JP2021038260A - Novel diamine - Google Patents

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JP2021038260A
JP2021038260A JP2020196944A JP2020196944A JP2021038260A JP 2021038260 A JP2021038260 A JP 2021038260A JP 2020196944 A JP2020196944 A JP 2020196944A JP 2020196944 A JP2020196944 A JP 2020196944A JP 2021038260 A JP2021038260 A JP 2021038260A
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crystal alignment
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早紀 相馬
Saki Soma
早紀 相馬
佳道 森本
Yoshimichi Morimoto
佳道 森本
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/42—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • 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

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Abstract

To provide: a liquid crystal alignment agent that makes it possible to obtain a liquid crystal alignment film that has excellent rubbing resistance, fast reduction of accumulated charge and a high alignment regulating force; a liquid crystal display element, particularly of the transverse electric field type, that has excellent display properties; and a novel diamine that serves as raw material for the liquid crystal alignment agent.SOLUTION: The present invention relates to a diamine represented by formula (4). (R1 is hydrogen or a monovalent organic group, Ar is a phenyl or naphthalene that can have a substituent group, and R3 is a single bond or a phenyl group that can have a substituent).SELECTED DRAWING: None

Description

本発明は、液晶表示素子に用いられる液晶配向剤、液晶配向膜、液晶表示素子、及び、液晶配向剤に含有する重合体の原料となる新規なジアミン化合物に関する。 The present invention relates to a liquid crystal alignment agent used for a liquid crystal display element, a liquid crystal alignment film, a liquid crystal display element, and a novel diamine compound which is a raw material of a polymer contained in the liquid crystal alignment agent.

液晶表示素子は、スマートフォン、パソコン、携帯電話、テレビ等の表示部として幅広く用いられている。液晶表示素子は、例えば素子基板とカラーフィルタ基板との間に挟持された液晶層、液晶層に電界を印加する画素電極及び共通電極、液晶層の液晶分子の配向性を制御する配向膜、画素電極に供給される電気信号をスイッチングする薄膜トランジスタ（ＴＦＴ）等を備えている。液晶分子の駆動方式としては、ＴＮ方式、ＶＡ方式等の縦電界方式や、ＩＰＳ方式、ＦＦＳ方式等の横電界方式が知られている。基板の片側のみに電極を形成させ、基板と平行方向に電界を印加する横電界方式では、従来の上下基板に形成された電極に電圧を印加して液晶を駆動させる縦電界方式と比べ、広い視野角特性を有し、また高品位な表示が可能な液晶表示素子として知られている。 Liquid crystal display elements are widely used as display units for smartphones, personal computers, mobile phones, televisions, and the like. The liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer, and pixels. It includes a thin film transistor (TFT) that switches the electrical signal supplied to the electrodes. As a driving method of liquid crystal molecules, a longitudinal electric field method such as a TN method and a VA method, and a horizontal electric field method such as an IPS method and an FFS method are known. The transverse electric field method in which electrodes are formed on only one side of the substrate and an electric field is applied in the direction parallel to the substrate is wider than the conventional longitudinal electric field method in which a voltage is applied to the electrodes formed on the upper and lower substrates to drive the liquid crystal. It is known as a liquid crystal display element that has viewing angle characteristics and is capable of high-quality display.

横電界方式の液晶セルは視野角特性に優れているものの、基板内に形成される電極部分が少ないために、電圧保持率が低いと液晶に十分な電圧がかからず表示コントラストが低下する。また、液晶配向の安定性が小さいと、液晶を長時間駆動させた際に液晶が初期の状態に戻らなくなり、コントラスト低下や残像の原因となるため、液晶配向の安定性が重要である。また、静電気が液晶セル内に蓄積されやすく、駆動によって生じる正負非対称電圧の印加によっても液晶セル内に電荷が蓄積され、これらの蓄積された電荷が液晶配向の乱れや残像として表示に影響を与え、液晶素子の表示品位を著しく低下させる。また、駆動直後にバックライト光が液晶セルに照射されることによっても電荷が蓄積され、短時間の駆動でも残像が発生する、駆動中にフリッカー（ちらつき）の大きさが変化する等の問題を生じてしまう。 Although the transverse electric field type liquid crystal cell is excellent in viewing angle characteristics, since there are few electrode portions formed in the substrate, if the voltage holding ratio is low, a sufficient voltage is not applied to the liquid crystal and the display contrast is lowered. Further, if the stability of the liquid crystal orientation is small, the liquid crystal does not return to the initial state when the liquid crystal is driven for a long time, which causes a decrease in contrast and an afterimage. Therefore, the stability of the liquid crystal orientation is important. In addition, static electricity is likely to be accumulated in the liquid crystal cell, and charges are accumulated in the liquid crystal cell even when a positive or negative asymmetric voltage generated by driving is applied, and these accumulated charges affect the display as a disorder of liquid crystal orientation or an afterimage. , The display quality of the liquid crystal element is significantly deteriorated. In addition, when the liquid crystal cell is irradiated with backlight light immediately after driving, electric charges are accumulated, afterimages are generated even after driving for a short time, and the size of flicker (flicker) changes during driving. It will occur.

一方、液晶表示素子の製造工程において、液晶配向膜は液晶配向剤を印刷し、乾燥、焼成を行った後にラビング処理を行って形成されるのが一般的である。横電界方式液晶セルでは、基板の片側のみに電極構造を有するため基板の凹凸が大きく、また、窒化珪素などの絶縁体が基板表面に形成されていることもあり、従来の配向剤と比較してより印刷性に優れた液晶配向剤が求められている。さらには、液晶配向の安定性を向上させるために従来の液晶セルよりも強くラビング処理を施すことから、ラビング処理による剥離やラビング削れを引き起こし易く、これらの剥がれや傷が表示品位を低下させる問題点がある。 On the other hand, in the manufacturing process of a liquid crystal display element, the liquid crystal alignment film is generally formed by printing a liquid crystal alignment agent, drying and firing, and then rubbing treatment. In the transverse electric field type liquid crystal cell, since the electrode structure is provided only on one side of the substrate, the unevenness of the substrate is large, and an insulator such as silicon nitride may be formed on the substrate surface, which is compared with the conventional alignment agent. There is a demand for a liquid crystal aligning agent having better printability. Furthermore, since the rubbing treatment is performed stronger than the conventional liquid crystal cell in order to improve the stability of the liquid crystal orientation, peeling and rubbing scraping due to the rubbing treatment are likely to occur, and these peeling and scratches deteriorate the display quality. There is a point.

このような横電界駆動液晶素子に用いた際、電圧保持率に優れ、かつ電荷蓄積を低減した液晶配向剤として、特許文献１には、特定ジアミンと脂肪族テトラカルボン酸誘導体とを含有する液晶配向剤が開示されている。また、液晶配向性、ラビング耐性、光透過率に優れ、広い温度範囲での残像低減に有効な液晶配向膜を形成する手段として、特許文献２には、特定ジアミンと芳香族テトラカルボン酸誘導体を含む液晶配向剤が開示されている。長時間熱ストレスが印加されても電圧保持率が低下することのなく、液晶配向性に優れる液晶配向剤として、特許文献３には、特定構造を有するポリアミック酸及びポリイミドよりなる群から選択される少なくとも一種の重合体を含有する液晶配向剤が開示される。
しかし、液晶表示素子の高性能化に伴い、液晶配向膜に要求される特性も厳しくなってきており、従来の技術のみでは全ての要求特性を満足することは難しい。 As a liquid crystal aligning agent having excellent voltage retention and reduced charge accumulation when used in such a transverse electric field drive liquid crystal element, Patent Document 1 describes a liquid crystal containing a specific diamine and an aliphatic tetracarboxylic acid derivative. Aligners are disclosed. Further, as a means for forming a liquid crystal alignment film which is excellent in liquid crystal orientation, rubbing resistance and light transmittance and is effective in reducing afterimages in a wide temperature range, Patent Document 2 describes a specific diamine and an aromatic tetracarboxylic acid derivative. Liquid crystal alignment agents containing are disclosed. Patent Document 3 selects from the group consisting of polyamic acids and polyimides having a specific structure as a liquid crystal alignment agent having excellent liquid crystal orientation without lowering the voltage retention rate even when thermal stress is applied for a long time. A liquid crystal alignment agent containing at least one polymer is disclosed.
However, as the performance of the liquid crystal display element is improved, the characteristics required for the liquid crystal alignment film are becoming stricter, and it is difficult to satisfy all the required characteristics only by the conventional technology.

国際公開公報ＷＯ２００４／０２１０７６号パンフレットInternational Publication WO2004 / 021076 Pamphlet 国際公開公報ＷＯ２０１３／０６２１１５号パンフレットInternational Publication WO2013 / 062115 Pamphlet 特開２０１０−０２６５０３JP 2010-026503

本発明は、ラビング耐性に優れ、蓄積電荷の緩和が早く、かつ液晶配向の安定性が高い、特に横電界駆動方式用液晶表示素子に適した液晶配向膜を得ることを課題とする。 An object of the present invention is to obtain a liquid crystal alignment film which is excellent in rubbing resistance, quickly relaxes accumulated charges, and has high stability of liquid crystal alignment, particularly suitable for a liquid crystal display element for a transverse electric field drive system.

本発明者らは、上記課題を解決するために鋭意検討を行った結果、液晶配向剤に含まれる重合体中に特定構造を導入することで種々の特性が同時に改善されることを見出し、本発明を完成した。
本発明は、下記を要旨とするものである。
１．下記式（１）で表される構造を主鎖に有する重合体を含有する液晶配向剤。

Figure 2021038260
（Ｒ１は水素、又は一価の有機基を表す。Ａｒは、置換基を有してもよいフェニル基若しくはナフタレン基である＊は他の基に結合する部位を示す。） As a result of diligent studies to solve the above problems, the present inventors have found that various properties can be improved at the same time by introducing a specific structure into the polymer contained in the liquid crystal alignment agent. The invention was completed.
The gist of the present invention is as follows.
1. 1. A liquid crystal alignment agent containing a polymer having a structure represented by the following formula (1) in the main chain.
Figure 2021038260
 (R 1 represents hydrogen or a monovalent organic group. Ar is a phenyl group or a naphthalene group which may have a substituent. * Indicates a site to be bonded to another group.)

本発明の液晶配向剤によれば、ラビング耐性に優れ、蓄積電荷の緩和が早く、かつ配向規制力の高い、特に横電界駆動方式用液晶表示素子に適した液晶配向膜、及び表示特性に優れた、特に横電界駆動方式の液晶表示素子が提供される。 According to the liquid crystal alignment agent of the present invention, the liquid crystal alignment film having excellent rubbing resistance, quick relaxation of accumulated charges, and high orientation control force, particularly suitable for a liquid crystal display element for a transverse electric field drive system, and excellent display characteristics. In particular, a horizontal electric field drive type liquid crystal display element is provided.

本発明の液晶配向剤は、下記式（１）で表される２価の基を主鎖に有する重合体（以下、特定重合体とも言う）を含有する液晶配向剤である。

Figure 2021038260
式（１）のＲ１は水素、又は一価の有機基を表す。一価の有機基としては、炭素数１〜２０のアルキル基やアルケニル基、シクロアルキル基、フェニル基、フッ素原子、又はこれらの組み合わせからなる基などが挙げられる。なかでも、水素原子、又は炭素数１〜３の直鎖アルキル基が好ましく、水素原子、又はメチル基がより好ましくい。 The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer having a divalent group represented by the following formula (1) in the main chain (hereinafter, also referred to as a specific polymer).
Figure 2021038260
 R 1 of the formula (1) represents hydrogen or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, a phenyl group, a fluorine atom, or a group composed of a combination thereof. Among them, a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.

