TW200930747A - Liquid crystal aligning agent and liquid crystal display element - Google Patents
Liquid crystal aligning agent and liquid crystal display element Download PDFInfo
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- TW200930747A TW200930747A TW097148338A TW97148338A TW200930747A TW 200930747 A TW200930747 A TW 200930747A TW 097148338 A TW097148338 A TW 097148338A TW 97148338 A TW97148338 A TW 97148338A TW 200930747 A TW200930747 A TW 200930747A
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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
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- 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
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Abstract
Description
200930747 六、發明說明: 【發明所屬之技術領域】 本發明涉及液晶配向劑和液晶顯示元件。更具體地說 ,涉及能夠形成電壓保持率和殘像性能優異的液晶配向膜 的液晶配向劑和殘像性能優異的液晶顯示元件。 【先前技術】200930747 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in voltage holding ratio and afterimage performance, and a liquid crystal display element excellent in afterimage performance. [Prior Art]
目前,作爲液晶顯示元件,具有所謂TN型(扭曲向列) 液晶胞的TN型液晶顯示元件已廣爲人知,其在設置了 ITO ® (氧化銦-氧化錫)膜等透明導電膜的基板表面上形成液晶 配向膜,作爲液晶顯示元件用的基板,將兩塊該基板相對 設置,在其間隙內形成具有正介電各向異性的向列型液晶 層,構成夾層結構的晶胞,液晶分子的長軸從一塊基板向 另一塊基板連續地扭轉90度。另外,還開發了與TN型液 晶顯示元件相比能夠達到更高對比度的 STN(超扭曲向列) 型液晶顯示元件。上述TN型和STN型液晶顯示元件中液 晶分子的配向通常由進行了打磨處理的液晶配向膜控制。 (Ο w 相比之下,還開發了在透明導電膜上設置突起,並由 其控制液晶分子配向的改善了視角性能的MVA(多疇垂直 配向)型液晶顯示元件(參見專利文獻1和非專利文獻1)、 由特殊電極構造控制液晶分子配向的EVA(強化垂直配向) 型液晶顯示元件(參見非專利文獻2)、採用光配向法的垂直 配向型液晶顯示元件(參見非專利文獻3)等垂直配向型液 晶顯示元件。這些垂直配向型液晶顯示元件視角性能、對 比度等優良,並且在形成液晶配向膜的過程中可以不進行 -4- 200930747 打磨處理等,因而在製造工序方面也是優良的。但是,與 上述TN型、STN型液晶顯示元件相比,性能還不是十分 好,特別是需要提高垂直配向性和液晶顯示元件殘像性能 等方面的性能。 爲解決上述問題,已嘗試了著眼於電壓保持率和殘像 性能的關係,將由具有烯丙基的二胺化合物合成的聚醯亞 胺或其醯亞胺化聚合物用於液晶配向膜,以提高電壓保持 率,並由此來改善殘留性能(參見專利文獻2),但是即使採 用該技術,殘像性能的改善仍然是不夠好。 另外,還嘗試了使用由含有1,2,3,4-環丁烷四羧酸二酐 和均苯四酸二酐的四羧酸二酐合成的聚醯胺酸作爲液晶配 向劑來改善電壓保持率、殘留電荷、殘像性能(參見專利文 獻3〜6),但是採用這些技術時存在不能得到足夠的電壓保 持率的問題。 〔專利文獻1〕日本特開平11-258605號公報 〔專利文獻2〕國際公開第W02005/052028號手冊 〔專利文獻3〕日本特願2001 — 206 1 68號公報 〔專利文獻4〕日本特表2001 - 5 1 0497號公報 〔專利文獻5〕曰本特開200 1 — 296525號公報 〔專利文獻6〕日本特開平1 0 — 1 97875號公報 〔專利文獻7〕日本特開平6 — 2223 66號公報 〔專利文獻8〕曰本特開平6— 281939號公報 〔專利文獻9〕日本特開平5一 1 07544號公報 〔非專利文獻 1〕“液晶”,V〇l. 3,1^〇.2,? 1 1 7(1 999年)。 200930747 〔非專利文獻2〕“液晶”,Vol. 3,No. 4,p272(1999年)。 〔非專利文獻 3〕“JpnAppl. phys.”,Vol. 36,p428(1997年) 【發明內容】 本發明是鑒於上述情況而作出的,其目的是提供一種 不但適用於TN型和STN型,而且在適用於垂直配向型液 晶顯示元件時,也能夠形成顯示出良好的液晶配向性、且 電壓保持率和殘像性能優異的液晶配向膜的液晶配向劑, 以及殘留性能優異的液晶顯示元件。 〇 本發明的其他目的和優點,由以下的說明可以看出。 根據本發明,本發明的上述目的,第一,由一種液晶 配向劑達成,其包含由聚醯胺酸以及其醯亞胺化聚合物構 成的群組中選出的至少一種聚合物,該聚醯胺酸由四羧酸 二酐與二胺反應所製得’該四羧酸二酐含有1,2,3,4-環丁烷 四羧酸二酐,該二胺含有下述式(1)表示的化合物和下述式 (2)表示的化合物,At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is widely known, and a substrate surface of a transparent conductive film such as an ITO ® (indium oxide-tin oxide) film is provided. A liquid crystal alignment film is formed on the substrate, and two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell of a sandwich structure, and liquid crystal molecules are formed. The long axis is continuously twisted 90 degrees from one substrate to the other. Further, an STN (Super Twisted Nematic) type liquid crystal display element capable of achieving higher contrast than a TN type liquid crystal display element has been developed. The alignment of the liquid crystal molecules in the above TN type and STN type liquid crystal display elements is usually controlled by a liquid crystal alignment film which has been subjected to a rubbing treatment. (In contrast, an MVA (Multi-Domain Vertical Alignment) type liquid crystal display element in which protrusions are provided on a transparent conductive film and the liquid crystal molecules are aligned to improve viewing angle performance has been developed (see Patent Document 1 and Patent Document 1), an EVA (Reinforced Vertical Alignment) type liquid crystal display element in which liquid crystal molecules are aligned by a special electrode structure (see Non-Patent Document 2), and a vertical alignment type liquid crystal display element using a photo-alignment method (see Non-Patent Document 3) A vertical alignment type liquid crystal display element. These vertical alignment type liquid crystal display elements are excellent in viewing angle performance, contrast, and the like, and can be polished in the process of forming a liquid crystal alignment film, and are also excellent in a manufacturing process. However, compared with the TN type and STN type liquid crystal display elements described above, the performance is not very good, and in particular, it is required to improve the vertical alignment and the residual image performance of the liquid crystal display element. In order to solve the above problems, an attempt has been made. A combination of voltage retention and afterimage performance, which is synthesized from a diamine compound having an allyl group. The imine or its quinone imidized polymer is used for a liquid crystal alignment film to improve the voltage holding ratio and thereby improve the residual property (see Patent Document 2), but even with this technique, the afterimage performance improvement is still insufficient. In addition, it has also been attempted to use a polyphthalic acid synthesized from a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride as a liquid crystal alignment agent. In order to improve the voltage holding ratio, the residual charge, and the afterimage performance (see Patent Documents 3 to 6), there is a problem that a sufficient voltage holding ratio cannot be obtained by using these techniques. [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258605 Patent Document 2] International Publication No. WO2005/052028 (Patent Document 3) Japanese Patent Application No. 2001-206 No. 68 (Patent Document 4) Japanese Patent Application Laid-Open No. Hei No. 2001-5119 (Patent Document 5) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Special Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〕 "Liquid Crystal", Vol. 3, No. 4, p272 (1999). [Non-Patent Document 3] "Jpn Appl. phys.", Vol. 36, p428 (1997) [Invention] The present invention is in view of the above The purpose of the present invention is to provide a TN type and an STN type which can be formed to exhibit good liquid crystal alignment, voltage retention and afterimage performance when applied to a vertical alignment type liquid crystal display element. A liquid crystal alignment agent excellent in liquid crystal alignment film, and a liquid crystal display element excellent in residual properties. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above object of the present invention, first, is achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and a ruthenium iodide polymer thereof. The amine acid is obtained by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride contains 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the diamine contains the following formula (1). a compound represented by the following formula (2),
(式(2)中,η爲16〜18的整數)。 本發明的上述目的’第二’由—種液晶顯示元件達成 200930747 ,其具有由上述液晶配向劑形成的液晶配向膜。 【實施方式】 <聚醯胺酸> 本發明液晶配向劑中所含的聚醯胺酸可以通過使含有 1,2,3,4-環丁烷四羧酸二酐的四羧酸二酐與含有上述式(1) 表示的化合物和上述式(2)表示的化合物的二胺反應而合 成。 [四羧酸二酐] 上述聚醯胺酸合成中使用的四羧酸二酐’至少含有 1,2,3,4-環丁烷四羧酸二酐。上述聚醯胺酸的合成時’還可 以聯用1,2,3,4-環丁烷四羧酸二酐以外的其他四羧酸二酐。 作爲這些其他四羧酸二酐,可以列舉例如丁烷四羧酸 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、1,3-二氯-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、 1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、 3,3’,4,4’-二環己基四羧酸二酐、2,3,5-三羧基環戊基醋酸 二酐、3,5,6-三羧基降冰片烷-2-醋酸二酐' 2,3,4,5-四氫呋 喃四羧酸二酐、l,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘[l,2-c]-呋喃-l,3-二酮、l,3,3a,4,5,9b-六氫-5-甲基-5-(四氮-2,5- 一氧代-3-咲喃基)-蔡[l,2-c] -咲喃-1,3-二酮、1,3,3&,4,5,91)-六氫-5-乙基-5-(四氫-2,5-二氧代-3-呋 喃基)-蔡[l,2-c]-咲喃-1,3-二嗣、l,3,3a,4,5,9b-六氯-7-甲基 -5-(四氫-2,5-二氧代-3-呋喃基)_萘[l,2-c]-呋喃-1,3 -二酮(In the formula (2), η is an integer of 16 to 18). The above object "second" of the present invention is achieved by a liquid crystal display element of the present invention, which has a liquid crystal alignment film formed of the above liquid crystal alignment agent. [Embodiment] <Polyproline> The polyphthalic acid contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting a tetracarboxylic acid containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride The anhydride is synthesized by reacting a diamine containing the compound represented by the above formula (1) and the compound represented by the above formula (2). [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the above polyamic acid contains at least 1,2,3,4-cyclobutanetetracarboxylic dianhydride. In the synthesis of the above polyamic acid, other tetracarboxylic dianhydrides other than 1,2,3,4-cyclobutanetetracarboxylic dianhydride may be used in combination. Examples of these other tetracarboxylic dianhydrides include butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 1,3-two. Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexyl Alkane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxyl Norbornane-2-acetic acid dianhydride '2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-( Tetranitro-2,5-monooxy-3-indolyl)-cai[l,2-c]-indolyl-1,3-dione, 1,3,3&,4,5,91) - hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-cai [l,2-c]-furan-1,3-dioxene, l, 3,3a,4,5,9b-hexachloro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1 , 3-dione
