopropylidene) φ-benzidine, 4,4,-(m-phenylenediisopropylidene)benzidine '丨,4_cyclohexanediamine'4,4, methylene bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene '4,4'-bis(4-amine Phenoxy group) biphenyl, a compound represented by the above formula (9) to (13), 2,6-diaminopyridinium, 3,4-diaminopyridin D'2,4-diamine The compound represented by the following formula (14) in the compound represented by the above formula (III), and the compound represented by the above formula (IV) The following formula (16) to (21) of the compound represented by the formula (15) and the compound represented by the above formula (V) The compound shown. 1360680 [Chemistry 12]

-20- 1360680-20- 1360680

(21) [聚醯胺酸的合成反應] ® 供聚醯胺酸合成反應的四羧酸二酸酐和二胺化合物的 使用比例，相對於1當量二胺化合物中含有的胺基，四羧 酸二酸酐的酸酐基較佳爲〇.2~2當量，而且更佳爲〇.3~1.2 當量。 聚醯胺酸的合成反應，較佳在有機溶劑中，在-20〜150 °C，更佳爲0~ 100 °C的溫度條件下進行。此處，作爲有機溶 劑，只要能夠溶解合成的聚醯胺酸就沒有特別限製，例如， 可以例示N-甲基-2-吡咯烷酮，N，N-二甲基乙醯胺，N，N-二 φ 甲基甲醯胺，二甲亞颯，γ-丁內酯，四甲基尿素，六甲基 磷醯三胺等非質子極性溶劑；間甲酚，二甲苯酚，苯酚， 鹵代苯酚等苯酚類溶劑。另外，有機溶劑的使用量（a)，較 佳爲使四羧酸二酸酐和二胺化合物的總量（b)，相對於全部 反應溶液的量（a + b)爲0.1~30重量％的量。 [弱溶劑] 在上述有機溶劑中，可以在所生成的聚醯胺酸不析出 的範圍內聯合使用聚醯胺酸的弱溶劑醇類，酮類，酯類， 醚類，鹵代烴類，烴類等。作爲該弱溶劑的具體實例，例 -21- 1360680 如，可以列舉甲醇’乙醇，異丙醇’環己醇，乙二醇，丙 二醇，1,4-丁二醇，三甘醇’乙二醇單甲酸，乳酸乙酯，乳 酸丁酯，丙酮，甲乙酮’甲基異丁酮，環己酮，乙酸甲酯， • 乙酸乙酯，乙酸丁酯’甲基甲氧基丙酸酯，乙基乙氧基丙 . 酸酯，草酸二乙酯’丙二酸二乙酯’***，乙二醇甲基醚， 乙二醇乙基醚，乙二醇正丙基醚’乙二醇異丙基醚，乙二 醇正丁基醚，乙二醇二甲基醚’乙二醇***乙酸酯，二乙 二醇二甲基醆，二乙二醇二***’二乙二醇單甲醚，二乙 φ 二醇單***，二乙二醇單甲醚乙酸酯，二乙二醇單***乙 酸酯，四氫呋喃，二氯甲烷，1,2-二氯乙烷，L4-二氯丁烷， 三氯乙烷，氯苯，鄰二氯苯，己烷，庚烷，辛烷，苯，甲 ' 苯，二甲苯等。 如上所述，得到溶解了聚醯胺酸而得的反應溶液。然 後，將該反應溶液注入大量的弱溶劑得到析出物，通過將 該析出物減壓乾燥可以得到聚醯胺酸。另外，通過進行1 次或數次將該聚醯胺酸再次溶解在有機溶劑中然後在弱溶 φ 劑中析出的工序，可以精製聚醯胺酸。 [醯亞胺化聚合物] <醯亞胺化聚合物> 構成本發明液晶配向劑的醯亞胺化聚合物，可以通過 將上述聚醯胺酸脫水閉環而製備。聚醯胺酸的脫水閉環， 例如可以（i)通過將聚醯胺酸加熱的方法，或者（ii)通過將聚 醯胺酸溶解在有機溶劑中’在該溶液中添加脫水劑和脫水 閉環催化劑並根據需要加熱的方法方便地進行。 上述（i)的將聚醯胺酸加熱方法的反應溫度，較佳爲 -22- 1360680 50〜20(TC，更佳60〜170°C。反應溫度不足5(TC，脫水閉環 反應難以進行充分，反應溫度超過200°C，所得醯亞胺化聚 合物分子量會降低。 • 另一方面，在上述（Π)的在聚醯胺酸溶液中添加脫水劑 . 和脫水閉環催化劑的方法中，作爲脫水劑，例如可以使用 乙酸酐，丙酸酐，三氟乙酸酐等酸酐。脫水劑的使用量， 相對於1莫耳聚醯胺酸重複單位較佳爲0.01〜20莫耳。另 外，作爲脫水閉環催化劑，可以使用例如吡啶，三甲基吡 φ 啶，二甲基吡啶，三乙胺等三級胺。但爲，並不限於這些。 脫水閉環催化劑的使用量，相對於1莫耳所使用的脫水劑 較佳爲0.01~10莫耳。另外，作爲脫水閉環反應中使用的 '有機溶劑，可以列舉與作爲在聚醯胺酸合成中使用的溶劑 所例示的有機溶劑相同的有機溶劑。而且，脫水閉環反應 的反應溫度，較佳爲0〜180°C，更佳爲10〜150°c。另外， 對於這樣得到的反應溶液，通過進行與聚醯胺酸精製方法 同樣的操作，可以精製醯亞胺化聚合物。 φ [部分醯亞胺] <含有亞胺基的聚醯胺酸> 本發明中使用的含有亞胺基的聚醯胺酸，具有將上述 聚醯胺酸部分地亞胺基化所得的結構。本發明中使用的含 有亞胺基的聚醯胺酸中的醯亞胺化率，較佳爲10 ~90% ,進 一步較佳爲30〜70%。此處，所謂“醯亞胺化率”，爲指以 %表示的相對於聚合物的重複單位總數，形成醯亞胺環而得 的重複單位數的比例。此時，醯亞胺化的一部分可以爲異 醯亞胺環。 -23- Γ360680 作爲合成含有亞胺基的聚醯胺酸的方法，可以使用例 如（i)通過將上述聚醯胺酸加熱部分脫水閉環合成的方法， (i!)將上述聚醯胺酸溶解在有機溶劑中，在該溶液中添力〇脫 水劑和脫水閉環催化劑並根據需要加熱，部分脫水閉環而 合成的方法，或（iii)混合四羧酸二酸酐、二胺化合物及二 異氰酸酯化合物，並根據需要進行加熱，縮合合成的方法， (iv)使聚醯胺酸預聚物和醯亞胺預聚物結合得到嵌段共聚 物的方法。 • 在上述⑴的方法中，反應溫度，較佳爲300 °C以下， 更佳1 00〜2 5 0°C。反應溫度如果超過300°C所得的含有亞胺 基的聚醯胺酸的分子量會降低。 另一方面，作爲在上述（ii)的方法中使用的脫水劑，可 以列舉例如乙酸酐，丙酸酐，三氟乙酸酐等酸酐。脫水劑 的使用量，相對於1莫耳聚醯胺酸重複單位較佳爲0.2〜20 莫耳。另外，作爲脫水閉環催化劑，可以使用例如吡啶， 三甲基吡啶，二甲基吡啶，三乙胺等三級胺。但爲，並不 φ 限於這些。另外，醯亞胺化催化劑的使用量，較佳爲相對 於1莫耳所使用的脫水劑較佳爲0.1 ~ 1 0莫耳。另外，作爲 脫水閉環反應中使用的有機溶劑，可以列舉與作爲在聚醯 胺酸合成中使用的溶劑所例示的有機溶劑相同的有機溶 劑。而且，脫水閉環反應的反應溫度，較佳爲0~ 1 80°C，更 佳爲60〜150°C。另外，對於這樣得到的反應溶液，通過進 行與聚醯胺酸精製方法同樣的操作，可以精製含有亞胺基 的聚醯胺酸。 作爲在上述（iii)反應中使用的二異氰酸酯化合物的具 -24- 1360680 體實例，可以列舉六亞甲基二異氰酸酯等脂肪族二異氰酸 酯；環己烷-1,2-二異氰酸酯，卜甲基環己烷-2,4-二異氰酸 酯，1，2-二甲基環己烷- ω，ω’-二異氰酸酯，1,4-二甲基環 . 己烷- ω，ω’-二異氰酸酯，異佛爾酮二異氰酸酯，1，3，5-三 _ 甲基-2-丙基環己烷1 ω，2 ω -二異氰酸酯，二環己基甲烷 -4,4’-二異氰酸酯等脂環族二異氰酸酯；二苯基甲烷-4,4’-二異氰酸酯，1，3-伸苯基二異氰酸酯，1,4-伸苯基二異氰酸 酯，1-甲基-2,4-伸苯基二異氰酸酯，1-甲，基-2,6-伸苯基二 0 異氰酸酯，下述式（22)〜（26)所示之二異氰酸酯等芳香族二 異氰酸酯。(21) [Synthesis reaction of poly-proline] ® The ratio of the use of the tetracarboxylic dianhydride and the diamine compound for the synthesis of the proline to the tetracarboxylic acid relative to the amine group contained in 1 equivalent of the diamine compound The acid anhydride group of the dianhydride is preferably from 2 to 2 equivalents, and more preferably from 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of from -20 to 150 ° C, more preferably from 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N, N-di can be exemplified. φ methylformamide, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine and other aprotic polar solvents; m-cresol, xylenol, phenol, halogenated phenol, etc. Phenol solvent. Further, the amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount of the reaction solution (a + b). the amount. [Weak solvent] In the above organic solvent, a weak solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon of polylysine may be used in combination within a range in which the produced polyamine does not precipitate. Hydrocarbons, etc. As a specific example of the weak solvent, Examples-21 to 1360680 include, for example, methanol 'ethanol, isopropanol' cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol 'ethylene glycol. Monoformic acid, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone 'methyl isobutyl ketone, cyclohexanone, methyl acetate, • ethyl acetate, butyl acetate 'methyl methoxy propionate, ethyl ethyl Oxypropane. Acid ester, diethyl oxalate 'diethyl malonate' ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether 'ethylene glycol isopropyl ether, Ethylene glycol n-butyl ether, ethylene glycol dimethyl ether 'ethylene glycol ether acetate, diethylene glycol dimethyl hydrazine, diethylene glycol diethyl ether 'diethylene glycol monomethyl ether, diethyl φ Glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, L4-dichlorobutane, trichloro Ethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, methyl benzene, xylene, and the like. As described above, a reaction solution obtained by dissolving polylysine was obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the poly-proline can be purified by repeating the step of dissolving the polyproline in an organic solvent once or several times and then depositing it in a weakly soluble φ agent. [醯i-imidized polymer] <醯i-imidized polymer> The quinone imidized polymer constituting the liquid crystal alignment agent of the present invention can be produced by dehydrating and ring-closing the above polyamic acid. Dehydration ring closure of polylysine, for example, may be (i) by heating polylysine or (ii) by dissolving polylysine in an organic solvent' by adding a dehydrating agent and a dehydration ring-closing catalyst And it is conveniently carried out according to the method of heating required. The reaction temperature of the polypyridic acid heating method of the above (i) is preferably -22 to 1360680 50 to 20 (TC, more preferably 60 to 170 ° C. The reaction temperature is less than 5 (TC, dehydration ring closure reaction is difficult to carry out sufficiently) When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium