JP2023052560A - Polymer, liquid crystal aligning agent produced using the same, liquid crystal alignment film, and liquid crystal display device using the same - Google Patents
Polymer, liquid crystal aligning agent produced using the same, liquid crystal alignment film, and liquid crystal display device using the same Download PDFInfo
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- JP2023052560A JP2023052560A JP2023007632A JP2023007632A JP2023052560A JP 2023052560 A JP2023052560 A JP 2023052560A JP 2023007632 A JP2023007632 A JP 2023007632A JP 2023007632 A JP2023007632 A JP 2023007632A JP 2023052560 A JP2023052560 A JP 2023052560A
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- liquid crystal
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- polymer
- carbon atoms
- aligning agent
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- 229920000642 polymer Polymers 0.000 title claims abstract description 91
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 30
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
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- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、液晶配向剤、それを得るための重合体、液晶配向膜、及びそれを用いた液晶表示素子に関する。 TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent, a polymer for obtaining the same, a liquid crystal aligning film, and a liquid crystal display device using the same.
液晶表示素子において液晶配向膜は、液晶を一定の方向に配向させる役割を担う。現在、工業的に利用されている主な液晶配向膜は、ポリアミド酸（ポリイミド前駆体やポリアミック酸ともいわれる。）やポリイミド溶液からなるポリイミド系の液晶配向剤を基板に塗布し、焼成することで成膜される。また、基板面に対して液晶を平行配向又は傾斜配向させる場合、成膜した後、ラビングによる表面延伸処理（ラビング処理）が行われている。ラビング処理に代わる方法として、偏光紫外線の照射等による異方性光化学反応を利用する方法も提案されている。 In the liquid crystal display element, the liquid crystal alignment film plays a role of orienting the liquid crystal in a certain direction. Currently, the main liquid crystal alignment films used industrially are made by coating a substrate with a polyimide-based liquid crystal alignment agent made of polyamic acid (also known as a polyimide precursor or polyamic acid) or a polyimide solution, followed by baking. A film is formed. Further, in the case of aligning the liquid crystal parallel or obliquely with respect to the substrate surface, surface stretching treatment by rubbing (rubbing treatment) is performed after film formation. As an alternative method to the rubbing treatment, a method utilizing an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like has also been proposed.
液晶表示素子の表示特性の向上のために、数々の技術が提案されてきた。例えば、特許文献１（特開平２－２８７３２４号公報）では、高い電圧保持率（ＶＨＲ）を得るために、特定の繰り返し構造を有するポリイミド樹脂を用いることが提案されている。また、特許文献２（特開平１０－１０４６３３号公報）では、残像が消去されるまでの時間を短くするために、イミド基以外に窒素原子を有する可溶性ポリイミドを用いることが提案されている。 Various techniques have been proposed to improve the display characteristics of liquid crystal display elements. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2-287324) proposes to use a polyimide resin having a specific repeating structure in order to obtain a high voltage holding ratio (VHR). In addition, Patent Document 2 (Japanese Patent Application Laid-Open No. 10-104633) proposes to use a soluble polyimide having a nitrogen atom in addition to the imide group in order to shorten the time until afterimages are erased.
近年、液晶ディスプレイ（ＬＣＤパネル）の多機能化・多様化に伴い、ガラス基板を用いたディスプレイから、樹脂基板（プラスチック基板、すなわちフィルム基板）を用いたフレキシブルなディスプレイへと、開発が進んでいる。それに従い、低温での焼成で得ることができる液晶配向膜が必要となってきており、加えて、液晶配向膜に要求される信頼性(高い電圧保持率等)も求められるようになってきている。 In recent years, along with the multi-functionalization and diversification of liquid crystal displays (LCD panels), development has progressed from displays using glass substrates to flexible displays using resin substrates (plastic substrates, i.e., film substrates). . Accordingly, a liquid crystal alignment film that can be obtained by firing at a low temperature is required, and in addition, the reliability required for the liquid crystal alignment film (high voltage holding ratio, etc.) is also required. there is
液晶配向膜に用いられる材料としては、ポリアミド酸やポリアミド酸エステル等のポリイミド前駆体や、それらを焼成により或いは化学反応により脱水することで得られるポリイミド等が挙げられる。このうち、ポリアミド酸は、その合成が容易であり、かつ溶媒への溶解性に優れるため、基板への塗布性・成膜性に優れる液晶配向剤を得ることができる。しかし、ポリアミド酸は、その構造上、加水分解等により分解しやすいため、これを用いて得た液晶配向膜では、長期に亘って信頼性を確保することが難しい。 Examples of materials used for liquid crystal alignment films include polyimide precursors such as polyamic acid and polyamic acid esters, and polyimides obtained by dehydrating them by baking or chemical reaction. Among these, polyamic acid is easy to synthesize and has excellent solubility in a solvent, so that a liquid crystal aligning agent having excellent coatability and film-forming properties on a substrate can be obtained. However, due to its structure, polyamic acid is easily decomposed by hydrolysis or the like. Therefore, it is difficult to ensure long-term reliability of a liquid crystal alignment film obtained using polyamic acid.
一方、可溶性ポリイミド（ポリアミド酸の脱水反応により得られる溶媒に可溶なポリイミド）は、プレイミド化されているため、加熱してイミド化させる熱硬化工程が必要なく、そのため、比較的低温での焼成が可能になる。また、化学的安定性・耐熱性に優れるため、可溶性ポリイミドを用いて得た液晶配向膜では、長期に亘って信頼性を確保しやすくなる。しかし、可溶性ポリイミドは、溶解させることができる溶媒の選択肢が少なく、それゆえに、使用できる溶媒が限られ、その結果、可溶性ポリイミドを用いる場合、塗布中・成膜中に析出等が生じ、塗膜に欠陥ができやすい。近年の、ＬＣＤパネルの大型化・高精細化・使用環境の多様化に伴い、それぞれの問題を解決するとともに、各種特性を向上させることができる手法の探索が求められている。 On the other hand, soluble polyimide (solvent-soluble polyimide obtained by the dehydration reaction of polyamic acid) is preimidized, so there is no need for a thermosetting process for imidization by heating, and therefore baking at a relatively low temperature is required. becomes possible. Moreover, since it is excellent in chemical stability and heat resistance, it becomes easy to ensure reliability over a long period of time in the liquid crystal aligning film obtained using a soluble polyimide. However, soluble polyimides have few options for solvents that can be dissolved, and therefore the solvents that can be used are limited. As a result, when soluble polyimides are used, precipitation etc. prone to defects. In recent years, with the increase in size and definition of LCD panels and the diversification of usage environments, there is a demand for methods that can solve these problems and improve various characteristics.
本発明は、上記の事情に鑑みなされたものであって、その課題は、低温での焼成が可能、かつ印刷性（得られる重合体の、有機溶媒への溶解性）が良好である液晶配向剤を提供することにある。また、上記液晶配向剤を得ることができる重合体を提供することにある。また、ラビング処理を行なう場合にはラビング耐性に優れる上液晶配向性が良好であり（すなわち、低プレチルト角を実現でき）、かつ電圧保持率が高い液晶配向膜を提供することにある。更に、上記液晶配向膜を有する液晶表示素子を提供することにある。 The present invention has been made in view of the above circumstances, and the problem is that the liquid crystal alignment can be fired at a low temperature and has good printability (solubility of the resulting polymer in an organic solvent). It is to provide agents. Moreover, it is providing the polymer which can obtain the said liquid crystal aligning agent. Another object of the present invention is to provide a liquid crystal alignment film which has excellent rubbing resistance, good liquid crystal alignment (that is, can achieve a low pretilt angle) and a high voltage holding ratio when a rubbing treatment is performed. A further object of the present invention is to provide a liquid crystal display device having the liquid crystal alignment film.
本発明者は、鋭意研究した結果、特定の構造を有する重合体、及びそれを用いた液晶配向剤が、上記の目的を達成するために有効であることを見出し、本発明を完成するに至った。なお、上記重合体は新規であり、上記重合体を得るためのモノマーも、新規化合物を含んでいる。 As a result of intensive research, the present inventors have found that a polymer having a specific structure and a liquid crystal aligning agent using the polymer are effective for achieving the above objects, and have completed the present invention. rice field. The above polymer is novel, and the monomers for obtaining the above polymer also contain novel compounds.
すなわち、本発明は、以下１．～９．を要旨とする。
１． 下式(１)で表される構造を有する、ポリウレア及びポリウレア共重合体である重合体を含有する、液晶配向剤。
That is, the present invention provides the following 1. ~ 9. is the gist.
1. A liquid crystal aligning agent containing a polyurea and a polyurea copolymer having a structure represented by the following formula (1).
２． 下式(２)で表されるジアミン誘導体と、ジイソシアネート誘導体と、から得られる、ポリウレア及びポリウレア共重合体である重合体を含有する、１．に記載の液晶配向剤。 2. 1. containing a polyurea and a polyurea copolymer obtained from a diamine derivative represented by the following formula (2) and a diisocyanate derivative; Liquid crystal aligning agent as described in .
３． 前記ジアミン誘導体のうち下式（３）で表されるジアミノ化合物と、ジイソシアネート誘導体と、から得られる、ポリウレア及びポリウレア共重合体である重合体を含有する、２．に記載の液晶配向剤。 3. 2. containing a polyurea and a polyurea copolymer obtained from a diamine compound represented by the following formula (3) among the diamine derivatives and a diisocyanate derivative; Liquid crystal aligning agent as described in .
４． 前記ジアミン誘導体のうち下式（３－ａ）で表されるジアミノ化合物と、ジイソシアネート誘導体と、から得られる、ポリウレア及びポリウレア共重合体である重合体を含有する、３．に記載の液晶配向剤。 4. 2. containing a polyurea and a polyurea copolymer obtained from a diamine compound represented by the following formula (3-a) among the diamine derivatives and a diisocyanate derivative; Liquid crystal aligning agent as described in .
５． 下式（３－１）で表されるジアミノ化合物と、ジイソシアネート誘導体と、から得られる、重合体。 5. A polymer obtained from a diamino compound represented by the following formula (3-1) and a diisocyanate derivative.
