JP2006016352A - Columnar liquid crystal compound exhibiting ferroelectricity - Google Patents

Columnar liquid crystal compound exhibiting ferroelectricity Download PDF

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JP2006016352A
JP2006016352A JP2004197064A JP2004197064A JP2006016352A JP 2006016352 A JP2006016352 A JP 2006016352A JP 2004197064 A JP2004197064 A JP 2004197064A JP 2004197064 A JP2004197064 A JP 2004197064A JP 2006016352 A JP2006016352 A JP 2006016352A
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JP4599552B2 (en
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Yoshiki Kishikawa
圭希 岸川
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Chiba University NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound more easily synthesizable at a lower cost, having higher orientation of molecules and capable of recording information with a higher density than the conventional optically active ferroelectric compounds. <P>SOLUTION: The liquid crystal compound exhibiting ferroelectricity has a polarizing part near the molecular center and exhibits columnar liquid crystal phase. The columnar structure has no optically active group but nevertheless has ferroelectricity and high orientation, and, as electrical repulsion between columnar structures is small, so polarization of each structure can be controlled. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、強誘電性の液晶相を示す液晶化合物に関し、特に柱状構造体からなる強誘電性液晶相を示す液晶化合物に関する。   The present invention relates to a liquid crystal compound exhibiting a ferroelectric liquid crystal phase, and more particularly to a liquid crystal compound exhibiting a ferroelectric liquid crystal phase comprising a columnar structure.

強誘電性を示す液晶化合物は、外部から印加される電界に沿って分極の向きを揃えることができ、この電界を取り去っても分極の向きを維持することができる。しかもこの強誘電性を示す液晶化合物の電界に対する応答は非常に高速である。よって、強誘電性を示す液晶化合物は主に高速応答かつメモリ性のある表示素子・記録素子への応用を中心に研究されている。なお他の応用例としては、電界をかけた状態で高分子化して各分子の配置を固定した材料が知られており、表裏の電圧が圧力により変化する圧電性材料や温度により変化する焦電性材料などがある。   A liquid crystal compound exhibiting ferroelectricity can align the direction of polarization along an externally applied electric field, and can maintain the direction of polarization even when the electric field is removed. Moreover, the response of the liquid crystal compound exhibiting ferroelectricity to the electric field is very fast. Therefore, liquid crystal compounds exhibiting ferroelectricity are mainly studied mainly for application to display elements and recording elements having high-speed response and memory characteristics. As other application examples, there are known materials in which the arrangement of each molecule is fixed by applying a polymer in a state where an electric field is applied. A piezoelectric material in which the voltage on the front and back changes with pressure, and a pyroelectric that changes with temperature. There are sex materials.

まず強誘電性液晶化合物の一例として、光学活性なスメクチックＣ相を示す液晶化合物が知られている。この相は複数の層が積層されたような層状構造を有しており、その各層では光学活性な棒状分子が層の垂線方向に対しある一定の角度で傾いて存在している。光学活性なスメクチックＣ相では分子が光学活性であるため、棒状分子の傾き方向と垂直な方向に分極が生じており、これが強誘電性を発現させるもととなる。そしてこの液晶化合物を数ミクロンの間隔で配置される面状の電極間に充填することで強誘電性を発現させることができる（図３参照）。この電極の間に電界を印加することで液晶分子の傾きを逆方向に向かせることができ、かつ、その電界を取り去っても、その状態を保つことができるのである。   First, as an example of a ferroelectric liquid crystal compound, a liquid crystal compound exhibiting an optically active smectic C phase is known. This phase has a layered structure in which a plurality of layers are stacked, and in each of the layers, optically active rod-shaped molecules are inclined at a certain angle with respect to the perpendicular direction of the layer. In the optically active smectic C phase, since the molecule is optically active, polarization occurs in a direction perpendicular to the tilt direction of the rod-like molecule, which causes ferroelectricity to be expressed. By filling this liquid crystal compound between planar electrodes arranged at intervals of several microns, ferroelectricity can be expressed (see FIG. 3). By applying an electric field between the electrodes, the tilt of the liquid crystal molecules can be reversed, and the state can be maintained even if the electric field is removed.

しかしながら、この“電界を取り去っても、分極が残る性質”（強誘電性）は、分極を維持する分子の数が減少すると生じなくなってしまう。たとえば、一層の半分の分子を逆方向に傾けて維持したり（図４参照）、縦方向に全ての層において数分子の幅でのみ、傾きを逆向きにして維持する（図５参照）ことはできない。これは他の層の分子やその層の他の分子における立体的または電子的影響を受けるためであり、仮に、局部的な電圧で、このような一部の分子のみを逆方向に傾けられたとしても、電圧を取り去れば他の分子の影響を大きく受け、他の分子と同一の方向に傾きは戻ってしまう。特に現状では小さくても数μｍ四方程度の領域で強誘電性を制御できる程度である。 However, the “property that polarization remains even when the electric field is removed” (ferroelectricity) does not occur when the number of molecules that maintain polarization decreases. For example, maintain one half of the molecules tilted in the opposite direction (see FIG. 4), or maintain the tilt in the opposite direction only in the width of several molecules in all layers in the vertical direction (see FIG. 5). I can't. This is due to the steric or electronic effects of other layers of molecules and other molecules of that layer, and only some of these molecules were tilted in the opposite direction by a local voltage. However, if the voltage is removed, it will be greatly affected by other molecules, and the tilt will return in the same direction as other molecules. In particular, at present, the ferroelectricity can be controlled in a region of a few μm square at least.

