JPH1150054A - Ferridielectric liquid crystal composition - Google Patents

Ferridielectric liquid crystal composition

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Publication number
JPH1150054A
JPH1150054A JP21188597A JP21188597A JPH1150054A JP H1150054 A JPH1150054 A JP H1150054A JP 21188597 A JP21188597 A JP 21188597A JP 21188597 A JP21188597 A JP 21188597A JP H1150054 A JPH1150054 A JP H1150054A
Authority
JP
Japan
Prior art keywords
liquid crystal
ferrielectric
phase
crystal composition
ferridielectric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP21188597A
Other languages
Japanese (ja)
Inventor
Hironori Motoyama
裕規 本山
Tomoyuki Yui
知之 油井
Masahiro Kino
正博 城野
Hiroshi Mineta
浩 嶺田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP21188597A priority Critical patent/JPH1150054A/en
Publication of JPH1150054A publication Critical patent/JPH1150054A/en
Pending legal-status Critical Current

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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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
    • C09K2019/044—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being a perfluoro chain used as an end group

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  • Liquid Crystal Substances (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, reduced in hysteresis, improved in orientation and useful for driving active matrices by incorporating a specific ferridielectric liquid crystal with a specific phenyl ester compound. SOLUTION: This composition is obtained by incorporating (A) a ferridielectric liquid crystal shown by formula I [R is a 6-12C straight-chain alkyl; Z is H or F; (q) is 5 to 7; and (s) is 2 or 4] with (B) a phenyl ester compound shown by formula II [(m) is 5 to 12; (n) is 1; (p) is 1 or 2; and X and Y are each H, or one being H and the other F], so as to preferably have the ferridielectric phase, with transition temperature of 40 deg.C; or more at the high- temperature side and 0 deg.C or less at the low-temperature side, and a smectic A phase at the side higher in temperature than the ferridielectric phase. The component B is included preferably at 10 to 50 mol.%, based on the whole composition, more preferably 1 to 30 mol.%. This composition is placed between substrates that carry a nonlinear active element (e.g. thin-film transistor or diode) for each image element, to obtain an active matrix liquid crystalline display element.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、新規なフェニルエステ
ル化合物とそれを含有するフェリ誘電性液晶組成物に関
し、これは各画素毎に駆動するアクティブマトリクス型
の液晶表示素子に好適に使用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenyl ester compound and a ferrielectric liquid crystal composition containing the same, which are suitably used for an active matrix type liquid crystal display device driven for each pixel. .

【０００２】[0002]

【従来の技術】液晶表示素子（ＬＣＤ）は、従来のブラ
ウン管ディスプレイに代わるフラットパネルディスプレ
イとして、既にポータブル機器を中心に普及しつつあ
る。最近のパーソナルコンピュータやワードプロセッサ
の機能拡大、および処理情報の大量化にともない、ＬＣ
Ｄにもより高い機能、すなわち、大表示容量化、フルカ
ラー表示、広視野角、高速応答、高コントラスト化等が
要求されている。2. Description of the Related Art Liquid crystal display devices (LCDs) are already becoming popular mainly in portable devices as flat panel displays replacing conventional CRT displays. With the recent expansion of the functions of personal computers and word processors and the increase in the amount of processing information, LC
D is also required to have higher functions, that is, large display capacity, full color display, wide viewing angle, high-speed response, high contrast, and the like.

【０００３】この様な要求に応える液晶表示方式（液晶
駆動方式）として、画面の各画素毎に薄膜トランジスタ
（ＴＦＴ）あるいはダイオード（ＭＩＭ）を形成し、各
画素毎に独立して液晶を駆動する方式であるアクディブ
マトリクス（ＡＭ）表示素子が提案実施されている。こ
の表示方式は、製造歩留まりが低いため低コスト化が困
難である、大画面化が困難であるなどの問題はあるが、
表示品質の高さにより従来主流であったＳＴＮ表示方式
を凌駕し、ＣＲＴに迫る勢いになっている。As a liquid crystal display system (liquid crystal driving system) that meets such a demand, a thin film transistor (TFT) or a diode (MIM) is formed for each pixel of a screen, and a liquid crystal is independently driven for each pixel. An active matrix (AM) display element is proposed and implemented. This display method has problems such as low production yield, low cost is difficult, and large screen is difficult.
Due to the high display quality, it has surpassed the STN display method which has been mainstream in the past, and is approaching the CRT.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、このよ
うなＡＭ表示素子において、液晶材料としてＴＮ（ツイ
ステッドネマチック）液晶を用いているため、次のよう
な問題が生じている。 (1) ＴＮ液晶はネマチック液晶であり、応答速度が一般
的に遅く（数十ｍｓ）、動画表示を行うとき良好な画質
が得られない。 (2) 液晶分子のねじれ状態（ツイスト配向）を利用して
表示するため、視野角が狭い。特に階調表示を行うと、
視野角が急激に狭くなる。すなわち、ディスプレイを見
る角度によって、コントラスト比、色などが変わってし
まう。However, in such an AM display element, the following problem occurs because a TN (twisted nematic) liquid crystal is used as a liquid crystal material. (1) The TN liquid crystal is a nematic liquid crystal, and its response speed is generally slow (several tens of ms), and good image quality cannot be obtained when displaying a moving image. (2) The display angle is narrow because display is performed by using the twisted state (twist alignment) of liquid crystal molecules. Especially when performing gradation display,
The viewing angle sharply narrows. That is, the contrast ratio, color, and the like change depending on the viewing angle of the display.