iodide polymer is lowered. • On the other hand, in the above method of adding a dehydrating agent to the polyamid acid solution and dehydrating the closed-loop catalyst, As the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol per 1 mol of the polyamido acid repeating unit. As the catalyst, a tertiary amine such as pyridine, trimethylpyridinium, lutidine or triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst used is relative to 1 mole. The amount of the dehydrating agent is preferably from 0.01 to 10 mol. The organic solvent used in the dehydration ring-closure reaction is the same as the organic solvent exemplified as the solvent used in the synthesis of polylysine. Take off The reaction temperature of the ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. Further, the reaction solution thus obtained can be purified by the same operation as the polyamic acid purification method. Aminated polymer φ [partial quinone imine] <imine group-containing poly-proline acid> The imine group-containing polyphthalic acid used in the present invention has the above-mentioned poly-proline The structure obtained by amination, the imidization ratio of the imine group-containing polyphthalic acid used in the present invention is preferably from 10 to 90%, more preferably from 30 to 70%. The "rhodium imidization ratio" refers to the ratio of the number of repeating units obtained by forming the quinone ring to the total number of repeating units of the polymer expressed in %. At this time, a part of the ruthenium may be isoindole. Imine ring -23- Γ360680 As a method of synthesizing a polyamine containing an imine group, for example, (i) a method of synthesizing a polyhydric acid by heating the above-mentioned polyglycolic acid to a closed-loop synthesis, (i!) The proline is dissolved in an organic solvent, and the dehydrating agent and dehydration are added to the solution. a method in which a ring catalyst is heated as needed, partially dehydrated and closed, or (iii) a tetracarboxylic acid dianhydride, a diamine compound, and a diisocyanate compound are mixed, and if necessary, heated, condensed and synthesized, (iv) polymerized A method of combining a proline prepolymer and a quinone imine to obtain a block copolymer. In the method of the above (1), the reaction temperature is preferably 300 ° C or less, more preferably 1 000 to 2 50 °. C. When the reaction temperature exceeds 300 ° C, the molecular weight of the imine group-containing polyphthalic acid is lowered. On the other hand, as the dehydrating agent used in the method (ii), for example, acetic anhydride, C, An acid anhydride, an acid anhydride such as trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.2 to 20 mols per 1 mol of the polyamido acid repeating unit. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. But for the sake of, it is not limited to these. Further, the amount of the ruthenium amide catalyst to be used is preferably from 0.1 to 10 moles per 100 parts of the dehydrating agent used. In addition, examples of the organic solvent used in the dehydration ring-closure reaction include the same organic solvents as those exemplified as the solvent used in the synthesis of polyamic acid. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 60 to 150 ° C. Further, the reaction solution thus obtained can be purified by the same operation as the polyamic acid purification method to obtain an imine group-containing polyamine. Examples of the tetra-isocyanate compound used in the above (iii) reaction are -1,360,680, and an aliphatic diisocyanate such as hexamethylene diisocyanate; cyclohexane-1,2-diisocyanate; Alkano-2,4-diisocyanate, 1,2-dimethylcyclohexane-ω,ω'-diisocyanate, 1,4-dimethylcyclohexane. Hexane-ω,ω'-diisocyanate, different buddha Erketone diisocyanate, 1,3,5-trimethyl-2-propylcyclohexane 1 ω, 2 ω - diisocyanate, cyclohexane diisocyanate such as dicyclohexylmethane-4,4'-diisocyanate Diphenylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1 -A, benzyl-2,6-phenylene bis-isocyanate, an aromatic diisocyanate such as a diisocyanate represented by the following formulas (22) to (26).

-25 1360680-25 1360680

其中，作爲較佳的例子可以列舉二環己基甲烷_4,4，· 二異氰酸酯’二苯基甲烷- 4,4、二異氰酸酯，1-甲基.2,4 -伸 φ 苯基二異氰酸酯’ 1-甲基-2,6 -伸苯基二異氰酸酯。它們可 以單獨或者將至少2種組合使用。另外，上述（丨⑴的反應 催化劑並非特別必要，反應溫度，較佳爲50~200°C，更佳 爲 100〜160°C。 在上述（iv)的方法中，醯胺酸預聚物，除調整四羧酸二 酸酐與二胺化合物的用量比而成爲末端具有胺基或酸酐基 的聚合物以外，還可以通過與上述聚醯胺酸合成方法柑同 的方法得到。 醯亞胺預聚物，除可以通過將上述醯胺酸預聚物脫水 -26- · 1360680 閉環的方法，或者，調整二異氰酸酯化合物與二胺化合物 的用量比而成爲末端具有胺基或異氰酸酯基的聚合物以 外’還可以通過與上述（iii)相同的方法而得到。 • 通過使這些預聚物中各末端的胺基和酸酐基，或者胺 . 基與異氰酸酯基反應，可以合成嵌段共聚物。 [末端修飾] <末端修飾型聚合物> 上述聚醯胺酸和含有亞胺基的聚醯胺酸，可以爲調節 • 了分子量的末端修飾型聚合物。通過使用該末端修飾型聚 合物’可以改善液晶配向劑的塗布特性等而不會使本發明 效果受損。這種末端修飾型聚合物，可以通過在合成聚醯 胺酸時，向反應體系中添加單酸酐，單胺化合物，單異氰 酸酯化合物等而合成。此處，作爲單酸酐，可以列舉馬來 酸酐，鄰苯二甲酸酐，依康酸酐，正癸基琥珀酸酐，正十 二烷基琥珀酸酐，正十四烷基琥珀酸酐，正十六烷基琥珀 酸酐等。另外，作爲單胺化合物，，可以列舉例如苯胺， φ 環己基胺，正丁胺’正戊胺，正己胺，正庚胺，正辛胺， 正壬胺，正癸胺，正十一胺，正十二胺，正十三胺，正十 四胺’正十五胺’正十六胺，正十七胺，正十八胺，正二 十胺等。另外，作爲單異氰酸酯化合物，可以列舉例如異 氰酸苯酯，異氰酸萘酯等。 [對數黏度] <聚合物的對數黏度> 如上得到的聚醯胺酸和含有亞胺基的聚醯胺酸的對數 黏度（ηΙη)値較佳爲〇·〇5〜l〇dl/g，更佳爲〇.〇5~5dI/g。 -27- 1360680 本發明的對數黏度（η ln)値，可以用N-甲基-2-吡咯院酮 作爲溶劑，對濃度爲〇.5g/100毫升的溶液在30 °C進行黏度 測定，由下式（A)求出。 • ln(溶液流下時間/溶劑流下時間） η * n _-------—~^ . (聚合物的重量濃度） <液晶配向劑> 本發明的液晶配向劑，較佳在有機溶劑中溶解含有上 述聚合物而構成。構成本發明液晶配向劑的聚合物，含有 # 占全部重複單位元40~60%的上述式（1-1)所示之重複單 .位。上述式（1-1)所示之重複單位：上述式（1-2)所示之重複 單位的比例較佳爲4 : 6~6 : 4，更佳爲5 : 5。 作爲構成本發明的液晶配向劑的有機溶劑，可以列舉 作爲在聚醯胺酸合成中使用的溶劑所例示的溶劑。另外， 也可以適宜選擇並用在聚醯胺酸合成反應時聯合使用的溶 劑例示的弱溶劑。 本發明的液晶配向劑中的固體成分濃度，可以考慮黏 Φ 性，揮發性等後選擇，較佳在1〜10重量％的範圍內。即， 本發明的液晶配向劑，塗布在基板表面，形成成爲液晶配 向膜的塗膜，但固體成分濃度不足1重量％的情況下，該塗 膜的膜厚過小而難以得到良好的液晶配向膜。固體成分濃 度超過10重量％的情況下，塗膜的膜厚過大而不能得到良 好的液晶配向膜，另外，液晶配向劑的黏性增大塗布特性 容易變差。另外，配製本發明液晶配向劑時的溫度，較佳 爲 Ot： ~200°C，更佳 20°C ~6(TC。 本發明的液晶配向劑，相對於1 00重量份聚合物至少 -28- 1360680 含有5重量份分子內至少具有2個環氧基之化合物（下面稱 爲“含環氧基之化合物”）。 