TWI698489B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
- Publication number
- TWI698489B TWI698489B TW104125315A TW104125315A TWI698489B TW I698489 B TWI698489 B TW I698489B TW 104125315 A TW104125315 A TW 104125315A TW 104125315 A TW104125315 A TW 104125315A TW I698489 B TWI698489 B TW I698489B
- Authority
- TW
- Taiwan
- Prior art keywords
- liquid crystal
- crystal alignment
- weight
- alignment agent
- film
- Prior art date
Links
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Nonlinear Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
本發明提供一種液晶配向劑,其利用噴墨塗布法的印刷性優異、且可提供電特性優異的液晶配向膜。本發明提供的液晶配向劑含有選自由使四羧酸二酐與二胺進行反應而獲得的聚醯胺酸、聚醯亞胺及聚醯胺酸酯所組成的組群中的至少一種聚合物(A)以及溶劑,並且該溶劑含有選自由二乙二醇丙基甲醚以及二乙二醇丁基甲醚所組成的組群中的至少一種。The present invention provides a liquid crystal alignment agent which has excellent printability by an inkjet coating method and can provide a liquid crystal alignment film with excellent electrical characteristics. The liquid crystal alignment agent provided by the present invention contains at least one polymer selected from the group consisting of polyamide acid, polyimide and polyamide ester obtained by reacting tetracarboxylic dianhydride and diamine (A) and a solvent, and the solvent contains at least one selected from the group consisting of diethylene glycol propyl methyl ether and diethylene glycol butyl methyl ether.
Description
本發明是有關於一種液晶配向劑、液晶配向膜以及液晶顯示元件。更詳細而言, 本發明特別是有關於一種在噴墨塗布法中塗布性良好的可提供液晶配向膜的液晶配向劑以及電特性優異的液晶顯示元件。The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element. In more detail, the present invention particularly relates to a liquid crystal alignment agent capable of providing a liquid crystal alignment film with good coatability in an inkjet coating method, and a liquid crystal display element with excellent electrical characteristics.
目前,作為液晶顯示元件,已知如下的具有所謂扭轉向列(Twisted Nematic,TN) 型液晶單元的TN 型液晶顯示元件,其於設置有氧化銦-氧化錫(Indium Tin Oxide, ITO) 等透明導電膜的基板表面,形成包含聚醯胺酸、聚醯亞胺等的液晶配向膜而作為液晶顯示元件用基板, 將該兩塊基板對向配置,在基板間的間隙內形成具有正的介電各向異性的向列型液晶的層而製成夾層結構的單元, 且使液晶分子的長軸自其中一塊基板朝向另一塊基板連續地扭轉90°而形成。另外,正在開發較TN 型液晶顯示元件而言對比度高、且視角依存性少的超扭轉向列(Super TwistedNematic,STN)型液晶顯示元件。該STN 型液晶顯示元件使用在向列型液晶中摻雜有作為光學活性物質的手性劑者作為液晶, 並利用通過液晶分子的長軸在基板間橫跨180°以上而成為連續扭轉的狀態所產生的雙折射效果。Currently, as a liquid crystal display element, the following TN type liquid crystal display element having a so-called twisted nematic (TN) type liquid crystal cell is known, which is provided with transparent indium oxide-tin oxide (Indium Tin Oxide, ITO), etc. On the surface of the substrate of the conductive film, a liquid crystal alignment film containing polyamide acid, polyimide, etc. is formed as a substrate for liquid crystal display elements. The two substrates are arranged facing each other, and a positive dielectric is formed in the gap between the substrates. A layer of electrically anisotropic nematic liquid crystal is formed into a sandwich structure unit, and the long axis of the liquid crystal molecule is continuously twisted by 90° from one substrate to the other substrate. In addition, a Super Twisted Nematic (STN) type liquid crystal display element with higher contrast and less viewing angle dependence than TN type liquid crystal display elements is under development. This STN type liquid crystal display element uses nematic liquid crystals doped with a chiral agent as an optically active material as the liquid crystal, and uses the long axis of the liquid crystal molecules to cross over 180° between the substrates to be in a continuously twisted state The resulting birefringence effect.
進而,近年來提出了橫向電場型液晶顯示元件,其將用以驅動液晶的兩個電極在一對基板中的其中一側的基板上配置為梳齒狀,通過產生與基板面平行的電場來控制液晶分子。該元件通常被稱為共面切換(In Plane Switching,IPS)型,已知視角優異而寬廣。特別是在將IPS型元件與光學補償膜併用的情況下,大的特徵在於:可進一步提高視角特性,獲得不存在灰階反轉或色調變化的與布朗管(Braun tube)也可匹敵的廣視角。Furthermore, in recent years, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving liquid crystal are arranged in a comb-tooth shape on one of a pair of substrates, and an electric field parallel to the substrate surface is generated. Control liquid crystal molecules. This device is usually called In Plane Switching (IPS) type, and it is known that the viewing angle is excellent and wide. Especially when the IPS-type element and the optical compensation film are used together, the big feature is that the viewing angle characteristics can be further improved, and there is no gray-scale inversion or hue change, which is comparable to the Braun tube. Perspective.
除了這些以外,還提出了使具有負的介電各向異性的液晶分子在基板上垂直地配向而成的稱為多域垂直配向(Multi-Domain Vertical Alignment,MVA)方式、或圖案垂直配向(Patterned Vertical Alignment,PVA)方式的垂直配向型液晶顯示元件(參照專利文獻1及非專利文獻1)。這些垂直配向方式的液晶顯示元件的視角、對比度等優異,也可以在液晶配向膜的形成中不進行摩擦處理等在製造步驟的方面也優異。In addition to these, a method called Multi-Domain Vertical Alignment (MVA) method, or pattern vertical alignment (Multi-Domain Vertical Alignment, MVA) method, in which liquid crystal molecules with negative dielectric anisotropy are vertically aligned on a substrate, has also been proposed. Patterned Vertical Alignment (PVA) type vertical alignment type liquid crystal display element (refer to Patent Document 1 and Non-Patent Document 1). These vertical alignment type liquid crystal display elements are excellent in viewing angles, contrast, etc., and they can also be excellent in terms of manufacturing steps without rubbing treatment during the formation of the liquid crystal alignment film.
近年來,液晶電視的普及推進,稱為所謂「第7代」的大型生產線正在運轉。另外,也預定建設更大型的「第8代」生產線。使用大型生產線來使基板大型化的優點可列舉:由於自基板一塊上取出多塊面板,故而可削減步驟時間,可減少成本的方面;或可對應液晶顯示元件自身的大型化的方面。另一方面,基板的大型化的缺點可列舉:難以遍及大面積來確保液晶配向劑的印刷的均勻性。尤其可列舉如下方面:若利用以往廣泛採用的膠版印刷機來進行大面積的成膜,則有時會產生因液晶配向劑的印刷不良而引起的液晶配向膜的電特性的不良。In recent years, the popularity of LCD TVs has advanced, and a large-scale production line called the "seventh generation" is operating. In addition, it is also planned to build a larger "8th generation" production line. The advantages of using a large-scale production line to increase the size of the substrate include: since multiple panels are taken out from one substrate, the step time can be reduced and the cost can be reduced; or the size of the liquid crystal display element itself can be coped with. On the other hand, the disadvantage of increasing the size of the substrate is that it is difficult to ensure the uniformity of printing of the liquid crystal alignment agent over a large area. In particular, the following points can be cited: If a large-area film is formed using an offset printing machine that has been widely used in the past, defects in the electrical properties of the liquid crystal alignment film may occur due to poor printing of the liquid crystal alignment agent.
為了解決所述問題,正在研究在液晶配向膜的形成中利用噴墨塗布法。噴墨塗布法的優點可列舉:由於印刷時使用的液晶配向劑與現實中塗布的液量實質上相等,故而可期待液晶配向劑的使用量削減。另外可列舉:由於不使用印刷版,故而不需要對其進行交換或洗滌等,可減少維護所花費的時間、勞力及成本,或具有可對應多種面板尺寸的柔軟性。 [現有技術文獻] [專利文獻]In order to solve the problem, it is being studied to use an inkjet coating method in the formation of a liquid crystal alignment film. The advantages of the inkjet coating method include: since the liquid crystal alignment agent used in printing is substantially equal to the amount of liquid applied in reality, it is expected that the amount of liquid crystal alignment agent used can be reduced. In addition, there is no need to exchange or wash the printing plate because it does not use the printing plate, which can reduce the time, labor, and cost for maintenance, or has flexibility that can correspond to a variety of panel sizes. [Prior Art Document] [Patent Document]
[專利文獻1]日本專利特開平11-258605號公報 [非專利文獻][Patent Document 1] Japanese Patent Laid-Open No. 11-258605 [Non-Patent Document]
[非專利文獻1]「液晶」第3卷(第2期)第117頁(1999年)[Non-Patent Document 1] "Liquid Crystals" Vol. 3 (No. 2) Page 117 (1999)
[發明所欲解決的問題][The problem to be solved by the invention]
由大型生產線製造的大型基板中,為了以高良率來製造液晶顯示元件,而於噴墨塗布法中,至今仍不斷要求印刷性優異的液晶配向劑。進而,近年來對顯示品質提高的要求變得更加嚴格。例如關於電特性,要求具有超過目前的特性的液晶配向膜。In order to manufacture liquid crystal display elements with high yield among large-scale substrates manufactured by large-scale production lines, in the inkjet coating method, a liquid crystal alignment agent with excellent printability is still continuously required. Furthermore, in recent years, the demand for improved display quality has become more stringent. For example, with regard to electrical characteristics, a liquid crystal alignment film having characteristics exceeding current characteristics is required.
本發明是鑒於所述情況而形成,其目的之一在於提供一種利用噴墨塗布法的印刷性特別優異、且可提供電特性優異的液晶配向膜的液晶配向劑。The present invention is formed in view of the foregoing circumstances, and one of its objects is to provide a liquid crystal alignment agent that has particularly excellent printability by an inkjet coating method and can provide a liquid crystal alignment film with excellent electrical characteristics.
本發明的進而其他的目的及優點是由以下的說明所明確。 [解決問題的技術手段]Still other objects and advantages of the present invention will be made clear from the following description. [Technical means to solve the problem]
第一,本發明的所述目的及優點是由一種液晶配向劑來實現,所述液晶配向劑含有選自由聚醯胺酸、聚醯亞胺及聚醯胺酸酯所組成的組群中的至少一種聚合物(A)以及溶劑,所述液晶配向劑的特徵在於:所述溶劑含有選自由二乙二醇丙基甲醚以及二乙二醇丁基甲醚所組成的組群中的至少一種。First, the objectives and advantages of the present invention are achieved by a liquid crystal alignment agent, the liquid crystal alignment agent containing selected from the group consisting of polyamide acid, polyimide and polyamide ester At least one polymer (A) and a solvent. The liquid crystal alignment agent is characterized in that the solvent contains at least one selected from the group consisting of diethylene glycol propyl methyl ether and diethylene glycol butyl methyl ether.
第二,本發明的所述目的及優點是由一種液晶顯示元件來實現,其包括由所述液晶配向劑來獲得的液晶配向膜。 [發明的效果]Second, the objectives and advantages of the present invention are achieved by a liquid crystal display element, which includes a liquid crystal alignment film obtained from the liquid crystal alignment agent. [Effects of the invention]
本發明的液晶配向劑特別是由於用於噴墨塗布法時的塗布性優異,故而可提高大型生產線的製造步驟中的製品良率。另外,由本發明的液晶配向劑獲得的液晶配向膜的電特性優異,適合應用於液晶顯示元件。The liquid crystal alignment agent of the present invention is particularly excellent in coating properties when used in an inkjet coating method, and therefore can improve the product yield in the manufacturing steps of a large-scale production line. In addition, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has excellent electrical properties and is suitable for application to liquid crystal display elements.
以下, 對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.
本發明的液晶配向劑包含選自由聚醯胺酸、聚醯亞胺及聚醯胺酸酯所組成的組群中的至少一種聚合物(A)作為聚合物成分,且製備成將該聚合物(A)分散或溶解於溶劑中而成的液狀組成物。 《聚合物(A)》 <聚醯胺酸>The liquid crystal alignment agent of the present invention contains at least one polymer (A) selected from the group consisting of polyamide acid, polyimide, and polyamide ester as a polymer component, and is prepared as the polymer (A) A liquid composition dispersed or dissolved in a solvent. "Polymer (A)" <Polyamic acid>
本發明中的聚醯胺酸可通過使四羧酸二酐與二胺進行反應而獲得。 (四羧酸二酐)The polyamide in the present invention can be obtained by reacting tetracarboxylic dianhydride and diamine. (Tetracarboxylic dianhydride)
聚醯胺酸的合成中使用的四羧酸二酐例如可列舉:脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作為這些四羧酸二酐的具體例, 脂肪族四羧酸二酐例如可列舉:1,2,3,4-丁烷四羧酸二酐等; 脂環式四羧酸二酐例如可列舉:1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺環-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-羧基甲基降冰片烷-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、4,9-二氧雜三環[5.3.1.02,6 ]十一烷-3,5,8,10-四酮、環己烷四羧酸二酐等; 芳香族四羧酸二酐例如可列舉:均苯四甲酸二酐等;除此以外,還可使用日本專利特開2010-97188號公報中記載的四羧酸二酐。此外,所述四羧酸二酐可單獨使用一種或者將兩種以上組合使用。Examples of the tetracarboxylic dianhydride used in the synthesis of the polyamide acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, the aliphatic tetracarboxylic dianhydrides include, for example, 1,2,3,4-butane tetracarboxylic dianhydride, etc.; and the alicyclic tetracarboxylic dianhydrides include, for example, :1,2,3,4-Cyclobutanetetracarboxylic dianhydride, 2,3,5-Tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[ 3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-di Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclic [5.3.1.0 2,6 ] ten Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc.; examples of aromatic tetracarboxylic dianhydrides include: pyromellitic dianhydride, etc.; in addition to this, it can also be used Tetracarboxylic dianhydride described in JP 2010-97188 A. In addition, the tetracarboxylic dianhydride may be used alone or in combination of two or more.