また、Ｒ１は、熱により脱離反応を生じ、水素原子に置き換わる保護基であってもよい。液晶配向剤の保存安定性の点から、この保護基は、室温においては脱離せず、好ましくは、８０℃以上、より好ましくは１００℃以上、特に好ましくは１５０〜２００℃で脱離し、水素原子になるのが好適である。例えば、１，１−ジメチル−２−クロロエトキシカルボニル基、１，１−ジメチル−２−シアノエトキシカルボニル基、tert−ブトキシカルボニル基等が挙げられ、好ましくはtert−ブトキシカルボニル基である。
式（１）のＡｒは、置換基を有してもよいフェニル基若しくはナフタレン基を表す。これらのうち、フェニル基が好ましい。また、これらのフェニル基又はナフタレン基の環部分に置換基が結合されていてもよい。置換基の具体例としては、フッ素原子やメチル基などが挙げられる。 Further, R 1 may be a protecting group that undergoes an elimination reaction by heat and replaces a hydrogen atom. From the viewpoint of storage stability of the liquid crystal alignment agent, this protecting group does not desorb at room temperature, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 150 to 200 ° C., and hydrogen atoms. Is preferable. For example, a 1,1-dimethyl-2-chloroethoxycarbonyl group, a 1,1-dimethyl-2-cyanoethoxycarbonyl group, a tert-butoxycarbonyl group and the like can be mentioned, and a tert-butoxycarbonyl group is preferable.
Ar in the formula (1) represents a phenyl group or a naphthalene group which may have a substituent. Of these, a phenyl group is preferred. Further, a substituent may be bonded to the ring portion of these phenyl group or naphthalene group. Specific examples of the substituent include a fluorine atom and a methyl group.

本発明において、式（１）で表される２価の基を主鎖に有する重合体の種類は特に限定されない。具体的にはポリアミド、ポリアミック酸、ポリアミック酸エステル、ポリイミド、ポリウレア、ポリシロキサン、ポリエステル等、一般的に液晶配向膜として用いられる重合体が挙げられる。なかでも、ポリアミック酸やポリアミック酸エステルなどのポリイミド前駆体、又はそれをイミド化して得られるポリイミドのうちの少なくとも１種の重合体が好ましい。 In the present invention, the type of polymer having a divalent group represented by the formula (1) in the main chain is not particularly limited. Specific examples thereof include polymers generally used as a liquid crystal alignment film, such as polyamide, polyamic acid, polyamic acid ester, polyimide, polyurea, polysiloxane, and polyester. Of these, a polyimide precursor such as a polyamic acid or a polyamic acid ester, or at least one polymer of a polyimide obtained by imidizing the polyimide precursor is preferable.

上記のポリイミド前駆体としては、テトラカルボン酸誘導体とジアミンとの反応で得られるポリアミック酸又はポリアミック酸エステルが挙げられる。このポリイミド前駆体の主鎖に、式（１）で表される２価の基を導入する手段としては、式（１）で表される２価の基を主鎖方向に有するテトラカルボン酸誘導体、又は、式（１）で表される２価の基を主鎖方向に有するジアミンから選ばれる少なくとも１種を、前記の反応に用いるテトラカルボン酸誘導体及びジアミンの一部又は全部に用いる方法が挙げられる。 Examples of the above-mentioned polyimide precursor include a polyamic acid or a polyamic acid ester obtained by reacting a tetracarboxylic acid derivative with a diamine. As a means for introducing a divalent group represented by the formula (1) into the main chain of this polyimide precursor, a tetracarboxylic acid derivative having a divalent group represented by the formula (1) in the main chain direction. Or, a method in which at least one selected from diamines having a divalent group represented by the formula (1) in the main chain direction is used for a part or all of the tetracarboxylic acid derivative and diamine used in the above reaction. Can be mentioned.

上記ポリイミド前駆体の製造に用いるテトラカルボン酸誘導体としては、テトラカルボン酸、テトラカルボン酸二無水物、テトラカルボン酸ジハライド、テトラカルボン酸ジアルキルエステル又はテトラカルボン酸ジアルキルエステルジハライドが挙げられる。例えば、式（１）で表される２価の基を主鎖方向に有するテトラカルボン酸は、下記式（１−１）で表すことができる。 Examples of the tetracarboxylic acid derivative used for producing the above-mentioned polyimide precursor include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester and tetracarboxylic acid dialkyl ester dihalide. For example, a tetracarboxylic acid having a divalent group represented by the formula (1) in the main chain direction can be represented by the following formula (1-1).

Figure 2021038260
式（１−１）中、Ｒ１及びＡｒは前記式（１）の定義と同じであり、Ａは３価の基を表し、２つのＡは同一であっても異なってもよい。Ａの例としては、シクロブタン環構造、シクロペンタン環構造、シクロヘキサン環構造、ベンゼン環構造及び下記式（Ａ−１）よりなる群から選ばれる少なくとも一種を有する３価の有機基が挙げられる。
Figure 2021038260
Figure 2021038260
 Wherein (1-1), R 1 and Ar are as defined in the formula (1), A represents a trivalent group, the two A may be the same or different. Examples of A include a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, a benzene ring structure, and a trivalent organic group having at least one selected from the group consisting of the following formula (A-1).
Figure 2021038260

また、式（１）で表される２価の基を主鎖方向に有するジアミンは、下記式（１−２）で表すことができる。

Figure 2021038260
式（１−２）中、Ｒ１及びＡｒは前記式（１）の定義と同じであり、Ｂは単結合又は２価の基を表し、２つのＢは同一であっても異なってもよい。Ｂが２価の基である場合、その例としては、ベンゼン環構造、炭素数が１〜１０、好ましくは１〜５を有する、アルキル構造、アルケニル構造、アルコキシ構造、フルオロアルキル構造、及びアミド構造よりなる群から選ばれる少なくとも一種を有する２価の有機基が挙げられる。 A diamine having a divalent group represented by the formula (1) in the main chain direction can be represented by the following formula (1-2).
Figure 2021038260
 Wherein (1-2), R 1 and Ar are as defined in the formula (1), B represents a single bond or a divalent group, the two B may be the same or different .. When B is a divalent group, examples thereof include a benzene ring structure, an alkyl structure, an alkenyl structure, an alkoxy structure, a fluoroalkyl structure, and an amide structure having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Examples thereof include divalent organic groups having at least one selected from the group consisting of.

なお、上記式（１−２）で示されるジアミンは、式（１）で表される２価の基を主鎖方向に有するポリウレアを得るのに用いることもできる。ポリウレアはジイソシアネートとジアミンの反応によって得られ、この反応の一部又は全部に式（１−２）のジアミンを用いて得られたポリウレアは、本発明の液晶配向剤に含有される特定重合体の一種となる。 The diamine represented by the above formula (1-2) can also be used to obtain a polyurea having a divalent group represented by the formula (1) in the main chain direction. Polyurea is obtained by the reaction of diisocyanate and diamine, and the polyurea obtained by using the diamine of the formula (1-2) in a part or all of this reaction is the specific polymer contained in the liquid crystal alignment agent of the present invention. It becomes a kind.

本発明に用いられる特定重合体は、下記式（２）で表される構造単位を含むポリイミド前駆体、及びそれをイミド化して得られるポリイミドから選ばれる少なくとも１種が好ましい。

Figure 2021038260
The specific polymer used in the present invention is preferably at least one selected from a polyimide precursor containing a structural unit represented by the following formula (2) and a polyimide obtained by imidizing the polyimide precursor.
Figure 2021038260

上記式（２）において、Ｘ１はテトラカルボン酸誘導体に由来する４価の有機基である。Ｙ１は式（１）の構造を主鎖方向に含むジアミンに由来する２価の有機基である。Ｒ2は水素原子又は炭素数１〜５のアルキル基である。Ｒ2は、加熱によるイミド化のしやすさの点から、水素原子、メチル基又はエチル基が好ましい。 In the above formula (2), X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative. Y 1 is a divalent organic group derived from a diamine containing the structure of the formula (1) in the main chain direction. R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 2 is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of ease of imidization by heating.

Ｘ１は、重合体の溶媒への溶解性や液晶配向剤の塗布性、液晶配向膜とした場合における液晶の配向性、電圧保持率、蓄積電荷など、必要とされる特性の程度に応じて適宜選択され、同一重合体中に１種類でも、２種類以上でもよい。
Ｘ１の具体例を示すならば、国際公開公報２０１５／１１９１６８の１３項〜１４項に掲載される、式（Ｘ−１）〜（Ｘ−４６）の構造などが挙げられる。 X 1 depends on the degree of required characteristics such as the solubility of the polymer in the solvent, the coatability of the liquid crystal alignment agent, the orientation of the liquid crystal when it is used as a liquid crystal alignment film, the voltage retention rate, and the accumulated charge. It may be appropriately selected and may be one kind or two or more kinds in the same polymer.
Specific examples of X 1 include the structures of the formulas (X-1) to (X-46) published in paragraphs 13 to 14 of International Publication 2015/111968.

以下に、好ましいＸ１の構造を示すが、本発明はこれらに限定されるものではない。

Figure 2021038260
The preferred structure of X 1 is shown below, but the present invention is not limited thereto.
Figure 2021038260

Figure 2021038260
Figure 2021038260

上記の構造のうち、（Ａ−１）、（Ａ−２）はラビング耐性の更なる向上という観点から特に好ましい。（Ａ−４）は蓄積電荷の緩和速度の更なる向上という観点から特に好ましい。（Ａ−１５）〜（Ａ−１７）は、液晶配向性と蓄積電荷の緩和速度の更なる向上という観点から特に好ましい。
式（２）において、Ｙ１の具体例としては前記式（１−２）のジアミンから２つのアミノ基を除いた構造を挙げることができる。なかでも、Ｙ１は下記式（３）の構造であるとより好ましい。 Of the above structures, (A-1) and (A-2) are particularly preferable from the viewpoint of further improving the rubbing resistance. (A-4) is particularly preferable from the viewpoint of further improving the relaxation rate of the accumulated charge. (A-15) to (A-17) are particularly preferable from the viewpoint of further improving the liquid crystal orientation and the relaxation rate of the accumulated charge.
In the formula (2), as a specific example of Y 1 , a structure obtained by removing two amino groups from the diamine of the formula (1-2) can be mentioned. Above all, it is more preferable that Y 1 has the structure of the following formula (3).

Figure 2021038260
式（３）において、Ｒ１及びＡｒは前記式（１）の定義と同じである。Ｒ３は単結合又は置換基を有してもよいフェニル基を表す。＊は―ＮＨ−に結合する部位を示す。Ｒ３はフェニル基が特に好ましい。
Figure 2021038260
 In the formula (3), R 1 and Ar are as defined in the formula (1). R 3 represents a phenyl group which may have a single bond or a substituent. * Indicates the site that binds to -NH-. R 3 is particularly preferably a phenyl group.

Ｙ１の特に好ましい構造を以下に示す。下記式において、Ｂｏｃはｔｅｒｔ−ブトキシカルボニル基を表し、＊は―ＮＨ−に結合する部位を表す。 A particularly preferable structure of Y 1 is shown below. In the formula below, Boc represents the tert-butoxycarbonyl group and * represents the site that binds to -NH-.