６． 前記ジアミノ化合物と、下式（４－１）～式（４－１１）及び式（４－１３）で表されるジイソシアネート誘導体の少なくとも１つと、から得られる、５．に記載の重合体。 6. 5. obtained from the diamino compound and at least one diisocyanate derivative represented by the following formulas (4-1) to (4-11) and (4-13); The polymer described in .
７． ５．又は６．に記載の重合体を用いた、液晶配向剤。 7. 5. or 6. Liquid crystal aligning agent using the polymer as described in 1.
８． １．～４．及び７．の何れか１つに記載の液晶配向剤から得られる、液晶配向膜。 8. 1. ~ 4. and 7. A liquid crystal aligning film obtained from the liquid crystal aligning agent according to any one of .
９． ８．に記載の液晶配向膜を用いた、液晶表示素子。 9. 8. A liquid crystal display device using the liquid crystal alignment film according to 1.
本発明によれば、低温での焼成が可能であり、高品位な液晶配向膜を得ることができる上、印刷性に優れる液晶配向剤を提供することができる。また、本発明によれば、上記液晶配向剤を得るための新規な重合体を提供することができる。また、本発明によれば、ラビング処理を行なう場合にはラビング耐性に優れる上、低プレチルト角を実現できるのに加えて、電圧保持率が高い液晶配向膜を提供することができる。更に、本発明によれば、上記液晶配向膜を用いた液晶表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, baking at low temperature is possible, a high-quality liquid crystal aligning film can be obtained, and also the liquid crystal aligning agent which is excellent in printability can be provided. Moreover, according to this invention, the novel polymer for obtaining the said liquid crystal aligning agent can be provided. Moreover, according to the present invention, it is possible to provide a liquid crystal alignment film which is excellent in rubbing resistance when a rubbing treatment is performed, can achieve a low pretilt angle, and has a high voltage holding ratio. Furthermore, according to the present invention, it is possible to provide a liquid crystal display device using the liquid crystal alignment film.
本発明の一態様である液晶配向剤は、式（２）で表されるジアミン誘導体(以下「ジアミン」と称することがある)と、ジイソシアネート誘導体(以下「ジイソシアネート」と称することがある)と、から得られる、本発明の一態様である重合体を含有する。 The liquid crystal aligning agent which is one aspect of the present invention comprises a diamine derivative (hereinafter sometimes referred to as "diamine") represented by formula (2), a diisocyanate derivative (hereinafter sometimes referred to as "diisocyanate"), It contains a polymer that is one embodiment of the present invention obtained from
＜本発明に使用するジアミン＞
本発明に使用するジアミンは、式（２）で表される。
<Diamine used in the present invention>
The diamine used in the present invention is represented by formula (2).
モノマーの重合反応性や、耐熱性や液晶配向性に優れた液晶配向膜を得ることができる、等の観点からは、式（２）中、Ａは芳香族炭化水素基、Ｂは炭素数１～３の脂肪族炭化水素基、Ｃは単結合、であると好ましい。式（２）は、具体的には以下の構造が挙げられる。 From the viewpoint of the ability to obtain a liquid crystal alignment film with excellent polymerization reactivity of the monomer, heat resistance, and liquid crystal alignment, in formula (2), A is an aromatic hydrocarbon group, and B has 1 carbon atom. ∼3 aliphatic hydrocarbon groups and C is a single bond. Formula (2) specifically includes the following structures.
ジアミンを合成するための試薬を入手するのが容易である、ジイソシアネートとの反応性が良好である、得られる上記重合体の物性が良好になる、等の観点を鑑みた場合、式（３）中、Ａｒはフェニル基が好ましく、Ｒ２は水素原子が好ましい。従って、式（３）は、好ましくは以下式（３－ａ）´で表される構造である。なかでも、式（３）中、Ｒａ及びＲｂはそれぞれ水素原子であることが好ましい。従って、式（３）は、特に好ましくは、式（３－ａ）で表される。 In view of the ease of obtaining a reagent for synthesizing a diamine, good reactivity with diisocyanate, and good physical properties of the obtained polymer, the formula (3) Among them, Ar is preferably a phenyl group, and R 2 is preferably a hydrogen atom. Therefore, formula (3) is preferably a structure represented by formula (3-a)' below. Above all, in formula (3), Ra and Rb are each preferably a hydrogen atom. Therefore, formula (3) is particularly preferably represented by formula (3-a).
目的とするモノマーを好適に得ることができる、上記の特性のすべてが良好になりやすい、等の観点からは、上記式（３－ａ）´は、好ましくは下式（３－１）で表される。 From the viewpoint that the desired monomer can be suitably obtained and that all of the above characteristics tend to be good, the above formula (3-a)' is preferably represented by the following formula (3-1). be done.
ただし、式（２）で表されるジアミンの具体例は、式（３）で表されるジアミンに限定されない。本発明の効果（例えば、低プレチルト角を実現できること）が損なわれない範囲であれば、上記重合体を合成するにあたり、式（２）又は式（３）で表されるジアミンの一部を、後述する式（５）で表されるジアミンに置き換えてもよい。 However, specific examples of the diamine represented by formula (2) are not limited to the diamine represented by formula (3). In synthesizing the above polymer, a part of the diamine represented by formula (2) or (3) is It may be replaced with a diamine represented by formula (5) described later.
＜本発明に使用するジイソシアネート＞
本発明に使用するジイソシアネートは、式（４）で表される。
<Diisocyanate used in the present invention>
The diisocyanate used in the present invention is represented by formula (4).
式（４－１）～式（４－５）で表される脂肪族ジイソシアネートを用いる場合は、式（４－６）～式（４－１３）で表される芳香族ジイソシアネートを用いる場合に比べ、得られる重合体が溶媒に良好に溶解するようになる。一方、上記芳香族ジイソシアネートは、上記脂肪族ジイソシアネートに比べ、ジアミンと良好に反応する。例えば、式（４－６）や式（４－７）に示すような芳香族ジイソシアネートは、ジアミンと良好に反応し、得られる液晶配向膜の耐熱性を向上させることができる。 When using an aliphatic diisocyanate represented by formulas (4-1) to (4-5), compared to the case of using an aromatic diisocyanate represented by formulas (4-6) to (4-13) , the resulting polymer becomes well soluble in the solvent. On the other hand, the aromatic diisocyanate reacts better with diamines than the aliphatic diisocyanate. For example, aromatic diisocyanates represented by formulas (4-6) and (4-7) react well with diamines and can improve the heat resistance of the resulting liquid crystal alignment film.
上記重合体を得るのに汎用性が高い化合物である、得られる上記重合体の特性が良好になる、等の観点からは、式（４）は、式（４－１）、式（４－７）、式（４－８）、式（４－９）、又は式（４－１０）が好ましい。また、式（４）は、得られる液晶配向膜の液晶配向性が良好になる観点からは、式（４－１３）が好ましい。 From the viewpoint of being a compound with high versatility for obtaining the polymer, the properties of the obtained polymer being good, etc., formula (4) is represented by formula (4-1), formula (4- 7), formula (4-8), formula (4-9), or formula (4-10) is preferred. Formula (4) is preferably Formula (4-13) from the viewpoint that the obtained liquid crystal alignment film has good liquid crystal orientation.
ただし、本発明の趣旨の範囲内であれば、式（４）は上記に限定されない。得られる重合体、液晶配向剤、及び液晶配向膜等の目標とする特性に応じて、入手が容易なジイソシアネートを好適に使用することができる。ジイソシアネートは、２種以上を併用して使用してもよい。 However, the formula (4) is not limited to the above as long as it is within the scope of the present invention. An easily available diisocyanate can be suitably used depending on the target properties of the resulting polymer, liquid crystal aligning agent, liquid crystal aligning film, and the like. Two or more diisocyanates may be used in combination.
＜ジアミン＞
上記重合体を得るにあたり、式(２)で表されるジアミンの一部を、それ以外のジアミン（他のジアミン）に置き換えてもよい。一般に、ジアミンは種類が豊富であり、また、様々な機能を有する有機基を持つ化合物が多いため、他のジアミンを併用することで、上記重合体に更なる効果を付与することができたり、上記ジアミンの上記効果を更に向上させることができたりする場合がある。式(２)で表されるジアミンのモル数に対する、他のジアミンのモル数の比は、本発明の効果（例えば、低プレチルト角を実現できること）が損なわれない範囲内で任意である。例えば、上記比は、０．５以下とすることができる。勿論、他のジアミンを併用しなくてもよい。このような他のジアミンとしては、例えば、下式（５）で表されるジアミンが挙げられる。
<Diamine>
In obtaining the above polymer, part of the diamine represented by formula (2) may be replaced with other diamine (other diamine). In general, there are many kinds of diamines, and there are many compounds having organic groups with various functions. In some cases, the above effects of the diamine can be further improved. The ratio of the number of moles of the other diamine to the number of moles of the diamine represented by formula (2) is arbitrary within a range that does not impair the effects of the present invention (for example, the ability to achieve a low pretilt angle). For example, the above ratio can be 0.5 or less. Of course, other diamines may not be used together. Such other diamines include, for example, diamines represented by the following formula (5).
＜重合体＞
ポリウレア及びポリウレア共重合体である重合体は、ポリウレア及び／又はポリウレア共重合体である重合体を意味する。かかる重合体は、式（１）で表される。
<Polymer>
Polymers that are polyureas and polyurea copolymers mean polymers that are polyureas and/or polyurea copolymers. Such polymers are represented by formula (1).
ポリウレアは、ウレア結合の部位の極性により強固な水素結合を結ぶため、得られる膜は機械強度に優れる。一方、その強い水素結合力がポリマーの凝集の要因となり、ポリマー溶液の安定性等を悪くする場合がある(ポリマー溶液の粘度が増加する、ポリマーの一部が析出する、ポリマー溶液がゲル化する、等)。そのため、ポリウレアの構造によっては、使用可能な溶媒が制限され、例えば、高極性かつ高沸点の溶媒を使用する必要がある。 Since polyurea forms strong hydrogen bonds due to the polarity of the urea bond sites, the resulting film has excellent mechanical strength. On the other hand, the strong hydrogen bonding force causes aggregation of the polymer, which may deteriorate the stability of the polymer solution (the viscosity of the polymer solution increases, part of the polymer precipitates, and the polymer solution gels). ,etc). Therefore, depending on the structure of polyurea, usable solvents are limited, and for example, it is necessary to use highly polar and high boiling point solvents.
