TW201226445A - Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- 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
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Abstract
Description
201226445 六、發明說明: 【發明所屬之技術領域】 本毛月關於適用於光配向的液晶配向劑、液晶配向 膜、液晶配向膜之形成方法以及液晶顯示元件。 【先前技術】 液晶顯示器(LCD)廣泛用於電視和各種監視器等中 作為LCD的顯不元件’已知具有TN(扭轉向列(丁_^ NematiC))型;S™(超扭轉向列(Super Twisted Nematic)) i,IPS(面内切換(In Piane Switching))型;改變as 型的 電極結構’提高顯示元件部分的開口率,從而提高亮度 的FFS(邊緣場開關(Fringe FieM Switching))型等之液晶 胞(參見專利文獻1及2)。 作為使該液晶胞的液晶進行配向的方法,已知在基 板表面形成液晶配向膜等的有機膜,用人造絲等布料在 個方向上擦拭该有機膜表面進行摩擦處理的方法;在 土板表面斜向蒸鍵氧化石夕的方法;使用langmuir-blodgett 法(LB法)形成具有長鏈烷基的單分子膜的方法等。其中 ’從基板尺寸、液晶的配向均勻性、處理時間和處理成 本的觀點出發,通常採用摩擦處理的方法。 然而’如果藉由摩擦處理使液晶進行配向,則由於 在步驟内會產生灰塵或產生靜電,在配向膜表面附著灰 塵’可此成為顯示不佳產生的原因。尤其是在具有TFT( '專膜電晶體(Thin Film Transistor))元件的基板的情況下 ’由於產生的靜電會破壞TFT元件的電路,有時還是成 率降低的原因。此外,在以後越來越高精細化的液晶 -4 - 201226445 顯示元 生凹凸 因 桂皮酸 從而賦 ,或作 向處理 電或灰 相比, 藉由在 上任意 放射線 問題。 處理法 不足的 件中,伴隨著像素的高密度 ,因此存在難以進行 t在基板表面產 此,作為迴避上,。,摩擦處理的傾向。 F馮迴避上述問題的方法, 酯等感# Μ堉替 已知在聚乙烯基 哥α先性溥膜上照射偏 予液a邮a X非偏光的放射線, 卞展日日配向能力的光配 為感光性薄膜的材匕見專利文獻3和4) 得朕的材枓使用聚 ^ ( ^ ^ ^ 兄胺Μ脂的液晶配 法(參見專利文獻5)。藉 鹿6t — a 由所迷方法,不會產生靜 塵,尨貫現均勻的液曰财a201226445 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element which are suitable for light alignment. [Prior Art] Liquid crystal display (LCD) is widely used as a display element of an LCD in televisions and various monitors and the like. It is known to have a TN (Twisted Nematic) type; STM (Super Torsion Nematic) (Super Twisted Nematic)) i, IPS (In Piane Switching) type; changing the as-type electrode structure's FFS (Fringe FieM Switching) to increase the aperture ratio of the display element portion and thereby improve the brightness Liquid crystal cell of the type or the like (see Patent Documents 1 and 2). As a method of aligning the liquid crystal of the liquid crystal cell, it is known to form an organic film such as a liquid crystal alignment film on the surface of the substrate, and to rub the surface of the organic film in a single direction with a cloth such as rayon to perform a rubbing treatment; A method of obliquely steaming a oxidized stone; a method of forming a monomolecular film having a long-chain alkyl group by using the langmuir-blodgett method (LB method). Among them, a method of rubbing treatment is generally employed from the viewpoints of substrate size, alignment uniformity of liquid crystal, processing time, and processing cost. However, if the liquid crystal is aligned by the rubbing treatment, dust or static electricity is generated in the step, and dust is attached to the surface of the alignment film, which may cause display failure. In particular, in the case of a substrate having a TFT ('Thin Film Transistor) element, the static electricity generated may damage the circuit of the TFT element, which may cause a decrease in productivity. In addition, in the future, the increasingly finer liquid crystal -4 - 201226445 shows that the metamorphic embossing is caused by cinnamic acid, or by arbitrarily arranging radiation or ash. In the case where the processing method is insufficient, the density of the pixel is high, so that it is difficult to perform t on the surface of the substrate as a avoidance. , the tendency of friction treatment. F Feng's method of avoiding the above problems, ester and other senses Μ堉 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知For the material of the photosensitive film, see Patent Documents 3 and 4). For the material of the obtained film, a liquid crystal method of poly(^^^ bromoamine resin) is used (see Patent Document 5). By deer 6t-a , it will not produce static dust, and it will be evenly distributed.
At . . ^ 日日配向。此外,與摩擦處理At . . ^ Day alignment. In addition, with friction treatment
月匕在任思方向上且精宋祕批&、A tf在地控制液晶配向方向。再 放射線照射時使用光格胺莖 ,、、 九掩膜專,從而能在一塊基板 形成液晶配向方向; π不同的多個領域。然而,存在 照射時必須加熱’ 4需要較大累計曝光量這樣的 此外,藉由使用聚酿亞胺樹脂的現有的液晶配向 ’儘管放射線照射時不需要加熱,但存在敏感度 問題。 雲於該狀況’期望開發液晶配向劑,其可以藉由低 照射量的光配向法’形成具有良好液晶配向性的液晶配 向膜’且能形成具有優異電特性等各性能的液晶顯示元 件°此外’還強烈期望開發使用該液晶配向劑的液晶配 向膜之形成方法和液晶配向膜、以及具有該液晶配向膜 之液晶顯示元件。 [先前技術文獻] [專利文獻] [專利文獻1]曰本特開昭56-9 1277號公報 [專利文獻2]曰本特開平1-120528號公報 201226445 [專利文獻3]日本特開平6 287453號公報 [專利文獻4]日本特開2〇〇3_3〇7736號公報 [專利文獻5]日本特開平9_2973 1 3號公報 【發明内容】 [發明所欲解決之課題] 本發明的目的是提供一種液晶配向劑,其能形成放 射線敏感度優異’藉由低照射量的光配向法能具有良好 的液晶配向性之液晶配向膜。此外,提供使用該液晶配 向劑的液晶配向膜之形成方法以及液晶配向膜、進而具 有該液晶配向膜’除了液晶配向性以外,電特性等各性 能也優異的液晶顯示元件。 [解決課題之手段] 用於解決上述課題的發明,係包含具有雙環[2.2.2] 辛烯骨架之聚醯胺酸及/或聚醯亞胺的液晶配向劑。 本發明的液晶配向劑藉由包含具有雙環[2.2.2]辛烯 骨架之聚醯胺酸及/或聚醯亞胺,從而能提高放射線敏感 度,因此,在低照射量下也能形成具有良好液晶配向性 的液晶配向膜。另外,藉由包含具有雙環[2.2.2]辛烯骨 架之聚醢胺酸及/或聚醯亞胺’從而能進一步提高放射線 敏感度的理由尚未明確,例如以下推定。認為聚醯胺酸 等藉由具有雙環[2.2 · 2 ]辛稀骨架’從而藉由例如狄爾斯-阿爾德反應,能引起聚醯胺酸等主鏈的分解、主鏈之間 結合而產生二聚化等,因此會藉由偏光產生光配向。在 該情況下’認為引起分解反應或結合反應的部分與例如 具有環丁烷骨架的聚醯胺酸等相比,引入立體結構,因 201226445 此在反應前後聚合物的結構變化更大。其結果是,可以 以更少量的照射量進行光配向。由此,可以減少光配向 必須的放射線照射量,因此精由該液晶配向劑1能實現 低成本化。此外,如果使用由該液晶配向劑形成的液晶 配向膜,則還能製造電特性等各性能也優異的液晶顯示 元件。 較佳為上述聚醯胺酸具有下述式(1)所示的結構單 元,上述聚醢亞胺具有下述式(2)所示的的結構單元。The Lunar New Year is in the direction of Ren Si and the Jing Song secret batch & A tf controls the liquid crystal alignment direction. When the radiation is irradiated, the light-glycol stems, and the nine masks are used, so that the liquid crystal alignment direction can be formed on one substrate; π different fields. However, there is a case where it is necessary to heat up at the time of irradiation, and a large cumulative exposure amount is required. Further, the existing liquid crystal alignment by using a polyimide resin does not require heating even when irradiated with radiation, but there is a problem of sensitivity. In this case, it is desired to develop a liquid crystal alignment agent which can form a liquid crystal alignment film having good liquid crystal alignment by a low-emission photoalignment method and can form a liquid crystal display element having various properties such as excellent electrical characteristics. It is also strongly desired to develop a method for forming a liquid crystal alignment film using the liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. [PATENT DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A liquid crystal alignment agent which can form a liquid crystal alignment film which is excellent in radiation sensitivity and which has a good liquid crystal alignment property by a light irradiation method of low irradiation amount. In addition, a method of forming a liquid crystal alignment film using the liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element having the same electrical properties as those of the liquid crystal alignment film are also provided. [Means for Solving the Problems] The invention for solving the above problems is a liquid crystal alignment agent containing a polyphosphonic acid having a bicyclo [2.2.2] octene skeleton and/or a polyimine. The liquid crystal alignment agent of the present invention can improve radiation sensitivity by containing polyglycolic acid and/or polyimine having a bicyclo[2.2.2]octene skeleton, and therefore can be formed at a low irradiation amount. Good liquid crystal alignment liquid crystal alignment film. Further, the reason why the radiation sensitivity can be further improved by including the poly-proline and/or polyimine having a bicyclo [2.2.2] octene skeleton has not been clarified, and for example, the following estimation is made. It is considered that poly-proline or the like can cause decomposition of a main chain such as poly-proline and a bond between main chains by, for example, a Diels-Alder reaction by having a bicyclo[2.2.2] octyl skeleton. Dimerization, etc., thus causing light alignment by polarization. In this case, the portion which is considered to cause the decomposition reaction or the binding reaction is introduced into a steric structure as compared with, for example, polyglycine having a cyclobutane skeleton, and the structural change of the polymer before and after the reaction is larger as of 201226445. As a result, the light alignment can be performed with a smaller amount of irradiation. Thereby, the amount of radiation irradiation necessary for the optical alignment can be reduced, so that the liquid crystal alignment agent 1 can be reduced in cost. Further, when a liquid crystal alignment film formed of the liquid crystal alignment agent is used, a liquid crystal display element having excellent electrical properties and the like can be produced. Preferably, the polyamic acid has a structural unit represented by the following formula (1), and the polyimine has a structural unit represented by the following formula (2).
