TWI504727B - Liquid crystal alignment agent, liquid crystal alignment film, mtrhod of forming liquid crystal alignment film, and liquid crystal display device - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, mtrhod of forming liquid crystal alignment film, and liquid crystal display device Download PDFInfo
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Description
本發明涉及一種適於光配向用的液晶配向劑、液晶配向膜、液晶配向膜的形成方法及液晶顯示元件。 The present invention relates to a liquid crystal alignment agent suitable for photoalignment, a liquid crystal alignment film, a method for forming a liquid crystal alignment film, and a liquid crystal display element.
液晶顯示器(Liquid crystal display,LCD)被廣泛利用於電視或各種顯示器等中。該LCD的顯示元件存在有扭轉向列(Twisted Nematic,TN)型、超扭轉向列(Super Twisted Nematic,STN)型、共面轉換(In Plane Switching,IPS)型等液晶單元,亦已知有變更IPS型等的電極結構,使顯示元件部分的數值孔徑提高而提高亮度的邊緣場切換(Fringe Field Switching,FFS)型等(參照日本專利特開昭56-91277號公報及日本專利特開平1-120528號公報)。 Liquid crystal displays (LCDs) are widely used in televisions or various displays. The display elements of the LCD include liquid crystal cells such as a twisted nematic (TN) type, a super twisted nematic (STN) type, and an in plan switching (IPS) type. In the case of changing the electrode structure of the IPS type, the fringe field switching (FFS) type, etc., which improves the numerical aperture of the display element portion and improves the brightness (refer to Japanese Patent Laid-Open No. Hei 56-91277 and Japanese Patent Laid-Open No. -120528).
使此種液晶單元的液晶配向的方法已知有:利用摩擦處理的方法,亦即於基板表面形成液晶配向膜等有機膜,用人造絲等布材對該有機膜的表面在一個方向上摩擦;於基板表面斜向蒸鍍氧化矽的方法;使用朗繆爾布洛傑特法(LB法)形成具有長鏈烷基的單分子膜的方法;通過對包含聚乙烯醇肉桂酸酯(polyvinyl cinnamate)、聚醯亞胺樹脂、聚醯胺酸(polyamic acid)等的感光性薄膜照射偏光或非偏光的放射線而賦予液晶配向能力的光配向法(參照日本專利特開平6-287453號公報、日本專利特開2003-307736號公報及日本專利 特開平9-297313號公報)等。 A method of aligning the liquid crystal of such a liquid crystal cell is known in which a method of rubbing treatment is used, that is, an organic film such as a liquid crystal alignment film is formed on the surface of the substrate, and the surface of the organic film is rubbed in one direction by a cloth such as rayon. a method of obliquely vaporizing ruthenium oxide on the surface of a substrate; a method of forming a monomolecular film having a long-chain alkyl group by using the Langmuir-Blodget method (LB method); by including polyvinyl cinnamate (polyvinyl) A photo-alignment method in which a photosensitive film such as a polyimine resin or a polyamic acid is irradiated with a polarized or non-polarized radiation to impart a liquid crystal alignment ability (refer to Japanese Laid-Open Patent Publication No. Hei 6-287453, Japanese Patent Laid-Open No. 2003-307736 and Japanese Patent Japanese Laid-Open Patent Publication No. Hei 9-297313, and the like.
在該些方法中,不產生靜電或塵埃、可實現均一的液晶配向、且可精密地控制液晶配向方向的上述光配向法的開發不斷被推進。若利用該光配向法,則可通過於照射放射線時使用光罩(photomask)等,而於一個基板上任意地形成液晶配向方向不同的多個區域。然而,使用聚醯亞胺樹脂、聚醯胺酸等的先前的光配向法存在如下的缺點:感光度並不充分,必須很大的累計曝光量。 In these methods, the development of the above-described optical alignment method which does not generate static electricity or dust, achieves uniform liquid crystal alignment, and can precisely control the liquid crystal alignment direction is progressing. According to this light alignment method, a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on one substrate by using a photomask or the like when irradiating the radiation. However, the prior photo-alignment method using a polyimide resin, poly-plycine or the like has the following disadvantages: sensitivity is not sufficient, and a large cumulative exposure amount is required.
[專利文獻1]日本專利特開昭56-91277號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 56-91277
[專利文獻2]日本專利特開平1-120528號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 1-120528
[專利文獻3]日本專利特開平6-287453號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-287453
[專利文獻4]日本專利特開2003-307736號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-307736
[專利文獻5]日本專利特開平9-297313號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 9-297313
本發明的目的在於提供放射線感光度優異、於低照射量的光配向法中可表現出良好的液晶配向性的液晶配向劑。而且,提供使用此種液晶配向劑的液晶配向膜的形成方法及液晶配向膜;提供包含該液晶配向膜,除了液晶配向性以外電氣特性等諸性能亦優異的液晶顯示元件;進一步提供成為該液晶配向劑的材料的化合物。 An object of the present invention is to provide a liquid crystal alignment agent which is excellent in radiation sensitivity and exhibits good liquid crystal alignment in a photo-alignment method having a low irradiation amount. Further, a method for forming a liquid crystal alignment film using such a liquid crystal alignment agent and a liquid crystal alignment film are provided, and a liquid crystal display element including the liquid crystal alignment film and having excellent electrical properties other than liquid crystal alignment properties is provided, and further provided as the liquid crystal. A compound of a material of an alignment agent.
為了解決上述課題而成的發明是一種液晶配向
劑,其含有:[A]具有包含下述式(1)所表示的基或式(2)所表示的基的結構單元(I)的聚合物(以下亦稱為“[A]聚合物”);
(式(1)中,R1及R2分別獨立為氫原子或1價有機基;X是氧原子或硫原子;式(2)中,R3及R4分別獨立為氫原子或1價有機基)。 (In the formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; X is an oxygen atom or a sulfur atom; and in the formula (2), R 3 and R 4 are each independently a hydrogen atom or a monovalent group. Organic base).
本發明的液晶配向劑含有上述具有特定結構的基的[A]聚合物,因此放射線感光度變高,其結果能夠以低照射量而形成具有良好的液晶配向性的液晶配向膜。另外,通過含有上述具有特定結構的基的[A]聚合物而使放射線感光度變得更高的理由未必明確,例如可如下所述地進行推斷。[A]聚合物具有如上述式(1)所表示的環丁烷(cyclobutane)骨架,因此例如由於狄爾斯-阿爾德反應(Diels-Alder reaction)而產生[A]聚合 物的主鏈分解,從而以高感光度產生由於偏光所造成的光配向。另外,由於鍵結於上述環丁烷骨架上的苯環所造成的空間位阻,變得更容易產生均一的光配向,該些的結果是變得能夠以更少的照射量而實現優異的光配向。如上所述,利用該液晶配向劑可減低光配向所必需的放射線照射量,因此可實現低成本化。另外,若使用由該液晶配向劑所形成的液晶配向膜,則可製造電氣特性等諸性能亦優異的液晶顯示元件。 Since the liquid crystal alignment agent of the present invention contains the [A] polymer having a specific structure as described above, the radiation sensitivity is high, and as a result, a liquid crystal alignment film having a good liquid crystal alignment property can be formed with a low irradiation amount. Moreover, the reason why the radiation sensitivity is made higher by the [A] polymer containing the above-described group having a specific structure is not necessarily clear, and can be estimated, for example, as follows. [A] The polymer has a cyclobutane skeleton represented by the above formula (1), and thus [A] polymerization is produced, for example, due to a Diels-Alder reaction. The main chain of the object is decomposed to generate light alignment due to polarized light with high sensitivity. In addition, due to the steric hindrance caused by the benzene ring bonded to the above-mentioned cyclobutane skeleton, it becomes easier to produce uniform optical alignment, and as a result, it becomes possible to achieve excellent irradiation with less irradiation amount. Light alignment. As described above, the liquid crystal alignment agent can reduce the amount of radiation irradiation necessary for light alignment, and thus cost reduction can be achieved. In addition, when a liquid crystal alignment film formed of the liquid crystal alignment agent is used, a liquid crystal display element having excellent electrical properties and the like can be produced.
[A]聚合物優選為聚酯(polyester)(以下亦稱為“聚酯(A1)”)或聚硫酯(polythioester)(以下亦稱為“聚硫酯(A2)”)。 The [A] polymer is preferably a polyester (hereinafter also referred to as "polyester (A1)") or a polythioester (hereinafter also referred to as "polythioester (A2)").
上述結構單元(I)優選為下述式(3)、式(4)或式(5)所表示的結構單元。 The structural unit (I) is preferably a structural unit represented by the following formula (3), formula (4) or formula (5).
[化2]
(式(3)~式(5)中,R1、R2及X與上述式(1)同義。Y1~Y3分別獨立為2價有機基) (In the formulas (3) to (5), R 1 , R 2 and X are synonymous with the above formula (1). Y 1 to Y 3 are each independently a divalent organic group)
該液晶配向劑由於[A]聚合物具有上述特定結構的結構單元(I),因此可具有更高感光度的光配向性。 This liquid crystal alignment agent can have a light sensitivity of higher sensitivity because the [A] polymer has the structural unit (I) of the above specific structure.