(Τ-Ι) (ΜΙ) 200930747 、1,3,3&,4,5,91)-六氫-7-乙基-5-(四氫-2,5-二氣代 )_萘[l,2-c] -呋喃-1,3-二酮、l,3,3a,4,5,9b-六氮名 四氫-2,5-二氧代-3-呋喃基)-萘[1,2-£:]-呋喃 上5 l,3,3a,4,5,9b-六氫-8-乙基- 5- (四氫- 2,5-二氧代 3 萘[l,2-c]-呋喃-1,3-二酮、1,3,3&,4,5,91)-六氮_5 -5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-(:]_呋喃 、5-(2,5 -二氧代四氫呋喃基)-3 -甲基-3-環己燦^ 酐、雙環[2.2_2]-辛-7-烯-2,3,5,6-四羧酸二酐、3 [3.2.1]辛烷-2,4 -二酮-6 -螺-3’-(四氫呋喃 _2,,5, 5-(2,5-二氧代四氫-3-呋喃基)-3 -甲基-3-環己缔 酸酐、3,5,6-三羧基-2-羧基降冰片烷-2:3,5:6.二@ 氧雜三環[5 .3 .1 ·02’6;Μ烷-3,5,8,1〇-四酮、下劲 或(Τ- II)表示的化合物等脂肪族或脂環式四竣酸 〇 (式(Τ— I)和(Τ— II)中,1^和R3表示具有芳香環 機基團,R2和R4表示氫原子或者烷基,存在的 R4各自可以相同,也可以不同) 均苯四酸二酐、3,3’,4,4, _二苯酮四羧酸二酐, -3 -呋喃基 ί-甲基-5-( 3-二酮、 -呋喃基)-,8-二甲基 •1,3- 一 酮 ,2-二甲酸 -氧雜雙環 -二酮)、 -1,2-二羧 i干、4,9-二 L 式(T — I) 二酐; 的2價有 多個R2和 ‘ 3,3,,4,4’- 200930747 二苯基碾四羧酸二酐、1,4,5,8·萘四羧酸二酐、2,3,6,7-萘 四羧酸二酐、3,3’,4,4’-二苯基醚四羧酸二酐、3,3’,4,4’-二(Τ-Ι) (ΜΙ) 200930747, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-generation)-naphthalene [l ,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexanitrotetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1 , 2-£:]-furan on 5 l,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo 3 naphthalene [l,2- c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexanitro-5-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-(:]-furan, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexancan anhydride, bicyclo[2.2_2]-oct-7- Alkene-2,3,5,6-tetracarboxylic dianhydride, 3 [3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,,5, 5-( 2,5-Dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexanic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5: 6. An aliphatic or a fatty acid such as a compound represented by bis-oxotricyclo[5 .3 .1 ·02'6; decane-3,5,8,1 fluorene-tetraketone, lowering or (Τ-II) In the case of cyclic tetradecanoic acid (formulae (I) and (Τ-II), 1^ and R3 represent an aromatic ring group, R2 and R4 represent a hydrogen atom or an alkyl group, and each of R4 may be the same. and also Different) pyromellitic dianhydride, 3,3',4,4, benzophenone tetracarboxylic dianhydride, -3 -furanyl ί-methyl-5-( 3-diketone, -furanyl )-, 8-dimethyl-1,3-1,3-one, 2-dicarboxylic acid-oxabicyclo-dione), -1,2-dicarboxyl dry, 4,9-di L (T-I The dianhydride has a plurality of R2 and '3,3,,4,4'- 200930747 diphenyl-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-di
甲基二苯基矽烷四羧酸二酐、3,3’,4,4’-四苯基矽烷四羧酸 二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙(3,4-二羧基苯氧基 )二苯基硫醚二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基颯二 酐、4,4’-雙(3,4-二羧基苯氧基)二苯基丙烷二酐、3,3’,4,4’-全氟異亞丙基二鄰苯二甲酸二酐、3,3’,4,4’-聯苯四羧酸二 酐、2,2’,3,3’-聯苯四羧酸二酐、雙(鄰苯二甲酸)苯膦氧化 物二酐、對亞苯基-雙(三苯基鄰苯二甲酸)二酐、間亞苯基-雙(三苯基鄰苯二甲酸)二酐、雙(三苯基鄰苯二甲酸)-4,4’-二苯醚二酐、雙(三苯基鄰苯二甲酸)-4,4’-二苯基甲烷二酐 、乙二醇-雙(脫水偏苯三酸酯)、丙二醇-二(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-二(脫 水偏苯三酸酯)、1,8-辛二醇-雙(脫水偏苯三酸酯)、2,2-雙 (4-羥苯基)丙烷-二(脫水偏苯三酸酯)、下述式(T-1)〜(T-4) 表示的化合物等芳香族四羧酸二酐。它們可以一種單獨或 兩種以上組合使用。 200930747Methyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4 '-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4' - bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4 , 4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Anhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-di(anhydroelellitic acid ester) , 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1,6-hexanediol-di(hydrogen trimellitate), 1,8-octanediol-bis (dehydrated benzene) Triester), 2,2-bis(4-hydroxyphenyl)propane-two (Dehydrated trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-4). They may be used alone or in combination of two or more. 200930747
其中,從能夠使其表現良好的液晶配向性的角度出發 ,較佳丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸 二酐、1,2,3,4-環戊烷四羧酸二酐、2,3,5-三羧基環戊基醋 酸二酐、1,3,3&,4,5,91>-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘[l,2-c] -呋喃-1,3 -二酮、l,3,3a,4,5,9b -六氫-8-甲基- 5- ( -10- 200930747 四氫-2,5-二氧代-3-呋喃基)-萘[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[l,2-c] -呋喃-1,3-二酮、雙環[2.2.2] -辛-7-烯- 2,3,5,6-四羧酸二酐、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺-3’-(四 氫呋喃-2’,5’-二酮)、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基 _3_環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基降冰片烷 -2:3,5:6-二酐、4,9-二氧雜三環[5.3.1.02’6]-!——烷-3,5,8,10-四酮、均苯四酸二酐、3,3’,4,4’-二苯酮四羧酸二酐、 3,3’,4,4’-二苯基碾四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐 、1,4,5,8-萘四羧酸二酐、上述式(T-I)表示的化合物中的 ,下述式(T— 5)〜(T - 7)表示的化合物以及上述式(T — II)表 示的化合物中的下述式(T- 8)表示的化合物。特佳的其他 四羧酸二酐爲均苯四酸二酐和2,3,5-三羧基環戊基醋酸二 酐。Among them, butane tetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride are preferred from the viewpoint of enabling liquid crystal alignment which is excellent in performance. 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91>-hexahydro- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b - Hexahydro-8-methyl-5-(-10-200930747 tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c -furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane -2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl _3_cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxa Tricyclic [5.3.1.02'6]-!-alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid Anhydride, 3, 3' 4,4'-diphenyltricarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above formula Among the compounds represented by the formula (TI), the compound represented by the following formula (T-5) to (T-7) and the compound represented by the following formula (T-8) in the compound represented by the above formula (T-II) . Particularly preferred other tetracarboxylic dianhydrides are pyromellitic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.
200930747 c200930747 c
(T-8) 本發明液晶配向劑中所含聚醯胺酸的合成中使用的四 竣酸二酐中,較佳相對於全部四羧酸二酐含有40莫耳%以 上1,2,3,4-環丁烷四羧酸二酐,更佳含有6〇莫耳%以上。 另外’本發明液晶配向劑中所含聚醯胺酸的合成中使 0 用的四竣酸二酐中,較佳除1,2,3,4 -環丁烷四羧酸二酐以外 ’還含有均苯四酸二酐或2,3,5 -三羧基環戊基醋酸二酐。 此時’均苯四酸二酐的使用比例,相對於全部四羧酸二酐 ’較佳爲1 0莫耳%以下,更佳爲1〜1 0莫耳%,進一步較 佳3〜8莫耳。/。。 2,3,5-三羧基環戊基醋酸二酐的使用比例,相對於全部 四竣酸二酐’較佳爲50莫耳%以下,更佳爲15〜45莫耳% ’進一步較佳20〜40莫耳%。還可以將均苯四酸二酐和 〇 2,3,5 -二殘基環戊基醋酸二酐分別以較佳上述範圍進行聯 用。 使用分別以上述比例含有各四羧酸二酐的四羧酸二酐 ’可以得到對於下述溶劑具有良好溶解性的聚合物,並且 ’由含有它的液晶配向劑形成的液晶配向膜配向性優異, 從這一點而言,是較佳的。 [二胺] 上述聚醯胺酸合成中使用的二胺,含有上述式(1)表示 的化合物和上述式(2)表示的化合物。 -12- 200930747 在上述聚醯胺酸的合成時,還可以聯用它們以外的其 他二胺。 作爲這些其他二胺,可以列舉例如具有甾體骨架的= 胺以及其他的二胺。 作爲上述具有甾體骨架的二胺,可以列舉例如下述式 (D _ I)表示的化合物,(T-8) The tetraphthalic acid dianhydride used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention preferably contains 40 mol% or more, 1, 2, 3 with respect to all the tetracarboxylic dianhydride. 4-cyclobutanetetracarboxylic dianhydride, more preferably 6 〇 mol% or more. Further, in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention, it is preferable to use a tetraphthalic acid dianhydride other than the 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Contains pyromellitic dianhydride or 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. In this case, the ratio of use of pyromellitic dianhydride is preferably 10% or less, more preferably 1 to 10% by mole, and still more preferably 3 to 8%, based on the total of the tetracarboxylic dianhydride. ear. /. . The ratio of use of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride is preferably 50 mol% or less, more preferably 15 to 45 mol% relative to all tetradecanoic acid dianhydrides. Further preferably 20 ~40 mol%. Further, pyromellitic dianhydride and ruthenium 2,3,5-di residue cyclopentyl acetic acid dianhydride may be used in combination in a preferred range. By using a tetracarboxylic dianhydride containing each tetracarboxylic dianhydride in the above ratio, a polymer having good solubility to the following solvent can be obtained, and 'the liquid crystal alignment film formed of the liquid crystal alignment agent containing the same is excellent in the alignment property. From this point of view, it is better. [Diamine] The diamine used in the synthesis of the polyamic acid contains the compound represented by the above formula (1) and the compound represented by the above formula (2). -12- 200930747 In the synthesis of the above polylysine, it is also possible to use other diamines other than them. Examples of these other diamines include an amine having a steroid skeleton and other diamines. The diamine having a steroid skeleton may, for example, be a compound represented by the following formula (D _ I).
h2n 〇 X1-R5 NH2 (D-I) (式(D — I)中,X1 表示選自-〇-、-COO-、-OCO-、-NHCO-、-CONH-以及- CO-的2價有機基團,R5表示具有甾體骨架 的1價有機基團)、下述式(D— II)表示的化合物, (D-Π)H2n 〇X1-R5 NH2 (DI) (In the formula (D-I), X1 represents a divalent organic group selected from the group consisting of -〇-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO- a group, R5 represents a monovalent organic group having a steroid skeleton, a compound represented by the following formula (D-II), (D-Π)
(式(D _ 11)中,X 2 表不選自-〇 _、· c 〇 〇 、_ 〇 c 〇 、_ n η 匚 〇 _ 、-CONH-以及- CO-的2價有機基團,R6表示具有甾體骨架 的2價有機基團)。作爲他們的具體例子,上述式(D —。表 示的化合物可以列舉例如下述式(D— 1}〜(D— 6)表示的化 合物等; 200930747 Ο(In the formula (D -11), the X 2 table is not selected from the group consisting of -〇_, · c 〇〇, _ 〇c 〇, _ n η 匚〇_ , -CONH-, and -CO-divalent organic groups, R6 represents a divalent organic group having a steroid skeleton). As a specific example thereof, the compound represented by the above formula (D-.) may, for example, be a compound represented by the following formula (D-1} to (D-6); 200930747 Ο
ΟΟ
-14- 200930747 (D - 7)〜 上述式(D- II)表示的化合物可以列舉例如下述式 (D- 9)表示的化合物等,-14-200930747 (D - 7) - The compound represented by the formula (D-II), for example, may be, for example, a compound represented by the following formula (D-9).