また、反強誘電性を示す液晶化合物も知られており、光学活性なスメクチックＣＡ相を示す液晶化合物が知られている。この相では、棒状分子が長軸方向に層状構造を形成し、一層ごとに分子は所定の角度で逆方向に傾いている（図６参照）。この相では、強誘電性液晶に見られる二つの安定状態に加えて、交互に分子が傾いた安定状態が存在する。このスメクチックＣＡ相のうち隣接層間の電子反発の少ないものは、各層毎に層内の分子の傾きを制御する可能性を有している。しかし、各層の部分的な分子の傾きの制御についてまでは立体的な影響により困難である。 Liquid crystal compounds exhibiting antiferroelectric properties are also known, and liquid crystal compounds exhibiting an optically active smectic CA phase are known. In this phase, rod-shaped molecules form a layered structure in the major axis direction, and the molecules are inclined in the opposite direction at a predetermined angle for each layer (see FIG. 6). In this phase, in addition to the two stable states found in ferroelectric liquid crystals, there are stable states in which the molecules are alternately tilted. Among the smectic CA phases, those having little electron repulsion between adjacent layers have a possibility of controlling the inclination of molecules in each layer. However, it is difficult to control the partial molecular inclination of each layer due to steric effects.

一方、楕円形の分子が柱状に積み重なった構造体（「分子が柱状に積み重なった構造体」を以下単に「柱状構造体」という。）を有する液晶化合物を利用した強誘電性を示す液晶化合物の開発も行われている（以下、柱状構造体から構成される液晶相を相系列に有する液晶化合物を単に「柱状液晶化合物」という。）。楕円形の分子が柱状構造体を形成し、しかも傾きを有している場合、この分子に光学活性を導入することでスメクチックＣ相と同様な原理で、強誘電性を柱状構造体の軸と垂直な方向に生じさせることができるのである。ただし、この場合においても柱状構造体の一つ一つを独立に制御することはできない。 On the other hand, a liquid crystal compound exhibiting ferroelectricity using a liquid crystal compound having a structure in which elliptical molecules are stacked in a column shape (hereinafter, “structure in which molecules are stacked in a column shape” is simply referred to as “columnar structure”). A liquid crystal compound having a liquid crystal phase composed of a columnar structure in a phase series is simply referred to as a “columnar liquid crystal compound”. When an elliptical molecule forms a columnar structure and has an inclination, by introducing optical activity into this molecule, the ferroelectricity is determined as the axis of the columnar structure by the same principle as the smectic C phase. It can be generated in a vertical direction. However, even in this case, each of the columnar structures cannot be controlled independently.

これに対し、柱状構造体の長軸と平行な方向に分極を有する柱状液晶化合物を合成する試みも行われている。ボウル状、円錐状の化合物は互いに同じ方向で重なる性質があるため、一つの柱状構造体において長軸と平行な方向に分極した構造を形成することができる。しかし、この場合であっても、結局、自発的に隣合う柱状構造体の分極が逆を向いて並び、分極を打ち消してしまう。そのため電圧を印加して柱状構造体を同一方向に並べても、自発的に分極を打ち消す方向に配列してしまい、強誘電性は示さない（図７参照）。なおこの柱状液晶化合物については下記非特許文献１に記載がある。
バシェーら、「新しい芳香族化合物の集合体からなる一次元ナノ構造体の合成、自己集合、および、スイッチング」、ジャーナル オブ ジ アメリカン ケミストリー、１２５巻、２００３年、ｐ８２６４−ｐ８２６９（Ｍａｒｋ Ｌ．Ｂｕｓｈｅｙ ｅｔ ａｌ．， 「Ｓｙｎｔｈｅｓｉｓ， Ｓｅｌｆ−Ａｓｓｅｍｂｌｙ， ａｎｄ Ｓｗｉｔｃｈｉｎｇ ｏｆ Ｏｎｅ−Ｄｉｍｅｎｓｉｏｎａｌ Ｎａｎｏｓｔｒｕｃｔｕｒｅｓ ｆｒｏｍ Ｎｅｗ Ｃｒｏｗｄｅｄ Ａｒｏｍａｔｉｃｓ」Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｓｔｒｙ，２００３，１２４，ｐ８２６４−ｐ８２６９） On the other hand, an attempt has been made to synthesize a columnar liquid crystal compound having polarization in a direction parallel to the long axis of the columnar structure. Since the bowl-shaped and conical compounds overlap each other in the same direction, it is possible to form a structure polarized in a direction parallel to the long axis in one columnar structure. However, even in this case, the polarizations of the columnar structures adjacent to each other spontaneously line up in the opposite direction and cancel the polarization. Therefore, even if the columnar structures are arranged in the same direction by applying a voltage, they are spontaneously arranged in the direction to cancel the polarization, and do not show ferroelectricity (see FIG. 7). This columnar liquid crystal compound is described in Non-Patent Document 1 below.
Bashe et al., “Synthesis, Self-Assembly, and Switching of One-Dimensional Nanostructures Composed of New Aromatic Compounds”, Journal of the American Chemistry, 125, 2003, p8264-p8269 (Mark L. Bushey et al. al., “Synthesis, Self-Assembly, and Switching of One-Dimensional Nanostructures from New Crowded Aromatics, Journal of the American Chem.

一方、柱状液晶化合物において、柱状構造体の長軸に分極の軸が平行で、かつ、各柱状構造体が独立にその分極の方向を外部電場で制御できかつ保持できるならば、柱状構造体毎に物理的な性質を変化させることができる。即ちこれを利用した情報記録素子や表示素子としての応用が可能となり、しかも数μｍ四方ではなく、分子の大きさレベルで強誘電性を制御できるためこの記録密度や表示密度は飛躍的に向上させることが期待できる。また、分子の分極方向を高効率で一方向に配列することができるので、圧電素子や焦電素子として用いた場合も性能の向上が期待できる。 On the other hand, in a columnar liquid crystal compound, if the axis of polarization is parallel to the major axis of the columnar structure and each columnar structure can independently control and hold the polarization direction with an external electric field, each columnar structure The physical properties can be changed. That is, it can be applied as an information recording element or a display element using this, and the ferroelectricity can be controlled at a molecular size level instead of a few μm square, so that the recording density and display density are dramatically improved. I can expect that. In addition, since the molecular polarization direction can be arranged in one direction with high efficiency, an improvement in performance can be expected even when used as a piezoelectric element or pyroelectric element.

本発明は以上の見地に基づいて行われるものであり、柱状構造体を有する強誘電性液晶相を示す液晶化合物を提供し、更にはそれを用いて高記録密度な情報記録素子、高画素密度な表示素子等の各種高性能な製品を提供することにある。   The present invention is carried out based on the above viewpoint, and provides a liquid crystal compound exhibiting a ferroelectric liquid crystal phase having a columnar structure, and further uses it to provide a high recording density information recording element and a high pixel density. It is to provide various high-performance products such as simple display elements.