【０００５】これらの問題を解決するため、ＴＮ液晶に
代えて、強誘電性液晶や反強誘電性液晶を採用したＡＭ
パネルの提案も近年行われているが（特開平5-249502、
同5-150257、同6-95080 等）、これらの液晶にも次のよ
うな問題点があり実用化の壁は厚いのが現状である。In order to solve these problems, an AM using a ferroelectric liquid crystal or an antiferroelectric liquid crystal instead of a TN liquid crystal has been proposed.
Panel proposals have also been made in recent years (Japanese Unexamined Patent Publication No.
5-150257, 6-95080, etc.) These liquid crystals also have the following problems, and the wall for practical use is currently thick.

【０００６】(A) 強誘電性液晶は自発分極を有している
が、自発分極が常に存在するため画面の焼き付きが起こ
りやすく駆動が困難となる。また、強誘電性液晶は表面
安定化型モードで表示する場合、黒、白の２値表示しか
できないため、階調表示は極めて困難である。階調表示
を行うとするときには特別な工夫が必要（例えば、単安
定を使用した強誘電性液晶素子；KeiichiNITO et.al, S
ID'94、Preprint, p48)であり、高度な実用化技術の開
発が必要とされる。(A) A ferroelectric liquid crystal has spontaneous polarization. However, since spontaneous polarization always exists, image burn-in easily occurs and driving is difficult. Further, when the ferroelectric liquid crystal is displayed in the surface stabilization mode, only binary display of black and white can be performed, so that gradation display is extremely difficult. A special device is required when performing gradation display (for example, a ferroelectric liquid crystal element using monostable; Keiichi NITO et.al, S
ID'94, Preprint, p48), requiring the development of advanced practical technology.

【０００７】(B) 反強誘電性液晶は、永久自発分極が存
在しないため上記(A) で述べられている焼き付の問題は
回避されている。ＡＭ駆動においては、少なくとも10Ｖ
以下で駆動する液晶材料が必要である。しかし、反強誘
電性液晶は一般にしきい値電圧が大きく、低電圧駆動は
困難である。また、光学応答に履歴（ヒステリシス）が
あるため階調表示が困難であるなどの問題を有してい
る。本発明の目的は、以上のような問題点を解決できる
ＡＭ駆動に適した新しい材料を提供することにあるが、
この新しい材料としてフェリ誘電相を有する液晶が考え
られる。(B) Since the antiferroelectric liquid crystal does not have permanent spontaneous polarization, the problem of burn-in described in (A) is avoided. At least 10V for AM drive
A liquid crystal material driven below is required. However, the antiferroelectric liquid crystal generally has a large threshold voltage, and it is difficult to drive at a low voltage. In addition, there is a problem that gradation display is difficult due to a history (hysteresis) in optical response. An object of the present invention is to provide a new material suitable for AM driving that can solve the above problems,
A liquid crystal having a ferrielectric phase can be considered as this new material.

【０００８】フェリ誘電相 (SCγ* 相）を有する液晶化
合物は、1989年、 4-(1-メチルヘプチロキシカルボニ
ル）フェニル＝4-(4'-オクチルオキシビフェニル）カル
ボキシレート (略称 MHPOBC)において初めて発見された
（Japanese Journal of Applied Physics, Vol.29, No.
1, 1990, pp.L131-137）。[0008] In 1989, a liquid crystal compound having a ferrielectric phase (SCγ * phase) was obtained from 4- (1-methylheptyloxycarbonyl) phenyl 4- (4'-octyloxybiphenyl) carboxylate (abbreviated as MHPOBC). First discovered (Japanese Journal of Applied Physics, Vol.29, No.
1, 1990, pp. L131-137).

【０００９】MHPOBCの構造式ならびに相転移温度（℃）
を次に示した。 構造式 : C8H17-O-Ph-Ph-COO-Ph-COO-C*H(CH3)-C6H13 但し、Phは1,4-フェニレン基、C*は不斉炭素を表す。 相系列 : I(147)SA(122)SCα*(121)SC*(119)SCγ*(11
8)SCA*(65)SIA*(30)Cr 但し、I は等方相、SAはスメクチックＡ相、SCα* はカ
イラルスメクチックＣα相、SC* はカイラルスメクチッ
クＣ相（強誘電相）、SCγ* はカイラルスメクチックＣ
γ相（フェリ誘電相）、SCA*はカイラルスメクチックＣ
Ａ相（反強誘電相）、SIA*はカイラルスメクチックＩＡ
相、Crは結晶相を示す。Structural formula of MHPOBC and phase transition temperature (° C.)
Is shown below. Structural formula: C8H17-O-Ph-Ph-COO-Ph-COO-C * H (CH3) -C6H13 where Ph represents a 1,4-phenylene group and C * represents an asymmetric carbon. Phase series: I (147) SA (122) SCα * (121) SC * (119) SCγ * (11
8) SCA * (65) SIA * (30) Cr where I is isotropic, SA is smectic A phase, SCα * is chiral smectic Cα phase, SC * is chiral smectic C phase (ferroelectric phase), SCγ * Is chiral smectic C
γ phase (ferrielectric phase), SCA * is chiral smectic C
A phase (antiferroelectric phase), SIA * is chiral smectic IA
The phase, Cr, indicates a crystalline phase.