Figure 2021038260
Figure 2021038260

なお、前記式（３）の構造を有するジアミンとしては、下記式（４）で表されるジアミンを挙げることができる。かかるジアミンの製造方法については後述する。

Figure 2021038260
式（４）において、Ｒ１及びＡｒは上記式（１）の定義と同じである。Ｒ３は単結合、又は置換基を有してもよいフェニル基を表す。Ｒ３はフェニル基が特に好ましい。 As the diamine having the structure of the formula (3), a diamine represented by the following formula (4) can be mentioned. The method for producing such a diamine will be described later.
Figure 2021038260
 In the formula (4), R 1 and Ar are as defined in the formula (1). R 3 represents a phenyl group which may have a single bond or a substituent. R 3 is particularly preferably a phenyl group.

式（２）で表される構造単位を含むポリイミド前駆体は、本発明の効果を損なわない範囲において、下記式（５）で表される構造単位を含んでいてもよい。

Figure 2021038260
The polyimide precursor containing the structural unit represented by the formula (2) may contain the structural unit represented by the following formula (5) as long as the effect of the present invention is not impaired.
Figure 2021038260

式（５）において、Ｘ２はテトラカルボン酸誘導体に由来する４価の有機基である。Ｙ２は、式（１）におけるＹ１の構造を主鎖方向に含まないジアミンに由来する２価の有機基である。Ｒ２は、前記式（２）における定義と同じであり、Ｒ４は水素原子又は炭素数１〜４のアルキル基である。また、２つあるＲ４の少なくとも一方は水素原子であることが好ましい。 In formula (5), X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative. Y 2 is a divalent organic group derived from a diamine that does not contain the structure of Y 1 in the formula (1) in the main chain direction. R 2 is the same as the definition in the above formula (2), and R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, it is preferable that at least one of twofold R 4 is a hydrogen atom.

Ｘ２の具体例としては、好ましい例も含めて式（２）のＸ１で例示したものと同じ構造を挙げることができる。また、Ｙ２は式（１）の構造を主鎖方向に含まないジアミンに由来する二価の有機基であり、その構造は特に限定されない。また、Ｙ２は重合体の溶媒への溶解性や液晶配向剤の塗布性、液晶配向膜とした場合における液晶の配向性、電圧保持率、蓄積電荷など、必要とされる特性の程度に応じて適宜選択され、同一重合体中に１種類でも又は２種類以上でもよい。 As a specific example of X 2, the same structure as that illustrated by X 1 of the formula (2) can be mentioned, including a preferable example. Further, Y 2 is a divalent organic group derived from a diamine that does not contain the structure of the formula (1) in the main chain direction, and its structure is not particularly limited. Further, Y 2 depends on the degree of required characteristics such as the solubility of the polymer in the solvent, the coatability of the liquid crystal alignment agent, the orientation of the liquid crystal when it is used as a liquid crystal alignment film, the voltage retention rate, and the accumulated charge. It may be appropriately selected and may be one kind or two or more kinds in the same polymer.

Ｙ２の具体例を示すならば、国際公開公報２０１５／１１９１６８の４頁に掲載される式（２）の構造、及び、８〜１２頁に掲載される、式（Ｙ−１）〜（Ｙ−９７）、（Ｙ−１０１）〜（Ｙ−１１８）；国際公開公報２０１３／００８９０６の６項に掲載される、式（２）からアミノ基を２つ除いた２価の有機基；国際公開公報２０１５／１２２４１３の８頁に掲載される式（１）からアミノ基を２つ除いた２価の有機基；国際公開公報２０１５／０６０３６０の８頁に掲載される式（３）；日本国公開特許公報２０１２−１７３５１４の８頁に記載される式（１）からアミノ基を２つ除いた二価の有機基；国際公開公報２０１０−０５０５２３の９頁に掲載される式（Ａ）〜（Ｆ）からアミノ基を２つ除いた二価の有機基などが挙げられる。 To give a specific example of Y 2 , the structure of the formula (2) published on page 4 of International Publication 2015/111968 and the formulas (Y-1) to (Y) published on pages 8 to 12 -97), (Y-101) to (Y-118); a divalent organic group obtained by removing two amino groups from the formula (2), which is published in Section 6 of International Publication 2013/008906; International Publication. A divalent organic group obtained by removing two amino groups from the formula (1) published on page 8 of Gazette 2015/122413; the formula (3) published on page 8 of International Publication 2015/060360; published in Japan. A divalent organic group obtained by removing two amino groups from the formula (1) described on page 8 of Patent Gazette 2012-173514; formulas (A) to (F) published on page 9 of International Publication No. 2010-050523. ) With two amino groups removed, and examples thereof include a divalent organic group.

Ｙ２の好ましい構造を以下に示すが、これらに限定されるものではない。

Figure 2021038260
The preferred structure of Y 2 is shown below, but is not limited thereto.
Figure 2021038260

Figure 2021038260
Figure 2021038260

Figure 2021038260
Figure 2021038260

Figure 2021038260
Figure 2021038260

上記のうち、（Ｂ−２８）、（Ｂ−２９）は、ラビング耐性の更なる向上という観点から特に好ましい。（Ｂ−１）〜（Ｂ−３）は、液晶配向性の更なる向上という観点から特に好ましい。（Ｂ−１４）〜（Ｂ−１８）及び（Ｂ−２７）は、蓄積電荷の緩和速度の更なる向上という観点から特に好ましい。 Of the above, (B-28) and (B-29) are particularly preferable from the viewpoint of further improving the rubbing resistance. (B-1) to (B-3) are particularly preferable from the viewpoint of further improving the liquid crystal orientation. (B-14) to (B-18) and (B-27) are particularly preferable from the viewpoint of further improving the relaxation rate of the accumulated charge.

式（２）で表される構造単位を含むポリイミド前駆体が、式（５）で表される構造単位を含む場合、式（２）で表される構造単位は、式（２）と式（５）の合計に対して１０モル％以上であることが好ましく、より好ましくは２０モル％以上であり、特に好ましくは３０モル％以上である。
本発明に用いるポリイミド前駆体の分子量は、重量平均分子量で２，０００〜５００，０００が好ましく、より好ましくは５，０００〜３００，０００であり、さらに好ましくは、１０，０００〜１００，０００である。 When the polyimide precursor containing the structural unit represented by the formula (2) contains the structural unit represented by the formula (5), the structural units represented by the formula (2) are the formula (2) and the formula (2). It is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more with respect to the total of 5).
The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000 in terms of weight average molecular weight. is there.

式（１）で表される２価の基を主鎖に有するポリイミドとしては、前記のポリイミド前駆体を閉環させて得られるポリイミドが挙げられる。このポリイミドにおいては、アミド酸基の閉環率（イミド化率ともいう）は必ずしも１００％である必要はなく、用途や目的に応じて任意に調整できる。
ポリイミド前駆体をイミド化させる方法としては、ポリイミド前駆体の溶液をそのまま加熱する熱イミド化、又はポリイミド前駆体の溶液に触媒を添加する触媒イミド化が挙げられる。 Examples of the polyimide having a divalent group represented by the formula (1) in the main chain include a polyimide obtained by ring-closing the above-mentioned polyimide precursor. In this polyimide, the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.

本発明の液晶配向剤は、上記特定重合体を含有するものであるが、異なる構造の特定重合体を２種以上含有していてもよい。また、特定重合体に加えて、その他の重合体、即ち式（１）で表される２価の基を主鎖に有さない重合体を含有していてもよい。その他の重合体の種類としては、ポリアミック酸、ポリイミド、ポリアミック酸エステル、ポリエステル、ポリアミド、ポリオルガノシロキサン、セルロース誘導体、ポリアセタール、ポリスチレン又はその誘導体、ポリ（スチレン−フェニルマレイミド）誘導体、ポリ（メタ）アクリレートなどを挙げることができる。本発明の液晶配向剤がその他の重合体を含有する場合、含有される全重合体成分に対する特定重合体の割合は５質量％以上であることが好ましく、その一例として５〜９５質量％が挙げられる。 The liquid crystal alignment agent of the present invention contains the above-mentioned specific polymer, but may contain two or more kinds of specific polymers having different structures. Further, in addition to the specific polymer, another polymer, that is, a polymer having no divalent group represented by the formula (1) in the main chain may be contained. Other types of polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate. And so on. When the liquid crystal alignment agent of the present invention contains other polymers, the ratio of the specific polymer to the total polymer components contained is preferably 5% by mass or more, and 5 to 95% by mass is given as an example. Be done.

液晶配向剤は、液晶配向膜を作製するために用いられるものであり、均一な薄膜を形成させるという観点から、一般的には溶液の形態をとる。本発明の液晶配向剤においても前記した重合体成分と、この重合体成分を溶解させる有機溶媒とを含有する溶液であることが好ましい。その際、液晶配向剤中の重合体の濃度は、形成させようとする塗膜の厚みの設定によって適宜変更することができる。均一で欠陥のない塗膜を形成させるという点からは、１質量％以上であることが好ましく、溶液の保存安定性の点からは、１０質量％以下とすることが好ましい。特に好ましい重合体の濃度は、２〜８質量％である。 The liquid crystal alignment agent is used for producing a liquid crystal alignment film, and generally takes the form of a solution from the viewpoint of forming a uniform thin film. The liquid crystal alignment agent of the present invention is also preferably a solution containing the above-mentioned polymer component and an organic solvent that dissolves the polymer component. At that time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferable concentration of the polymer is 2 to 8% by mass.

液晶配向剤に含有される有機溶媒は、重合体成分が均一に溶解するものであれば特に限定されない。その具体例を挙げるならば、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、ジメチルスルホキシド、γ−ブチロラクトン、１，３−ジメチル−イミダゾリジノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、４−ヒドロキシ−４−メチル−２−ペンタノンなどを挙げることができる。なかでも、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、又はγ−ブチロラクトンを用いることが好ましい。 The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl. -Imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like can be mentioned. Of these, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

また、液晶配向剤に含有される有機溶媒は、上記のような溶媒に加えて液晶配向剤を塗布する際の塗布性や塗膜の表面平滑性を向上させる溶媒を併用した混合溶媒を使用することが一般的であり、本発明の液晶配向剤においてもこのような混合溶媒は好適に用いられる。併用する有機溶媒の具体例は、液晶配向剤に関する公知の文献に種々開示されているとおりであるが、その一例を示すなら、国際公開公報２０１５／０６０３５７号パンフレットの５３頁［0104］〜５５頁［0105］に開示されている溶媒などが挙げられる。このような溶媒の種類及び含有量は、液晶配向剤の塗布装置、塗布条件、塗布環境などに応じて適宜選択される。 Further, as the organic solvent contained in the liquid crystal alignment agent, a mixed solvent in which a solvent for improving the coatability when applying the liquid crystal alignment agent and the surface smoothness of the coating film is used in addition to the above-mentioned solvent is used. This is common, and such a mixed solvent is preferably used in the liquid crystal alignment agent of the present invention. Specific examples of the organic solvent used in combination are as variously disclosed in known documents relating to liquid crystal alignment agents. To give an example thereof, see pages 53 [0104] to 55 of the International Publication No. 2015/060357 pamphlet. Examples thereof include the solvent disclosed in [0105]. The type and content of such a solvent are appropriately selected according to the coating apparatus for the liquid crystal alignment agent, coating conditions, coating environment, and the like.