作爲該含環氧基之化合物’可以列舉例如下式（I)所示 之化合物 [化 14] ⑴Among them, preferred examples include dicyclohexylmethane_4,4,diisocyanate 'diphenylmethane-4,4,diisocyanate, 1-methyl.2,4-extended phenylphenyl diisocyanate' 1-Methyl-2,6-phenylene diisocyanate. They may be used singly or in combination of at least two. Further, the above ((1) reaction catalyst is not particularly necessary, and the reaction temperature is preferably from 50 to 200 ° C, more preferably from 100 to 160 ° C. In the method of the above (iv), the proline prepolymer, In addition to adjusting the ratio of the amount of the tetracarboxylic dianhydride to the diamine compound to form a polymer having an amine group or an acid anhydride group at the terminal, it can also be obtained by the same method as the above-mentioned polyamic acid synthesis method. In addition to the method of dehydrating the above-mentioned proline prepolymer -26- 1360680, or adjusting the ratio of the diisocyanate compound to the diamine compound to become a polymer having an amine group or an isocyanate group at the end. It can also be obtained by the same method as (iii) above. • The block copolymer can be synthesized by reacting an amine group and an acid anhydride group at each terminal of the prepolymer or an amine group with an isocyanate group. <Terminal-modified polymer> The poly-proline and the imine-containing poly-proline may be a terminal-modified polymer having a molecular weight adjusted by using the terminal modification. The polymer 'can improve the coating characteristics and the like of the liquid crystal alignment agent without impairing the effect of the present invention. The terminal modified type polymer can be added to the reaction system by adding a monoanhydride, a monoamine, in the synthesis of the polyamic acid. A compound, a monoisocyanate compound, or the like is synthesized. Here, examples of the monoanhydride include maleic anhydride, phthalic anhydride, isocanic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and n-tetradecane. Further, succinic anhydride, n-hexadecyl succinic anhydride, etc. Further, as the monoamine compound, for example, aniline, φ cyclohexylamine, n-butylamine 'n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine n-pentadecylamine n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, positive The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. [Logarithmic viscosity] <Logarithmic viscosity of polymer> Polylysine obtained above and containing Logarithm of amino-based polylysine The viscosity (ηΙη) 値 is preferably 〇·〇5~l〇dl/g, more preferably 〇.〇5~5dI/g. -27- 1360680 The logarithmic viscosity (η ln) of the present invention can be N- Methyl-2-pyrrolidone was used as a solvent, and the viscosity of the solution having a concentration of 〇.5g/100 ml was measured at 30 ° C, and was determined by the following formula (A). • ln (solution flow time / solvent flow time) η * n _---------^. (weight concentration of the polymer) <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably composed of an organic solvent dissolved in the above-mentioned polymer. The polymer constituting the liquid crystal alignment agent of the present invention contains a repeating unit represented by the above formula (1-1) in an amount of 40 to 60% by weight of all repeating units. The repeating unit represented by the above formula (1-1): the ratio of the repeating unit represented by the above formula (1-2) is preferably 4:6 to 6:4, more preferably 5:5. The organic solvent constituting the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the synthesis of polylysine. Further, a weak solvent exemplified as a solvent to be used in combination in the polyamic acid synthesis reaction can be suitably selected and used. The solid content concentration in the liquid crystal alignment agent of the present invention can be selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film to be a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. . When the solid content concentration is more than 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is liable to be deteriorated. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably Ot: ~200 ° C, more preferably 20 ° C ~ 6 (TC. The liquid crystal alignment agent of the present invention, at least -28 with respect to 100 parts by weight of the polymer - 1360680, which contains 5 parts by weight of a compound having at least two epoxy groups in the molecule (hereinafter referred to as "epoxy group-containing compound"). The epoxy group-containing compound 'is, for example, the following formula (I) Compound [Chemical 14] (1)

H2C-C-—C--0-R10-Ο-C·---c-CH \/ H2 H2 \/ Ο 0 此處.，R111表示2價脂肪基，和下式（2)所示之化合物H2C-C-—C--0-R10-Ο-C·---c-CH \/ H2 H2 \/ Ο 0 Here, R111 represents a divalent aliphatic group, and is represented by the following formula (2) Compound

[化 15][化15]

此處，Rn表示2價有機基。含環氧基化合物，可以單 獨或至少2種組合使用。 作爲該含環氧基化合物，較佳的可以列舉例如乙二醇 φ二縮水甘油醚，聚乙二醇二縮水甘油醚，丙二醇二縮水甘 油醚，三丙二醇二縮水甘油醚，聚丙二醇二縮水甘油醚， 新戊二醇二縮水甘油醚，1,6-己二醇二縮水甘油醚，甘油二 縮水甘油醚，2,2-二溴新戊二醇二縮水甘油醚’ 1,3,5’ 6-四縮水甘油基-2,4-己二醇，N，N,N’，N’-四縮水甘油基-間二 甲苯二胺，1,3-雙（Ν,Ν-二縮水甘油基胺基甲基）環己烷， Ν，Ν，Ν’，Ν，-四縮水甘油基·4,4’-二胺基二苯基甲烷等。作爲 該含環氧基化合物的含量，相對於1〇〇重量份配向劑中含 有上述特定聚合物較佳爲5~40重量份’更佳爲1〇〜30重量 -29- 1360680 之 烷 矽 性 匕匕 ο ▲目 有官 含含 內有 度含 程以 的可 性劑 特向 劑配 向晶 配液 爲的 作明 損發 無本 在’ 以外 可另 份 化合物。作爲該含官能性矽烷之化合物，可以列舉例如3-胺基丙基三甲氧基矽烷，3·胺基丙基三乙氧基矽烷，2-胺 基丙基二甲氧基砍院，2 -胺基丙基三乙氧基政院，N-(2 -胺 基乙基）-3-胺基丙基三甲氧基矽烷，N· (2-胺基乙基）-3-胺基 丙基甲基二甲氧基矽烷，3·脲基丙基三甲氧基矽烷，3-脲 基丙基三乙氧基矽烷，N-乙氧基羰基-3-胺基丙基三甲氧基 φ 矽烷，N-乙氧基羰基-3-胺基丙基三乙氧基矽烷，N-三乙氧 基矽烷基丙基三亞乙基三胺，N-三甲氧基矽烷基丙基三亞 乙基三胺’ 10-三甲氧基矽烷基-1，4,7-三氮雜癸烷，10-三乙 ' 氧基矽烷基-1,4,7-三氮雜癸烷，9-三甲氧基矽烷基-3,6-二 氮雜壬基乙酸酯，9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸 酯’ N-苄基-3-胺基丙基三甲氧基矽烷，N-苄基-3-胺基丙基 三乙氧基矽烷，N·苯基-3-胺基丙基三甲氧基矽烷，N-苯基 -3-胺基丙基三乙氧基矽烷，N-雙（氧化乙烯）-3-胺基丙基三 φ 甲氧基矽烷，N-雙（氧化乙烯）-3-胺基丙基三乙氧基矽烷等。 這些含官能性矽烷之化合物的混合比例，相對於1〇〇 重量份聚合物，較佳爲不高於40重量份，更佳爲0.1 ~30 "重量份。 <液晶顯示元件> 使用本發明的液晶配向劑得到的液晶顯示元件，可以 通過例如下述方法製造。 (1)通過例如滾塗法，旋轉法，印刷法，噴墨法等方法， 在設置了圖案化透明導電膜的基板的一面上塗布本發明液 -30- 1360680 晶配向劑，然後，通過將塗布面加熱形成塗膜。此處，作 爲基板，例如可以使用浮法玻璃，鈉玻璃等玻璃：由聚對 苯二甲酸乙二醇酯，聚對苯二甲酸丁二醇酯，聚醆楓，聚 - 碳酸酯等塑膠形成的透明基板。作爲設置在基板一面上的 _ 透明導電膜，可以使用由氧化錫（SnO〇形成的NESA膜（美 國PPG公司注冊商標），氧化銦-氧化錫（ImCh-SnCh)形成的 IT0膜等。這些透明導電膜的圖案，可以使用光蝕刻法或 用預掩模的方法。反射電極中可以使用A1或Ag等金屬， φ 或者，含有這些金屬的合金等。只要具有充分的反射率就 不限於這些》液晶配向劑的塗布時，爲了使基板表面和透 明導電膜或反射電極與塗膜的黏合性更好，可以在基板的 該表面預先塗布含官能性矽烷之化合物、含官能性鈦之化 合物等。液晶配向劑塗布後的加熱溫度，較佳爲80~300°C， 更佳爲1 2 0 ~ 2 5 0 °C。含有聚醯胺酸的本發明液晶配向劑，通 過塗布除去有機溶劑形成成爲配向膜的塗膜，再通過加熱 進行脫水閉環，可以成爲進一步醯亞胺化的塗膜。形成塗 φ膜的膜厚’較佳爲0.001〜Ιμιη，.更佳爲0.0〇5〜0·5μιη。 (2)對形成的塗膜面用纏有例如由尼龍、人造絲、棉等 纖維形成的布卷起的滾筒沿一定方向摩擦而進行摩擦處 理。這樣’在塗膜上賦予了液晶分子配向能力，形成液晶 配向膜。 另外’由本發明液晶配向劑形成的液晶配向膜，通過 進行如日本特開平6-222366號公報或日本特開平6-281937 號公報所示的，通過局部照射紫外線改變預斜角的處理， 或者進行如日本特開平5-107544號公報所示的，在實施摩 -31- 1360680 擦處理的液晶配向膜表面局部形成保護膜，與先前摩擦處 理不同方向進行摩擦處理後除去保護膜，以改變液晶配向 膜的液晶配向能力的處理，可以改善液晶顯示元件的視野 - 特性。 (3)製作兩片如上所述形成液晶配向膜的基板，分別使 液晶配向膜的摩擦方向垂直或逆平行，將兩片基板***間 隙（單元間隔）對向配置，將兩片基板的周圍部分用密封劑 黏貼，在通過基板表面和密封劑區分的間隙內注入塡充液 # 晶，密封注入孔並構成液晶胞。而且，液晶胞的外表面， 即，構成液晶胞的透明基板一側，通過配置偏光板，得到 液晶顯示元件。 ' 此處，作爲密封劑，可以使用例如固化劑和作爲墊片 的含有氧化鋁球的環氧樹脂等。 作爲液晶，可以列舉向列型液晶和層列型液晶。其中 較佳向列型液晶，例如可以使用席夫鹼類液晶，氧化偶氮 類液晶，聯苯類液晶，苯基環己烷類液晶，酯類液晶，聯 φ 三苯類液晶，聯苯基環己烷類液晶，嘧啶類液晶，二噁烷 類液晶，二環辛烷類液晶，立方烷類液晶等。另外，可以 在这些液晶中，添加例如膽固醇氯化物，膽固醇壬酸酯， 膽固醇碳酸酯等膽固醇型液晶或作爲商品名“ C-1 5 ” “ CB_1 5” （默克社製）销售的對掌劑等而使用。而且，也可 以使用對癸氧基亞苄基-對胺基-2-甲基丁基桂皮酸酯等強 導電性液晶。 另外，作爲黏貼在液晶胞的外表面上的偏振光片，可 以列舉例如在使聚乙烯醇伸展配向的同時吸收碘的被稱爲 -32- 1360680 Η膜的偏振光膜用乙酸纖維素保護膜夾持的偏振光片或者 Η膜自身形成的偏振光片。 [實施例] - 下面，通過實施例對本發明具體說明，但本發明並不 . 限於這些實施例。實施例和比較例的透明性、電壓保持率、 燒結性通過以下方法評價。 [透明性] 測定裝置使用HITACHI U-2010型分光光度計（日立製 # 作所（股）製）。在厚度1.5mm的石英基板上，用旋轉器塗布 如上製備的本發明液晶配向劑，通過在1 80°C乾燥1小時， 形成乾燥膜厚800A的塗膜。進行所製作的塗膜透過率的測 定。透過率測定，求出在波長700nm，600nm，500nm，450nm， 400nm，350nm和300nm的値。在任何測定波長的透過率均 在爲90%以上的情況判斷爲良好，除此之外的情況判斷爲 不好。 [電壓保持率] φ 在液晶顯示元件上在6 0微秒的加壓時間，以1 6 7毫秒 的間隔施加5 V的電壓後，測定從解除加壓到】67毫秒後的 電壓保持率。測定裝置使用（股）東陽Technica製VHR-1。 電壓保持率爲90%以上判斷爲良好，除此之外判斷爲不好。 [燒結] 在液晶顯示元件上在7 0 °C的環境溫度下施加1小時密 集1.0V直流電的30Hz’ 2.0V的矩形波，將剛切斷直流電 壓後液晶胞內殘留的電壓通過閃爍消除法求出殘留的DC 電壓。殘留的DC値不限於構成液晶顯示元件的電極種類 -33- 1360680 爲不高於2V，各電極種類之間的殘留DC的差異爲不高於 0.5 V的情況判斷爲良好，除此之外的情況判斷爲不好。 合成例1 . 將224.1 7g(0.5莫耳）2,3,5-三羧基環戊基乙酸二酸酐和 157.14£(0.5莫耳）1，3,33,4,5,91)-六氫-8-甲基-5-(四氫-2,5-二 氧代-3-呋喃基）·萘並[l，2-c] -呋喃-1，3 -二酮作爲四羧酸二 酸酐，94.62g(0.875 莫耳）對苯二胺，32.02g(0.1 莫耳）2,2，-二三氟甲基-4,4’-二胺基聯苯和6.43g(0.01莫耳）3,6-雙（4- # 胺基苯甲醯氧基）膽甾醇作爲二胺化合物，10.85g(〇.〇3莫 耳）4-胺基苯基十八烷基醚作爲單胺溶解在4，500gN-甲基 -2-吡咯烷酮中’在60°C反應6小時。然後，將反應溶液注 " 入大量過剩的甲醇中使反應產物沈澱。然後，用甲醇洗滌， 減壓下在40°C乾燥15小時，得到410g對數黏度〇.87dl/g 的聚醯胺酸。將30g所得聚醯胺酸溶解在570gN_甲基-2_啦 咯烷酮中’添加23.4g吡啶和18.1g乙酸酐並在li〇°c脫水 閉環4小時，與上述同樣地進行沈澱、洗滌、減壓，得到 • 17.5g對數黏度〇.8〇dl/g的聚醯亞胺（將其稱爲“聚酿亞 胺，，（A · 1))。 合成例2 將224.1 7g(0.5莫耳）2,3,5-三羧基環戊基乙酸二酸野和 1 5 7，1 4 g (0 · 5 莫耳）1，3，3 a，4，5，9 b -六氫· 8 ·甲基-5 -(四氫 _ 2 5 ·二 氧代-3-呋喃基）-萘並[u — c]-呋喃-二酮作爲四竣酸二 酸酐，94.62g(〇.87 5莫耳）對苯二胺，24.85g((M莫耳）雙胺 基丙基四甲基二矽氧烷和6.43g(〇.〇1莫耳）36雙（4胺基苯 甲醯氧基）膽甾醇作爲二胺化合物’ l〇 85g(〇 〇3莫耳）4胺 -34- 1360680 基苯基十八烷基醚作爲單胺溶解在4,500gN-甲基-2-吡咯烷 酮中，在60°C反應6小時。然後，將反應溶液注入大量過 剩的甲醇中使反應產物沈澱。然後，用甲醇洗滌，減壓下 - 在40°C乾燥15小時，得到370g對數黏度0.82dl/g的聚醯 胺酸。將30g所得聚醯胺酸溶解在57 OgN-甲基-2-吡咯烷酮 中，添加23.4g吡啶和18.lg乙酸酐並在110 °C脫水閉環4 小時，與上述同樣地進行沈澱、洗滌、減壓，得到18.5g 對數黏度0.77dl/g的聚醯亞胺（將其稱爲“聚醯亞胺” φ (A-2))。 合成例3 將22.42g(0.05莫耳）2,3,5-三羧基環戊基乙酸二酸酐和 298.57£(0.95莫耳）1，3,38,4,5,91)-六氫-8-甲基-5-(四氫.2,5- 二氧代-3-呋喃基）-萘並[l，2-c]-呋喃-1,3-二酮作爲四羧酸 二酸酐，83.81g(0.775 莫耳）對苯二胺，64.04g(0.2 莫耳）2,2，-二三氟甲基-4,4’-二胺基聯苯和6.43g(0.01莫耳）3,6-雙（4-胺基苯甲醯氧基）膽甾醇作爲二胺化合物，2.79g(0.03莫耳） 馨苯胺作爲單胺溶解在4，500gN-甲基-2-吡咯烷酮中，在6〇 °C反應6小時。然後，將反應溶液注入大量過剩的甲醇中 使反應產物沈澱。然後，用甲醇洗滌，減壓下在40 °C乾燥 15小時，得到410g對數黏度〇.85dl/g的聚醯胺酸。將3〇g 所得聚醯胺酸溶解在570gN-甲基-2-吡咯烷酮中，添加23.4g 吡啶和18.lg乙酸酐並在110 °C脫水閉環4小時，與上述同 樣地進行沈澱、洗滌、減壓’得到1 5 · 1 g對數黏度〇. 8 3 dl/g 的聚醯亞胺（將其稱爲“聚醯亞胺” （A_3))。 合成例4 -35- 1360680 在合成例2中，用95.7g(〇.8 85莫耳）對苯二胺， 24.85g(0.1莫耳）雙胺基丙基四甲基二矽氧烷（上述式（VI)所 示之化合物）和作爲單胺用8.09g(0.03莫耳）正十八烷基胺 ‘ 以外，與合成例2同樣地，得到i9.4g對數黏度0.65dl/g . 的聚醯亞胺（稱之爲“聚醯亞胺”（A-4)p 合成例5 將196.12g(1.0莫耳）環丁烷四羧酸二酸酐作爲四羧酸 二酸酐’將212g(1.0莫耳）2,2’-二甲基-4,4’-二胺基聯苯作 # 爲二胺化合物溶解在4500gN-甲基-2-吡咯烷酮中並在60°C 反應6小時。然後’將反應液注入大量過剩的甲醇中沈澱 反應產物。然後’通過用甲醇洗滌，減壓下在4(TC乾燥15 小時’得到410g對數黏度〇.90dl/g的聚醯胺酸（稱之爲“聚 醯胺酸”（B_l))。 合成例6 在合成例5中，除用l〇9.06g(0_5莫耳）均苯四甲酸二 酸酐和98.06g(0.5莫耳）環丁院四竣酸二酸酐作爲四竣酸二 φ 酸酐’用200.2g(1.0莫耳）4,4’-二胺基二苯基醚作爲二胺化 合物以外，與合成例5同樣地，得到41 〇g對數黏度爲 0.93dl/g的聚醯胺酸（稱之爲“聚醯胺酸” 合成例7 在合成例5中’除用i〇9.06g(0.5莫耳）均苯四甲酸二 酸酉干和98_06g(0.5莫耳）環丁垸四殘酸二酸肝作爲四竣酸二 酸酐’用198.3g(1.0莫耳）4,4’-二胺基二苯基甲院作爲二胺 化合物以外，與合成例5同樣地，得到410g對數黏度爲 0.95dl/g的聚醯胺酸（稱之爲"聚醯胺酸”（B_3))。 -36- 1360680 合成例8 除去合成例1中的單胺化合物4-胺基苯基十八烷基 醚，用96.24g(0.89莫耳）對苯二胺以外，與合成例1同樣 . 地合成醯亞胺預聚物，將其溶解在N-甲基-2-吡咯烷酮形成 固體成分濃度爲10重量％的溶液。另外，將上述合成例6 得到的聚醯胺酸（B-2)用作醯胺酸預聚物，同樣地溶解在N-甲基-2-吡咯烷酮形成固體成分濃度爲1〇重量％的溶液》然 後，將5 00g醯亞胺預聚物溶液和500g醯胺酸預聚物混合 φ 並攪拌2小時後，將反應溶液注入大量過剩的甲醇中沈澱 反應產物。然後，通過用甲醇洗滌，減壓下在4 0 °C乾燥15 小時，得到100g對數黏度爲0.95dl/g的由聚酿胺酸和聚醯 亞胺形成的聚合物（聚醯胺酸的比例，以重量比計爲 50%)(稱之爲"聚合物（C-1))。 合成例9 在合成例2中除去單胺4-胺基苯基十八烷基醚，用 96.24 g (0.89莫耳）對苯二胺外，與合成例2同樣地合成醯亞 φ 胺預聚物，將其溶解在N-甲基-2-吡咯烷酮中形成固體成分 濃度爲1 0重量％的溶液。另外，將上述合成例5得到的聚 醯胺酸（B-1)用作醯胺酸預聚物，同樣地將其溶解在N-甲基 -2-吡咯烷酮中形成固體成分濃度10重量％的溶液。然後， 將500g醯亞胺預聚物溶液和500g醯胺酸預聚物混合並攪 拌2小時後，將反應溶液注入大量過剩的甲醇中沈澱反應 產物。然後，通過用甲醇洗滌，減壓下在4 0 °C乾燥15小時， 得到100g對數黏度爲0.93dl/g的由聚醯胺酸和聚醯亞胺形 成的聚合物（聚醢胺酸的比例，以重量計爲50%)(稱之爲 -37- 1360680 "聚合物（C-2))。 合成例1 0 在合成例4中除去單胺4-胺基苯基十八烷基醚，用 - 97.32g(0.90莫耳）對苯二胺外，與合成例4同樣地合成醯亞 . 胺預聚物，將其溶解在N-甲基-2-吡咯烷酮中形成固體成分 濃度爲10重量％的溶液。另外，將上述合成例7得到的聚 醯胺酸（B-3)用作醯胺酸預聚物，同樣地將其溶解在N-甲基 -2-吡咯烷酮中形成固體成分濃度1〇重量％的溶液。然後， # 將500g醯亞胺預聚物溶液和500g醯胺酸預聚物混合並攪 拌2小時後，將反應溶液注入大量過剩的甲醇中沈澱反應 產物。然後，通過用甲醇洗滌，減壓下在40°C乾燥15小時， ' 得到l〇〇g對數黏度爲〇.97dl/g的由聚醯胺酸和聚醯亞胺形 成的聚合物（聚醯胺酸的比例，以重量計爲50%)(稱之爲 “聚合物（C-3))。 實施例1 使合成例1得到的聚醯亞胺（A-1)和合成例5得到的聚 φ 醯胺酸（B-1)以聚醯亞胺：聚醯胺酸= 50: 50(重量比），溶 解在N-甲基-2-吡咯烷酮/γ-丁內酯的混合溶劑中（重量比 30/70)，相對於100重量份聚合物溶解10重量份（Phr)聚乙 二醇二縮水甘油醚（分子量約4 00)形成固體成分濃度爲4重 量％的溶液，充分攪拌後，將該溶液用孔徑1 μιη的篩檢程 式過濾，調製本發明的液晶配向劑。將上述液晶配向劑用 旋轉器塗布（旋轉數：2,000rpm，塗布時間：1分鐘）到由設 置在厚度爲1mm的玻璃基板一面上的ITO膜形成的透明導 電膜上，和由A1形成的反射膜上，在200°C乾燥1小時形 -38- Γ360680 成乾燥膜厚爲0.08 μπι的保護膜。在該保護膜上用具有纏繞 了人造絲布的滾筒的摩擦器，以滾筒的轉數400rpm，台移 動速度3cm/秒，毛刷腳壓入長度0.4mm進行摩擦處理。將 • 上述液晶配向膜塗布基板在異丙醇中浸漬1分鐘後，在100 乞的電熱板上乾燥5分鐘》然後，在具有一對透明電極/透 明電極基板，和一對透明電極/反射電極基板的上述液晶配 向膜塗布基板的液晶配向膜分別在外周，塗布直徑5.5 μιη 的摻入氧化鋁球的環氧樹脂黏合劑後，相對於液晶配向膜 φ 面重疊壓合’使黏合劑固化。然后，從液晶注入口向基板 间塡充向列型液晶（默克社製，MLC-6221)后，用丙烯酸类 光固化黏合劑密封液晶注入口，在基板的外側兩面黏合偏 ' 振光片，製作液晶显·示元件。評價所得液晶顯示元件的電 壓保持率、燒結性。在厚度爲1.5mm的石英基板上，用旋 轉器塗布上述調製的本發明液晶配向劑，與液晶顯示元件 製作時同樣地形成塗膜。從製作的塗膜透過率測定評價透 明性。結果示於表1中。可以確認本發明所得液晶配向劑 φ 的電壓保持率和閃爍特性良好。 實施例2 ~ 1 5 根據下述表1所述的方案，將合成例1〜10所得的聚醯 亞胺（Α-1)~(Α-4)、聚醯胺酸（B-1)〜（B-3)、部分醯亞胺 (C-1)〜（C-3)和含環氧基之化合物溶解在以γ·丁內酯爲主成 分的混合溶劑中得到固體成分濃度爲4.0%的溶液，將該溶 液通過孔徑爲1 μιη的篩檢程式過濾，調製本發明的液晶配 向劑。分別用如此調製的液晶配向劑，於實施例1同樣地， 在基板表面上形成保護膜，使用該形成液晶配向膜的基板 -39- 1360680 製作液晶顯示元件。而且，評價透明性、電壓保持率和燒 結性。結果示於表1。 比較例1~5 根據下述表1所示的方案，於實施例同樣地製作液晶 顯示元件。而且，評價透明性、電壓保持率和燒結性。結 果示於表1。Here, Rn represents a divalent organic group. The epoxy group-containing compound may be used singly or in combination of at least two. Preferred examples of the epoxy group-containing compound include ethylene glycol φ diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether ' 1,3,5' 6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, fluorene-diglycidyl) Aminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, hydrazine, tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. The content of the epoxy group-containing compound is preferably from 5 to 40 parts by weight, more preferably from 1 to 30 parts by weight to -29 to 1360680, per 1 part by weight of the alignment agent.