【００１０】フェリ誘電性液晶を説明するために、図１
にフェリ誘電相における分子配列状態を、図２にフェリ
誘電相の三角波に対する光学応答を示した。フェリ誘電
相では図１の FI(+)（印加電圧が正の場合）あるいはFI
(-)(印加電圧が負の場合）の分子配列をしている。電場
のない状態では、 FI(+)とFI(-) とは等価であるので共
存している。従って、平均的な光軸は層法線方向とな
り、図１に示した偏光板の条件下では暗状態となる。こ
の状態は、図２において電圧０で透過光強度が０のとこ
ろに相当する。In order to explain a ferrielectric liquid crystal, FIG.
2 shows the molecular arrangement state in the ferrielectric phase, and FIG. 2 shows the optical response of the ferrielectric phase to a triangular wave. In the ferrielectric phase, FI (+) (when the applied voltage is positive) or FI
The molecular arrangement is (-) (when the applied voltage is negative). In the absence of an electric field, FI (+) and FI (-) coexist because they are equivalent. Therefore, the average optical axis is in the direction of the normal to the layer, and is in a dark state under the conditions of the polarizing plate shown in FIG. This state corresponds to a state where the transmitted light intensity is 0 at a voltage of 0 in FIG.

【００１１】また、 FI(+)およびFI(-) は、分子配列状
態から明らかなようにそれぞれ自発分極を有するが、こ
れらの共存状態では自発分極を打ち消し合うため、平均
的な自発分極は零となる。このことから、フェリ誘電性
液晶は、反強誘電性液晶と同様に強誘電性液晶に見られ
る焼き付き現象から逃れられる。Further, FI (+) and FI (-) have spontaneous polarizations, respectively, as evident from the molecular arrangement state. However, in the coexistence state, the spontaneous polarizations cancel each other, so that the average spontaneous polarization is zero. Becomes For this reason, the ferrielectric liquid crystal escapes the image sticking phenomenon observed in the ferroelectric liquid crystal, like the antiferroelectric liquid crystal.

【００１２】フェリ誘電性液晶に電圧を印加していく
と、強誘電状態に達するよりも低い電圧で、消光位を持
つ領域（ドメイン）が現れる。この領域は、強誘電状態
ほどではないが、法線方向より傾いた方向に光軸を有し
ていることを示している。この中間的な状態が FI(+)ま
たはFI(-) と考えられる。なお、この場合、図２におい
て、電圧 0Ｖと 4Ｖの間で連続的な透過光強度の変化で
はなく、階段上の透過光強度が観測されるはずである。
しかし、図２では連続的な透過光強度が観測された。こ
れは FI(+)→FO(+) 、または FI(-)→FO(-) へのしきい
値電圧が明確でないことによると考えられる。本発明で
は、以上説明した中間状態が必ず観測される液晶相をフ
ェリ誘電相と、該フェリ誘電相がその相系列中で最も広
い液晶化合物をフェリ誘電性液晶と呼ぶ。When a voltage is applied to the ferrielectric liquid crystal, a region (domain) having an extinction position appears at a lower voltage than when the ferroelectric state is reached. This region has an optical axis in a direction inclined from the normal direction, though not so much as in the ferroelectric state. This intermediate state is considered FI (+) or FI (-). In this case, in FIG. 2, the transmitted light intensity on the stairs should be observed instead of a continuous change in the transmitted light intensity between the voltages 0 V and 4 V.
However, continuous transmitted light intensity was observed in FIG. This is probably because the threshold voltage of FI (+) → FO (+) or FI (-) → FO (-) is not clear. In the present invention, a liquid crystal phase in which the intermediate state described above is always observed is referred to as a ferrielectric phase, and a liquid crystal compound in which the ferrielectric phase is the broadest in the phase series is referred to as a ferrielectric liquid crystal.

【００１３】さらに、印加電圧を高くすると、電場の向
きに応じ安定な状態である強誘電相FO(+) またはFO(-)
に相転移する。すなわち、図２において透過光強度が飽
和状態（左右の平坦部）となったものが FO(+)またはFO
(-) である。この強誘電状態 FO(+)またはFO(-) では、
フェリ誘電状態 FI(+)またはFI(-)より更に大きな自発
分極が発現することが図１より分かる。以上のように、
フェリ誘電相では、 FI(+)とFI(-) の共存状態を暗、強
誘電状態 FO(+)およびFO(-) を明として使用できる。Further, when the applied voltage is increased, the ferroelectric phase FO (+) or FO (-) which is in a stable state according to the direction of the electric field is increased.
Phase transition. That is, in FIG. 2, the transmitted light intensity is in a saturated state (a flat portion on the left and right), and the intensity is FO (+) or FO
(-). In this ferroelectric state FO (+) or FO (-),
It can be seen from FIG. 1 that a spontaneous polarization larger than that of the ferrielectric state FI (+) or FI (-) appears. As mentioned above,
In the ferrielectric phase, the coexistence state of FI (+) and FI (-) can be used as dark, and the ferroelectric states FO (+) and FO (-) can be used as light.

【００１４】従来の強誘電性液晶は、FO(+) 、FO(-) 間
のスイッチングであったのに対し、フェリ誘電性液晶で
は FO(+)、 FI(+)、FI(-) および FO(-)の４状態間でス
イッチングをするという大きな特徴を有している。ま
た、その表示原理はいずれも液晶の複屈折性を利用した
ものであり、視角依存性の小さな表示素子の作製が可能
である。Conventional ferroelectric liquid crystals switch between FO (+) and FO (-), while ferrielectric liquid crystals have FO (+), FI (+), FI (-) and It has the great feature of switching between the four states of FO (-). In addition, all of the display principles use birefringence of liquid crystal, and a display element with small viewing angle dependence can be manufactured.