上記目的を達成するため本発明者が鋭意検討を重ねた結果、柱状構造を有する液晶相の分子の中心部近傍に分極部位を有し、柱状構造体内部で分子が柱状構造体の軸に沿って同じ方向を向くことが有用であることに思い至った。即ち、分子の中心部近傍に分極部位を持たせれば、形成された柱状構造体の中心部付近に分極が集中し、隣接する柱状構造体の分極から離れた位置が確保でき、柱状構造体同士の電子反発がもっとも弱くなるのである。なおこの場合において外部から電場を印加する方向も柱状構造の長軸方向とほぼ同じ方向に印加させることが望ましい。そして更に、分極部に近いところ（または同一のところ）に分子間水素結合の作用する部位を配置すれば、柱状構造体における分子間の関係をより接近させ、より強く固定することができて極めて望ましい（図８参照）。さらに、柱状構造内のほぼすべての分子が柱状構造体の軸に沿って同一方向を向けば、柱状構造全体で大きな分極が発生して強誘電性を発現させ、印加電圧によって分極方向を制御できる。前述のように、液晶化合物の分子の分極部位が分子の中央近傍に配置されているため、分極部位同士が離れて存在しているので、印加電圧を除去した後も、隣接する柱状構造体の分極の影響を受けることなく、分極方向は維持される。   As a result of intensive studies by the inventor in order to achieve the above object, the liquid crystal phase having a columnar structure has a polarization site near the center of the molecule, and the molecules are aligned along the axis of the columnar structure inside the columnar structure. I found it useful to face in the same direction. That is, if a polarization site is provided in the vicinity of the center of the molecule, the polarization is concentrated near the center of the formed columnar structure, and a position away from the polarization of the adjacent columnar structure can be secured. The electronic repulsion is the weakest. In this case, it is desirable to apply the electric field from the outside in substantially the same direction as the major axis direction of the columnar structure. Furthermore, if the site where the intermolecular hydrogen bond acts is located near (or at the same place) the polarization part, the intermolecular relationship in the columnar structure can be brought closer and more strongly fixed. Desirable (see FIG. 8). Furthermore, if almost all the molecules in the columnar structure are directed in the same direction along the axis of the columnar structure, large polarization occurs in the entire columnar structure to develop ferroelectricity, and the polarization direction can be controlled by the applied voltage. . As described above, since the polarization sites of the molecules of the liquid crystal compound are arranged in the vicinity of the center of the molecules, the polarization sites are separated from each other. Therefore, even after the applied voltage is removed, the adjacent columnar structures The polarization direction is maintained without being affected by the polarization.

即ち、本発明は具体的な手段として、以下の手段を採用する。
まず、第一の手段として、分子の中央近傍に分極部位を有する強誘電性を示す柱状液晶化合物とする。ここで、柱状液晶化合物とは、柱状構造体からなる液晶相を相系列に有する液晶化合物をいう。また分極部位とは、原子の電気陰性度の差異によりモーメントを発生させる官能基などの部位をいい、例えばウレア基が該当し、それ以外にも、−ＣＯＮＨ−（アミド）、−Ｏ−ＣＯ−ＮＨ−（ウレタン）、−ＮＨ−（アミン）、−ＣＨ（ＯＨ）−（アルコール）、などが該当する。
またこの場合、分子の中央近傍に水素結合部位を有することも極めて望ましい。これにより、柱状構造体における分子の間に水素結合を形成することができ、柱状構造体を固定し、より強誘電性を安定化させることができるのである。この具体的な例としては、ウレア基、−ＣＯＮＨ−（アミド）、−Ｏ−ＣＯ−ＮＨ−（ウレタン）、−ＮＨ−（アミン）、−ＣＨ（ＯＨ）−（アルコール）、などが該当する。特にこれらの場合は、分極部位と水素結合部位とを双方有しているため、より効率よく強誘電性を発現させることができる。なお、水素結合が強度及び合成の容易さの観点からより望ましいが、金属−金属の相互作用、金属−ヘテロ結合の配位結合、イオン結合もありえる。
また、分極部位及び水素結合以外の部位においては、柱状液晶相を発現させるためにできるかぎり電気的に中性である程度の長さを有する部位が望ましく、例えば、アルキル、アルキル基又はアルコキシ基で置換された芳香族化合物、アルキル基又はアルコキシ基で置換された脂環式化合物、アルキル基で置換されたフェニル基、アルキル基で置換されたナフチル基、アルキル基で置換されたアントラニル基、アルキル基で置換されたシクロアルキル基、アルコキシ基で置換されたフェニル基、アルコキシ基で置換されたナフチル基、アルコキシ基で置換されたアントラニル基、アルコキシ基で置換されたシクロアルキル基、フッ素で一部又は全部を置換されたアルキル基で置換されたフェニル基、フッ素で一部又は全部を置換されたアルキル基で置換されたナフチル基、フッ素で一部又は全部を置換されたアルキル基で置換されたアントラニル基、フッ素で一部又は全部を置換されたアルキル基で置換されたシクロアルキル基、フッ素で一部又は全部を置換されたアルコキシ基で置換されたフェニル基、フッ素で一部又は全部を置換されたアルコキシ基で置換されたナフチル基、フッ素で一部又は全部を置換されたアルコキシ基で置換されたアントラニル基、フッ素で一部又は全部を置換されたアルコキシ基で置換されたシクロアルキル基のいずれかであることが望ましい。なおこれは下記で示す第二若しくは第三の手段において同様である。
またこの場合において、分子の中央近傍以外の部分にアクリル酸誘導体、メタクリル酸誘導体、けい皮酸誘導体、アリル基、又はビニル基の導入により重合されたものとすることも望ましい。液晶状態は液体であるため、この場合光、開始剤、触媒、酸、塩基などを使って、その組織のまま重合体へと導け、固体化するので材料として利用しやすくなる。 That is, the present invention employs the following means as specific means.
First, as a first means, a columnar liquid crystal compound having ferroelectricity having a polarization site in the vicinity of the center of the molecule is used. Here, the columnar liquid crystal compound refers to a liquid crystal compound having a liquid crystal phase composed of a columnar structure in a phase series. Further, the polarization site refers to a site such as a functional group that generates a moment due to a difference in electronegativity of atoms. For example, it corresponds to a urea group, and other than that, -CONH- (amide), -O-CO- NH- (urethane), -NH- (amine), -CH (OH)-(alcohol), and the like are applicable.
In this case, it is also highly desirable to have a hydrogen bonding site near the center of the molecule. Thereby, hydrogen bonds can be formed between molecules in the columnar structure, and the columnar structure can be fixed and the ferroelectricity can be further stabilized. Specific examples of this include urea groups, -CONH- (amide), -O-CO-NH- (urethane), -NH- (amine), -CH (OH)-(alcohol), and the like. . Particularly in these cases, since both the polarization site and the hydrogen bonding site are included, ferroelectricity can be expressed more efficiently. In addition, although a hydrogen bond is more desirable from a viewpoint of intensity | strength and the ease of a synthesis | combination, a metal-metal interaction, a coordination bond of a metal-hetero bond, and an ionic bond can also exist.
In addition to the polarization site and the hydrogen bond, a site that is as neutral as possible and has a certain length is desirable in order to develop a columnar liquid crystal phase. For example, substitution with an alkyl, alkyl group, or alkoxy group is preferable. Aromatic compounds substituted with alkyl groups or alkoxy groups, phenyl groups substituted with alkyl groups, naphthyl groups substituted with alkyl groups, anthranyl groups substituted with alkyl groups, alkyl groups A substituted cycloalkyl group, a phenyl group substituted with an alkoxy group, a naphthyl group substituted with an alkoxy group, an anthranyl group substituted with an alkoxy group, a cycloalkyl group substituted with an alkoxy group, part or all of fluorine A phenyl group substituted with a substituted alkyl group, an alkyl partially or fully substituted with fluorine A naphthyl group substituted with a group, an anthranyl group substituted with an alkyl group partially or fully substituted with fluorine, a cycloalkyl group substituted with an alkyl group partially or fully substituted with fluorine, and a fluorine A phenyl group substituted by a partially or fully substituted alkoxy group, a naphthyl group substituted by an alkoxy group partially or fully substituted by fluorine, or an alkoxy group partially or fully substituted by fluorine. And an anthranyl group and a cycloalkyl group substituted with an alkoxy group partially or wholly substituted with fluorine. This is the same in the second or third means described below.
In this case, it is also desirable that the polymer is polymerized by introducing an acrylic acid derivative, a methacrylic acid derivative, a cinnamic acid derivative, an allyl group or a vinyl group in a portion other than the vicinity of the center of the molecule. Since the liquid crystal state is a liquid, in this case, light, an initiator, a catalyst, an acid, a base, and the like are used, and the structure is guided to a polymer and solidified, so that it can be easily used as a material.