作爲上述其他的二胺,可以列舉例如對苯二 二胺、4,4’-二氨基二苯基甲烷、4,4’-二氨基二苯 4,4’-二氨基二苯基硫醚、4,4’-二氨基二苯基碾、 基-4,4’-二氨基聯苯、4,4’-二氨基苯甲醯苯胺、 基二苯醚、1,5-二氨基萘、2,2’-二甲基-4,4’-二氨 3,3’-二甲基-4,4’-二氨基聯苯、2,2’-二(三氟甲基 氨基聯苯、3,3’-二(三氟甲基)-4,4’-二氨基聯苯 -1-(4’-氨基苯基)-1,3,3-三甲基茚滿、6-氨基-1-( 基)-1,3,3-三甲基茚滿、3,4’-二氨基二苯基醚、3, 二苯酮、3,4’-二氨基二苯酮、4,4’-二氨基二苯画 胺、間苯 基乙烷、 3,3,-二甲 4,4,-二氨 ,基聯苯、 )-4,4,-二 、5-氨基 4’-氨基苯 3’-二氨基 哥、2,2-雙 200930747 [4-(4-氨基苯氧基)苯基]丙烷、2,2-雙[4-(4-氨基苯氧基)苯 基]六氟丙烷、2,2-雙(4-氨基苯基)六氟丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]颯、1,4-雙(4-氨基苯氧基)苯、1,3-雙(4-氨基苯氧基)苯、1,3_雙(3-氨基苯氧基)苯、9,9-雙(4-氨基 苯基)-10-氫蒽、2,7-二氨基芴、9,9-二甲基-2,7-二氨基芴 、9,9 -雙(4 -氨基苯基)芴、4,4’-亞甲基-雙(2 -氯苯胺)、 2,2’,5,5’-四氯-4,4’-二氨基聯苯、2,2’-二氯-4,4’-二氨基 -5,5’-二甲氧基聯苯、3, 3’-二甲氧基-4,4’-二氨基聯苯、 Ο 1,4,4’-(對亞苯基異亞丙基)二苯胺、4,4’-(間亞苯基異亞丙 基)二苯胺、2,2’-雙[4-(4-氨基-2-三氟甲基苯氧基)苯基]六 氟丙烷、4,4’-二氨基-2,2’-雙(三氟甲基)聯苯、4,4’-雙[(4-氨基-2-三氟甲基)苯氧基]-八氟聯苯等芳香族二胺; 1,1 -間苯二甲胺、1,3 -丙二胺、丁二胺、戊二胺、己二 胺、庚二胺、辛二胺、壬二胺、4,4-二氨基庚二胺、1,4-二氨基環己烷、異佛爾酮二胺、四氫二環戊二烯二胺、六 氫-4,7-甲撐茚二亞甲基二胺、三環[6.2.1.02,7]十一碳烯二 ^ 甲二胺、4,4’-亞甲基二(環己胺)、1,3-二(氨基甲基)環己烷 、1,4-二(氨基甲基)環己烷等脂肪族或脂環式二胺; 2,3 -二氨基吡啶、2,6 -二氨基吡啶、3,4 -二氨基吡啶、 2.4- 二氨基嘧啶、5,6-二氨基-2,3 -二氰基吡嗪、5,6-二氨基 -2,4-二羥基嘧啶、2,4-二氨基-6-二甲氨基-1,3,5-三嗪、1,4-雙(3-氨基丙基)呱嗪、2,4-二氨基-6-異丙氧基-1,3,5-三嗪、 2.4- 二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-苯基 -1,3,5-三嗪、2,4-二氨基-6-甲基-s-三嗪、2,4-二氨基-1,3,5- -16- 200930747 三嗪、4,6-二氨基-2-乙烯基-s-三嗪、2,4-二氨基-5-苯基噻 唑、2,6-二氨基嘌呤、5,6-二氨基-1,3-二甲基尿嘧啶、3,5-二氨基-1,2,4-三唑、6,9-二氨基-2-乙氧基吖啶乳酸酯、3,8-二氨基-6-苯基菲啶、1,4 -二氨基呱嗪、3,6 -二氨基吖啶、 雙(4-氨基苯基)苯基胺、3,6-二氨基嗓唑、N-甲基-3,6-二氨 基嗦唑、N-乙基-3,6-二氨基嘮唑、N-苯基-3,6-二氨基嗦唑 、N,N’-二(4-氨基苯基)聯苯胺 '下述式(D- III)表示的化合 物,Examples of the other diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl 4,4'-diaminodiphenyl sulfide. 4,4'-diaminodiphenyl milling, yl-4,4'-diaminobiphenyl, 4,4'-diaminobenzamide, phenyldiphenyl ether, 1,5-diaminonaphthalene, 2 , 2'-Dimethyl-4,4'-diamino 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethylaminobiphenyl, 3 , 3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1 -(yl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3, benzophenone, 3,4'-diaminobenzophenone, 4,4' -diaminodiphenylamine, m-phenylethane, 3,3,-dimethyl 4,4,-diamino, phenyl, -4,4,-di, 5-amino 4'-aminobenzene 3'-diaminoglycol, 2,2-double 200930747 [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4- Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3_bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)- 10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene Base-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, Ο 1,4,4'-(p-phenylene isopropylidene) Aniline, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane , 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro An aromatic diamine such as biphenyl; 1,1-m-xylylenediamine, 1,3-dipropylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-Diaminoheptanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethylene Diamine, three [6.2.1.02,7]undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4- An aliphatic or alicyclic diamine such as bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5 ,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5- Triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2.4-diamino-6-methoxy Base-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2 ,4-diamino-1,3,5- -16- 200930747 Triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2 ,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethyl Oxyloacyl lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenyl Amine, 3,6-diaminocarbazole , N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-di ( 4-aminophenyl)benzidine's compound represented by the following formula (D-III),
〇X3~R7 ,-πη Η2Ν νη2 (式(D— III)中,R7表示選自吡啶、嘧啶、三嗪、呱啶以及 呱嗪的具有含氮原子環狀結構的1價有機基團,X3表示2 價的有機基團)、下述式(D- IV)表示的化合物,〇X3~R7 , -πη Η2Ν νη2 (In the formula (D-III), R7 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and pyridazine, X3 a compound represented by a divalent organic group), a compound represented by the following formula (D-IV),
(式(D— IV)中’ R8表示選自吡啶、嘧啶、三嗪、呱啶以及 狐嗪的具有含氮原子環狀結構的2價有機基團,χ4表示2價 的有機基團,存在的多個X4各自可以相同,也可以不同) 等分子內具有2個伯氨基以及該伯氨基以外的氮原子的二 胺; 下述式(D— V)表示的化合物, -17- 200930747 h2n(In the formula (D-IV), 'R8 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and fox azine, and χ4 represents a divalent organic group, and exists. Each of the plurality of X4 may be the same or different) a diamine having two primary amino groups and a nitrogen atom other than the primary amino group; a compound represented by the following formula (D-V), -17-200930747 h2n
x5-r9 nh2 (D-V) (式(D_V)中,X5 表示選自·〇_、_C00_' _〇c〇 、_nhc〇 、-CONH-以及-CO-的2價有機基團’ R9表示真有氣原子的 1價有機基團或者碳原子數爲6〜30的烷基);下述式(D 一 VI)表示的化合物,X5-r9 nh2 (DV) (In the formula (D_V), X5 represents a divalent organic group selected from 〇_, _C00_' _〇c〇, _nhc〇, -CONH-, and -CO-' R9 means that there is gas a monovalent organic group of an atom or an alkyl group having 6 to 30 carbon atoms; a compound represented by the following formula (D-VI),
H2N-( CHH2N-( CH
(式(D_VI)中,R1。表示碳原子數爲1〜12的烴基,存在的 多個R1G各自可以相同,也可以不同,p爲丨〜3的整數,q 爲1〜20的整數);下述式(D_1〇)或(D— u)袠示的化合物 等,(In the formula (D_VI), R1 represents a hydrocarbon group having 1 to 12 carbon atoms, and each of the plurality of R1Gs may be the same or different, p is an integer of 丨3, and q is an integer of 1 to 20); a compound represented by the following formula (D_1〇) or (D-u),
(式(D — 1 〇)中的 〜5的整數)。這 y爲2〜12的整數,式(D— 11)中的Z爲 些二胺可以單獨或者兩種以上組合使用 -18- 200930747 其中,較佳具有甾體骨架的二胺、對苯二胺、4,4’-二 氨基二苯甲烷、4,4’-二氨基二苯硫醚、1,5-二氨基萘、2,2’-二甲基-4,4’-二氨基聯苯、2,2’-二(三氟甲基)-4,4’-二氨基 聯苯、2,7-二氨基芴、4,4’-二氨基二苯基醚、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、9,9-雙(4-氨基苯基)芴、2,2-雙 [4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-雙(4-氨基苯基)六 氟丙烷、4,4’-(對亞苯基二異亞丙基)二苯胺、4,4’-(間亞苯 基二異亞丙基)二苯胺、1,4-二(4-氨基苯氧基)苯、4,4’-雙 ^ (4-氨基苯氧基)聯苯、1,4-環己烷二胺、4,4’-亞甲基二(環 己胺)、1,3-雙(氨基甲基)環己烷、2,6-二氨基吡啶、3,4-二 氨基吡啶、2,4 -二氨基嘧啶、3,6 -二氨基吖啶、3,6 -二氨基 嘮唑、N -甲基-3,6 -二氨基卩弄唑、N -乙基-3,6 -二氨基嘮唑、 N-苯基-3,6-二氨基嘮唑、N,N’-二(4-氨基苯基)聯苯胺、上 述式(D - III)表示的化合物中的下述式(D- 12)表示的化合 物、上述式(D— IV)表示的化合物中的下述式(D - 13)表示 的化合物、 〇(an integer of 〜5 in the formula (D - 1 〇)). y is an integer of 2 to 12, and Z in the formula (D-11) may be used alone or in combination of two or more. -18-200930747 wherein a diamine or p-phenylenediamine having a steroid skeleton is preferred. , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl , 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-dual [ 4-(4-Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diiso) Propyl)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4 , 4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-di Aminoguanidine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, the above The compound represented by the following formula (D-12) in the compound represented by the formula (D-III), and the compound represented by the following formula (D-13) in the compound represented by the above formula (D-IV), 〇
h2n -〇-nO c3h6 (D—13) 上述式(D— V)表示的化合物中的十二烷氧基-2,4-二氨基苯 、十五烷氧基-2,4-二氨基苯、十六烷氧基-2,4-二氨基苯、 -19- 200930747 十八院氧基-2,4-二氨基苯、十二烷氧基-2,5-二氨基苯、十 五烷氧基-2,5-二氨基苯、十六烷氧基_2,5_二氨基苯、十八 烷氧基-2,5 -二氨基苯、下述式(D — 14)〜(D — 表示的化 合物或者上述式(D - VI)表示的化合物中的1,3 -雙(3 -氨基 丙基)-四甲基二矽氧烷。H2n -〇-nO c3h6 (D-13) Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene in the compound represented by the above formula (D-V) ,hexadecaneoxy-2,4-diaminobenzene, -19- 200930747 18-yard oxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane Oxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-14)~(D - a compound represented by the compound or 1,3 -bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D - VI).