【００１５】フェリ誘電相は図２に示されているよう
に、一般的にフェリ誘電状態から強誘電状態へ変化する
電圧と、強誘電状態からフェリ誘電状態へ変化する電圧
の差が小さい、即ちヒステリシスの幅が非常にせまい傾
向が強く、Ｖ字形の光学応答性を示すのが特徴で、ＡＭ
駆動及びＡＭ駆動における階調表示に適した性質を持っ
ている。また、フェリ誘電性液晶の電圧による変化に於
て、フェリ誘電状態から強誘電状態へ変化する電圧であ
るしきい値電圧は、反強誘電性液晶に比べてはるかに小
さい傾向を有し、フェリ誘電性液晶はＡＭ駆動に適して
いるといえる。As shown in FIG. 2, the ferrielectric phase generally has a small difference between the voltage at which the ferrielectric state changes to the ferroelectric state and the voltage at which the ferroelectric state changes to the ferrielectric state. It is characterized by a very narrow hysteresis width and a V-shaped optical response.
It has properties suitable for gradation display in driving and AM driving. In addition, the threshold voltage, which is the voltage at which the ferrielectric liquid crystal changes from a ferrielectric state to a ferroelectric state, tends to be much smaller than that of an antiferroelectric liquid crystal. It can be said that the dielectric liquid crystal is suitable for AM driving.

【００１６】[0016]

【発明が解決しようとする課題】しかしながら、現在ま
でに合成されたフェリ誘電性液晶の数は極めて少なく、
更に従来知られていたフェリ誘電性液晶単体は、ＡＭ駆
動素子への応用を考えたとき、次のような問題点があっ
た。まず、フェリ誘電性液晶は、電圧に対する光学応答
においてヒステリシスの幅は極めて小さいが、完全にな
くなってはいない。そのため階調表示に問題が生じてき
ており、出来るだけヒステリシスの幅を無くすことが求
められている。次に、フェリ誘電性液晶は配向性がそれ
ほど優れていない。そのため現在のネマチック液晶を用
いたアクティブマトリックス駆動表示素子に比べて、コ
ントラストの点で劣っている。本発明は、これらの点を
改善することにあり、フェリ誘電性液晶のヒステリシス
を小さくし、かつ配向性を改善する添加物及びこれを含
有するＡＭ駆動に好適に使用されるそれを含むフェリ誘
電性液晶組成物に関する。However, the number of ferrielectric liquid crystals synthesized to date is extremely small,
Further, the conventionally known ferrielectric liquid crystal alone has the following problems when applied to an AM driving element. First, the ferrielectric liquid crystal has a very small hysteresis width in the optical response to voltage, but is not completely eliminated. For this reason, a problem has arisen in gradation display, and it is required to reduce the width of hysteresis as much as possible. Second, ferrielectric liquid crystals are not so excellent in orientation. Therefore, it is inferior in contrast in comparison with the current active matrix drive display device using a nematic liquid crystal. An object of the present invention is to improve these points, to reduce the hysteresis of a ferrielectric liquid crystal, and to improve an alignment property, and an additive containing the additive, which is preferably used for an AM drive and containing the same. Liquid crystal composition.

【００１７】[0017]

【課題を解決するための手段】すなわち、本発明は、下
記一般式(1) で示されるフェニルエステル化合物を下記
一般式(2) で示されるフェリ誘電性液晶に添加してなる
フェリ誘電性液晶組成物である。一般式(2) においてｒ
が９であるフェリ誘電性液晶を用いるのが、配向性に優
れたフェリ誘電性液晶組成物を与えるので望ましい。一
般式(1) であらわされるフェニルエステル化合物の添加
量が組成物の１〜50モル％が好ましく、より好ましくは
１〜30モル％である。フェリ誘電性液晶液晶組成物とし
ては、該フェリ誘電相の高温側の転移温度が40℃以上
で、低温側の転移温度が 0℃以下であり、該フェリ誘電
相よりも高温側にスメクチックＡ相を有することが好ま
しい。That is, the present invention provides a ferrielectric liquid crystal obtained by adding a phenyl ester compound represented by the following general formula (1) to a ferrielectric liquid crystal represented by the following general formula (2). A composition. In the general formula (2), r
It is desirable to use a ferrielectric liquid crystal having a ratio of 9 because it gives a ferrielectric liquid crystal composition having excellent alignment properties. The addition amount of the phenyl ester compound represented by the general formula (1) is preferably from 1 to 50 mol%, more preferably from 1 to 30 mol% of the composition. The ferrielectric liquid crystal liquid crystal composition has a transition temperature on the high-temperature side of the ferrielectric phase of 40 ° C. or higher and a transition temperature on the low-temperature side of 0 ° C. or lower. It is preferable to have

【００１８】[0018]

【化２】 （式(1) 中、ｍは 5〜12、ｎは 1、ｐは１または２、
Ｘ、ＹはＨ原子又は一方がＨ原子で他方がＦ原子であ
り、式(2) 中、ｒは炭素数６〜12の直鎖アルキル基、Ｚ
はＨ原子またはＦ原子、ｑは５〜７の整数、ｓは２、４
の整数である。）Embedded image (In the formula (1), m is 5 to 12, n is 1, p is 1 or 2,
X and Y are H atoms or one is an H atom and the other is an F atom. In the formula (2), r is a straight-chain alkyl group having 6 to 12 carbon atoms;
Is an H atom or an F atom, q is an integer of 5 to 7, s is 2, 4
Is an integer. )

【００１９】そして、本発明のフェリ誘電性液晶液晶組
成物は、各画素毎に薄膜トランジスタあるいはダイオー
ド等の非線形能動素子を設置した基板間に狭持して、ア
クティブマトリクス液晶表示素子とされ、それは非線形
能動素子を用いた液晶の電圧による駆動を２つのフェリ
誘電状態と２つの強誘電状態、及びその中間状態へのス
イッチングにて行われる。The ferrielectric liquid crystal liquid crystal composition of the present invention is sandwiched between substrates on which a non-linear active element such as a thin film transistor or a diode is provided for each pixel to form an active matrix liquid crystal display element. The driving of the liquid crystal by the voltage using the active element is performed by switching between two ferrielectric states, two ferroelectric states, and an intermediate state between them.