本発明の液晶配向剤は、本発明の効果を損なわない範囲において、重合体成分及び有機溶媒以外の成分を追加的に含有してもよい。このような追加成分としては、液晶配向膜と基板との密着性や液晶配向膜とシール材との密着性を高めるための密着助剤、液晶配向膜の強度を高めるための架橋剤、液晶配向膜の誘電率や電気抵抗を調整するための誘電体や導電物質などが挙げられる。これら追加成分の具体例としては、液晶配向剤に関する公知の文献に種々開示されているとおりであるが、その例を示すなら、国際公開公報２０１５／０６０３５７号パンフレットの５３頁［0105］〜５５頁［0116］に開示されている成分などが挙げられる。 The liquid crystal alignment agent of the present invention may additionally contain components other than the polymer component and the organic solvent as long as the effects of the present invention are not impaired. Such additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a cross-linking agent for increasing the strength of the liquid crystal alignment film, and a liquid crystal alignment. Examples thereof include a dielectric and a conductive substance for adjusting the dielectric constant and electrical resistance of the film. Specific examples of these additional components are as disclosed in various known literatures on liquid crystal alignment agents. For example, pages 53 [0105] to 55 of the International Publication No. 2015/060357 pamphlet. Examples thereof include the components disclosed in [0116].

本発明の液晶配向剤から液晶配向膜を得る方法の一例を挙げるなら、塗布液形態の液晶配向剤を基板に塗布し、乾燥し、焼成して得られた膜に対してラビング処理法又は光配向処理法で配向処理を施す方法が挙げられる。
液晶配向剤を塗布する基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板とともに、アクリル基板やポリカーボネート基板などのプラスチック基板等を用いることもできる。その際、液晶を駆動させるためのＩＴＯ電極などが形成された基板を用いると、プロセスの簡素化の点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならば、シリコンウエハーなどの不透明な物でも使用でき、この場合の電極にはアルミニウムなどの光を反射する材料も使用できる。 To give an example of a method for obtaining a liquid crystal alignment film from the liquid crystal alignment agent of the present invention, a rubbing treatment method or light is applied to a film obtained by applying a liquid crystal alignment agent in the form of a coating liquid to a substrate, drying and firing. An example is a method of performing an orientation treatment by an orientation treatment method.
The substrate on which the liquid crystal alignment agent is applied is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display element, if only one side of the substrate is used, an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.

液晶配向剤の塗布方法は、特に限定されないが、スクリーン印刷、オフセット印刷、フレキソ印刷、インクジェット法などが一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナー法、スプレー法などがあり、目的に応じてこれらを用いてもよい。
液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン、ＩＲ（赤外線）型オーブンなどの加熱手段により、溶媒を蒸発させ、焼成する。液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択することができる。通常は、含有される溶媒を十分に除去するために、５０〜１２０℃で１〜１０分焼成し、その後、１５０〜３００℃で、５〜１２０分焼成する手段が挙げられる。 The method for applying the liquid crystal alignment agent is not particularly limited, but screen printing, offset printing, flexographic printing, an inkjet method, and the like are common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and these may be used depending on the purpose.
After applying the liquid crystal aligning agent on the substrate, the solvent is evaporated and fired by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. Any temperature and time can be selected for the drying and firing steps after applying the liquid crystal alignment agent. Usually, in order to sufficiently remove the contained solvent, a means of firing at 50 to 120 ° C. for 1 to 10 minutes and then firing at 150 to 300 ° C. for 5 to 120 minutes can be mentioned.

焼成後の液晶配向膜の厚みは、特に限定されないが、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、５〜３００ｎｍであることが好ましく、１０〜２００ｎｍがより好ましい。
本発明の液晶配向膜は、ＩＰＳ方式やＦＦＳ方式などの横電界方式の液晶表示素子の液晶配向膜として好適であり、特に、ＦＦＳ方式の液晶表示素子の液晶配向膜として有用である。
本発明の液晶表示素子は、上記液晶配向剤から得られる液晶配向膜付きの基板を得た後、既知の方法で液晶セルを作製し、該液晶セルを使用して素子としたものである。 The thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a transverse electric field type liquid crystal display element such as an IPS system or an FFS system, and is particularly useful as a liquid crystal alignment film for an FFS type liquid crystal display element.
In the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal cell is produced by a known method, and the liquid crystal cell is used as an element.

液晶セルの作製方法の一例として、パッシブマトリクス構造の液晶表示素子を例にとり説明する。なお、画像表示を構成する各画素部分にＴＦＴ（Thin Film Transistor）などのスイッチング素子が設けられたアクティブマトリクス構造の液晶表示素子であってもよい。
具体的には、透明なガラス製の基板を準備し、一方の基板の上にコモン電極を、他方の基板の上にセグメント電極を設ける。これらの電極は、例えばＩＴＯ電極とすることができ、所望の画像表示ができるようパターニングされている。次いで、各基板の上に、コモン電極とセグメント電極を被覆するようにして絶縁膜を設ける。絶縁膜は、例えば、ゾル−ゲル法によって形成されたＳｉＯ２−ＴｉＯ２からなる膜とすることができる。次に、前記のような条件で、各基板の上に液晶配向膜を形成する。 As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. A liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
Specifically, a transparent glass substrate is prepared, and a common electrode is provided on one substrate and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes and are patterned so as to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of SiO 2- TiO 2 formed by the sol-gel method. Next, a liquid crystal alignment film is formed on each substrate under the above conditions.

次いで、液晶配向膜を形成した２枚の基板のうちの一方の基板上の所定の場所に例えば紫外線硬化性のシール材を配置し、さらに液晶配向膜面上の所定の数カ所に液晶を配置した後、液晶配向膜が対向するように他方の基板を貼り合わせて圧着することにより液晶を液晶配向膜前面に押し広げた後、基板の全面に紫外線を照射してシール材を硬化することで液晶セルを得る。 Next, for example, an ultraviolet curable sealing material was placed at a predetermined position on one of the two substrates on which the liquid crystal alignment film was formed, and liquid crystals were further placed at a predetermined position on the liquid crystal alignment film surface. After that, the other substrate is bonded and crimped so that the liquid crystal alignment film faces each other to spread the liquid crystal to the front surface of the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the liquid crystal. Get the cell.

また、基板の上に液晶配向膜を形成した後の工程として、一方の基板上の所定の場所にシール材を配置する際に、外部から液晶を充填可能な開口部を設けておき、液晶を配置しないで基板を貼り合わせた後、シール材に設けた開口部を通じて液晶セル内に液晶材料を注入し、次いで、この開口部を接着剤で封止して液晶セルを得る。液晶材料の注入には、真空注入法でもよいし、大気中で毛細管現象を利用した方法でもよい。
上記のいずれの方法においても、液晶セル内に液晶材料が充填される空間を確保する為に、一方の基板上に柱状の突起を設けるか、一方の基板上にスペーサーを散布するか、シール材にスペーサーを混入するか、又はこれらを組み合わせるなどの手段を取ることが好ましい。 Further, as a step after forming the liquid crystal alignment film on the substrate, when arranging the sealing material at a predetermined place on one of the substrates, an opening capable of filling the liquid crystal from the outside is provided to provide the liquid crystal. After the substrates are bonded together without being arranged, the liquid crystal material is injected into the liquid crystal cell through the opening provided in the sealing material, and then the opening is sealed with an adhesive to obtain the liquid crystal cell. The liquid crystal material may be injected by a vacuum injection method or a method using a capillary phenomenon in the atmosphere.
In any of the above methods, in order to secure a space for filling the liquid crystal material in the liquid crystal cell, a columnar protrusion is provided on one substrate, a spacer is sprayed on one substrate, or a sealing material is provided. It is preferable to take measures such as mixing spacers in the liquid crystal or combining them.

上記の液晶材料としては、ネマチック液晶及びスメクチック液晶を挙げることができ、その中でもネマチック液晶が好ましく、ポジ型液晶材料やネガ型液晶材料のいずれを用いてもよい。次に、偏光板の設置を行う。具体的には、２枚の基板の液晶層とは反対側の面に一対の偏光板を貼り付けることが好ましい。
なお、本発明の液晶配向膜及び液晶表示素子は、本発明の液晶配向剤を用いている限り上記の記載に限定されるものではなく、その他の公知の手法で作製されたものであってもよい。液晶配向剤から液晶表示素子を得るまでの工程は、例えば日本特開２０１５−１３５３９３の１７頁［0074］〜１９頁［0081］に開示されている。 Examples of the liquid crystal material include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable, and either positive liquid crystal material or negative liquid crystal material may be used. Next, the polarizing plate is installed. Specifically, it is preferable to attach a pair of polarizing plates to the surfaces of the two substrates opposite to the liquid crystal layer.
The liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above description as long as the liquid crystal alignment agent of the present invention is used, and may be manufactured by other known methods. Good. The steps from obtaining a liquid crystal display element from a liquid crystal aligning agent are disclosed, for example, on pages 17 [0074] to 19 [0081] of Japanese Patent Application Laid-Open No. 2015-135393.

＜本発明のジアミン＞
以下に、前述した下記式（４）で表されるジアミンを得る方法について説明する。

Figure 2021038260
<Diamine of the present invention>
The method for obtaining the diamine represented by the following formula (4) described above will be described below.
Figure 2021038260

式（４）において、Ｒ１及びＡｒは上記式（１）の定義と同じである。Ｒ３は単結合、又は置換基を有してもよいフェニル基を表す。Ｒ３はフェニル基が特に好ましい。
式（４）で表されるジアミンの好ましい具体例としては、下記式（４−１）〜（４−７）のジアミンを挙げることができる。式中、Ｂｏｃは、tert−ブトキシカルボニル基を表し、Ｍｅはメチル基を表す。 In the formula (4), R 1 and Ar are as defined in the formula (1). R 3 represents a phenyl group which may have a single bond or a substituent. R 3 is particularly preferably a phenyl group.
As a preferable specific example of the diamine represented by the formula (4), the diamines of the following formulas (4-1) to (4-7) can be mentioned. In the formula, Boc represents a tert-butoxycarbonyl group and Me represents a methyl group.

Figure 2021038260
Figure 2021038260

上記式（４）で表されるジアミンを製造する方法は特に限定されないが、好ましい方法としては、以下の製法が挙げられる。
チアゾール骨格を有するアミン化合物（ａ１）と、ニトロ化合物（ａ２）を反応させることにより以下のジニトロ体（ａ３）を製造する。その後ニトロ基を還元することで目的のジアミン（ａ４）を得ることができる。 The method for producing the diamine represented by the above formula (4) is not particularly limited, but preferred methods include the following production methods.
The following dinitro compound (a3) is produced by reacting an amine compound (a1) having a thiazole skeleton with a nitro compound (a2). After that, the desired diamine (a4) can be obtained by reducing the nitro group.