本發明的液晶配向劑適宜用作光配向用。該液晶配向劑對放射線的感光度高,可以低照射量的放射線而形成具有優異的液晶配向能力(liquid crystal aligning ability)的液晶配向膜。 The liquid crystal alignment agent of the present invention is suitably used for photoalignment. The liquid crystal alignment agent has high sensitivity to radiation and can form a liquid crystal alignment property with a low irradiation amount of radiation. Liquid crystal alignment film.
本發明的液晶配向膜的形成方法包含如下步驟: (1)使用本發明的液晶配向劑而於基板上形成塗膜的步驟、及 (2)對上述塗膜照射已偏光的紫外線,賦予液晶配向能力的步驟。 The method for forming a liquid crystal alignment film of the present invention comprises the following steps: (1) a step of forming a coating film on a substrate using the liquid crystal alignment agent of the present invention, and (2) A step of irradiating the coating film with polarized ultraviolet rays to impart alignment ability to the liquid crystal.
根據本發明的形成方法,即使利用少量的放射線照射亦可進行光配向,因此可效率良好地製造液晶配向膜,生產性高且有助於削減製造成本。 According to the formation method of the present invention, the light alignment can be performed even with a small amount of radiation irradiation, so that the liquid crystal alignment film can be efficiently produced, and the productivity is high and the manufacturing cost can be reduced.
本發明亦包含由該液晶配向劑所形成的液晶配向膜。本發明的液晶配向膜由該液晶配向劑而形成,因此對放射線的感光度高,於其形成步驟中,可利用低照射量的放射線而賦予液晶配向能力,因此生產效率良好且製造成本亦可得到削減。 The present invention also encompasses a liquid crystal alignment film formed of the liquid crystal alignment agent. Since the liquid crystal alignment film of the present invention is formed of the liquid crystal alignment agent, the sensitivity to radiation is high, and in the step of forming the liquid crystal alignment ability can be imparted by using a low irradiation amount of radiation, the production efficiency is good and the manufacturing cost can be improved. Get cuts.
本發明的液晶顯示元件包含該液晶配向膜。該液晶顯示元件包含上述放射線感光度及液晶配向性優異的該液晶配向膜,因此可較先前更廉價地進行製造,且亦可充分保持電氣特性等諸性能。 The liquid crystal display element of the present invention comprises the liquid crystal alignment film. Since the liquid crystal display element includes the liquid crystal alignment film having excellent radiation sensitivity and liquid crystal alignment, it can be manufactured at a lower cost than before, and performance such as electrical characteristics can be sufficiently maintained.
本發明的聚合物具有下述式(3)所表示的結構單元。 The polymer of the present invention has a structural unit represented by the following formula (3).
[化3]
(式(3)中,R1及R2分別獨立為氫原子或1價有機基。x是氧原子或硫原子。Y1是2價有機基) (In the formula (3), R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group. x is an oxygen atom or a sulfur atom. Y 1 is a divalent organic group)
本發明的聚合物具有上述特定結構,因此可作為該液晶配向劑中的[A]聚合物而適宜地使用,含有本發明的聚合物的該液晶配向劑對放射線的感光度高,可以低照射量的放射線而形成具有優異的液晶配向能的液晶配向膜。 Since the polymer of the present invention has the above specific structure, it can be suitably used as the [A] polymer in the liquid crystal alignment agent, and the liquid crystal alignment agent containing the polymer of the present invention has high sensitivity to radiation and can be irradiated low. The amount of radiation forms a liquid crystal alignment film having excellent liquid crystal alignment energy.
另外,此處“光配向用”中的“光”與“放射線”同義地使用,是包含可見光線、紫外線、遠紫外線、X射線、帶電粒子束等的概念。 In addition, "light" in "for optical alignment" is used synonymously with "radiation", and is a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.
本發明的液晶配向劑的放射線感光度高,可以低照射量的放射線照射而形成具有優異的液晶配向性的液晶配向膜,因此其生產效率好,可削減生產成本。另外,包含使用本發明的液晶配向劑而形成的液晶配向膜的液晶顯示元件的電氣特性等諸性能均優異。因此,本發明的液晶配向劑、液晶配向膜、該液晶配向膜的形成方法及液晶顯示元件可適宜地用於IPS型、FFS型等液晶 顯示元件中。 Since the liquid crystal alignment agent of the present invention has high radiation sensitivity and can form a liquid crystal alignment film having excellent liquid crystal alignment properties by radiation irradiation with a low irradiation amount, the production efficiency is high and the production cost can be reduced. In addition, the liquid crystal display element including the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention is excellent in electrical properties and the like. Therefore, the liquid crystal alignment agent, the liquid crystal alignment film, the method for forming the liquid crystal alignment film, and the liquid crystal display element of the present invention can be suitably used for liquid crystals such as IPS type and FFS type. In the display component.
為讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。 The above described features and advantages of the present invention will be more apparent from the following description.
本發明的液晶配向劑含有在主鏈具有結構單元(I)之[A]聚合物,所述結構單元(I)包含上述式(1)所表示的基或式(2)所表示的基。該液晶配向劑含有具有上述特定結構的基的[A]聚合物,因此放射線感光度提高,能夠以低照射量的放射線而形成具有優異的液晶配向性的液晶配向膜。而且,具有該液晶配向膜的液晶顯示元件的電氣特性等諸性能亦優異。本發明的液晶配向劑除了必需成分[A]聚合物以外,只要不損及本發明的效果,則亦可含有其他成分。以下,對各成分加以詳述。 The liquid crystal alignment agent of the present invention contains a [A] polymer having a structural unit (I) in a main chain, and the structural unit (I) contains a group represented by the above formula (1) or a group represented by the formula (2). Since the liquid crystal alignment agent contains the [A] polymer having the above-described specific structure, the radiation sensitivity is improved, and a liquid crystal alignment film having excellent liquid crystal alignment properties can be formed with a low irradiation amount of radiation. Further, the liquid crystal display element having the liquid crystal alignment film is excellent in electrical properties and the like. The liquid crystal alignment agent of the present invention may contain other components in addition to the essential component [A] polymer as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.
[A]聚合物是具有結構單元(I)的聚合物。[A]聚合物若為具有上述結構單元(I)的聚合物則並無特別限定,優選為聚酯(A1)或聚硫酯(A2)。[A]聚合物為具有上述結構單元(I)的聚酯(A1)或聚硫酯(A2),因此該液晶配向劑可形成具有優異的液晶配向性的液晶配向膜。 The [A] polymer is a polymer having a structural unit (I). The polymer [A] is not particularly limited as long as it is a polymer having the above structural unit (I), and is preferably a polyester (A1) or a polythioester (A2). [A] The polymer is the polyester (A1) or the polythioester (A2) having the above structural unit (I), and therefore the liquid crystal alignment agent can form a liquid crystal alignment film having excellent liquid crystal alignment.
結構單元(I)包含上述式(1)所表示的基或式(2) 所表示的基。 The structural unit (I) includes the group represented by the above formula (1) or the formula (2) The base represented.
上述式(1)中,R1及R2分別獨立為氫原子或1價有機基。X為氧原子或硫原子。 In the above formula (1), R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group. X is an oxygen atom or a sulfur atom.
上述式(2)中,R3及R4分別獨立為氫原子或1價有機基。 In the above formula (2), R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group.
上述R1~R4所表示的1價有機基例如可列舉碳數為1~10的鏈烴基(chain hydrocarbon)、碳數為3~10的脂環族烴基(alicyclic hydrocarbon)、碳數為6~10的芳香族烴基、該些基與雜原子(hetero atom)組合而成的基等。 Examples of the monovalent organic group represented by the above R 1 to R 4 include a chain hydrocarbon having 1 to 10 carbon atoms, an alicyclic hydrocarbon having 3 to 10 carbon atoms, and a carbon number of 6 An aromatic hydrocarbon group of ~10, a group in which these groups are combined with a hetero atom, and the like.
上述碳數為1~10的鏈烴基例如可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、叔丁基(tert-butyl)、正戊基、異戊基等。 Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, and an isopenic group. Base.
上述碳數為3~10的脂環族烴基例如可列舉環丙基、環丁基、環戊基、環己基等。 Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
上述碳數為6~10的芳香族烴基例如可列舉苯基、萘基等。 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
上述雜原子可列舉氧原子、硫原子、氮原子等。 Examples of the above hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
上述R1~R4優選為氫原子、碳數為1~10的鏈烴基及碳數為3~10的脂環族烴基,更優選為氫原子。 R 1 to R 4 are preferably a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and more preferably a hydrogen atom.
X優選為氧原子。 X is preferably an oxygen atom.