【００２０】本発明におけるフェニルエステル化合物
は、本発明者らの先の出願（特願平08-278013 号によっ
て容易に製造できる。その製造法を一般式(1) において
m＝6,n＝1, p＝1, X＝H, Y＝H である化合物について
示せば、次の通りである。 (1) HO-Ph-COOH + C6H13COCl → C6H13COO-Ph-COOH (2) C6H13COO-Ph-COOH +SOCl2 → C6H13COO-Ph-COCl (3) C6H13COO-Ph-COCl + CF3CH2OH → C6H13COO-Ph-COOCH2CF3 式中、Phは1,4-フェニレン基を示す。(1) はp-ヒドロキ
シ安息香酸とヘプタン酸クロライドとの反応である。
(2) はエステル(1) と塩化チオニルの反応である。(3)
は酸クロライド(2) とトリフルオロエタノールとの反応
による目的物の生成である。The phenyl ester compound in the present invention can be easily produced by the inventors' earlier application (Japanese Patent Application No. 08-278013. The production method is represented by the general formula (1).
A compound having m = 6, n = 1, p = 1, X = H, Y = H is as follows. (1) HO-Ph-COOH + C 6 H 13 COCl → C 6 H 13 COO-Ph-COOH (2) C 6 H 13 COO-Ph-COOH + SOCl 2 → C 6 H 13 COO-Ph-COCl ( 3) C 6 H 13 COO-Ph-COCl + CF 3 CH 2 OH → C 6 H 13 COO-Ph-COOCH 2 CF 3 In the formula, Ph represents a 1,4-phenylene group. (1) shows the reaction between p-hydroxybenzoic acid and heptanoic acid chloride.
(2) is the reaction of ester (1) with thionyl chloride. (3)
Is the production of the desired product by the reaction of acid chloride (2) with trifluoroethanol.

【００２１】本発明におけるフェリ誘電性液晶は、本発
明者らの特願平8-91235 号によって容易に製造できる。
その製造法の概略を一般式(2) において p=3, q=2 であ
る化合物について示せば、次の通りである。 (1) AcO-Ph(3X)-COOH + SOCl2 → AcO-Ph(3X)-COCl (2) (1) + CF3C*H(OH)(CH2)3OC2H5 → AcO-Ph(3X)-COO-C*H(CF3)(CH2)3OC2H5 (3) (2) + (Ph-CH2NH2) → HO-Ph(3X)-COO-C*H(CF3)(CH2)3OC2H5 (4) R-O-Ph-Ph-COOH + SOCl2 → R-O-Ph-Ph-COCl (5) (3) + (4) → 目的フェリ誘電性液晶 式中、AcO はアセチル基、Phは1,4-フェニレン基、Ph(3
X)はフェニレン基の水酸基残基を基準に３位置へＦ置換
していてもよい1,4-フェニレン基、C*は不斉炭素を示
す。The ferrielectric liquid crystal in the present invention can be easily manufactured by the present inventors in Japanese Patent Application No. 8-91235.
The outline of the production method is as follows for a compound in which p = 3 and q = 2 in the general formula (2). (1) AcO-Ph (3X) -COOH + SOCl 2 → AcO-Ph (3X) -COCl (2) (1) + CF 3 C * H (OH) (CH 2 ) 3 OC 2 H 5 → AcO- Ph (3X) -COO-C * H (CF 3 ) (CH 2 ) 3 OC 2 H 5 (3) (2) + (Ph-CH 2 NH 2 ) → HO-Ph (3X) -COO-C * H (CF 3 ) (CH 2 ) 3 OC 2 H 5 (4) RO-Ph-Ph-COOH + SOCl 2 → RO-Ph-Ph-COCl (5) (3) + (4) → Desired ferrielectricity In the formula, AcO is an acetyl group, Ph is a 1,4-phenylene group, and Ph (3
X) is a 1,4-phenylene group which may be F-substituted at the 3-position based on the hydroxyl group residue of the phenylene group, and C * represents an asymmetric carbon.

【００２２】上記製造法を簡単に説明すると次の通りで
ある。(1) はフッ素置換あるいは無置換のp-アセトキシ
安息香酸の塩化チオニルによる塩素化反応である。(2)
は塩化物(1) と光学活性アルコールとの反応によるエス
テルの生成である。(3) はエステル(2) の脱アセチル化
である。(4) は 4'-アルキルオキシビフェニル−4-カル
ボン酸の塩素化である。(5) はフェノール(3) と塩化物
(4) との反応による液晶の製造である。The above-mentioned manufacturing method is briefly described as follows. (1) is a chlorination reaction of fluorine-substituted or unsubstituted p-acetoxybenzoic acid with thionyl chloride. (2)
Is the formation of an ester by the reaction of chloride (1) with an optically active alcohol. (3) is the deacetylation of ester (2). (4) is the chlorination of 4'-alkyloxybiphenyl-4-carboxylic acid. (5) is phenol (3) and chloride
(4) to produce a liquid crystal.

【００２３】[0023]

【発明の効果】本発明は、新規なフェニルエステル化合
物を含むフェリ誘電性液晶組成物を提供する。そして、
本発明により提供された新規なフェリ誘電性液晶組成物
は、ヒステリシスが大幅に減少し、かつ配向性に優れて
いる。そのため表示品質の高いフェリ誘電性液晶表示素
子を実現できる。The present invention provides a ferrielectric liquid crystal composition containing a novel phenyl ester compound. And
The novel ferrielectric liquid crystal composition provided by the present invention has greatly reduced hysteresis and excellent alignment. Therefore, a ferrielectric liquid crystal display element having high display quality can be realized.