また、第二の手段として、Ｒ１−ＮＨ−ＣＯ−ＮＨ−Ｒ２の分子構造を有する強誘電性を示す柱状液晶化合物とする（図１参照）。ここで、Ｒ１とＲ２は、水素、アルキル、又はアルキル基若しくはアルコキシ基で置換された芳香族若しくは脂環式化合物の置換基が望ましい。 As a second means, a columnar liquid crystal compound having ferroelectricity having a molecular structure of R 1 —NH—CO—NH—R 2 is used (see FIG. 1). Here, R 1 and R 2 are preferably hydrogen, alkyl, or a substituent of an aromatic or alicyclic compound substituted with an alkyl group or an alkoxy group.

また、第三の手段として、Ａｒ１−ＮＨ−ＣＯ−ＮＨ−Ａｒ２の分子構造を有する強誘電性を示す柱状液晶化合物とする（図２参照）。ここで、Ａｒ１とＡｒ２は、アルキル基、アルコキシ基、フッ素で一部または全てを置換されたアルキル基若しくはアルコキシ基、で置換されたフェニル基、ナフチル基、アントラニル基、又はシクロアルキル基が望ましい。 As a third means, a columnar liquid crystal compound having ferroelectricity having a molecular structure of Ar 1 —NH—CO—NH—Ar 2 is used (see FIG. 2). Here, Ar 1 and Ar 2 are an alkyl group, an alkoxy group, a phenyl group, a naphthyl group, an anthranyl group, or a cycloalkyl group substituted with an alkyl group or an alkoxy group partially or completely substituted with fluorine. desirable.

また、第二の手段におけるＲ１、Ｒ２に、又は第三の手段におけるＡｒ１、Ａｒ２に、アクリル酸誘導体、メタクリル酸誘導体、けい皮酸誘導体、アリル基、ビニル基等の重合性の置換基を導入すれば、液晶状態は液体であるため、光、開始剤、触媒、酸、塩基などを使って、その組織のまま重合体へと導け、固体化するので材料として利用しやすくなる。 In addition, R 1 and R 2 in the second means, or Ar 1 and Ar 2 in the third means are polymerizable with an acrylic acid derivative, a methacrylic acid derivative, a cinnamic acid derivative, an allyl group, a vinyl group, or the like. If a substituent is introduced, the liquid crystal state is liquid, so light, initiator, catalyst, acid, base, etc. can be used to guide the polymer to the polymer as it is and solidify it, making it easy to use as a material. .

また、上記第一乃至第三の手段のうちいずれかを用いた記録素子、又は表示素子とする。第一乃至第三の手段の液晶化合物は分子の中央近傍に分極を有するため、隣り合う柱状構造体間の電気的作用が小さく、一つの柱状構造体ごとに独立にその分極の方向を制御又は維持できる。現在、操作型トンネル顕微鏡（ＳＴＭ）などにより、分子ごとに電圧をかけることが可能でなり、この技術と組み合わせることで柱状構造体ごとに分極を制御することが可能となり、特に分極部分にカルボニル酸素が存在しているような場合（例えば図９参照）、表面にカルボニル酸素があるか否かを見分けることもできるので分子レベルの記録素子や表示素子として利用ができる。 A recording element or a display element using any one of the first to third means is used. Since the liquid crystal compounds of the first to third means have polarization near the center of the molecule, the electrical action between adjacent columnar structures is small, and the direction of polarization is controlled independently for each columnar structure or Can be maintained. At present, it is possible to apply a voltage to each molecule by using an operational tunneling microscope (STM), etc., and in combination with this technology, it becomes possible to control the polarization for each columnar structure. Can be discriminated whether or not there is carbonyl oxygen on the surface, so that it can be used as a molecular level recording element or display element.