結構單元(1)若為包含上述式(1)所表示的基或式(2)所表示的基的結構單元則並無特別限定,優選為上述式(3)~式(5)所表示的結構單元,更優選為 式(3)所表示的結構單元。 The structural unit (1) is not particularly limited as long as it is a structural unit containing a group represented by the above formula (1) or a group represented by the formula (2), and is preferably represented by the above formulas (3) to (5). Structural unit, more preferably A structural unit represented by the formula (3).
上述式(3)~式(5)中,R1、R2及X與上述式(1)同義。Y1~Y3分別獨立為2價有機基。 In the above formulas (3) to (5), R 1 , R 2 and X have the same meanings as in the above formula (1). Y 1 to Y 3 are each independently a divalent organic group.
上述Y1~Y3所表示的2價有機基例如可列舉碳數為1~20的2價鏈烴基、碳數為3~20的2價脂環族烴基、碳數為6~20的2價芳香族烴基、該些基與雜原子組合而成的基等。 Examples of the divalent organic group represented by the above Y 1 to Y 3 include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 2 carbon atoms having 6 to 20 carbon atoms. a valent aromatic hydrocarbon group, a group in which these groups are combined with a hetero atom, and the like.
上述碳數為1~20的2價鏈烴基例如可列舉亞甲基、乙二基(ethanediyl)、丙二基(propanediyl)、丁二基、戊二基、己二基、辛二基等。 Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include a methylene group, an ethanediyl group, a propanediyl group, a butyldiyl group, a pentanediyl group, a hexamethylene group, and a octyldiyl group.
上述碳數為3~20之2價脂環族烴基例如可列舉環丙二基(cyclo propanediyl)、環丁二基、環戊二基、環己二基、環辛二基等。 Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentadienyl group, a cyclohexanediyl group, and a cyclooctyldiyl group.
上述碳數為6~20的2價芳香族烴基例如可列舉伸苯基(phenylene)、伸萘基(naphthylene)、伸蒽基(anthracenylene)等。 Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene, naphthylene, and anthracenylene.
上述Y1~Y3所表示的2價有機基亦可具有的上述雜原子可列舉氧原子、硫原子、氮原子等。該些中優選為氧原子。 The hetero atom which the divalent organic group represented by the above Y 1 to Y 3 may have includes an oxygen atom, a sulfur atom, a nitrogen atom and the like. Among these, an oxygen atom is preferred.
上述Y1~Y3優選為碳數為1~20的2價鏈烴基、碳數為3~20的2價脂環族烴基或碳數為6~20的2價芳香族烴基與雜原子組合而成的基,更優選為碳數為1~20的2價鏈烴基與雜原子組合而成的基,進一步更優選為碳數為2~4的2價鏈烴基與氧原子組合而成的 基,特別優選為以-CH2-O-(CH2)n-O-CH2-而表示的基。其中,n為1~10的整數。 The above Y 1 to Y 3 are preferably a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms combined with a hetero atom. The group to be formed is more preferably a group in which a divalent chain hydrocarbon group having 1 to 20 carbon atoms is combined with a hetero atom, and more preferably a combination of a divalent chain hydrocarbon group having 2 to 4 carbon atoms and an oxygen atom. The group is particularly preferably a group represented by -CH 2 -O-(CH 2 ) n -O-CH 2 -. Where n is an integer from 1 to 10.
[A]聚合物中的結構單元(I)的含有率優選為10mol%以上100mol%以下,更優選為60mol%以上100mol%以下,進一步更優選為80mol%以上100mol%以下,特別優選為90mol%以上100mol%以下。通過使[A]聚合物中的結構單元(I)的含有率為上述特定範圍,該液晶配向劑可進一步提高放射線感光度。 The content of the structural unit (I) in the polymer is preferably 10 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less, still more preferably 80 mol% or more and 100 mol% or less, and particularly preferably 90 mol%. Above 100 mol% or less. By setting the content of the structural unit (I) in the [A] polymer to the above specific range, the liquid crystal alignment agent can further improve the radiation sensitivity.
上述結構單元(I)可如後述的[A]聚合物的合成方法中所詳細說明那樣,通過使包含上述式(1)所表示的基或式(2)所表示的基的二羧酸化合物與二環氧化合物聚合等而獲得。 The structural unit (I) can be a dicarboxylic acid compound containing a group represented by the above formula (1) or a group represented by the formula (2), as described in detail in the method for synthesizing the [A] polymer described later. It is obtained by polymerization or the like with a diepoxy compound.
[A]聚合物優選為聚酯(A1)及聚硫酯(A2),更優選該些聚合物所具有的結構單元(I)以上述式(3)、式(4)或式(5)而表示。 The [A] polymer is preferably a polyester (A1) and a polythioester (A2), and more preferably, the structural unit (I) of the polymers has the above formula (3), formula (4) or formula (5) And said.
作為[A]聚合物的合成方法,於以下對聚酯(A1)及聚硫酯(A2)的合成方法加以詳述,但本发明中的[A]聚合物的合成方法並不限定於該些合成方法。 As a method for synthesizing the [A] polymer, a method for synthesizing the polyester (A1) and the polythioester (A2) will be described in detail below, but the method for synthesizing the [A] polymer in the present invention is not limited to this. Some synthetic methods.
聚酯(A1)例如可通過使包含上述式(1)所表示的基的二羧酸化合物與二環氧化合物在有機溶劑中反應而合成。 The polyester (A1) can be synthesized, for example, by reacting a dicarboxylic acid compound containing a group represented by the above formula (1) with a diepoxy compound in an organic solvent.
包含上述式(1)所表示的基的二羧酸化合物例如 可依照下述流程而合成。 A dicarboxylic acid compound containing a group represented by the above formula (1), for example It can be synthesized according to the following procedure.
例如將(E)-肉桂酸(cinnamic acid)於水/乙醇=1:1溶液等溶劑中進行加熱而使其完全溶解,加以冷卻而使其再結晶,由此可獲得(E)-肉桂酸的α-結晶。上述加熱溫度優選為70℃~200℃,更優選為80℃~120℃。 For example, (E)-cinnamic acid is heated in a solvent such as water/ethanol = 1:1 solution to completely dissolve it, and then cooled and recrystallized, whereby (E)-cinnamic acid can be obtained. Alpha-crystallization. The heating temperature is preferably 70 ° C to 200 ° C, and more preferably 80 ° C to 120 ° C.
上述冷卻溫度優選為20℃~60℃,更優選為40℃~55℃。其次,將再結晶而所得的α-結晶在研缽等中搗碎直至成為粉末狀,用二枚Pyrex(注冊商標)玻璃板等進行夾持,對於以成為均等的厚度的方式調製而成者,使用500W高壓水銀燈進行光照射,由此可合成上述式(B-1)所表示的二羧酸化合物。上述光照射時間優選為2小時~10小時,更優選為3小時~6小時。 The cooling temperature is preferably 20 ° C to 60 ° C, and more preferably 40 ° C to 55 ° C. Then, the α-crystal obtained by recrystallization is pulverized in a mortar or the like until it is in a powder form, and is sandwiched between two Pyrex (registered trademark) glass plates or the like, and is prepared so as to have a uniform thickness. The dicarboxylic acid compound represented by the above formula (B-1) can be synthesized by light irradiation using a 500 W high pressure mercury lamp. The light irradiation time is preferably 2 hours to 10 hours, and more preferably 3 hours to 6 hours.
上述二環氧化合物例如可列舉下述式所表示的化 合物等。 Examples of the above-mentioned diepoxy compound include the compounds represented by the following formulas. Compounds, etc.
作為二環氧(diepoxy)化合物,於使用具有3元環的環氧基(環氧乙烷(oxirane))的化合物的情況下, 可形成上述式(2)及式(3)所表示的結構單元。相對於此,於使用具有4元環的環氧基(環氧丙烷(oxetane))的化合物的情況下,可形成上述式(4)所表示的結構單元。 As a diepoxy compound, in the case of using a compound having a 3-membered ring epoxy group (oxirane), The structural unit represented by the above formula (2) and formula (3) can be formed. On the other hand, in the case of using a compound having a 4-membered ring epoxy group (oxetane), the structural unit represented by the above formula (4) can be formed.
於本發明中所使用的聚酯(A1)的合成中,亦可與包含上述式(1)所表示的基的二羧酸化合物一同合併使用其他二羧酸化合物。 In the synthesis of the polyester (A1) used in the present invention, other dicarboxylic acid compounds may be used in combination with the dicarboxylic acid compound containing the group represented by the above formula (1).