【００２４】[0024]

【実施例】次に、実施例及び比較例を掲げて本発明を更
に具体的に説明するが、本発明はもちろんこれに限定さ
れるものではない。実施例１〜４下記式で示されるフェ
リ誘電性液晶(2A)に、次のフェニルエステル化合物 (1A
〜1C) をそれぞれ20モル％添加して、フェリ誘電性液晶
組成物を得た。相系列、ヒステリシス、配向性を測定し
た結果を表１に示した。Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is of course not limited thereto. Examples 1 to 4 The following phenyl ester compound (1A) was added to a ferrielectric liquid crystal (2A) represented by the following formula.
To 1C) were added in an amount of 20 mol% each to obtain a ferrielectric liquid crystal composition. Table 1 shows the measurement results of the phase series, hysteresis, and orientation.

【００２５】 1A ；C6H13-COO-Ph-COO-CH2CF3 (実施例1) 1B ；C9H19-COO-Ph(3F)-COO-CH2CF3 (実施例2) 1C ；C9H19-COO-Ph(2F)-COO-CH2CF3 (実施例3) 1D ；C9H19-COO-Ph-COO-CH2C2F5 (実施例4) 2A ；C9H19-O-Ph-Ph-COO-Ph(3F)-COO-C*H(CF3)(CH2)3OC
2H5 式中のPhは1,4-フェニレン基、フェニレン基の水酸基残
基を基準にPh(2F)は2-位置にフッ素置換した1,4-フェニ
レン基、Ph(3F)は3-位置にフッ素置換した1,4-フェニレ
ン基をそれぞれ示し、C*は不斉炭素である。1A; C 6 H 13 -COO-Ph-COO-CH 2 CF 3 (Example 1) 1B; C 9 H 19 -COO-Ph (3F) -COO-CH 2 CF 3 (Example 2) 1C; C 9 H 19 -COO- Ph (2F) -COO-CH 2 CF 3 ( example 3) 1D; C 9 H 19 -COO-Ph-COO-CH 2 C 2 F 5 ( example 4) 2A ; C 9 H 19 -O-Ph-Ph-COO-Ph (3F) -COO-C * H (CF 3 ) (CH 2 ) 3 OC
The Ph in 2 H 5 Formula 1,4-phenylene group, a 1,4-phenylene group Ph (2F) is based on the hydroxyl residues phenylene group and fluorine-substituted in the 2-position, Ph (3F) is 3- Each position represents a fluorine-substituted 1,4-phenylene group, and C * is an asymmetric carbon.

【００２６】相の同定を、テクスチャー観察、コノスコ
ープ像の観察及びDSC(示差走差熱量計）の測定により行
なった。コノスコープ像の観察はフェリ誘電相の同定に
有力な手段である。コノスコープ像の観察は文献(J. Ap
pl. Phys. 31, 793, (1992))に従って行った。The phases were identified by texture observation, observation of a conoscopic image, and measurement by DSC (differential scanning calorimeter). Observation of a conoscopic image is a powerful tool for identifying a ferrielectric phase. Observation of conoscopic images is described in the literature (J. Ap
pl. Phys. 31, 793, (1992)).

【００２７】ヒステリシスなどは次の手順で測定した。
絶縁膜(SiO2,膜厚50nm) 、ITO 電極付きのガラス基板を
ポリイミドコ−ティング後（膜厚約80nm）、一対のガラ
ス基板の片方のみをラビング処理した。粒径 1.6μｍの
スペーサを介し、一対のガラス基板を貼り合わせテスト
セルとした。セル厚は２μｍであった。液晶が等方相と
なる温度まで加熱し、毛細管現象によりテストセル中に
前記液晶を注入した。その後、１℃／分の速度で徐冷し
液晶を平行配向させた。次に、25℃において、テストセ
ルに、±10V, 50mHzの３角波電圧を印加し、駆動を行い
ヒステリシスを観測した。The hysteresis and the like were measured by the following procedure.
After polyimide coating of a glass substrate provided with an insulating film (SiO 2 , 50 nm thick) and ITO electrode (about 80 nm thick), only one of the pair of glass substrates was rubbed. A pair of glass substrates were bonded together via a spacer having a particle size of 1.6 μm to form a test cell. The cell thickness was 2 μm. The liquid crystal was heated to a temperature at which the liquid crystal became an isotropic phase, and the liquid crystal was injected into a test cell by capillary action. Thereafter, the liquid crystal was gradually cooled at a rate of 1 ° C./min to parallel align the liquid crystal. Next, a triangular wave voltage of ± 10 V, 50 mHz was applied to the test cell at 25 ° C., and the test cell was driven to observe the hysteresis.

【００２８】25℃において、空セルを直交する偏光板間
におき、光の透過光量を求め、この透過光量を０％とし
た。次にテストセルをおき、強誘電状態の透過光量を求
め、この透過光量を 100％とした。25℃において、この
テストセルに印加電圧 0の状態において、光の透過光量
を求め、この光漏れの値により、配向性の優劣の評価と
した。また、比較のために、フェリ誘電性液晶(2A)につ
いて、測定温度を40℃とする他は上記と同様にして特性
評価した。結果を表１に示した。At 25 ° C., an empty cell was placed between orthogonal polarizing plates, and the amount of transmitted light was determined. The amount of transmitted light was set to 0%. Next, a test cell was placed, and the amount of transmitted light in the ferroelectric state was determined, and the amount of transmitted light was set to 100%. At 25 ° C., the applied light amount to the test cell was 0, the amount of transmitted light was determined, and the value of the light leakage was used to evaluate the degree of orientation. Further, for comparison, the characteristics of the ferrielectric liquid crystal (2A) were evaluated in the same manner as described above, except that the measurement temperature was 40 ° C. The results are shown in Table 1.