また、上記第一乃至第三の手段のうちいずれかを用いた焦電素子、又は圧電素子とする。第一乃至第三の液晶化合物は効率よく大きな分極を生じるため、圧電素子や焦電素子の材料として利用すれば、より少量で同等な効果を得ることができる。しかもこれによって、より小さく、より軽く、より薄い素子の開発が可能となる。 Also, a pyroelectric element or a piezoelectric element using any one of the first to third means is used. Since the first to third liquid crystal compounds efficiently generate large polarization, the same effect can be obtained with a smaller amount when used as a material for a piezoelectric element or a pyroelectric element. In addition, this makes it possible to develop smaller, lighter and thinner elements.

なお、第一乃至第三の手段のいずれかを用いてコンデンサーとすることも可能である。第一乃至第三の液晶化合物はいずれも、効率的に柱状構造体全体で非常に大きな分極を生じるため、一対の電極間にこの強誘電性物質をコンデンサーの電極間物質として配置すれば、非常に薄い膜で十分な電荷を保持することができる。 Note that any one of the first to third means may be used as a capacitor. Any of the first to third liquid crystal compounds efficiently generates a very large polarization in the entire columnar structure. Therefore, if this ferroelectric substance is placed between a pair of electrodes as an interelectrode substance of a capacitor, A sufficiently thin film can hold a sufficient charge.

以上本発明により、柱状構造を有する強誘電性液晶相を示す液晶化合物、更にはそれを用いた高記録密度な情報記録素子、高い画素密度の表示素子等の各種高性能な製品を提供することができる。 As described above, the present invention provides various high-performance products such as liquid crystal compounds having a ferroelectric liquid crystal phase having a columnar structure, as well as high recording density information recording elements and high pixel density display elements using the same. Can do.

以下、本発明を実施するための形態について図面を用いて説明するが、本発明については種々の変更が可能であり、実施の形態及び実施例に記載される発明に狭く限定されるものではない。   DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, modes for carrying out the invention will be described with reference to the drawings. However, the invention can be variously modified and is not limited to the invention described in the embodiments and examples. .

以下、本発明の液晶化合物についての実施例を示す。
（合成方法）
まず、ピロガロール４．１５ｇとオクチルブチルブロミド２４．５ｇとをＫ２ＣＯ３２６．２ｇを塩基としてＤＭＦ（５０ｍｌ）中において６０℃で４時間反応させ、１，２，３‐トリオクチロキシベンゼン９．５９ｇを得た。そして硝酸を吸着させたシリカゲル２４．６ｇを用いてこの１，２，３‐トリオクチロキシベンゼンをジクロロメタン３０ｍｌ中で室温でニトロ化し、３，４，５−トリオクチロキシニトロベンゼン６．９４ｇを得た。更にこの３，４，５−トリオクチロキシニトロベンゼン５．０５ｇをグラファイト存在下でヒドラジン一水和物３ｍｌにエタノール１０ｍｌを加え、２４時間加熱還流により還元し、３、４、５−トリオクチロキシアニリン３．５６ｇを得た。そして更にこの３，４，５−トリオクチロキシアニリン２．５０ｇとＮ，Ｎ’−カルボニルジイミダゾールと０．６９ｇとをＤＭＦ５０ｍｌ中、室温で６時間反応させて、Ｎ，Ｎ’‐ビス（３、４、５−トリオクチロキシ）フェニル尿素１．８３ｇを合成した（以下この化合物を単に「Ａ」と表記する。）。 Examples of the liquid crystal compound of the present invention are shown below.
(Synthesis method)
First, 4.15 g of pyrogallol and 24.5 g of octylbutyl bromide were reacted for 4 hours at 60 ° C. in DMF (50 ml) using 26.2 g of K 2 CO 3 as a base, and 1,2,3-trioctyloxybenzene 9 .59 g was obtained. This 1,2,3-trioctyloxybenzene was nitrated in 30 ml of dichloromethane at room temperature using 24.6 g of silica gel adsorbed with nitric acid to obtain 6.94 g of 3,4,5-trioctyloxynitrobenzene. . Further, 5.05 g of this 3,4,5-trioctyloxynitrobenzene was added to 3 ml of hydrazine monohydrate in the presence of graphite and 10 ml of ethanol was reduced by heating under reflux for 24 hours to obtain 3,4,5-trioctyloxyaniline. 3.56 g was obtained. Further, 2.50 g of this 3,4,5-trioctyloxyaniline, N, N′-carbonyldiimidazole and 0.69 g were reacted in 50 ml of DMF at room temperature for 6 hours to obtain N, N′-bis (3 1,83 g of 4,5-trioctyloxy) phenylurea was synthesized (hereinafter this compound is simply referred to as “A”).

なお、上記において、オクチルブロミドの代わりにドデシルブロミド、ヘキサデシルブロミドを用い、同様な反応を行うことによって同様のＮ、Ｎ’
‐ビス（３、４、５−トリドデシロキシフェニル）尿素（以下、この化合物を単に「Ｂ」と表記する。）、Ｎ、Ｎ’ ‐ビス（３、４、５−トリヘキサデシロキシフェニル）尿素（以下、この化合物を単に「Ｃ」と表記する。）、をそれぞれ得た。なお液晶化合物Ａ、Ｂ、Ｃとは炭素の数において差異を有している。 In the above, by using dodecyl bromide and hexadecyl bromide in place of octyl bromide, the same N, N ′
-Bis (3,4,5-tridodecyloxyphenyl) urea (hereinafter, this compound is simply referred to as “B”), N, N′-bis (3,4,5-trihexadecyloxyphenyl) ) Urea (hereinafter, this compound is simply referred to as “C”). The liquid crystal compounds A, B, and C have a difference in the number of carbons.