作為合成中使用的四羧酸二酐,就透明性以及對溶劑的溶解性等觀點而言,優選為包含脂環式四羧酸二酐。另外,脂環式四羧酸二酐中,優選為包含選自由2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、以及1,2,3,4-環丁烷四羧酸二酐所組成的組群中的至少一種,特別優選為包含選自由2,3,5-三羧基環戊基乙酸二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、以及1,2,3,4-環丁烷四羧酸二酐所組成的組群中的至少一種。As the tetracarboxylic dianhydride used in the synthesis, it is preferable to include an alicyclic tetracarboxylic dianhydride from the viewpoints of transparency and solubility in solvents. In addition, among the alicyclic tetracarboxylic dianhydrides, it is preferable to contain 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 8-Methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6,8 -At least one of the group consisting of tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, Particularly preferably, it contains selected from 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride , And at least one of the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
在包含選自由2,3,5-三羧基環戊基乙酸二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、以及1,2,3,4-環丁烷四羧酸二酐所組成的組群中的至少一種作為所述四羧酸二酐的情況下,相對於聚醯胺酸的合成中使用的四羧酸二酐的總量,這些化合物的合計含量優選為10莫耳%以上,更優選為20莫耳%~100莫耳%。 (二胺)In containing selected from 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, and When at least one of the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride is used as the tetracarboxylic dianhydride, compared to the tetracarboxylic dianhydride used in the synthesis of polyamide acid The total amount of the acid dianhydride, the total content of these compounds is preferably 10 mol% or more, and more preferably 20 mol% to 100 mol%. (Diamine)
聚醯胺酸的合成中使用的二胺例如可列舉脂肪族二胺、脂環式二胺、芳香族二胺、二胺基有機矽氧烷等。作為這些二胺的具體例,脂肪族二胺例如可列舉:間苯二甲胺、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等; 脂環式二胺例如可列舉:1,4-二胺基環己烷、4,4'-亞甲基雙(環己基胺)、1,3-雙(胺基甲基)環己烷等; 芳香族二胺例如可列舉:對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基硫醚、1,5-二胺基萘、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、2,7-二胺基茀、4,4'-二胺基二苯基醚、1,3-雙(4-胺基苯氧基)丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、9,9-雙(4-胺基苯基)茀、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4'-(對伸苯基二亞異丙基)雙苯胺、4,4'-(間伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基咔唑、N-苯基-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'-二甲基聯苯胺、1,4-雙-(4-胺基苯基)-哌嗪、1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-5-胺、1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-6-胺、3,5-二胺基苯甲酸、十八烷氧基-2,5-二胺基苯、膽甾烷氧基-3,5-二胺基苯、膽甾烯氧基-3,5-二胺基苯、膽甾烷氧基-2,4-二胺基苯、膽甾烯氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、4-(4'-三氟甲氧基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、4-(4'-三氟甲基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯氧基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯基)甲基)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、3-胺基苄基胺、以及下述式(D-1) [化1](式(D-1)中,XI 及XII 分別獨立地為單鍵、-O-、*-COO-、*-OCO-或*-NH-CO-(其中,帶有「*」的結合鍵與二胺基苯基鍵結),RI 及RII 分別獨立地為碳數1~3的烷二基,a為0或1,b為0~2的整數,c為1~20的整數,n為0或1,m為0或1;其中,a及b不會同時成為0,在XI 為*-NH-CO-的情況下,n為0) 所表示的化合物等; 二胺基有機矽氧烷例如可列舉:1,3-雙(3-胺基丙基)-四甲基二矽氧烷等;除此以外,還可使用日本專利特開2010-97188號公報中記載的二胺。此外,這些二胺可單獨使用一種或者將兩種以上組合使用。Examples of the diamine used in the synthesis of polyamide acid include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes. As specific examples of these diamines, aliphatic diamines include, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine Etc.; Examples of alicyclic diamines include: 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexyl Alkanes, etc.; examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diamino Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7- Diaminopyridine, 4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)propane, 2,2-bis[4-(4-aminophenoxy) )Phenyl]propane, 9,9-bis(4-aminophenyl)pyridium, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis (4-Aminophenyl) hexafluoropropane, 4,4'-(p-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene diisopropylidene) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diamino Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis (4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2 ,3-Dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl -1H-indene-6-amine, 3,5-diaminobenzoic acid, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, Cholesterenoxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholestenoxy-2,4-diaminobenzene, 3,5-diaminobenzene Cholesteryl aminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate, 3,6-bis(4-amino) Benzyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzyloxy)cyclohexyl-3, 5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-( (Aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane , 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl) Phenyl)-4-(4-heptylcyclohexyl) Cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, and the following formula (D-1) [Chemical 1 ] (In formula (D-1), X I and X II are independently a single bond, -O-, *-COO-, *-OCO- or *-NH-CO- (wherein, those with "*" The bond is bonded to the diamino phenyl group), R I and R II are each independently an alkanediyl group having 1 to 3 carbons, a is 0 or 1, b is an integer of 0 to 2, and c is 1 to 20 N is 0 or 1, m is 0 or 1; where a and b will not become 0 at the same time, and when X I is *-NH-CO-, n is 0) the compound represented by; Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc.; in addition, Japanese Patent Laid-Open No. 2010-97188 can also be used Diamine described in. Moreover, these diamines can be used individually by 1 type or in combination of 2 or more types.
所述式(D-1)中的「-XI -(RI -XII )n -」所表示的二價基優選為碳數1~3的烷二基、*-O-、*-COO-、*-O-C2 H4 -O-或*-NH-CO-(其中,帶有「*」的結合鍵與二胺基苯基鍵結)。The divalent group represented by "-X I -(R I -X II ) n -" in the formula (D-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, *-O-, *- COO-, *-OC 2 H 4 -O- or *-NH-CO- (wherein, the bond with "*" is bonded to the diamino phenyl group).
作為基團「-Cc H2c +1 」的具體例,例如可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基等。二胺基苯基中的兩個胺基優選為相對於其他基團而位於2,4-位或3,5-位。Specific examples of the group "-C c H 2c +1 "include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n Nonadecyl, n-eicosyl, etc. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.
作為所述式(D-1)所表示的化合物的具體例,例如可列舉下述式(D-1-1)~式(D-1-4)分別所表示的化合物等。 [化2]此外,作為二胺可將這些化合物的一種單獨使用或者將兩種以上組合使用。As a specific example of the compound represented by the said formula (D-1), the compound etc. respectively represented by following formula (D-1-1)-formula (D-1-4), for example are mentioned. [化2] In addition, as the diamine, one kind of these compounds may be used alone or in combination of two or more kinds.
合成本發明中的聚醯胺酸時使用的二胺優選為相對於全部二胺而包含30莫耳%以上的芳香族二胺,更優選為包含50莫耳%以上,特別優選為包含80莫耳%以上。The diamine used when synthesizing the polyamide acid in the present invention preferably contains 30 mol% or more of aromatic diamine relative to all diamines, more preferably contains 50 mol% or more, and particularly preferably contains 80 mol%. Ear% above.
在製成TN型、STN型或者垂直配向型液晶顯示元件用的液晶配向劑的情況下,為了賦予良好的液晶配向性,宜使用具有預傾成分者作為二胺。作為此種具有預傾成分的二胺,可列舉:具有選自由碳數4~20的烷基、碳數4~20的氟烷基、碳數4~20的烷氧基、碳數17~51的具有類固醇骨架的基團、以及多個環直接或者經由連結基而鍵結的基團所組成的組群中的至少一種作為預傾成分的二胺。具體而言,例如可列舉:十二烷氧基-2,4-二胺基苯、十四烷氧基-2,4-二胺基苯、十五烷氧基-2,4-二胺基苯、十六烷氧基-2,4-二胺基苯、十八烷氧基-2,4-二胺基苯、十二烷氧基-2,5-二胺基苯、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-2,5-二胺基苯、十八烷氧基-2,5-二胺基苯、膽甾烷氧基-3,5-二胺基苯、膽甾烯氧基-3,5-二胺基苯、膽甾烯氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、4-(4'-三氟甲氧基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、4-(4'-三氟甲基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯氧基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-(4-庚基環己基)環己烷、所述式(D-1)所表示的二胺等。此外,具有預傾成分的二胺可單獨使用一種或者將兩種以上組合使用。In the case of making a liquid crystal alignment agent for a TN-type, STN-type, or vertical alignment-type liquid crystal display element, in order to impart good liquid crystal alignment, it is preferable to use a diamine having a pretilt component. Examples of such diamines having pretilt components include those having an alkyl group having 4 to 20 carbons, a fluoroalkyl group having 4 to 20 carbons, an alkoxy group having 4 to 20 carbons, and a carbon number of 17 to 20. At least one of the group consisting of a group having a steroid skeleton of 51 and a group in which a plurality of rings are bonded directly or via a linking group is a diamine as a pretilt component. Specifically, for example, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diamine Benzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, fourteen Alkoxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2 ,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestenoxy-3,5-diaminobenzene, cholestenoxy-2,4-diamine Benzene, Cholesteryl 3,5-Diaminobenzoate, Cholesteryl 3,5-Diaminobenzoate, Lanosteryl 3,5-Diaminobenzoate, 3, 6-bis(4-aminobenzyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzyl) Oxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1 ,1-Bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-(( Aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, the diamine represented by the above formula (D-1), and the like. In addition, the diamine having a pretilt component may be used alone or in combination of two or more.
具有預傾成分的二胺優選為其合計量相對於全部二胺而包含5莫耳%以上,更優選為包含10莫耳%以上。The total amount of diamine having a pretilt component is preferably 5 mol% or more, and more preferably 10 mol% or more with respect to all diamines.
在利用光配向法對使用本發明的液晶配向劑來製作的塗膜賦予液晶配向性的情況下,優選為將本發明的液晶配向劑的製備中所使用的聚合物(A)的一部分或者全部設為具有光配向性結構的聚合物。此處,所謂光配向性結構是包含光配向性基以及分解型光配向部的兩者的概念。光配向性結構具體而言可採用由通過光異構化或光二聚化、光分解等而表現出光配向性的多種化合物而來的結構,例如可列舉:含有偶氮苯或其衍生物作為基本骨架的含偶氮苯的基團、含有肉桂酸或其衍生物作為基本骨架的具有肉桂酸結構的基團、含有查耳酮或其衍生物作為基本骨架的含查耳酮的基團、含有二苯甲酮或其衍生物作為基本骨架的含二苯甲酮的基團、含有香豆素或其衍生物作為基本骨架的含香豆素的基團、含有聚醯亞胺或其衍生物作為基本骨架的含聚醯亞胺的結構等。 (分子量調節劑)When the photo-alignment method is used to impart liquid crystal alignment to the coating film produced using the liquid crystal alignment agent of the present invention, it is preferable to use a part or all of the polymer (A) used in the preparation of the liquid crystal alignment agent of the present invention Set as a polymer having a photo-alignment structure. Here, the so-called photo-alignment structure is a concept including both a photo-alignment group and a decomposition-type photo-alignment portion. Specifically, the photo-alignment structure can be a structure derived from a variety of compounds that exhibit photo-alignment properties through photoisomerization, photodimerization, photolysis, etc., for example: containing azobenzene or its derivatives as the base Azobenzene-containing group of the skeleton, a group having a cinnamic acid structure containing cinnamic acid or its derivative as the basic skeleton, a chalcone-containing group containing chalcone or its derivative as the basic skeleton, Benzophenone or its derivative as the basic skeleton of a benzophenone-containing group, a coumarin or its derivative as a basic skeleton of a coumarin-containing group, or a polyimide or its derivative Polyimide-containing structure as the basic skeleton, etc. (Molecular weight regulator)
合成聚醯胺酸時,可如上所述與四羧酸二酐及二胺一起,使用適當的分子量調節劑來合成末端修飾型聚合物。通過製成所述末端修飾型的聚合物,可在不損及本發明效果的情況下進一步改善液晶配向劑的塗布性(印刷性)。When synthesizing polyamide acid, as described above, together with tetracarboxylic dianhydride and diamine, a suitable molecular weight regulator can be used to synthesize a terminal modified polymer. By making the terminal modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effect of the present invention.
分子量調節劑例如可列舉酸單酐、單胺化合物、單異氰酸酯化合物等。作為這些化合物的具體例,酸單酐例如可列舉:順丁烯二酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基丁二酸酐、正十二烷基丁二酸酐、正十四烷基丁二酸酐、正十六烷基丁二酸酐等;單胺化合物例如可列舉:苯胺、環己基胺、正丁基胺等;單異氰酸酯化合物例如可列舉:異氰酸苯基酯、異氰酸萘基酯等。Examples of the molecular weight modifier include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. As specific examples of these compounds, acid monoanhydrides include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecane Benzyl succinic anhydride, n-hexadecyl succinic anhydride, etc.; monoamine compounds include, for example, aniline, cyclohexylamine, n-butylamine, etc.; monoisocyanate compounds include, for example, phenyl isocyanate, isocyanate Acid naphthyl ester and so on.
相對於所使用的四羧酸二酐及二胺的合計100重量份,分子量調節劑的使用比例優選為設為20重量份以下,更優選為設為10重量份以下。 <聚醯胺酸的合成>The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used. <Synthesis of polyamide acid>
提供給聚醯胺酸的合成反應的四羧酸二酐與二胺的使用比例優選為相對於二胺的胺基1當量,四羧酸二酐的酸酐基成為0.2當量~2當量的比例,更優選為成為0.3當量~1.2當量的比例。The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of polyamide acid is preferably 1 equivalent relative to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents, More preferably, it is a ratio of 0.3 equivalent to 1.2 equivalent.
聚醯胺酸的合成反應優選為在有機溶媒中進行。此時的反應溫度優選為-20℃~150℃,更優選為0℃~100℃。另外,反應時間優選為0.1小時~24小時,更優選為0.5小時~12小時。The synthesis reaction of polyamide acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. In addition, the reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.
此處,有機溶媒例如可列舉:非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。Here, the organic solvent includes, for example, aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons.