匕匕ο ▲ 目 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有As the compound containing a functional decane, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyldimethoxy sulfoxide, 2 - Aminopropyl triethoxylate, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N. (2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3·ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxycyclodecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethyl'oxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate 'N-benzyl-3-aminopropyltrimethoxydecane , N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine Alkyl, N-bis(ethylene oxide)-3-aminopropyltris(n)methoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, and the like. The mixing ratio of the functional decane-containing compound is preferably not more than 40 parts by weight, more preferably 0.1 to 30 parts by weight based on 1 part by weight of the polymer. <Liquid crystal display element> The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) Applying the liquid 30-40360680 crystallizing agent of the present invention to one surface of a substrate on which a patterned transparent conductive film is provided by, for example, a roll coating method, a spin method, a printing method, an inkjet method, or the like, and then passing The coated surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda glass may be used: it is formed of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyfluorene, poly-carbonate or the like. Transparent substrate. As the transparent conductive film provided on one surface of the substrate, an OTO film formed of tin oxide (NSA film formed by SnO〇 (registered trademark of PPG, USA), indium oxide-tin oxide (ImCh-SnCh), etc. can be used. The pattern of the conductive film may be a photolithography method or a method using a pre-mask. A metal such as A1 or Ag, φ or an alloy containing these metals may be used as the reflective electrode, and it is not limited to these as long as it has sufficient reflectance. In the application of the liquid crystal alignment agent, in order to improve the adhesion between the surface of the substrate and the transparent conductive film or the reflective electrode and the coating film, a compound containing a functional decane, a compound containing a functional titanium, or the like may be applied to the surface of the substrate in advance. The heating temperature after application of the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 1 2 0 to 250 ° C. The liquid crystal alignment agent of the present invention containing polylysine is formed by removing an organic solvent by coating. The coating film of the alignment film is further subjected to dehydration ring closure by heating, and the film may be further imidized. The film thickness of the film to be coated is preferably 0.001 to Ιμιη, more preferably 0.0. 〇5~0·5μιη. (2) The formed coating film surface is rubbed in a predetermined direction by a roller wound with a cloth formed of fibers such as nylon, rayon, cotton, etc., and rubbed. In the liquid crystal alignment film, the liquid crystal alignment film is provided, and the liquid crystal alignment film is formed by the liquid crystal alignment agent of the present invention. The process of changing the pretilt angle by the partial irradiation of the ultraviolet ray, or the protective film formed on the surface of the liquid crystal alignment film which is subjected to the rubbing treatment of the Mo-31- 1360680, as shown in Japanese Laid-Open Patent Publication No. H5-107544, is different from the previous rubbing treatment. After the rubbing treatment is performed in the direction, the protective film is removed to change the liquid crystal alignment ability of the liquid crystal alignment film, and the field of view of the liquid crystal display element can be improved. (3) Two substrates for forming a liquid crystal alignment film as described above are formed, respectively, and liquid crystals are respectively formed. The rubbing direction of the alignment film is perpendicular or anti-parallel, and the two substrates are inserted into the gap (unit spacing) to face each other, and the two substrates are surrounded. The sealing agent is adhered, and the filling liquid is injected into the gap which is separated by the surface of the substrate and the sealing agent, and the injection hole is sealed to constitute a liquid crystal cell. Further, the outer surface of the liquid crystal cell, that is, the transparent substrate side constituting the liquid crystal cell A liquid crystal display element is obtained by disposing a polarizing plate. Here, as the sealing agent, for example, a curing agent and an epoxy resin containing alumina balls as a gasket can be used. Examples of the liquid crystal include nematic liquid crystal and layers. Columnar liquid crystal. Among them, a nematic liquid crystal is preferably used, for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a φ triphenyl liquid crystal. , biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, dicyclooctane liquid crystal, cubic liquid crystal liquid crystal, and the like. Further, in these liquid crystals, a cholesteric liquid crystal such as cholesterol chloride, cholesterol phthalate or cholesterol carbonate or a brand name "C-1 5 " "CB_1 5" (manufactured by Merck) can be added. Used in the case of agents. Further, a strong conductive liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate may also be used. In addition, as the polarizing plate which is adhered to the outer surface of the liquid crystal cell, for example, a cellulose acetate protective film for a polarizing film called a -32-1360680 yttrium film which absorbs iodine while stretching the polyvinyl alcohol is exemplified. A polarizing plate that is clamped or a polarizing plate formed by the ruthenium film itself. [Examples] - Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The transparency, voltage holding ratio, and sinterability of the examples and the comparative examples were evaluated by the following methods. [Transparency] The measuring device was a HITACHI U-2010 spectrophotometer (manufactured by Hitachi Ltd.). On the quartz substrate having a thickness of 1.5 mm, the liquid crystal alignment agent of the present invention prepared as above was applied by a spinner, and dried at 180 ° C for 1 hour to form a coating film having a dry film thickness of 800 A. The measurement of the transmittance of the produced coating film was carried out. The transmittance at 700 nm, 600 nm, 500 nm, 450 nm, 400 nm, 350 nm, and 300 nm was determined by transmittance measurement. When the transmittance at any measurement wavelength was 90% or more, it was judged to be good, and the other cases were judged to be bad. [Voltage retention ratio] φ A voltage of 5 V was applied to the liquid crystal display element at a pressure of 60 μsec at intervals of 167 msec, and then the voltage holding ratio from the release of the pressure to 67 ms was measured. The measuring device used (share) VHR-1 manufactured by Dongyang Technica. The voltage holding ratio was judged to be good at 90% or more, and it was judged to be bad otherwise. [Sintering] A 30 Hz '2.0 V rectangular wave with a dense 1.0 V DC applied for 1 hour at an ambient temperature of 70 ° C on a liquid crystal display element, and the voltage remaining in the liquid crystal cell after the DC voltage was cut off was passed through a scintillation elimination method. Find the residual DC voltage. The residual DC 値 is not limited to the type of the electrode constituting the liquid crystal display element - 33 - 1360680 is not higher than 2 V, and the difference in residual DC between the electrode types is not higher than 0.5 V, and it is judged to be good, and otherwise. The situation is judged to be bad. Synthesis Example 1. 