其他二羧酸化合物例如可列舉間苯二甲酸(isophthalic acid)、對苯二甲酸(terephthalic acid)、二苯醚-4,4'-二甲酸、二苯基碸-4,4'-二甲酸、二苯甲酮(benzophenone)-4,4'-二甲酸、4,4'-聯苯二甲酸、2,2'-雙(4-羧基苯基)六氟丙烷、1,3-雙(羧基苯基)-1,1,3,3-四甲基二矽氧烷、丙二酸(malonic acid)、琥珀酸(succinic acid)、戊二酸(glutaric acid)、己二酸(adipic acid)、庚二酸、辛二酸、壬二酸、癸二酸(sebacic acid)、馬來酸(malcic acid)等。該些其他二羧酸化合物可單獨使用或者將2種以上組合使用。 Examples of other dicarboxylic acid compounds include isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, and diphenylphosphonium-4,4'-dicarboxylic acid. , benzophenone-4,4'-dicarboxylic acid, 4,4'-diphenyl phthalate, 2,2'-bis(4-carboxyphenyl)hexafluoropropane, 1,3-double ( Carboxyphenyl)-1,1,3,3-tetramethyldioxane, malonic acid, succinic acid, glutaric acid, adipic acid ), pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, and the like. These other dicarboxylic acid compounds may be used singly or in combination of two or more.
作為聚酯(A1)的合成反應中所使用的二環氧化合物與二羧酸化合物(包含上述式(1)所表示的基的二羧酸化合物及其他二羧酸化合物的合計)的使用比例,相對於二羧酸化合物中所含的羧基1當量而言,二環氧化合物的環氧基優選為0.2當量~2當量,更優選為0.3當量~1.2當量。 Ratio of use of the diepoxy compound used in the synthesis reaction of the polyester (A1) to the dicarboxylic acid compound (the total of the dicarboxylic acid compound and the other dicarboxylic acid compound including the group represented by the above formula (1)) The epoxy group of the diepoxy compound is preferably 0.2 equivalents to 2 equivalents, more preferably 0.3 equivalents to 1.2 equivalents, per equivalent of the carboxyl group contained in the dicarboxylic acid compound.
合成反應優選於有機溶劑中進行。反應溫度優選為 0℃~250℃,更優選為50℃~180℃。反應時間優選為0.5小時~24小時,更優選為2小時~12小時。 The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably 0 ° C ~ 250 ° C, more preferably 50 ° C ~ 180 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 2 to 12 hours.
有機溶劑若為可溶解所合成的聚酯的有機溶劑則並無特別限制,例如可列舉N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、N,N-二甲基乙醯胺(N,N-dimethylacetamide)、N,N-二甲基甲醯胺(N,N-dimethylformamide)、N,N-二甲基咪唑啉酮(N,N-dimethyl imidazolidinone)、二甲基亞碸(dimethyl sulfoxide)、γ-丁內酯(γ-butyrolactone)、四甲基脲(tetramethylurea)、六甲基磷醯三胺等非質子系極性溶劑;間甲酚、二甲苯酚、苯酚、鹵代酚等酚系溶劑。 The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the synthesized polyester, and examples thereof include N-methyl-2-pyrrolidone (NMP) and N,N-dimethyl group. N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, phenol A phenolic solvent such as a halogenated phenol.
作為有機溶劑的使用量(a),相對於二環氧化合物及二羧酸化合物的總量(b)與有機溶劑的使用量(a)的合計(a+b)而言,優選為0.1質量%~50質量%,更優選為5質量%~30質量%。 The amount (a) to be used as the organic solvent is preferably 0.1 mass based on the total amount (a+b) of the total amount (b) of the diepoxy compound and the dicarboxylic acid compound and the amount (a) of the organic solvent used. %~50% by mass, more preferably 5% by mass to 30% by mass.
聚酯(A1)中的源自上述二羧酸化合物與上述二環氧化合物的上述式(3)~式(5)所表示的結構單元(I)的含有比例,相對於所有聚合物的所有結構單元而言優選為50mol%~100mol%,更優選為60mol%~100mol%,進一步更優選為80mol%~100mol%。 The content ratio of the structural unit (I) represented by the above formula (3) to formula (5) derived from the above dicarboxylic acid compound and the above-mentioned diepoxy compound in the polyester (A1) is relative to all of the polymers. The structural unit is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, still more preferably 80 mol% to 100 mol%.
反應後所得的聚酯(A1)溶液可直接用於液晶配向劑的調製中,也可以將反應溶液中所含的聚酯(A1)離析後用於液晶配向劑的調製中,也可以對所離析的聚酯進行純化後用於液晶配向劑的調製中。聚酯(A1) 的離析方法例如可列舉:於減壓下對將反應溶液注入於大量不良溶劑中而所得的析出物進行乾燥的方法;利用蒸發器對反應溶液進行減壓蒸餾除去的方法等。聚酯的純化方法可列舉:將離析的聚酯(A1)再次溶解於有機溶劑中、利用不良溶劑使其析出的方法;進行1次利用蒸發器將有機溶劑等減壓蒸餾除去的步驟或者進行多次的方法。 The polyester (A1) solution obtained after the reaction can be directly used in the preparation of the liquid crystal alignment agent, or the polyester (A1) contained in the reaction solution can be isolated and used for the preparation of the liquid crystal alignment agent, or The isolated polyester is purified and used in the preparation of a liquid crystal alignment agent. Polyester (A1) For example, a method of drying a precipitate obtained by injecting a reaction solution into a large amount of a poor solvent under reduced pressure, and a method of subjecting the reaction solution to distillation under reduced pressure by an evaporator may be mentioned. The method for purifying the polyester is a method in which the isolated polyester (A1) is dissolved again in an organic solvent, and precipitated by a poor solvent; and the step of performing distillation under reduced pressure using an evaporator or the like is performed once. Multiple methods.
於上述聚酯(A1)的合成中,除了上述二環氧化合物及二羧酸化合物以外,亦可使用適當的分子量調節劑而合成末端改性型聚合物。通過製成該末端改性型聚合物,可並不損及本發明的效果地進一步改善液晶配向劑的塗布性(印刷性)。 In the synthesis of the above polyester (A1), in addition to the above-mentioned diepoxy compound and dicarboxylic acid compound, a terminal-modified polymer can be synthesized by using an appropriate molecular weight modifier. By preparing the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.
上述分子量調節劑可列舉酸單酐、單胺化合物、單異氰酸酯化合物等。 Examples of the molecular weight modifier include an acid monoanhydride, a monoamine compound, and a monoisocyanate compound.
酸單酐可列舉馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐、正十六烷基琥珀酸酐等。 Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like.
單胺化合物可列舉苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺等。 Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine.
單異氰酸酯化合物可列舉異氰酸苯酯、異氰酸萘酯等。 The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate.
作為分子量調節劑的使用比例,相對於所使用的二環氧化合物及二羧酸化合物的合計100質量份而言,優選為20質量份以下,更優選為10質量份以下。 The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the diepoxy compound and the dicarboxylic acid compound to be used.
聚硫酯(A2)例如可通過使包含上述式(1)所表示的基的二硫代-S-酸化合物及二環氧化合物於有機溶劑中反應而獲得。 The polythioester (A2) can be obtained, for example, by reacting a dithio-S-acid compound containing a group represented by the above formula (1) and a diepoxide compound in an organic solvent.
上述二環氧化合物可列舉與作為聚酯(A1)的合成中所使用的二環氧化合物而例示的化合物同樣的化合物。 The above-mentioned diepoxy compound is the same as the compound exemplified as the diepoxy compound used for the synthesis of the polyester (A1).
含有所得的聚硫酯(A2)的反應溶液可將其直接供至液晶配向劑的調製中,亦可自反應溶液中除去脫水劑及脫水閉環催化劑後供至液晶配向劑的調製中,亦可使聚硫酯(A2)離析後供至液晶配向劑的調製中,或者亦可對所離析的聚硫酯(A2)進行純化後供至液晶配向劑的調製中。該些純化操作可依照公知的方法而進行。 The reaction solution containing the obtained polythioester (A2) can be directly supplied to the preparation of the liquid crystal alignment agent, or can be supplied to the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or The polythioester (A2) is isolated and supplied to the preparation of the liquid crystal alignment agent, or the isolated polythioester (A2) may be purified and supplied to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method.
作為如上所述而所得的聚酯(A1)及聚硫酯(A2),於將其製成濃度為10質量%的溶液時,優選具有20mPa.s~800mPa.s的溶液粘度,更優選具有30mPa.s~500mPa.s的溶液粘度。上述[A]聚合物的溶液粘度(mPa.s)是對使用該聚合物的良溶劑(例如γ-丁內酯、N-甲基-2-吡咯烷酮等)而調製的濃度為10重量%的聚合物溶液,使用E型旋轉粘度計而於25℃下所測定的值。 The polyester (A1) and the polythioester (A2) obtained as described above are preferably 20 mPa when formed into a solution having a concentration of 10% by mass. s~800mPa. The solution viscosity of s, more preferably 30 mPa. s~500mPa. The solution viscosity of s. The solution viscosity (mPa.s) of the above [A] polymer is a concentration of 10% by weight prepared for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured at 25 ° C using an E-type rotational viscometer.
本發明的液晶配向劑含有[A]聚合物作為必需成 分,亦可視需要而含有其他成分。該其他成分例如可列舉上述[A]聚合物以外的其他聚合物、於分子內具有至少一個環氧基的化合物(以下亦稱為“環氧化合物”)、官能性矽烷化合物等。 The liquid crystal alignment agent of the present invention contains [A] polymer as an essential component Points may also contain other ingredients as needed. Examples of the other component include a polymer other than the above [A] polymer, a compound having at least one epoxy group in the molecule (hereinafter also referred to as "epoxy compound"), a functional decane compound, and the like.