作為這些有機溶媒的具體例,非質子性極性溶媒例如可列舉:N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑烷酮、N-乙基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺等;酚系溶媒例如可列舉:苯酚、間甲酚、二甲酚、鹵化苯酚等; 醇例如可列舉:甲基醇、乙基醇、異丙基醇、環己醇、乙二醇、丙二醇、1,4-丁二醇、三乙二醇、乙二醇單甲醚等;酮例如可列舉:丙酮、甲基乙基酮、甲基異丁基酮、環己酮等;酯例如可列舉:乳酸乙酯、乳酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、乙二酸二乙酯、丙二酸二乙酯、丙酸異戊酯、異丁酸異戊酯等; 醚例如可列舉:二乙醚、乙二醇甲醚、乙二醇乙醚、乙二醇-正丙醚、乙二醇-正丁醚、乙二醇二甲醚、乙二醇乙醚乙酸酯、二乙二醇二甲醚、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇丙基甲醚、二乙二醇丁基甲醚、四氫呋喃、二異戊基醚等; 鹵化烴例如可列舉:二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯等;所述烴例如可列舉:己烷、庚烷、辛烷、苯、甲苯、二甲苯等。As specific examples of these organic solvents, aprotic polar solvents include, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N ,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfide, γ-butyrolactone, tetramethylurea, hexamethylphosphatidylamine, etc.; phenolic solvent For example, phenol, m-cresol, xylenol, halogenated phenol, etc. may be mentioned; examples of alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- Butylene glycol, triethylene glycol, ethylene glycol monomethyl ether, etc.; examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; examples of esters include ethyl lactate , Butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, propylene Isoamyl acid, isoamyl isobutyrate, etc.; ethers include, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, and ethylene two Diethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol propyl methyl ether, two Ethylene glycol butyl methyl ether, tetrahydrofuran, diisoamyl ether, etc.; halogenated hydrocarbons include, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, and chlorobenzene , O-dichlorobenzene, etc.; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, and xylene.
這些有機溶媒中,優選為使用選自由非質子性極性溶媒以及酚系溶媒所組成的組群(以下稱為有機溶媒X)中的一種以上,或者選自有機溶媒X中的一種以上與選自由醇、酮、酯、醚、鹵化烴及烴所組成的組群(以下稱為有機溶媒Y)中的一種以上的混合物。在後者的情況下,相對於有機溶媒X及有機溶媒Y的合計量,有機溶媒Y的使用比例優選為50重量%以下,更優選為40重量%以下,尤其優選為30重量%以下。Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (hereinafter referred to as organic solvent X), or one or more selected from organic solvents X and selected from A mixture of one or more kinds of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (hereinafter referred to as organic solvent Y). In the latter case, the use ratio of the organic solvent Y relative to the total amount of the organic solvent X and the organic solvent Y is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.
有機溶媒的使用量(a)優選為設為相對於反應溶液的總量(a+b),四羧酸二酐以及二胺的合計量(b)成為0.1重量%~50重量%的量。The use amount (a) of the organic solvent is preferably such an amount that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1% by weight to 50% by weight relative to the total amount (a+b) of the reaction solution.
以如上所述的方式,獲得將聚醯胺酸溶解而成的反應溶液。該反應溶液可直接提供給液晶配向劑的製備,也可以將反應溶液中所含的聚醯胺酸分離後再提供給液晶配向劑的製備,或者還可以將分離的聚醯胺酸純化後再提供給液晶配向劑的製備。在將聚醯胺酸進行脫水閉環而形成聚醯亞胺的情況下,可將所述反應溶液直接提供給脫水閉環反應,也可以將反應溶液中所含的聚醯胺酸分離後再提供給脫水閉環反應,或者還可以將分離的聚醯胺酸純化後再提供給脫水閉環反應。聚醯胺酸的分離以及純化可依據公知的方法來進行。 <聚醯亞胺>In the manner as described above, a reaction solution obtained by dissolving polyamide acid is obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the polyamide acid contained in the reaction solution can be separated and then supplied to the preparation of the liquid crystal alignment agent, or the separated polyamide acid can also be purified before Provided for the preparation of liquid crystal alignment agents. In the case of dehydrating and ring-closing polyamide to form polyimide, the reaction solution can be directly supplied to the dehydration ring-closing reaction, or the polyamide acid contained in the reaction solution can be separated and then supplied to The dehydration ring-closing reaction, or the separated polyamide acid can be purified and then supplied to the dehydration ring-closing reaction. The isolation and purification of polyamic acid can be carried out according to a known method. <Polyimide>
本發明的液晶配向劑中所含有的聚醯亞胺可通過將以所述方式合成的聚醯胺酸進行脫水閉環而醯亞胺化來獲得。The polyimide contained in the liquid crystal alignment agent of the present invention can be obtained by dehydrating and ring-closing the polyimide synthesized in the above manner to imidize it.
所述聚醯亞胺可以是將作為其前驅物的聚醯胺酸所具有的醯胺酸結構全部進行脫水閉環而成的完全醯亞胺化物,也可以是僅將醯胺酸結構的一部分進行脫水閉環而使醯胺酸結構與醯亞胺環結構並存的部分醯亞胺化物。本發明中的聚醯亞胺的醯亞胺化率優選為30%以上,更優選為40%~99%,尤其優選為50%~99%。該醯亞胺化率是相對於聚醯亞胺的醯胺酸結構的數量與醯亞胺環結構的數量的合計,以百分率來表示醯亞胺環結構的數量所占的比例。此處,醯亞胺環的一部分也可以是異醯亞胺環。The polyimide may be a complete amide compound obtained by dehydrating and ring-closing all the amide acid structure of the polyamide acid as its precursor, or it may be a part of the amide acid structure. A partial amide compound in which an amide acid structure and an amide ring structure coexist by dehydration and ring closure. The imidization rate of the polyimide in the present invention is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99%. The imidization rate is the sum of the number of amide acid structures and the number of amide ring structures with respect to the polyimide, and the ratio of the number of amide ring structures is expressed as a percentage. Here, a part of the imine ring may be an isoimide ring.
聚醯胺酸的脫水閉環優選為利用以下方法來進行:對聚醯胺酸進行加熱的方法;或者將聚醯胺酸溶解於有機溶媒中,在該溶液中添加脫水劑以及脫水閉環催化劑,視需要進行加熱的方法。其中,優選為利用後者的方法。The dehydration ring closure of polyamide acid is preferably carried out by the following method: a method of heating polyamide acid; or dissolving polyamide acid in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, depending on A method of heating is required. Among them, the latter method is preferred.
在所述聚醯胺酸的溶液中添加脫水劑及脫水閉環催化劑的方法中,脫水劑例如可使用乙酸酐、丙酸酐、三氟乙酸酐等酸酐。相對於聚醯胺酸的醯胺酸結構的1莫耳,脫水劑的使用量優選為設為0.01莫耳~20莫耳。脫水閉環催化劑例如可使用吡啶、三甲吡啶、二甲吡啶、三乙基胺等三級胺。相對於所使用的脫水劑1莫耳,脫水閉環催化劑的使用量優選為設為0.01莫耳~10莫耳。脫水閉環反應中使用的有機溶媒可列舉作為聚醯胺酸的合成中使用者而例示的有機溶媒。脫水閉環反應的反應溫度優選為0℃~180℃,更優選為10℃~150℃。反應時間優選為1.0小時~120小時,更優選為2.0小時~30小時。In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyamide acid solution, the dehydrating agent can be, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol with respect to 1 mol of the amide acid structure of the polyamide acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include organic solvents exemplified as users in the synthesis of polyamide acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C, more preferably 10°C to 150°C. The reaction time is preferably 1.0 hour to 120 hours, more preferably 2.0 hours to 30 hours.
以所述方式獲得含有聚醯亞胺的反應溶液。該反應溶液可直接提供給液晶配向劑的製備,也可以自反應溶液中去除脫水劑及脫水閉環催化劑後再提供給液晶配向劑的製備,也可以將聚醯亞胺分離後再提供給液晶配向劑的製備,或者還可以將分離的聚醯亞胺純化後再提供給液晶配向劑的製備。這些純化操作可依據公知的方法來進行。 <聚醯胺酸酯>In the manner described, a reaction solution containing polyimine is obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or it can be supplied to the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or it can be supplied to the liquid crystal alignment agent after the polyimide is separated Preparation of the liquid crystal alignment agent, or the isolated polyimine can be purified and then supplied to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to known methods. <Polyurate>
本發明的液晶配向劑中所含有的聚醯胺酸酯例如可利用以下方法來獲得:[I]通過使由所述合成反應獲得的聚醯胺酸與含羥基的化合物、鹵化物、含環氧基的化合物等進行反應來合成的方法;[II]使四羧酸二酯與二胺進行反應的方法;[III]使四羧酸二酯二鹵化物與二胺進行反應的方法。The polyamide ester contained in the liquid crystal alignment agent of the present invention can be obtained, for example, by the following method: [I] By combining the polyamide acid obtained by the synthesis reaction with a hydroxyl-containing compound, halide, and ring-containing A method of reacting a compound of an oxy group to synthesize; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
此處,方法[I]中使用的含羥基的化合物例如可列舉:甲醇、乙醇、丙醇等醇類;苯酚、甲酚等酚類等。另外,鹵化物例如可列舉:溴代甲烷、溴代乙烷、溴代十八烷、氯代甲烷、氯代十八烷、1,1,1-三氟-2-碘乙烷等,含環氧基的化合物例如可列舉環氧丙烷等。方法[II]中使用的四羧酸二酯例如可通過使用所述醇類,將所述聚醯胺酸的合成中例示的四羧酸二酐進行開環而獲得。另外,方法[III]中使用的四羧酸二酯二鹵化物可通過使以所述方式獲得的四羧酸二酯與亞硫醯氯等適當的氯化劑進行反應而獲得。方法[II]及方法[III]中使用的二胺可使用所述聚醯胺酸的合成中例示的二胺等。此外,聚醯胺酸酯可僅具有醯胺酸酯結構,也可以是醯胺酸結構與醯胺酸酯結構並存的部分酯化物。Here, the hydroxyl group-containing compound used in the method [I] includes, for example, alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. In addition, the halide includes, for example, bromomethane, bromoethane, bromooctadecane, chloromethane, chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, etc., including Examples of epoxy-based compounds include propylene oxide. The tetracarboxylic acid diester used in the method [II] can be obtained by, for example, ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamide acid using the alcohols. In addition, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained in the above-mentioned manner with an appropriate chlorinating agent such as sulfite chloride. As the diamine used in the method [II] and the method [III], the diamines and the like exemplified in the synthesis of the polyamide acid can be used. In addition, the polyamide ester may have only an amide acid ester structure, or may be a partial ester product in which an amide acid structure and an amide acid ester structure coexist.
含有聚醯胺酸酯的反應溶液可直接提供給液晶配向劑的製備,也可以自反應溶液中去除脫水劑及脫水閉環催化劑後再提供給液晶配向劑的製備,也可以將聚醯胺酸酯分離後再提供給液晶配向劑的製備,或者還可以將分離的聚醯胺酸酯純化後再提供給液晶配向劑的製備。這些純化操作可依據公知的方法來進行。 <溶液黏度、還原黏度以及重量平均分子量>The reaction solution containing the polyamide ester can be directly supplied to the preparation of the liquid crystal alignment agent, or it can be supplied to the preparation of the liquid crystal alignment agent after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, or the polyamide ester After the separation, it is provided to the preparation of the liquid crystal alignment agent, or the separated polyamide ester can be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to known methods. <Solution viscosity, reduction viscosity and weight average molecular weight>
以所述方式獲得的聚醯胺酸、聚醯亞胺及聚醯胺酸酯優選為當將其製成濃度為10重量%的溶液時,具有10 mPa·s~800 mPa·s的溶液黏度者,更優選為具有15 mPa·s~500 mPa·s的溶液黏度者。此外,所述聚合物的溶液黏度(mPa·s)是對使用該聚合物的良溶媒(例如γ-丁內酯、N-甲基-2-吡咯烷酮等)來製備的濃度為10重量%的聚合物溶液,使用E型旋轉黏度計,在25℃下測定而得的值。The polyamide acid, polyimide and polyamide ester obtained in the above manner preferably have a solution viscosity of 10 mPa·s to 800 mPa·s when they are made into a solution with a concentration of 10% by weight Those are more preferably those having a solution viscosity of 15 mPa·s to 500 mPa·s. In addition, the solution viscosity (mPa·s) of the polymer is a concentration of 10% by weight based on a good solvent for the polymer (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The polymer solution was measured at 25°C using an E-type rotary viscometer.
還原黏度只要是可形成均勻塗膜的範圍,則並無特別限定,優選為0.05 dl/g~3.0 dl/g,更優選為0.1 dl/g~2.5 dl/g,尤其優選為0.3 dl/g~1.5 dl/g。The reduced viscosity is not particularly limited as long as it is a range that can form a uniform coating film, but is preferably 0.05 dl/g to 3.0 dl/g, more preferably 0.1 dl/g to 2.5 dl/g, and particularly preferably 0.3 dl/g ~1.5 dl/g.
對於本發明的液晶配向劑中所含有的聚醯胺酸、聚醯亞胺以及聚醯胺酸酯,利用凝膠滲透層析法(Gel Permeation Chromatography,GPC)來測定的聚苯乙烯換算的重量平均分子量優選為500~100,000,更優選為1,000~50,000。 《溶劑》For the polyamide acid, polyimide, and polyamide ester contained in the liquid crystal alignment agent of the present invention, the weight in terms of polystyrene is measured by Gel Permeation Chromatography (GPC) The average molecular weight is preferably 500 to 100,000, more preferably 1,000 to 50,000. "Solvent"
本發明的液晶配向劑含有選自由二乙二醇丙基甲醚以及二乙二醇丁基甲醚所組成的組群中的至少一種(以下稱為特定溶劑(B))作為溶劑成分。通過使此種特定溶劑(B)含有於液晶配向劑中,而成為噴墨塗布法中的印刷性特別優異者。The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of diethylene glycol propyl methyl ether and diethylene glycol butyl methyl ether (hereinafter referred to as specific solvent (B)) as a solvent component. By containing such a specific solvent (B) in a liquid crystal alignment agent, it becomes a thing which is especially excellent in printability in an inkjet coating method.