(在式(1)及(2)中,R1及R2各自獨立地表示2價的有機 基。) 該液晶配向劑藉由使上述聚醯胺酸和聚醯亞胺具有 上述特定結構,從而能具有更高敏感度的光配向性。 本發明的液晶配向劑適宜用於光配向。該液晶配向 劑對於放射線的敏感度高,藉由低照射量的放射線就能 形成具有優異性能的液晶配向能力的液晶配向膜。 本發明液晶配向膜之形成方法包括: 201226445 (1) 在基板上塗布本發 之步驟,及 月的液晶配向劑且形成塗膜 (2) 在上述塗膜上照射 向能力之步驟。 光的紫外線且賦予液晶配 在本發明的形成方法 也能進行光配向,^ ^ 1 Μ 4 @㈣線照射’ 性高,此外,還能減少;造:: 也製造液晶配向膜,生產 本發明亦較佳為包括 。 曰由该液晶配向劑形成的、'右曰 配向膜。本發明的液晶 t成的液- J踢错由該液晶配向劑形杰 因此對放射線的敏感度高,.4 A 土 則$成, n 在該形成步驟中,藉由柄日3 射量的放射線,能賦予液晶 , 配向能力,因此生產效率声 好,亦能降低製造成本》 度双丰良 本發明的液晶配向元件具有該液晶配向膜曰 配向膜由本發明的液晶配向劑 "日日 J形成,因此藉由比 少的放射線照射量,就能賦予液晶配向能力。因此更 有該液晶配向膜的液晶顯示元件能比目前更廉價地製: 此外,本發明的液晶顯示元件還能充 = 各性能。 ^冤特性等 另外,本說明書中所謂的「光配向用」中的「“ 係包括可見光線、紫外線、遠紫外線、x射線、帶光」 击位 冲电粒子 束4的概念。此外,所謂的「放射線」係電磁線、 束以外,還包括上述「光」的概念。 泣子 [發明之效果] 本發明的液晶配向劑放射線敏感度高,在低照射旦 的放射線照射下,也能形成具有優異的液晶配向性的液 201226445 晶配向膜,因此其生產效率高,還能減少生產成本。此 外’具有使用本發明液晶配向劑形成的液晶配向膜的液 晶顯示元件在電特性等各性能上也是優異的。 【實施方式】 [用以實施發明之形態] <液晶配向劑> 本發明的液晶配向劑包含具有雙環[2.2.2]辛烯骨架 之聚酿胺酸及/或聚醯亞胺。可以形成包含具有雙環 [2.2.2]辛烯骨架之聚醯胺酸及/或聚醯亞胺、放射線敏感 度提高、在低照射量的放射 的液晶配向膜。此外,具有 件在電特性等之各性能上亦 在不損害本發明的效果下, 醯胺酸及/或聚醯亞胺以外, ’分別對其進行描述。 [聚醯胺酸] 線下具有優異的液晶配向性 該液晶配向膜的液晶顯示元 優異。本發明的液晶配向劑 除了作為必須成分的上述聚 還可以加入其他成分。以下 發明中所使用的聚醯胺酸具有雙環[2.2.2]辛烯骨 辛稀骨加夕中硫:,、要疋在其結構中具有雙環[2.2_2] 木Λ _胺醆,就沒有特別的限定,該聚醯胺酸 可以藉由例如具有雙淨? ★ 裒[2.2·2]辛烯骨架的四羧酸二酎與 一 5物在有機溶劑中反應而合成。 作為具有雙環「2 9 ο 1 jL· lx ••辛稀骨架的四缓g交二酐,可以 =如雙環[2.2.2]辛…,3,5,6·丄^ [2 2又2^2·2·2]辛·7务2,3,5,6.四緩酸二^6基-雙環 • ·]辛:稀_2,3,5,6_四竣酸雙環 201226445 [2.2.2] 辛-7 -烯-2,3,5,6-四羧酸二酐、7-正丁基-雙環 [2.2·2]辛-7-烯-2,3,5,6-四羧酸二酐、7-二級丁基-雙環 [2.2.2] 辛-7-烯-2,3,5,6-四羧酸二酐、1-曱基-雙環[2.2.2] 辛-7-烯-2,3,5,6-四羧酸二酐、1-甲基-7 -甲基-雙環[2.2.2] 辛-7-烯-2,3,5,6-四羧酸二酐、1-曱基-7-乙基-雙環[2_2.2] 辛-7-烯-2,3,5,6-四羧酸二酐、1-曱基-7-正丙基-雙環 [2.2.2] 辛-7-烯-2,3,5,6-四羧酸二酐、1-甲基-7-正丁基-雙 极[2_2.2]辛-7 -稀- 2,3,5,6-四竣酸二針、1-甲基-7 -二級丁 基-雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐等。 其中,較佳為雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二 酐、1-甲基-雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、7-甲基-雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、1-曱基-7-曱基-雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐。其中,更 佳為雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、7-曱基-雙 環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、特佳為雙環 [2.2.2] 辛-7-烯-2,3,5,6-四羧酸二酐。 本發明中所使用的聚醯胺酸較佳為具有上式(1)所 示之結構單元的物。藉由使用該具有特定結構的聚醯胺 酸,從而藉由偏光紫外線照射,就能使液晶分子相對於 偏光方向,而能在一定的方向上且均勻穩定地配向。 在上式(1)中,R1表示的2價的有機基為來自二胺的 基。作為二胺化合物的具體例,只要是在通常的聚醯胺 酸或聚醯亞胺的合成中所使用的一級二胺,就沒有特別 的限定,但可列舉例如脂肪族二胺、脂環式二胺、芳香 族二胺、二胺基有機矽氧烷等。 -10- 201226445 作為脂肪族二胺,可以列舉例如間二甲苯二胺、13- 丙二胺'四亞曱基二胺、五亞曱基二胺、>亞甲基二胺 等。 ’、 作為脂環式二胺,可以列舉例如丨,4_二胺環己烷、 4,4’-亞甲基雙(環己胺)、j 3_雙 ’ 又(甲胺)環己烷等。 作為二胺基有機矽氧烷,可以列舉例如丨,3_雙(3_胺 基丙基)-四甲基二矽氧烷等。 作為芳香族二胺,可以列舉例如鄰苯二胺、間苯二 胺、對笨二胺、4,4,-二胺基二苯基甲烷、4,4、二胺基二 苯基硫醚、1,5-二胺萘、2,2,-二曱基_4,4,_二胺基聯苯、 4,4’_二胺基_2,2,-雙(三氟甲基)聯笨、2,7-二胺基第、4,4’-一胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、 9,9_雙胺基苯基)第、2,2_雙[4-(4-胺基苯氧基)苯基]六 氧丙院、2,2-雙(4·胺基苯基)六氟丙烷、4,4,_(對苯二亞 異丙基)雙(苯胺)、4,4’-(間苯二亞異丙基)雙(苯胺)、ι,4-雙(4-胺基笨氧基)苯、4,4,-雙(4_胺基苯氧基)聯苯、2,6_ 一胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶'3,6-二 胺基°丫呼、3,6-二胺基咔唑、N-曱基-3,6-二胺基咔唑、 N -乙基-3,6-二胺基咔唑、N_笨基-3,6_二胺基咔唑、n,n,_ 雙(4-胺基苯基)·聯苯胺、n,n,_雙(4_胺基苯基)_N,N,_二 曱基聯苯胺、1,4·雙(4-胺基笨基)_哌啶、3,5-二胺基苯曱 酸、十二烧氧基_2,4-二胺基苯、十四烷氧基-2,4-二胺基 笨、十五烧氧基-2,4-二胺基笨、十六烷氧基-2,4-二胺基 笨、十八烧氧基-2,4 -二胺基苯、十二烷氧基-2*5 -二胺基 •11- 201226445 苯、十四烷氧基-2,5-二胺基苯、十五烷氧基-2,5_二胺基 苯、十六烷氧基-2,5-二胺基笨、十八烷氧基-2,5_二胺基 苯、膽留烷氧基-3,5-二胺基苯、膽留烯氧基·3,5_二胺基 苯、膽留烷氧基-2,4-二胺基苯、膽留烯氧基-2,4_二胺基 苯、3,5-二胺基苯甲酸膽留烧基酯、3,5 -二胺基苯甲酸膽 甾烯基酯、3,5-二胺基苯曱酸羊毛留烷基酯、3,6_雙(4_ 胺基苯甲醯氧基)膽留烷、3,6-雙(4-胺基苯氧基)膽留烷 、4-(4’-三氟曱氧基苯曱醯基)環己基-3,5_二胺基苯甲酸 Θ旨、4-(4’-三氟曱基苯曱醯基)環己基-3,5_二胺基苯甲酸 醋、1,1-雙(4-((胺基苯基)甲基)苯基)_4_丁基環己烷、丨,^ 雙(4-((胺基苯基)曱基)苯基)_4_庚基環己烷、M..雙(4_(( 胺基苯基)曱基)苯基)-4-庚基環己烷、匕卜雙(4_((胺基笨 基)曱基)苯基)-4-(4-庚基環己基)環己烷、2,4_二胺基 -N,N-二烯丙基苯胺、4_胺基苄基胺、%胺基苄基胺、 201226445(In the formulae (1) and (2), R1 and R2 each independently represent a divalent organic group.) The liquid crystal alignment agent can have the above specific structure by allowing the above polyamic acid and polyimine. Light alignability with higher sensitivity. The liquid crystal alignment agent of the present invention is suitably used for photoalignment. The liquid crystal alignment agent is highly sensitive to radiation, and a liquid crystal alignment film having excellent liquid crystal alignment ability can be formed by radiation of a low irradiation amount. The method for forming a liquid crystal alignment film of the present invention comprises: 201226445 (1) a step of applying the present step on a substrate, and a liquid crystal alignment agent of a month to form a coating film (2) on the coating film. The ultraviolet ray of light and the liquid crystal distribution can also perform photoalignment in the formation method of the present invention, and the ^ ^ 1 Μ 4 @ (four) line irradiation is highly high, and can be reduced, and the liquid crystal alignment film is also produced to produce the present invention. It is also preferably included. A right-right alignment film formed of the liquid crystal alignment agent. The liquid crystal J of the present invention is formed by the liquid crystal alignment agent, so that the sensitivity to radiation is high, and the amount of .4 A soil is $, n in the forming step, by the amount of the handle Radiation, can impart liquid crystal, alignment ability, so the production efficiency is good, and the manufacturing cost can also be reduced." Shuangfengliang The liquid crystal alignment element of the present invention has the liquid crystal alignment film 曰 alignment film by the liquid crystal alignment agent of the present invention "日日J Since it is formed, it is possible to impart liquid crystal alignment ability by a small amount of radiation irradiation. Therefore, the liquid crystal display element having the liquid crystal alignment film can be made cheaper than the current ones: In addition, the liquid crystal display element of the present invention can also charge various properties.冤 冤 冤 冤 另外 另外 「 「 「 「 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 。 In addition, the term "radiation" includes the concept of "light" in addition to the electromagnetic wires and bundles. [Effects of the Invention] The liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid 201226445 crystal alignment film having excellent liquid crystal alignment properties under low-radiation radiation irradiation, so that the production efficiency is high and Can reduce production costs. Further, the liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention is excellent in various properties such as electrical characteristics. [Embodiment] [Formation for Carrying Out the Invention] <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention comprises polybrene acid having a bicyclo [2.2.2] octene skeleton and/or polyimine. A liquid crystal alignment film containing polyphosphoric acid having a bicyclo [2.2.2] octene skeleton and/or polyimine, radiation having improved radiation sensitivity, and emission at a low irradiation amount can be formed. Further, the respective members are described separately in terms of the properties of the electric properties and the like without damaging the effects of the present invention, other than proline and/or polyimine. [Polyuric acid] Excellent liquid crystal alignment under the line The liquid crystal display element of the liquid crystal alignment film is excellent. The liquid crystal alignment agent of the present invention may contain other components in addition to the above-mentioned aggregation as an essential component. The polylysine used in the following invention has a bicyclo [2.2.2] octene bone sympathetic bone and a sulfur in the sulphate:, and has a bicyclo [2.2_2] hibisin amide in its structure, there is no In particular, the polylysine can be made, for example, by having a double net? ★ The ruthenium [2.2.2] octene skeleton of tetracarboxylic acid dioxime is reacted with a compound in an organic solvent to synthesize it. As a four-glow g dianhydride with a double ring "2 9 ο 1 jL · lx •• anaerobic skeleton, it can be = such as double ring [2.2.2] 辛..., 3, 5, 6·丄^ [2 2 and 2^ 2·2·2] Xin·7wu 2,3,5,6. Four-salt acid di^6-based-bicyclic • ·] Xin: dilute _2,3,5,6_tetradecanoic acid double ring 201226445 [2.2. 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 7-n-butyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Acid dianhydride, 7-second butyl-bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-indenyl-bicyclo[2.2.2] octane- 7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-7-methyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Acid dianhydride, 1-mercapto-7-ethyl-bicyclo[2_2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-indolyl-7-n-propyl -bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-7-n-butyl-bipolar [2_2.2] octa-7-thin - 2,3,5,6-tetradecanoic acid two-needle, 1-methyl-7-tert-butyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid A dianhydride or the like. Among them, a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-bicyclo[2.2.2]oct-7- is preferred. Alkene-2,3,5,6-tetracarboxylic dianhydride, 7-methyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetra Acid dianhydride, 1-mercapto-7-fluorenyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Among them, more preferably bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 7-fluorenyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid The anhydride is particularly preferably a bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. The polyglycolic acid used in the present invention preferably has the above formula (1). By using the polyamic acid having a specific structure, by polarized ultraviolet light irradiation, liquid crystal molecules can be aligned in a certain direction with respect to a polarization direction, and can be uniformly and stably aligned. In the above formula (1), the divalent organic group represented by R1 is a group derived from a diamine. Specific examples of the diamine compound are as long as it is in the synthesis of a usual polyamine or polyimine. The primary diamine to be used is not particularly limited, and examples thereof include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. -10- 201226445 As an aliphatic diamine For example, m-xylylenediamine, 13-propylenediamine 'tetradecyldiamine, and five Yue diamine, > methylene diamine. 