上述其他聚合物可用以改善溶液特性及電氣特性。 The other polymers described above can be used to improve solution properties and electrical properties.
該其他聚合物是上述聚酯(A1)、上述聚硫酯(A2)等[A]聚合物以外的聚合物,例如可列舉使不具上述式(1)所表示的結構的二羧酸化合物與二環氧化合物反應而所得的聚酯(以下亦稱為“其他聚酯”)、不具有上述式(1)所表示的結構的聚硫酯、聚醯胺、聚矽氧烷、纖維素衍生物、聚縮醛(polyacetal)、聚苯乙烯衍生物、聚(苯乙烯-苯基馬來醯亞胺)(Poly(styrene-phenylmaleimide)衍生物、聚(甲基)丙烯酸酯等。該些化合物中優選其他聚酯、其他聚硫酯,更優選其他聚酯。 The other polymer is a polymer other than the polymer [A] such as the polyester (A1) or the above-mentioned polythioester (A2), and examples thereof include a dicarboxylic acid compound having a structure represented by the above formula (1) and a polyester obtained by reacting a diepoxy compound (hereinafter also referred to as "other polyester"), a polythioester having no structure represented by the above formula (1), polyamine, polyoxyalkylene, cellulose derivative , polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide derivative, poly(meth)acrylate, etc. These compounds Other polyesters, other polythioesters are preferred, and other polyesters are more preferred.
用以合成上述其他聚酯或其他聚硫酯的二羧酸化合物可列舉與作為用以合成聚酯(A1)的其他二羧酸化合物而所述者相同的化合物。 The dicarboxylic acid compound for synthesizing the above other polyester or other polythioester may be the same as those described for the other dicarboxylic acid compound for synthesizing the polyester (A1).
用以合成上述其他聚酯或其他聚硫酯的二環氧化合物可列舉與作為用以合成聚酯(A1)及聚硫酯(A2)時所使用的二環氧化合物而所例示者相同的化合物等。 The diepoxy compound used for the synthesis of the above other polyester or other polythioester may be exemplified as the exemplified as the diepoxy compound used in the synthesis of the polyester (A1) and the polythioester (A2). Compounds, etc.
作為其他聚合物的使用比例,相對於[A]聚合物而言優選為50質量%以下,更優選為40質量%以下,進一步更優選為30質量%以下。 The use ratio of the other polymer is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less based on the [A] polymer.
上述環氧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-間苯二甲胺、1,3-雙(N,N-二縮水甘油胺甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷、N,N-二縮水甘油基-苯甲胺、N,N-二縮水甘油基-氨基甲基環己烷、N,N-二縮水甘油基-環己胺等作為優選的環氧化合物。 Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol condensed water. Glycerol ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminemethyl)cyclohexane, N,N,N',N'-tetrahydration Glyceryl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-bi-drink Glyceryl-cyclohexylamine or the like is preferred as the epoxy compound.
作為該些環氧化合物的調配比例,相對於聚合物的合計100質量份而言優選為40質量份以下,更優選為0.1質量份~30質量份。 The blending ratio of the epoxy compounds is preferably 40 parts by mass or less, and more preferably 0.1 parts by mass to 30 parts by mass, based on 100 parts by mass of the total of the polymer.
上述官能性矽烷化合物例如可列舉3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、2-氨基丙基三甲氧基矽烷、2-氨基丙基三乙氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-氨基丙基三甲氧基矽烷、N-乙氧基羰基-3-氨基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲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、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三甲氧基矽烷基-3,6-二氮雜壬酸甲酯、9-三乙氧基矽烷基-3,6-二氮雜壬酸甲酯、N-苄基-3-氨基丙基三甲氧基矽烷、N-苄基-3-氨基丙基三乙氧基矽烷、N-苯基-3-氨基丙基三甲氧基矽烷、N-苯基-3-氨基丙基三乙氧基矽烷、縮水甘油氧基甲基三甲氧基矽烷、縮水甘油氧基甲基三乙氧基矽烷、2-縮水甘油氧基乙基三甲氧基矽烷、2-縮水甘油氧基乙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等。 Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethyl Oxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane , N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7- Triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9- Trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecyl-3 , methyl 6-diazepine, methyl 9-triethoxydecyl-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyl Trimethoxy decane, glycidoxymethyl triethoxy decane, 2-glycidoxyethyl trimethoxy decane, 2-glycidoxyethyl triethoxy decane, 3-glycidoxy Propyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like.
作為該些官能性矽烷化合物的調配比例,相對於聚合物的合計100質量份而言優選為2質量份以下,更優選為0.02質量份~0.2質量份。 The blending ratio of the functional decane compound is preferably 2 parts by mass or less, and more preferably 0.02 parts by mass to 0.2 parts by mass, based on 100 parts by mass of the total of the polymer.
本發明的液晶配向劑是上述聚酯(A1)、聚硫酯(A2)等[A]聚合物、以及視需要而任意地調配的其他成分優選溶解含有於有機溶劑中而構成的。 The liquid crystal alignment agent of the present invention is preferably composed of the above-mentioned polyester (A1), polythioester (A2) or the like [A] polymer, and other components optionally arbitrarily formulated and dissolved in an organic solvent.
本發明的液晶配向劑中所使用的有機溶劑例如可列舉N-甲基-2-吡咯烷酮、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、4-羥基-4-甲基-2-戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇乙醚、 乙二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚(丁基溶纖劑)、乙二醇二甲醚、乙二醇乙醚乙酸酯、二乙二醇二甲醚、二乙二醇二乙醚、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、二異丁酮、丙酸異戊酯、異丁酸異戊酯、二異戊醚、碳酸乙二酯、碳酸丙二酯等。該些有機溶劑可單獨使用或者將2種以上混合使用。 Examples of the organic solvent used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide, N,N-dimethylformamide, and N. N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxypropyl Ethyl acetate, ethylene glycol methyl ether, ethylene glycol ether, Ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Alcohol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate , isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These organic solvents may be used singly or in combination of two or more.
本發明的液晶配向劑中的固形物濃度(液晶配向劑中的除溶劑以外的成分的合計質量於液晶配向劑的總質量中所占的比例)可考慮粘性、揮發性等而適宜選擇,優選為1質量%~10質量%的範圍。亦即,本發明的液晶配向劑可如後所述那樣塗布於基板表面上,優選進行加熱而形成作為液晶配向膜的塗膜或成為液晶配向膜的塗膜,但於固形物濃度不足1質量%時,該塗膜的膜厚變得過小而無法獲得良好的液晶配向膜;另一方面,於固形物濃度超過10質量%時,塗膜的膜厚變得過大而無法獲得良好的液晶配向膜,而且,液晶配向劑的粘性增大而造成塗布特性變差。 The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total mass of the components other than the solvent in the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. It is in the range of 1% by mass to 10% by mass. In other words, the liquid crystal alignment agent of the present invention can be applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film, but the solid content is less than 1 mass. In the case of %, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment. Further, the film and the viscosity of the liquid crystal alignment agent are increased to cause deterioration in coating properties.
特別優選的固形物濃度的範圍因將液晶配向劑塗布於基板上時所使用的方法而異。例如,於利用旋塗法的情況時,特別優選固形物濃度為1.5質量%~4.5質量%的範圍。於利用印刷法的情況時,特別優選使固形物濃度為3質量%~9質量%的範圍,由此而使溶液粘度成為12mPa.s~50mPa.s的範圍。於利用噴墨法的情況 時,特別優選使固形物濃度為1質量%~5質量%的範圍,由此使溶液粘度成為3mPa.s~15mPa.s的範圍。 A particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using the spin coating method, the solid content concentration is particularly preferably in the range of 1.5% by mass to 4.5% by mass. In the case of using the printing method, it is particularly preferable to set the solid content to a range of 3% by mass to 9% by mass, thereby making the solution viscosity 12 mPa. s~50mPa. The scope of s. In the case of using the inkjet method In particular, it is particularly preferable to set the solid content to a range of 1% by mass to 5% by mass, thereby making the solution viscosity 3mPa. s~15mPa. The scope of s.
於調製本發明的液晶配向劑時的溫度優選為10℃~50℃,更優選為20℃~30℃。 The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.
本發明的液晶配向膜可由該液晶配向劑而形成。因此,於形成步驟中可利用低照射量的放射線而賦予優異的液晶配向能。另外,無需放射線的照射中及照射後的加熱步驟,因此生產效率良好且製造成本亦可得到削減。 The liquid crystal alignment film of the present invention can be formed by the liquid crystal alignment agent. Therefore, it is possible to impart excellent liquid crystal alignment energy by using radiation of a low irradiation amount in the formation step. Further, since the irradiation step of the radiation and the heating step after the irradiation are not required, the production efficiency is good and the manufacturing cost can be reduced.