224.1 7 g (0.5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 157.14 £ (0.5 mol) 1,3,33,4,5,91)-hexahydro- 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphtho[l,2-c]-furan-1,3-dione as tetracarboxylic acid dianhydride 94.62 g (0.875 mol) p-phenylenediamine, 32.02 g (0.1 mol) 2,2,-ditrifluoromethyl-4,4'-diaminobiphenyl and 6.43 g (0.01 mol) 3, 6-bis(4-#aminobenzylideneoxy)cholesterol as a diamine compound, 10.85 g (〇.〇3 mol) 4-aminophenyl stearyl ether as a monoamine dissolved in 4, 500 g of N-methyl-2-pyrrolidone was reacted at 60 ° C for 6 hours. Then, the reaction solution was injected into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 410 g of a polyamic acid having a logarithmic viscosity of 87.87 dl / g. 30 g of the obtained polylysine was dissolved in 570 g of N-methyl-2-brolopropanone, and 23.4 g of pyridine and 18.1 g of acetic anhydride were added and dehydrated and closed for 4 hours at li ° C, and precipitation and washing were carried out in the same manner as above. Under reduced pressure, 17.5 g of a polyimine having a logarithmic viscosity of 〇8 dl/g (referred to as "polyimine, (A · 1)) was obtained. Synthesis Example 2 224.1 7 g (0.5 Mo Ear) 2,3,5-tricarboxycyclopentyl acetic acid diacid field and 1 5 7,1 4 g (0 · 5 mol) 1,3,3 a,4,5,9 b -hexahydro·8 ·Methyl-5-(tetrahydro-25 5 dioxo-3-furanyl)-naphtho[u-c]-furan-dione as tetracarboxylic acid dianhydride, 94.62 g (〇.87 5 Mo Ear) p-phenylenediamine, 24.85 g ((M mole) bis-aminopropyl tetramethyldioxane and 6.43 g (〇.〇1 molar) 36 bis (4 aminobenzhydryloxy) Cholesterol as a diamine compound 'l〇85g(〇〇3mol)4amine-34- 1360680-phenylphenyl stearyl ether as a monoamine dissolved in 4,500g N-methyl-2-pyrrolidone at 60° C is reacted for 6 hours. Then, the reaction solution is poured into a large excess of methanol to precipitate a reaction product, and then washed with methanol, minus Pressing - drying at 40 ° C for 15 hours gave 370 g of poly-proline with a logarithmic viscosity of 0.82 dl / g. 30 g of the obtained poly-proline was dissolved in 57 Og N-methyl-2-pyrrolidone, adding 23.4 g of pyridine and 18. g of acetic anhydride was dehydrated and closed at 110 ° C for 4 hours, and precipitated, washed, and decompressed in the same manner as above to obtain 18.5 g of a polyimine having a logarithmic viscosity of 0.77 dl/g (referred to as "poly" Amine" φ (A-2)). Synthesis Example 3 22.42 g (0.05 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 298.57 £ (0.95 mol) 1,3,38,4 ,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3- Diketone as tetracarboxylic acid dianhydride, 83.81 g (0.775 mol) p-phenylenediamine, 64.04 g (0.2 mol) 2,2,-ditrifluoromethyl-4,4'-diaminobiphenyl and 6.43 g (0.01 mol) of 3,6-bis(4-aminobenzylideneoxy)cholesterol as a diamine compound, 2.79 g (0.03 mol) of aniline as a monoamine dissolved in 4,500 g of N-methyl In 2-pyrrolidone, the reaction is carried out for 6 hours at 6 ° C. Then, the reaction solution is poured into a large excess of methanol to precipitate a reaction product. The alcohol was washed and dried at 40 ° C for 15 hours under reduced pressure to obtain 410 g of a polyamic acid having a logarithmic viscosity of 8585 dl/g. 3 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 18. g of acetic anhydride were added thereto, and the mixture was dehydrated and closed at 110 ° C for 4 hours, and precipitated and washed in the same manner as above. The reduced pressure 'obtained 1 5 · 1 g logarithmic viscosity 8 8 3 dl / g of polyimine (referred to as "polyimine" (A_3)). Synthesis Example 4 - 35 - 1360680 In Synthesis Example 2, 95.7 g (〇·8 85 mol) of p-phenylenediamine, 24.85 g (0.1 mol) of bisaminopropyltetramethyldioxane (described above) In the same manner as in Synthesis Example 2, a compound having a logarithmic viscosity of 0.65 dl/g was obtained in the same manner as in Synthesis Example 2 except that the compound represented by the formula (VI) and 8.09 g (0.03 mol) of n-octadecylamine were used as the monoamine. Yttrium imine (referred to as "polyimine" (A-4) p Synthesis Example 5 196.12 g (1.0 mol) cyclobutane tetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride '212 g (1.0 Mo Ear) 2,2'-dimethyl-4,4'-diaminobiphenyl as #diamine compound was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction solution was poured into a large excess of methanol to precipitate the reaction product. Then, by washing with methanol, under reduced pressure at 4 (TC drying for 15 hours), 410 g of a logarithmic viscosity of 90.90 dl/g of polylysine was obtained (referred to as "poly" "Proline" (B_l)). Synthesis Example 6 In Synthesis Example 5, except that 9.06 g (0-5 mol) of pyromellitic dianhydride and 98.06 g (0.5 mol) of cyclobutyric acid tetradecanoic acid were used. Anhydride as tetradecanoic acid di-anthracene anhydride' In the same manner as in Synthesis Example 5 except that 0.2 g (1.0 mol) of 4,4'-diaminodiphenyl ether was used as the diamine compound, a polyglycine having a logarithmic viscosity of 0.93 dl/g was obtained. It is "polyglycine" Synthesis Example 7 In Synthesis Example 5 'except i 〇 9.06 g (0.5 mol) of pyromellitic acid bismuth dichloride and 98_06 g (0.5 mol) of cyclobutane tetrahydro acid In the same manner as in Synthesis Example 5, a logarithmic viscosity of 410 g was obtained in the same manner as in Synthesis Example 5 except that 198.3 g (1.0 mol) of 4,4'-diaminodiphenylcarbendate was used as the diamine compound. /g polylysine (referred to as "polyproline acid (B_3)). -36- 1360680 Synthesis Example 8 Removal of the monoamine compound 4-aminophenyl octadecyl ether in Synthesis Example 1 In the same manner as in Synthesis Example 1, except that 96.24 g (0.89 mol) of p-phenylenediamine was used, the quinone imine prepolymer was synthesized and dissolved in N-methyl-2-pyrrolidone to form a solid concentration of 10% by weight. Further, the polyamic acid (B-2) obtained in the above Synthesis Example 6 was used as a proline prepolymer, and similarly dissolved in N-methyl-2-pyrrolidone to form a solid concentration of 1 〇. % dissolution Then, a mixture of 500 g of the imine prepolymer solution