關於所述特定溶劑(B),二乙二醇丙基甲醚的丙基可以是直鏈狀、分支狀的任一種,具體而言可列舉:二乙二醇正丙基甲醚、二乙二醇異丙基甲醚。優選為二乙二醇異丙基甲醚。另外,二乙二醇丁基甲醚的丁基部分可以是直鏈狀、分支狀的任一種,具體而言可列舉:二乙二醇正丁基甲醚、二乙二醇異丁基甲醚、二乙二醇第二丁基甲醚等。優選為二乙二醇正丁基甲醚。此外,特定溶劑(B)可單獨使用一種或者將兩種以上組合使用。 (其他溶劑)Regarding the specific solvent (B), the propyl group of diethylene glycol propyl methyl ether may be either linear or branched. Specifically, examples include diethylene glycol n-propyl methyl ether, diethylene glycol Alcohol isopropyl methyl ether. Preferably, it is diethylene glycol isopropyl methyl ether. In addition, the butyl moiety of diethylene glycol butyl methyl ether may be either linear or branched. Specifically, examples include diethylene glycol n-butyl methyl ether, diethylene glycol isobutyl methyl ether, and diethylene glycol Dibutyl methyl ether and so on. Preferably, it is diethylene glycol n-butyl methyl ether. In addition, the specific solvent (B) may be used alone or in combination of two or more. (Other solvents)
本發明的液晶配向劑優選為含有所述特定溶劑(B)以外的其他溶劑作為溶劑成分。該其他溶劑可列舉:可將本發明的液晶配向劑中所含有的聚合物(A)溶解的溶媒(以下也稱為「第一溶劑」)、作為該聚合物(A)的不良溶媒且為所述特定溶劑(B)以外的有機溶媒等。The liquid crystal alignment agent of the present invention preferably contains other solvents other than the specific solvent (B) as a solvent component. Examples of such other solvents include: a solvent capable of dissolving the polymer (A) contained in the liquid crystal alignment agent of the present invention (hereinafter also referred to as "first solvent"), and a poor solvent for the polymer (A). Organic solvents other than the specific solvent (B), etc.
所述第一溶劑只要是所述聚合物(A)的良溶媒即可,作為其優選的具體例,例如可列舉:N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-戊基-2-吡咯烷酮、3-甲氧基-N,N-二甲基丙醯胺、N,N,2-三甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1,3-二甲基-2-咪唑烷酮、N-乙基-2-吡咯烷酮、二甲基亞碸、四甲基脲、六甲基磷醯三胺、間甲酚等。此外,第一溶劑可將所述者單獨使用一種或者將兩種以上混合使用。The first solvent may be a good solvent for the polymer (A), and preferred specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N -Pentyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, N,N,2-trimethylpropanamide, 3-butoxy-N,N-dimethyl Propyl propionamide, γ-butyrolactone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2- Imidazolidinone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamine, m-cresol, etc. In addition, the first solvent may be used alone or in combination of two or more.
另外,作為所述聚合物(A)的不良溶媒且為所述特定溶劑(B)以外的有機溶媒例如可列舉:2-羥基異丁酸甲酯、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、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)、乙二醇二甲醚、乙二醇乙醚乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、二丙二醇單甲醚(dipropylene glycol monomethyl ether,DPM)、二異丁基酮、丙酸異戊酯、異丁酸異戊酯、碳酸伸乙酯、碳酸伸丙酯、二丙酮醇、二乙二醇二乙醚、二異戊基醚、丙二醇二乙酸酯等。該有機溶媒可將所述者單獨使用一種或者將兩種以上混合使用。此外,以下,將由作為所述聚合物(A)的不良溶媒且所述特定溶劑(B)以外的有機溶媒以及所述特定溶劑(B)所組成的組群也稱為「第二溶劑」。In addition, organic solvents other than the specific solvent (B) that are poor solvents for the polymer (A) include, for example, methyl 2-hydroxyisobutyrate, ethylene glycol monomethyl ether, butyl lactate, Butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethyl Glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether ethyl Ester, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate , Propylene carbonate, diacetone alcohol, diethylene glycol diethyl ether, diisoamyl ether, propylene glycol diacetate, etc. The organic solvent can be used alone or in combination of two or more. In addition, hereinafter, a group consisting of an organic solvent other than the specific solvent (B) and the specific solvent (B) as a poor solvent for the polymer (A) is also referred to as a “second solvent”.
就使利用噴墨塗布法的印刷性良好,並且抑制聚合物(A)的析出的觀點而言,相對於液晶配向劑中所含的溶劑的總量,特定溶劑(B)的含有比例(在使用兩種以上的情況下為其合計量)優選為設為90重量%以下。更優選為85重量%以下,尤其優選為80重量%以下,特別優選為75重量%以下。另外,該含有比例的下限值並無特別限制,優選為設為1重量%以上。From the viewpoint of achieving good printability by the inkjet coating method and suppressing the precipitation of the polymer (A), the content ratio of the specific solvent (B) relative to the total amount of the solvent contained in the liquid crystal alignment agent (in When two or more are used, the total amount is preferably set to 90% by weight or less. It is more preferably 85% by weight or less, particularly preferably 80% by weight or less, and particularly preferably 75% by weight or less. In addition, the lower limit of the content ratio is not particularly limited, but it is preferably 1% by weight or more.
就抑制聚合物(A)的析出的觀點而言,相對於液晶配向劑中所含的溶劑的總量,所述第一溶劑的含有比例優選為5重量%以上,更優選為10重量%以上,尤其優選為20重量%以上。另外,就適當獲得由所述特定溶劑(B)的添加帶來的效果的觀點而言,相對於液晶配向劑中所含的溶劑的總量,所述第一溶劑的含有比例的上限值優選為95重量%以下,更優選為90重量%以下,尤其優選為85重量%以下。From the viewpoint of suppressing the precipitation of the polymer (A), the content of the first solvent is preferably 5% by weight or more, and more preferably 10% by weight or more with respect to the total amount of solvents contained in the liquid crystal alignment agent , Particularly preferably 20% by weight or more. In addition, from the viewpoint of appropriately obtaining the effect brought about by the addition of the specific solvent (B), the upper limit of the content ratio of the first solvent with respect to the total amount of the solvent contained in the liquid crystal alignment agent It is preferably 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.
所述第二溶劑中,相對於液晶配向劑中所含的溶劑的總量,所述特定溶劑(B)以外的有機溶媒的含有比例優選為80重量%以下,更優選為70重量%以下,尤其優選為50重量%以下,特別優選為30重量%以下。In the second solvent, the content ratio of organic solvents other than the specific solvent (B) is preferably 80% by weight or less, and more preferably 70% by weight or less, relative to the total amount of solvents contained in the liquid crystal alignment agent. It is particularly preferably 50% by weight or less, and particularly preferably 30% by weight or less.
就使對基板的塗布性良好的觀點而言,第一溶劑與第二溶劑的比率優選為相對於第一溶劑的使用量,將第二溶劑的使用量設為0.03倍(重量)以上,更優選為設為0.05倍(重量)以上。另外,就抑制聚合物的析出的觀點而言,優選為設為2.5倍(重量)以下,更優選為設為2.0倍(重量)以下。 《其他成分》From the viewpoint of making the coatability to the substrate good, the ratio of the first solvent to the second solvent is preferably set to 0.03 times (weight) or more with respect to the used amount of the first solvent. Preferably, it is 0.05 times (weight) or more. In addition, from the viewpoint of suppressing the precipitation of the polymer, it is preferably 2.5 times (weight) or less, and more preferably 2.0 times (weight) or less. "Other Ingredients"
本發明的液晶配向劑如上所述含有聚合物(A)以及溶劑,也可以視需要而含有其他成分。所述其他成分例如可列舉:所述聚合物(A)以外的其他聚合物、分子內具有至少一個環氧基的化合物(以下稱為「含環氧基的化合物」)、官能性矽烷化合物等。 [其他聚合物]The liquid crystal alignment agent of the present invention contains the polymer (A) and the solvent as described above, and may contain other components as necessary. Examples of the other components include polymers other than the polymer (A), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compounds"), functional silane compounds, etc. . [Other polymers]
所述其他聚合物可用於改善溶液特性或電特性。所述其他聚合物例如可列舉:聚酯、聚醯胺、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基順丁烯二醯亞胺)衍生物、聚(甲基)丙烯酸酯等。這些聚合物中,優選為選自由聚酯、聚有機矽氧烷及聚(甲基)丙烯酸酯所組成的組群中的至少一種聚合物,更優選為聚有機矽氧烷。The other polymers can be used to improve solution properties or electrical properties. Examples of the other polymers include polyesters, polyamides, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenyl maleic acid) Amine) derivatives, poly(meth)acrylates, etc. Among these polymers, at least one polymer selected from the group consisting of polyester, polyorganosiloxane, and poly(meth)acrylate is preferable, and polyorganosiloxane is more preferable.
另外,所述其他聚合物也可以使用具有光配向性結構的聚合物。具體而言,優選為設為具有光配向性基的聚合物,更優選為設為導入有具有肉桂酸結構的基團作為光配向性基的聚合物。其中,就容易將光配向性基導入至聚合物中的方面而言,可優選使用具有肉桂酸結構的聚矽氧烷。In addition, the other polymer may also use a polymer having a photo-alignment structure. Specifically, it is preferably a polymer having a photo-alignment group, and more preferably a polymer having a cinnamic acid structure introduced as a photo-alignment group. Among them, the polysiloxane having a cinnamic acid structure can be preferably used in terms of easy introduction of the photoalignment group into the polymer.
此外,具有光配向性基的聚合物可利用現有公知的方法來合成。例如,具有光配向性基的聚矽氧烷可通過優選為在醚、酯、酮等有機溶媒中,在四級銨鹽等催化劑的存在下,使具有環氧基的聚矽氧烷與具有光配向性基的羧酸進行反應來合成。In addition, the polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, a polysiloxane with a photo-alignment group can be combined with a polysiloxane with an epoxy group in the presence of a catalyst such as a quaternary ammonium salt in an organic solvent such as ether, ester, and ketone. The carboxylic acid of the photoalignment group is synthesized by reacting.
詳細而言,聚矽氧烷例如可通過使水解性的矽烷化合物進行水解·縮合而獲得。聚矽氧烷的合成中使用的矽烷化合物例如可列舉:四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷等,可將這些化合物中的一種單獨使用或者將兩種以上組合使用。Specifically, polysiloxane can be obtained, for example, by subjecting a hydrolyzable silane compound to hydrolysis and condensation. Silane compounds used in the synthesis of polysiloxanes include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane. Silane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-ring (Oxycyclohexyl) ethyl triethoxy silane, 3-(meth) acryloxy propyl trimethoxy silane, vinyl trimethoxy silane, etc., one of these compounds can be used alone or two Use a combination of the above.
所述水解·縮合反應可通過優選為在適當的催化劑以及有機溶媒的存在下,使如上所述的矽烷化合物的一種或者兩種以上與水進行反應來進行。水解·縮合反應時,相對於矽烷化合物(合計量)1莫耳,水的使用比例優選為0.5莫耳~100莫耳,更優選為1莫耳~30莫耳。The hydrolysis/condensation reaction can be carried out by reacting one or two or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis/condensation reaction, the use ratio of water is preferably 0.5 mol to 100 mol, and more preferably 1 mol to 30 mol relative to 1 mol of the silane compound (total amount).
水解·縮合反應時使用的催化劑例如可列舉:酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物等。催化劑的使用量根據催化劑的種類、溫度等反應條件等而不同,可適當設定,例如相對於矽烷化合物的合計量,優選為0.01倍莫耳~3倍莫耳,更優選為0.05倍莫耳~1倍莫耳。Examples of the catalyst used in the hydrolysis and condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and can be appropriately set. For example, relative to the total amount of the silane compound, it is preferably 0.01 times mol to 3 times mol, more preferably 0.05 times mol to 1 times mole.
所述水解·縮合反應時使用的有機溶媒例如可列舉烴、酮、酯、醚、醇等。這些有劑溶媒中,優選為使用非水溶性或者難水溶性的有機溶媒。相對於反應中使用的矽烷化合物的合計100重量份,有機溶媒的使用比例優選為10重量份~10,000重量份,更優選為50重量份~1,000重量份。Examples of the organic solvent used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these solvents, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by weight to 10,000 parts by weight, and more preferably 50 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the total of the silane compounds used in the reaction.
所述水解·縮合反應優選為例如利用油浴等進行加熱來實施。水解·縮合反應時,優選為將加熱溫度設為130℃以下,更優選為設為40℃~100℃。加熱時間優選為設為0.5小時~12小時,更優選為設為1小時~8小時。在加熱中,可將混合液進行攪拌,也可以置於回流下。另外,優選為在反應結束後,將自反應液中分取出的有機溶媒層以水洗滌。該洗滌時,通過使用包含少量鹽的水(例如0.2重量%左右的硝酸銨水溶液等)進行洗滌,就洗滌操作變得容易的方面而言優選。洗滌進行至洗滌後的水層成為中性為止,然後,將有機溶媒層視需要以無水硫酸鈣、分子篩等乾燥劑進行乾燥後,去除溶媒,由此可獲得聚矽氧烷。另外,可通過使所得的聚矽氧烷、與反應性化合物(例如具有光配向性基的羧酸等)進行反應,而獲得具有反應性基的聚矽氧烷。The hydrolysis/condensation reaction is preferably carried out by heating with an oil bath or the like, for example. In the case of the hydrolysis/condensation reaction, the heating temperature is preferably 130°C or lower, and more preferably 40°C to 100°C. The heating time is preferably 0.5 hour to 12 hours, and more preferably 1 hour to 8 hours. During heating, the mixture can be stirred or placed under reflux. In addition, it is preferable to wash the organic solvent layer separated from the reaction liquid with water after the completion of the reaction. In this washing, washing with water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight, etc.) is preferable in terms of easy washing operation. Washing is performed until the washed water layer becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate, molecular sieve, etc., if necessary, and then the solvent is removed, thereby obtaining polysiloxane. In addition, by reacting the obtained polysiloxane with a reactive compound (for example, a carboxylic acid having a photoalignment group, etc.), a polysiloxane having a reactive group can be obtained.