特佳的其他二胺爲具有甾體骨架的二胺,其中較佳上 述式(D— I)或(D— π)表示的化合物。 Φ發明液晶配向劑中含有的聚醯胺酸的合成所用的二 胺’較佳相對於全部二胺含有40莫耳%以上上述式(1)表示 的化合物’更佳含有50〜80莫耳%,進一步較佳含有55 〜75莫耳%。上述聚醯胺酸的合成所用的二胺,較佳相對 於全部二胺含有20莫耳%以上上述式(2)表示的化合物,更 -20- 200930747 佳含有30〜60莫耳%,進一步較佳含有35〜55莫耳。/。。 上述聚醯胺酸的合成中所用的二胺中,作爲其他的二 胺,較佳含有具有甾體骨架的二胺,此時,具有甾體骨架 的二胺的使用比例,較佳相對於全部二胺爲5 0莫耳%以下 ,更佳爲1 0〜3 0莫耳%。 通過使用分別以上述比例含有各種二胺的二胺,可以 得到能夠形成電壓保持率和殘像性能優異的液晶配向膜的 液晶配向劑,因此是較佳的。 〇 [聚醯胺酸的合成] 本發明液晶配向劑中可含的聚醯胺酸可以通過使含有 1,2,3,4-環丁烷四羧酸二酐的四羧酸二酐與含有上述式(1) 表示的化合物和上述式(2)表示的化合物的二胺反應而製 得。 供給聚醯胺酸合成反應的四羧酸二酐與二胺的使用比 例,較佳相對於1當量二胺的氨基,使四羧酸二酐的酸酐 基爲0.5〜2當量的比例,更佳使其爲0.7〜1.2當量的比例 〇 〇 聚醯胺酸的合成反應,較佳在有機溶劑中,較佳於-20 〜150 °C、更佳於0〜100 °C的溫度條件下,較佳進行1〜48 小時,更佳進行2〜1 2小時。這裏,作爲有機溶劑,只要 能夠溶解生成的聚醯胺酸,則對其沒有特別的限制,可以 例示例如1-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、3-丁氧基-N,N-二甲基丙醯胺、3-甲氧基 -N,N-二甲基丙醯胺、3-己氧基-N,N-二甲基丙醯胺等醯胺 -21 - 200930747 類化合物、二甲基亞碾、r-丁內酯、四甲基脲、六甲基磷 醯三胺等非質子性化合物;間甲基酚、二甲苯酚、苯酚、 鹵代苯酚等酚類化合物等。有機溶劑的用量(a)通常較佳爲 使四羧酸二酐和二胺化合物的總量(b)相對於反應溶液的 總量(a + b)爲0 · 1〜3 0重量%的量。 上述有機溶劑中,在不使生成的聚醯胺酸析出的範圍 內,還可以聯用聚醯胺酸的不良溶劑醇類、酮類、酯類、 醚類、鹵代烴類、烴類等。作爲這種不良溶劑的具體例子 〇 ,可以列舉例如甲醇、乙醇、異丙醇、環己醇、4-羥基-4-甲基-2-戊酮、乙二醇、丙二醇、1,4-丁二醇、三甘醇、乙 二醇單甲醚 '乳酸乙酯、乳酸丁酯、丙酮、甲基乙基酮、 甲基異丁基酮、環己酮、醋酸甲酯、醋酸乙酯、醋酸丁酯 、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙酯、丙二 酸二乙酯、乙醚、乙二醇甲醚、乙二醇乙醚、乙二醇正丙 醚、乙二醇異丙醚、乙二醇正丁醚、乙二醇二甲基醚、乙 二醇乙醚乙酸酯、二甘醇二甲醚、二甘醇二乙醚、二甘醇 €) 單甲醚、二甘醇單乙醚、二甘醇單甲醚乙酸酯、二甘醇單 乙醚乙酸酯、四氫呋喃、二氯甲烷、1,2 -二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、辛 烷、苯、甲苯、二甲苯、二異丁基酮、丙酸異戊酯、異丁 酸異戊酯、異戊醚等。 當有機溶劑與不良溶劑聯用時,不良溶劑的使用量可 在不使生成的聚醯胺酸析出的範圍內適當地設定,較佳相 對於全部溶劑量爲30重量%以下,更佳爲20重量%以下。 -22- 200930747 如上所述’得到溶解了聚醯胺酸的反應溶液。可以將 該反應溶液直接供給液晶配向劑的配製,也可以將反應溶 液中所含的聚醯胺酸分離出來後供給液晶配向劑的配製, 或者也可以將分離出的聚醯胺酸精製後再供給液晶配向劑 的配製。聚醯胺酸的分離,可以通過將上述反應溶液投入 到大量的不良溶劑中’得到析出物,再減壓乾燥該析出物 的方法’或者將反應溶液用蒸發器減壓蒸餾的方法進行。 另外’通過進行一次或者幾次使該聚醯胺酸再次溶解於有 ® 機溶劑中,然後用不良溶劑使其析出的方法,或用蒸發器 減壓蒸餾的工序,可以精製聚醯胺酸。 <醯亞胺化聚合物> 本發明液晶配向劑可含有的醯亞胺化聚合物,可以通 過將如上述聚醯胺酸脫水閉環進行醯亞胺化而製得。 作爲上述醯亞胺化聚合物的合成中所用的四羧酸二酐 ’可以列舉與上述聚醯胺酸合成中所用的四羧酸二酐相同 的化合物。並且’作爲本發明液晶配向劑中所含醯亞胺化Particularly preferred other diamines are diamines having a steroid skeleton in which a compound represented by the above formula (D-I) or (D-π) is preferred. Φ The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent is preferably contained in an amount of 40 mol% or more based on the total diamine. The compound represented by the above formula (1) preferably contains 50 to 80 mol%. Further preferably, it contains 55 to 75 mol%. The diamine used for the synthesis of the above polyamic acid preferably contains 20 mol% or more of the compound represented by the above formula (2) with respect to all the diamines, and more preferably 30 to 60 mol%, more preferably -20-200930747, further Good contains 35~55 m. /. . In the diamine used in the synthesis of the polyamic acid, the diamine having a steroid skeleton is preferably contained as the other diamine. In this case, the ratio of the diamine having a steroid skeleton is preferably relative to all. The diamine is 50% by mole or less, more preferably 10% to 30% by mole. By using a diamine containing various diamines in the above ratio, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent voltage holding ratio and afterimage performance can be obtained, which is preferable. 〇 [Synthesis of poly-proline] The poly-proline which may be contained in the liquid crystal alignment agent of the present invention can be obtained by including tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride The compound represented by the above formula (1) is obtained by reacting a diamine of the compound represented by the above formula (2). The ratio of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.5 to 2 equivalents, more preferably the ratio of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine. The synthesis reaction of the poly-proline in a ratio of 0.7 to 1.2 equivalents is preferably carried out in an organic solvent, preferably at a temperature of -20 to 150 ° C, more preferably 0 to 100 ° C. Good for 1 to 48 hours, better for 2 to 1 2 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N. - dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropionamine and other indoleamine-21 - 200930747 compounds, dimethyl sub-milling, r-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine and other aprotic compounds; Phenolic compounds such as phenol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent (a) is usually preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0 to 1 to 30% by weight based on the total amount (a + b) of the reaction solution. . In the organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like may be used in combination with a polyglycine in a range in which the produced polyamine is not precipitated. . Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butylene. Glycol, triethylene glycol, ethylene glycol monomethyl ether 'ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, acetic acid Butyl ester, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol, monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isova Ether, etc. When the organic solvent is used in combination with the poor solvent, the amount of the poor solvent to be used can be appropriately set within a range in which the produced polyaminic acid is not precipitated, and is preferably 30% by weight or less, and more preferably 20% based on the total amount of the solvent. Below weight%. -22- 200930747 The reaction solution in which polylysine was dissolved was obtained as described above. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by adding the above-mentioned reaction solution to a large amount of poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. Further, poly-proline can be purified by repeating the process of re-dissolving the polyamine in a solvent of a solvent and then precipitating it with a poor solvent or by vacuum distillation using an evaporator. <醯i-Iminylated Polymer> The ruthenium iodide polymer which may be contained in the liquid crystal alignment agent of the present invention can be obtained by hydrazine imidization by dehydration ring closure as described above. The tetracarboxylic dianhydride used in the synthesis of the above ruthenium iodide can be exemplified by the same compound as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. And as a ruthenium imidization contained in the liquid crystal alignment agent of the present invention
Q 聚合物的合成中所用的二胺,可以列舉與上述聚醯胺酸合 成中所用的二胺化合物相同的二胺。 本發明液晶配向劑中所含的醯亞胺化聚合物,可以是 聚醯胺酸原料所含的醯胺酸結構全部脫水閉環的完全醯亞 胺化物’也可以是僅一部分醯胺酸結構脫水閉環,醯胺酸 結構與醯亞胺環結構並存的部分醯亞胺化物。 本發明液晶配向劑中所含的醯亞胺化聚合物,其醯亞 胺化率較佳爲60%以上,更佳爲70%以上,進一步較佳爲 -23 - 200930747 8 0%以上。通過使用醯亞胺化率爲6〇%以上的醯亞胺化聚合 物’可以獲得能夠形成殘像性能優異的液晶配向膜的液晶 配向劑。 上述醯亞胺化率是指相對於酿亞胺化聚合物中的酿胺 酸結構和醯亞胺環結構的合計數量,醯亞胺環結構數量所 占的比例用百分率表示的値。此時,醯亞胺環的一部分還 可以是異醯亞胺環。醯亞胺化率可以通過將醯亞胺化聚合 物溶於適當的氘代溶劑(例如氘代二甲基亞礪)中,以四甲 〇 基矽烷爲基準物質,在室溫下測定1 Η - N M R,由測定結果按 照下述公式(i)求出。 醯亞胺化率(%)= (1 — aVa2x α )xl00 (i) (公式(i)中,A1爲化學位移10 ppm附近出現的源於NH 基質子的峰面積,A2爲源於其他質子的峰面積,α爲相對 於醯亞胺化聚合物前驅物(聚醯胺酸)中的1個ΝΗ基質子, 其他質子的個數比例)。 ^ 聚醯胺酸的脫水閉環較佳⑴通過加熱聚醯胺酸的方法 ,或者(ii)通過將聚醯胺酸溶解於有機溶劑中,向該溶液中 加入脫水劑和脫水閉環催化劑並根據需要加熱的方法進行 〇 上述(i)的加熱聚醯胺酸的方法中的反應溫度,較佳爲 5 0〜200 °C,更佳爲60〜170 °C。反應時間較佳爲1〜120小 時,更佳爲2〜4 8小時。當反應溫度不足5 0 °C時,則脫水閉 環反應不能進行充分’若反應溫度超過200°C,則會出現所 得醯亞胺化聚合物的分子量下降的情況。 -24- 200930747 另一方面,在上述(ii)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,可以使用例如 醋酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的用量根據 所需的醯亞胺化率而定,較佳相對於1莫耳聚醯胺酸的醯 胺酸結構爲0.01〜20莫耳。另外,作爲脫水閉環催化劑, 可以使用例如吡啶、三甲吡啶、二甲基吡啶、三乙胺等三 級胺。但是,並不局限於這些。脫水閉環催化劑的用量, 相對於1莫耳所用脫水劑,較佳爲0.0 1〜1 0莫耳。上述脫 水劑、脫水閉環催化劑的用量越多,則可使醯亞胺化率越 高。作爲脫水閉環反應中所用的有機溶劑,可以列舉作爲 聚醯胺酸合成中所用溶劑而例示的有機溶劑。脫水閉環反 應的反應溫度,較佳爲0〜180 °C,更佳爲10〜150 °C。反 應時間較佳爲1〜24小時,更佳爲2〜8小時。 在上述方法(ii)中,得到含有如上所述的醯亞胺化聚合 物的反應溶液。該反應溶液可以直接供給液晶配向劑的配 製,也可以從反應溶液中除去脫水劑和脫水閉環催化劑之 後供給液晶配向劑的配製,還可以將醯亞胺化聚合物分離 出來後供給液晶配向劑的配製’或者也可以將分離的醯亞 胺化聚合物精製後再供給液晶配向劑的配製。從反應溶液 除去脫水劑和脫水閉環催化劑’可以採用例如溶劑置換等 方法。醯亞胺化聚合物的分離、精製’可以採取與上述作 爲聚醯胺酸的分離、精製方法同樣的操作而進行° -末端修飾型的聚合物- 本發明液晶配向劑中所含的聚醯胺酸或醯亞胺化聚合 -25 - 200930747 物還可以是進行了分子量調節的末端修飾型聚合物。通過 使用這種末端修飾型的聚合物,可以在不損害本發明效果 的前提下改善液晶配向劑的塗敷特性等。這種末端修飾型 聚合物可以通過在聚醯胺酸的合成時,向聚合反應體系中 加入分子量調節劑等而製備。作爲分子量調節劑,可以列 舉一元酸酐、單胺化合物、單異氰酸酯化合物等。 作爲上述一元酸酐,可以列舉例如馬來酸酐、鄰苯二 甲酸酐、衣康酸酐、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。