and 500 g of the proline prepolymer was mixed and stirred for 2 hours, and then the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. Then, by washing with methanol, Drying at 40 ° C for 15 hours under reduced pressure gave 100 g of a polymer having a logarithmic viscosity of 0.95 dl/g and consisting of polyacrylamide and polyimine (the ratio of polyamine to 50 by weight) %) (referred to as "polymer (C-1)). Synthesis Example 9 The monoamine 4-aminophenyl octadecyl ether was removed in Synthesis Example 2, and the yttrium ytamine prepolymer was synthesized in the same manner as in Synthesis Example 2 except that 96.24 g (0.89 mol) of p-phenylenediamine was used. The solution was dissolved in N-methyl-2-pyrrolidone to form a solution having a solid concentration of 10% by weight. Further, the polyamic acid (B-1) obtained in the above Synthesis Example 5 was used as a proline prepolymer, and similarly dissolved in N-methyl-2-pyrrolidone to form a solid concentration of 10% by weight. Solution. Then, 500 g of the quinone imine prepolymer solution and 500 g of the proline prepolymer were mixed and stirred for 2 hours, and then the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. Then, by washing with methanol and drying at 40 ° C for 15 hours under reduced pressure, 100 g of a polymer having a logarithmic viscosity of 0.93 dl/g and formed of polyglycine and polyimine (polyamine ratio) was obtained. , 50% by weight) (referred to as -37-1360680 " polymer (C-2)). Synthesis Example 10 A monoamine 4-aminophenyl octadecyl ether was removed in Synthesis Example 4, and a ruthenium was synthesized in the same manner as in Synthesis Example 4 except that - 97.32 g (0.90 mol) of p-phenylenediamine was used. The prepolymer was dissolved in N-methyl-2-pyrrolidone to form a solution having a solid concentration of 10% by weight. Further, the polyamic acid (B-3) obtained in the above Synthesis Example 7 was used as a proline prepolymer, and similarly dissolved in N-methyl-2-pyrrolidone to form a solid concentration of 1% by weight. The solution. Then, #500 g of the imine prepolymer solution and 500 g of the proline prepolymer were mixed and stirred for 2 hours, and then the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, by washing with methanol and drying at 40 ° C for 15 hours under reduced pressure, 'a polymer having a logarithmic viscosity of 97.97 dl/g of polyglycine and polyimine was obtained. The ratio of the amine acid was 50% by weight (referred to as "polymer (C-3)). Example 1 The obtained polyimine (A-1) obtained in Synthesis Example 1 and Synthesis Example 5 were obtained. Polyφ-proline (B-1) is dissolved in a mixed solvent of N-methyl-2-pyrrolidone/γ-butyrolactone at a polyimine:polyamine acid = 50:50 (by weight) a weight ratio of 30/70), 10 parts by weight (Phr) of polyethylene glycol diglycidyl ether (molecular weight of about 400) is dissolved in 100 parts by weight of the polymer to form a solution having a solid concentration of 4% by weight, and after sufficiently stirring, The solution was filtered with a sieve having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. The liquid crystal alignment agent was coated with a spinner (rotation number: 2,000 rpm, coating time: 1 minute) to be set to a thickness of 1 mm. On the transparent conductive film formed on the ITO film on one side of the glass substrate, and on the reflective film formed by A1, dried at 200 ° C for 1 hour. -38- Γ360680 A protective film having a dry film thickness of 0.08 μm was used. A friction device having a roller wrapped with rayon cloth was used on the protective film, the number of revolutions of the drum was 400 rpm, the moving speed of the table was 3 cm/sec, and the length of the brush foot was 0.4. Mm is rubbed. The above liquid crystal alignment film coated substrate is immersed in isopropyl alcohol for 1 minute, and then dried on a 100 电 hot plate for 5 minutes. Then, there is a pair of transparent electrodes/transparent electrode substrates, and a pair The liquid crystal alignment film of the liquid crystal alignment film-coated substrate of the transparent electrode/reflective electrode substrate is coated on the outer periphery by an epoxy resin doped with an alumina ball having a diameter of 5.5 μm, and then laminated with respect to the liquid crystal alignment film φ surface. After the binder is cured, the nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Ltd.) is filled from the liquid crystal injection port, and the liquid crystal injection port is sealed with an acrylic photocurable adhesive to bond on both outer sides of the substrate. A polarizing plate was used to produce a liquid crystal display element. The voltage holding ratio and sinterability of the obtained liquid crystal display element were evaluated. On a quartz substrate having a thickness of 1.5 mm, it was coated with a spinner. The liquid crystal alignment agent of the present invention was prepared in the same manner as in the production of a liquid crystal display device. The transparency was evaluated from the measured transmittance of the coating film. The results are shown in Table 1. The voltage of the liquid crystal alignment agent φ obtained in the present invention was confirmed. The retention ratio and the scintillation characteristics were good. Examples 2 to 15 5 The polyimine (Α-1)~(Α-4) obtained from Synthesis Examples 1 to 10, polyamine was obtained according to the protocol described in Table 1 below. The acid (B-1) to (B-3), the partial quinone imine (C-1) to (C-3), and the epoxy group-containing compound are dissolved in a mixed solvent containing γ·butyrolactone as a main component. A solution having a solid concentration of 4.0% was obtained, and the solution was filtered through a sieve having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. In the same manner as in Example 1, a protective film was formed on the surface of the substrate in the same manner as in Example 1 by using the liquid crystal alignment agent thus prepared, and a liquid crystal display element was produced using the substrate -39-1360680 which forms the liquid crystal alignment film. Further, transparency, voltage holding ratio, and sintering property were evaluated. The results are shown in Table 1. Comparative Examples 1 to 5 Liquid crystal display elements were produced in the same manner as in the examples shown in the following Table 1. Moreover, transparency, voltage holding ratio, and sinterability were evaluated. The results are shown in Table 1.