'As an alicyclic diamine, for example, hydrazine, 4-diamine cyclohexane, 4,4'-methylene bis(cyclohexylamine), j 3 bis '-methane (methylamine) cyclohexane Wait. Examples of the diamine organooxosiloxane include hydrazine, 3-bis(3-aminopropyl)-tetramethyldioxane and the like. Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-diphenylamine, 4,4,-diaminodiphenylmethane, 4,4, and diaminodiphenyl sulfide. 1,5-Diamine naphthalene, 2,2,-dimercapto-4,4,-diaminobiphenyl, 4,4'-diamino 2,2,-bis(trifluoromethyl) Stupid, 2,7-diamino, 4,4'-monoaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9_ Diaminophenyl) 1,2,2-bis[4-(4-aminophenoxy)phenyl]hexaethoxypropane, 2,2-bis(4.aminophenyl)hexafluoropropane, 4,4,_(p-phenylenediisopropyl)bis(aniline), 4,4'-(m-phenylenediisopropyl)bis(aniline), ι,4-bis(4-amine-based oxy Benzo, 4,4,-bis(4-aminophenoxy)biphenyl, 2,6-monoaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine '3, 6-Diamino-based, 3,6-diaminocarbazole, N-mercapto-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N _stupyl-3,6-diaminocarbazole, n,n,_bis(4-aminophenyl)-benzidine, n,n,_bis(4-aminophenyl)_N,N, _Dimercaptobenzidine, 1,4· (4-Amino-phenyl)-piperidine, 3,5-diaminobenzoic acid, dodecyloxy 2,4-diaminobenzene, tetradecyloxy-2,4-diamine Stupid, fifteen alkoxy-2,4-diamino stupid, cetyloxy-2,4-diamino stupid, octadecyloxy-2,4-diaminobenzene, twelve Alkoxy-2*5-diamino group•11- 201226445 Benzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecane Oxy-2,5-diamino stupid, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy·3, 5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl Ester, cholesteryl 3,5-diaminobenzoic acid, lanyl alkyl 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzyl methoxy) cholesteryl Alkane, 3,6-bis(4-aminophenoxy)cholane, 4-(4'-trifluorodecylphenyl)cyclohexyl-3,5-diaminobenzoic acid , 4-(4'-trifluoromethylphenyl)cyclohexyl-3,5-diaminobenzoic acid vinegar, 1,1-bis(4-((aminophenyl)methyl)phenyl )_4_ Cyclohexane, hydrazine, bis(4-((aminophenyl)indenyl)phenyl)-4-heptylcyclohexane, M.. bis(4_((aminophenyl)indenyl)benzene -4-heptylcyclohexane, bismuth (4-((aminophenyl) decyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamine base-N,N-diallylaniline, 4-aminobenzylamine, %aminobenzylamine, 201226445
X1 — R3 — X2 1-(2,4-二胺基笨基)哌啶_4_羧酸、4_(味啉_4_基)苯—丨,、 二胺、1,3-雙(Ν-(4·胺基苯基)哌啶基)丙烷、α胺基 胺基苯基伸烷基、下式(A-丨)所示的化合物等。 H2N^=X1 — R3 — X2 1-(2,4-diaminophenyl)piperidine-4-carboxylic acid, 4-(sodium benzo-4-yl)benzene-anthracene, diamine, 1,3-bis(Ν -(4.Aminophenyl)piperidinyl)propane, an α-aminoaminophenylalkylene group, a compound represented by the following formula (A-indole), and the like. H2N^=
CcH2c+i (A -1 ) (在式(A_l)中,X1及χ2各自為單鍵、*〇、*_c〇〇_ 或c〇 ”中’具冑「*」的連接鍵在χ1中與二胺基 苯基結合/在χ2中與R3結合。R3為亞甲基、亞乙基或亞 丙基。a是0或1。匕為〇〜2的馨龢 . . 約 们堂数。c為1〜20的整數。其中 ,a和b不同時為〇。、 -12- 201226445 在上式(A-l)中’作為_χ1_κ3_χ2_表示的2價基,較佳 為亞甲基、碳原子數為2或3的伸烷基、*-〇-、*-COO-或 *_0-CH2CH2-0-。其中,具有「*」的連接鍵與二胺基苯 基結合。 在上式(A-1)中,作為-CcH2c+1表示的基,可以列舉 曱基、乙基、正丙基、正丁基、正戊基、正己基、正庚 基、正辛基、正壬基、土癸基、正十二烷基、正十三烷 基、正十四烧基、正十五烧基、正十六院基 '正十七烧 基、正十八烧基、正十九烧基、正一十烧基專。 此外,二胺基苯暴中的2個胺基相對於其他基為2,4 ·* 位或3,5-位。CcH2c+i (A -1 ) (In the formula (A_l), X1 and χ2 are each a single bond, *〇, *_c〇〇_ or c〇" in the connection key with 胄"*" in χ1 The diaminophenyl group binds/bonds to R3 in χ 2. R3 is a methylene group, an ethylene group or a propylene group. a is 0 or 1. 匕 is a bismuth of 〇~2. An integer of 1 to 20, wherein a and b are not simultaneously 〇., -12- 201226445 In the above formula (Al), 'divalent group represented by _χ1_κ3_χ2_, preferably methylene group, carbon number It is a 2 or 3 alkylene group, *-〇-, *-COO- or *_0-CH2CH2-0-, wherein a bond having a "*" bond is bonded to a diaminophenyl group. In 1), examples of the group represented by -CcH2c+1 include a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, a n-decyl group, and a ruthenium. Base, n-dodecyl, n-tridecyl, n-tetradecyl, n-five-burning, n-five-family 'n-seventeen-burning base, n-octadecene base, positive nineteen-burning base, In addition, the two amine groups in the diamino benzene storm are 2,4 ·* or 3,5-position relative to the other groups.
作為上式(A-1)表济的化合物’可以列舉下式(A-l」n 、(A-1-2)、(A-1-3)表斧的化合物等。 H〇NExamples of the compound of the above formula (A-1) include a compound of the following formula (A-1, n, (A-1-2), (A-1-3), and the like.
C5H” C5^ii (A-1-2)C5H” C5^ii (A-1-2)
-13- 201226445 作為上述以外的二胺,可以使用日本特開 20 10-97 1 88號公報記載的二胺。此外,在使用上式(A-1) 表示的二胺、具有含長鏈丙烯酸側鏈或膽留醇骨架的側 鏈的二胺的情況下,還可以作為適合VA(垂直排列 (Vertical Alignment))型液晶顯示元件的液晶配向劑。在 這些二胺中,較佳為芳香族二胺。 [聚醯胺酸之合成] 本發明中所使用的聚醯胺酸可以藉由例如使具有雙 環[2.2.2]辛烯骨架的四羧酸二酐與上述二胺化合物在有 機溶劑中反應獲得。 來自具有雙環[2.2.2]辛烯骨架的四羧 的醯胺酸結構單亓& I + y , i , 、δ有比例,在本發明中所使用的-13-201226445 As the diamine other than the above, a diamine described in JP-A-10-10 1978 can be used. Further, in the case of using a diamine represented by the above formula (A-1), a diamine having a side chain containing a long-chain acrylic side chain or a cholesteric skeleton, it is also suitable as a VA (Vertical Alignment). A liquid crystal alignment agent of a liquid crystal display element. Among these diamines, aromatic diamines are preferred. [Synthesis of Polylysine] The polylysine used in the present invention can be obtained, for example, by reacting a tetracarboxylic dianhydride having a bicyclo [2.2.2] octene skeleton with the above diamine compound in an organic solvent. . a proline structure derived from a tetracarboxylic [2.2.2] octene skeleton having a guanidine & I + y , i , δ ratio, as used in the present invention
十於王。PV合物的全部結構單元,較佳為 〇.1〜1〇〇莫耳%,更佳為s〜μ曾甘W 耳%。 旯佳為5〜95莫耳%,特佳為50〜90莫 在本發明中所使用的聚醯胺酸中, 環阳]辛稀骨架的…二針與其他四緩有雙 。例如’作為其他四緩酸二針,可以列舉脂二:軒併用 二酐、脂環式四羧酸-舡^壬祕 伽肪麵四綾酸 作為〜 軒 '方香族四緩酸二軒等。 ★乍為匕們的具體例,分別可以列舉丁俨 等之脂肪族四羧酸二酐; 凡羧酸二酐 1,2,3,4-環丁烷四羧酸二酐、2 酸二針…—氮_5… 基)_萘并[l,2-c]呋喃-丨3 _ 氣-3-呋喃 基-5-(四氫.25 _氣3, — ,,Μ,5,%-六氫I甲 飞2,5-_氧_3·吱喃基)萘并π,2外夫。南]丄二 -14- 201226445 酮、3-側氧雙環[3.2.1]辛烷-2,4-二酮-6-螺-3’-(四氫呋喃 -2’,5’-二酮)、5-(2,5-二氧四氫-3-呋喃基)-3 -曱基-3-環己 烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基甲基降莰烯 -2:3,5:6-二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2,4,6,8- 二酐、4,9-二氧三環[5.3.1.02’6]-!--碳-3,5,8,10-四酮等脂 環式四羧酸二酐; 苯均四酸二酐等的芳香族四羧酸二酐,此外,還可 以列舉曰本特開20 10-97 188號中記載的四羧酸二酐。 這些其他的四羧酸二酐可以單獨使用1種,也可以將 2種以上組合使用。 作為在聚醯胺酸合成中所使用的有機溶劑,可以列 舉非質子性極性溶劑、苯盼及其衍生物、醇、酮、醋、 謎、_化烴、烴等。 作為它們的具體例,可以分別列舉: N-曱基-2-吡咯啶酮、N,N-二甲基乙醯胺、Ν,Ν-二甲 基曱醯胺、二甲亞砜、7-丁内酯、四甲基脲、六甲基膦 三醯胺等之非質子性極性溶劑; 間甲酚、二甲苯酚、鹵化苯酚等之苯酚衍生物; 甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、 1,4-丁二醇、三乙二醇、乙二醇單曱醚等之醇; 丙酮、甲乙酮、甲基異丁基酮、環己酮等之酮; 乳酸乙酯、乳酸丁酯、乙酸曱酯、乙酸乙酯、乙酸 丁酯、曱基曱氧基丙酸酯、乙基環氧基丙酸酯、草酸二 乙酯、丙二酸二乙酯等之酯; -15- 201226445 、乙二 醇乙醚 乙二醇 酯、二 、氣苯 己 酯、異 在 性溶劑 或從上 酮、酉旨 以上之 比例相 為50質 以下。 乙醚、乙二醇甲喊、乙二醇乙蜮、乙二醇正丙醚 醇異丙喊、乙二醇正丁㈣、乙二醇二甲醚、乙二 抑^酉曰—乙一醇二甲越、二乙二醇二己謎、二 早曱醚、二乙二醇單 吁平、二乙二醇單甲醚乙酸 乙二醇單乙醚乙酸酿、四氫。夫喃等之謎; 氣甲烷、1,2-二氯乙烷、M•二氯丁烷、三氣乙烷 、鄰二氯苯等之_化烴; 、元庚炫•辛统、苯、曱笨、二甲苯、丙酸異戊 丁酸異戊酯、二異戊基醚等之烴。 k二有機命劑中,較佳為使用選自由非質子性極 、苯酚及其衍生物所構成的群組⑴中之"重以上; 述群組⑴的有機溶劑中選出的1種以上,與由醇、 醚、齒化烴和烴所構成的群組中選出的】種 混合物。在後者的情況下,(ii)的有機溶劑的使用 對於⑴的有機溶劑和(ii)的有機溶劑的總和,較佳 量%以下,更佳為4 0質量。/。以下,特佳為3 〇質量% 有機溶劑的使用量是四羧酸二酐和二胺的總量相對 於反應溶液的總量,較佳為〇 . 1〜5 〇質量%。 在上述溶劑中溶解聚酿胺酸得到的反應溶液可以直 接用於液晶配向劑的製備,亦可在分離反應溶液中包含 的聚醯胺酸後,用於液晶配向劑的製備❶還可以將分離 出的聚醯胺酸精製後,用於液晶配向劑的製備。在將聚 醯胺酸脫水閉環,形成聚醯亞胺的情況下,可以將上述 反應溶液直接用於脫水閉環反應,也可以在分離出反應 -16 - 201226445 溶液中包含的聚醯胺酸後,用於脫水閉環反應;或可以 將分離出的聚醯胺酸精製後,用於脫水閉環反應。又, 聚酿胺酸的分離和精製可以根據公知的方法進行。 用於聚醯胺酸合成反應的四羧酸二酐與二胺的使用 比例為,相對於1當量二胺的胺基,四羧酸二酐的酸軒基 較佳為0.2〜2當量,更佳為0.3〜1.2當量。 合成反應的溫度較佳為-20°C〜15CTC,更佳為〇〜 1 00°C。合成反應的時間較佳為〇丨〜24小時,更佳為〇 5 〜12小時。 在上述聚醯胺酸的合成中,除了上述四羧酸二針和 二胺’還可以使用適當的分子量調節劑合成末端修飾型 的聚合物。藉由形成該末端修飾型的聚合物,可以在不 損害本發明效果下,進一步改善液晶配向劑的塗布性( 印刷性)。 作為上述分子量調節劑’可以列舉單酐、單胺化合 物、單異氰酸酯化合物等。 作為單酐,可以列舉順丁烯二酸酐、鄰苯二曱酸肝 、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。 作為單胺化合物’可以列舉苯胺、環己胺、正丁胺 、正戊胺、正己胺、正庚胺、正辛胺等。 作為單異氰酸酯化合物’可以列舉苯異氰酸酯、萘 異氰酸酯等。 分子量調節劑的使用比例相對於總和i 〇 〇質量份而 使用的四羧酸二酐和二胺,較佳為20質量份以下,更佳 為1 0質量份以下。 -17- 201226445 [聚醯亞胺] 本心明中所使用的聚醯亞胺具有雙環[2 2 2]辛烯骨 架。在其結構中,只要是具有雙環[2·2 2]辛烯骨架的物 質,就沒有特別的限定,但例如可以藉由將如上合成的 聚醯胺酸脫水閉環且醯亞胺化而獲得。 本發明中所使用的聚醯亞胺較佳為具有以上式(2) 所示的結構單元。液晶配向逾丨技山Α丄 欣日日Π ^稭由含有該特定結構的聚 醢亞胺’藉由偏光紫外線的照射,從而液晶分子相對於 偏光方肖’能在-定的方向上且均句穩定地配向。 本發明中的聚醯亞胺可以是將作為其前驅物的聚酿 胺酸所:有的醯胺酸結構全部脫水閉環的完全醯亞胺化 口物還可以是僅將醯胺酸結構的—部分脫水閉環,醯 胺酸結構與醯亞胺環結構並存的部分醯亞胺化合物。本 毛月中的聚醯亞胺較佳為其醯亞胺化率為3 〇 %以上,更 佳為5 0 9 9 /〇’進-步更佳為6 5〜9 9 %。該醞亞胺化率是 將醯亞胺環結構的數量占聚醢亞胺的醯胺酸結構的數量 與醯亞胺環結構數量總和的比例用百分比表示的數值。 其中’ II亞胺環的—部分可以是異酿亞胺環。 [聚醯亞胺的合成] 本發明中所使用的聚醯亞胺如上所述,可以藉由將 如上述合成的聚醯胺酸脫水閉環且醯亞胺化而得到。 、永醯胺馱的脫水閉環較佳為藉由將聚醯胺酸加熱的 方法或在有機溶劑中溶解聚醯胺酸,在該溶液中添加 脫水Μ和脫水閉環催化劑,根據需要進行加熱的方法進 行。其中,較佳為藉由後述方法進行。 -18 - 201226445 在上述聚醢胺酸的溶液中添心盼u杰, 艰加脫水劑和脫水閉環催 化劑的方法中’作為脫水劑,可以柹 J M便用例如乙酸酐、丙 酸酐、三氟乙酸酐等酸酐。脫水劍的往田曰Λ •Ν 4的使用量相對於丨莫耳 聚醯胺酸的醯胺酸結構,較佳為〇 〇丨〜 , 旲年。作為脫 水閉環催化劑,可以使用例如吡咭、=田* 又 二T暴D比。定、二甲 基吡啶、三乙胺等三級胺。