作爲 上述單胺化合物,可以列舉例如苯胺、環己胺、正丁胺、 正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺,、正 十一烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十 五烷胺、正十六烷胺、正十七烷胺、正十八烷胺、正二十 烷胺等。作爲上述單異氰酸酯化合物,可以列舉例如異氰 酸苯酯、異氰酸萘基酯等。 分子量調節劑的使用比例,相對於1 00重量份聚醯胺 酸合成時所使用的四羧酸二酐和二胺的合計量,較佳爲20 重量份以下,更佳爲1 0重量份以下。 一溶液粘度- 如上所得的聚醯胺酸或醯亞胺化聚合物,較佳當配成 濃度爲10重量%的溶液時,具有20〜800 mPa*s的溶液粘 度,更佳具有30〜500 mPa.s的溶液粘度。 上述聚合物的溶液粘度(mP a· s)是採用該聚合物的良溶 劑(例如r -丁內酯)配製成濃度爲1 0重量%的聚合物溶液時 -26 - 200930747 ,用E型旋轉粘度計在2 5 °C下測定的値。 <其他的添加劑> 本發明的液晶配向膜含有選自如上所述的聚醯胺酸及 其醯亞胺化聚合物中的至少一種聚合物。作爲本發明液晶 配向劑中所含的聚合物,較佳爲醯亞胺化聚合物。 本發明的液晶配向膜含有如上所述的聚合物作爲必需 成分,並且還可以根據需要含有其他成分。作爲這種其他 成分,可以列舉例如分子內具有兩個以上環氧基的化合物 0 (以下稱爲“環氧基化合物”)、官能性矽烷化合物等。 作爲上述環氧基化合物,可以列舉例如乙二醇二縮水 甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、 三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二 醇二縮水甘油醚、1,6 -己二醇二縮水甘油醚、甘油二縮水 甘油醚、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-間苯二甲胺 、1,3-雙(N,N-二縮水甘油基氨基甲基)環己烷、N,N,N’,N’-M 四縮水甘油基-4,4’-二氨基二苯基甲烷、3-(N-烯丙基-N-縮 水甘油基)氨基丙基三甲氧基矽烷、3-(N,N-二縮水甘油基) 氨基丙基三甲氧基矽烷等。 如上述環氧基化合物的使用比例,相對於1〇〇重量份 聚合物總量(是指液晶配向劑中所含的上述聚醯胺酸及其 醯亞胺化聚合物的合計量)’較佳爲40重量份以下,更佳 爲0.1〜30重量份。 作爲上述官能性矽烷化合物’可以列舉例如3 -氨基丙 -27 - 200930747 〇The diamine used in the synthesis of the Q polymer may, for example, be the same diamine as the diamine compound used in the synthesis of the above polyamic acid. The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention may be a complete ruthenium imide of a glycine structure containing all of the proline structure contained in the polyproline acid material, or may be a part of the proline structure dehydration. Closed-loop, a partial ruthenium imide of a proline structure with a quinone ring structure. The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium amination ratio of 60% or more, more preferably 70% or more, further preferably -23 - 200930747 80% or more. A liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in afterimage performance can be obtained by using a ruthenium iodide polymer having a ruthenium iodide ratio of 6 〇 or more. The above ruthenium iodide ratio means the total amount of the alanine structure and the quinone ring structure in the brewed imidized polymer, and the ratio of the number of the quinone ring structure is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium imidization rate can be determined by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) and tetramethyl decyl decane as a reference material at room temperature. - NMR, which was determined from the measurement results according to the following formula (i). Ruthenium amination rate (%) = (1 - aVa2x α )xl00 (i) (In equation (i), A1 is the peak area originating from the NH matrix near the chemical shift of 10 ppm, and A2 is derived from other protons. The peak area, α is the ratio of the number of other protons relative to the one ruthenium matrix in the ruthenium polymer precursor (polyglycolic acid). ^ Dehydration ring closure of poly-proline is preferably (1) by heating poly-proline, or (ii) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and as needed The reaction temperature in the method of heating the polyamic acid of the above (i) is carried out by heating, preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction time is preferably from 1 to 120 hours, more preferably from 2 to 4 hours. When the reaction temperature is less than 50 °C, the dehydration and ring closure reaction cannot be carried out sufficiently. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained ruthenium iodide polymer may be lowered. -24- 200930747 On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, for example, acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like can be used. Anhydride. The amount of the dehydrating agent is determined depending on the desired hydrazine imidation ratio, preferably 0.01 to 20 moles per mole of the methionine structure of the 1 mole of polyglycine. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0.01 to 10 moles per mole of the dehydrating agent used. The more the amount of the above-mentioned dehydrating agent and dehydration ring-closing catalyst, the higher the yield of ruthenium. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polylysine. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably from 1 to 24 hours, more preferably from 2 to 8 hours. In the above method (ii), a reaction solution containing the ruthenium iodide polymer as described above is obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and may also be separated from the sulfiminated polymer and then supplied to the liquid crystal alignment agent. Formulation 'or it is also possible to refine the separated quinone imidized polymer and then supply it to the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as the above-described separation and purification method as polylysine, and the polymer contained in the liquid crystal alignment agent of the present invention Amino acid or hydrazine imidization polymerization-25 - 200930747 The material may also be a terminal modified polymer having a molecular weight adjustment. By using such a terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be produced by adding a molecular weight modifier or the like to a polymerization reaction system during the synthesis of poly-proline. The molecular weight modifier may, for example, be a monobasic acid anhydride, a monoamine compound or a monoisocyanate compound. As the above monobasic acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The ratio of use of the molecular weight modifier to the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. . A solution viscosity - the polyaminic acid or quinone imidized polymer obtained as above, preferably having a solution viscosity of 20 to 800 mPa*s when formulated into a solution having a concentration of 10% by weight, more preferably 30 to 500 The solution viscosity of mPa.s. The solution viscosity (mPa·s) of the above polymer is a good solution of the polymer (for example, r-butyrolactone) to prepare a polymer solution having a concentration of 10% by weight -26 - 200930747, with type E Rotational viscometer measured at 25 ° C. <Other Additives> The liquid crystal alignment film of the present invention contains at least one polymer selected from the group consisting of polylysine as described above and a ruthenium iodide polymer thereof. The polymer contained in the liquid crystal alignment agent of the present invention is preferably a ruthenium iodide polymer. The liquid crystal alignment film of the present invention contains the polymer as described above as an essential component, and may further contain other components as needed. Examples of such other components include compound 0 (hereinafter referred to as "epoxy compound") having two or more epoxy groups in the molecule, and a functional decane compound. Examples of the epoxy group compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, N,N,N',N'_tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) ring Hexane, N, N, N', N'-M tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethyl Oxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. The ratio of use of the above epoxy group compound is relative to 1 part by weight of the total amount of the polymer (refers to the total amount of the above polylysine and its ruthenium iodide polymer contained in the liquid crystal alignment agent). It is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight. As the above functional decane compound, for example, 3-aminopropane-27 - 200930747 〇