本發明的液晶配向劑可作為光配向法的液晶配向膜材料而適宜地使用。而且,可適宜地用以形成具有TN型或STN型液晶單元的液晶顯示元件、或具有IPS型、FFS型等液晶單元的橫向電場方式液晶顯示元件中所使用的液晶配向膜。本發明的液晶配向劑特別是在適用於具有IPS型、FFS型液晶單元的液晶顯示元件中時,變得最大限度地發揮本發明的效果,從而優選使用。 The liquid crystal alignment agent of the present invention can be suitably used as a liquid crystal alignment film material of a photo-alignment method. Further, it can be suitably used to form a liquid crystal display element having a TN type or STN type liquid crystal cell, or a liquid crystal alignment film used in a lateral electric field type liquid crystal display element having a liquid crystal cell such as an IPS type or an FFS type. In particular, when the liquid crystal alignment agent of the present invention is applied to a liquid crystal display device having an IPS type or FFS type liquid crystal cell, the effect of the present invention is maximized, and it is preferably used.
本發明的液晶配向膜的形成方法包含如下步驟: The method for forming a liquid crystal alignment film of the present invention comprises the following steps:
(1)使用本發明的液晶配向劑,於基板上形成塗膜的步驟(以下亦稱為「步驟(1)」)、及(2)對上述塗膜照射已偏光的紫外線,賦予液晶配向能的步驟(以下亦稱為「步驟(2)」)。以下,對各步驟加以詳述。 (1) a step of forming a coating film on a substrate by using the liquid crystal alignment agent of the present invention (hereinafter also referred to as "step (1)"), and (2) irradiating the coating film with polarized ultraviolet rays to impart alignment energy to the liquid crystal The steps (hereinafter also referred to as "step (2)"). Hereinafter, each step will be described in detail.
此處,於將本發明的液晶配向劑適用於具有TN型或STN型液晶單元的液晶顯示元件中的情況下,將2枚設有圖案化的透明導電膜的基板作為一對,於其各透明性導電膜形成面上塗布本發明的液晶配向劑而形成塗膜。另一方面,於將本發明的液晶配向劑適用於具有IPS型、FFS型液晶單元的液晶顯示元件中的情況下,將在單面具有透明導電膜或金屬膜圖案化為梳齒狀而成的電極的基板、與未設置電極的對向基板作為一對,於梳齒狀電極的形成面、對向基板的單面分別塗布本發明的液晶配向劑而形成塗膜。 Here, when the liquid crystal alignment agent of the present invention is applied to a liquid crystal display device having a TN type or STN type liquid crystal cell, two substrates each having a patterned transparent conductive film are provided as a pair. The liquid crystal alignment agent of the present invention is applied onto the transparent conductive film forming surface to form a coating film. On the other hand, when the liquid crystal alignment agent of the present invention is applied to a liquid crystal display device having an IPS type or FFS type liquid crystal cell, a transparent conductive film or a metal film is patterned on one surface into a comb shape. The substrate of the electrode and the counter substrate not provided with the electrode are paired, and the liquid crystal alignment agent of the present invention is applied to each of the forming surface of the comb-shaped electrode and the single surface of the counter substrate to form a coating film.
於任意的情況下,上述基板例如可使用包含如浮法玻璃、鈉玻璃這樣的玻璃,如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯這樣的塑膠的透明基板等。上述透明導電膜例如可使用包含In2O3-SnO2的ITO膜、包含SnO2的NESA(注冊商標)膜等。上述金屬膜例如可使用包含鉻等金屬的膜。於透明導電膜及金屬膜的圖案化中,例如可利用:於形成無圖案的透明導電膜後,利用光蝕刻法、濺鍍法等而形成圖案的方法;於形成透明導電膜時使用具有所期望的圖案的掩模的方法等。 In any case, the substrate may be, for example, a glass such as float glass or soda glass, such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate. Plastic transparent substrate, etc. As the transparent conductive film, for example, an ITO film containing In 2 O 3 —SnO 2 , a NESA (registered trademark) film containing SnO 2 , or the like can be used. As the metal film, for example, a film containing a metal such as chromium can be used. In the patterning of the transparent conductive film and the metal film, for example, a method of forming a pattern by a photolithography method, a sputtering method, or the like after forming a transparent conductive film having no pattern can be used, and a method for forming a transparent conductive film can be used. A method of masking a desired pattern, and the like.
於基板上塗布液晶配向劑時為了使基板或導電膜或者電極與塗膜之接著性進一步良好,亦可於基板及電極上預先塗布官能性矽烷化合物、鈦酸酯(titanate)等。 When the liquid crystal alignment agent is applied onto the substrate, in order to further improve the adhesion between the substrate or the conductive film or the electrode and the coating film, a functional decane compound, titanate or the like may be applied to the substrate and the electrode in advance.
於基板上塗布液晶配向劑可優選利用膠版印刷 法、旋塗法、輥塗法、噴墨印刷法等適宜的塗布方法而進行,其次,對塗布面進行預熱(預烘),其次進行煆燒(後烘),由此而形成塗膜。預烘條件例如是於40℃~120℃下進行0.1分鐘~5分鐘,後烘條件是在優選為120℃~300℃、更優選為150℃~250℃下進行優選為5分鐘~200分鐘,更優選為10分鐘~100分鐘。後烘後的塗膜的膜厚優選為0.001μm~1μm,更優選為0.005μm~0.5μm。 Coating the liquid crystal alignment agent on the substrate can preferably use offset printing By a suitable coating method such as a method, a spin coating method, a roll coating method, or an inkjet printing method, second, the coated surface is preheated (prebaked), and then calcined (post-baked) to form a coating film. . The prebaking conditions are, for example, from 40 ° C to 120 ° C for 0.1 minutes to 5 minutes, and the post-baking conditions are preferably from 120 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C, preferably from 5 minutes to 200 minutes. More preferably, it is 10 minutes - 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.
通過對如此而形成的塗膜照射已偏光的放射線而賦予液晶配向能。此處,放射線例如可使用包含150nm~800nm的波長的光的紫外線及可見光線,優選為包含200nm~400nm的波長的光的紫外線。 The coating film formed in this manner is irradiated with the polarized radiation to impart liquid crystal alignment energy. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 200 nm to 400 nm are preferable.
所使用的光源例如可使用低壓水銀燈、高壓水銀燈、氘燈、金鹵燈、氫共振燈、氙氣燈、准分子鐳射等。上述優選的波長區域的紫外線可通過將上述光源與例如濾鏡、衍射光柵等並用的方法等而獲得。 As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a hydrogen resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the above preferred wavelength region can be obtained by a method in which the above-mentioned light source is used in combination with, for example, a filter, a diffraction grating, or the like.
若使用本發明的液晶配向劑,則在通常必需照射10,000J/m2以上的紫外線的情況下,即使是8000J/m2亦可賦予良好的液晶配向能,有助於液晶顯示元件的生產性提高與製造成本的削減。 When the liquid crystal alignment agent of the present invention is used, when it is necessary to irradiate ultraviolet rays of 10,000 J/m 2 or more, it is possible to impart good liquid crystal alignment energy even at 8000 J/m 2 , which contributes to productivity of the liquid crystal display element. Increase and cut manufacturing costs.
本發明的液晶顯示元件包含使用該液晶配向劑而形成的液晶配向膜,因此能夠以較先前更少的放射線照 射量而賦予液晶配向能。因此,包含該液晶配向膜的液晶顯示元件能夠較先前更廉價地製造。本發明的液晶顯示元件例如可以如下方式而製造。 The liquid crystal display element of the present invention contains a liquid crystal alignment film formed using the liquid crystal alignment agent, and thus can be irradiated with less radiation than before. The amount of radiation gives the liquid crystal alignment energy. Therefore, the liquid crystal display element including the liquid crystal alignment film can be manufactured at a lower cost than before. The liquid crystal display element of the present invention can be produced, for example, in the following manner.
準備如上所述地形成有液晶配向膜的一對基板,製造於該一對基板間狹持有液晶的構成的液晶單元。製造液晶單元例如可列舉以下2種方法。 A pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a liquid crystal structure between the pair of substrates is manufactured. The following two methods are exemplified for the production of the liquid crystal cell.
第一種方法是自先前以來所已知的方法。以各個液晶配向膜相對向的方式介隔間隙(單元間隙)而將2枚基板對向配置,使用密封劑對2枚基板的周邊部進行貼合,於由基板表面及密封劑而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。 The first method is a method known from the previous one. The liquid crystal alignment film is opposed to each other so that the two substrates are opposed to each other with a gap (cell gap) therebetween, and the peripheral portions of the two substrates are bonded together using a sealant, and the cells are divided by the substrate surface and the sealant. After the filling liquid crystal is injected into the gap, the injection hole is sealed, whereby the liquid crystal cell can be manufactured.