脫水閉環催化劑的使用量相 對於1莫耳使用的脫水劑,較佳為〇.〇1〜1〇莫耳。作為脫 水閉環反應中所使用的有機溶劑’可以列舉作為在聚酿 胺酸的合成中所使用的溶劑,所例示的有機溶劑。脫水 閉環反應的反應溫度較佳為0〜1 8〇,Ten Yu Wang. The entire structural unit of the PV compound is preferably 〇.1 to 1 〇〇 mol%, more preferably s~μ.旯佳 is 5 to 95% by mole, and particularly preferably 50 to 90%. In the polylysine used in the present invention, the ring-shaped symplectic skeleton...the two needles are doubled with the other four. For example, 'as the other four acid-low-needle needles, it can be exemplified by the fat two: Xuan and dianhydride, alicyclic tetracarboxylic acid-舡^壬 伽 肪 面 绫 绫 〜 〜 〜 方 方 方 方 方 fang fang fang fang . ★ As a specific example of 匕, we can list aliphatic tetracarboxylic dianhydrides such as butyl hydrazine; carboxylic acid dianhydride 1,2,3,4-cyclobutane tetracarboxylic dianhydride, two acid two needles ...—nitrogen_5...yl)_naphtho[l,2-c]furan-丨3 _ gas-3-furanyl-5-(tetrahydro.25 _ gas 3, — ,,Μ,5,%- Hexahydro-I-methyl 2,5--oxygen_3·pyranyl)naphthoquinone π, 2 exogenous. South]丄二-14- 201226445 Ketone, 3-oxobicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxyl Base decene-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2,4,6,8-dianhydride, 4,9- Dioxatricyclo[5.3.1.02'6]-!--carbon-3,5,8,10-tetraketone and other alicyclic tetracarboxylic dianhydride; aromatic tetracarboxylic acid such as pyromellitic dianhydride Further, the dianhydride may be a tetracarboxylic dianhydride described in JP-A No. 20 10-97 188. These other tetracarboxylic dianhydrides may be used alone or in combination of two or more. Examples of the organic solvent used in the synthesis of polylysine include an aprotic polar solvent, benzophenone and a derivative thereof, an alcohol, a ketone, a vinegar, a mystery, a hydrocarbon, a hydrocarbon, and the like. As specific examples thereof, N-mercapto-2-pyrrolidone, N,N-dimethylacetamide, hydrazine, hydrazine-dimethyl decylamine, dimethyl sulfoxide, 7- Aprotic polar solvent such as butyrolactone, tetramethyl urea, hexamethylphosphine tridecylamine; phenol derivative such as m-cresol, xylenol or halogenated phenol; methanol, ethanol, isopropanol, cyclohexane An alcohol such as an alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol or ethylene glycol monoterpene ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; Ethyl ester, butyl lactate, decyl acetate, ethyl acetate, butyl acetate, decyloxy propionate, ethyl epoxy propionate, diethyl oxalate, diethyl malonate, etc. Ester; -15- 201226445, ethylene glycol diethyl ether glycol ester, di-p-phenylhexyl ester, heterogeneous solvent or from the upper ketone, the ratio of the above phase is 50 or less. Ether, ethylene glycol, shouting, ethylene glycol oxime, ethylene glycol n-propyl ether, isopropyl sulfonate, ethylene glycol n-butyl (tetra), ethylene glycol dimethyl ether, ethylene bismuth Diethylene glycol dihexyl, diammonium ether, diethylene glycol monotopine, diethylene glycol monomethyl ether acetate ethylene glycol monoethyl ether acetate, tetrahydrogen. The mystery of Fu et al; gasification of methane, 1,2-dichloroethane, M•dichlorobutane, tri-ethane ethane, o-dichlorobenzene, etc.; Yuan Gengxuan • Xin Tong, benzene, A hydrocarbon such as stupid, xylene, isoamyl propionate, diisoamyl ether or the like. In the k-diorganic agent, it is preferred to use one or more selected from the group consisting of an aprotic electrode, a phenol and a derivative thereof, and an organic solvent selected from the group (1). a mixture selected from the group consisting of alcohols, ethers, dentate hydrocarbons, and hydrocarbons. In the latter case, the use of the organic solvent of (ii) is preferably less than or equal to the total of the organic solvent of (1) and the organic solvent of (ii), more preferably 40% by mass. /. In the following, it is particularly preferable that the amount of the organic solvent used is 3, and the total amount of the tetracarboxylic dianhydride and the diamine is preferably 〇 1 to 5 % by mass based on the total amount of the reaction solution. The reaction solution obtained by dissolving polylactoic acid in the above solvent can be directly used for the preparation of the liquid crystal alignment agent, and can also be used for the preparation of the liquid crystal alignment agent after separating the polylysine contained in the reaction solution. The purified polyamic acid is used for the preparation of a liquid crystal alignment agent. In the case of dehydration of poly-proline to form a polyimine, the above reaction solution may be directly used for the dehydration ring closure reaction, or after the polyamine acid contained in the reaction-16 - 201226445 solution is separated. It is used for dehydration ring closure reaction; or the separated polyamic acid can be refined and used for dehydration ring closure reaction. Further, the separation and purification of the poly-aracine can be carried out according to a known method. The ratio of the tetracarboxylic dianhydride to the diamine used in the polyamine acid synthesis reaction is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group of the diamine. Good is 0.3 to 1.2 equivalents. The temperature of the synthesis reaction is preferably from -20 ° C to 15 CTC, more preferably from 〇 to 1 00 ° C. The synthesis reaction time is preferably from 〇丨 to 24 hours, more preferably from 5 to 12 hours. In the synthesis of the above polyamic acid, a terminal modified type polymer can be synthesized by using a suitable molecular weight modifier in addition to the above tetracarboxylic acid di-needle and diamine. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. The above-mentioned molecular weight modifier "monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned. Examples of the monoanhydride include maleic anhydride, liver of phthalic acid, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. The monoamine compound ' can be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine or n-octylamine. Examples of the monoisocyanate compound' include phenyl isocyanate and naphthalene isocyanate. The tetracarboxylic dianhydride and the diamine used in the use ratio of the molecular weight modifier are preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on the total amount of i 〇 〇 by mass. -17- 201226445 [Polyimide] The polyimine used in the present invention has a bicyclo[2 2 2]octene skeleton. In the structure, it is not particularly limited as long as it is a substance having a bicyclo[2·2 2]octene skeleton. However, it can be obtained, for example, by dehydration ring closure of the polylysine synthesized as above and ruthenium ruthenium. The polyimine used in the present invention preferably has a structural unit represented by the above formula (2). The liquid crystal molecules are irradiated by polarized ultraviolet rays by the polyimine containing the specific structure, so that the liquid crystal molecules can be in a certain direction with respect to the polarized light. The sentence is steadily aligned. The polyimine in the present invention may be a poly-aracine which is used as a precursor thereof: a lysine structure in which all of the proline structures are dehydrated and closed, or a structure of only a proline- Partial dehydration ring closure, partial quinone imine compound with a proline structure and a quinone ring structure. The polyimine in the present month preferably has a sulfhydrylation ratio of 3 〇 % or more, more preferably 5 0 9 9 /〇', and more preferably 6 5 to 9 9 %. The ruthenium imidization ratio is a numerical value in which the ratio of the number of the quinone imine ring structure to the sum of the number of the ruthenium structure of the polyimine and the sum of the quinone ring structures is expressed as a percentage. The portion of the 'II imine ring' may be a racered imine ring. [Synthesis of Polyimine] The polyimine used in the present invention can be obtained by dehydrating ring-opening and hydrazine imidation of the polylysine synthesized as described above. The dehydration ring closure of the acesulfame is preferably a method of heating the poly phthalic acid or dissolving the polyaminic acid in an organic solvent, adding dehydration hydrazine and a dehydration ring closure catalyst to the solution, and heating as needed. get on. Among them, it is preferably carried out by a method described later. -18 - 201226445 In the above solution of polylysine, I am looking forward to the process of adding dehydrating agent and dehydration ring-closing catalyst. As a dehydrating agent, I can use, for example, acetic anhydride, propionic anhydride, trifluoroethane. An acid anhydride such as an acid anhydride. Dehydrated sword to the field 曰Λ 的 4 The amount of Ν 4 used relative to the 醯 耳 耳 耳 醯 醯 醯 , , , , , , , , , , , , , , , , , , , , , , As the dehydration ring-closing catalyst, for example, pyridinium, =Tian*, and T-storm D ratio can be used. A tertiary amine such as dimethylpyridine or triethylamine. The dehydration ring-closing catalyst is preferably used in an amount of from 1 to 1 mol per mol of the dehydrating agent used per 1 mol. The organic solvent used in the dehydration ring-closure reaction is exemplified as the solvent used in the synthesis of the polyamic acid, and the organic solvent exemplified. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 18 Torr.