（相系列及び粉末Ｘ線回折）
次にこの化合物が示す液晶性について確認する実験を行い、相転移温度について測定を行った。図１０に上記各液晶化合物の相系列を示す。なおこの測定は、ＤＳＣ測定（５℃／分）によって行った（なおＤＳＣにおける温度変化は５℃／分である。）。ここで、Ｃｒは結晶相を、Ｃｏｌｒは矩形柱状液晶相を、Ｃｏｌｈは六方柱状相を、Ｉは等方相を示す。 (Phase series and powder X-ray diffraction)
Next, an experiment for confirming the liquid crystal properties of the compound was performed, and the phase transition temperature was measured. FIG. 10 shows a phase sequence of each liquid crystal compound. This measurement was performed by DSC measurement (5 ° C./min) (the temperature change in DSC is 5 ° C./min). Here, Cr represents a crystal phase, Colr represents a rectangular columnar liquid crystal phase, Colh represents a hexagonal columnar phase, and I represents an isotropic phase.

なお上記各化合物に対する相構造の特定は、粉末Ｘ線回折試料Ａ、Ｂ、Ｃに対してそれぞれ粉末Ｘ線回折測定を行った。解析結果を下記表１に示す。この結果から、観測された相は柱状構造のＣｏｌｒ（矩形柱状液晶相）とＣｏｌｈ（六方柱状液晶相）に分類された。なおこのうち、強誘電性を示す相はＣｏｌｈ相であった。   In addition, the identification of the phase structure with respect to each of the above compounds was performed by performing powder X-ray diffraction measurement on each of powder X-ray diffraction samples A, B, and C. The analysis results are shown in Table 1 below. From these results, the observed phases were classified into columnar structures such as Colr (rectangular columnar liquid crystal phase) and Colh (hexagonal columnar liquid crystal phase). Of these, the phase exhibiting ferroelectricity was the Colh phase.

（自発分極の測定）
次に、これら液晶化合物それぞれについて自発分極の大きさについての測定を行った。この測定は、１ｃｍ×１ｃｍのＩＴＯ（Ｉｎｄｉｕｍ‐Ｔｉｎ‐Ｏｘｉｄｅ）が形成されたガラス基板を５μｍの間隔を対向するよう配置し、その間に液晶化合物を注入して液晶セルを作成し、この液晶セルに三角波電圧（振幅±２０Ｖ／μｍ、６Ｈｚ周期）を印加することで行った。この結果、いずれの液晶化合物も六方柱状相のときに液晶分子の反転ピークが観察され、強誘電性液晶であることを確認できた。図１１〜１３に自発分極により生ずる電流のピークを示す。図１１は液晶化合物Ａについて、図１２は液晶化合物Ｂについて、図１３は液晶化合物Ｃについてそれぞれ示すものである。この測定の結果、Ａの液晶化合物の自発分極は１１００ｎＣ／ｃｍ２、Ｂの液晶化合物の自発分極は１５７０ｎＣ／ｃｍ２、Ｃの液晶化合物の自発分極は１２６０ｎＣ／ｃｍ２、であった（この自発分極を測定したときの温度はそれぞれ１７５℃、１６０℃、１４５℃であった）。 (Measurement of spontaneous polarization)
Next, the magnitude of spontaneous polarization was measured for each of these liquid crystal compounds. In this measurement, a glass substrate on which 1 cm × 1 cm ITO (Indium-Tin-Oxide) is formed is arranged so as to oppose a space of 5 μm, and a liquid crystal compound is injected therebetween to form a liquid crystal cell. Was applied by applying a triangular wave voltage (amplitude ± 20 V / μm, 6 Hz period). As a result, when all the liquid crystal compounds were in the hexagonal columnar phase, the inversion peak of the liquid crystal molecules was observed, confirming that it was a ferroelectric liquid crystal. FIGS. 11 to 13 show current peaks caused by spontaneous polarization. 11 shows the liquid crystal compound A, FIG. 12 shows the liquid crystal compound B, and FIG. 13 shows the liquid crystal compound C. The result of this measurement, spontaneous polarization of the liquid crystal compound A is the spontaneous polarization of the liquid crystal compound 1100nC / cm 2, B is the spontaneous polarization of the liquid crystal compound 1570nC / cm 2, C was 1260nC / cm 2, (the spontaneous The temperature when the polarization was measured was 175 ° C., 160 ° C. and 145 ° C., respectively).

（顕微鏡観察）
また、自発分極の測定において使用した液晶セルを用い、偏光顕微鏡による観察を行ったところ、３０Ｖ（即ち６Ｖ／μｍ）の電圧を印加することにより、水平配向の組織（フォーカルコニック組織）が、真っ暗な垂直配向組織（ホメオトロピック組織）へと変化し、電圧を取り去っても垂直配向組織のまま水平配向組織へ戻ることは無かった。 (Microscopic observation)
In addition, when the liquid crystal cell used in the measurement of spontaneous polarization was used and observed with a polarizing microscope, when a voltage of 30 V (that is, 6 V / μm) was applied, the horizontally oriented structure (focal conic structure) was completely dark. It changed to a vertical alignment structure (homeotropic structure), and even when the voltage was removed, the vertical alignment structure did not return to the horizontal alignment structure.

