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JPH0959640A - Ferrielectric liquid crystal composition and liquid crystal display element - Google Patents

Ferrielectric liquid crystal composition and liquid crystal display element

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Publication number
JPH0959640A
JPH0959640A JP8133540A JP13354096A JPH0959640A JP H0959640 A JPH0959640 A JP H0959640A JP 8133540 A JP8133540 A JP 8133540A JP 13354096 A JP13354096 A JP 13354096A JP H0959640 A JPH0959640 A JP H0959640A
Authority
JP
Japan
Prior art keywords
liquid crystal
ferrielectric
crystal composition
phase
general formula
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
JP8133540A
Other languages
Japanese (ja)
Inventor
Masahiro Kino
正博 城野
Tomoyuki Yui
知之 油井
Hironori Motoyama
裕規 本山
Teruyo Tomiyama
照予 冨山
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 JP8133540A priority Critical patent/JPH0959640A/en
Publication of JPH0959640A publication Critical patent/JPH0959640A/en
Pending legal-status Critical Current

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  • Liquid Crystal Substances (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a novel ferrielectric liq. crystal compsn. which can be suitably used for AM drive. SOLUTION: This compsn. is prepd. by mixing a phenyl ester compd. represented by formula I (wherein (m) is an integer of 3-12; (n)is an integer of 1-11; X<1> and X<2> are each H or F provided at least one of them is H; and A is H or CH3 ) with a liq. crystal compd. having a ferrielectric phase and represented by formula II (wherein R 15 a 7-12C linear alkyl; Y<1> and Y<2> are each H or F provided at least one of them is H; and (s) and (t) are each an integer of 2-4).

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明は、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
されるフェリ誘電性液晶組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ferrielectric liquid crystal composition suitable for use in an active matrix type liquid crystal display element driven for each pixel.

【0002】[0002]

【従来の技術】液晶表示素子は、低電圧作動性、低消費
電力性、薄型表示が可能である事等により、現在までに
各種の小型表示素子に利用されてきた。しかし、昨今の
情報、OA関連機器分野、あるいは、テレビ分野への液
晶表示素子の応用、用途拡大に伴って、これまでのCR
T表示素子を上回る表示容量、表示品質を持つ高性能大
型液晶表示素子の要求が、急速に高まってきた。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。このような
要請に応える液晶表示方式(液晶駆動方式)として、現
在ネマチック液晶材料を用いる単純マトリックス駆動で
あるSTN液晶表示素子とアクテイブマトリックス駆動
であるTFT或いはMIM液晶表示素子がある。
2. Description of the Related Art Liquid crystal display devices have been used for various small display devices to date because of their low voltage operability, low power consumption, and thin display capability. However, with the recent information, the application of liquid crystal display elements to the OA related equipment field, or the television field, and the expansion of applications, the CR
The demand for a high-performance large-sized liquid crystal display device having a display capacity and display quality higher than that of a T display device has been rapidly increasing. That is, a large display capacity, full-color display, wide viewing angle, high-speed response, high contrast, etc. are required. Liquid crystal display systems (liquid crystal drive systems) that meet such demands include STN liquid crystal display devices that are currently driven by a simple matrix using a nematic liquid crystal material and TFT or MIM liquid crystal display devices that are driven by an active matrix.

【0003】これらの表示方式に於いて、最近応答速度
の遅さ、視野角の狭さが大きな問題になっている。すな
わち、応答速度が数十msオーダーであり動画表示を行
うとき良好な画質が得られない。また、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
角が必然的に狭くなる。特に階調表示を行うと、視野角
が急激に狭くなり、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。この問題の
改善は現在強力に進められているが、ネマチック液晶を
用いている限りは根本的な解決は難しい。従って、CR
Tと同等以上の表示品質は得られていないのが現状であ
る。
In these display systems, a slow response speed and a narrow viewing angle have recently become serious problems. That is, the response speed is on the order of several tens of ms, and good image quality cannot be obtained when displaying a moving image. In addition, since the display is performed by using the twisted state (twist alignment) of the liquid crystal molecules, the viewing angle is necessarily narrowed. Especially when gradation display is performed, the viewing angle sharply narrows, and depending on the viewing angle,
The contrast ratio, color, etc. will change. Although this problem is being strongly improved at present, the fundamental solution is difficult as long as nematic liquid crystal is used. Therefore, CR
At present, the display quality equal to or higher than T is not obtained.