1 玄 1 (J 1 5 Q C。反應時間較佳為以〜^小時,更佳為2 〇〜3〇小時 〇 所得含有聚醯亞胺的反應溶劑可以將其直接用於液 晶T向劑的製備;還可以從反應溶液除去脫水劑和脫水 閉裱催化劑後,用於液晶配向劑的製備;還可以在分離 聚醯亞胺後,用於液晶配向劑的製備;或者可以將:離 出的聚醯亞胺精製後’用於液晶配向劑的製備。這些精 製操作可以藉由公知的方法進行。 片如上獲仔的聚醯胺酸或聚醯亞胺,在將其形成濃度 10質罝%的溶液時,較佳為具有2〇〜8〇〇mPa s的溶液黏 度更佳為具有30〜500 mPa.s的溶液黏度。 上述聚合物的溶液黏度(mPa . s)是對使用該聚合物 的良溶劑(例如7 · 丁内酯、N-甲基-2-吼咯啶酮等)製備的 濃度1 0貝里%的聚合物溶液,使用Ε型旋轉黏 ,’ °C下測定的值。 在25 -19- 201226445 [其他成分] 本發明的液晶配向劑含有上述聚醯胺酸及/或聚醯 亞胺作為必須成分,根據需要,還可以含有其他成分。 作為該其他成分,可以列舉例如其他聚合物、在分子内 具有至少一個環氧基的化合物(以下,亦稱為「環氧化合 物j )、官能性矽烷化合物。 (其他聚合物) 上述其他聚合物可以用於改善溶液特性及電特性。 該其他聚合物為上述聚醯胺酸或上述聚醯亞胺以外的聚 合物’可以列舉例如使具有雙環[2.2.2]辛烯骨架的四叛 酸二酐以外的四羧酸二酐與二胺反應得到的聚醯胺酸( 以下’亦稱為「其他聚醯胺酸」)、將上述聚醯胺酸脫水 閉環得到的聚醯亞胺(以下,亦稱為「其他聚醯亞胺」) 、聚醯胺酸酯、聚酯、聚醯胺、聚矽氧烷、纖維素衍生 物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基順丁歸 ~~醯亞胺)衍生物、聚(甲基)丙烯酸酯等。其中’較佳為 其他聚醯胺酸或其他聚醯亞胺,更佳為其他聚醯胺酸。 用於合成上述其他聚酿胺酸或其他聚醯亞胺的四緩 酸二酐’可以列舉作為用於合成本發明中所使用的聚醯 胺酸的四羧酸二酐’與以上描述相同的物質’但較佳為 使用選自由1,2,3,4-環丁烷四鲮酸二酐、苯均四酸二軒、 2,3,5-二叛基ϊ衣戊基缓酸一 if和i,3 3a 4,5,91>-六乳-5-(四 氫-2,5-二氧-3-呋喃基)-萘并[nq呋喃4,3-二酮構成的 群中之至少1種。 •20- 201226445 就用於上扯# &地其他聚醢胺酸或其他聚醯亞胺的二胺而 言,可以列舉你, 卞為合成本發明中所使用的聚醯胺酸時之 使用的二胺,你 _ 糸在以上述例示的物中選出的至少1種。作 為用於合成JL仙 、 /、他聚醢胺酸或其他聚醯亞胺的二胺,較佳 為使用選自由4 4,一 ^^甘 ’4 - 一月女基一本基甲烧、2,2’-二甲基-4 4,- '一胺基聯菜、Hit s留醇氧基-2,4 -二胺基苯、3,5 -二胺基苯 曱酸和1,4 -雔η 又('胺基苯基)-略听所構成的群中之至少1 種。 作為 ΧΛτ . 、 眾合物的使用比例,相對於聚合物的總和( 所謂上述聚酼^ & 胺SiL及/或其他聚合物的總和。以下相同。 ),較佳為50哲θ ^買董%以下,更佳為(^〜扣質量。/。,進一步 更佳為0·1〜30質量%。 (環氧化合物) 4乍為 . 述環氧化合物,可以列舉例如乙二醇二縮水 甘油峻、聚7 ^ 、_ A 一醇二縮水甘油醚、丙二醇二縮水甘油醚 ,~~ 一醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新 戊-醇墙 > 一 ’水甘油喊、1,6 -己二醇二縮水甘油醚、甘油 二縮水甘油_ . 、、二經甲基丙炫三縮水甘油醚、2:, 2 -二溴 新戊二醇-始u . ―細水甘油醚、N,N,N’N,-四縮水甘油基-間二 曱苯二胺、〗2 μ χτ ,3_雙(Ν,Ν-二縮水甘油基胺基曱基)環己烷、 ν,ν,ν,ΝΛ 一 ’ -四縮水甘油基-4,4,-二胺基二苯基甲烷、Ν,Ν- 一縮水甘油1 & @卷-卞基胺、Ν,Ν-二縮水甘油基-胺基曱基環 己烧、Ν "Μ _ &水甘油基-環己基胺等作為較佳的物。 14二環氧化合物的混和比例相對於總和1 〇〇質量份的 t合物,動i杜& / Λ 0曰 平又佳為40質量份以下,更佳為0.1〜30質量份。 -21 - 201226445 (功能性矽烷化合物) 作為上述功能性石夕烧化合物,可以列舉例如3 -胺基 丙基二甲氧基石夕烧、3 -胺基丙基三乙氧基梦炫、2 -胺基 丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺 基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)_3· 胺基丙基甲基二甲氧基矽烷、3_脲基丙基三甲氧基矽烷 、3·脲基丙基三乙氧基矽烷、N_乙氧基羰基-3_胺基丙基 二甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷 、N-三乙氧基甲矽烷基丙基三乙烯三胺、N_三甲氧基甲 $夕燒基丙基三乙烯三胺、1〇_三曱氧基曱矽烷基_i,4,7·三 氮雜石夕烧、10-三乙氧基甲矽烷基-M,7_三氮雜矽烷、9_ 〜甲氧基甲石夕烧基-3,6 -二氮雜壬基乙酸酯、9 -三曱氧基 甲砂烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基甲石夕院基 3’6 -二氮雜壬基乙酸酯、9 -三甲氧基甲石夕烧基_3,6 -二氮 雜壬酸曱i旨' 9-三乙氧基甲矽烷基_3,6_二氮雜壬酸甲❿ 、苄基-3-胺基丙基三甲氧基矽烷、N_苄基-3_胺基丙曰 二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、n f 基、3-胺基丙基三乙氧基矽烷、縮水甘油氧基甲基二笨 基石夕烷、縮水甘油氧基曱基三乙氧基矽烷' 2_縮水氣 氣基乙基三曱氧基矽烷、2 -縮水甘油氧基乙基: ’由 你燒、3-縮水甘油氧基丙基三曱氧基矽烷、3_输水 土 氣基丙基三乙氧基石夕烧等。 '电 這些功能性矽烷化合物的混和比例相對於 1 Q Λ 貝ΐ份的聚合物’較佳為2質量份以下,更佳為 質量份。 .、、〇.〇2〜0.2 -22- 201226445 <液晶配向劑之調製> 本發明的液晶配向劑較佳為將上述聚醯胺酸或聚醯 山工冰根據需要任意混合的其他成分溶解含於有機溶劑 ^ ί在本發明的液晶配向劑中所使用的有機溶劑, 醋、ϋ例如Ν甲基-2_°比略咬酮、厂丁内醋、ι丁内 甲基-^-古一甲基甲醯胺〜沐…二曱基乙醯胺〜仁羥基-4- 氧美&納酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲 乳卷丙酸甲酯、贫 乙醚、_ 乙軋基丙酸乙酯、乙二醇甲醚、乙二醇 丁其審=二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚( J |賽璐蘇)、 _ 1 ^ 二醇_ —酵二甲_、乙二醇乙醚乙酸酯、二乙 口子~~甲醚、_ _ 二醇單7 、,— 酵二乙醚、二乙二醇單甲醚、二乙 乙酸酯、——乙二醇单甲趟乙酸醋、二乙二醇單乙醚 、二晨士好異丁基酮、異戊基丙酸酯、異戊基異丁酸酯 穴々•基鍵、#祕,μ 單獨伟 厌&乙烯酯、碳酸丙烯酯等。這些可以 Π3 5 jL _ ± ^ 可以將2種以上混合使用。 本發明液曰 溶劑以外成八曰曰配向劑中的固體含量濃度(液晶配向劑 以考慮黏性刀的總質量占液晶配向劑總質量的比例)可 範圍内β 、揮發性等適當選擇’較佳在1〜10質量%的 1 。即,士 面塗布,幹 發明的液晶配向劑如後所述,在基板表 能形成液Γ佳為藉由加熱形成作為液晶配向膜的塗膜或 ’人日曰酉己> 0/〇的情況下 °膜的塗膜,但在固體含量濃度不足1質量 晶配向犋.°亥塗膜的膜厚過小,則無法獲得良好的液 情况下,塗—方面,在固體含量濃度超過1 0質量。/〇的 獏;此外,^ :瞑厚過大,則無法獲得良好的液晶配向 之晶配向劑的黏性增大,塗布特性惡化。 -23- 201226445 特佳的固體含量濃度的範圍根據在基板上塗布液晶 配向劑時使用的方法有所不同。例如,在藉由旋塗法的 情況下’固體含量濃度較佳在1 5〜4 5質量%的範圍内。 在藉由印刷法的情況下,特佳為固體含量濃度為3〜9質 量%的濃度’由此,溶液黏度在12〜5QmPa s的範圍内。 在藉由喷墨法的情況下,特佳為固體含量濃度在卜5質 量%的範圍内,由此,溶液逢 冷及黏度在3〜1 5 mpa . s的範圍内 〇 調製本發明液晶配向劑時 J Μ "于的皿度較佳為丨〇〜5 〇, 更佳為20〜30°C。 <液晶配向膜> 本發明的液晶配向膜葬由兮,广曰 、糟由6玄液日日配向劑形成。因此 ,在形成步驟中,藉由供θ ‘ ·“、、射1的放射線就能賦予優異 的液晶配向能力。此外,兩 …、而放射線照射中和日s射後的 加熱步驟,因此生產效率 ….射後的1 Xuan 1 (J 1 5 QC. The reaction time is preferably ~ ^ hour, more preferably 2 〇 ~ 3 〇 〇 〇 〇 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有It can also be used for the preparation of liquid crystal alignment agent after removing the dehydrating agent and the dehydrated ruthenium catalyst from the reaction solution; it can also be used for the preparation of the liquid crystal alignment agent after separating the polyimine, or can be: Preparation of liquid crystal alignment agent after refining of quinone imine. These refining operations can be carried out by a known method. The poly-proline or polyimine obtained as above is formed at a concentration of 10% by mass. In the case of a solution, it is preferred that the solution viscosity of 2 〇 8 8 mPa s is more preferably a solution viscosity of 30 to 500 mPa·s. The solution viscosity (mPa . s) of the above polymer is for the use of the polymer. A polymer solution having a concentration of 10 mil % prepared by a good solvent (for example, 7 · butyrolactone, N-methyl-2-pyrrolidone, etc.), using a Ε-type rotational viscosity, a value measured at ° C. 25 -19 - 201226445 [Other Ingredients] The liquid crystal alignment agent of the present invention contains the above polyfluorene The amine acid and/or the polyimide may be an essential component, and may contain other components as needed. Examples of the other component include other polymers and compounds having at least one epoxy group in the molecule (hereinafter also referred to as It is an "epoxy compound j" or a functional decane compound. (Other polymers) The above other polymers can be used to improve solution characteristics and electrical properties. The other polymer is other than the above polylysine or the above polyimine. The polymer 'is, for example, a polyglycine which is obtained by reacting a tetracarboxylic dianhydride other than tetrareoxalic dianhydride having a bicyclo [2.2.2] octene skeleton with a diamine (hereinafter referred to as "other polyfluorene" Amino acid"), a polyimine obtained by dehydration of the above polylysine (hereinafter also referred to as "other polyimine"), polyglycolate, polyester, polyamine, polyoxyl An alkane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenyl cis-butane) derivative, a poly(meth) acrylate, etc., wherein 'preferably Other polyaminic acid or other polyimine More preferably, it is another poly-proline. The tetra-hypo-dianhydride used for the synthesis of the above other poly-aramidic acid or other polyimine is exemplified as a tetracarboxylic acid for synthesizing the poly-proline used in the present invention. The acid dianhydride 'is the same as described above' but is preferably selected from the group consisting of 1,2,3,4-cyclobutane tetraphthalic acid dianhydride, pyromellitic acid dioxins, 2,3,5-two rebellion Base pentyl basal acid-if and i, 3 3a 4,5,91>-hexamil-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[nqfuran 4, At least one of the groups consisting of 3-diketones. • 20- 201226445 For the diamines of other poly-proline or other polyimine, it can be enumerated. The diamine used in the case of the poly-proline used in the present invention is at least one selected from the above-exemplified ones. As a diamine for synthesizing JL, /, poly-polyamine or other polyimine, it is preferred to use a base selected from 4 4, a ^ ^ ^ '4 - January female base, 2,2'-Dimethyl-4 4,- 'mono-Azate, Hit s-alcohol-2,4-diaminobenzene, 3,5-diaminobenzoic acid and 1,4 - 雔 η ('Aminophenyl) - Listen at least one of the groups formed. The ratio of use of ΧΛτ. and the complex is relative to the sum of the polymers (the sum of the above-mentioned poly sulfonium & amine SiL and/or other polymers. The same applies hereinafter.), preferably 50 哲θ ^Budong % or less, more preferably (^~ buckle mass. /., further more preferably 0. 1 to 30% by mass. (epoxy compound) 4 乍 is an epoxy compound, and examples thereof include ethylene glycol diglycidyl Jun, poly 7 ^, _ A-alcohol diglycidyl ether, propylene glycol diglycidyl ether, ~~ monool diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl alcohol wall > 1,6-hexanediol diglycidyl ether, glycerol diglycidyl _., dimethicone triglycidyl ether, 2:, 2-dibromo neopentyl glycol-starting u. Ether, N,N,N'N,-tetraglycidyl-m-diphenylene diamine, 〖2 μ χτ, 3_bis(Ν,Ν-diglycidylamino) hexane, ν , ν, ν, ΝΛ a 'tetraglycidyl-4,4,-diaminodiphenylmethane, hydrazine, hydrazine-glycidol 1 & @卷-卞-amine, hydrazine, hydrazine-bi-hydration Oil-amino-mercaptocyclohexene, Ν "Μ _ & glyceryl-cyclohexylamine, etc. as a preferred material. 14 Mixture ratio of the diepoxide compound relative to the sum of 1 〇〇 by mass of t The compound, the dying i & / Λ 0 曰 flat is preferably 40 parts by mass or less, more preferably 0.1 to 30 parts by mass. -21 - 201226445 (functional decane compound) as the above-mentioned functional stone smelting compound, can For example, 3-aminopropyldimethoxycarbazide, 3-aminopropyltriethoxymethane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane , N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)_3·aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3·ureidopropyltriethoxydecane, N_ethoxycarbonyl-3-aminopropyldimethoxydecane, N-ethoxycarbonyl-3-amine Propyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxymethyl decylpropyltriethylenetriamine, 1〇-trioxyloxydecane Base _i, 4, 7 · triazepine, 10-triethoxy Formyl-M,7-triazanonane, 9-methoxymethoxycarbazide-3,6-diazaindolyl acetate, 9-tridecyloxymethylalkyl-3, 6-diazaindolyl acetate, 9-triethoxymethylglycine 3'6-diazaindolyl acetate, 9-trimethoxymethylglycine _3,6-二 旨 旨 ' ' ' 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 3_Aminopropyl hydrazine diethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, nf group, 3-aminopropyl triethoxy decane, glycidoxymethyl dimethyl Stupid base, glycidyloxydecyl triethoxydecane' 2_ shrinking gas, ethyl tridecyloxydecane, 2-glycidoxyethyl: 'burned by you, 3-glycidoxy Propyl tridecyloxydecane, 3_water, urethane, triethoxy, and the like. 