上記重合体は、式（１）で表される構造、すなわち、ポリウレアのＮ原子上に式（１－１）で表される有機基が置換された構造を有している。式（１－１）で表される有機基が水素結合の形成を阻害し、これにより、ポリマー同士の凝集を妨ぐことができる。このため、ポリマー溶液の安定性が大きく向上する。よって、ポリウレアのポリマー溶液を得るにあたり、使用可能な溶媒の選択の幅を広げることができ、ひいては、低温での焼成や、印刷性の大きな改善も可能となる。なお、ウレア結合の部位は、成膜時の焼成温度によっては、ヒダントイン環や分子間架橋を形成する場合がある。 The polymer has a structure represented by formula (1), that is, a structure in which an N atom of polyurea is substituted with an organic group represented by formula (1-1). The organic group represented by formula (1-1) inhibits the formation of hydrogen bonds, thereby preventing the aggregation of polymers. Therefore, the stability of the polymer solution is greatly improved. Therefore, in obtaining a polyurea polymer solution, it is possible to expand the range of selection of solvents that can be used, and in turn, it is possible to bake at a low temperature and greatly improve printability. The urea bond site may form a hydantoin ring or an intermolecular crosslink depending on the baking temperature during film formation.
＜反応溶液＞
反応溶液（上記重合体を得る為の反応に用いる有機溶媒）としては、上記重合体が溶解する溶液であれば特に限定されない。その具体例としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、イソプロピルアルコール、メトキシメチルペンタノール、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、ジオキサン、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド等が挙げられる。これらは単独で使用しても、２種以上を混合して使用してもよい。上記重合体が析出しない範囲であれば、上記重合体を溶解させない溶液であっても、上記反応溶液に混合して使用することができる。
<Reaction solution>
The reaction solution (organic solvent used in the reaction for obtaining the polymer) is not particularly limited as long as it is a solution in which the polymer is dissolved. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, Dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl Butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3 -ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and the like. These may be used alone or in combination of two or more. Even a solution that does not dissolve the polymer can be mixed with the reaction solution and used as long as the polymer does not precipitate.
また、反応溶液中の水分は重合反応を阻害し、更には生成した重合体を加水分解させる原因となるので、脱水乾燥させた反応溶液を用いることが好ましい。ジイソシアネートとジアミンとを反応溶液中で反応させる際には、ジアミンを分散或いは溶解させた反応溶液を攪拌させ、ジイソシアネートをそのまま、又は反応溶液に分散或いは溶解させて添加する方法、逆にジイソシアネートを分散又は溶解させた反応溶液にジアミンを添加する方法、ジイソシアネートとジアミンとを反応溶液に交互に添加する方法等が挙げられ、これらの何れの方法を用いてもよい。 Moreover, water in the reaction solution inhibits the polymerization reaction and further causes hydrolysis of the polymer produced, so it is preferable to use a reaction solution that has been dehydrated and dried. When the diisocyanate and the diamine are reacted in the reaction solution, the reaction solution in which the diamine is dispersed or dissolved is stirred, and the diisocyanate is added as it is or after being dispersed or dissolved in the reaction solution. Conversely, the diisocyanate is dispersed. Alternatively, a method of adding a diamine to a dissolved reaction solution, a method of alternately adding a diisocyanate and a diamine to a reaction solution, etc., may be used.
また、ジイソシアネート又はジアミンが複数種の化合物からなる場合は、予め混合した状態で反応させてもよく、個別に順次反応させてもよく、更に個別に反応させた低分子量体を混合反応させ高分子量体としてもよい。その際の重合温度は－２０℃から１５０℃の任意の温度を選択することができるが、好ましくは－５℃から１００℃の範囲である。また、反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応溶液の粘性が高くなり過ぎて均一な攪拌が困難となるので、ジイソシアネートとジアミンの反応溶液中での合計濃度は、好ましくは１質量％から５０質量％、より好ましくは５質量％から３０質量％である。反応初期は高濃度で行い、その後、反応溶液を追加することもできる。 In addition, when the diisocyanate or diamine is composed of a plurality of types of compounds, the reaction may be performed in a pre-mixed state, or may be reacted individually in sequence. It can be a body. The polymerization temperature at that time may be any temperature from -20°C to 150°C, preferably from -5°C to 100°C. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high-molecular-weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the total concentration of diisocyanate and diamine in the reaction solution is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass. It is also possible to carry out the reaction at a high concentration at the beginning of the reaction and then add the reaction solution.
ポリウレアの重合反応においては、ジイソシアネートの合計モル数と、ジアミンの合計モル数と、の比は０．８から１．２であることが好ましい。通常の重縮合反応と同様、このモル比が１．０に近いほど、生成する重合体の分子量は大きくなる。 In the polyurea polymerization reaction, the ratio of the total number of moles of diisocyanate to the total number of moles of diamine is preferably 0.8 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1.0, the higher the molecular weight of the resulting polymer.
[重合体の回収]
反応溶液から、生成した上記重合体を回収するには、反応溶液を貧溶媒に投入して上記重合体を沈殿させればよい。貧溶媒としては、メタノール、アセトン、ヘキサン、ブチルセロソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、水等を挙げることができる。貧溶媒に投入して沈殿させた上記重合体は、濾過して回収した後、常圧又は減圧下で、常温又は加熱して乾燥させることができる。また、回収した上記重合体を有機溶媒に再溶解させ、再沈殿及び再回収する操作を２回から１０回繰り返すと、上記重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの内から選ばれる３種以上の貧溶媒を用いると、精製の効率がより一層上がるので好ましい。
[Recovery of polymer]
In order to recover the produced polymer from the reaction solution, the reaction solution is poured into a poor solvent to precipitate the polymer. Poor solvents include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer precipitated by putting it in a poor solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by re-dissolving the recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering again 2 to 10 times. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more poor solvents selected from these, because the purification efficiency is further increased.
上記重合体の分子量は、上記重合体から得られる塗膜の強度、及び、塗膜を形成する時の作業の容易性、塗膜の膜厚の均一性、等を考慮した場合、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）法で測定した重量平均分子量で５，０００から１，０００，０００とするのが好ましく、より好ましくは、１０，０００から１５０，０００である。 The molecular weight of the polymer is determined by GPC (Gel The weight average molecular weight measured by Permeation Chromatography is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
＜液晶配向剤＞
本発明の一態様である液晶配向剤は、液晶配向膜を形成するための塗布液であり、塗膜（樹脂被膜）を形成するための樹脂成分が有機溶媒に溶解している。樹脂成分は、少なくとも一種の上記重合体を含む。液晶配向剤中の、樹脂成分の含有量は２質量％から２０質量％が好ましく、より好ましくは３質量％から１５質量％、特に好ましくは３質量％から１０質量％である。本発明において、樹脂成分に含まれる重合体は、その全てが上記重合体であってもよく、本発明の趣旨の範囲内であれば、それ以外の重合体（他の重合体）が含まれていてもよい。樹脂成分中、他の重合体の含有量は０．５質量％から１５質量％、好ましくは１質量％から１０質量％である。かかる他の重合体は、例えば、アクリルポリマー、メタクリルポリマー、ノボラック樹脂、ポリヒドロキシスチレン、ポリイミド前駆体、ポリイミド、ポリアミド、ポリエステル、セルロース、ポリシロキサン等が挙げられる。
<Liquid crystal aligning agent>
A liquid crystal aligning agent that is one aspect of the present invention is a coating liquid for forming a liquid crystal alignment film, and a resin component for forming a coating film (resin film) is dissolved in an organic solvent. The resin component contains at least one polymer described above. The content of the resin component in the liquid crystal aligning agent is preferably from 2% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, and particularly preferably from 3% by mass to 10% by mass. In the present invention, all of the polymers contained in the resin component may be the above polymers, and other polymers (other polymers) may be included within the scope of the present invention. may be The content of the other polymer in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass. Such other polymers include, for example, acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, cellulose, polysiloxanes, and the like.
上記液晶配向剤に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、２－ピロリドン、Ｎ－エチルピロリドン、Ｎ－ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、１，３－ジメチル－イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン等が挙げられる。これらは単独で使用しても、２種以上を混合して使用してもよい。 The organic solvent used for the said liquid crystal aligning agent will not be specifically limited if it is an organic solvent which dissolves a resin component. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethyl Propanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2 - Pentanone and the like. These may be used alone or in combination of two or more.
上記液晶配向剤は、上記以外の成分を含有してもよい。その例としては、液晶配向剤を塗布して形成される塗膜の、膜厚の均一性や表面の平滑性を向上させる溶媒や化合物、又は、液晶配向膜と基板との密着性を向上させる化合物等である。 The said liquid crystal aligning agent may contain the component of that excepting the above. Examples thereof include solvents and compounds that improve the uniformity and surface smoothness of the coating film formed by applying a liquid crystal alignment agent, or improve the adhesion between the liquid crystal alignment film and the substrate. compounds and the like.
膜厚の均一性や表面の平滑性を向上させる溶媒（貧溶媒）としては、低表面張力を有する溶媒、例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、１－ヘキサノール、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、１－ブトキシ－２－プロパノール、１－フェノキシ－２－プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート、プロピレングリコール－１－モノエチルエーテル－２－アセテート、ジプロピレングリコール、２－（２－エトキシプロポキシ）プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸ｎ－プロピルエステル、乳酸ｎ－ブチルエステル、乳酸イソアミルエステル等が挙げられる。これらの貧溶媒は１種でも複数種を混合して用いてもよい。上記貧溶媒を用いる場合は、液晶配向剤に含まれる有機溶媒全体の５質量％から８０質量％であることが好ましく、より好ましくは２０質量％から６０質量％である。 Solvents (poor solvents) that improve film thickness uniformity and surface smoothness include solvents with low surface tension, such as isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene Glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1- Phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2- ethoxypropoxy)propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester and the like. These poor solvents may be used singly or in combination. When using the said poor solvent, it is preferable that it is 5 mass % to 80 mass % of the whole organic solvent contained in a liquid crystal aligning agent, More preferably, it is 20 mass % to 60 mass %.