-40- 1360680 表1-40- 1360680 Table 1

聚雜 聚合物 混合比 添加劑種類 添加量 (phr) 透明性 電壓保持率 燒結性 透過型 反射型 透過型 反射型 實施例1 A-1 B-1 50/50 聚乙二醇二縮水甘油醚 10 良好 良好 良好 良好 良好 實施例2 A-2 B-1 40/60 聚乙二醇二縮水甘油醚 20 良好 良好 良好 良好 良好 實施例3 A-3 B-3 50/50 聚乙二醇二縮水甘油醚 10 良好 良好 良好 良好 良好 實施例4 A-3 B-3 50/50 1，3,5,6-四縮水甘油基-2,4-己二醇 10 良好 良好 良好 良好 良好 實施例5 A-3 B-2 50/50 1，3,5,6-四縮水甘油基-2,4- 己二醇 10 良好 良好 良好 良好 良好 實施例6 A-2 B-2 40/60 1，3-雙(N，N-二縮水甘油基 胺基甲基)環已烷 10 良好 良好 良好 良好 良好 實施例7 A-4 B-2 50/50 1,3-雙(Ν,Ν-二縮水甘油基 胺基甲基)環己烷 10 良好 良好 良好 良好 良好 實施例8 A-4 B-3 50/50 Ν，Ν,Ν’，Ν’-四縮水甘油基 -4,4’-二胺基二苯基甲烷 20 良好 良好 良好 良好 良好 實施例9 A-1 B-1 50/50 聚乙二醇二縮水甘油醚 5 良好 良好 良好 良好 良好 實施例10 A-1 B-1 50/50 Ν，Ν,Ν’，Ν’-四縮水甘油基 -4,4’-間二甲苯二胺 5 良好 良好 良好 良好 良好 實施例11 A-2 B-3 45/55 聚乙二醇二縮水甘油醚 20 良好 良好 良好 良好 良好 實施例12 A-1 B-3 50/50 乙二醇二縮水甘油醚 20 良好 良好 良好 良好 良好 實施例13 C-1 聚乙二醇二縮水甘油醚 20 良好 良好 良好 良好 良好 實施例14 C-2 乙二醇二縮水甘油醚 20 良好 良好 良好 良好 良好 實施例15 C-3 Ν，Ν，Ν’，Ν’-四縮水甘油基 -4,4’-二胺基二苯基甲烷 20 良好 良好 良好 良好 良好 比較例1 A-1 聚乙二醇二縮水甘油醚 10 良好 良好 良好 良好 不好 比較例2 A-1 B-1 50/50 良好 良好 良好 良好 不好 比較例3 B-3 1,3-雙(Ν，Ν-二縮水甘油基 胺基甲基)環己烷 10 良好 良好 良好 不好 良好 比較例4 C-1 良好 良好 良好 良好 不好 比較例5 C-3 良好 良好 良好 良好 不好 -41-Polyheteropolymer mixture ratio additive type addition amount (phr) Transparency voltage retention rate Sinterability transmissive reflection type transmission type reflection type Example 1 A-1 B-1 50/50 Polyethylene glycol diglycidyl ether 10 Good Good Good Good Good Example 2 A-2 B-1 40/60 Polyethylene Glycol Diglycidyl Ether 20 Good Good Good Good Good Example 3 A-3 B-3 50/50 Polyethylene Glycol Diglycidyl Ether 10 Good Good Good Good Good Example 4 A-3 B-3 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Good Good Good Good Good Example 5 A-3 B-2 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Good Good Good Good Good Example 6 A-2 B-2 40/60 1,3-double ( N,N-diglycidylaminomethyl)cyclohexane 10 Good good Good good Good Example 7 A-4 B-2 50/50 1,3-bis(indole, fluorene-diglycidylamino group Methyl)cyclohexane 10 Good good Good Good Good Example 8 A-4 B-3 50/50 Ν,Ν,Ν',Ν'-tetraglycidyl-4,4'-diaminodiphenyl Methane 20 is good and good Good and good Example 9 A-1 B-1 50/50 Polyethylene glycol diglycidyl ether 5 Good good Good Good Good Example 10 A-1 B-1 50/50 Ν, Ν, Ν ', Ν '- Tetraglycidyl-4,4'-m-xylenediamine 5 Good Good Good Good Good Example 11 A-2 B-3 45/55 Polyethylene Glycol Diglycidyl Ether 20 Good Good Good Good Good Example 12 A-1 B-3 50/50 ethylene glycol diglycidyl ether 20 Good good Good good Good Example 13 C-1 Polyethylene glycol diglycidyl ether 20 Good good Good good Good Example 14 C-2 Ethylene Alcohol diglycidyl ether 20 Good good Good good Good Example 15 C-3 Ν,Ν,Ν',Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 Good good Good good good Comparative Example 1 A-1 Polyethylene glycol diglycidyl ether 10 Good good Good good Good Comparative Example 2 A-1 B-1 50/50 Good good Good good Good Comparative Example 3 B-3 1,3-double (Ν, Ν-diglycidylaminomethyl) cyclohexane 10 Good good, good, bad, good Comparative Example 4 C-1 Good Good Good Good Not Good Comparative Example 5 C-3 Good Good Good Good Not Good -41-

Claims (1)

1360680 ，叫日修正本I修正本 第094 1043 3 3號「液晶配向劑及液晶配向膜之製造方法」 專利案 (2011年12月9日修正） 十、申請專利範圍： 1 ·一種液晶配向劑，其特徵在於該液晶配向劑係含有1 00 重量份具有下式（1-1)所示之重複單位及下式（卜2)所示之 重複單位、且式（1-1)所示之重複單位的比例以重量計占 全部重複單位4 〇 %〜6 0 %的聚合物，和至少5簠量份分子 內具有至少2個環氧基之化合物，且該聚合物爲具有式 (1-1)所示之重複單位的聚醯胺酸及具有式（1-2)所示之重 複單位的聚醯亞胺之混合物，1360680, called the Japanese version of this amendment No. 094 1043 3 3 "Method for manufacturing liquid crystal alignment agent and liquid crystal alignment film" Patent case (amended on December 9, 2011) X. Patent application scope: 1 · A liquid crystal alignment agent It is characterized in that the liquid crystal alignment agent contains 100 parts by weight of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (b), and is represented by the formula (1-1). The ratio of the repeating unit is 4 〇% to 60% by weight of the total repeating unit of the polymer, and at least 5 Å of the compound having at least 2 epoxy groups in the molecule, and the polymer has the formula (1- 1) a mixture of a repeating unit of polylysine and a polyimine having a repeating unit of the formula (1-2), (I-D(I-D (式中，P爲式（1)或式（i，）所示之4價有機基 2價有機基） 且Q1爲(wherein P is a tetravalent organic divalent organic group represented by formula (1) or formula (i,)) and Q1 is (式中，R爲鹵素原子、甲基或乙基；3爲〇或i的整數； b爲〇~6的整數） 1360680 t(wherein R is a halogen atom, a methyl group or an ethyl group; 3 is an integer of 〇 or i; b is an integer of 〇~6) 1360680 t (式中’ P2爲4價有機基’且Q2爲2價有機基卜 2 .如申請專利範圍第1項之液晶配向劑，其中分子內具有 至少2個環氧基之化合物爲至少一種選自於下式（1)所示 之化合物和下式（2)所示之化合物所構成族群的含環氧基 之化合物，(In the formula, P2 is a tetravalent organic group and Q2 is a divalent organic group. The liquid crystal alignment agent of claim 1, wherein the compound having at least two epoxy groups in the molecule is at least one selected from the group consisting of An epoxy group-containing compound of a group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), S 厂 0—R10 0——c-h2S Factory 0—R10 0——c-h2 ⑴ (式中，Rl(l表示2價脂肪族基）(1) (wherein, Rl (l represents a divalent aliphatic group) (2) (式中，Ru表示2價有機基）。 3 . —種液晶配向膜之製造方法，其特徵在於將如申請專利 範圍第1或2項之液晶配向劑塗布於設置有透明導電膜 或反射電極的基板之一面上，接著通過將塗布面加熱之 步驟(2) (wherein Ru represents a divalent organic group). A method for producing a liquid crystal alignment film, which comprises applying a liquid crystal alignment agent according to claim 1 or 2 to a surface of a substrate provided with a transparent conductive film or a reflective electrode, followed by heating the coated surface Step
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