基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、2-氨基丙基 三甲氧基矽烷、2-氨基丙基三乙氧基矽烷、Ν-(2-氨基乙基 )-3-氨基丙基三甲氧基矽烷、Ν-(2-氨基乙基)-3-氨基丙基甲 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-乙氧羰基-3-氨基丙基三甲氧基矽烷、N-乙氧羰基-3-氨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-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 -氨基丙基三甲氧基矽烷、N -苄基-3-氨基丙基三乙氧基矽 烷、N-苯基-3-氨基丙基三甲氧基矽烷、N-苯基-3-氨基丙基 三乙氧基矽烷、N-雙(氧乙烯基)-3-氨基丙基三甲氧基矽烷 、N-雙(氧乙烯基)-3-氨基丙基三乙氧基矽烷等。 如上述官能性矽烷化合物的使用比例,相對於1 00重 量份聚合物總量,較佳爲2重量份以下,更佳爲〇. 2重量 份以下。 <液晶配向劑> 本發明的液晶配向劑是將由上述聚醯胺酸及其醯亞胺 化聚合物構成的群組中選出的至少一種以及根據需要任選 混合的其他添加劑較佳溶解含於有機溶劑中而構成的。 作爲上述有機溶劑,可以列舉作爲聚醯胺酸合成反應 中所用的溶劑而例示的溶劑。另外,還可以適當地選擇聯 用作爲聚醯胺酸的合成反應時可聯用的而例示的不良溶胃。 -28 - 200930747 作爲本發明液晶配向劑中使用的特佳的有機溶劑,可 以列舉例如N-甲基-2·吡咯烷酮、r-丁內酯、r-丁內醯胺 、N,N-二甲基甲醯胺、N,N_:甲基乙醯胺、4-羥基-4-甲基 -2-戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙 酸甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇乙醚、乙 二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚(丁基溶纖劑) 、乙二醇二甲基醚、乙二醇乙醚乙酸酯、二甘醇二甲醚、 二甘醇二乙醚、二甘醇單甲醚、二甘醇單乙醚、二甘醇單 甲醚乙酸酯、二甘醇單乙醚乙酸酯、丙酸異戊酯、異丁酸 異戊酯、異戊醚等。這些溶劑可以單獨使用,或者也可以 兩種以’上混合使用》 本發明液晶配向劑中固體含量濃度(液晶配向劑中除 溶劑以外的成分的合計重量占液晶配向劑總重量的比例) 考慮粘性、揮發性等而適宜進行選擇,較佳爲1〜10重量 %的範圍。也就是說,將本發明液晶配向劑如下所述塗敷 於基板表面,較佳通過加熱形成作爲液晶配向膜的塗膜’ 當固體含量濃度不足1重量%時,將導致該塗膜的厚度過 小,從而不能獲得良好的液晶配向膜;另一方面,當固體 含量濃度超過10重量%時’將導致塗膜厚度過厚而不能獲 得良好的液晶配向膜’並且’液晶配向劑的粘性增大’導 致塗敷性能變差。 特佳的固體含量濃度範圍’根據將液晶配向劑塗敷于 基板時所採用的方法而不同。例如’當採用旋塗法時’特 佳1.5〜4.5重量%的範圍。當採用印刷法時’特佳使固體 -29- 200930747 含量濃度爲3〜9重量%的範圍,這樣,可以使溶液 在12〜50 mP a. s的範圍。當採用噴墨法時,特佳 含量濃度爲1〜5重量%的範圍,這樣,可以使溶液 在3〜15 mPa.s的範圍。 配製本發明液晶配向劑時的溫度,較佳爲0 °C -,更佳爲2 0 °C〜6 0 °C。 <液晶顯示元件> 本發明的液晶顯示元件具有由如上所述的本發 〇 配向劑形成的液晶配向膜。 本發明的液晶顯示元件可以通過例如以下(1 V 工序製造。 (1)首先,以兩塊設有形成圖案的透明導電膜的 爲一對,在其各個形成透明導電膜的面上,通過例 法、旋塗法、膠版印刷法、噴墨印刷法等適當的塗 ,分別塗敷本發明的液晶配向劑,接著,通過對各 進行加熱形成塗膜。這裏,作爲基板,可以使用例 〇 w 玻璃、鈉鈣玻璃等玻璃;聚對苯二甲酸乙二醇酯、 二甲酸丁二醇酯、聚醚楓、聚碳酸酯、聚(脂環式少 塑膠制透明基板。作爲基板一面上設置的透明導電 以使用氧化錫(Sn02)製的NESA膜(美國PPG公司注 )、氧化銦一氧化錫(ln203 - Sn02)製的ITO膜等,形 的透明導電膜的獲得,可採用例如在形成無圖案的 電膜後通過光刻蝕形成圖案的方法 '或者在透明導 成時採用具有所需圖案的掩模的方法等。在液晶配Trimethoxy decane, 3-aminopropyltriethoxy decane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, fluorenyl-(2-aminoethyl)-3- Aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethyl Oxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylene Triamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane-1,4,7-triazadecane, 10-triethoxydecyl-1,4, 7-Triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate , N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene 3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3- Propyl triethoxy silane-yl and the like. The proportion of the functional decane compound to be used is preferably 2 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the total amount of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably at least one selected from the group consisting of the above polylysine and its ruthenium iodide polymer, and other additives optionally mixed as needed. It is composed of an organic solvent. The above-mentioned organic solvent may, for example, be a solvent exemplified as a solvent used in the polyamido acid synthesis reaction. Further, it is also possible to appropriately select a poorly dissolved stomach which is exemplified in combination with the synthesis reaction of polylysine. -28 - 200930747 As a particularly preferable organic solvent used in the liquid crystal alignment agent of the present invention, for example, N-methyl-2·pyrrolidone, r-butyrolactone, r-butylide, N,N-dimethyl Carbamide, N, N_: methyl acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionate Ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol Ethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. These solvents may be used singly or in combination of two kinds. The solid content concentration of the liquid crystal alignment agent of the present invention (the total weight of components other than the solvent in the liquid crystal alignment agent is a ratio of the total weight of the liquid crystal alignment agent) It is suitably selected in terms of volatility, etc., and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below, preferably by heating to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small. Therefore, a good liquid crystal alignment film cannot be obtained; on the other hand, when the solid content concentration exceeds 10% by weight, 'the coating film thickness is too thick to obtain a good liquid crystal alignment film' and the viscosity of the liquid crystal alignment agent increases. This leads to poor coating properties. The particularly preferable solid content concentration range ' differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, 'when the spin coating method is employed' is preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, the content of the solid -29-200930747 is in the range of 3 to 9 wt%, so that the solution can be in the range of 12 to 50 mP a.s. When the ink jet method is employed, the concentration is particularly preferably in the range of 1 to 5 % by weight, so that the solution can be in the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably 0 ° C - and more preferably 20 ° C to 60 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the above-described hair styling agent as described above. The liquid crystal display device of the present invention can be produced, for example, by the following steps (1 V). (1) First, a pair of transparent conductive films having a pattern is provided in a pair, and a surface on which each of the transparent conductive films is formed is passed through A liquid crystal alignment agent of the present invention is applied by a suitable coating such as a method, a spin coating method, an offset printing method, or an inkjet printing method, and then a coating film is formed by heating each. Here, as the substrate, an example can be used. Glass such as glass or soda lime glass; polyethylene terephthalate, butylene glycol dicarboxylate, polyether maple, polycarbonate, poly (aliphatic plastic transparent substrate). The transparent conductive material is obtained by using a NESA film made of tin oxide (Sn02) (an injection of PPG, USA), an ITO film made of indium tin oxide (ln203 - SnO 2 ), or the like, and a transparent conductive film can be obtained, for example, in formation. a method of forming a pattern by photolithography after patterning an electric film, or a method of using a mask having a desired pattern when transparently forming, etc.
粘度落 使固體 粘度落 ^ 2 00°C 明液晶 -(3)的 基板作 如輥塗 敷方法 塗敷面 如浮法 聚對苯 给烴)等 膜,可 冊商標 成圖案 透明導 電膜形 向劑的 -30- 200930747 塗敷時,爲了進一步改善基板表面和透明導電膜與塗膜的 粘合性,還可以在基板表面中的要形成塗膜的面上,進行 預先塗敷官能性矽烷化合物、官能性鈦化合物等的前處理 〇 液晶配向劑塗敷後的加熱溫度較佳爲30〜300 t:,更 佳爲40〜250 °C,加熱時間較佳爲1〜30分鐘,更佳爲5 〜20分鐘。形成的塗膜的厚度較佳爲〇·〇〇!〜 1μπι,更佳爲 0.005 〜0.5μπχ 〇 η (2) 然後,採用纏有例如尼龍、人造纖維、棉花等纖維 制的布的輥對如上形成的塗膜面進行以一定方向摩擦的打 磨處理。這樣,使塗膜上產生液晶分子配向能,製成液晶 配向膜。另外’對於垂直配向型液晶顯示元件,也有不進 行打磨處理的。此時,可以將上述塗膜直接作爲液晶配向 膜使用。 另外’對由本發明液晶配向劑形成的液晶配向膜,進 行例如專利文獻7(日本特開平6-222366號公報)或專利文The viscosity falls so that the viscosity of the solid falls to 20,000 ° C. The liquid crystal-(3) substrate is used as a coating method such as a roll coating method such as a float poly(p-phenylene to hydrocarbon) film, and can be labeled as a pattern transparent conductive film shape. -30- 200930747 When coating, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, it is also possible to apply a functional decane compound to the surface of the substrate surface on which the coating film is to be formed. The pretreatment of the functional titanium compound or the like, the heating temperature after application of the liquid crystal alignment agent is preferably from 30 to 300 t: more preferably from 40 to 250 ° C, and the heating time is preferably from 1 to 30 minutes, more preferably 5 to 20 minutes. The thickness of the formed coating film is preferably 〇·〇〇!~1μπι, more preferably 0.005 to 0.5μπχ 〇η (2) Then, a roller pair wound with a cloth made of fibers such as nylon, rayon, cotton or the like is used. The formed coating film surface is subjected to a rubbing treatment in which rubbing is performed in a certain direction. Thus, the alignment energy of the liquid crystal molecules is generated on the coating film to form a liquid crystal alignment film. Further, the vertical alignment type liquid crystal display element is also not subjected to the rubbing treatment. In this case, the above coating film can be directly used as a liquid crystal alignment film. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is disclosed in, for example, Patent Document 7 (JP-A-H06-222366) or Patent Document.