膜厚の均一性や塗膜表面の平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノニオン系界面活性剤等が挙げられる。より具体的には、例えば、エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（トーケムプロダクツ社製）、メガファックＦ１７１、Ｆ１７３、Ｒ－３０（大日本インキ社製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム社製）、アサヒガードＡＧ７１０、サーフロンＳ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子社製）等が挙げられる。これらの界面活性剤の使用割合は、液晶配向剤に含まれる樹脂成分の１００質量部に対して、好ましくは０．０１質量部から２質量部、より好ましくは０．０１質量部から１質量部である。 Compounds that improve the uniformity of the film thickness and the smoothness of the coating surface include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M). , Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. is.
液晶配向膜と基板との密着性を向上させる化合物の具体例としては、次に示す官能性シラン含有化合物やエポキシ基含有化合物等が挙げられる。例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、２－アミノプロピルトリメトキシシラン、２－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリメトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリエトキシシラン、Ｎ－トリエトキシシリルプロピルトリエチレントリアミン、Ｎ－トリメトキシシリルプロピルトリエチレントリアミン、１０－トリメトキシシリル－１，４，７－トリアザデカン、１０－トリエトキシシリル－１，４，７－トリアザデカン、９－トリメトキシシリル－３，６－ジアザノニルアセテート、９－トリエトキシシリル－３，６－ジアザノニルアセテート、Ｎ－ベンジル－３－アミノプロピルトリメトキシシラン、Ｎ－ベンジル－３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリエトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリメトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリエトキシシラン、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、２，２－ジブロモネオペンチルグリコールジグリシジルエーテル、１，３，５，６－テトラグリシジル－２，４－ヘキサンジオール、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－４、４’－ジアミノジフェニルメタン等が挙げられる。 Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. , N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl- 1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl -4,4'-diaminodiphenylmethane and the like.
更に、基板と膜の密着性の向上に加え、バックライトによる光の照射が原因となる電気特性の低下等を防ぐ目的で、以下のようなフェノプラスト系の添加剤を添加してもよい。具体的なフェノプラスト系添加剤を以下に示すが、この構造に限定されない。 Furthermore, in addition to improving the adhesion between the substrate and the film, the following phenoplast additives may be added for the purpose of preventing deterioration of electrical properties caused by light irradiation from the backlight. Specific phenoplast-based additives are shown below, but are not limited to this structure.
基板と膜との密着性を向上させる化合物を使用する場合、その化合物の使用量は、液晶配向剤に含まれる樹脂成分の１００質量部に対して０．１質量部から３０質量部であることが好ましく、より好ましくは１質量部から２０質量部である。使用量が上記値未満であると密着性が向上しにくくなり、上記値よりも多くなると液晶配向性が悪くなる場合がある。 When using a compound that improves the adhesion between the substrate and the film, the amount of the compound used is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. is preferred, more preferably 1 to 20 parts by mass. If the amount used is less than the above value, the adhesion may be difficult to improve, and if the amount exceeds the above value, the liquid crystal orientation may deteriorate.
上記液晶配向剤には、上記のような溶媒や化合物の他、本発明の効果が損なわれない範囲であれば、液晶配向膜の誘電率や導電性等の電気特性を変化させる目的で、誘電体や導電物質、更には、液晶配向膜にした際の膜の硬度や緻密度を高める目的で、所定の架橋性化合物を添加してもよい。 In addition to the solvents and compounds as described above, the liquid crystal aligning agent may include a dielectric for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. A predetermined cross-linking compound may be added for the purpose of increasing the hardness and denseness of the film when it is formed into a liquid crystal alignment film, as well as a conductive material.
＜液晶配向膜・液晶表示素子＞
上記液晶配向剤を、基板上に塗布して焼成した後、ラビングや光照射等で配向処理をすることで、本発明の一態様である液晶配向膜を得ることができる。基板としては、透明性の高いガラス基板、又はプラスチック基板（例えば、アクリル基板やポリカーボネート基板）等を用いることができる。また、液晶を駆動させるためのＩＴＯ電極等が形成された基板を用いることが、液晶表示素子を製造するプロセスを簡素化させる観点から好ましい。また、反射型の液晶表示素子では、片側の基板にシリコンウエハー等の不透明な物でも使用でき、この場合の電極は、アルミ等の光を反射する材料も使用できる。液晶配向剤を塗布する方法は特に限定されないが、工業的には、スピンコート印刷、スクリーン印刷、オフセット印刷、フレキソ印刷、インクジェット印刷等が一般的である。その他の塗布方法としては、ディップ、ロールコーター、スリットコーター、スピンナー等があり、目的に応じてこれらの方法を用いてもよい。
<Liquid crystal alignment film/liquid crystal display element>
The liquid crystal alignment film which is one aspect of the present invention can be obtained by coating the liquid crystal alignment agent on a substrate and baking the substrate, followed by alignment treatment by rubbing, light irradiation, or the like. As the substrate, a highly transparent glass substrate, a plastic substrate (for example, an acrylic substrate or a polycarbonate substrate), or the like can be used. Further, it is preferable to use a substrate on which ITO electrodes and the like for driving liquid crystal are formed, from the viewpoint of simplifying the process of manufacturing the liquid crystal display element. In addition, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for one substrate, and a light-reflecting material such as aluminum can be used for the electrodes in this case. Although the method of applying the liquid crystal aligning agent is not particularly limited, industrially, spin coat printing, screen printing, offset printing, flexographic printing, inkjet printing, and the like are common. Other coating methods include dipping, roll coater, slit coater, spinner and the like, and these methods may be used depending on the purpose.
焼成は、ホットプレート等の加熱手段により５０℃から３００℃、好ましくは８０℃から２５０℃で行うことができる。液晶配向剤中の有機溶媒を蒸発させることで、塗膜を形成させることができる。塗膜の厚みは、厚すぎると液晶表示素子の消費電力が増えやすく、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは５ｎｍから３００ｎｍ、より好ましくは１０ｎｍから１５０ｎｍである。液晶を水平配向や傾斜配向させる場合は、焼成後の塗膜を、ラビング又は偏光紫外線照射等で配向処理する。 Firing can be performed at 50° C. to 300° C., preferably 80° C. to 250° C. by heating means such as a hot plate. A coating film can be formed by evaporating the organic solvent in a liquid crystal aligning agent. The thickness of the coating film is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm, because if it is too thick, the power consumption of the liquid crystal display element tends to increase, and if it is too thin, the reliability of the liquid crystal display element may decrease. . When the liquid crystal is horizontally aligned or tilted, the coating film after baking is subjected to an alignment treatment such as rubbing or irradiation with polarized ultraviolet rays.
上記した手法により、上記液晶配向剤から、液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製することで、本発明の一態様である液晶表示素子を得ることができる。液晶セルを作製する手法の一例としては、液晶配向膜の形成された１対の基板を用意し、片方の基板の液晶配向膜上にスペーサーを散布し、液晶配向膜面が内側になるようにして、もう片方の基板を貼り合わせ、液晶を減圧注入して封止する方法が挙げられる。又は、スペーサーを散布した液晶配向膜面に液晶を滴下した後に、基板を貼り合わせて封止を行う方法が挙げられる。このときのスペーサーの厚みは、好ましくは１μｍから３０μｍ、より好ましくは２μｍから１０μｍである。上記液晶配向剤を用いて作製された上記液晶表示素子は、信頼性に優れるため、大画面で高精細の液晶テレビ等に好適に利用できる。 After obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent by the method described above, a liquid crystal display element that is one embodiment of the present invention can be obtained by producing a liquid crystal cell by a known method. As an example of a method for producing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers are dispersed on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface faces inside. Then, the other substrate is bonded together, and liquid crystal is injected under reduced pressure for sealing. Alternatively, a method of dropping liquid crystals onto the surface of the liquid crystal alignment film on which spacers are dispersed and then bonding the substrates together for sealing may be used. The thickness of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. Since the liquid crystal display element produced using the liquid crystal aligning agent is excellent in reliability, it can be suitably used for large-screen, high-definition liquid crystal televisions and the like.