'Electricity The mixing ratio of these functional decane compounds is preferably 2 parts by mass or less, more preferably parts by mass, based on the polymer of the 1 Q fluorene compound. ., 〇.〇2~0.2 -22-201226445 <Preparation of Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention is preferably another component which is arbitrarily mixed as needed with the above polylysine or polyaluminum Dissolving organic solvent used in the liquid crystal alignment agent of the present invention, vinegar, hydrazine, for example, hydrazine methyl-2_° ratio acetophenone, butyl vinegar, ι butyl methyl-^-gu Monomethylmethamine ~ Mu... Dimercaptoacetamide ~ hydroxy hydroxy-4-oxo & naloxin, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl lactobionate ,ethyl ether, _ acetonitrile ethyl propionate, ethylene glycol methyl ether, ethylene glycol butyl phthalate = glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (J | Sai Su) , _ 1 ^ diol _ - yeast dimethyl _, ethylene glycol ethyl ether acetate, diethyl ether ~ ~ methyl ether, _ _ diol single 7 ,, - yeast diethyl ether, diethylene glycol monomethyl ether, Diacetate, ethylene glycol monomethyl hydrazine acetate, diethylene glycol monoethyl ether, two mornings, isobutyl ketone, isoamyl propionate, isoamyl isobutyrate Base key, #秘,μ separate Wei Rasp & vinyl ester, propylene carbonate and the like. These can be Π3 5 jL _ ± ^. Two or more types can be used in combination. The solid content concentration in the octagonal alignment agent other than the liquid hydrazine solvent of the present invention (the liquid crystal alignment agent takes into account the ratio of the total mass of the viscous knives to the total mass of the liquid crystal alignment agent) can be appropriately selected within the range of β, volatility, etc. Good at 1 to 10% by mass of 1%. In other words, the liquid crystal alignment agent of the invention is as described later, and it is preferable to form a liquid film on the substrate surface by heating to form a coating film as a liquid crystal alignment film or 'human 曰酉 曰酉 & 0 0 0 0 0 0 In the case of the film coating of the film, but the solid content concentration is less than 1 mass, the film thickness of the film is too small, the film thickness is too small to obtain a good liquid, in terms of coating, the solid content concentration exceeds 10%. . In addition, when the thickness of the crucible is too large, the viscosity of the crystal alignment agent which does not obtain a good liquid crystal alignment increases, and the coating property deteriorates. -23- 201226445 The range of particularly good solid content concentrations varies depending on the method used to coat the liquid crystal alignment agent on the substrate. For example, in the case of the spin coating method, the solid content concentration is preferably in the range of 15 to 45 mass%. In the case of the printing method, a concentration of solid content concentration of 3 to 9% by mass is particularly preferable. Thus, the solution viscosity is in the range of 12 to 5 QmPa s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 5% by mass, whereby the solution is cooled and the viscosity is in the range of 3 to 15 mPa·s to modulate the liquid crystal alignment of the present invention. When the agent is J Μ ", the degree of the dish is preferably 丨〇~5 〇, more preferably 20~30 °C. <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is formed of 兮, 曰, and 由 from 6 玄液日日. Therefore, in the forming step, the liquid crystal alignment ability can be imparted by the radiation of θ ' · ·, and the radiation 1. In addition, the heating step after the radiation irradiation and the solar ray irradiation is performed, and thus the production efficiency .... after shooting
民好且亦降低製造成本Q <液日日配向膜之形成方法> 本發明的液晶配向劑 劏了以適宜用作根據光配向法的 浪日日配向膜的材料。此外, 的Good and Reduced Manufacturing Cost Q <Formation Method of Liquid Day Alignment Film> The liquid crystal alignment agent of the present invention has a material suitable for use as a day alignment film according to the photoalignment method. In addition,
蜇或STN型液晶胞之液曰- t成在,、有TN 咕 夜日日顯不兀件、或具有IPS型、Fpq蜇 or STN type liquid crystal cell liquid 曰 - t is in, there is TN 咕 night and day, or IPS type, Fpq
变等之液晶胞的橫電場方彳M t a - FFS 浪晶配向膜。本發明的液a 是用的 戍日日配向劑尤其是在用於且 梨、FFS型液晶胞的液晶g _ 、/、有IPs 顯不兀件時,能啬士 up洚以 出本發明的效果,故為較佳。 、又發揮 本發明液晶配向犋之形成方法包括: -24- 201226445 (1) 在基板上塗布本發明的液晶配向劑且形成塗膜 之步驟(以下,亦稱為「步驟(1)'」),及 (2) 在上述塗膜上照射偏光的紫外線且賦予液晶配 向能力之步驟(以下,亦稱為「步驟(2)」)。以下,針對 各步驟進行詳細說明。 [步驟 其中,在將本發明的液晶配向劑適用於具有TN型或 STN型液晶胞的液晶顯示元件的情況下,將2張設置了圖 案化的透明導電膜的基板作為一對,在該各透明性導電 膜形成面上塗布本發明的液晶配向劑而形成塗膜。另一 方面, 液晶胞 金屬膜 的對向 板的一 在 法玻璃 二曱酸 板等。 構成的 為上述 。對於 成沒有 形成圖 圖案的 將本發明的液晶配向劑用於具有lps型、FFs型 的液晶顯示元件時,將具有在一面透明導電膜或 形成鋸齒狀圖案的電極之基板、與沒有設置電極 基板作為一對,在鋸齒狀電極的形成面與對向基 面分別塗布本發明的液晶配向劑而形成塗膜。土 所有的It ;兄下’作為上述基板,彳以使用例如浮 、鈉玻璃等玻璃、聚對苯二曱酸乙二酯、聚對苯 丁二酯、聚醚砜、聚碳酸酯等塑膠構成的透明基 作為上述透明導電膜,可以使用例如In203-Sn02 IT〇膜、由Sn〇2構成的NESA(註冊商標)膜等。作 =;,可以使用例如由鉻等之金屬所構成的膜 :導電膜和金屬膜的圖案,可以採用例如在形 透明導電膜後由光姓刻法、賤射法等 =方法、在形成透明導電膜時,使用具有期望 九罩的方法等。 -25- 201226445 在基板上塗布液晶配向劑時,4了進高導 膜或電極與塗膜的黏合性, ^ , At liL j Λ在基板和電極上預先塗 功3b性矽烷化合物、鈦酸酯等。 在基板上塗布液晶配向劑可以較佳為藉由膠板印刷 :_、旋塗法、輥塗法、噴墨印刷法等適當的塗布方法進 了 ’然後’對塗布面進行預加熱(預供烤)、然後燒製(後 火、烤)而形成塗膜1烘烤的條件例如在4〇〜i2(rc下進 行0.1〜5分鐘;後烘烤的條件較佳在i2〇〜3〇(rc,更佳 為在150 250 CT,較佳為進行5〜扇分鐘更佳為進 行ίο〜1〇〇分鐘。後烘烤後的塗膜的膜厚較佳為〇 〇〇ι〜 ’ 更佳為 0.005 〜〇 5μηι。 [步驟(2)] 藉由在由此形成的塗膜中照射偏光的放射線,從而 賦予液晶配向能力。其中’作為放射線,可以使用例如 包含150〜800nm波長光線的紫外線和可見光線,較佳為 包含200nm〜400nm波長光線的紫外線。 作為使用的光源,可以使用例如低壓水銀燈、高壓 水銀燈、重氫水銀燈、金屬南化物燈、氬氣共振燈、氙 燈、激生分子雷射等。上述較佳為波長區域的紫外線可 以藉由將上述光源與例如過濾器、繞射晶格等併用的方 法獲得。 如果使用本發明的液晶配向劑,則通常需要照射 10000J/m以上的紫外線,即使為8〇〇〇J/m2,也能賦予良 好的液晶配向能力,可以提高液晶顯示元件的生產性並 減少製造成本。 ' 26 - 201226445 <液晶顯示元件> 本發明的液晶顯示元件具有使用該液晶配向劑形成 的液晶配向膜’因此在比目前更少的照射量下,也能賦 予液晶配向能力。因此,具有該液晶配向膜的液晶顯示 元件能夠比目前更廉價地製造。本發明的液晶顯示元件 例如可以如下製造。 如上準備形成液晶配向膜的一對基板,製備在該一 對基板之間夾持液晶的結構的液晶胞。為了製造液晶胞 ,可以列舉例如以下2種方法。 第一方法是目前已知的方法。藉由間隙(胞間隙)將2 張基板對向設置’使各液晶配向膜對向,使用密封劑貼 合2張基板的周邊部分,在藉由基板表面和密封劑劃分的 胞間隙内注入填充液晶後,密封注入孔,從而製備液晶 胞。 第二方法係稱為ODF(液晶滴注法(〇ne Drop Fill))方 式的方法。在形成液晶配向膜的2張基板中的一張基板上 的規定部位上’例如塗布紫外光硬化性的密封材料,再 於液晶配向膜上滴下液晶,然後貼合另一張基板,使液 晶配向膜對向,然後在基板的整個面上照射紫外光,使 密封劑硬化’從而能製備液晶胞。 在藉由任意方法的情況下,較佳均為接著將液晶胞 加熱至使利的液晶形成各向同性㈣溫度,然後緩慢 冷卻至室溫,從而除去填充液晶時 此外’藉由在液晶胞的外側表 可以獲得本發明的液晶顯示元件。 的流動配向。 面貼合偏光板,從而 其中,在形成液晶配 •27- 201226445 射的直線偏光放射線的# 偏光板的角度’從而能习蔓 向膜的2張基板中,適當調整昭 光方向所夾的角度和各基板與 得期望的液晶顯示元件。 作為上述密封劑,可m h J U使用例如包含作為墊片的氧 化鋁球和硬化劑的環氧樹脂等。 作為上述液晶’可以使用例如向列型液晶、層列型 液曰曰等u為能形成向列型液晶的具有正的介電各向 異性的物質,例如聯笨類液晶、苯基環己烧類液晶、龜 類液晶、聯二苯類液晶、聯苯環己烷類液晶、嘧啶類液 M、一嘮烷類液晶、雙環辛烷類液晶、立方烷類液晶等 。此外,在上述液晶中,還可以進一步添加例如膽甾烷 氯化物、膽留醇壬酸酯、膽留醇碳酸酯等膽留液晶; 以商品名「C·15」、「CB_15」(以上為Merck公司製 造)出售的手性劑; 對癸氧基亞苄基-對胺基_2_甲基丁基桂皮酸酯等之 鐵電性液晶等。 作為在液晶胞外側使用的偏光板,可以列舉對聚乙 烯醇延伸配向,且用乙酸纖維素保護膜夾持吸收了碘的 稱為「Η膜」的偏光膜的偏光板,或由η膜本身構成的偏 光板等。 由此製造的本發明的液晶顯示元件係在顯示特性、 電特性等之各性能上優異。 [實施例] 以下’藉由實施例對本發明進行具體的說明,但本 發明並不受到這些實施例的限制。 -28 ^ 201226445 <聚醯胺酸的合成> [合成例1 ] 在373.26g N_甲基-2-°比洛咬_中溶解〇.1莫耳 (24.82g)雙環[2.2.2]辛-7-酮-2,3,5,6-四羧酸二酐和〇」莫 耳(41.05g) 2,2-雙[4-(4-胺基苯氧基)苯基]丙烷,在室溫 下反應6小時。接著,將反應混合物與非常過量的曱醇混 和,沉澱反應產物。然後’用曱醇洗淨,在減壓4 〇下 乾燥15小時,獲得658聚醯胺酸八-1(產率98.7%)。 [合成例2〜3 ] 除了二胺化合物為下述D - 2〜D - 3以外,與合成例1 同樣獲得聚醯胺酸聚合物A-2〜A-3。 [二胺化合物] D-l : 2,2-雙[4-(4-胺基苯氧基)苯基]丙烷 D-2 :對苯二胺 D-3 : 4,4’-二胺基二苯基醚 [比較合成例1 ] 在343.74gN-曱基_2_〇比洛咬_中溶解莫耳 U9.61g) 1,2,3,4-環丁烷四羧酸二酐和〇1莫耳(41〇5§)上 述D -1化合物,在至溫下反應6小時。接著,將反應混合 物與非常過量的曱醇混和,沉澱反應產物。然後,用曱 醇洗淨’在減壓40 下乾燥1 5小時,獲得60g聚醯胺酸 a~U產率 98.9%)。 [比較合成例2〜3 ] 除了二胺化合物為上述D-2〜D-3以外,與比較合成 例1同樣獲得聚醯胺酸聚合物a_2〜a_3。 -29- 201226445 <液晶配向劑的製備> [實施例1 ] 在上述合成例1獲得的含有聚醯胺酸(A_1}的溶液中 ,加入N-甲基-2-吡咯啶酮(NMP)和丁基赛璐蘇(BC),再 相對於總和100質量份的聚合物,添加2〇質量份 N,N,N,,N’-四縮水甘油基-4,4、二胺基二苯基甲烷作為 環氧化合物,充分攪拌,形成溶劑組成為NM:p:BC = 60:40(質量比)’固體含量濃度為25質量%的溶液。將該 漆液用孔徑Ιμπι的過濾'器過渡,從而製備液晶配向劑 (Β-1) ° [實施例2〜3,比較例1〜3 ] 在實施例1中,除了分別使用合成例2〜3、比較合成 例1〜3獲得的聚醯胺酸Α_2〜Α-3、〜a_3代替a-ι以外 ’與實施例1同樣製備液晶配向劑B - 2〜B - 3、b -1〜b - 3。 β液晶顯不元件的製造> 在具有由ΙΤΟ膜構成的帶有透明電極的玻璃基板的 透明電極面上’使用旋塗器分別塗布上述製備的液晶配 向劑(Β-1〜Β-3、b-Ι〜b-3) ’使膜厚為01μηι,在2〇〇。(:下 乾燥1小時,形成薄膜。在該薄膜表面使用H g - X <;燈,從 基板法線方向照射 8,000 J/m2、1 〇,〇〇 〇 j/m2 或 5 〇,〇 〇〇 j/m2 包含254nm光線的偏光的紫外線。然後,對進行了上述 光照射處理的一對基板,在形成液晶配向膜的面的邊緣 保留液晶注入口,篩網印刷塗布加入有直徑5 5 μηι的氧化 #呂球的環氧樹脂黏合劑,之後重合而壓接基板,使光照 -30- 201226445 射方向反向平行,在15(rc下使黏合劑熱硬化丨小時。然 後,由液晶注入口向一對基板之間填充向列型液晶 (Merck公司製造’ ZLM 565),之後用環氧類黏合劑將液 晶注入口密封。進而為了除去液晶注入時的流動配向, 將其加熱至1 50°C後,緩慢冷卻至室溫。然後在基板的外 侧兩面貼合偏光板,使其偏光方向彼此垂直,且液晶配 向膜的偏光紫外線的光軸向基板面的投影方向與一個方 向垂直,與另一方向平行,從而製備液晶顯示元件。 對上述各個液晶顯示元件進行下述評價。結果在表i 示出。 <評價> [液晶配向性] 在液晶顯示元件中’用偏光顯微鏡觀察開•關(施加 、解除)電壓時候有無異常區域,將沒有異常區域的情況 判定為「良好」,即使異常區域存在一處也判定為「不 良」。 [電壓保持率] 於偏光紫外線照射量8,0〇〇J/m2製備的液晶顯示元件 施加60毫秒5V的電壓,以間隔167ms的方式施加,然後 從解除施加開始1 67毫秒後,測定電壓保持率。測定裝置 使用T〇Y〇 Technica公司製造的vhR-Ι。將電壓保持率為 9〇%以上的情況判斷為「良好」,將其他的情況判斷為 「不良」。 -31- 201226445 1 j ______ 液晶配向劑 液晶配向性 壓保持率(%) 紫外線照射量 (J/cm〇 一線照射量(J/cm2) 8,000 10,000 50,000 ____ 8,000 實施例1 Β-1__ 良好 良好 良好 ___ 99 實施例2 Β-2 良好 良好 良好 _____ 99 實施例3 良好 良好 良好 _ 99 比較例1 b-1 不良 良好 良好 98 比較例2 b-2 不良 良好 良好 99 比較例3 b-3 ____^ 不良 良好 良好 98 如表1所示,包含具有雙環[2·2·2]骨架的實施例的聚 醯胺酸的液晶配向劑對放射線的敏感度高,即使在 8000J/m2的低照射量下,具有所得液晶配向膜的液晶顯 示元件的液晶配向性也良好。