以上本実施例によると、柱状液晶化合物において、光学不活性な化合物であっても強誘電性液晶相を実現することができる。スメクチックＣ相、スメクチックＣＡ相、および、傾いて楕円形分子が重なった柱状液晶相の場合には、光学活性な置換基の導入が必要であり、このことにより、合成はステップ数が多くなり、ラセミ体の分離などが困難になり、合成のコストが高くなるが。本実施例による強誘電性液晶化合物は、不斉炭素を持たないため、合成が簡単であり、合成コストの大幅な削減が可能となる。なお光学活性な置換基を持たないバナナ型液晶化合物も、強誘電性液晶や反強誘電性液晶になるが、配列制御が難しくデバイスへの応用が困難である一方、これら化合物は電圧印加によりその配列を簡単に制御できる。更に、本実施例における強誘電性液晶化合物は、外部からの印加電圧に応答して、その分極方向を揃えるとともに、印加電圧を除去しても、その分極を維持することができる。他の光学不活性な柱状液晶化合物では、隣り合う柱状構造体同士の電気的な作用で、柱状構造体が自発的に再配列し分極の維持ができないが、本発明の液晶化合物では、このような再配列が起こらないので、分極を維持することができる。 As described above, according to the present embodiment, a ferroelectric liquid crystal phase can be realized even if the columnar liquid crystal compound is an optically inactive compound. Smectic C phase, smectic C A phase, and, in the case of the columnar crystal phases overlapping elliptical molecules tilted, it is necessary to introduce an optically active substituent, Thus, synthesis becomes large number of steps However, separation of racemates becomes difficult and the cost of synthesis increases. Since the ferroelectric liquid crystal compound according to this example does not have asymmetric carbon, the synthesis is simple and the synthesis cost can be greatly reduced. Banana-type liquid crystal compounds that do not have optically active substituents also become ferroelectric liquid crystals and antiferroelectric liquid crystals, but their alignment control is difficult and their application to devices is difficult. The array can be easily controlled. Furthermore, the ferroelectric liquid crystal compound in the present embodiment aligns the polarization direction in response to an externally applied voltage, and can maintain the polarization even when the applied voltage is removed. In other optically inactive columnar liquid crystal compounds, the columnar structures are spontaneously rearranged due to the electrical action between adjacent columnar structures, and the polarization cannot be maintained. Since no rearrangement occurs, polarization can be maintained.

（比較例についての検討）
一方で、本実施例と同様に炭素数が４のＮ、Ｎ’ ‐ビス（３、４、５−トリブチロキシフェニル）尿素についても合成を行い、相系列及びＸ線回折について同様の測定を行ったが、この液晶化合物では結晶を示すのみで、強誘電性の液晶相を示すことはなかった。
従って分局部位や水素結合部位以外の直鎖アルキル分の炭素（以下単に「炭素の数」という）の数は４より大きくする必要があり、望ましくは８以上であることがより望ましい。
またこの結果の別の見地によると、形成された柱状構造体の中心部付近に分極を集中させ、かつ、隣接する柱状構造体の分極から離れた位置を確保するために、分極部位は少なくとも炭素数が８の全分子長に対する分極部位の長さ以下の範囲に入っていることが望ましいといえる。一方で、実際の分子長については測定が極めて難しいため、分子の設計は計算方法により分子長を求めて判定の目安とすることができる。具体的には、例えば分子動力学計算ＭＭ２によると直鎖アルキル分の炭素数が８である場合の液晶化合物Ａの全体の長さはおよそ３６Åであり、その分極部分長さはおよそ２．５Åと見積もることができる。このことから全分子長に対する分極部分の長さの比が０．０６９以下であることが望ましいといえ、「分子の中心近傍」の範囲にあるといってよい。尚、Ａ、Ｂ、Ｃそれぞれの表１における柱状構造体の直径の実測値をこれに取り入れた場合は、２．５Åをそれぞれの実測値で割るり０．１１、０．１０、０．０９の値が求まり、０．１１以下であることが望ましくなる。 (Examination of comparative example)
On the other hand, N, N′-bis (3,4,5-tributyloxyphenyl) urea having 4 carbon atoms was synthesized in the same manner as in this example, and the same measurement was performed for the phase sequence and X-ray diffraction. However, this liquid crystal compound showed only crystals and did not show a ferroelectric liquid crystal phase.
Therefore, the number of carbons (hereinafter simply referred to as “the number of carbons”) of the linear alkyl component other than the branching sites and hydrogen bonding sites needs to be larger than 4, and more desirably 8 or more.
According to another aspect of this result, in order to concentrate the polarization near the center of the formed columnar structure and to secure a position away from the polarization of the adjacent columnar structure, the polarization site must be at least carbon. It can be said that it is desirable that the number falls within the range of the length of the polarization site with respect to the total molecular length of 8. On the other hand, since the actual molecular length is extremely difficult to measure, the molecular design can be used as a standard for determination by obtaining the molecular length by a calculation method. Specifically, for example, according to the molecular dynamics calculation MM2, the total length of the liquid crystal compound A when the carbon number of the linear alkyl component is 8 is about 36 mm, and the length of the polarization portion is about 2.5 mm. Can be estimated. From this, it can be said that the ratio of the length of the polarized portion to the total molecular length is preferably 0.069 or less, and can be said to be in the range of “near the center of the molecule”. In addition, when the measured value of the diameter of the columnar structure in Table 1 of each of A, B, and C is taken into this, 2.5 mm is divided by each measured value, and 0.11, 0.10, 0.09 It is desirable that the value of be equal to or less than 0.11.

（圧電、焦電素子）
強誘電性を示す化合物Ａの置換基として、Ｒ＝（ＣＨ２）１１−ＯＣＯＣＨ＝ＣＨ２や（ＣＨ２）１１−ＯＣＨ２ＣＨ＝ＣＨ２のような重合性の置換基を用い、薄膜としてＣｏｌｈ相の状態で、一方向に電圧をかけながら重合反応を行うことで強誘電性における分子配向が保持されたままポリマー化できる。この材料は圧力などでの変形や温度変化による変形がおこると分子配置に変化がおこり、薄膜の裏表の電圧差に変化をおこすことができる。この電圧差を検知することにより、圧力や温度のセンサーとして利用できる。
もちろん、実施例１における液晶化合物Ｂ、Ｃについても同様に適用できる。 (Piezoelectric, pyroelectric element)
A polymerizable substituent such as R = (CH 2 ) 11 —OCOCH═CH 2 or (CH 2 ) 11 —OCH 2 CH═CH 2 is used as a substituent of the compound A exhibiting ferroelectricity, and the Colh is used as a thin film. Polymerization can be performed while maintaining the molecular orientation in the ferroelectricity by carrying out the polymerization reaction while applying a voltage in one direction in the phase state. When this material is deformed by pressure or by temperature change, the molecular arrangement is changed, and the voltage difference between the front and back of the thin film can be changed. By detecting this voltage difference, it can be used as a pressure or temperature sensor.
Of course, the same applies to the liquid crystal compounds B and C in Example 1.