＜ジアミンの合成＞
実施例１
ｅｔｈｙｌ（４－ａｍｉｎｏｂｅｎｚｙｌ）ｇｌｙｃｉｎａｔｅ[ＮＧ４ＡＢＡ]の合成
<Synthesis of diamine>
Example 1
Synthesis of ethyl(4-aminobenzyl) glycinate [NG4ABA]
第１工程
窒素導入管と還流管を備えた１Ｌの４口フラスコに、グリシンエチル塩酸塩１０５．６ｇ（０．６９４ｍｏｌ）、ＴＨＦ５００ｇ、トリエチルアミン９３．６ｇ（０．９２５ｍｏｌ）を加え、メカニカルスターラーを用いて室温で１時間撹拌した後、ＴＨＦが還流する温度(設定７０℃)で加熱し、４－ニトロベンジルブロミド５０．０ｇ（０．２３１ｍｏｌ）をＴＨＦ５００．０ｇに溶解させてこれをゆっくり滴下し、滴下終了後、更に２４時間反応させた。４－ニトロベンジルブロミドが消失した時点で反応終了とし、析出している固体を濾過により除去し、ＴＨＦをロータリーエバポレーターで除去し、得られた粗物を酢酸エチル３００．０ｇで再溶解させた。この溶液を純水１００ｇで３回洗浄し、１０％塩酸水溶液３００ｇを加え、１時間撹拌し、水層側を回収して、その水層を酢酸エチル１００ｇで３回洗浄した。水層に更に酢酸エチル３００ｇを加え、炭酸カリウムをゆっくり加え、ｐＨを１０程にして１時間撹拌し、有機相側を回収し、純水１００ｇで３回洗浄した。この有機相に無水硫酸マグネシウムを加えて乾燥させ、濾過し、活性炭を加えしばらく撹拌した後、濾過により活性炭を取り除き、ロータリーエバポレーターで溶媒を除去して、目的物（ニトロ体）である薄黄色の粘体４６．０ｇ（０．１９３ｍｏｌ）を得た。目的物が得られたことを、１Ｈ－ＮＭＲで確認した。
１Ｈ ＮＭＲ (５００ＭＨｚ、ＣＤＣｌ３)：δ ８．２（２Ｈ）、７．５３（２Ｈ）、４．２２（２Ｈ）、３．９３（２Ｈ）、３．４２（２Ｈ）、１．８９（１Ｈ）、１．２７（３Ｈ）
Step 1 105.6 g (0.694 mol) of ethyl glycine hydrochloride, 500 g of THF, and 93.6 g (0.925 mol) of triethylamine are added to a 1 L four-necked flask equipped with a nitrogen inlet tube and a reflux tube, and stirred using a mechanical stirrer. After stirring at room temperature for 1 hour, the mixture was heated at a temperature at which THF was refluxed (set at 70°C), 50.0 g (0.231 mol) of 4-nitrobenzyl bromide was dissolved in 500.0 g of THF, and this was slowly added dropwise. After the dropwise addition was completed, the reaction was further continued for 24 hours. The reaction was completed when 4-nitrobenzyl bromide disappeared, the precipitated solid was removed by filtration, THF was removed with a rotary evaporator, and the resulting crude product was redissolved in 300.0 g of ethyl acetate. This solution was washed 3 times with 100 g of pure water, 300 g of 10% hydrochloric acid aqueous solution was added, stirred for 1 hour, the aqueous layer side was recovered, and the aqueous layer was washed 3 times with 100 g of ethyl acetate. Further, 300 g of ethyl acetate was added to the water layer, and potassium carbonate was slowly added to adjust the pH to about 10, followed by stirring for 1 hour. Anhydrous magnesium sulfate is added to this organic phase to dry it, filtered, activated carbon is added and stirred for a while, the activated carbon is removed by filtration, the solvent is removed by a rotary evaporator, and the desired product (nitro compound) is obtained as a light yellow color. 46.0 g (0.193 mol) of a viscous substance was obtained. It was confirmed by 1 H-NMR that the desired product was obtained.
1 H NMR (500 MHz, CDCl 3 ): δ 8.2 (2H), 7.53 (2H), 4.22 (2H), 3.93 (2H), 3.42 (2H), 1.89 ( 1H), 1.27 (3H)
第２工程
窒素導入管と撹拌子を備えた５００ｍｌの４口フラスコに、上記で得られたニトロ体４５．０ｇ（０．１９ｍｏｌ）、ＴＨＦ３００．０ｇ、鉄ドープ型白金カーボン４．５ｇを加え、容器内を注意深く水素雰囲気下に置換し、室温で２４時間反応させた。原料が消失した時点で反応終了とし、白金カーボンをメンブランフィルターで除去し、ろ液に活性炭(白鷺製)を加え、４０℃で３０分撹拌した。その後、再び濾過し、ロータリーエバポレーターで溶媒を除去した後、高真空ポンプで乾燥させ、目的物である薄黄色の粘体３５．４ｇ（０．１７ｍｏｌ：収率８９％）を得た。目的物（ＮＧ４ＡＢＡ）が得られたことを、１Ｈ－ＮＭＲで確認した。
１Ｈ ＮＭＲ (５００ＭＨｚ、ＣＤＣｌ３)：δ ６．９９（２Ｈ）、６．６３（２Ｈ）、４．１５（２Ｈ）、３．７０（２Ｈ）、３．３８（２Ｈ）、３．００（２Ｈ）、１．２４（３Ｈ）
Step 2: 45.0 g (0.19 mol) of the nitro compound obtained above, 300.0 g of THF, and 4.5 g of iron-doped platinum carbon were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube and a stirrer, The inside of the vessel was carefully replaced with a hydrogen atmosphere, and the reaction was allowed to proceed at room temperature for 24 hours. The reaction was terminated when the raw materials disappeared, platinum carbon was removed with a membrane filter, activated carbon (manufactured by Shirasagi) was added to the filtrate, and the mixture was stirred at 40°C for 30 minutes. Then, it was filtered again, the solvent was removed with a rotary evaporator, and the residue was dried with a high-vacuum pump to obtain 35.4 g (0.17 mol: yield 89%) of a light yellow viscous substance, which is the target product. It was confirmed by 1 H-NMR that the desired product (NG4ABA) was obtained.
1 H NMR (500 MHz, CDCl 3 ): δ 6.99 (2H), 6.63 (2H), 4.15 (2H), 3.70 (2H), 3.38 (2H), 3.00 ( 2H), 1.24 (3H)
実施例２
ｅｔｈｙｌ（３－ａｍｉｎｏｂｅｎｚｙｌ）ｇｌｙｃｉｎａｔｅ[ＮＧ３ＡＢＡ]の合成
Example 2
Synthesis of ethyl(3-aminobenzyl) glycinate [NG3ABA]
実施例１から、原料である４－ニトロベンジルブロミドを３－ニトロベンジルブロミドに変更して合成した。目的物（ＮＧ３ＡＢＡ）は薄黄色の固体として得られ、その収量は３７．４ｇ（０．１８ｍｏｌ：９４％）であった。目的物が得られたことは、１Ｈ－ＮＭＲで確認した。
１Ｈ ＮＭＲ (５００ＭＨｚ、ＣＤＣｌ３)：δ ７．１０（１Ｈ）、６．６５（１Ｈ）、６．５７（１Ｈ）、４．１６（２Ｈ）、３．７０（２Ｈ）、３．３９（２Ｈ）、３．０９（２Ｈ）、１．２５（３Ｈ）
It was synthesized from Example 1 by changing the starting material 4-nitrobenzyl bromide to 3-nitrobenzyl bromide. The target product (NG3ABA) was obtained as a pale yellow solid, and the yield was 37.4 g (0.18 mol: 94%). It was confirmed by 1 H-NMR that the desired product was obtained.
1 H NMR (500 MHz, CDCl 3 ): δ 7.10 (1H), 6.65 (1H), 6.57 (1H), 4.16 (2H), 3.70 (2H), 3.39 ( 2H), 3.09 (2H), 1.25 (3H)
実施例３
ｅｔｈｙｌ（４－ａｍｉｎｏｐｈｅｎｅｔｈｙｌ）ｇｌｙｃｉｎａｔｅ[ＮＧ４ＡＰｈＡ]の合成
Synthesis of ethyl(4-aminophenyl) glycinate [NG4APhA]
第１工程
窒素導入管と還流管を備えた１Ｌの４口フラスコに、４－ニトロフェネチルアミン塩酸塩５０ｇ（０．２４６ｍｏｌ）、ＴＨＦ５００ｇ、トリエチルアミン６２．１ｇ（０．６０４ｍｏｌ）を加え、メカニカルスターラーを用いて室温で１時間撹拌し、ＴＨＦが還流する温度(設定７０℃)で加熱し、２－クロロ酢酸エチル２５．１ｇ（０．２０５ｍｏｌ）をＴＨＦ３００ｇに溶解させてこれをゆっくり滴下し、滴下終了後、更に２４時間反応させた。２－クロロ酢酸エチルが消失(ＨＰＬＣにて確認)した時点で反応終了とし、析出している固体を濾過により除去し、ＴＨＦをロータリーエバポレーターで除去し、得られた粗物を酢酸エチル５００ｇで再溶解させた。この溶液を純水１００ｇで３回洗浄し、１０％塩酸水溶液５００ｇを加え、１時間撹拌し、水層側を回収して、その水層を酢酸エチル１００ｇで３回洗浄した。水層に更に酢酸エチル５００ｇを加え、炭酸カリウムをゆっくり加え、ｐＨを１０程にして１時間撹拌し、有機相側を回収し、純水１００ｇで３回洗浄した。この有機相に無水硫酸マグネシウムを加えて乾燥させ、濾過し、活性炭を加えしばらく撹拌した後、濾過により活性炭を取り除き、ロータリーエバポレーターで溶媒を除去し、目的物である薄黄色の粘体３４．２ｇ（０．１３６ｍｏｌ：収率６６％）を得た。目的物（ニトロ体）が得られたことを、１Ｈ－ＮＭＲで確認した。
１Ｈ ＮＭＲ (５００ＭＨｚ、ＣＤＣｌ３)：δ ８．１４（２Ｈ）、７．３７(２Ｈ)、４．１６（２Ｈ）、３．４３（２Ｈ）、２．９５（４Ｈ）、２．１９（１Ｈ）、１．２５（３Ｈ）
Step 1 50 g (0.246 mol) of 4-nitrophenethylamine hydrochloride, 500 g of THF, and 62.1 g (0.604 mol) of triethylamine are added to a 1 L four-necked flask equipped with a nitrogen inlet tube and a reflux tube, and stirred using a mechanical stirrer. 25.1 g (0.205 mol) of ethyl 2-chloroacetate was dissolved in 300 g of THF and slowly added dropwise. was allowed to react for an additional 24 hours. When ethyl 2-chloroacetate disappeared (confirmed by HPLC), the reaction was completed, the precipitated solid was removed by filtration, THF was removed by a rotary evaporator, and the obtained crude product was reconstituted with 500 g of ethyl acetate. Dissolved. This solution was washed three times with 100 g of pure water, 500 g of a 10% hydrochloric acid aqueous solution was added, stirred for 1 hour, the aqueous layer was recovered, and the aqueous layer was washed three times with 100 g of ethyl acetate. Further, 500 g of ethyl acetate was added to the aqueous layer, and potassium carbonate was slowly added to adjust the pH to about 10, followed by stirring for 1 hour. Anhydrous magnesium sulfate was added to the organic phase to dry it, filtered, activated carbon was added and stirred for a while, the activated carbon was removed by filtration, the solvent was removed by a rotary evaporator, and 34.2 g of the target pale yellow viscous substance was obtained. 0.136 mol: yield 66%). It was confirmed by 1 H-NMR that the desired product (nitro compound) was obtained.