此外,電壓保持率也良好 。與之相比,在比較例中,在8000 J/m2的低照射量下, 觀察到異常區域,液晶配向性不良。由上述可知,本發 明的液晶配向劑放射線敏感度高,在低照射量的放射線 照射下’也能形成具有優異液晶配向性的液晶配向膜。 [產業上之可利用性] 本發明的液晶配向劑放射線敏感度高,藉由低照射 量的光配向法’也能形成具有良好的液晶配向性和電特 性等之各性能的液晶配向膜以及具有該液晶配向膜的液 晶顯示元件。藉由本發明的液晶配向劑,能降低光配向 所需要的放射線照射量,因此能實現低成本化。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 -32-The transverse electric field of the liquid crystal cell is changed to M t a - FFS wave crystal alignment film. The liquid a of the present invention is used as a day-to-day alignment agent, especially when the liquid crystals of the pear, FFS type liquid crystal cells have a liquid crystal g _ , /, and there are IPs, and the present invention can be used for the present invention. The effect is better. Further, the method for forming the liquid crystal alignment crucible of the present invention includes: -24-201226445 (1) a step of applying the liquid crystal alignment agent of the present invention to a substrate and forming a coating film (hereinafter, also referred to as "step (1)'") And (2) a step of irradiating the polarized ultraviolet light on the coating film and imparting a liquid crystal alignment ability (hereinafter also referred to as "step (2)"). Hereinafter, each step will be described in detail. [Steps In the case where the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a TN type or STN type liquid crystal cell, two substrates each having a patterned transparent conductive film are provided as a pair, The liquid crystal alignment agent of the present invention is applied onto the transparent conductive film forming surface to form a coating film. On the other hand, an in-glass diacetate plate or the like of the opposite plate of the liquid crystal cell film. The composition is as above. When the liquid crystal alignment agent of the present invention is used for a liquid crystal display element having an lps type or an FFs type without forming a pattern, a substrate having an electrode on one side of a transparent conductive film or a zigzag pattern, and an electrode substrate not provided As a pair, the liquid crystal alignment agent of the present invention is applied to the formation surface of the zigzag electrode and the opposite base surface to form a coating film. All of the earth's It; brother's as the above substrate, 彳 used to use glass such as float, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and other plastics As the transparent conductive film, for example, an In203-Sn02 IT tantalum film, a NESA (registered trademark) film made of Sn 2 , or the like can be used. For example, a film made of a metal such as chrome: a pattern of a conductive film and a metal film may be used, for example, a transparent conductive film may be used, followed by a method of photolithography, sputtering, etc. In the case of a conductive film, a method having a desired nine cover or the like is used. -25- 201226445 When the liquid crystal alignment agent is coated on the substrate, the adhesion of the high-conductivity film or the electrode to the coating film is obtained, ^ , At liL j 预先 pre-coating the 3b decane compound, titanate on the substrate and the electrode Wait. The liquid crystal alignment agent may be coated on the substrate. Preferably, the coated surface is pre-heated by a suitable coating method such as offset printing, spin coating, roll coating, or ink jet printing. Baking), and then firing (post-fire, roasting) to form the coating film 1 for baking conditions, for example, at 4 〇 to i2 (rc for 0.1 to 5 minutes; post-baking conditions are preferably at i2 〇 to 3 〇 ( Rc, more preferably 150 250 CT, preferably 5 to fan minutes, preferably ίο~1 〇〇 minutes. The film thickness of the film after post-baking is preferably 〇〇〇ι~ 'better It is 0.005 to 〇5μηι. [Step (2)] The liquid crystal alignment ability is imparted by irradiating the polarized radiation in the thus formed coating film. [As the radiation, for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm can be used. The visible light line is preferably ultraviolet light containing light having a wavelength of from 200 nm to 400 nm. As the light source used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen mercury lamp, a metal hydride lamp, an argon resonance lamp, a xenon lamp, an excited molecular laser can be used. Etc. The above is preferred wavelength The ultraviolet ray of the domain can be obtained by a method in which the above-mentioned light source is used in combination with, for example, a filter, a diffraction lattice, etc. If the liquid crystal alignment agent of the present invention is used, it is usually required to irradiate ultraviolet rays of 10000 J/m or more, even if it is 8 Å. J/m2 can also impart good liquid crystal alignment ability, can improve the productivity of the liquid crystal display element, and reduce the manufacturing cost. ' 26 - 201226445 <Liquid crystal display element> The liquid crystal display element of the present invention has a liquid crystal alignment agent formed using the liquid crystal alignment agent The liquid crystal alignment film 'is therefore capable of imparting alignment ability to the liquid crystal at a lower irradiation amount than the present. Therefore, the liquid crystal display element having the liquid crystal alignment film can be manufactured at a lower cost than the current one. The liquid crystal display element of the present invention can be, for example, The liquid crystal cell having a structure in which liquid crystal is sandwiched between the pair of substrates is prepared as described above. The liquid crystal cell having a structure in which liquid crystal is sandwiched between the pair of substrates is prepared. For the production of the liquid crystal cell, for example, the following two methods are available. Known method. Set the two substrates oppositely by the gap (cell gap) to make the liquid crystal alignment films face each other. The peripheral portion of the two substrates is bonded together with a sealant, and after filling the liquid crystal into the interstitial space defined by the surface of the substrate and the sealant, the injection hole is sealed to prepare a liquid crystal cell. The second method is called ODF (liquid crystal instillation). Method of 〇ne Drop Fill). On a predetermined portion of one of two substrates forming a liquid crystal alignment film, for example, an ultraviolet curable sealing material is applied, and liquid crystal is dropped on the liquid crystal alignment film. Then, another substrate is bonded to face the liquid crystal alignment film, and then ultraviolet light is irradiated on the entire surface of the substrate to harden the sealant to prepare a liquid crystal cell. In any case, preferably The liquid crystal display element of the present invention can be obtained by heating the liquid crystal cell to a temperature at which the liquid crystal is formed to an isotropic (four) temperature, and then slowly cooling to room temperature to remove the liquid crystal. Flow alignment. The polarizing plate is attached to the surface, and thus, the angle of the polarizing plate of the linear polarized radiation which is formed by the liquid crystal distribution is 27-201226445, so that the angles of the light-incident direction can be appropriately adjusted in the two substrates of the film. Each substrate is a desired liquid crystal display element. As the above-mentioned sealant, for example, an epoxy resin containing an alumina-oxidized ball as a spacer and a curing agent can be used. As the liquid crystal ', for example, a nematic liquid crystal or a smectic liquid enthalpy can be used as a material having a positive dielectric anisotropy capable of forming a nematic liquid crystal, for example, a biphenyl liquid crystal or a phenylcyclohexene. Liquid crystal, turtle liquid crystal, biphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid M, monodecane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, in the liquid crystal, a cholesteric liquid crystal such as cholestane chloride, cholesteryl phthalate or cholesteryl carbonate may be further added; under the trade names "C·15" and "CB_15" (above) A chiral agent sold by Merck Co., Ltd.; a ferroelectric liquid crystal such as a nonoxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate in which a polyvinyl alcohol is stretched and aligned, and a polarizing film called a "ruthenium film" which absorbs iodine is sandwiched by a cellulose acetate protective film, or the ? film itself A polarizing plate or the like is formed. The liquid crystal display element of the present invention thus produced is excellent in various properties such as display characteristics and electrical characteristics. [Examples] The present invention is specifically described by the following examples, but the present invention is not limited by the examples. -28 ^ 201226445 <Synthesis of polyglycolic acid> [Synthesis Example 1] In 373.26 g of N_methyl-2-°Bilobital _ dissolved 〇.1 mol (24.82 g) of bicyclo [2.2.2 Oct-7-keto-2,3,5,6-tetracarboxylic dianhydride and oxime" (41.05 g) 2,2-bis[4-(4-aminophenoxy)phenyl]propane , react at room