本発明の液晶化合物の一例を示す図。The figure which shows an example of the liquid crystal compound of this invention. 本発明の液晶化合物の一例を示す図。The figure which shows an example of the liquid crystal compound of this invention. 強誘電性を示す液晶化合物の外部電界への応答の概略図。Schematic of the response to the external electric field of the liquid crystal compound which shows ferroelectricity. 強誘電性を示す液晶化合物についての説明図。Explanatory drawing about the liquid crystal compound which shows ferroelectricity. 反強誘電性を示す液晶化合物についての説明図。Explanatory drawing about the liquid crystal compound which shows antiferroelectricity. 強誘電性を示す液晶化合物についての説明図。Explanatory drawing about the liquid crystal compound which shows ferroelectricity. ボウル型、円錐型の柱状構造体を有する液晶化合物の概略図。Schematic of the liquid crystal compound which has a columnar structure of a bowl type and a cone type. 本発明の液晶化合物における柱状構造体の概略図。Schematic of the columnar structure in the liquid crystal compound of the present invention. 本発明の液晶化合物に対し操作型トンネル顕微鏡を用いて分子ごとに電圧をかける場合を示す概略図。Schematic which shows the case where a voltage is applied for every molecule | numerator using the operation type tunnel microscope with respect to the liquid crystal compound of this invention. 実施例１において合成した液晶化合物の相系列を示す図。FIG. 3 shows a phase sequence of a liquid crystal compound synthesized in Example 1. 液晶化合物Ａを用いたセルに三角波電圧を印加した場合の実験結果を示す図。The figure which shows the experimental result at the time of applying a triangular wave voltage to the cell using the liquid crystal compound A. 液晶化合物Ｂを用いたセルに三角波電圧を印加した場合の実験結果を示す図。The figure which shows the experimental result at the time of applying a triangular wave voltage to the cell using the liquid crystal compound B. FIG. 液晶化合物Ｃを用いたセルに三角波電圧を印加した場合の実験結果を示す図。The figure which shows the experimental result at the time of applying a triangular wave voltage to the cell using the liquid crystal compound C.

Claims (11)

分子の中央近傍に分極部位を有する強誘電性を示す柱状液晶化合物。   A columnar liquid crystal compound exhibiting ferroelectricity having a polarization site near the center of the molecule. 分子の中央近傍に水素結合部位を有することを特徴とする請求項１記載の柱状液晶化合物。   2. The columnar liquid crystal compound according to claim 1, which has a hydrogen bonding site near the center of the molecule. Ｒ１−ＮＨ−ＣＯ−ＮＨ−Ｒ２の分子構造を有する強誘電性を示す柱状液晶化合物（Ｒ１とＲ２は、水素、アルキル、アルキル基若しくはアルコキシ基で置換された芳香族、又は、アルキル基若しくはアルコキシ基で置換された脂環式化合物の置換基のいずれか）。 Columnar liquid crystal compound having ferroelectricity having a molecular structure of R 1 —NH—CO—NH—R 2 (R 1 and R 2 are aromatic substituted with hydrogen, alkyl, alkyl group or alkoxy group, or Either a substituent of an alicyclic compound substituted with an alkyl group or an alkoxy group). Ａｒ１−ＮＨ−ＣＯ−ＮＨ−Ａｒ２の分子構造を有する強誘電性を示す柱状液晶化合物（Ａｒ１とＡｒ２は、アルキル基、アルコキシ基、フッ素で置換されたアルキル基、又は、フッ素で置換されたアルコキシ基、のいずれかで置換されたフェニル基、ナフチル基、アントラニル基、又はシクロアルキル基のいずれか）。 A columnar liquid crystal compound having a molecular structure of Ar 1 —NH—CO—NH—Ar 2 and having ferroelectricity (Ar 1 and Ar 2 are an alkyl group, an alkoxy group, an alkyl group substituted with fluorine, or fluorine. Any one of a substituted alkoxy group, a phenyl group, a naphthyl group, an anthranyl group, or a cycloalkyl group. 前記Ｒ１、Ｒ２の炭素の数は８以上であることを特徴とする請求項３記載の柱状液晶化合物。 The columnar liquid crystal compound according to claim 3, wherein the number of carbon atoms of R 1 and R 2 is 8 or more. 前記Ｒ１、Ｒ２にアクリル酸誘導体、メタクリル酸誘導体、けい皮酸誘導体、アリル基、又はビニル基を導入することにより重合されたことを特徴とする請求項３記載の柱状液晶化合物。 The columnar liquid crystal compound according to claim 3, wherein the columnar liquid crystal compound is polymerized by introducing an acrylic acid derivative, a methacrylic acid derivative, a cinnamic acid derivative, an allyl group, or a vinyl group into the R 1 and R 2 . 前記Ａｒ１、Ａｒ２にアクリル酸誘導体、メタクリル酸誘導体、けい皮酸誘導体、アリル基、ビニル基を導入することにより重合されたことを特徴とする請求項４記載の柱状液晶化合物。 The columnar liquid crystal compound according to claim 4, wherein the columnar liquid crystal compound is polymerized by introducing an acrylic acid derivative, a methacrylic acid derivative, a cinnamic acid derivative, an allyl group, or a vinyl group into the Ar 1 and Ar 2 . 請求項１〜７のいずれかに記載の柱状液晶化合物を利用した記録素子。 A recording element using the columnar liquid crystal compound according to claim 1. 請求項１〜７のいずれかに記載の柱状液晶化合物を利用した表示素子。 The display element using the columnar liquid crystal compound in any one of Claims 1-7. 請求項１〜７のいずれかに記載の柱状液晶化合物を利用した焦電素子。 A pyroelectric element using the columnar liquid crystal compound according to claim 1. 請求項１〜７のいずれかに記載の柱状液晶化合物を利用した圧電素子。



A piezoelectric element using the columnar liquid crystal compound according to claim 1.



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