本發明的液晶配向劑中所含有的聚矽氧烷優選為利用GPC來測定的聚苯乙烯換算的重量平均分子量(Mw)在100~50,000的範圍內,更優選為在200~10,000的範圍內。若聚矽氧烷的重量平均分子量在所述範圍內,則在製造液晶配向膜時容易操作,另外,所得的液晶配向膜成為具有充分的材料強度以及特性者。The polysiloxane contained in the liquid crystal alignment agent of the present invention preferably has a polystyrene conversion weight average molecular weight (Mw) measured by GPC in the range of 100 to 50,000, and more preferably in the range of 200 to 10,000 . If the weight average molecular weight of the polysiloxane is within the above range, it is easy to handle when manufacturing the liquid crystal alignment film, and the obtained liquid crystal alignment film has sufficient material strength and characteristics.
在將所述其他聚合物添加於液晶配向劑中的情況下,相對於液晶配向劑中的全部聚合物100重量份,所述其他聚合物的調配比率優選為設為50重量份以下,更優選為設為0.1重量份~40重量份,尤其優選為設為0.1重量份~30重量份。In the case where the other polymer is added to the liquid crystal alignment agent, the blending ratio of the other polymer is preferably 50 parts by weight or less, more preferably, relative to 100 parts by weight of the total polymer in the liquid crystal alignment agent It is 0.1 weight part-40 weight part, Especially preferably, it is 0.1 weight part-30 weight part.
關於本發明的液晶配向劑中所含有的聚合物成分,優選態樣可列舉以下的態樣。 (I)僅含有聚合物(A)作為聚合物成分的態樣。 (II)含有聚合物(A)及其他聚合物作為聚合物成分,且其他聚合物為聚矽氧烷的態樣。With regard to the polymer component contained in the liquid crystal alignment agent of the present invention, the following aspects are preferable as examples. (I) An aspect that contains only the polymer (A) as a polymer component. (II) Containing polymer (A) and other polymers as polymer components, and the other polymers are polysiloxanes.
這些態樣中,就電特性良好的方面而言,優選為所述(II)的態樣。Among these aspects, the aspect (II) described above is preferable in terms of good electrical characteristics.
在使聚矽氧烷含有於液晶配向劑中的情況下,就獲得充分的印刷性及電特性的改善效果的觀點而言,相對於聚合物(A)的合計100重量份,所述聚矽氧烷的調配比率優選為設為0.5重量份~90重量份,更優選為設為1重量份~85重量份,尤其優選為設為3重量份~80重量份。 [含環氧基的化合物]When polysiloxane is contained in the liquid crystal alignment agent, from the viewpoint of obtaining sufficient printability and electrical characteristics improvement effects, relative to 100 parts by weight of the polymer (A) in total, the polysiloxane The blending ratio of the oxane is preferably 0.5 parts by weight to 90 parts by weight, more preferably 1 part by weight to 85 parts by weight, and particularly preferably 3 parts by weight to 80 parts by weight. [Epoxy-containing compounds]
含環氧基的化合物可用於提高液晶配向膜的與基板表面的黏接性。此處,含環氧基的化合物例如可列舉: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、三羥甲基丙烷三縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、N,N-二縮水甘油基-苄基胺、N,N-二縮水甘油基-胺基甲基環己烷、N,N-二縮水甘油基-環己基胺等。The epoxy-containing compound can be used to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. Here, the epoxy group-containing compound includes, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether Ether, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N, N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethyl Cyclohexane, N,N-diglycidyl-cyclohexylamine, etc.
在將這些環氧化合物添加於液晶配向劑中的情況下,相對於液晶配向劑中所含的聚合物的合計100重量份,所述環氧化合物的調配比率優選為40重量份以下,更優選為0.1重量份~30重量份。 [官能性矽烷化合物]In the case of adding these epoxy compounds to the liquid crystal alignment agent, the blending ratio of the epoxy compound is preferably 40 parts by weight or less, more preferably, relative to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent It is 0.1 parts by weight to 30 parts by weight. [Functional Silane Compound]
所述官能性矽烷化合物可出於提高液晶配向劑的印刷性的目的而使用。此種官能性矽烷化合物例如可列舉:3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-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、9-三甲氧基矽烷基-3,6-二氮雜壬酸甲酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、縮水甘油氧基甲基三甲氧基矽烷、2-縮水甘油氧基乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等。The functional silane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxy Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetic acid Ester, 9-trimethoxysilyl-3,6-diazanonanoate methyl ester, N-benzyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethyl Oxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc.
在將這些官能性矽烷化合物添加於液晶配向劑中的情況下,相對於聚合物的合計100重量份,所述官能性矽烷化合物的調配比率優選為2重量份以下,更優選為0.02重量份~0.2重量份。When these functional silane compounds are added to the liquid crystal alignment agent, the blending ratio of the functional silane compound is preferably 2 parts by weight or less, more preferably 0.02 parts by weight to 100 parts by weight in total of the polymer. 0.2 parts by weight.
本發明的液晶配向劑中的固體成分濃度(液晶配向劑的溶媒以外的成分的合計重量在液晶配向劑的總重量中所占的比例)可考慮到黏性、揮發性等來適當選擇,優選為1重量%~10重量%的範圍。即,本發明的液晶配向劑通過以後述方式塗布於基板表面,優選為進行加熱,從而形成作為液晶配向膜的塗膜或者成為液晶配向膜的塗膜。此時,在固體成分濃度小於1重量%的情況下,塗膜的膜厚變得過小而難以獲得良好的液晶配向膜。另一方面,在固體成分濃度超過10重量%的情況下,塗膜的膜厚變得過大而難以獲得良好的液晶配向膜,另外,液晶配向劑的黏性增大而塗布特性劣化。The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably It is in the range of 1% by weight to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate in the manner described below, preferably by heating, to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases and coating characteristics deteriorate.
特別優選的固體成分濃度的範圍根據在基板上塗布液晶配向劑時使用的方法而不同。例如在利用旋轉塗布法的情況下,固體成分濃度特別優選為1.5重量%~4.5重量%的範圍。在利用膠版印刷法的情況下,特別優選為將固體成分濃度設為3重量%~9重量%的範圍,由此將溶液黏度設為12 mPa·s~50 mPa·s的範圍。在利用噴墨印刷法的情況下,特別優選為將固體成分濃度設為1重量%~8重量%的範圍,由此將溶液黏度設為3 mPa·s~20 mPa·s的範圍。製備本發明的液晶配向劑時的溫度優選為10℃~50℃,更優選為20℃~30℃。 <液晶配向膜以及液晶顯示元件>The particularly preferable range of the solid content concentration varies depending on the method used when applying the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5% by weight to 4.5% by weight. In the case of using the offset printing method, it is particularly preferable to set the solid content concentration to the range of 3% by weight to 9% by weight, thereby setting the solution viscosity to the range of 12 mPa·s to 50 mPa·s. In the case of using the inkjet printing method, it is particularly preferable to set the solid content concentration to the range of 1% by weight to 8% by weight, thereby setting the solution viscosity to the range of 3 mPa·s to 20 mPa·s. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 10°C to 50°C, more preferably 20°C to 30°C. <Liquid crystal alignment film and liquid crystal display element>
本發明的液晶配向膜可利用以所述方式製備的液晶配向劑來形成。另外,本發明的液晶顯示元件包括使用本發明的液晶配向劑來形成的液晶配向膜。應用本發明的液晶顯示元件的驅動模式並無特別限定,可應用於TN型、STN型、IPS型、FFS型、VA型、MVA型等多種驅動模式。以下,對本發明的液晶顯示元件的製造方法進行說明,並且在其說明中對本發明的液晶配向膜的製造方法進行說明。The liquid crystal alignment film of the present invention can be formed using the liquid crystal alignment agent prepared in the manner described above. In addition, the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention. The driving mode of the liquid crystal display element to which the present invention is applied is not particularly limited, and can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, and MVA type. Hereinafter, the manufacturing method of the liquid crystal display element of the present invention will be described, and in the description, the manufacturing method of the liquid crystal alignment film of the present invention will be described.
本發明的液晶顯示元件例如可通過以下的(1)~(3)的步驟來製造。步驟(1)根據所需的驅動模式而使用不同的基板。步驟(2)及步驟(3)在各驅動模式中共用。 [步驟(1):塗膜的形成]The liquid crystal display element of the present invention can be manufactured by the following steps (1) to (3), for example. Step (1) Use different substrates according to the required drive mode. Steps (2) and (3) are shared in each drive mode. [Step (1): Formation of coating film]
首先,在基板上塗布本發明的液晶配向劑,繼而對塗布面進行加熱,由此在基板上形成塗膜。First, the liquid crystal alignment agent of the present invention is coated on the substrate, and then the coated surface is heated, thereby forming a coating film on the substrate.
(1-1)在製造TN型、STN型或者VA型液晶顯示元件的情況下,將兩塊設置有經圖案化的透明導電膜的基板作為一對,在所述基板的各透明導電膜的形成面上,優選為利用膠版印刷法、旋轉塗布法、輥塗布機法或者噴墨印刷法來分別塗布本發明的液晶配向劑。本發明的液晶配向劑在採用噴墨印刷法作為塗布方法的情況下,具有可發揮特別良好的塗布性(印刷性)的優點。(1-1) In the case of manufacturing a TN type, STN type or VA type liquid crystal display element, two substrates provided with a patterned transparent conductive film are used as a pair, and each transparent conductive film on the substrate On the forming surface, it is preferable to apply the liquid crystal alignment agent of the present invention separately by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. The liquid crystal alignment agent of the present invention has an advantage that it can exhibit particularly good coating properties (printability) when the inkjet printing method is adopted as the coating method.
此處,基板例如可使用:浮法玻璃、鈉玻璃等玻璃;包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚(脂環式烯烴)等塑膠的透明基板。設置於基板的其中一面的透明導電膜可使用包含氧化錫(SnO2 )的奈塞(NESA)膜(美國PPG公司註冊商標)、包含氧化銦-氧化錫(In2 O3 -SnO2 )的氧化銦錫(Indium Tin Oxide,ITO)膜等。為了獲得經圖案化的透明導電膜,例如可利用以下方法:形成無圖案的透明導電膜後,通過光蝕刻來形成圖案的方法;形成透明導電膜時使用具有所需圖案的遮罩的方法等。塗布液晶配向劑時,為了使基板表面以及透明導電膜與塗膜的黏接性更良好,也可以對基板表面中應形成塗膜的面,實施預先塗布官能性矽烷化合物、官能性鈦化合物等的預處理。Here, the substrate can be, for example, glass such as float glass and soda glass; including polyethylene terephthalate, polybutylene terephthalate, polyether alkene, polycarbonate, poly(alicyclic olefin) ) And other plastic transparent substrates. The transparent conductive film provided on one side of the substrate can use NESA film containing tin oxide (SnO 2 ) (registered trademark of PPG Corporation in the United States), or indium oxide-tin oxide (In 2 O 3 -SnO 2 ). Indium Tin Oxide (ITO) film, etc. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern; a method of using a mask with a desired pattern when forming a transparent conductive film, etc. . When applying the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate surface where the coating film should be formed can also be pre-coated with functional silane compounds, functional titanium compounds, etc. The pretreatment.
塗布液晶配向劑後,出於防止所塗布的配向劑的流掛等目的,優選為實施預加熱(預烘烤)。預烘烤溫度優選為30℃~200℃,更優選為40℃~150℃,特別優選為40℃~100℃。預烘烤時間優選為0.25分鐘~10分鐘,更優選為0.5分鐘~5分鐘。然後,出於將溶劑完全去除,視需要將存在於聚合物中的醯胺酸結構進行熱醯亞胺化的目的,而實施煅燒(後烘烤)步驟。該煅燒(後烘烤)溫度優選為80℃~300℃,更優選為120℃~250℃。後烘烤時間優選為5分鐘~200分鐘,更優選為10分鐘~100分鐘。以所述方式形成的膜的膜厚優選為0.001 μm~1 μm,更優選為0.005 μm~0.5 μm。After the liquid crystal alignment agent is applied, for the purpose of preventing sagging of the applied alignment agent, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30°C to 200°C, more preferably 40°C to 150°C, and particularly preferably 40°C to 100°C. The pre-baking time is preferably 0.25 minutes to 10 minutes, more preferably 0.5 minutes to 5 minutes. Then, for the purpose of completely removing the solvent and thermally imidizing the amide structure existing in the polymer as necessary, a calcination (post-baking) step is performed. The calcination (post-baking) temperature is preferably 80°C to 300°C, more preferably 120°C to 250°C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.
(1-2)在製造IPS型或FFS型液晶顯示元件的情況下,在基板的設置有包含經圖案化為梳齒型的透明導電膜或者金屬膜的電極的電極形成面、與未設置電極的對向基板的一面,分別塗布本發明的液晶配向劑,繼而對各塗布面進行加熱,由此形成塗膜。此時所使用的基板以及透明導電膜的材質、塗布方法、塗布後的加熱條件、透明導電膜或者金屬膜的圖案化方法、基板的預處理以及所形成的塗膜的優選膜厚與所述(1-1)相同。金屬膜可使用例如包含鉻等金屬的膜。(1-2) In the case of manufacturing IPS-type or FFS-type liquid crystal display elements, the electrode formation surface of the substrate is provided with electrodes including a transparent conductive film or a metal film patterned into a comb tooth shape, and the electrode is not provided. On one side of the opposed substrate, the liquid crystal alignment agent of the present invention is respectively coated, and then each coated surface is heated, thereby forming a coating film. At this time, the material of the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are as described above. (1-1) Same. As the metal film, for example, a film containing metal such as chromium can be used.