1 H NMR (500 MHz, CDCl 3 ): δ 8.14 (2H), 7.37 (2H), 4.16 (2H), 3.43 (2H), 2.95 (4H), 2.19 ( 1H), 1.25 (3H)
第２工程
窒素導入管と撹拌子を備えた５００ｍｌの４口フラスコに、上記で得られたニトロ体３０．０ｇ、ＴＨＦ３００ｇ、鉄ドープ型白金カーボン３．０ｇを加え、容器内を注意深く水素雰囲気下に置換し、室温で２４時間反応させた。原料が消失した時点で反応終了とし、白金カーボンをメンブランフィルターで除去し、ろ液に活性炭（白鷺製）を加え、４０℃で３０分撹拌した。その後、再び濾過し、ロータリーエバポレーターで溶媒を除去した後、高真空ポンプで乾燥させ、目的物（ＮＧ４ＡＰｈＡ）である薄黄色の粘体２５．１ｇ（０．１１３ｍｏｌ：収率９５％）を得た。目的物が得られたことを１Ｈ－ＮＭＲで確認した。
１Ｈ ＮＭＲ (５００ＭＨｚ、ＣＤＣｌ３)：δ ６．９９（２Ｈ）、６．６０（２Ｈ）、４．１８（２Ｈ）、３．４２（２Ｈ）、２．８９（２Ｈ）、２．８６（２Ｈ）、２．７５（２Ｈ）、１．２４（３Ｈ）
Step 2: 30.0 g of the nitro compound obtained above, 300 g of THF, and 3.0 g of iron-doped platinum carbon were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube and a stirrer, and the inside of the vessel was carefully placed under a hydrogen atmosphere. and reacted at room temperature for 24 hours. The reaction was terminated when the raw materials disappeared, platinum carbon was removed with a membrane filter, activated carbon (manufactured by Shirasagi) was added to the filtrate, and the mixture was stirred at 40°C for 30 minutes. Then, it was filtered again, the solvent was removed with a rotary evaporator, and the residue was dried with a high vacuum pump to obtain 25.1 g (0.113 mol: yield 95%) of a light yellow viscous substance (NG4APhA), which is the target product. It was confirmed by 1 H-NMR that the desired product was obtained.
1 H NMR (500 MHz, CDCl 3 ): δ 6.99 (2H), 6.60 (2H), 4.18 (2H), 3.42 (2H), 2.89 (2H), 2.86 ( 2H), 2.75 (2H), 1.24 (3H)
＜略語＞
液晶配向剤の調製で用いる略号は以下の通りである。
（ジイソシアネート）
ＩＤＩ：イソホロンジイソシアネート
４ＩＢＩ：（イソシアナトメチル）フェニル－イソシアネート
ＤＩ－３ＭＧ：１，３－ビス（４－イソシアナトフェノキシ）プロパン
ＤＩ－２ＭＧ：１，２－ビス（４－イソシアナトフェノキシ）エタン
<Abbreviation>
The abbreviations used in the preparation of the liquid crystal aligning agent are as follows.
(Diisocyanate)
IDI: isophorone diisocyanate 4IBI: (isocyanatomethyl)phenyl-isocyanate DI-3MG: 1,3-bis(4-isocyanatophenoxy)propane DI-2MG: 1,2-bis(4-isocyanatophenoxy)ethane
（ジアミン）
ＮＧ４ＡＢＡ：エチル（４－アミノベンジル）グリシネート
ＮＧ３ＡＢＡ：エチル（３－アミノベンジル）グリシネート
ＮＧ４ＡＰｈＡ：エチル（４－アミノフェネチル）グリシネート
Ｍｅ３ＡＢＡ：Ｎ－メチル－３－アミノベンジルアミン
Ｍｅ４ＡＰｈＡ：Ｎ－メチル－４－アミノフェネチルアミン
ＤＡ－３ＭＧ：１，３－ジ（４－アミノフェノキシ）プロパン
(diamine)
NG4ABA: ethyl (4-aminobenzyl) glycinate NG3ABA: ethyl (3-aminobenzyl) glycinate NG4APhA: ethyl (4-aminophenethyl) glycinate Me3ABA: N-methyl-3-aminobenzylamine Me4APhA: N-methyl-4-amino Phenethylamine DA-3MG: 1,3-di(4-aminophenoxy)propane
（溶媒）
ＮＭＰ：Ｎ－メチル－２－ピロリドン
ＢＣＳ：ブチルセロソルブ
ＧＢＬ：γブチロラクトン
(solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve GBL: γ-butyrolactone
また、ポリイミドの分子量測定条件は、以下の通りである。
装置：センシュー科学社製 常温ゲル浸透クロマトグラフィー（ＧＰＣ）装置（ＳＳＣ－７２００）
カラム：Ｓｈｏｄｅｘ社製カラム（ＫＤ－８０３、ＫＤ－８０５）
カラム温度：５０℃
溶離液：Ｎ，Ｎ’－ジメチルホルムアミド（添加剤として、臭化リチウム－水和物（ＬｉＢｒ・Ｈ２Ｏ）が３０ｍｍｏｌ／Ｌ、リン酸・無水結晶（ｏ－リン酸）が３０ｍｍｏｌ／Ｌ、ＴＨＦが１０ｍｌ／Ｌ）
流速：１．０ｍｌ／分
検量線作成用標準サンプル：東ソー社製 ＴＳＫ 標準ポリエチレンオキサイド（分子量約９０００，０００、１５０，０００、１００，０００、３０，０００）、及び、ポリマーラボラトリー社製 ポリエチレングリコール（分子量 約１２，０００、４，０００、１，０００）
Moreover, the molecular weight measurement conditions of polyimide are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Shodex column (KD-803, KD-805)
Column temperature: 50°C
Eluent: N,N'-dimethylformamide (as additives, lithium bromide-hydrate (LiBr.H 2 O) at 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphoric acid) at 30 mmol/L, THF is 10ml/L)
Flow rate: 1.0 ml/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight of about 9000,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratory ( Molecular weight about 12,000, 4,000, 1,000)
＜重合体の合成＞
実施例４
ＤＩ－２ＭＧ／ＮＧ３ＡＢＡ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、ＮＧ３ＡＢＡ１．００ｇ（４．８０ｍｍｏｌ）を測り取り、ＮＭＰ１３．４３ｇを加え溶解させ、ＤＩ－２ＭＧ１．３７ｇ（４．６０ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度４２０ｍＰａｓ、の重合体（ポリマー溶液：Ｐ－１)を得た。得られた重合体の重量平均分子量はＭｗ：４６２００であった。
<Synthesis of polymer>
Example 4
DI-2MG/NG3ABA
1.00 g (4.80 mmol) of NG3ABA was weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, 13.43 g of NMP was added and dissolved, 1.37 g (4.60 mmol) of DI-2MG was added, and nitrogen was added. The reaction was carried out at 40° C. for 24 hours in an atmosphere. As a result, a polymer (polymer solution: P-1) having a concentration of 15% by mass and a viscosity of 420 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 46,200.
実施例５
ＤＩ－２ＭＧ／ＮＧ４ＡＢＡ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、ＮＧ４ＡＢＡ１．００ｇ（４．８０ｍｍｏｌ）を測り取り、ＮＭＰ１３．３２ｇを加え溶解させ、ＤＩ－２ＭＧ１．３５ｇ（４．５６ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度３７０ｍＰａｓ、の重合体（ポリマー溶液：Ｐ－２)を得た。得られた重合体の重量平均分子量はＭｗ：３９８００であった。
Example 5
DI-2MG/NG4ABA
1.00 g (4.80 mmol) of NG4ABA was measured and dissolved in a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, 13.32 g of NMP was added and dissolved, 1.35 g (4.56 mmol) of DI-2MG was added, and nitrogen was added. The reaction was carried out at 40° C. for 24 hours in an atmosphere. As a result, a polymer (polymer solution: P-2) having a concentration of 15% by mass and a viscosity of 370 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw:39,800.
実施例６
ＤＩ－３ＭＧ／ＮＧ４ＡＰｈＡ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、ＮＧ４ＡＰｈＡ１．００ｇ（４．５０ｍｍｏｌ）を測り取り、ＮＭＰ１３．２０ｇを加え溶解させ、ＤＩ－３ＭＧ１．３３ｇ（４．２８ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度４４０ｍＰａｓ、の重合体（ポリマー溶液：Ｐ－３)を得た。得られた重合体の重量平均分子量はＭｗ：４６３００であった。
Example 6
DI-3MG/NG4APhA
1.00 g (4.50 mmol) of NG4APhA was weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, 13.20 g of NMP was added and dissolved, 1.33 g (4.28 mmol) of DI-3MG was added, and nitrogen was added. The reaction was carried out at 40° C. for 24 hours in an atmosphere. As a result, a polymer (polymer solution: P-3) having a concentration of 15 mass % and a viscosity of 440 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 46,300.
実施例７
４ＩＢＩ／ＮＧ４ＡＰｈＡ、ＤＡ－３ＭＧ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、ＮＧ４ＡＰｈＡ０．５０ｇ（２．２５ｍｍｏｌ）、ＤＡ－３ＭＧ０．５８ｇ（２．２５ｍｍｏｌ）を測り取り、ＮＭＰ１０．４８ｇを加え溶解させ、４ＩＢＩ０．７７ｇ（４．４１ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度２８０ｍＰａｓ、の重合体（ポリマー溶液：Ｐ－４)を得た。得られた重合体の重量平均分子量はＭｗ：３７３００であった。
Example 7
4IBI/NG4APhA, DA-3MG
0.50 g (2.25 mmol) of NG4APhA and 0.58 g (2.25 mmol) of DA-3MG were weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, and 10.48 g of NMP was added and dissolved, followed by 0.77 g of 4IBI. (4.41 mmol) was added and reacted at 40° C. for 24 hours under nitrogen atmosphere. As a result, a polymer (polymer solution: P-4) having a concentration of 15% by mass and a viscosity of 280 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 37,300.