J 獻8(曰本特開平6—281939號公報)中所示的、對液晶配向 膜的一部分照射紫外線而使液晶配向膜一部分區域預傾角 改變的處理,或者進行專利文獻9(日本特開平5- 107544 號公報)中所示的、在液晶配向膜部分表面上形成保護膜後 ’以與先前打磨處理不同的方向進行打磨處理後除去保護 膜的處理’使液晶配向膜每一區域具有不同液晶配向能, 這樣能夠改善所得液晶顯示元件的視角特性。 (3) 將一對如上形成液晶配向膜的基板通過間隙(晶胞 -31- 200930747 間隙)相對放置,使兩塊基板的液晶配向膜的打磨方向垂直 或逆平行,將兩塊基板周邊部位用密封劑貼合,向由基板 表面和密封劑分割出的晶胞間隙內注充液晶,封閉注入孔 ,構成液晶胞。然後,在液晶胞的外表面上貼合偏光板, 使其偏振方向與各基板上形成的液晶配向膜的打磨方向一 致或垂直,這樣便可製得液晶顯示元件。這裏,作爲密封 劑,可以使用例如含作爲固化劑和分隔物的氧化鋁球的環 氧樹脂等。作爲液晶,可以列舉向列型液晶和碟狀型液晶 © ,其中較佳向列型液晶,可以使用例如希夫氏鹼類液晶、 氧化偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶、酯 類液晶、三聯苯類液晶、聯苯基環己烷類液晶、嘧啶類,液 晶、二氧六環類液晶、雙環辛烷類液晶、立方烷類液晶等 。此外,這些液晶中還可以進一步添加例如氯化胆甾醇、 胆甾醇壬酸酯、胆甾醇碳酸酯等胆甾型液晶;以商品名 “C-15”、“CB-15”(MERCK公司製造)銷售的手性劑;對癸氧 基苯亞甲基-對氨基-2-甲基丁基肉桂酸酯等鐵電性液晶等 ^ 而進行使用。 作爲液晶胞外表面上貼合的偏光板,可以列舉將聚乙 烯醇延伸配向同時吸收碘所得的稱作爲“ Η膜”的偏光膜 夾在醋酸纖維保護膜中而製成的偏光板或者Η膜自身製成 的偏光板。 【實施例】 以下’通過實施例對本發明進行更具體的說明,但是 本發明並不局限於這些實施例。 -32- 200930747 另外,以下的合成例中醯亞胺化聚合物中的醯亞胺化 率’是通過將醯亞胺化聚合物在室溫下充分減壓乾燥後, 溶於氘代二甲基亞颯中,以四甲基矽烷爲基準物質,在室 溫下測定1H-NMR ’由測定結果按照上述公式⑴求出的。 合成例1 將作爲四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐98g (0.5莫耳),以及作爲二胺化合物的2,4_二氨基·Ν,Ν_二烯 丙基苯胺61g(0.3莫耳)和3,5-雙(4-氨基苯甲醯氨基)苯甲 酸正十六烷基酯123g(0.2莫耳)溶於1127g N -甲基-2-吡咯 烷酮中,在60 °C下反應6小時,得到含有聚醯胺酸的聚合 物溶液。取少量所得聚醯胺酸溶液,加入N-甲基-2-吡略烷 酮’配成聚醯胺酸濃度爲1 0重量%的溶液,測定的溶液粘 度爲 50mPa.s。 然後,向所得聚醯胺酸溶液中追加1 409 g N-甲基-2-吡咯烷酮,再加入198g吡啶和204g醋酸酐,在ll〇t下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的吡啶和醋酸酐除去至體系外),得到約 1 300g含有醯亞胺化率約爲94%的醯亞胺化聚合物(A- 1) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ_ 丁 內酯溶液,配成聚合物濃度爲1 0重量%的溶液,測定的溶 液粘度爲60 mPa · s。 合成例2 將作爲四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐98g -33 - 200930747 (0.5莫耳),以及作爲二胺化合物的2,4-二氨基-N,N-二烯 丙基苯胺61g(0.3莫耳)和3,5-雙(4-氨基苯甲醯氨基)苯甲 酸正十八烷基酯128g(0.2莫耳)溶於1149g N-甲基-2-吡咯 烷酮中,在60°C下反應6小時,得到含有聚醯胺酸的聚合 物溶液。取少量所得聚醯胺酸溶液,加入N ·甲基-2 -吡咯烷 酮,配成聚醯胺酸濃度爲10重量%的溶液,測定的溶液粘 度爲 52mPa.seA process of irradiating a part of a liquid crystal alignment film with ultraviolet rays to change a pretilt angle of a partial region of a liquid crystal alignment film, or performing a patent document 9 (Japanese Patent Laid-Open No. Hei No. Hei No. Hei 6-281939) In the case where a protective film is formed on the surface of the liquid crystal alignment film portion, the process of removing the protective film after polishing in a direction different from the previous polishing process is shown in the '107544, 'the liquid crystal alignment film has different liquid crystals in each region. The alignment energy can improve the viewing angle characteristics of the resulting liquid crystal display element. (3) A pair of substrates forming the liquid crystal alignment film as described above are placed oppositely through the gap (cell -31 - 200930747 gap), so that the polishing direction of the liquid crystal alignment film of the two substrates is perpendicular or anti-parallel, and the peripheral portions of the two substrates are used. The sealant is bonded, and liquid crystal is injected into the cell gap which is divided by the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizing plate is attached to the outer surface of the liquid crystal cell so that the polarization direction thereof is uniform or perpendicular to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal ©, and among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. An alkane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine, a liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in these liquid crystals, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added; and the trade names are "C-15" and "CB-15" (manufactured by MERCK Co., Ltd.). A chiral agent for sale; a ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or a ruthenium film formed by sandwiching a polarizing film called a "ruthenium film" obtained by stretching a polyvinyl alcohol and absorbing iodine. A polarizing plate made by itself. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the examples. -32- 200930747 In addition, in the following synthesis examples, the ruthenium imidization rate in the ruthenium iodide polymer is dissolved in deuterated dimethyl by drying the ruthenium iodide polymer under reduced pressure at room temperature. In the hydrazide, 1H-NMR ' was measured at room temperature using tetramethyl decane as a reference material, and the measurement result was obtained according to the above formula (1). Synthesis Example 1 98 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and 2,4-diamino·anthracene as a diamine compound _ Diallyl aniline 61 g (0.3 mol) and 3,5-bis(4-aminobenzhydrylamino)benzoic acid n-hexadecyl ester 123 g (0.2 mol) dissolved in 1127 g N-methyl-2 In the pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 50 mPa·s. Then, 1 409 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at 11 °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain about 1 300 g of hydrazine. A polymer solution of an imidization polymer (A-1) having an imidization ratio of about 94%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 60 mPa·s. Synthesis Example 2 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g -33 - 200930747 (0.5 mol) as a tetracarboxylic dianhydride, and 2,4-diamino as a diamine compound -N,N-diallylaniline 61 g (0.3 mol) and 3,5-bis(4-aminobenzimidino)benzoic acid n-octadecyl ester 128 g (0.2 mol) dissolved in 1149 g N- The methyl-2-pyrrolidone was reacted at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and N·methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 52 mPa·se.
然後,向所得聚醯胺酸溶液中追加1437g N -甲基-2-吡略烷酮,再加入198g吡啶和204g醋酸酐,在ll〇°C下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內·’酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的耻啶和醋酸酐除去至體系外),得到約 131〇g含有醯亞胺化率約爲95%的醯亞胺化聚合物(Α— 2) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ-丁 內酯溶液,配成聚合物濃度爲1 〇重量%的溶液,測定的溶 液粘度爲63 mPa.s。 合成例3 將作爲四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐93g (0.48莫耳)和均苯四酸二酐5g(〇.〇3莫耳),以及作爲二胺 化合物的2,4-二氨基->^,:^-二烯丙基苯胺618(0.3莫耳)和 3,5-雙(4-氨基苯甲醯氨基)苯甲酸正十六烷基酯i23g(02莫 耳)溶於1129g N-甲基-2-吡咯烷酮中,在60°C下反應6小 時’得到含有聚醯胺酸的聚合物溶液。取少量所得聚醯胺 酸溶液’加入N-甲基-2-吡咯烷酮,配成聚醯胺酸濃度爲 -34- 200930747 10重量%的溶液’測定的溶液粘度爲55inpa · S。 然後,向所得聚醯胺酸溶液中追加1411g N -甲基-2-啦略院酮,再加入198gnJt陡和204g醋酸酐,在11〇。(:下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的吡啶和醋酸酐除去至體系外),得到約 1 320g含有醯亞胺化率約爲94%的醯亞胺化聚合物(Α— 3) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ_ 丁 內酯溶液,配成聚合物濃度爲10重量%的溶液,測定的溶 液粘度爲65 mPa.s。 合成例4' 將作爲四羧酸二酐的1,2,3,4-環丁院四羧酸二酐93g (0,48莫耳)和均苯四酸二酐5g(0.03莫耳),以及作爲二胺 化合物的 2,4-二氨基-N,N-二烯丙基苯胺 61g(0_3莫耳)和 3, 5-雙(4-氨基苯甲醯氨基)苯甲酸正十八烷基酯128 g(〇.2 莫耳)溶於1152g N-甲基-2-吡咯烷酮中,在60°C下反應6 小時,得到含有聚醯胺酸的聚合物溶液。取少量所得聚酿 胺酸溶液,加入N-甲基-2-吡咯烷嗣,配成聚醯胺酸濃度爲 1 〇重量%的溶液,測定的溶液粘度爲5 6 m P a · s。 然後,向所得聚醯胺酸溶液中追加 M40g N -甲基_2-吡咯烷酮,再加入198g吡啶和204g醋酸酐,在ll〇°C下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的毗啶和醋酸酐除去至體系外),得到約 -35 - 200930747 1310g含有醯亞胺化率約爲93%的醯亞胺化聚合物(A- 4) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ_丁 內酯溶液,配成聚合物濃度爲1 0重量%的溶液,測定的溶 液粘度爲65 mPa · s。 合成例5 將作爲四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐93g (0.48莫耳)和均苯四酸二酐5g(0.03莫耳),以及作爲二胺 化合物的2,4-二氨基-N,N-二烯丙基苯胺71g(0.35莫耳)、 U 3,5-雙(4-氨基苯甲醯氨基)苯甲酸正十六烷基酯61g(0.1莫 耳)和上述式(D—3)表示的化合物 26g(0.05莫耳)溶於 1029gN-甲基-2-吡咯烷酮中,在60°C下反應6小時,得到 含有聚醯胺酸的聚合物溶液。取少量所得聚醯胺酸溶液, 加入N -甲基-2-吡咯烷酮,配成聚醯胺酸濃度爲10重量% 的溶液,測定的溶液粘度爲5 0 mP a · s。 然後,向所得聚醯胺酸溶液中追加1 2 86g N-甲基-2-吡咯烷酮,再加入198g吡啶和204g醋酸酐,在ll〇°C下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的吡啶和醋酸酐除去至體系外),得到約 1 300g含有醯亞胺化率約爲93%的醯亞胺化聚合物(Α— 5) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ-丁 內酯溶液,配成聚合物濃度爲1 0重量%的溶液,測定的溶 液粘度爲60mPa.s。 合成例6 -36 - 200930747 將作爲四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐64g (0.33莫耳)、2,3,5-三羧基環戊基醋酸二酐34§(0.15莫耳) 和均苯四酸二酐5g(0,03莫耳),以及作爲二胺化合物的 2,4-二氨基-N,N-二烯丙基苯胺61g(0.3莫耳)和3,5-雙(4-氨基苯甲醯氨基)苯甲酸正十六烷基酯123g(0.2莫耳)溶於 1146gN -甲基-2 -吡咯烷酮中,在60°C下反應6小時,得到 含有聚醯胺酸的聚合物溶液。取少量所得聚醯胺酸溶液, 加入N-甲基-2-吡咯烷酮,配成聚醯胺酸濃度爲1〇重量% 的溶液,測定的溶液粘度爲5 5 m P a · s。 然後,向所得聚醯胺酸溶液中追加1433g N -甲基-2-吡咯烷酮,再加入198g吡啶和204g醋酸酐,在ll〇°C下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的吡啶和醋酸酐除去至體系外),得到約 1 3 00g含有醯亞胺化率約爲93%的醯亞胺化聚合物(Α— 6) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ-丁 內酯溶液,配成聚合物濃度爲1 0重量%的溶液,測定的溶 液粘度爲65 mPa · s。 比較合成例1 將作爲四羧酸二酐的1,2,3,4 -環丁烷四羧酸二酐98g (0_5莫耳),以及作爲二胺化合物的2,4-二氨基-N,N-二烯 丙基苯胺61g(0.3莫耳)和4-[4-(4·反式正庚基環己基)苯氧 基]-1,3-二氨基苯76g(0.2莫耳)溶於941g N-甲基-2-吡咯院 酮中,在60°C下反應6小時,得到含有聚醯胺酸的聚合物 -37- 200930747 溶液。取少量所得聚醯胺酸溶液,加入N-甲基-2-吡咯烷酮 ,配成聚醯胺酸濃度爲1 0重量%的溶液,測定的溶液粘度 爲 48mPa-s。 然後,向所得聚醯胺酸溶液中追加1 177g N-甲基-2-吡咯烷酮,再加入198g吡啶和204g醋酸酐,在110°C下 進行4小時脫水閉環反應。脫水閉環反應後,通過將體系 內的溶劑用新的γ-丁內酯進行溶劑置換(在此操作中將脫 水閉環反應中使用的吡啶和醋酸酐除去至體系外),得到約 〇 w 1300g含有醯亞胺化率約爲95%的醯亞胺化聚合物(8—1) 的聚合物溶液。取少量該醯亞胺化聚合物溶液,加入γ-丁 內酯溶液,配成聚合物濃度爲10重量%的溶液,測定的溶 液粘度爲55 mPa · s。 實施例1 <液晶配向劑的配製> 向上述合成例1中製得的含有醯亞胺化聚合物(A-1) 的溶液中,加入7 -丁內酯(BL)、N-甲基-2-吡咯烷酮(NMP) 和丁基溶纖劑(B C),配成溶劑組成爲B L : Ν Μ P : B C = 7 1 : 1 7 : 1 2 (重量比)、固體含量濃度爲4重量%的溶液,將該溶液用孔 徑爲1 μιη的濾器過濾,配製出液晶配向劑。 <電壓保持率的評價>Then, 1437 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring-closure reaction, the solvent in the system was replaced with a new γ-butane·' ester (in this operation, the guanidine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system) to obtain about 131. 〇g contains a polymer solution of a ruthenium iodide polymer (Α-2) having a ruthenium iodide ratio of about 95%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 1% by weight, and the viscosity of the solution was determined to be 63 mPa·s. Synthesis Example 3 93 g (0.48 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 5 g of pyromellitic dianhydride (〇.