在所述(1-1)及(1-2)的任一種情況下,均通過在基板上塗布液晶配向劑後,去除有機溶媒而形成成為配向膜的塗膜。此時,在本發明的液晶配向劑中所含有的聚合物為聚醯胺酸,或為聚醯胺酸酯,或者是具有醯亞胺環結構及醯胺酸結構的醯亞胺化聚合物的情況下,也可通過在塗膜形成後進一步加熱而進行脫水閉環反應,從而形成進一步經醯亞胺化的塗膜。 [步驟(I-2):配向能力賦予處理]In any of the above (1-1) and (1-2), after applying a liquid crystal alignment agent on the substrate, the organic solvent is removed to form a coating film that becomes an alignment film. In this case, the polymer contained in the liquid crystal alignment agent of the present invention is polyamide acid, or polyamide acid ester, or an amide polymer having an amide ring structure and an amide acid structure. In the case of the coating film, it is also possible to perform a dehydration ring-closure reaction by further heating after the coating film is formed, thereby forming a coating film that is further imidized. [Step (I-2): Alignment ability grant processing]
在製造TN型、STN型、IPS型或者FFS型液晶顯示元件的情況下,實施對所述步驟(I-1)中形成的塗膜賦予液晶配向能力的處理。由此,液晶分子的配向能力被賦予至塗膜而成為液晶配向膜。賦予液晶配向能力的處理可列舉摩擦處理及光配向處理等,所述摩擦處理利用捲繞有包含例如尼龍、人造絲、棉等纖維的布的輥,將塗膜向一定方向擦拭;所述光配向處理對塗膜照射偏光或者非偏光的放射線。另一方面,在製造VA型液晶顯示元件的情況下,可將所述步驟(I-1)中形成的塗膜直接用作液晶配向膜,但也可以對該塗膜實施配向能力賦予處理。In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a process of imparting liquid crystal alignment ability to the coating film formed in the step (I-1) is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. The treatment for imparting liquid crystal alignment ability includes rubbing treatment and photo-alignment treatment. The rubbing treatment uses a roller wound with a cloth containing fibers such as nylon, rayon, cotton, etc., to wipe the coating film in a certain direction; The alignment treatment irradiates the coating film with polarized or non-polarized radiation. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (I-1) can be directly used as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
在光配向處理中,對塗膜照射的放射線例如可使用包含150 nm~800 nm波長的光的紫外線以及可見光線。在放射線為偏光的情況下,可以是直線偏光,也可以是部分偏光。另外,在所使用的放射線為直線偏光或者部分偏光的情況下,可自垂直的方向對基板面進行照射,也可以自傾斜方向進行照射,或者還可以將這些照射組合進行。在照射非偏光的放射線的情況下,照射的方向設為傾斜方向。In the photo-alignment process, the radiation irradiated to the coating film can use, for example, ultraviolet rays and visible rays including light with a wavelength of 150 nm to 800 nm. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, the substrate surface may be irradiated from a vertical direction, may be irradiated from an oblique direction, or these irradiations may be combined. In the case of irradiating non-polarized radiation, the direction of irradiation is an oblique direction.
所使用的光源例如可使用:低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、準分子雷射等。優選的波長區域的紫外線可通過將光源與例如濾光器、繞射光柵等併用的方法等而獲得。放射線的照射量優選為100 J/m2 ~50,000 J/m2 ,更優選為300 J/m2 ~20,000 J/m2 。另外,為了提高反應性,也可以一邊對塗膜加溫一邊對塗膜進行光照射。加溫時的溫度通常為30℃~250℃,優選為40℃~200℃,更優選為50℃~150℃。As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet rays in a preferred wavelength range can be obtained by a method of using a light source in combination with, for example, an optical filter and a diffraction grating. The radiation dose is preferably 100 J/m 2 to 50,000 J/m 2 , and more preferably 300 J/m 2 to 20,000 J/m 2 . In addition, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. The temperature during heating is usually 30°C to 250°C, preferably 40°C to 200°C, and more preferably 50°C to 150°C.
此外,也可以對摩擦處理後的液晶配向膜進一步進行以下處理,以使液晶配向膜在每個區域具有不同的液晶配向能力:通過對液晶配向膜的一部分照射紫外線,而使液晶配向膜的一部分區域的預傾角變化的處理;或在液晶配向膜表面的一部分形成抗蝕劑膜後,在與剛才的摩擦處理不同的方向上進行摩擦處理後,將抗蝕劑膜去除的處理。該情況下,能夠改善所得的液晶顯示元件的視野特性。適合於VA型液晶顯示元件的液晶配向膜也可以適合用於聚合物穩定配向(Polymer sustained alignment,PSA)型液晶顯示元件。 [步驟(3):液晶單元的構築]In addition, the liquid crystal alignment film after the rubbing treatment can be further subjected to the following treatment to make the liquid crystal alignment film have different liquid crystal alignment capabilities in each region: by irradiating a part of the liquid crystal alignment film with ultraviolet rays, a part of the liquid crystal alignment film The process of changing the pretilt angle of the region; or the process of removing the resist film after forming a resist film on a part of the surface of the liquid crystal alignment film and then performing a rubbing treatment in a direction different from the previous rubbing treatment. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. The liquid crystal alignment film suitable for VA-type liquid crystal display elements can also be suitably used for polymer sustained alignment (PSA)-type liquid crystal display elements. [Step (3): Construction of the liquid crystal cell]
準備兩塊以所述方式形成有液晶配向膜的基板,在對向配置的兩塊基板間配置液晶,由此製造液晶單元。為了製造液晶單元,例如可列舉以下的兩種方法。Two substrates on which the liquid crystal alignment film is formed in the manner described above are prepared, and liquid crystals are arranged between the two substrates arranged opposite to each other, thereby manufacturing a liquid crystal cell. To manufacture the liquid crystal cell, for example, the following two methods can be cited.
第一方法為以前已知的方法。首先,以各個液晶配向膜對向的方式,經由間隙(單元間隙)而將兩塊基板對向配置,使用密封劑將兩塊基板的周邊部貼合,在由基板表面以及密封劑所劃分的單元間隙內注入填充液晶後,將注入孔密封,由此可製造液晶單元。另外,第二方法為稱為液晶滴注(One Drop Fill,ODF)方式的方法。在形成有液晶配向膜的兩塊基板中的其中一塊基板上的既定部位,例如塗布紫外光硬化性的密封材,進而在液晶配向膜面上的既定的數個部位滴加液晶後,以液晶配向膜對向的方式貼合另一塊基板,並且使液晶在基板的整個面上鋪開,繼而對基板的整個面照射紫外光而使密封劑硬化,由此可製造液晶單元。在利用任一種方法的情況下,均理想為對以所述方式製造的液晶單元,進而加熱至所使用的液晶取得各向同性相的溫度為止,然後緩緩冷卻至室溫,由此消除液晶填充時的流動配向。The first method is a previously known method. First, the two substrates are arranged to face each other through a gap (cell gap) in such a way that the respective liquid crystal alignment films are opposed to each other, and the peripheral parts of the two substrates are bonded using a sealant. After injecting and filling the liquid crystal into the cell gap, the injection hole is sealed, so that a liquid crystal cell can be manufactured. In addition, the second method is a method called One Drop Fill (ODF) method. On a predetermined part of one of the two substrates on which the liquid crystal alignment film is formed, for example, a UV-curable sealing material is coated, and then liquid crystal is dropped on a predetermined number of positions on the liquid crystal alignment film surface, and then the liquid crystal The alignment film is bonded to another substrate in an opposing manner, and the liquid crystal is spread on the entire surface of the substrate, and then ultraviolet light is irradiated to the entire surface of the substrate to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using either method, it is ideal to heat the liquid crystal cell manufactured in the above manner until the temperature at which the liquid crystal used obtains the isotropic phase, and then slowly cool to room temperature, thereby eliminating the liquid crystal Flow alignment during filling.
作為密封劑,例如可使用含有硬化劑以及作為間隔物的氧化鋁球的環氧樹脂等。As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used.
液晶可列舉向列型液晶以及層列型液晶,其中優選為向列型液晶,例如可使用:希夫鹼(Schiff base)系液晶、氧化偶氮(azoxy)系液晶、聯苯系液晶、苯基環己烷系液晶、酯系液晶、三聯苯系液晶、聯苯基環己烷系液晶、嘧啶系液晶、二噁烷系液晶、雙環辛烷系液晶、立方烷(cubane)系液晶等。另外,也可以在這些液晶中添加以下物質來使用:例如氯化膽甾醇(cholesteryl chloride)、膽甾醇壬酸酯(cholesteryl nonanoate)、膽甾醇碳酸酯(cholesteryl carbonate)等膽甾醇液晶(cholesteric liquid crystal);以商品名「C-15」、「CB-15」(默克(Merck)公司製造)來銷售的手性劑;對癸氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯等鐵電液晶等。The liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, and benzene can be used. Cyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubane-based liquid crystal, etc. In addition, the following substances can also be added to these liquid crystals for use: for example, cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate and other cholesteric liquid crystals. ); chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl Ferroelectric liquid crystals such as cinnamate.
然後,可通過在液晶單元的外側表面貼合偏光板來獲得本發明的液晶顯示元件。貼合於液晶單元的外表面的偏光板可列舉:以乙酸纖維素保護膜夾持被稱為「H膜」的偏光膜而成的偏光板或者包含H膜其本身的偏光板,所述「H膜」是使聚乙烯醇一邊延伸配向一邊吸收碘而成的膜。此外,在對塗膜進行摩擦處理的情況下,兩塊基板是以各塗膜中的摩擦方向彼此形成既定的角度,例如正交或者反平行的方式對向配置。Then, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include: a polarizing plate formed by sandwiching a polarizing film called "H film" with a cellulose acetate protective film or a polarizing plate containing the H film itself. "H film" is a film formed by absorbing iodine while extending and aligning polyvinyl alcohol. In addition, when the coating film is rubbed, the two substrates are arranged so that the rubbing direction in each coating film forms a predetermined angle with each other, for example, orthogonal or antiparallel.
本發明的液晶顯示元件可有效地應用於多種裝置,例如可用於:桌上型電腦、手錶、座鐘、手機、計數顯示板、文字處理器、個人電腦、液晶電視、便攜型遊戲機、汽車導航系統、攝錄機、個人數位助理(Personal Digital Assistant,PDA)、數位照相機、智慧手機、各種監視器等的顯示裝置。 [實施例]The liquid crystal display element of the present invention can be effectively applied to various devices, such as: desktop computers, watches, desk clocks, mobile phones, counter display panels, word processors, personal computers, LCD TVs, portable game consoles, car navigation Display devices for systems, camcorders, personal digital assistants (PDAs), digital cameras, smart phones, various monitors, etc. [Example]
以下,通過實施例,對本發明進一步進行具體說明,但本發明並不限定於這些實施例。 [聚合物的重量平均分子量]Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited to these examples. [Weight average molecular weight of polymer]
重量平均分子量Mw是利用以下條件下的凝膠滲透層析法來測定的聚苯乙烯換算值。 管柱:東曹(Tosoh)(股)製造,TSKgelGRCXLII 溶劑:四氫呋喃 溫度:40℃ 壓力:68 kgf/cm2 [聚合物溶液的溶液黏度]The weight average molecular weight Mw is a polystyrene conversion value measured by gel permeation chromatography under the following conditions. Column: manufactured by Tosoh (Stock), TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40℃ Pressure: 68 kgf/cm 2 [Solution viscosity of polymer solution]
聚合物溶液的溶液黏度[mPa·s]是對使用既定的溶媒而製備成聚合物濃度10重量%的溶液,利用E型旋轉黏度計,在25℃下測定。The solution viscosity [mPa·s] of the polymer solution is a solution prepared with a polymer concentration of 10% by weight using a predetermined solvent, and measured at 25° C. with an E-type rotary viscometer.