temperature for 6 hours. Next, the reaction mixture was mixed with a very large excess of sterol to precipitate a reaction product. Then, it was washed with decyl alcohol and dried under reduced pressure of 4 Torr for 15 hours to obtain 658 polyacetic acid octa-1 (yield 98.7%). [Synthesis Examples 2 to 3] Polyphthalic acid polymers A-2 to A-3 were obtained in the same manner as in Synthesis Example 1 except that the diamine compound was the following D-2 to D-3. [Diamine compound] Dl : 2,2-bis[4-(4-aminophenoxy)phenyl]propane D-2 : p-phenylenediamine D-3 : 4,4'-diaminodiphenyl Base ether [Comparative Synthesis Example 1] Dissolve Moer U9.61g in 343.74g N-mercapto_2_〇 洛 洛 _ _ 1, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride and 〇 1 Mo Ear (41 〇 5 §) The above D-1 compound was reacted at room temperature for 6 hours. Next, the reaction mixture was mixed with a very large excess of sterol to precipitate a reaction product. Then, it was washed with decyl alcohol and dried under reduced pressure of 40 for 15 hours to obtain a yield of 60 g of polyamidamine a~U (98.9%). [Comparative Synthesis Examples 2 to 3] Polyphthalic acid polymers a_2 to a_3 were obtained in the same manner as in Comparative Synthesis Example 1, except that the diamine compound was the above D-2 to D-3. -29-201226445 <Preparation of liquid crystal alignment agent> [Example 1] N-methyl-2-pyrrolidone (NMP) was added to the solution containing polyglycine (A_1} obtained in the above Synthesis Example 1. And butyl cyanidin (BC), and then add 2 parts by mass of N, N, N, N'-tetraglycidyl-4,4, diamino 2 to 100 parts by mass of the polymer. Phenylmethane is used as an epoxy compound and stirred sufficiently to form a solution having a solvent composition of NM:p:BC = 60:40 (mass ratio)' solid content concentration of 25% by mass. The lacquer liquid is filtered with a pore size Ιμπι The liquid crystal alignment agent (Β-1) was prepared by the transition. [Examples 2 to 3, Comparative Examples 1 to 3] In Example 1, except that the polymerizations obtained in Synthesis Examples 2 to 3 and Comparative Synthesis Examples 1 to 3, respectively. In the same manner as in Example 1, a liquid crystal alignment agent B - 2 to B - 3 and b -1 to b - 3 were prepared in the same manner as in Example 1 except that yttrium ruthenate Α 2 Α Α 、 、 、 a & & & & & & & & & & & & β β Applying the above-prepared liquid crystal alignment agent (Β-1 to Β-3, b-Ι) on a transparent electrode surface having a glass substrate with a transparent electrode composed of a ruthenium film using a spin coater B-3) 'Making the film thickness to 01 μηι, at 2 〇〇. (: drying for 1 hour, forming a film. Using H g - X <; lamp on the surface of the film, illuminating 8,000 J from the normal direction of the substrate /m2, 1 〇, 〇〇〇j/m2 or 5 〇, 〇〇〇j/m2 contains polarized ultraviolet light of 254 nm light. Then, a pair of substrates subjected to the above light irradiation treatment are formed in the liquid crystal alignment film. The edge of the surface retains the liquid crystal injection port, and the epoxy resin adhesive of oxidized #吕球 with a diameter of 5 5 μηι is added by screen printing, and then the substrate is pressed and pressed to make the illumination direction -30-201226445 anti-parallel, 15 (The adhesive is thermally hardened for 15 hours under rc. Then, a nematic liquid crystal (manufactured by Merck's ZLM 565) is filled between the pair of substrates by the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it is heated to 150 ° C and then slowly cooled to room temperature. Then, the polarizing plates are attached to the outer sides of the substrate so that the polarization directions thereof are perpendicular to each other, and the liquid crystal alignment film is Polarized ultraviolet light optical axis substrate The projection direction of the surface was perpendicular to one direction and parallel to the other direction to prepare a liquid crystal display element. Each of the above liquid crystal display elements was subjected to the following evaluation. The results are shown in Table 1. <Evaluation> [Liquid alignment property] In the liquid crystal display device, 'there is an abnormal region when the voltage is turned on/off (applied or released) by a polarizing microscope, and the case where there is no abnormal region is judged as "good", and even if there is one abnormal region, it is judged as "poor". [Voltage Retention Rate] A liquid crystal display element prepared by polarizing ultraviolet light irradiation at 8,0 J/m2 was applied with a voltage of 5 V for 60 msec, applied at intervals of 167 ms, and then measured for voltage retention after 167 ms from the start of release application. rate. As the measuring device, vhR-Ι manufactured by T〇Y〇 Technica Co., Ltd. was used. The case where the voltage holding ratio is 9% or more is judged as "good", and the other case is judged as "bad". -31- 201226445 1 j ______ Liquid crystal alignment agent liquid crystal alignment pressure retention ratio (%) UV irradiation amount (J/cm 〇 first line irradiation amount (J/cm2) 8,000 10,000 50,000 ____ 8,000 Example 1 Β-1__ Good and good ___ 99 Example 2 Β-2 Good Good Good _____ 99 Example 3 Good Good Good _ 99 Comparative Example 1 b-1 Poor Good Good 98 Comparative Example 2 b-2 Poor Good Good 99 Comparative Example 3 b-3 ____ ^ Poor good and good 98 As shown in Table 1, the liquid crystal alignment agent containing the polyglycine having the bicyclo[2·2·2] skeleton has high sensitivity to radiation, even at a low irradiation dose of 8000 J/m 2 In the liquid crystal display device having the obtained liquid crystal alignment film, the liquid crystal alignment property was also good, and the voltage holding ratio was also good. In the comparative example, an abnormality was observed at a low irradiation amount of 8000 J/m 2 . In the above, it is known that the liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid crystal alignment film having excellent liquid crystal alignment properties under low-radiation radiation irradiation. The liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid crystal alignment film having excellent properties such as liquid crystal alignment property and electrical characteristics by a low-emission photoalignment method, and has the liquid crystal alignment film. The liquid crystal display element of the present invention can reduce the amount of radiation required for light alignment by the liquid crystal alignment agent of the present invention, so that cost reduction can be achieved. [Simplified description of the drawing] No. [Description of main component symbols] None. -32-
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CN110156980B (en) * | 2019-06-03 | 2020-07-07 | 中国科学院上海有机化学研究所 | Colorless polyimide and preparation method and application thereof |
CN111103719B (en) * | 2020-01-07 | 2022-07-08 | 哈尔滨工业大学 | Method for preparing flexible trans-polymer dispersed liquid crystal film by utilizing LB (Langmuir-Blodgett) film technology |
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JP3357502B2 (en) * | 1994-05-17 | 2002-12-16 | シャープ株式会社 | Manufacturing method of liquid crystal display element |
JP3389718B2 (en) * | 1994-12-16 | 2003-03-24 | ジェイエスアール株式会社 | Liquid crystal alignment agent |
JP3603446B2 (en) * | 1996-02-01 | 2004-12-22 | Jsr株式会社 | Liquid crystal alignment agent |
WO1999015576A1 (en) * | 1997-09-25 | 1999-04-01 | Rolic Ag | Photocrosslinkable polyimides |
US6265520B1 (en) * | 1999-11-29 | 2001-07-24 | Industrial Technology Research Institute | Solvent soluble polyimide and a method for making thereof |
JP2001213962A (en) | 2000-02-04 | 2001-08-07 | Maruzen Petrochem Co Ltd | Polyimide resin for laser processing and solution composition thereof |
JP4062068B2 (en) * | 2002-11-20 | 2008-03-19 | 日立電線株式会社 | Liquid crystal display element |
KR100548625B1 (en) * | 2003-03-24 | 2006-01-31 | 주식회사 엘지화학 | High heat resistant transparent polyimide precursor and photosensitive resin composition using same |
KR20070035683A (en) * | 2005-09-28 | 2007-04-02 | 삼성전자주식회사 | Liquid crystal display and method for manufacturing the same |
KR101363301B1 (en) * | 2005-12-23 | 2014-02-18 | 롤리크 아게 | Photocrosslinkable materials |
JP5088561B2 (en) * | 2007-02-23 | 2012-12-05 | Jsr株式会社 | Liquid crystal alignment agent |
KR100851787B1 (en) * | 2007-04-11 | 2008-08-13 | 제일모직주식회사 | Polyimide resin synthesized from 3,4-dicarboxy-1,2,3,4-tetrahydro-6-t-butyl-1-naphthalenesuccinic acid dianhydride and aligning agent containing the same |
KR100952965B1 (en) * | 2007-08-30 | 2010-04-16 | 제일모직주식회사 | Alignment agent of liquid crystal, and alignment film of liquid crystal manufactured by the same |
KR100882586B1 (en) * | 2007-10-10 | 2009-02-13 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
KR100913605B1 (en) * | 2007-12-07 | 2009-08-26 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
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US9366907B2 (en) | 2012-09-10 | 2016-06-14 | Lg Chem, Ltd. | Composition for photo-alignment layer and photo-alignment layer |
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TWI523892B (en) | 2016-03-01 |
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