Figure 2021038260
Figure 2021038260

Figure 2021038260
Figure 2021038260

上記反応式［１］、［２］中、Ｒ’、Ｒ”は１価の有機基であり、Ｘはハロゲン原子を示し、Ｆ、Ｃｌ、Ｂｒ又はＩ原子を意味する。
上記は式（４）におけるＲ１が水素原子である場合の例であるが、Ｒ１が水素原子以外の場合はジニトロ体（ａ３）に、Ｒ１に対応する１価の有機基を導入すればよい。１価の有機基を導入するにあたっては、アミン類と反応が可能な化合物であればよく、例えば、酸ハライド、酸無水物、イソシアネート類、エポキシ類、オキセタン類、ハロゲン化アリール類、ハロゲン化アルキル類が挙げられる。また、アルコールの水酸基をＯＭｓ、ＯＴｆ、ＯＴｓ等の脱離基に置換したアルコール類などが使用できる。 In the above reaction formulas [1] and [2], R'and R "are monovalent organic groups, X represents a halogen atom, and means F, Cl, Br or I atom.
The above is an example when R 1 in the formula (4) is a hydrogen atom, but when R 1 is other than a hydrogen atom, a monovalent organic group corresponding to R 1 is introduced into the dinitro compound (a3). Just do it. When introducing a monovalent organic group, any compound that can react with amines may be used, for example, acid halides, acid anhydrides, isocyanates, epoxys, oxetans, aryl halides, alkyl halides. Kind. Further, alcohols in which the hydroxyl group of the alcohol is replaced with a leaving group such as OMs, OTf, OTs or the like can be used.

チアゾール骨格を有するアミン化合物（ａ１）の合成法は特に限定されないが、一般的な合成法として、下記に示すように、ニトロ基を有するα-ハロケトン（ａ５）とチオ尿素との反応により合成することができる。

Figure 2021038260
The method for synthesizing the amine compound (a1) having a thiazole skeleton is not particularly limited, but as a general synthesis method, it is synthesized by reacting α-haloketone (a5) having a nitro group with thiourea as shown below. be able to.
Figure 2021038260

使用する塩基は、例えば、炭酸水素ナトリウム、炭酸水素カリウム、燐酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウムなどの無機塩基、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、キノリン、コリジンなどのアミン類、水素化ナトリウム、水素化カリウムなどの塩基を使用できる。 The bases used are, for example, inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropyl. Amines such as ethylamine, pyridine, quinoline and colisine, and bases such as sodium hydride and potassium hydride can be used.

溶媒に関しても、原料と反応しない溶媒であれば使用することができ、非プロトン性極性有機溶媒（Ｎ，Ｎ−ジメチルホルムアミド 、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン など）、エーテル類（ジエチルエーテル、ジイソプロピルエーテル、メチルtertブチルエーテル 、シクロペンチルメチルエーテル、テトラヒドロフラン、ジオキサンなど）、脂肪族炭化水素類（ペンタン、へキサン、ヘプタン、石油エーテルなど）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）、ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）、低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）、ニトリル類（アセトニトリル、プロピオニトリル、ブチロニトリル等）が使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、この場合、上記溶媒は1種単独で又は2種以上混合して用いることができる。また場合によっては、適当な脱水剤や乾燥剤を用いて非水溶媒として用いることもできる。反応温度は−１００℃から使用する溶媒の沸点までの範囲で任意の温度を選択することができるが、好ましくは−５０〜１５０℃の範囲である。反応時間は０．１〜１０００時間の範囲で任意に選択することができる。生成物は、再結晶、蒸留、シリカゲルカラムクロマトグラフィーなどで精製してもよい。 As for the solvent, any solvent that does not react with the raw material can be used, and an aprotonic polar organic solvent (N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.) can be used. ), Ethers (diethyl ether, diisopropyl ether, methyl tertbutyl ether, cyclopentylmethyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, etc.) , Toluene, xylene, mesityrene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, etc.) Methyl propionate, etc.) and nitriles (nitrile, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more. In some cases, it can also be used as a non-aqueous solvent by using an appropriate dehydrating agent or desiccant. The reaction temperature can be selected from -100 ° C. to the boiling point of the solvent used, but is preferably in the range of -50 to 150 ° C. The reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours. The product may be purified by recrystallization, distillation, silica gel column chromatography and the like.

上記反応式［１］に関して、ＸがＦ又はＣｌであって、かつ、ＮＯ２基がＸに対して２位、又は４位にあれば、塩基の存在下、ハロゲン化アリールと脂肪族アミン化合物とを反応させ、ジニトロ体（ａ３）を得ることができる。使用する塩基は、前述の塩基を使用することができる。反応溶媒、反応温度は前記の記載に準ずる。生成物は、再結晶、蒸留、シリカゲルカラムクロマトグラフィーなどで精製してもよい。 Regarding the above reaction formula [1], if X is F or Cl and the two NO groups are at the 2-position or 4-position with respect to X, the aryl halide and the aliphatic amine compound are present in the presence of a base. And can be reacted to obtain a dinitro compound (a3). As the base to be used, the above-mentioned base can be used. The reaction solvent and reaction temperature are in accordance with the above description. The product may be purified by recrystallization, distillation, silica gel column chromatography and the like.

また、Ｘが、Ｂｒ又はＩであれば、ＮＯ２基がＸに対して２位でも３位でも４位でもよく、適当な金属触媒、配位子、塩基存在下でＣ−Ｎクロスカップリング反応を用いることでもジニトロ体を得ることができる。金属触媒の例としては、酢酸パラジウム、塩化パラジウム、塩化パラジウム-アセトニトリル錯体、パラジウム−活性炭、ビス（ジベンジリデンアセトン）パラジウム、トリス（ジベンジリデンアセトン）ジパラジウム、ビス（アセトニトリル）ジクロロパラジウム、ビス（ベンゾニトリル）ジクロロパラジウム、ＣｕＣｌ、ＣｕＢｒ、ＣｕＩ、ＣｕＣＮ等が挙げられる。配位子の例としては、トリフェニルホスフィン、トリ−ｏ−トリルホスフィン、ジフェニルメチルホスフィン、フェニルジメチルホスフィン、１，２−ビス（ジフェニルホスフィノ）エタン、１，３−ビス（ジフェニルホスフィノ）プロパン、１，４−ビス（ジフェニルホスフィノ）ブタン、１，１’−ビス（ジフェニルホスフィノ）フェロセン、トリメチルホスファイト、トリエチルホスファイト、トリフェニルホスファイト、トリ−ｔｅｒｔ−ブチルホスフィン等が挙げられる。塩基の例としては前述の塩基を用いることができる。反応溶媒、反応温度は、前記の記載に準ずる。生成物は、再結晶、蒸留、シリカゲルカラムクロマトグラフィーなどで精製してもよい。 If X is Br or I, the two NO groups may be at the 2-position, 3-position, or 4-position with respect to X, and CN cross-coupling in the presence of an appropriate metal catalyst, ligand, or base. A dinitro compound can also be obtained by using a reaction. Examples of metal catalysts include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated coal, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo). (Nitrile) Dichloropalladium, CuCl, CuBr, CuI, CuCN and the like can be mentioned. Examples of ligands are triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane. , 1,4-Bis (diphenylphosphine) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphine, triethylphosphine, triphenylphosphine, tri-tert-butylphosphine and the like. As an example of the base, the above-mentioned base can be used. The reaction solvent and reaction temperature are in accordance with the above description. The product may be purified by recrystallization, distillation, silica gel column chromatography and the like.

上記反応［２］にかける還元反応は、触媒の存在下における水素添加反応、プロトンの共存下に行う還元反応、蟻酸を水素源とする還元、ヒドラジンを水素源とする還元反応などがあり、これらの還元反応を組み合わせでもよい。ジニトロ化合物の構造と還元反応の反応性を考慮し、水素添加反応が好ましい。
還元反応に用いられる触媒は、市販品として入手できる活性炭担持金属が好ましく、例えば、パラジウム−活性炭、白金−活性炭、ロジウム−活性炭などが挙げられる。また、水酸化パラジウム、酸化白金、ラネーニッケルなど必ずしも活性炭担持型の金属触媒でなくてもよい。一般的に広く使用されているパラジウム−活性炭が、良好な結果が得られるので好ましい。 The reduction reaction applied to the above reaction [2] includes a hydrogenation reaction in the presence of a catalyst, a reduction reaction performed in the presence of protons, a reduction reaction using formic acid as a hydrogen source, a reduction reaction using hydrazine as a hydrogen source, and the like. The reduction reaction of may be combined. The hydrogenation reaction is preferable in consideration of the structure of the dinitro compound and the reactivity of the reduction reaction.
The catalyst used in the reduction reaction is preferably an activated carbon-supported metal available as a commercially available product, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, it does not necessarily have to be an activated carbon-supported metal catalyst such as palladium hydroxide, platinum oxide, and Raney nickel. Palladium-activated carbon, which is generally widely used, is preferred because it gives good results.

還元反応をより効果的に進行させるため、活性炭の共存下で反応を実施することもある。この時、使用する活性炭の量は特に限定されないが、ジニトロ化合物（ａ３，Ｘ１）に対して１〜３０質量％の範囲が好ましく、１０〜２０質量％がより好ましい。同様な理由により、加圧下で反応を実施する場合もある。この場合、ベンゼン核の還元を避けるため、２０気圧までの加圧範囲で行う。好ましくは１０気圧までの範囲で反応を実施する。 In order to allow the reduction reaction to proceed more effectively, the reaction may be carried out in the presence of activated carbon. At this time, the amount of activated carbon used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass, based on the dinitro compound (a3, X1). For the same reason, the reaction may be carried out under pressure. In this case, in order to avoid reduction of benzene nuclei, the pressure range is up to 20 atm. The reaction is preferably carried out in the range of up to 10 atm.

溶媒は、各原料と反応しない溶媒であれば、制限なく使用することができる。例えば、非プロトン性極性有機溶媒（Ｎ，Ｎ−ジメチルホルムアミド 、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン など）；エーテル類（ジエチルエーテル、ジイソプロピルエーテル、メチルtertブチルエーテル 、シクロペンチルメチルエーテル、テトラヒドロフラン、ジオキサンなど）；脂肪族炭化水素類（ペンタン、へキサン、ヘプタン、石油エーテルなど）；芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）；ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）；低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）；ニトリル類（アセトニトリル、プロピオニトリル、ブチロニトリル等）；などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、１種単独で又は２種以上混合して用いることができる。必要に応じて、適当な脱水剤や乾燥剤を用いて溶媒を乾燥し、非水溶媒として用いることもできる。 The solvent can be used without limitation as long as it is a solvent that does not react with each raw material. For example, aprotonic polar organic solvents (N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); ethers (diethyl ether, diisopropyl ether, methyl tertbutyl ether, cyclopentyl, etc.) Methyl ether, tetrahydrofuran, dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.) ); Halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); Etc.); etc. can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent can be dried with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.

溶媒の使用量（反応濃度）は特に限定されないが、ジニトロ化合物に対し、０．１〜１００質量倍である。好ましくは０．５〜３０質量倍であり、さらに好ましくは１〜１０質量倍である。
反応温度は特に限定されないが、−１００℃から使用する溶媒の沸点までの範囲、好ましくは、−５０〜１５０℃である。反応時間は、通常０．０５〜３５０時間、好ましくは０．５〜１００時間である。 The amount of the solvent used (reaction concentration) is not particularly limited, but is 0.1 to 100 times by mass with respect to the dinitro compound. It is preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass.
The reaction temperature is not particularly limited, but is in the range from −100 ° C. to the boiling point of the solvent used, preferably −50 to 150 ° C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

以下に実施例等を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下における化合物の略号及び特性評価の方法は、以下のとおりである。 Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these Examples. The abbreviations of the compounds and the method for evaluating the properties in the following are as follows.