此外,以下實施例中使用的原料化合物以及聚合物的需要量是通過視需要重複進行下述合成例中所示的合成規模下的原料化合物以及聚合物的合成來確保。 [聚醯胺酸的合成] [合成例1]In addition, the required amounts of raw material compounds and polymers used in the following examples are ensured by repeating the synthesis of the raw material compounds and polymers on the synthesis scale shown in the following synthesis examples as necessary. [Synthesis of Polyamide Acid] [Synthesis Example 1]
將作為四羧酸二酐的112 g(0.50莫耳)的2,3,5-三羧基環戊基乙酸二酐及157 g(0.50莫耳)的1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮,以及作為二胺化合物的95 g(0.88莫耳)的對苯二胺、32 g(0.10莫耳)的2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、6.4 g(0.010莫耳)的3,6-雙(4-胺基苯甲醯氧基)膽甾烷及4.0 g(0.015莫耳)的十八烷氧基-2,5-二胺基苯,溶解於960 g的N-甲基-2-吡咯烷酮中,在60℃下進行9小時反應。將所得的聚醯胺酸溶液(PA-1)分取少量,添加N-甲基-2-吡咯烷酮而製成濃度為10重量%的溶液,測定而得的溶液黏度為58 mPa·s。 [具有環氧基的聚有機矽氧烷的合成] [合成例2]Combine 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 157 g (0.50 mol) of 1,3,3a,4,5,9b -Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, and as Diamine compound 95 g (0.88 mol) of p-phenylenediamine, 32 g (0.10 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 6.4 g (0.010 mol) of 3,6-bis(4-aminobenzyloxy)cholestane and 4.0 g (0.015 mol) of octadecyloxy-2,5-diaminobenzene, It was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60°C for 9 hours. The obtained polyamide acid solution (PA-1) was aliquoted in a small amount, and N-methyl-2-pyrrolidone was added to prepare a solution with a concentration of 10% by weight. The measured viscosity of the solution was 58 mPa·s. [Synthesis of polyorganosiloxane having epoxy group] [Synthesis Example 2]
在具備攪拌機、溫度計、滴加漏斗及回流冷卻管的反應容器中,加入100.0 g的2-(3,4-環氧基環己基)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane,ECETS)、500 g的甲基異丁基酮以及10.0 g的三乙基胺,在室溫下進行混合。繼而,自滴加漏斗中花30分鐘滴加100 g的去離子水後,一邊在回流下進行混合,一邊在80℃下進行6小時反應。反應結束後,取出有機層,利用0.2重量%的硝酸銨水溶液洗滌至洗滌後的水成為中性為止,然後在減壓下蒸餾去除溶媒及水,由此以黏稠的透明液體的形式獲得具有環氧基的聚有機矽氧烷。 [光配向性聚有機矽氧烷的合成] [合成例3]In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux cooling tube, add 100.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane (2-(3,4-epoxycyclohexyl) ) ethyl trimethoxy silane, ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, mixed at room temperature. Then, 100 g of deionized water was dropped into the dropping funnel for 30 minutes, and the reaction was carried out at 80°C for 6 hours while mixing under reflux. After the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid with a ring Oxy-based polyorganosiloxane. [Synthesis of photoalignment polyorganosiloxane] [Synthesis Example 3]
在100 mL的三口燒瓶中,加入9.3 g的所述合成例2中獲得的具有環氧基的聚有機矽氧烷、26 g的甲基異丁基酮、3 g的下述肉桂酸衍生物(K-1)以及0.10 g的商品名「UCAT 18X」(三亞普羅(San-Apro)(股)製造的四級胺鹽),在80℃下攪拌12小時。反應結束後,以甲醇進行再沉澱,將沉澱物溶解於乙酸乙酯而獲得溶液,將該溶液水洗3次後,蒸餾去除溶劑,由此以白色粉末的形式獲得6.3 g的光配向性聚有機矽氧烷化合物(S-1)。光配向性聚有機矽氧烷化合物(S-1)的重量平均分子量Mw為3,500。 [化3][合成例4]In a 100 mL three-necked flask, 9.3 g of the epoxy-containing polyorganosiloxane obtained in Synthesis Example 2, 26 g of methyl isobutyl ketone, and 3 g of the following cinnamic acid derivative were added (K-1) and 0.10 g of the trade name "UCAT 18X" (quaternary amine salt manufactured by San-Apro Co., Ltd.), stirred at 80°C for 12 hours. After the reaction, reprecipitate with methanol and dissolve the precipitate in ethyl acetate to obtain a solution. After washing the solution three times with water, the solvent was distilled off to obtain 6.3 g of photo-aligned polyorganic in the form of white powder. Siloxane compound (S-1). The weight average molecular weight Mw of the photo-alignable polyorganosiloxane compound (S-1) is 3,500. [化3] [Synthesis Example 4]
(化合物(K-2)的合成) [化4] (Synthesis of Compound (K-2)) [Chemical 4]
在具備回流管及氮氣導入管的100 mL茄型燒瓶中添加4.63 g的化合物(A-1)、50 mL的亞硫醯氯以及0.05 mL的N,N-二甲基甲醯胺,回流1小時。反應結束後,通過減壓濃縮而使其乾固後,添加75 mL的四氫呋喃(作為(A-2)液)。另一方面,在具備溫度計及氮氣導入管的100 mL三口燒瓶中添加2.62 g的4-羥基肉桂酸、4.41 g的碳酸鉀、38 mL的水、19 mL的四氫呋喃以及0.15 g的溴化四丁基銨,冰浴冷卻至5℃以下。繼而,花30分鐘添加剛才製備的(A-2液)後,恢復至室溫,攪拌4小時。反應結束後,添加100 mL的乙酸乙酯以及200 mL的1N鹽酸水來洗滌,然後以100 mL的水進行3次分液洗滌。接著,將有機層以硫酸鎂乾燥後,進行過濾、減壓濃縮,將析出的白色結晶進行過濾、乾燥而獲得1.8 g的化合物(K-2)。 [合成例5]Add 4.63 g of compound (A-1), 50 mL of thionyl chloride and 0.05 mL of N,N-dimethylformamide to a 100 mL eggplant-shaped flask equipped with a reflux tube and nitrogen inlet tube, and reflux 1 hour. After the reaction was completed, it was dried by concentration under reduced pressure, and then 75 mL of tetrahydrofuran (as (A-2) liquid) was added. On the other hand, add 2.62 g of 4-hydroxycinnamic acid, 4.41 g of potassium carbonate, 38 mL of water, 19 mL of tetrahydrofuran, and 0.15 g of tetrabutyl bromide to a 100 mL three-necked flask equipped with a thermometer and nitrogen introduction tube. Base ammonium, cooled in an ice bath to below 5°C. Then, after adding the just prepared (A-2 liquid) over 30 minutes, it returned to room temperature and stirred for 4 hours. After the reaction, 100 mL of ethyl acetate and 200 mL of 1N hydrochloric acid water were added for washing, and then 100 mL of water was used for 3 separate washing. Next, after drying the organic layer with magnesium sulfate, it filtered and concentrated under reduced pressure, and the precipitated white crystal was filtered and dried, and 1.8 g of compound (K-2) was obtained. [Synthesis Example 5]
(化合物(K-3)的合成) [化5] (Synthesis of Compound (K-3)) [Chemical 5]
在加入了攪拌子的300 mL三口燒瓶中加入5.09 g的氯化鋰、1.64 g的氯化鋅,進行氮氣置換。在其中添加120 mL的伸乙基氯化鎂-四氫呋喃1 mol/L溶液,在室溫下攪拌1小時後,冷卻至0℃,在其中滴加12.6 g的環辛酮,在室溫下進行15小時反應(作為(A-5)液)。然後,一邊進行冰浴一邊將飽和氯化銨水溶液滴加於(A-5)液中,添加300 mL的乙酸乙酯。將有機層以300 mL的水進行3次分液洗滌後,利用硫酸鎂將有機層乾燥。然後,通過利用旋轉蒸發器進行濃縮,蒸餾去除溶媒,將殘渣進行蒸餾,由此獲得11.7 g的化合物(A-3)。Into a 300 mL three-necked flask containing a stir bar, 5.09 g of lithium chloride and 1.64 g of zinc chloride were added, and nitrogen replacement was performed. Add 120 mL of ethylene magnesium chloride-tetrahydrofuran 1 mol/L solution, stir at room temperature for 1 hour, then cool to 0°C, add 12.6 g of cyclooctanone dropwise to it, and continue at room temperature for 15 hours Reaction (as (A-5) solution). Then, while performing an ice bath, a saturated aqueous ammonium chloride solution was added dropwise to the solution (A-5), and 300 mL of ethyl acetate was added. After the organic layer was separated and washed with 300 mL of water three times, the organic layer was dried with magnesium sulfate. Then, by concentrating with a rotary evaporator, the solvent was distilled off, and the residue was distilled to obtain 11.7 g of compound (A-3).
在加入了攪拌子的300 mL三口燒瓶中,加入10.9 g的化合物(A-3),冰浴至0℃。向其中滴加134 mL的正丁基鋰-己烷1.6 mol/L溶液,在0℃下攪拌20分鐘後,滴加在30 mL的四氫呋喃中溶解有13.9 g的4-(氯羰基)苯甲酸甲酯的溶液,在0℃下攪拌2小時。向其中滴加5 mL的水,添加200 mL的乙酸乙酯。將有機層以300 mL的水進行3次分液洗滌後,利用硫酸鎂使有機層乾燥。然後,通過利用旋轉蒸發器進行濃縮而獲得13.4 g的化合物(A-4)。In a 300 mL three-necked flask with a stir bar, add 10.9 g of compound (A-3), and ice-bath to 0°C. 134 mL of n-butyllithium-hexane 1.6 mol/L solution was added dropwise, after stirring at 0°C for 20 minutes, 13.9 g of 4-(chlorocarbonyl)benzoic acid was dissolved in 30 mL of tetrahydrofuran. The methyl ester solution was stirred at 0°C for 2 hours. 5 mL of water was added dropwise, and 200 mL of ethyl acetate was added. After the organic layer was separated and washed with 300 mL of water three times, the organic layer was dried with magnesium sulfate. Then, 13.4 g of the compound (A-4) was obtained by concentration using a rotary evaporator.
在加入了攪拌子的100 mL三口燒瓶中,添加9.55 g的化合物(A-4)、30 g的甲醇、10 g的水、2.52 g的氫氧化鋰一水合物,在室溫下攪拌1小時後,在反應液中添加50 mL的乙酸乙酯。將有機層以10 mL的稀鹽酸進行1次分液洗滌,以50 mL的水進行3次分液洗滌後,利用硫酸鎂使有機層乾燥。然後,利用旋轉蒸發器進行濃縮,緩緩濃縮至內容量成為20 g為止,通過過濾來回收中途析出的白色固體。通過對該白色固體進行真空乾燥而獲得5.5 g的化合物(K-3)。 [合成例6]In a 100 mL three-necked flask with a stir bar, add 9.55 g of compound (A-4), 30 g of methanol, 10 g of water, and 2.52 g of lithium hydroxide monohydrate, and stir at room temperature for 1 hour Then, 50 mL of ethyl acetate was added to the reaction solution. The organic layer was separated and washed with 10 mL of dilute hydrochloric acid once, and was separated and washed with 50 mL of water three times, and then the organic layer was dried with magnesium sulfate. Then, it was concentrated by a rotary evaporator and gradually concentrated until the content became 20 g, and the white solid precipitated in the middle was recovered by filtration. The white solid was vacuum-dried to obtain 5.5 g of compound (K-3). [Synthesis Example 6]
在100 mL的三口燒瓶中,加入9.3 g的所述合成例2中獲得的具有環氧基的聚有機矽氧烷、26 g的甲基異丁基酮、5.8 g的所述合成例4中獲得的化合物(K-2)以及0.10 g的商品名「UCAT 18X」(三亞普羅(San-Apro)(股)製造的四級胺鹽),在80℃下攪拌12小時。反應結束後,以甲醇進行再沉澱,將沉澱物溶解於乙酸乙酯中而獲得溶液,將該溶液進行3次水洗後,蒸餾去除溶劑,由此以白色粉末的形式獲得9.1 g的光配向性聚有機矽氧烷化合物(S-2)。光配向性聚有機矽氧烷化合物(S-2)的重量平均分子量Mw為3,600。 [合成例7]In a 100 mL three-necked flask, 9.3 g of the epoxy-containing polyorganosiloxane obtained in Synthesis Example 2, 26 g of methyl isobutyl ketone, and 5.8 g of Synthesis Example 4 were added The obtained compound (K-2) and 0.10 g of the trade name "UCAT 18X" (quaternary amine salt manufactured by San-Apro Co., Ltd.) were stirred at 80°C for 12 hours. After the reaction, reprecipitate with methanol and dissolve the precipitate in ethyl acetate to obtain a solution. After washing the solution with water three times, the solvent was distilled off to obtain 9.1 g of optical alignment in the form of white powder Polyorganosiloxane compound (S-2). The weight average molecular weight Mw of the photo-alignable polyorganosiloxane compound (S-2) is 3,600. [Synthesis Example 7]
在100 mL的三口燒瓶中,加入9.3 g的所述合成例2中獲得的具有環氧基的聚有機矽氧烷、26 g的甲基異丁基酮、5.8 g的所述合成例4中獲得的(K-2)、1.8 g的所述合成例5中獲得的(K-3)以及0.10 g的商品名「UCAT 18X」(三亞普羅(San-Apro)(股)製造的四級胺鹽),在80℃下攪拌12小時。反應結束後,以甲醇進行再沉澱,將沉澱物溶解於乙酸乙酯中而獲得溶液,將該溶液進行3次水洗後,蒸餾去除溶劑,由此以白色粉末的形式獲得6.3 g的光配向性聚有機矽氧烷化合物(S-3)。光配向性聚有機矽氧烷化合物(S-3)的重量平均分子量Mw為3,500。 [實施例1]In a 100 mL three-necked flask, 9.3 g of the epoxy-containing polyorganosiloxane obtained in Synthesis Example 2, 26 g of methyl isobutyl ketone, and 5.8 g of Synthesis Example 4 were added (K-2) obtained, 1.8 g of (K-3) obtained in Synthesis Example 5, and 0.10 g of the trade name "UCAT 18X" (quaternary amine manufactured by San-Apro (Stock) Salt) and stirred at 80°C for 12 hours. After the reaction, reprecipitate with methanol and dissolve the precipitate in ethyl acetate to obtain a solution. After washing the solution with water three times, the solvent was distilled off to obtain 6.3 g of photo-alignment in the form of white powder Polyorganosiloxane compound (S-3). The weight average molecular weight Mw of the photo-alignable polyorganosiloxane compound (S-3) is 3,500. [Example 1]
在所述合成例1中獲得的聚醯胺酸溶液(PA-1)中,相對於聚醯胺酸100重量份而添加8重量份的合成例3中獲得的光配向性聚有機矽氧烷(S-1),進而添加N-甲基-2-吡咯烷酮、二乙二醇異丙基甲醚,製成溶劑組成為N-甲基-2-吡咯烷酮:二乙二醇異丙基甲醚=30:70(重量比)、固體成分濃度為3.0%的溶液。利用孔徑為0.2 μm的過濾器將所述溶液進行過濾,然後提供給以下的評價。 <噴墨塗布性的評價>In the polyamide acid solution (PA-1) obtained in the synthesis example 1, 8 parts by weight of the photo-aligned polyorganosiloxane obtained in the synthesis example 3 were added to 100 parts by weight of the polyamide acid (S-1), and then add N-methyl-2-pyrrolidone and diethylene glycol isopropyl methyl ether to make a solvent composition of N-methyl-2-pyrrolidone: diethylene glycol isopropyl methyl ether = 30: 70 (weight ratio), a solution with a solid content of 3.0%. The solution was filtered with a filter with a pore size of 0.2 μm, and then provided for the following evaluation. <Evaluation of inkjet coating properties>
作為塗布液晶配向劑的基板,使用將帶有包含ITO的透明電極的玻璃基板在200℃的加熱板上加熱1分鐘,繼而進行紫外線/臭氧洗滌,使透明電極面的水的接觸角成為10°以下之後不久的基板。As a substrate coated with a liquid crystal alignment agent, a glass substrate with a transparent electrode containing ITO was heated on a hot plate at 200°C for 1 minute, followed by ultraviolet/ozone washing, so that the contact angle of water on the transparent electrode surface was 10° Following the substrate shortly after.