第二種方法是被稱為滴注(One Drop Fill,ODF)方式的手法。於形成有液晶配向膜的2枚基板中的其中一枚基板上的規定位置塗布例如紫外光硬化性密封材料,進一步於液晶配向膜面上滴加液晶後,以液晶配向膜相對向的方式貼合另外一枚基板,其次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。 The second method is called the One Drop Fill (ODF) method. For example, an ultraviolet curable sealing material is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is further dropped on the liquid crystal alignment film surface, and then the liquid crystal alignment film is opposed to each other. The other substrate is bonded, and the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing agent, whereby the liquid crystal cell can be manufactured.
於利用任意方法的情況時,理想的是其次將液晶單元進一步加熱至所使用的液晶成為各向同性相的溫度,然後緩冷至室溫,由此而除去液晶填充時的流動配向。 In the case of using any method, it is preferred to further heat the liquid crystal cell to a temperature at which the liquid crystal used becomes an isotropic phase, and then gradually cool to room temperature, thereby removing the flow alignment at the time of liquid crystal filling.
其次,通過於液晶單元的外側表面貼合偏光板而可獲得本發明的液晶顯示元件。此處,可通過適當地調整形成有液晶配向膜的2枚基板上所照射的直線偏光放 射線的偏光方向所成的角度及各個基板與偏光板的角度而獲得所期望的液晶顯示元件。 Next, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, the linear polarized light irradiated on the two substrates on which the liquid crystal alignment film is formed can be appropriately adjusted. The angle formed by the polarization direction of the ray and the angle of each substrate and the polarizing plate are used to obtain a desired liquid crystal display element.
上述密封劑例如可使用作為間隔物的氧化鋁球及含有硬化劑的環氧樹脂等。 As the sealing agent, for example, an alumina ball as a spacer, an epoxy resin containing a curing agent, or the like can be used.
上述液晶例如可使用向列型液晶、層列型液晶等。 優選形成向列型液晶的具有正的介電各向異性的液晶,例如使用聯苯類液晶、苯基環己烷類液晶、酯類液晶、聯三苯(terphenyl)類液晶、聯苯基環己烷類液晶、嘧啶(pyrimidine)類液晶、二噁烷類液晶、雙環辛烷類液晶、立方烷類液晶等。而且,於上述液晶中例如亦可進一步添加如下化合物而使用:氯化膽甾醇、膽甾醇壬酸酯、膽甾醇碳酸酯等膽甾醇型液晶;作為商品名“C-15”、“CB-15”(以上由默克公司製造)而市售的手性劑;對癸氧基苯亞甲基-對氨基-2-甲基丁基肉桂酸酯(p-decyloxy benzylidene-p-amino-2-methyl butyl cinnamate)等鐵電(ferroelectric)液晶等。 For the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. It is preferable to form a liquid crystal having a positive dielectric anisotropy of a nematic liquid crystal, for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl ring. A hexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, for example, a cholesteric liquid crystal such as cholesteryl alcohol, cholesteryl phthalate or cholesteryl carbonate may be further added to the liquid crystal; for example, trade names "C-15" and "CB-15" (available from Merck) commercially available chiral agent; p-decyloxy-benzyl-2-methylbutyl cinnamate (p-decyloxy benzylidene-p-amino-2-) Methyl butyl cinnamate and other ferroelectric liquid crystals.
作為於液晶單元的外側所使用的偏光板,可列舉以乙酸纖維素保護膜夾持被稱為“H膜”的偏光膜(所述H膜是一面使聚乙烯醇延伸配向一面吸收碘而成的偏光膜)而成的偏光板或包含H膜自身的偏光板等。如上所述而製造的本發明的液晶顯示元件的顯示特性、電氣特性等諸性能優異。 The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing film called "H film" sandwiched between a cellulose acetate protective film (the H film is formed by absorbing iodine on one side of the polyvinyl alcohol. A polarizing film made of a polarizing film or a polarizing plate including the H film itself. The liquid crystal display element of the present invention produced as described above is excellent in display characteristics and electrical characteristics.
本發明的液晶配向劑所含有的聚合物具有包含上述式(1)或式(2)所表示的基的結構單元(I)。該聚合物優選為聚酯或聚硫酯,上述結構單元(I)更優選為上述式(3)、式(4)或式(5)所表示的結構單元,進一步更優選為上述式(3)所表示的結構單元。本發明的聚合物具有上述特定結構,因此作為該液晶配向劑中的[A]聚合物而適宜地使用,含有本發明的聚合物的該液晶配向劑對放射線的感光度高,可利用低照射量的放射線而形成具有優異的液晶配向能的液晶配向膜。另外,關於本發明的聚合物,可適用該液晶配向劑所含有的[A]聚合物的說明,因此省略此處的詳細說明。 The polymer contained in the liquid crystal alignment agent of the present invention has a structural unit (I) containing a group represented by the above formula (1) or formula (2). The polymer is preferably a polyester or a polythioester, and the structural unit (I) is more preferably a structural unit represented by the above formula (3), formula (4) or formula (5), and still more preferably the above formula (3). ) the structural unit represented. Since the polymer of the present invention has the above specific structure, it is suitably used as the [A] polymer in the liquid crystal alignment agent, and the liquid crystal alignment agent containing the polymer of the present invention has high sensitivity to radiation and can be used with low irradiation. The amount of radiation forms a liquid crystal alignment film having excellent liquid crystal alignment energy. Further, the description of the [A] polymer contained in the liquid crystal alignment agent can be applied to the polymer of the present invention, and thus the detailed description herein will be omitted.
以下,通過實例對本發明加以更具體的說明,但本發明並不受該些實例限制。 Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples.
依照下述流程而合成下述式(B-1)所表示的化合物。 The compound represented by the following formula (B-1) was synthesized according to the following scheme.
[化6]
將(E)-肉桂酸2.00g加入至水/乙醇=1/1溶液10mL中,於油浴中加熱至90℃而使其完全溶解。使油浴的設定為50℃,緩緩進行結晶化,獲得1.3g(產率為65%)的(E)-肉桂酸的α-結晶。將再結晶而所得的α-結晶150mg在研缽中搗碎直至成為粉末狀,用2枚Pyrex(注冊商標)玻璃板進行夾持,以成為均等的厚度的方式而調製。使用500W的高壓水銀燈而進行4h的光照射,獲得上述式(B-1)所表示的化合物(B-1)147mg。另外,以上述的標度反覆進行合成,由此而確保以後的聚酯的合成例中的必需量。 2.00 g of (E)-cinnamic acid was added to 10 mL of a water/ethanol = 1/1 solution, and heated to 90 ° C in an oil bath to completely dissolve. The oil bath was set to 50 ° C, and crystallization was gradually carried out to obtain 1.3 g (yield of 65%) of α-crystal of (E)-cinnamic acid. 150 mg of the α-crystal obtained by recrystallization was pulverized in a mortar until it was in a powder form, and it was prepared by sandwiching two Pyrex (registered trademark) glass plates to have a uniform thickness. Light irradiation was performed for 4 hours using a 500 W high pressure mercury lamp, and 147 mg of the compound (B-1) represented by the above formula (B-1) was obtained. Further, the synthesis is repeated over the above-described scale, thereby ensuring the necessary amount in the subsequent synthesis example of the polyester.
聚酯的合成中所使用的二環氧化合物如下所示。 The diepoxy compounds used in the synthesis of the polyester are as follows.
[化7]
將化合物(B-1)0.1莫耳(29.62g)與上述式(E-1)所表示的二環氧化合物(E-1)0.1莫耳(17.72g)溶解於N-甲基-2-吡咯烷酮110.46g中,於140℃下使其反應9小時。其次,將反應混合物與大量過剩的甲醇混合,使反應生成物沉澱。其後,用甲醇加以清洗,於減壓下、40℃下使其乾燥15小時而獲得聚酯(A-1)45.9g(產率為97.0%)。 0.1 mol (29.62 g) of the compound (B-1) and 0.1 mol (17.72 g) of the diepoxy compound (E-1) represented by the above formula (E-1) were dissolved in N-methyl-2- In 110.46 g of pyrrolidone, the reaction was carried out at 140 ° C for 9 hours. Next, the reaction mixture was mixed with a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 45.9 g of a polyester (A-1) (yield: 97.0%).
將二環氧化合物設為上述式(E-2)所表示的化合物(E-2),除此以外與實例1同樣地進行而獲得聚酯(A-2)。 A polyester (A-2) was obtained in the same manner as in Example 1 except that the compound (E-2) represented by the above formula (E-2) was used.
將1,2,3,4-環丁烷四甲酸二酐0.1莫耳(19.61g)與下述二胺化合物(D-1)0.1莫耳(41.05g)溶解於N-甲基-2-吡咯烷酮343.74g中,於室溫下進行6小時的反應。其次,將反應混合物與大量過剩的甲醇混合,使 反應生成物沉澱。其後,以甲醇加以清洗,於減壓下、40℃下進行15小時的乾燥而獲得聚醯胺酸(a-1)60g(產率98.9%)。 0.1 mol (1. 156 g) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 0.1 mol (41.05 g) of the following diamine compound (D-1) were dissolved in N-methyl-2- The reaction was carried out for 6 hours at room temperature in 343.74 g of pyrrolidone. Second, the reaction mixture is mixed with a large excess of methanol to make The reaction product precipitated. Thereafter, the mixture was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 60 g of polylysine (a-1) (yield 98.9%).