Figure 2021038260
Figure 2021038260
Figure 2021038260
Figure 2021038260

＜有機溶媒＞
ＮＭＰ：Ｎ−メチル−２−ピロリドン、 ＧＢＬ：γ―ブチロラクトン
ＢＣＳ：ブチルセロソルブ、 Ｐｄ／Ｃ：パラジウムカーボン
ＤＭＳＯ：ジメチルスルオキシド、 ＴＨＦ：テトラヒドロフラン
＜添加剤＞
ＬＳ−４６６８：３−グリシドキシプロピルトリエトキシシラン <Organic solvent>
NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone BCS: Butyl cellosolve, Pd / C: Palladium carbon DMSO: Dimethyl sulfoxide, THF: tetrahydrofuran <Additives>
LS-4668: 3-glycidoxypropyltriethoxysilane

（１Ｈ−ＮＭＲの測定）
装置：Ｖａｒｉａｎ ＮＭＲ ｓｙｓｔｅｍ ４００ＮＢ（４００ＭＨｚ）（Ｖａｒｉａｎ社製）、及びＪＭＴＣ−５００／５４／ＳＳ（５００ＭＨｚ）（ＪＥＯＬ社製）
測定溶媒：ＣＤＣｌ３（重水素化クロロホルム），ＤＭＳＯ−ｄ６（重水素化ジメチルスルホキシド）
基準物質：ＴＭＳ（テトラメチルシラン）（δ：０．０ｐｐｍ，１Ｈ）及びＣＤＣｌ３（δ：７７．０ｐｐｍ，１３Ｃ） (Measurement of 1H-NMR)
Equipment: Varian NMR system 400NB (400MHz) (manufactured by Varian), and JMTC-500 / 54 / SS (500MHz) (manufactured by JEOL)
Measuring solvent: CDCl3 (deuterated chloroform), DMSO-d6 (deuterated dimethyl sulfoxide)
Reference substance: TMS (tetramethylsilane) (δ: 0.0 ppm, 1H) and CDCl3 (δ: 77.0 ppm, 13C)

＜ジアミン化合物（ＤＡ-１）の合成＞

Figure 2021038260
<Synthesis of diamine compound (DA-1)>
Figure 2021038260

２Ｌ(リットル)の四つ口フラスコに２−ブロモー４−ニトロフェニルアセトフェノン（１００ｇ，４１０ｍｍｏｌ）、チオ尿素（３１．２ｇ, ４１０ｍｍｏｌ）、及びＮＭＰ（６００ｇ）を仕込み、羽攪拌下に６０℃にまで昇温し、トリエチルアミン（８３．０ｇ，８２０ｍｍｏｌ）を１０分掛けて滴下し，１時間攪拌した。ＨＰＬＣ(高速液体クロマトグラフィ)にて反応終了を確認した後、メタノール（１５００ｇ）加え、５℃に冷却後１時間攪拌した。析出した結晶を減圧濾過し、２−プロパノール（２００ｇ）で洗浄した後、乾燥し、粉末結晶（１）を得た（収量８７ｇ，収率９６％）。
1H-NMR(CDCl3,δppm)；8.25-8.20(2H, m), 8.10-8.03(2H, m),7.42(1H, s), 7.25(1H, s) 2-Bromo-4-nitrophenylacetophenone (100 g, 410 mmol), thiourea (31.2 g, 410 mmol), and NMP (600 g) were placed in a 2 L (liter) four-necked flask, and the temperature was raised to 60 ° C. under agitation of the wings. The temperature was raised, triethylamine (83.0 g, 820 mmol) was added dropwise over 10 minutes, and the mixture was stirred for 1 hour. After confirming the completion of the reaction by HPLC (High Performance Liquid Chromatography), methanol (1500 g) was added, the mixture was cooled to 5 ° C., and the mixture was stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (200 g), and then dried to obtain powder crystals (1) (yield 87 g, yield 96%).
1H-NMR (CDCl3, δppm); 8.25-8.20 (2H, m), 8.10-8.03 (2H, m), 7.42 (1H, s), 7.25 (1H, s)

Figure 2021038260
Figure 2021038260

１Ｌの四つ口フラスコに化合物（１）（５０ｇ，２２６ｍｍｏｌ）、４−フルオロニトロベンゼン（３８．３ｇ, ２７１ｍｍｏｌ）、炭酸セシウム（７３．６ｇ, ２２６ｍｍｏｌ）、ＤＭＳＯ（５００ｇ）、水（１０ｇ）を仕込み、羽攪拌下に６０℃にまで昇温し、１２時間攪拌した。その後更に炭酸セシウム（７３．６ｇ, ２２６ｍｍｏｌ）を加え、１２時間撹拌した。得られた反応液を濾過することにより、塩を除去し、メタノール（５００ｇ）―水（５００ｇ）を滴下し、５℃に冷却後１時間攪拌した。析出した結晶を減圧濾過し、メタノール（５００ｇ）で３回リパルプ洗浄した後、乾燥し、粉末結晶（２）を得た（収量４２ｇ，収率５４％）。
1H-NMR(DMSO-d6,δppm)；11.2(1H, s), 8.30-8.22(6H, m), 7.98-7.94(3H, m) Compound (1) (50 g, 226 mmol), 4-fluoronitrobenzene (38.3 g, 271 mmol), cesium carbonate (73.6 g, 226 mmol), DMSO (500 g), and water (10 g) are charged in a 1 L four-necked flask. The temperature was raised to 60 ° C. under stirring the blades, and the mixture was stirred for 12 hours. Then, cesium carbonate (73.6 g, 226 mmol) was further added, and the mixture was stirred for 12 hours. The obtained reaction solution was filtered to remove salts, methanol (500 g) -water (500 g) was added dropwise, and the mixture was cooled to 5 ° C. and stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with methanol (500 g) three times, and then dried to obtain powder crystals (2) (yield 42 g, yield 54%).
1H-NMR (DMSO-d6, δppm); 11.2 (1H, s), 8.30-8.22 (6H, m), 7.98-7.94 (3H, m)

Figure 2021038260
Figure 2021038260

化合物（２）（２０ｇ，２９．２ｍｍｏｌ）、５質量％Ｐｄ／Ｃ（５０％含水型）、及びＴＨＦ(２００ｇ)の混合物を、水素加圧条件下に６０℃で１２時間攪拌した。反応終了後、触媒をろ過した後、濃縮を行い、トルエン（２００ｇ）にてスラリー洗浄した。析出した結晶を減圧濾過し、トルエン（４０ｇ）で洗浄した後、乾燥し、粉末結晶ＤＡ−１を得た（収量１６ｇ，収率９１％）。
1H-NMR(DMSO-d6,δppm)；9.55(1H, s), 7.55-7.50(2H, m), 7.28-7.25(2H, m),6.72(1H, s),6.58-6.45(m-4H),5.20(1H, s), 4.82(2H, s) A mixture of compound (2) (20 g, 29.2 mmol), 5 mass% Pd / C (50% water content) and THF (200 g) was stirred at 60 ° C. for 12 hours under hydrogen pressurization conditions. After completion of the reaction, the catalyst was filtered, concentrated, and slurry-washed with toluene (200 g). The precipitated crystals were filtered under reduced pressure, washed with toluene (40 g), and then dried to obtain powdered crystals DA-1 (yield 16 g, yield 91%).
1H-NMR (DMSO-d6, δppm); 9.55 (1H, s), 7.55-7.50 (2H, m), 7.28-7.25 (2H, m), 6.72 (1H, s), 6.58-6.45 (m-4H) ), 5.20 (1H, s), 4.82 (2H, s)

＜化合物（ＤＡ-３）の合成＞

Figure 2021038260
<Synthesis of compound (DA-3)>
Figure 2021038260

合成原料である２−アミノ−６−ニトロベンゾチアゾールは、東京化成工業社の製品をそのまま使用した。２−アミノ−６−ニトロベンゾチアゾール（９７．６ｇ、０．５０ｍｏｌ）、５質量％Ｐｄ／Ｃ（５０％含水型）、及びエタノール(３０００ｇ)の混合物を、水素加圧条件下に６０℃で１２時間攪拌した。反応終了後、触媒をろ過した後、濃縮を行い、得られた結晶を２−プロパノール（２００ｇ）にてスラリー洗浄した。結晶を減圧濾過し、２−プロパノール（４０ｇ）で洗浄した後、乾燥し、粉末結晶ＤＡ−３を得た（収量４４．８ｇ，収率５４％）。 As the synthetic raw material 2-amino-6-nitrobenzothiazole, the product of Tokyo Chemical Industry Co., Ltd. was used as it was. A mixture of 2-amino-6-nitrobenzothiazole (97.6 g, 0.50 mol), 5 mass% Pd / C (50% hydrous) and ethanol (3000 g) at 60 ° C. under hydrogen pressurization conditions. The mixture was stirred for 12 hours. After completion of the reaction, the catalyst was filtered and concentrated, and the obtained crystals were slurry-washed with 2-propanol (200 g). The crystals were filtered under reduced pressure, washed with 2-propanol (40 g), and then dried to obtain powdered crystals DA-3 (yield 44.8 g, yield 54%).

＜重合体の合成＞
［合成例１］
撹拌装置付き及び窒素導入管付きの５０ｍｌ四つ口フラスコにＤＡ−１を（２．２６ｇ，８．０ｍｍｏｌ）加えた後、ＮＭＰ２６．０ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−２を（１．５７ｇ，８．０ｍｍｏｌ）加え、ＮＭＰを６．５ｇ加えた後、さらに２５℃条件下にて１２時間攪拌することで樹脂固形分濃度１２質量％のポリアミック酸溶液（ＰＡＡ−１）を得た。このポリアミック酸溶液の粘度は３００ｍＰａ・ｓであった。 <Synthesis of polymer>
[Synthesis Example 1]
After adding DA-1 (2.26 g, 8.0 mmol) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 26.0 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-2 (1.57 g, 8.0 mmol) was added, 6.5 g of NMP was added, and then the mixture was further stirred under 25 ° C. conditions for 12 hours to obtain a resin solid content concentration of 12 mass. % Polyamic acid solution (PAA-1) was obtained. The viscosity of this polyamic acid solution was 300 mPa · s.

［合成例２］
撹拌装置付き及び窒素導入管付きの５０ｍｌ四つ口フラスコにＤＡ−１を（１．９８ｇ，７．０ｍｍｏｌ）加えた後、ＮＭＰ２３．４ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−１を（１．３９ｇ，６．４ｍｍｏｌ）加え、ＮＭＰを５．９ｇ加えた後、さらに５０℃条件下にて１２時間攪拌することで樹脂固形分濃度１２質量％のポリアミック酸溶液（ＰＡＡ−２）を得た。このポリアミック酸溶液の粘度は２７５ｍＰａ・ｓであった。 [Synthesis Example 2]
After adding DA-1 (1.98 g, 7.0 mmol) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 23.4 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-1 (1.39 g, 6.4 mmol) was added, 5.9 g of NMP was added, and then the mixture was further stirred under 50 ° C. conditions for 12 hours to obtain a resin solid content concentration of 12 mass. % Polyamic acid solution (PAA-2) was obtained. The viscosity of this polyamic acid solution was 275 mPa · s.