【００２９】比較例１〜５ 実施例１で使用したフェリ誘電性液晶(2A)に、下記のフ
ェニルエステル化合物(1E〜1H) をそれぞれ20モル％添
加して、フェリ誘電性液晶組成物を得た。相系列、ヒス
テリシス、配向性を実施例1 と同様にして測定した結果
を表１に示した。比較例１〜５で得られた液晶組成物
は、融点が室温近辺にあるもの、スメクチックＡ相を持
たないものなどの欠点を有し、実用上問題であった。Comparative Examples 1 to 5 The following phenyl ester compounds (1E to 1H) were added to the ferrielectric liquid crystal (2A) used in Example 1 in an amount of 20 mol% each to obtain a ferrielectric liquid crystal composition. Was. Table 1 shows the results of measurement of the phase series, hysteresis, and orientation in the same manner as in Example 1. The liquid crystal compositions obtained in Comparative Examples 1 to 5 had drawbacks such as those having a melting point near room temperature and those having no smectic A phase, and were practically problematic.

【００３０】 1E ；C9H19-COO-Ph-COO-CH2C3F7 (比較例1) 1F ；C9H19-COO-Ph-COO-CH2C7F15 (比較例2) 1G ；C9H19-COO-Ph-COO-CH2C9F19 (比較例3) 1H ；C9H19-COO-Ph-COO-CH2CH2C6F13 (比較例4) 1K ；C9H19-COO-Ph(3F)-COO-CH2CH2CH2CF3 （比較例5) 式中のPhは1,4-フェニレン基、Ph(3F)はフェニル基の水
酸基残基を基準に3-位置にフッ素置換した1,4-フェニレ
ン基を示す。1E; C 9 H 19 -COO-Ph-COO-CH 2 C 3 F 7 (Comparative Example 1) 1F; C 9 H 19 -COO-Ph-COO-CH 2 C 7 F 15 (Comparative Example 2) 1G; C 9 H 19 -COO-Ph-COO-CH 2 C 9 F 19 (Comparative Example 3) 1H; C 9 H 19 -COO-Ph-COO-CH 2 CH 2 C 6 F 13 (Comparative Example 4) 1K; C 9 H 19 -COO-Ph (3F) -COO-CH 2 CH 2 CH 2 CF 3 (Comparative Example 5) In the formula, Ph is a 1,4-phenylene group, and Ph (3F) is a phenyl group. The 1,4-phenylene group substituted with fluorine at the 3-position based on the hydroxyl residue is shown.

【００３１】[0031]

【表１】 光漏れ 測定温度 相 系 列 (％) (℃) 実施例１ Cr(<-20)SCγ*(77)SA(86)I 1.2 30 実施例２ Cr(<-20)SCγ*(68)SA(82)I 1.1 30 実施例３ Cr(<-20)SCγ*(66)SA(79)I 2.8 30 実施例４ Cr(<-20)SCγ*(76)SA(82)I 2.7 30 比較例１ Cr(<-10)SCγ*(77)I 比較例２ Cr(15)SCγ*(101)SA(103)I 比較例３ Cr(22)SCγ*(89)SA(91)I 比較例４ Cr(<-15)SCγ*(85)I 比較例５ Cr(<-10)SCγ*(80)I 液晶２Ａ Cr(34)SCγ*(101)SA(103)I 3.0 40 上記相系列中の () 内の数値は転移温度 (℃) 、Crは結
晶相、SCγ* はカイラルスメクチックＣγ相（フェリ誘
電相）、SAはスメクチックＡ相、Ｉは等方相をそれぞれ
示す。[Table 1] Light leakage Measurement temperature phase sequence (%) (° C) Example 1 Cr (<-20) SCγ * (77) SA (86) I 1.2 30 Example 2 Cr (<-20) SCγ * ( 68) SA (82) I 1.1 30 Example 3 Cr (<-20) SCγ * (66) SA (79) I 2.8 30 Example 4 Cr (<-20) SCγ * (76) SA (82) I 2.7 30 Comparative Example 1 Cr (<-10) SCγ * (77) I Comparative Example 2 Cr (15) SCγ * (101) SA (103) I Comparative Example 3 Cr (22) SCγ * (89) SA (91) I Comparative Example 4 Cr (<-15) SCγ * (85) I Comparative Example 5 Cr (<-10) SCγ * (80) I Liquid Crystal 2A Cr (34) SCγ * (101) SA (103) I 3.0 40 Above Phase The numbers in parentheses in the series indicate the transition temperature (° C.), Cr indicates the crystal phase, SCγ * indicates the chiral smectic Cγ phase (ferrielectric phase), SA indicates the smectic A phase, and I indicates the isotropic phase.

【図面の簡単な説明】[Brief description of the drawings]

【図１】フェリ誘電相における分子配列状態を示す。FI
(+), FI(-)はフェリ誘電状態、FO(+), FO(-)は強誘電状
態を表す。FIG. 1 shows a molecular arrangement state in a ferrielectric phase. FI
(+) And FI (-) indicate a ferrielectric state, and FO (+) and FO (-) indicate a ferroelectric state.

【図２】フェリ誘電相における三角波に対する光学応答
の例である。FIG. 2 is an example of an optical response to a triangular wave in a ferrielectric phase.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 嶺田 浩 茨城県つくば市和台22番地 三菱瓦斯化学 株式会社総合研究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Mineda 22 Wadai, Tsukuba, Ibaraki Pref.