実施例８
ＩＤＩ、ＤＩ－３ＭＧ／ＮＧ４ＡＢＡ、ＤＡ－３ＭＧ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、ＮＧ４ＡＢＡ０．５０ｇ（２．４０ｍｍｏｌ）、ＤＡ－３ＭＧ０．６２ｇ（２．４０ｍｍｏｌ）を測り取り、ＮＭＰ１３．６０ｇを加え溶解させ、ＤＩ－３ＭＧ０．７４ｇ（２．４０ｍｍｏｌ）、ＩＤＩ０．５４ｇ（２．４２ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度３３０ｍＰａｓ、の重合体（ポリマー溶液：Ｐ－５)を得た。得られた重合体の重量平均分子量はＭｗ：４１６００であった。
Example 8
IDI, DI-3MG/NG4ABA, DA-3MG
0.50 g (2.40 mmol) of NG4ABA and 0.62 g (2.40 mmol) of DA-3MG are weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, and 13.60 g of NMP is added and dissolved, followed by DI-3MG0. .74 g (2.40 mmol) and 0.54 g (2.42 mmol) of IDI were added and reacted at 40° C. for 24 hours under a nitrogen atmosphere. As a result, a polymer (polymer solution: P-5) having a concentration of 15 mass % and a viscosity of 330 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 41,600.
比較例１
ＤＩ－２ＭＧ／Ｍｅ３ＡＢＡ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、Ｍｅ３ＡＢＡ１．００ｇ（７．３４ｍｍｏｌ）を測り取り、ＮＭＰ１９．３６ｇを加え溶解させ、ＤＩ－２ＭＧ２．２４ｇ（７．５７ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度５３０ｍＰａｓ、の重合体（ポリマー溶液：ＰＲｅｆ－１)を得た。得られた重合体の重量平均分子量はＭｗ：３９９００であった。
Comparative example 1
DI-2MG/Me3ABA
1.00 g (7.34 mmol) of Me3ABA was weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, 19.36 g of NMP was added and dissolved, 2.24 g (7.57 mmol) of DI-2MG was added, and nitrogen was added. The reaction was carried out at 40° C. for 24 hours in an atmosphere. As a result, a polymer (polymer solution: PRef-1) having a concentration of 15 mass % and a viscosity of 530 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw:39,900.
比較例２
ＤＩ－２ＭＧ／Ｍｅ４ＡＰｈＡ
窒素導入管と撹拌子を備えた５０ｍｌの２口フラスコに、Ｍｅ４ＡＰｈＡ１．００ｇ（６．６６ｍｍｏｌ）を測り取り、ＮＭＰ１６．３８ｇを加え溶解させ、ＤＩ－２ＭＧ１．８９ｇ（６．３９ｍｍｏｌ）を加え、窒素雰囲気下４０℃で２４時間反応させた。これにより、濃度１５質量％、粘度４９０ｍＰａｓ、の重合体（ポリマー溶液：ＰＲｅｆ－２)を得た。得られたポリマーの重量平均分子量はＭｗ：４１３００であった。
Comparative example 2
DI-2MG/Me4APhA
1.00 g (6.66 mmol) of Me4APhA was weighed into a 50 ml two-necked flask equipped with a nitrogen inlet tube and a stirrer, 16.38 g of NMP was added and dissolved, 1.89 g (6.39 mmol) of DI-2MG was added, and nitrogen was added. The reaction was carried out at 40° C. for 24 hours in an atmosphere. As a result, a polymer (polymer solution: PRef-2) having a concentration of 15 mass % and a viscosity of 490 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 41,300.
＜液晶配向剤の調整＞
実施例９
撹拌子を備えた５０ｍｌの三角フラスコに、実施例４で得られた重合体（Ｐ－１）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－１）を得た。
<Adjustment of liquid crystal aligning agent>
Example 9
10.0 g of the polymer (P-1) obtained in Example 4 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-1) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass, and BCS of 30% by mass was obtained.
実施例１０
撹拌子を備えた５０ｍｌの三角フラスコに、実施例５で得られた重合体（Ｐ－２）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－２）を得た。
Example 10
10.0 g of the polymer (P-2) obtained in Example 5 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-2) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass and BCS of 30% by mass was obtained.
実施例１１
撹拌子を備えた５０ｍｌの三角フラスコに、実施例６で得られた重合体（Ｐ－３）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－３）を得た。
Example 11
10.0 g of the polymer (P-3) obtained in Example 6 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-3) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass and BCS of 30% by mass was obtained.
実施例１２
撹拌子を備えた５０ｍｌの三角フラスコに、実施例７で得られた重合体（Ｐ－４）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－４）を得た。
Example 12
10.0 g of the polymer (P-4) obtained in Example 7 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-4) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass and BCS of 30% by mass was obtained.
実施例１３
撹拌子を備えた５０ｍｌの三角フラスコに、実施例８で得られた重合体（Ｐ－５）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－５）を得た。
Example 13
10.0 g of the polymer (P-5) obtained in Example 8 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. Then, a liquid crystal aligning agent (AL-5) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass, and BCS of 30% by mass was obtained.
比較例３
撹拌子を備えた５０ｍｌの三角フラスコに、比較例１で得られた重合体（ＰＲｅｆ－１）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－６）を得た。
Comparative example 3
10.0 g of the polymer (PRef-1) obtained in Comparative Example 1 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, and 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-6) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass and BCS of 30% by mass was obtained.
比較例４
撹拌子を備えた５０ｍｌの三角フラスコに、比較例２で得られた重合体（ＰＲｅｆ－２）１０．０ｇを測りとり、ＮＭＰ２．５ｇ、ＧＢＬ５．０ｇ、ＢＣＳ７．５ｇを加え室温で３０分撹拌し、固形分６．０質量％、ＮＭＰ４４質量％、ＧＢＬ２０質量％、ＢＣＳ３０質量％の、液晶配向剤（ＡＬ－７）を得た。
Comparative example 4
10.0 g of the polymer (PRef-2) obtained in Comparative Example 2 was weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added and stirred at room temperature for 30 minutes. A liquid crystal aligning agent (AL-7) having a solid content of 6.0% by mass, NMP of 44% by mass, GBL of 20% by mass and BCS of 30% by mass was obtained.
比較例５
日産化学（株）社製のＳＥ－６４１４を、液晶配向剤（ＡＬ－８）として用いた。
Comparative example 5
SE-6414 manufactured by Nissan Chemical Industries, Ltd. was used as a liquid crystal aligning agent (AL-8).
実施例９～１３の液晶配向剤（ＡＬ－１～ＡＬ－５）及び比較例３～５の液晶配向剤（ＡＬ－６～ＡＬ－８）を用いて、下記手法に基づき、液晶配向膜を評価した。 Using the liquid crystal aligning agents (AL-1 to AL-5) of Examples 9 to 13 and the liquid crystal aligning agents (AL-6 to AL-8) of Comparative Examples 3 to 5, a liquid crystal alignment film was formed according to the following method. evaluated.
＜白化耐性及び塗布性（印刷性）の評価＞
得られた液晶配向剤を、よく洗浄したＣｒ基板にそれぞれ１滴たらし、室温２５℃、湿度６０％で放置して、白くなる（白化する）までの時間を測定した。測定した時間に基づき、白化耐性を評価した。
<Evaluation of whitening resistance and coatability (printability)>
One drop of the obtained liquid crystal aligning agent was dropped on each well-washed Cr substrate, and the substrate was allowed to stand at a room temperature of 25° C. and a humidity of 60%, and the time until whitening (whitening) was measured. Whitening resistance was evaluated based on the measured time.
液晶配向剤を１．０μｍのフィルターで濾過した後、洗浄したＣｒ板上に配向膜印刷機（日本写真印刷社製「オングストローマー」）を用いてフレキソ印刷を行うことにより、塗布性試験を行った。 After filtering the liquid crystal aligning agent with a 1.0 μm filter, flexographic printing is performed on the washed Cr plate using an alignment film printer (“Angstromer” manufactured by Nissha Printing Co., Ltd.) to conduct a coating test. gone.
アニロックスロールに約１．０ｍｌの液晶配向剤を滴下し、空運転を１０回実施した後、１０分間印刷機を止め、印刷版を乾燥させた。その後、Ｃｒ基板１枚に印刷を行い、印刷後の基板を７０℃のホットプレート上に５分間放置して、塗膜の仮乾燥を行い、膜状態を観察した。目視と、光学顕微鏡（ニコン社製「ＥＣＬＩＰＳＥ ＭＥ６００」）での倍率５０倍とで、主に膜厚ムラやエッジ部の膜厚ムラを観察した。 About 1.0 ml of liquid crystal aligning agent was added dropwise to the anilox roll, and after 10 idle runs, the printing machine was stopped for 10 minutes to dry the printing plate. Thereafter, printing was performed on one Cr substrate, and the printed substrate was left on a hot plate at 70° C. for 5 minutes to temporarily dry the coating film, and the film state was observed. The film thickness unevenness and the film thickness unevenness at the edges were mainly observed visually and with an optical microscope ("ECLIPSE ME600" manufactured by Nikon Corporation) at a magnification of 50 times.