將二胺化合物分別設為下述(D-2)或(D-3),除此以外與比較合成例1同樣地進行而分別獲得聚醯胺酸(a-2)及聚醯胺酸(a-3)。 In the same manner as in Comparative Synthesis Example 1, except that the diamine compound was used as the following (D-2) or (D-3), respectively, polyphosphoric acid (a-2) and polylysine were obtained. A-3).
D-1:2,2-雙[4-(4-氨基苯氧基)苯基]丙烷 D-1: 2,2-bis[4-(4-aminophenoxy)phenyl]propane
D-2:對苯二胺 D-2: p-phenylenediamine
D-3:4,4'-二氨基二苯醚 D-3: 4,4'-diaminodiphenyl ether
於含有上述合成例1中所得的聚酯(A-1)的溶液中加入N-甲基-2-吡咯烷酮(NMP)及丁基溶纖劑(BC),相對於聚醯胺酸(A1-1)之合計100質量份而進一步加入20質量份的N,N,N',N'-四縮水甘油基-4,4'-二氨基二苯基甲烷作為環氧化合物,進行充分攪拌,製成溶劑組成為NMP:BC=60:40(質量比)、固形物濃度為2.5質量%的溶液。使用孔徑為1μm的篩檢程式對該溶液進行過濾,由此調製液晶配向劑(S-1)。 N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solution containing the polyester (A-1) obtained in the above Synthesis Example 1, relative to poly-proline (A1-1) 100 parts by mass in total, and further adding 20 parts by mass of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane as an epoxy compound, and sufficiently stirred to prepare a solvent The composition was a solution of NMP: BC = 60: 40 (mass ratio) and a solid concentration of 2.5% by mass. This solution was filtered using a screening procedure having a pore size of 1 μm to prepare a liquid crystal alignment agent (S-1).
於實例3中,分別使用聚酯(A-2)、聚醯胺酸(a-1)~聚醯胺酸(a-3)代替聚酯(A-1),除此以外與實例3 同樣地進行而調製液晶配向劑S-2、液晶配向劑s-1~液晶配向劑s-3。 In Example 3, polyester (A-2) and polylysine (a-1)-polyproline (a-3) were used instead of polyester (A-1), respectively, and Example 3 was used. The liquid crystal alignment agent S-2, the liquid crystal alignment agent s-1 to the liquid crystal alignment agent s-3 were prepared in the same manner.
將上述所調製的液晶配向劑(S-1~S-2及s-1~s-3),分別使用旋轉器而以膜厚成為0.1μm的方式塗布於包含ITO膜的附有透明電極的玻璃基板的透明電極面上,於200℃下進行1小時的乾燥而形成塗膜。使用Hg-Xe燈,自基板法線方向對該塗膜表面照射包含254um的明線的偏光紫外線8,000J/m2、10,000J/m2或50,000J/m2,形成液晶配向膜。其次,對於進行了上述光照射處理的一對基板,於形成有液晶配向膜的面的邊緣,留出液晶注入口而絲網印刷塗布放入有直徑為5.5μm的氧化鋁球的環氧樹脂接著劑,然後以光照射方向成為逆平行的方式重疊基板而進行壓接,於150℃下以1小時而使接著劑熱硬化。其次,自液晶注入口於一對基板間填充向列型液晶(默克公司製造、ZLI-1565),然後用環氧系接著劑對液晶注入口進行密封。進一步於150℃下對其進行加熱後緩冷至室溫以除去液晶注入時的流動配向。其次,以使偏光板的偏光方向互相正交、且其中一個與液晶配向膜的偏光紫外線的光軸在基板面上的投影方向正交、另外一個變平行的方式,於基板的外側的兩個面貼合偏光板,從而製作液晶顯示元件。 The liquid crystal alignment agents (S-1 to S-2 and s-1 to s-3) prepared as described above were applied to a transparent electrode containing an ITO film so as to have a film thickness of 0.1 μm using a rotator. The transparent electrode surface of the glass substrate was dried at 200 ° C for 1 hour to form a coating film. Using a Hg-Xe lamp, the surface of the coating film was irradiated with a polarized ultraviolet ray of 8,000 J/m 2 , 10,000 J/m 2 or 50,000 J/m 2 of a bright line of 254 μm from the normal direction of the substrate to form a liquid crystal alignment film. Next, for the pair of substrates subjected to the above-described light irradiation treatment, an epoxy resin having a diameter of 5.5 μm was placed on the edge of the surface on which the liquid crystal alignment film was formed, leaving a liquid crystal injection port and screen-printing and applying an alumina ball having a diameter of 5.5 μm. Next, the substrate was laminated so that the light irradiation direction became antiparallel, and the pressure was bonded, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a nematic liquid crystal (manufactured by Merck & Co., Ltd., ZLI-1565) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, it was heated at 150 ° C and then slowly cooled to room temperature to remove the flow alignment at the time of liquid crystal injection. Next, two of the outer sides of the substrate are arranged such that the polarization directions of the polarizing plates are orthogonal to each other, and one of the optical axes of the polarized ultraviolet rays of the liquid crystal alignment film on the substrate surface is orthogonal to each other and the other is parallelized. The polarizing plate is attached to the surface to fabricate a liquid crystal display element.
對上述各個液晶顯示元件進行下述評價。將結果示於表1中。 Each of the above liquid crystal display elements was subjected to the following evaluation. The results are shown in Table 1.
用偏光顯微鏡觀察在液晶顯示元件中,開/關(施加/解除)電壓時的異常區的有無,將不存在異常區的情況判斷為“良好”,將即使存在一個異常區的情況也判定為“不良”。 The presence or absence of an abnormal region when the voltage is turned on/off (applied/released) in the liquid crystal display device is observed with a polarizing microscope, and the case where the abnormal region is not present is judged as "good", and even if there is one abnormal region, it is determined as "bad".
對偏光紫外線照射量為8,000J/m2而製作的液晶顯示元件,以60微秒的施加、167毫秒的跨距(span)而施加5V的電壓後,測定解除施加167毫秒後的電壓保持率。測定裝置使用東陽技術公司製造的VHR-1。將電壓保持率為90%以上的情況判斷為“良好”,將其以外的情況判斷為“不良”。 A liquid crystal display element produced by irradiating a polarized ultraviolet ray of 8,000 J/m 2 was applied with a voltage of 5 V after application of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate after 167 milliseconds of application was released. . The measuring device used VHR-1 manufactured by Dongyang Technology Co., Ltd. The case where the voltage holding ratio was 90% or more was judged as "good", and the other cases were judged as "bad".
如表1所示,實例的液晶配向劑對放射線的感光度高,即使在8,000J/m2的低照射量下,包含所得的液晶配向膜的液晶顯示元件的液晶配向性亦變良好。而且,電壓保持率亦良好。與其加以比較,於比較例中,在8,000J/m2的低照射量下,觀察到異常區,液晶配向性 變得不良。根據以上可知:本發明的液晶配向劑的放射線感光度優異,能夠以低照射量的放射線照射而形成具有優異的液晶配向性的液晶配向膜。 As shown in Table 1, the liquid crystal alignment agent of the example has high sensitivity to radiation, and even at a low irradiation amount of 8,000 J/m 2 , the liquid crystal alignment property of the liquid crystal display element including the obtained liquid crystal alignment film is also improved. Moreover, the voltage holding ratio is also good. In comparison with this, in the comparative example, an abnormal region was observed at a low irradiation amount of 8,000 J/m 2 , and liquid crystal alignment became poor. According to the above, the liquid crystal alignment agent of the present invention is excellent in radiation sensitivity, and can form a liquid crystal alignment film having excellent liquid crystal alignment properties by irradiation with a low irradiation amount.
本發明的液晶配向劑的放射線感光度高,能夠以低照射量的放射線照射而形成具有優異的液晶配向性的液晶配向膜,因此其生產效率良好,可削減生產成本。另外,包含使用本發明的液晶配向劑而形成的液晶配向膜的液晶顯示元件的電氣特性等諸性能亦優異。因此,本發明的液晶配向劑、液晶配向膜、該液晶配向膜的形成方法及液晶顯示元件可於IPS型、FFS型等液晶顯示元件中適宜地使用。 Since the liquid crystal alignment agent of the present invention has high radiation sensitivity and can form a liquid crystal alignment film having excellent liquid crystal alignment properties by irradiation with a low irradiation amount, the production efficiency is good, and the production cost can be reduced. In addition, the liquid crystal display element including the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention is also excellent in electrical characteristics and the like. Therefore, the liquid crystal alignment agent, the liquid crystal alignment film, the method of forming the liquid crystal alignment film, and the liquid crystal display element of the present invention can be suitably used for liquid crystal display elements such as IPS type and FFS type.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,故本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
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