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 下記一般式(1) で示されるフェニルエス
テル化合物を下記一般式(2) で示されるフェリ誘電性液
晶に添加してなるフェリ誘電性液晶組成物。 【化１】 （式(1) 中、ｍは 5〜12、ｎは 1、ｐは１または２、
Ｘ、ＹはＨ原子又は一方がＨ原子で他方がＦ原子であ
り、式(2) 中、ｒは炭素数６〜12の直鎖アルキル基、Ｚ
はＨ原子またはＦ原子、ｑは５〜７の整数、ｓは２、４
の整数である。）1. A ferrielectric liquid crystal composition obtained by adding a phenyl ester compound represented by the following general formula (1) to a ferrielectric liquid crystal represented by the following general formula (2). Embedded image (In the formula (1), m is 5 to 12, n is 1, p is 1 or 2,
X and Y are H atoms or one is an H atom and the other is an F atom. In the formula (2), r is a straight-chain alkyl group having 6 to 12 carbon atoms;
Is an H atom or an F atom, q is an integer of 5 to 7, s is 2, 4
Is an integer. ) 【請求項２】 該一般式(2) において、ｒが９である請
求項１記載のフェリ誘電性液晶組成物。2. The ferrielectric liquid crystal composition according to claim 1, wherein r is 9 in the general formula (2). 【請求項３】 該一般式(1) で示されるフェニルエステ
ル化合物の添加量が組成物の１〜50モル％である請求項
１記載のフェリ誘電性液晶組成物。3. The ferrielectric liquid crystal composition according to claim 1, wherein the amount of the phenyl ester compound represented by the general formula (1) is 1 to 50 mol% of the composition. 【請求項４】 該一般式(1) で示されるフェニルエステ
ル化合物の添加量が組成物の１〜30モル％である請求項
１記載のフェリ誘電性液晶組成物。4. The ferrielectric liquid crystal composition according to claim 1, wherein the amount of the phenyl ester compound represented by the general formula (1) is 1 to 30 mol% of the composition. 【請求項５】 該フェリ誘電相の高温側の転移温度が40
℃以上で、低温側の転移温度が 0℃以下であり、該フェ
リ誘電相よりも高温側にスメクチックＡ相を有する請求
項１記載のフェリ誘電性液晶組成物。5. The ferrielectric phase having a transition temperature on the high temperature side of 40.
The ferrielectric liquid crystal composition according to claim 1, wherein the transition temperature on the low temperature side is 0 ° C or lower at a temperature of not less than 0 ° C and the smectic A phase is on the higher temperature side than the ferrielectric phase. 【請求項６】 請求項１記載のフェリ誘電性液晶組成物
を、各画素毎に薄膜トランジスタあるいはダイオード等
の非線形能動素子を設置した基板間に狭持することを特
徴とするアクティブマトリクス液晶表示素子6. An active matrix liquid crystal display device, wherein the ferrielectric liquid crystal composition according to claim 1 is sandwiched between substrates on which a non-linear active element such as a thin film transistor or a diode is provided for each pixel. 【請求項７】 非線形能動素子を用いた液晶の電圧によ
る駆動を２つのフェリ誘電状態の共存状態、２つの強誘
電状態及びそれらの中間状態へのスイッチングにて行う
請求項６記載のアクテイ ブマトリックス液晶表示素子。7. The active matrix according to claim 6, wherein the driving of the liquid crystal by the voltage using the nonlinear active element is performed by switching to a coexistence state of two ferrielectric states, two ferroelectric states, and an intermediate state between them. Liquid crystal display element.
JP21188597A 1997-08-06 1997-08-06 Ferridielectric liquid crystal composition Pending JPH1150054A (en)

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WO2012128306A1 (en) * 2011-03-24 2012-09-27 富士フイルム株式会社 Liquid crystal orientation promoter, liquid crystal composition, polymer material, and film
JP2013173881A (en) * 2012-02-27 2013-09-05 Fujifilm Corp Compound, liquid crystalline composition, polymer material and film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005002164A (en) * 2003-06-10 2005-01-06 Dainippon Ink & Chem Inc Liquid crystal orientation accelerator, liquid crystal composition and optically anisotropic item
JP4506105B2 (en) * 2003-06-10 2010-07-21 Ｄｉｃ株式会社 Liquid crystal alignment accelerator, liquid crystal composition and optical anisotropic body
WO2012128306A1 (en) * 2011-03-24 2012-09-27 富士フイルム株式会社 Liquid crystal orientation promoter, liquid crystal composition, polymer material, and film
JP2012211306A (en) * 2011-03-24 2012-11-01 Fujifilm Corp Liquid crystal orientation promoter, liquid crystal composition, polymer material, and film
US9290697B2 (en) 2011-03-24 2016-03-22 Fujifilm Corporation Liquid crystal orientation promoter, liquid crystalline composition, macromolecular material and film
JP2013173881A (en) * 2012-02-27 2013-09-05 Fujifilm Corp Compound, liquid crystalline composition, polymer material and film
WO2013129121A1 (en) * 2012-02-27 2013-09-06 富士フイルム株式会社 Compound, liquid crystal composition, polymer material, and film
CN104136577A (en) * 2012-02-27 2014-11-05 富士胶片株式会社 Compound, liquid crystal composition, polymer material, and film
CN104136577B (en) * 2012-02-27 2016-08-24 富士胶片株式会社 Compound, liquid-crystal composition, macromolecular material and film
US9464232B2 (en) 2012-02-27 2016-10-11 Fujifilm Corporation Compound, liquid crystal composition, polymer material, and film

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