〇3 mol), And 2,4-diamino->^,:^-diallylaniline 618 (0.3 mol) and 3,5-bis(4-aminobenzhydrylamino)benzoic acid as a diamine compound The hexaalkyl ester i23g (02 mole) was dissolved in 1129 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of -34 to 200930747 10% by weight. The solution viscosity was 55 inpa · S. Then, 1411 g of N-methyl-2-laredanone was added to the obtained polyamic acid solution, and 198 g of nJt steep and 204 g of acetic anhydride were further added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to Outside the system, about 1 320 g of a polymer solution containing a ruthenium iodide polymer (Α-3) having a ruthenium iodide ratio of about 94% is obtained. A small amount of the ruthenium iodide polymer solution is added to the γ_ The ester solution was formulated into a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 65 mPa·s. Synthesis Example 4' 1,2,3,4-cyclobutanine tetracarboxylic acid as tetracarboxylic dianhydride Acid dianhydride 93g (0,48 moles) and pyromellitic dianhydride 5g (0.03 moles), and 2,4-diamino-N,N-diallylaniline as a diamine compound 61g (0_3) Mole) and n-octadecyl 3,5-bis(4-aminobenzimidino)benzoate 128 g (〇.2 mol) dissolved in 1152 g of N-methyl-2-pyrrolidone at 60 The reaction was carried out for 6 hours at ° C to obtain a polymer solution containing poly-proline. A small amount of the obtained poly-branched acid solution was added, and N-methyl-2-pyrrolidinium was added to prepare a poly-proline concentration. 1 〇% by weight of the solution, the measured solution viscosity is 5 6 m P a · s. Then, M40g N-methyl-2-pyrrolidone is added to the obtained polyamic acid solution, and then 198g of pyridine and 204g of acetic anhydride are added. The dehydration ring-closure reaction was carried out for 4 hours at ll 〇 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent (in this operation, the pyridinium used in the dehydration ring-closure reaction was The acetic anhydride was removed to the outside of the system to obtain a polymer solution of about 35-35 - 200930747 1310 g of a ruthenium iodide polymer (A-4) having a ruthenium iodide ratio of about 93%. The solution was added to a γ-butyrolactone solution to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 65 mPa·s. Synthesis Example 5 1,2,3 as tetracarboxylic dianhydride , 4-cyclobutane tetracarboxylic dianhydride 93 g (0.48 mol) and pyromellitic dianhydride 5 g (0.03 mol), and 2,4-diamino-N,N-diene as diamine compound Propylaniline 71g (0.35 mol), U 3,5-bis(4-aminobenzhydrylamino)benzoic acid n-hexadecyl ester 61g (0.1 mol) and above 26 g (0.05 mol) of the compound represented by the formula (D-3) was dissolved in 1029 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a polymer solution containing polyglycine. The obtained polyaminic acid solution was added with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 50 mPa·s. Then, the obtained polyamine was obtained. 1 2 86 g of N-methyl-2-pyrrolidone was added to the acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain about 1 300 g of hydrazine. A polymer solution of an imidization polymer (Α-5) having an imidization ratio of about 93%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the viscosity of the solution was measured to be 60 mPa·s. Synthesis Example 6 -36 - 200930747 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride 64 g (0.33 mol), 2,3,5-tricarboxycyclopentyl acetic acid Dihydride 34 § (0.15 mol) and pyromellitic dianhydride 5 g (0,03 mol), and 2,4-diamino-N,N-diallylaniline as a diamine compound 61 g (0.3 Mohr) and 3,5-bis(4-aminobenzimidino)benzoic acid n-hexadecyl ester 123g (0.2 mol) dissolved in 1146g N-methyl-2-pyrrolidone, reacted at 60 ° C After 6 hours, a polymer solution containing polylysine was obtained. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 5 5 m P a · s. Then, 1433 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain about 1 300 g of the solvent. A polymer solution of a ruthenium iodide polymer (Α-6) having a ruthenium iodide ratio of about 93%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 65 mPa·s. Comparative Synthesis Example 1 98 g (0-5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and 2,4-diamino-N as a diamine compound, N-diallylaniline 61g (0.3 mol) and 4-[4-(4·trans n-heptylcyclohexyl)phenoxy]-1,3-diaminobenzene 76 g (0.2 mol) are soluble In 941 g of N-methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a poly-proline-containing polymer-37-200930747 solution. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 48 mPa-s. Then, 1 177 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction are removed to the outside of the system) to obtain about 1300 g of the solvent. A polymer solution of a ruthenium iodide polymer (8-1) having a ruthenium iodide ratio of about 95%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 55 mPa·s. Example 1 <Preparation of Liquid Crystal Aligning Agent> To a solution containing the ruthenium iodide polymer (A-1) prepared in the above Synthesis Example 1, 7-butyrolactone (BL), N-A was added. Base-2-pyrrolidone (NMP) and butyl cellosolve (BC) in a solvent composition of BL: Ν Μ P : BC = 7 1 : 1 7 : 1 2 (by weight), solid content concentration of 4% by weight The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. <Evaluation of voltage retention rate>
採用液晶配向膜印刷機(日本寫真印刷機(株)製造),將 上述配製的液晶配向劑塗敷於帶有ΙΤΟ膜制的透明電極的 玻璃基板的透明電極面上,在80°C的加熱板上加熱1分鐘 ,再在200 °C的加熱板上加熱10分鐘,形成平均膜厚爲600 A -38 - 200930747 的塗膜。重複進行該操作’製造兩塊(一對)具有塗膜的基 板。將這些基板上的塗膜用倍率爲20倍的顯微鏡觀察,沒 有發現印刷不均和氣孔’塗敷性良好。 在帶有該塗膜的一對基板的具有液晶配向膜的各外緣 上,塗敷加入了直徑爲5.5μιη的氧化鋁球的環氧樹脂粘合 劑後,使液晶配向膜面相對進行重疊並壓合,使粘合劑固 化。接著,通過液晶注入口向一對基板間塡充負型液晶 (MERK公司製造,MLC-2 0 3 8),然後用丙烯酸類光固化黏 〇 w 合劑封閉液晶注入口,製得用於評價電壓保持率的液晶盒 〇 在6 (TC的環境溫度下,在167毫秒的,時間跨度內,對 該液晶盒施加5V的電壓,電壓施加時間爲60微秒,然後 測定從電壓解除至1 67毫秒後的電壓保持率。測定裝置採 用(株)TOTO Corporation製造的VHR-1。電壓保持率爲95°/。 以上的情況電壓保持率評爲“合格”。 ^ <殘像性能的評價> 〇 除了基板採用第1圖所示的帶有IT0電極的基板以外 ’按照上述<電壓保持率的評價>中所述的方法,製造用於 殘像性能評價的液晶盒。在室溫下向電極A施加6.0V的直 流電壓,向電極B施加0.5V的直流電壓,施加24小時。 電壓解除後,評價向電極A、B以0.1V的梯度施加0.1〜 5.0V直流電壓時電極A和B相應區域的亮度差。若亮度差 小’則殘像性能評價爲“良”,當亮度差大時,殘像性能 評價爲“不良”。 -39- 200930747 實施例2〜6和比較例1 除了分別使用含有表1中所列的聚合物的溶液代替含 有醯亞胺化聚合物(A - 1)的溶液以外,與上述實施例1同 樣地配製液晶配向劑並進行評價。評價結果列於表1。 表1 液晶配向劑 液晶 抱 聚合物種類 塗敷性 電壓保持率 殘像性能 實施例1 A- 1 良好 良 良 實施例2 A-2 良好 良 良 實施例3 A-3 良好 良 良 實施例4 A-4 良好 良 良 實施例5 A-5 良好 良 良 實施例6 A- 6 良好 良 良 比較例1 B— 1 良好 良 不良 【圖式簡單說明】 第1圖爲殘像性能評價而製造的液晶盒的模式圖。 €) 【主要元件符號說明】 -far 無0 -40-The liquid crystal alignment agent prepared above was applied to a transparent electrode surface of a glass substrate having a transparent electrode made of a ruthenium film by a liquid crystal alignment film printing machine (manufactured by Nippon Photographic Printing Co., Ltd.), and heated at 80 ° C. The plate was heated for 1 minute and then heated on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 A -38 - 200930747. This operation was repeated to manufacture two (one pair) substrates having a coating film. When the coating film on these substrates was observed with a microscope having a magnification of 20 times, it was found that printing unevenness and pores were excellent in coating properties. On the outer edges of the pair of substrates having the coating film having the liquid crystal alignment film, an epoxy resin binder to which alumina balls having a diameter of 5.5 μm is applied is applied, and the liquid crystal alignment film faces are relatively overlapped. And press to cure the adhesive. Next, a negative liquid crystal (manufactured by MERK Corporation, MLC-2 0 3 8) is interposed between the pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive mixture to prepare a voltage for evaluation. The retention rate of the liquid crystal cell 〇 at 6 TC ambient temperature, within 167 milliseconds, within the time span, a voltage of 5V was applied to the liquid crystal cell, the voltage application time was 60 microseconds, and then the voltage was released from the voltage to 1 67 milliseconds. The voltage holding ratio was measured. The measuring device was VHR-1 manufactured by TOTO Corporation, and the voltage holding ratio was 95°/. In the above case, the voltage holding ratio was rated as “acceptable.” ^ <Evaluation of afterimage performance> In addition to the substrate having the IT0 electrode shown in Fig. 1, the liquid crystal cell for evaluation of after-image performance was produced by the method described in the above <Evaluation of voltage holding ratio>. A DC voltage of 6.0 V was applied to the electrode A, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the voltage was released, it was evaluated that the electrode A and the electrode A and B were applied with a gradient of 0.1 V at a voltage of 0.1 V. B brightness of the corresponding area If the difference in luminance is small, the afterimage performance is evaluated as "good", and when the luminance difference is large, the afterimage performance is evaluated as "poor". -39- 200930747 Examples 2 to 6 and Comparative Example 1 A solution of the polymer listed in 1 was prepared and evaluated in the same manner as in Example 1 except that the solution containing the ruthenium iodide polymer (A-1) was used. The evaluation results are shown in Table 1. Table 1 Liquid crystal alignment agent liquid crystal polymer type coating voltage retention rate afterimage performance Example 1 A-1 Good good example 2 A-2 Good good example 3 A-3 Good good example 4 A-4 Good and good example 5 A-5 Good good example 6 A- 6 Good good comparative example 1 B-1 Good and bad [Simplified description of the drawing] Fig. 1 shows the liquid crystal cell manufactured by the evaluation of afterimage performance Mode diagram. €) [Main component symbol description] -far No 0 -40-
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CN103969889A (en) * | 2013-01-28 | 2014-08-06 | 胜华科技股份有限公司 | Method for forming liquid crystal alignment film, manufacturing method of display board and display board |
KR102212324B1 (en) | 2014-02-21 | 2021-02-04 | 삼성디스플레이 주식회사 | Photo alignment agent and liquid crystal display device including the same |
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CN112225675B (en) * | 2020-09-22 | 2021-07-06 | 江苏三月科技股份有限公司 | Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element |
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