［合成例３］
撹拌装置付き及び窒素導入管付きの５０ｍｌ四つ口フラスコにＤＡ−１を（１．８１ｇ，６．４ｍｍｏｌ）、ＤＡ−４を（０．３９ｇ、１．６ｍｍol）加えた後、ＮＭＰ２０．４ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−２を（０．６４ｇ，３．３ｍｍｏｌ）加え、ＮＭＰを２．１ｇ加えた後、２５℃条件下にて１時間攪拌した。その後、ＣＡ−１を（０．８７ｇ，４．０ｍｍｏｌ）加え、ＮＭＰを３．０ｇ加えた後、さらに５０℃条件下にて１２時間攪拌することで樹脂固形分濃度１５質量％のポリアミック酸溶液（ＰＡＡ−３）を得た。このポリアミック酸溶液の粘度は５９３ｍＰａ・ｓであった。 [Synthesis Example 3]
Add DA-1 (1.81 g, 6.4 mmol) and DA-4 (0.39 g, 1.6 mmol) to a 50 ml four-necked flask with a stirrer and a nitrogen introduction tube, and then add 20.4 g of NMP. In addition, nitrogen was fed and stirred to dissolve. While stirring this diamine solution, CA-2 (0.64 g, 3.3 mmol) was added, 2.1 g of NMP was added, and then the mixture was stirred under 25 ° C. conditions for 1 hour. Then, CA-1 (0.87 g, 4.0 mmol) was added, 3.0 g of NMP was added, and then the mixture was further stirred under the condition of 50 ° C. for 12 hours to obtain a polyamic acid solution having a resin solid content concentration of 15% by mass. (PAA-3) was obtained. The viscosity of this polyamic acid solution was 593 mPa · s.

［合成例４］
合成例１で得られたポリアミック酸溶液（ＰＡＡ−１）を８．３ｇ分取し、攪拌しながらＮＭＰを６．５ｇ、ＢＣＳを５．２ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を０．８ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−１）を得た。 [Synthesis Example 4]
8.3 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 was taken, and while stirring, the NMP solution containing 6.5 g of NMP, 5.2 g of BCS, and 1 wt% of LS-4668 was added to 0. 0.8 g was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-1).

［合成例５］
合成例２で得られたポリアミック酸溶液（ＰＡＡ−２）を１０．２ｇ分取し、攪拌しながらＮＭＰを５．８ｇ、ＢＣＳを５．７ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を１．０ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−２）を得た。 [Synthesis Example 5]
10.2 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 was taken, and 1 NMP solution containing 5.8 g of NMP, 5.7 g of BCS, and 1% by weight of LS-4668 was added while stirring. .0 g was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-2).

［合成例６］
合成例３で得られたポリアミック酸溶液（ＰＡＡ−３）を７．１ｇ分取し、攪拌しながらＮＭＰを４．１ｇ、ＢＣＳを４．９ｇ、ＧＢＬを７．４２ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を１．１ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−３）を得た。 [Synthesis Example 6]
7.1 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 3 was taken, and while stirring, 4.1 g of NMP, 4.9 g of BCS, 7.42 g of GBL, and 1 weight of LS-4668 were added. 1.1 g of NMP solution containing% was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-3).

［比較合成例１］
撹拌装置付き及び窒素導入管付きの５０ｍｌ四つ口フラスコにＤＡ−２を（１．３９ｇ，７．０ｍｍｏｌ）加えた後、ＮＭＰ１９．４ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−２を（１．１５ｇ，５．９ｍｍｏｌ）加え、ＮＭＰを４．２ｇ加えた後、さらに２５℃条件下にて１２時間攪拌することで樹脂固形分濃度１２質量％のポリアミック酸溶液（ＰＡＡ−４）を得た。このポリアミック酸溶液の粘度は２８０ｍＰａ・ｓであった。 [Comparative Synthesis Example 1]
After adding DA-2 (1.39 g, 7.0 mmol) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 19.4 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-2 (1.15 g, 5.9 mmol) was added, 4.2 g of NMP was added, and then the mixture was further stirred under 25 ° C. conditions for 12 hours to obtain a resin solid content concentration of 12 mass. % Polyamic acid solution (PAA-4) was obtained. The viscosity of this polyamic acid solution was 280 mPa · s.

［比較合成例２］
撹拌装置付き及び窒素導入管付きの１００ｍｌ四つ口フラスコにＤＡ−４を（４．８９ｇ，２０．０ｍｍｏｌ）加えた後、ＮＭＰ５９．１ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−２（１．５７ｇ，８．０ｍｍｏｌ）、ＣＡ−１を（２．１８ｇ，１０．０ｍｍｏｌ）加え、ＮＭＰを１４．８ｇ加えた後、さらに５０℃条件下にて１２時間攪拌することで樹脂固形分濃度１２質量％のポリアミック酸溶液（ＰＡＡ−５）を得た。このポリアミック酸溶液の粘度は２７０ｍＰａ・ｓであった。 [Comparative synthesis example 2]
After adding DA-4 (4.89 g, 20.0 mmol) to a 100 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 59.1 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-2 (1.57 g, 8.0 mmol) and CA-1 (2.18 g, 10.0 mmol) were added, 14.8 g of NMP was added, and then under 50 ° C. conditions. A polyamic acid solution (PAA-5) having a resin solid content concentration of 12% by mass was obtained by stirring for 12 hours. The viscosity of this polyamic acid solution was 270 mPa · s.

［比較合成例３］
撹拌装置付き及び窒素導入管付きの５０ｍｌ四つ口フラスコにＤＡ−３を（１．３２ｇ，８．０ｍｍｏｌ）加えた後、ＮＭＰ２４．６ｇを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらＣＡ−１を（１．６９ｇ，７．８ｍｍｏｌ）加え、ＮＭＰを６．２ｇ加えた後、さらに２５℃条件下にて１２時間攪拌することで樹脂固形分濃度１０質量％のポリアミック酸溶液（ＰＡＡ−６）を得た。このポリアミック酸溶液の粘度は１５０ｍＰａ・ｓであった。 [Comparative Synthesis Example 3]
After adding DA-3 (1.32 g, 8.0 mmol) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 24.6 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-1 (1.69 g, 7.8 mmol) was added, 6.2 g of NMP was added, and then the mixture was further stirred under 25 ° C. conditions for 12 hours to obtain a resin solid content concentration of 10 mass. % Polyamic acid solution (PAA-6) was obtained. The viscosity of this polyamic acid solution was 150 mPa · s.

［比較合成例４］
比較合成例１で得られたポリアミック酸溶液（ＰＡＡ−４）を１０．８ｇ分取し、攪拌しながらＮＭＰを６．８ｇ、ＢＣＳを６．２ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を１．１ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−４）を得た。 [Comparative Synthesis Example 4]
10.8 g of the polyamic acid solution (PAA-4) obtained in Comparative Synthesis Example 1 was taken, and an NMP solution containing 6.8 g of NMP, 6.2 g of BCS, and 1% by weight of LS-4668 was prepared with stirring. 1.1 g was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-4).

［比較合成例５］
比較合成例２で得られたポリアミック酸溶液（ＰＡＡ−５）を７．３ｇ分取し、攪拌しながらＮＭＰを６．８ｇ、ＢＣＳを４．７ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を０．９ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−５）を得た。 [Comparative Synthesis Example 5]
7.3 g of the polyamic acid solution (PAA-5) obtained in Comparative Synthesis Example 2 was taken, and an NMP solution containing 6.8 g of NMP, 4.7 g of BCS, and 1% by weight of LS-4668 was prepared with stirring. 0.9 g was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-5).

［比較合成例６］
比較合成例３で得られたポリアミック酸溶液（ＰＡＡ−６）を１０．７ｇ分取し、攪拌しながらＮＭＰを５．５ｇ、ＢＣＳを５．０ｇ、ＬＳ−４６６８を１重量％含むＮＭＰ溶液を１．１ｇ加え、更に室温で２時間撹拌し液晶配配向剤（Ｑ−６）を得た。 [Comparative Synthesis Example 6]
10.7 g of the polyamic acid solution (PAA-6) obtained in Comparative Synthesis Example 3 was taken, and an NMP solution containing 5.5 g of NMP, 5.0 g of BCS, and 1% by weight of LS-4668 was prepared with stirring. 1.1 g was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (Q-6).

＜ポリイミド前駆体及びイミド化重合体の分子量測定＞
ポリイミド前駆体及びイミド化重合体の分子量は、常温ゲル浸透クロマトグラフィー（ＧＰＣ）装置（ＧＰＣ−１０１）（昭和電工社製）、及びカラム（ＫＤ−８０３，ＫＤ−８０５）（Ｓｈｏｄｅｘ社製）を用いて、以下のようにして測定した。
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（リットル）、リン酸・無水結晶（ｏ−リン酸）が３０ｍｍｏｌ／Ｌ、テトラヒドロフラン（ＴＨＦ）が１０ｍｌ／Ｌ）
流速：１．０ｍｌ／分
検量線作成用標準サンプル：ＴＳＫ 標準ポリエチレンオキサイド（分子量；約９００,０００、１５０,０００、１００,０００、及び３０,０００）（東ソー社製）及びポリエチレングリコール（分子量；約１２,０００、４,０００、及び１,０００）（ポリマーラボラトリー社製）。 <Measurement of molecular weight of polyimide precursor and imidized polymer>
For the molecular weight of the polyimide precursor and the imidized polymer, use a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805) (manufactured by Shodex). Using, it was measured as follows.
Column temperature: 50 ° C
Eluent: N, N'-dimethylformamide (30 mmol / L (liter) of lithium bromide-hydrate (LiBr · H2O) and 30 mmol / L of phosphoric acid / anhydrous crystals (o-phosphoric acid) as additives) , Tetrahydrofuran (THF) is 10 ml / L)
Flow velocity: 1.0 ml / Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; Approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory).

＜粘度測定＞
ポリアミック酸溶液の粘度は、Ｅ型粘度計ＴＶＥ−２２Ｈ（東機産業社製）を用い、サンプル量１．１ｍＬ、コーンロータＴＥ−１（１°３４’、Ｒ２４）にて、２５℃で測定した。 <Viscosity measurement>
The viscosity of the polyamic acid solution was measured at 25 ° C. using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1 ° 34', R24). did.

＜ラビング耐性評価＞
得られた液晶配向剤を１．０μｍのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、８０℃のホットプレート上で５分間乾燥させた後、２３０℃で２０分間焼成して、膜厚１００ｎｍのポリイミド膜を得た。このポリイミド膜をレーヨン布で１回ラビング（ロール径１２０ｍｍ、回転数１０００ｒｐｍ、移動速度２０ｍｍ／ｓｅｃ、押し込み量０．４ｍｍ）した。この膜表面を、共焦点レーザー顕微鏡を用いて表面状態を観察し、倍率１００倍で削れカスの有無と傷の有無を観察した。削れカスや傷がほとんど見られないものを「良好」と定義して評価し、多くの削れカスやラビング傷が見られるものは「不良」と定義して評価した。 <Rubbing resistance evaluation>
The obtained liquid crystal alignment agent is filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then fired at 230 ° C. for 20 minutes. , A polyimide film having a film thickness of 100 nm was obtained. This polyimide film was rubbed once with a rayon cloth (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, pushing amount 0.4 mm). The surface state of this film surface was observed using a confocal laser scanning microscope, and the presence or absence of shavings and scratches were observed at a magnification of 100 times. Those with almost no shavings or scratches were defined as "good" and evaluated, and those with many shavings or rubbing scratches were defined as "bad" and evaluated.