＜液晶配向性、電圧保持率、及びプレチルト角の評価＞
［液晶配向性の観察、及び液晶セルの作製］
液晶配向剤を１．０μｍのフィルターで濾過した後、電極付き基板（横３０ｍｍ×縦４０ｍｍの大きさで、厚さが１．１ｍｍのガラス基板。電極は幅１０ｍｍ×長さ４０ｍｍの矩形で、厚さ３５ｎｍのＩＴＯ電極）に、スピンコート印刷により塗布した。５０℃のホットプレート上で５分間乾燥させた後、１８０℃のＩＲ式オーブンで２０分間焼成を行い、膜厚１００ｎｍの塗膜を形成させた。この膜をレーヨン布（吉川化工製ＹＡ－２０Ｒ）でラビング（ローラー直径：１２０ｍｍ、ローラー回転数：１０００ｒｐｍ、移動速度：２０ｍｍ／ｓｅｃ、押し込み長：０．４ｍｍ）した後、純水中で１分間、超音波を照射して洗浄し、エアブローで水滴を除去した後、８０℃で１５分間乾燥して液晶配向膜付き基板を得た。
<Evaluation of Liquid Crystal Alignment, Voltage Holding Ratio, and Pretilt Angle>
[Observation of liquid crystal orientation and production of liquid crystal cell]
After filtering the liquid crystal aligning agent with a 1.0 μm filter, a substrate with electrodes (a glass substrate with a size of 30 mm wide × 40 mm long and a thickness of 1.1 mm. The electrodes are rectangular with a width of 10 mm × length of 40 mm, 35 nm thick ITO electrode) was applied by spin coat printing. After drying on a hot plate at 50° C. for 5 minutes, baking was performed in an IR oven at 180° C. for 20 minutes to form a coating film with a thickness of 100 nm. After rubbing this film with a rayon cloth (Yoshikawa Kako YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), immerse in pure water for 1 minute. After cleaning by irradiating ultrasonic waves and removing water droplets by air blow, the substrate was dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
上記の液晶配向膜付き基板を２枚用意し、その１枚の液晶配向膜面上に４μｍのスペーサーを散布した後、その上からシール剤を印刷し、もう１枚の基板をラビング方向が逆方向、かつ膜面が向き合うようにして張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、ＭＬＣ－２０４１（メルク株式会社製）を注入し、注入口を封止して液晶セルを得た。その後、液晶配向性を観察した後、液晶セルを１１０℃で１時間加熱し、２３℃で一晩放置し、電圧保持率測定用の液晶セルを得た。 Prepare two substrates with the above liquid crystal alignment film, sprinkle a 4 μm spacer on the surface of one of the liquid crystal alignment films, then print a sealant from above, and rub the other substrate in the opposite direction. After laminating in such a manner that the directions and film surfaces face each other, the sealant is cured to prepare an empty cell. MLC-2041 (manufactured by Merck Ltd.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. Then, after observing the liquid crystal orientation, the liquid crystal cell was heated at 110° C. for 1 hour and allowed to stand at 23° C. overnight to obtain a liquid crystal cell for voltage holding rate measurement.
上記の手順で得られた電圧保持率測定用の液晶セルを用いて、６０℃の温度下で１Ｖの電圧を６０μｓ間印加し、１６６．７ｍｓ後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率として計算した。なお、電圧保持率の測定には東陽テクニカ社製のＶＨＲ－１電圧保持率測定装置を使用した。 Using the liquid crystal cell for voltage holding ratio measurement obtained by the above procedure, a voltage of 1 V was applied for 60 μs at a temperature of 60° C., and the voltage was measured after 166.7 ms to determine how long the voltage could be held. The dolphin was calculated as the voltage holding ratio. To measure the voltage holding rate, a VHR-1 voltage holding rate measuring device manufactured by Toyo Technica Co., Ltd. was used.
［プレチルト角の評価］
プレチルト角の測定にはオプトメトリクス社製 Ａｘｏ Ｓｃａｎ ミュラーマトリクスポーラリメーターを用いた。
[Evaluation of pretilt angle]
An Axo Scan Muller matrix polarimeter manufactured by Optometrix was used to measure the pretilt angle.
［ラビング耐性の評価］
液晶配向剤を１．０μｍのフィルターで濾過した後、電極付き基板（横３０ｍｍ×縦４０ｍｍの大きさで、厚さが１．１ｍｍのガラス基板。電極は幅１０ｍｍ×長さ４０ｍｍの矩形で、厚さ３５ｎｍのＩＴＯ電極）に、スピンコート印刷により塗布した。５０℃のホットプレート上で５分間乾燥させた後、１８０℃のＩＲ式オーブンで２０分間焼成を行い、膜厚１００ｎｍの塗膜を形成させた。この膜をレーヨン布（吉川化工製ＹＡ－２０Ｒ）でラビング（ローラー直径：１２０ｍｍ、ローラー回転数：１０００ｒｐｍ、移動速度：２０ｍｍ／ｓｅｃ、押し込み長：０．４ｍｍ）した後、共焦点レーザー顕微鏡を用いてラビング耐性を評価した。膜が剥離している場合は×、膜上に削れカスや傷が多く見られた場合は△、良好な場合（膜の剥離が見られず、かつ膜上に削れカスや傷が多く見られない場合）は○とする。各種評価の結果を表１に示す。
[Evaluation of rubbing resistance]
After filtering the liquid crystal aligning agent with a 1.0 μm filter, a substrate with electrodes (a glass substrate with a size of 30 mm wide × 40 mm long and a thickness of 1.1 mm. The electrodes are rectangular with a width of 10 mm × length of 40 mm, 35 nm thick ITO electrode) was applied by spin coat printing. After drying on a hot plate at 50° C. for 5 minutes, baking was performed in an IR oven at 180° C. for 20 minutes to form a coating film with a thickness of 100 nm. After rubbing this film with a rayon cloth (Yoshikawa Kako YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), a confocal laser microscope was used. was evaluated for rubbing resistance. Poor if the film was peeled off, △ if many scrapes and scratches were observed on the film, and Good (no peeling of the film and many scrapes and scratches were observed on the film). If not), mark as ○. Table 1 shows the results of various evaluations.
実施例９～１３の液晶配向剤は、比較例と比べて大幅に白化耐性に優れており、また印刷性も良好である。比較例５は、ポリアミック酸系の材料であるため、白化耐性や印刷性は良好な材料系ではある。実施例９～１３は、白化耐性や印刷性について、比較例５と同等以上の特性を得ることができると期待される。式（１－１）で表される有機基は、分子内での反応や分子間の架橋等にも費やされることが考えられるため、比較例３及び４と比べても、実施例９～１３はラビング耐性が非常に良好である。比較例５はイミド化反応が進まない為、ラビング耐性が悪い結果になったと考えられる。 The liquid crystal aligning agents of Examples 9 to 13 are significantly superior in resistance to whitening and have good printability as compared with Comparative Examples. Since Comparative Example 5 is a polyamic acid-based material, it is a material system with good whitening resistance and printability. In Examples 9 to 13, it is expected that whitening resistance and printability equivalent to or higher than those in Comparative Example 5 can be obtained. Since it is considered that the organic group represented by formula (1-1) is also used for intramolecular reactions and intermolecular cross-linking, etc., compared with Comparative Examples 3 and 4, Examples 9 to 13 has very good rubbing resistance. In Comparative Example 5, the imidization reaction did not proceed, so it is considered that the rubbing resistance was poor.
また、実施例９～１３の液晶配向剤を用いて得られた液晶セルでは、低プレチルト角かつ高い電圧保持率が得られている。これは、式（１－１）で表される有機基が種々反応に用いられるのと、ポリアミック酸のように分解反応を伴わない結果であると考察できる。よって、本発明の一態様である液晶配向膜は、低温での焼成で得ることができる液晶配向膜として非常に有望であると考えられる。なお、実施例７～１０の何れの液晶配向剤を用いても、液晶配向膜及び液晶表示素子を好適に得ることができた。 In addition, the liquid crystal cells obtained using the liquid crystal aligning agents of Examples 9 to 13 have a low pretilt angle and a high voltage holding ratio. It can be considered that this is because the organic group represented by the formula (1-1) is used in various reactions and does not involve a decomposition reaction unlike polyamic acid. Therefore, the liquid crystal alignment film that is one embodiment of the present invention is considered to be very promising as a liquid crystal alignment film that can be obtained by baking at a low temperature. A liquid crystal aligning film and a liquid crystal display element could be suitably obtained using any of the liquid crystal aligning agents of Examples 7 to 10.
本発明の液晶配向剤を用いて作製した液晶表示素子は、信頼性の高い液晶表示デバイスとすることができ、ＩＰＳ液晶表示素子、ＦＦＳ液晶表示素子等、種々の方式による表示素子に好適に用いることができる。
A liquid crystal display device produced using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device, and is suitably used for display devices of various types such as an IPS liquid crystal display device and an FFS liquid crystal display device. be able to.
本発明は、重合体、それを用いた液晶配向剤、液晶配向膜、及びそれを用いた液晶表示素子に関する。 TECHNICAL FIELD The present invention relates to a polymer, a liquid crystal aligning agent using the same , a liquid crystal aligning film, and a liquid crystal display element using the same.
ジアミンを合成するための試薬を入手するのが容易である、ジイソシアネートとの反応性が良好である、得られる上記重合体の物性が良好になる、等の観点を鑑みた場合、式（３）中、Ａｒはフェニレン基が好ましく、Ｒ２は水素原子が好ましい。従って、式（３）は、好ましくは以下式（３－ａ）´で表される構造である。なかでも、式（３）中、Ｒａ及びＲｂはそれぞれ水素原子であることが好ましい。従って、式（３）は、特に好ましくは、式（３－ａ）で表される。
In view of the ease of obtaining a reagent for synthesizing a diamine, good reactivity with diisocyanate, and good physical properties of the obtained polymer, the formula (3) Among them, Ar is preferably a phenylene group , and R 2 is preferably a hydrogen atom. Therefore, formula (3) is preferably a structure represented by formula (3-a)' below. Above all, in formula (3), Ra and Rb are each preferably a hydrogen atom. Therefore, formula (3) is particularly preferably represented by formula (3-a).
Claims (9)
A liquid crystal display device using the liquid crystal alignment film according to claim 8 .
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| JP2018057182 | 2018-03-23 | ||
| JP2018057182 | 2018-03-23 | ||
| PCT/JP2019/011906 WO2019182070A1 (en) | 2018-03-23 | 2019-03-20 | Liquid crystal aligning agent, polymer for obtaining same, liquid crystal alignment film, and liquid crystal display element using same |
| JP2020507905A JP7239900B2 (en) | 2018-03-23 | 2019-03-20 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same |
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