使用噴墨塗布機(芝浦機電(Shibaura Mechatronics)(股)製造),將所述製備的液晶配向劑(過濾後的液晶配向劑)塗布於所述帶有透明電極的玻璃基板的透明電極面上。此時的塗布條件設為:在2,500次/(噴嘴·分鐘)、噴出量250 mg/10秒下塗布兩個往返(計4次)。在塗布後靜置1分鐘後,進行加熱,由此形成平均膜厚為0.1 μm的塗膜。對於所得的塗膜,在干涉條紋測量燈(鈉燈)的照射下,以肉眼進行觀察,進行不均以及凹陷的評價。加熱溫度設為50℃、60℃、80℃,將在任一溫度下均未發現不均及凹陷這兩者的情況作為噴墨塗布性「良好A(◎)」,在其中一個加熱溫度下發現不均及/或凹陷的情況作為「良好B(○)」,將在兩個加熱溫度下發現不均及/或凹陷的情況作為「可(△)」,將在所有加熱溫度下發現不均及/或凹陷的情況作為「不良(×)」。該實施例的液晶配向劑的噴墨塗布性為「良好B(○)」。 <液晶單元的製造>Use an inkjet coater (manufactured by Shibaura Mechatronics (stock)) to coat the prepared liquid crystal alignment agent (filtered liquid crystal alignment agent) on the transparent electrode surface of the glass substrate with transparent electrodes . The coating conditions at this time were as follows: two reciprocating coatings (4 times in total) at 2,500 times/(nozzle·min) and a discharge amount of 250 mg/10 seconds. After being allowed to stand for 1 minute after coating, heating was performed to form a coating film having an average film thickness of 0.1 μm. The obtained coating film was observed with the naked eye under the irradiation of an interference fringe measuring lamp (sodium lamp), and the evaluation of unevenness and depression was performed. The heating temperature was set to 50°C, 60°C, and 80°C, and the case where neither unevenness nor depression was found at any temperature was regarded as inkjet coatability "good A (◎)", and it was found at one of the heating temperatures Unevenness and/or dents are regarded as "good B (○)", and the situation where unevenness and/or dents are found at two heating temperatures is regarded as "possible (△)", and unevenness will be found at all heating temperatures And/or dents are regarded as "bad (×)". The inkjet coatability of the liquid crystal alignment agent of this example was "good B (○)". <Manufacture of liquid crystal cell>
以如下方式製造用以進行液晶配向性以及電壓保持率的評價的液晶單元。此外,在液晶單元的製造中,利用旋轉塗布法來進行液晶配向劑的塗布,其原因在於可與噴墨塗布性差的後述比較例進行比較。The liquid crystal cell used for evaluation of liquid crystal orientation and voltage retention was manufactured in the following manner. In addition, in the manufacture of the liquid crystal cell, the spin coating method is used to apply the liquid crystal alignment agent. The reason for this is that it can be compared with a comparative example described later, which has poor inkjet coating properties.
利用旋轉塗布法,將所述製備的液晶配向劑(過濾後的液晶配向劑)塗布於帶有包含ITO膜的透明電極的玻璃基板的透明電極面上,在80℃的加熱板上預烘烤1分鐘,繼而在200℃的加熱板上後烘烤10分鐘,由此形成平均膜厚為0.1 μm的塗膜。重複相同的操作,製造一對(兩塊)在透明導電膜上具有塗膜的基板。然後,對具有塗膜的一側的基板表面,使用Hg-Xe燈以及格蘭泰勒棱鏡(Glan-Taylor prism),自基板面的垂直方向照射1,000 J/m2 的偏光紫外線,獲得具有膜厚為0.1 μm的液晶配向膜的一對基板。Using the spin coating method, the prepared liquid crystal alignment agent (filtered liquid crystal alignment agent) was coated on the transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film, and pre-baked on a hot plate at 80°C For 1 minute, then post-baking on a hot plate at 200°C for 10 minutes, thereby forming a coating film with an average film thickness of 0.1 μm. Repeat the same operation to produce a pair (two) of substrates with a coating film on the transparent conductive film. Then, using Hg-Xe lamp and Glan-Taylor prism on the substrate surface on the side with the coating film, irradiate 1,000 J/m 2 of polarized ultraviolet rays from the vertical direction of the substrate surface to obtain a film thickness It is a pair of substrates of 0.1 μm liquid crystal alignment film.
在所述一對基板的具有液晶配向膜的各個外緣,塗布加入有直徑為5.5 μm的氧化鋁球的環氧樹脂黏接劑後,以液晶配向膜面相對的方式重疊壓接,使黏接劑硬化。繼而,自液晶注入口向一對基板間填充向列型液晶(默克(Merck)公司製造,MLC-6601)後,利用丙烯酸系光硬化黏接劑將液晶注入口密封,由此製造液晶單元。 <電壓保持率的評價>After coating each outer edge of the pair of substrates with a liquid crystal alignment film with an epoxy resin adhesive added with an alumina ball with a diameter of 5.5 μm, the liquid crystal alignment film faces are overlapped and pressed together to make the adhesive The adhesive hardens. Then, a nematic liquid crystal (MLC-6601, manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port is sealed with an acrylic light-curing adhesive, thereby manufacturing a liquid crystal cell . <Evaluation of voltage holding rate>
對於所述獲得的液晶單元,以60微秒的施加時間、167毫秒的跨度來施加5 V的電壓後,測定自施加解除起167毫秒後的電壓保持率。測定裝置是使用東陽特克尼卡(Toyo Technica)(股)製造的VHR-1。將該值為95%以上的情況評價為電壓保持率「良好A(◎)」,將小於95%且93%以上的情況評價為電壓保持率「良好B(○)」,將小於93%的情況評價為電壓保持率「可(△)」,將無法評價的情況評價為電壓保持率「不良(×)」,結果為,該實施例的液晶單元的電壓保持率為「良好(◎)」。 [實施例2~實施例11以及比較例1~比較例4、比較例6]To the obtained liquid crystal cell, after applying a voltage of 5 V with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention rate after 167 milliseconds from the release of the application was measured. The measuring device used VHR-1 manufactured by Toyo Technica (stock). The case where the value is 95% or more is evaluated as the voltage retention rate "good A (◎)", the case where the value is less than 95% and 93% or more is evaluated as the voltage retention rate "good B (○)", and the voltage retention rate is less than 93% The case was evaluated as the voltage retention rate "acceptable (△)", and the case that could not be evaluated was evaluated as the voltage retention rate "bad (×)". As a result, the voltage retention rate of the liquid crystal cell of this example was "good (◎)" . [Example 2 to Example 11 and Comparative Example 1 to Comparative Example 4, and Comparative Example 6]
除了在所述實施例1中,分別使用下述表1中所示的種類·量的聚合物及溶劑以外,以與實施例1相同的方式製備液晶配向劑,並且進行各種評價。評價結果示於下述表1中。 [實施例12以及比較例5]A liquid crystal alignment agent was prepared in the same manner as in Example 1, except that the types and amounts of polymers and solvents shown in Table 1 below were used in Example 1, and various evaluations were performed. The evaluation results are shown in Table 1 below. [Example 12 and Comparative Example 5]
除了在所述實施例1中,分別使用下述表1中所示的種類·量的聚合物及溶劑的方面,以及在製造液晶單元時進行摩擦處理來代替光配向處理的方面以外,以與實施例1相同的方式製備液晶配向劑,並且進行各種評價。使用具有捲繞有尼龍製布的輥的摩擦機器,以輥的轉數1,000 rpm、平臺的移動速度25 mm/秒、毛壓入長度0.4 mm來進行摩擦處理。評價結果示於下述表1中。Except for the aspects of using the types and amounts of polymers and solvents shown in Table 1 below in the above-mentioned Example 1, and the aspect of performing rubbing treatment instead of the photo-alignment treatment when manufacturing the liquid crystal cell, it is used with The liquid crystal alignment agent was prepared in the same manner as in Example 1, and various evaluations were performed. Using a rubbing machine with a roll wound with nylon cloth, the rubbing treatment was performed at a roll rotation speed of 1,000 rpm, a table moving speed of 25 mm/sec, and a wool press-in length of 0.4 mm. The evaluation results are shown in Table 1 below.
[表1]
如表1所示,實施例1~實施例12中任一者的利用噴墨塗布法的印刷性及電壓保持率為「良好A(◎)」或者「良好B(○)」的評價。與此相對,比較例的利用噴墨塗布法的印刷性及電壓保持率的至少一者較實施例差。As shown in Table 1, the printability and voltage retention rate by the inkjet coating method in any of Examples 1 to 12 were evaluated as "good A (◎)" or "good B (○)". In contrast, the comparative example is inferior to the examples in at least one of printability and voltage retention by the inkjet coating method.
無no
無no
Claims (3)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-174760 | 2014-08-29 | ||
JP2014174760 | 2014-08-29 | ||
JP2015019485 | 2015-02-03 | ||
JP2015-19485 | 2015-02-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201607990A TW201607990A (en) | 2016-03-01 |
TWI698489B true TWI698489B (en) | 2020-07-11 |
Family
ID=55418246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW104125315A TWI698489B (en) | 2014-08-29 | 2015-08-05 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6492982B2 (en) |
KR (1) | KR102313135B1 (en) |
CN (1) | CN105385457B (en) |
TW (1) | TWI698489B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110546561B (en) * | 2017-04-25 | 2022-06-17 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
JP2019070766A (en) * | 2017-10-11 | 2019-05-09 | シャープ株式会社 | Method for manufacturing liquid crystal panel |
KR20200058281A (en) * | 2018-11-19 | 2020-05-27 | 제이엔씨 주식회사 | Liquid crystal aligning agents for forming liquid crystal alignment films, liquid crystal alignment films and liquid crystal display devices using the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009080156A (en) * | 2007-09-25 | 2009-04-16 | Seiko Epson Corp | Composition for forming liquid crystal alignment layer, and method of manufacturing liquid crystal display device |
TW200922972A (en) * | 2007-09-06 | 2009-06-01 | Seiko Epson Corp | Composition for forming alignment film and method for manufacturing liquid crystal device |
TW200925743A (en) * | 2007-09-06 | 2009-06-16 | Seiko Epson Corp | Composition for forming alignment film, and method for manufacturing liquid crystal device |
TW201418848A (en) * | 2012-11-07 | 2014-05-16 | Jsr Corp | Liquid crystal alignment agent, liquid crystal alignment film and method for producing the same, liquid crystal display device |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1113312A3 (en) | 1997-06-12 | 2004-08-04 | Fujitsu Display Technologies Corporation | Vertically-aligned (VA) liquid crystal display device |
JP5331312B2 (en) * | 2007-05-18 | 2013-10-30 | Dic株式会社 | Manufacturing method of optical anisotropic body |
TWI501027B (en) * | 2008-11-18 | 2015-09-21 | Sumitomo Chemical Co | Photosensitive resin composition and display device |
KR101615926B1 (en) * | 2009-07-28 | 2016-04-28 | 삼성디스플레이 주식회사 | Liquid crystal display device and method of manufacturing the same |
JP5552894B2 (en) * | 2010-05-14 | 2014-07-16 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5642435B2 (en) * | 2010-06-30 | 2014-12-17 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
KR102115015B1 (en) * | 2012-08-30 | 2020-05-25 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent and liquid crystal display element using same |
-
2015
- 2015-06-02 JP JP2015112477A patent/JP6492982B2/en active Active
- 2015-07-14 KR KR1020150099818A patent/KR102313135B1/en active IP Right Grant
- 2015-08-04 CN CN201510471076.7A patent/CN105385457B/en active Active
- 2015-08-05 TW TW104125315A patent/TWI698489B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200922972A (en) * | 2007-09-06 | 2009-06-01 | Seiko Epson Corp | Composition for forming alignment film and method for manufacturing liquid crystal device |
TW200925743A (en) * | 2007-09-06 | 2009-06-16 | Seiko Epson Corp | Composition for forming alignment film, and method for manufacturing liquid crystal device |
JP2009080156A (en) * | 2007-09-25 | 2009-04-16 | Seiko Epson Corp | Composition for forming liquid crystal alignment layer, and method of manufacturing liquid crystal display device |
TW201418848A (en) * | 2012-11-07 | 2014-05-16 | Jsr Corp | Liquid crystal alignment agent, liquid crystal alignment film and method for producing the same, liquid crystal display device |
Also Published As
Publication number | Publication date |
---|---|
CN105385457A (en) | 2016-03-09 |
CN105385457B (en) | 2021-03-30 |
KR20160026671A (en) | 2016-03-09 |
KR102313135B1 (en) | 2021-10-14 |
JP2016145951A (en) | 2016-08-12 |
TW201607990A (en) | 2016-03-01 |
JP6492982B2 (en) | 2019-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6146135B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display element | |
TWI709611B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film and method for manufacturing the same, polymer and compound | |
TWI677516B (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
JP5057056B2 (en) | Liquid crystal aligning agent, method for producing liquid crystal aligning film, polyamic acid, polyimide and diamine compound | |
JP5413610B2 (en) | Liquid crystal aligning agent and method for forming liquid crystal aligning film | |
JP5477572B2 (en) | Liquid crystal aligning agent and method for forming liquid crystal aligning film | |
JP5849391B2 (en) | Liquid crystal aligning agent and liquid crystal display element | |
TWI718117B (en) | Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal element, polymer, diamine and acid dianhydride | |
JPWO2009017252A1 (en) | Liquid crystal aligning agent, liquid crystal aligning film, method for forming the same, and liquid crystal display element | |
KR102005299B1 (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device | |
TWI657115B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound | |
JP6179261B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
JP5668907B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
KR20160013801A (en) | Liquid crystal aligning agent, liquid crystal alignment film and method for producing same, liquid crystal display device, polymer and compound | |
JP2014211515A (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display, phase difference film, method of producing phase difference film, polymer and compound | |
TWI698489B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
JP2014224975A (en) | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element, retardation film, production method of retardation film, polymer, and compound | |
JP5845849B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, liquid crystal display element and compound | |
KR101746043B1 (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device | |
JP5691610B2 (en) | Composition for forming liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element | |
JP6424609B2 (en) | Liquid crystal alignment agent, method of manufacturing liquid crystal display element, liquid crystal alignment film and liquid crystal display element | |
JPWO2009041708A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
JPWO2018124166A1 (en) | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element | |
JP5832847B2 (en) | Liquid crystal aligning agent and liquid crystal display element | |
JP7159755B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, optical film and liquid crystal element |