＜液晶表示素子の作製＞
始めに電極付きの基板を準備した。基板は、３０ｍｍ×３５ｍｍの大きさで、厚さが０．７ｍｍのガラス基板である。基板上には第１層目として対向電極を構成する、ベタ状のパターンを備えたＩＺＯ電極が形成されている。第１層目の対向電極の上には第２層目として、ＣＶＤ法により成膜されたＳｉＮ（窒化珪素）膜が形成されている。第２層目のＳｉＮ膜の膜厚は５００ｎｍであり、層間絶縁膜として機能する。第２層目のＳｉＮ膜の上には、第３層目としてＩＺＯ膜をパターニングして形成された櫛歯状の画素電極が配置され、第１画素及び第２画素の２つの画素を形成している。各画素のサイズは、縦１０ｍｍで横約５ｍｍである。このとき、第１層目の対向電極と第３層目の画素電極とは、第２層目のＳｉＮ膜の作用により電気的に絶縁されている。 <Manufacturing of liquid crystal display element>
First, a substrate with electrodes was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An IZO electrode having a solid pattern, which constitutes a counter electrode as a first layer, is formed on the substrate. A SiN (silicon nitride) film formed by a CVD method is formed as a second layer on the counter electrode of the first layer. The thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an IZO film as a third layer is arranged on the SiN film of the second layer to form two pixels, a first pixel and a second pixel. ing. The size of each pixel is 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

第３層目の画素電極は、日本国特開２０１４−７７８４５に記載の図と同様、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は３μｍであり、電極要素間の間隔は６μｍである。各画素を形成する画素電極が、中央部分の屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字の「くの字」に似た形状を備える。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第１領域と下側の第２領域を有する。 The pixel electrode of the third layer has a comb-tooth shape formed by arranging a plurality of dogleg-shaped electrode elements whose central portion is bent, as in the figure described in Japanese Patent Application Laid-Open No. 2014-77745. .. The width of each electrode element in the lateral direction is 3 μm, and the distance between the electrode elements is 6 μm. Since the pixel electrodes forming each pixel are formed by arranging a plurality of bent dogleg-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that resembles a bold "dogleg" that bends. Then, each pixel is divided into upper and lower parts with a bent portion in the center as a boundary, and has a first region on the upper side and a second region on the lower side of the bent portion.

各画素の第１領域と第２領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっている。すなわち、後述する液晶配向膜のラビング方向を基準とした場合、画素の第１領域では画素電極の電極要素が＋１０°の角度（時計回り）をなすように形成され、画素の第２領域では画素電極の電極要素が−１０°の角度（時計回り）をなすように形成されている。すなわち、各画素の第１領域と第２領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作（インプレーン・スイッチング）の方向が互いに逆方向となるように構成されている。 Comparing the first region and the second region of each pixel, the forming directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle (clockwise) of + 10 ° in the first region of the pixel, and the pixel is formed in the second region of the pixel. The electrode elements of the electrodes are formed so as to form an angle of −10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational movement (inplane switching) of the liquid crystal induced by the application of the voltage between the pixel electrode and the counter electrode in the substrate surface are mutually different. It is configured to be in the opposite direction.

次に、得られた液晶配向剤を１．０μｍのフィルターで濾過した後、準備された上記電極付き基板と対向基板として裏面にＩＴＯ膜が成膜されており、かつ高さ４μｍの柱状のスペーサーを有するガラス基板のそれぞれにスピンコートした。次いで、８０℃のホットプレート上で５分間乾燥後、２３０℃で２０分間焼成して膜厚６０ｎｍの塗膜として、各基板上にポリイミド膜を得た。このポリイミド膜上を、所定のラビング方向で、レーヨン布によりラビング（ロール径１２０ｍｍ、回転数５００ｒｐｍ、移動速度３０ｍｍ／ｓｅｃ、押し込み量０．３ｍｍ）した後、純水中にて１分間超音波照射を行い、８０℃で１０分間乾燥した。 Next, after filtering the obtained liquid crystal alignment agent with a 1.0 μm filter, an ITO film is formed on the back surface of the prepared substrate with electrodes as a facing substrate, and a columnar spacer having a height of 4 μm is formed. Each of the glass substrates having the above was spin-coated. Then, after drying on a hot plate at 80 ° C. for 5 minutes, it was fired at 230 ° C. for 20 minutes to obtain a polyimide film on each substrate as a coating film having a film thickness of 60 nm. After rubbing (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm) on this polyimide film with a rayon cloth in a predetermined rubbing direction, ultrasonic irradiation is performed in pure water for 1 minute. And dried at 80 ° C. for 10 minutes.

その後、上記液晶配向膜付きの２種類の基板を用いて、それぞれのラビング方向が逆平行になるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが３．８μｍの空セルを作製した。この空セルに液晶（ＭＬＣ−３０１９、メルク社製）を常温で真空注入したのち、注入口を封止してアンチパラレル配向の液晶セルとした。得られた液晶セルは、ＦＦＳモード液晶表示素子を構成する。その後、得られた液晶セルを１２０℃で１時間加熱し、一晩放置してから各評価に使用した。 After that, using the above two types of substrates with a liquid crystal alignment film, they are combined so that their rubbing directions are antiparallel, and the surroundings are sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.8 μm is created. Made. A liquid crystal (MLC-3019, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and then the injection port was sealed to obtain an anti-parallel oriented liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Then, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour, left overnight, and then used for each evaluation.

＜残像消去時間の評価＞
以下の光学系等を用いて残像の評価を行った。作製した液晶セルを偏光軸が直交するように配置された２枚の偏光板の間に設置し、電圧無印加の状態でＬＥＤバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。 <Evaluation of afterimage erasure time>
The afterimage was evaluated using the following optical system and the like. The produced liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the LED backlight is turned on in a state where no voltage is applied so that the brightness of the transmitted light is minimized. The arrangement angle of the liquid crystal cell was adjusted.

次に、この液晶セルに周波数３０Ｈｚの交流電圧を印加しながらＶ−Ｔカーブ（電圧−透過率曲線）を測定し、相対透過率が２３％となる交流電圧を駆動電圧として算出した。
残像評価では、相対透過率が２３％となる周波数３０Ｈｚの交流電圧を印加して液晶セルを駆動させながら、同時に１Ｖの直流電圧を印加し、３０分間駆動させた。その後、印加直流電圧値を０Ｖにして直流電圧の印加のみを停止し、その状態でさらに１５分駆動した。 Next, the VT curve (voltage-transmittance curve) was measured while applying an AC voltage having a frequency of 30 Hz to the liquid crystal cell, and the AC voltage having a relative transmittance of 23% was calculated as the drive voltage.
In the afterimage evaluation, an AC voltage having a frequency of 30 Hz having a relative transmittance of 23% was applied to drive the liquid crystal cell, and at the same time, a DC voltage of 1 V was applied to drive the liquid crystal cell for 30 minutes. After that, the applied DC voltage value was set to 0 V, only the application of the DC voltage was stopped, and the vehicle was driven for another 15 minutes in that state.

残像評価は、直流電圧の印加を開始した時点から６０分間が経過するまでに、相対透過率が３０％以下に低下した時間を数値化した。相対透過率が３０％以下に低下するまでに６０分間以上を要した場合には、残像消去不可と定義して評価した。そして、上述した方法に従う残像評価は、液晶セルの温度が２３℃の状態の温度条件下で行った。 In the afterimage evaluation, the time during which the relative transmittance decreased to 30% or less was quantified from the time when the application of the DC voltage was started until 60 minutes passed. When it took 60 minutes or more for the relative transmittance to decrease to 30% or less, the afterimage was defined as non-erasable and evaluated. Then, the afterimage evaluation according to the above-mentioned method was performed under the temperature condition in which the temperature of the liquid crystal cell was 23 ° C.

＜液晶配向の安定性評価＞
この液晶セルを用い、６０℃の恒温環境下、周波数３０Ｈｚで１０ＶＰＰの交流電圧を１６８時間印加した。その後、液晶セルの画素電極と対向電極との間を短絡させた状態にし、そのまま室温に一日放置した。
放置の後、液晶セルを偏光軸が直交するように配置された２枚の偏光板の間に設置し、電圧無印加の状態でバックライトを点灯させておき、透過光の輝度が最も小さくなるように液晶セルの配置角度を調整した。そして、第１画素の第２領域が最も暗くなる角度から第１領域が最も暗くなる角度まで液晶セルを回転させたときの回転角度を角度Δとして算出した。第２画素でも同様に、第２領域と第１領域とを比較し、同様の角度Δを算出した。そして、第１画素と第２画素の角度Δ値の平均値を液晶セルの角度Δとして算出した。この液晶セルの角度Δの値が低いほど良好、高いほど不良として評価した。 <Evaluation of stability of liquid crystal orientation>
Using this liquid crystal cell, an AC voltage of 10 VPP was applied for 168 hours at a frequency of 30 Hz in a constant temperature environment of 60 ° C. Then, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left at room temperature for one day.
After being left unattended, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on in a state where no voltage is applied so that the brightness of the transmitted light is minimized. The arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became the darkest to the angle at which the first region became the darkest was calculated as the angle Δ. Similarly, in the second pixel, the second region and the first region were compared, and the same angle Δ was calculated. Then, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. The lower the value of the angle Δ of the liquid crystal cell, the better, and the higher the value, the worse.

＜実施例１〜３＞
合成例４〜６で得られた液晶配向剤を（Ｑ−１〜Ｑ−３）を用いて、ラビング耐性評価、残像消去時間の評価、液晶配向の安定性評価を行った。結果を表１に示す。 <Examples 1 to 3>
Using the liquid crystal alignment agents obtained in Synthesis Examples 4 to 6 (Q-1 to Q-3), rubbing resistance evaluation, afterimage erasing time evaluation, and liquid crystal orientation stability evaluation were performed. The results are shown in Table 1.

＜比較例１〜３＞
比較合成例４〜６で得られた液晶配向剤（Ｑ−４〜Ｑ−６）を用いて、ラビング耐性、残像消去時間、及び液晶配向の安定性の各評価を行った。結果を表１に示す。 <Comparative Examples 1 to 3>
Using the liquid crystal alignment agents (Q-4 to Q-6) obtained in Comparative Synthesis Examples 4 to 6, each evaluation of rubbing resistance, afterimage elimination time, and stability of liquid crystal orientation was performed. The results are shown in Table 1.

Figure 2021038260
Figure 2021038260

以上の結果より、本発明の液晶配向剤によって、ラビング耐性に優れ、蓄積電荷の緩和が早く、かつ液晶配向の安定性が高いなどの特性を同時に実現することが可能な液晶配向膜が得られることが判る。 From the above results, the liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment film capable of simultaneously realizing characteristics such as excellent rubbing resistance, quick relaxation of accumulated charges, and high stability of liquid crystal alignment. It turns out.

本発明の液晶配向剤は、スマートフォン、携帯電話、パソコン、テレビ等の表示部に使用される液晶表示素子、特に、横電界方式の液晶表示素子における液晶配向膜の形成に広く使用される。
なお、２０１５年１０月１４日に出願された日本特許出願２０１５−２０３２７８号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The liquid crystal aligning agent of the present invention is widely used for forming a liquid crystal alignment film in a liquid crystal display element used in a display unit of a smartphone, a mobile phone, a personal computer, a television, or the like, particularly in a transverse electric field type liquid crystal display element.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2015-203278 filed on October 14, 2015 are cited here as disclosure of the specification of the present invention. , Incorporate.

Claims (1)

下記式（４）で表されるジアミン。
Figure 2021038260
 （Ｒ１は水素、又は一価の有機基である。Ａｒは、置換基を有してもよいフェニル若しくはナフタレンである。Ｒ３は単結合、又は置換基を有してもよいフェニル基を表す。） A diamine represented by the following formula (4).
Figure 2021038260
 (R 1 is a hydrogen or a monovalent organic group. Ar is a phenyl or naphthalene which may have a substituent. R 3 is a phenyl group which may have a single bond or a substituent. Represent.)
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