【0004】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、
特開平5-150257、特開平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。 (1) 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;Keiichi NITO et.al,SID'94 、Preprin
t,p48)であり、高度な実用化技術の開発が必要とされ
る。
In order to solve these problems, an AM adopting a ferroelectric liquid crystal or an antiferroelectric liquid crystal instead of the TN liquid crystal.
Panel proposals have also been made in recent years (Japanese Unexamined Patent Publication No.
JP-A-5-150257, JP-A-6-95080, etc.), and these liquid crystals also have the following problems, and there are currently many barriers to practical use. (1) Ferroelectric liquid crystals have spontaneous polarization, but since spontaneous polarization is always present, image sticking easily occurs and driving is difficult. Further, since the ferroelectric liquid crystal can display only binary images of black and white when displaying in the surface stabilization mode,
Gradation display is extremely difficult. Special consideration is required when performing gradation display (for example, ferroelectric liquid crystal device using monostable; Keiichi NITO et.al, SID'94, Preprin
t, p48), which requires the development of advanced practical technology.

【0005】(2) 反強誘電性液晶は、永久自発分極が存
在しないため上記(1) 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10
V以下で駆動する液晶材料が必要であるが、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。
(2) Since the antiferroelectric liquid crystal has no permanent spontaneous polarization, the problem of image sticking described in (1) above is avoided. In AM drive, at least 10
A liquid crystal material that can be driven at V or lower is required, but an antiferroelectric liquid crystal generally has a large threshold voltage and 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.

【0006】この問題点を解決できるAM駆動に適した
新しい材料としてフェリ誘電相を有する液晶化合物が考
えられる。フェリ誘電相(=SCγ* )を有する液晶化合物
は、1989年、4-(4−オクチルオキシフェニル)安息香酸
-4-(1-メチルヘプチロキシカルボニル)フェニル (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.L131-13
7 )。
A liquid crystal compound having a ferrielectric phase is considered as a new material suitable for AM driving that can solve this problem. A liquid crystal compound having a ferrielectric phase (= SCγ *) was developed in 1989 by 4- (4-octyloxyphenyl) benzoic acid.
-4- (1-methylheptyloxycarbonyl) phenyl (abbreviation
First discovered in MHPOBC (Japanese Journal
of Applied Physics, Vol.29, No.1, 1990, pp.L131-13
7).

【0007】MHPOBCは式: C8H17-O-Ph-Ph-COO-Ph-COO
-C*H(CH3)C6H13 (式中のPhは1,4-フェニレン基、C*は不斉炭素、アルキ
ル基は直鎖アルキル基)で表され、その相系列は Cr(30)SIA*(65)SCA*(118) SCγ*(119)SC*(121)SCα*(12
2)SA(147)I (但し、Crは結晶相、SIA*はカイラルスメクチックIA
相、SCA*はカイラルスメクチックCA相(反強誘電相)、
SCγ* はカイラルスメクチックCγ相(フェリ誘電
相)、SC* はカイラルスメクチックC相(強誘電相)、
SCα* はカイラルスメクチックCα相、SAはスメクチッ
クA相、I は等方相、括弧内は相転移温度 (℃)を示
す。)
MHPOBC has the formula: C 8 H 17 -O-Ph-Ph-COO-Ph-COO
-C * H (CH 3) C 6 H 13 (Ph in the formula 1,4-phenylene group, C * is an asymmetric carbon, the alkyl group is a straight chain alkyl group) is represented by, the phase sequence is Cr ( 30) SIA * (65) SCA * (118) SCγ * (119) SC * (121) SCα * (12
2) SA (147) I (where Cr is the crystalline phase, SIA * is the chiral smectic IA
Phase, SCA * is the chiral smectic CA phase (antiferroelectric phase),
SCγ * is the chiral smectic Cγ phase (ferrielectric phase), SC * is the chiral smectic C phase (ferroelectric phase),
SCα * indicates a chiral smectic Cα phase, SA indicates a smectic A phase, I indicates an isotropic phase, and parentheses indicate a phase transition temperature (° C). )

【0008】フェリ誘電性相における液晶の状態を説明
するために図1にフェリ誘電相における分子配列状態の
一例を、図2にフェリ誘電相の三角波に対する光学応答
の一例を示した。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、共存していると考え
られる。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 the state of the liquid crystal in the ferrielectric phase, FIG. 1 shows an example of the state of molecular alignment in the ferrielectric phase, and FIG. 2 shows an example of the optical response of the ferrielectric phase to a triangular wave. In the ferrielectric phase, the molecular arrangement of FI (+) (when the applied voltage is positive) or FI (-) (when the applied voltage is negative) in Fig. 1 is used. In the absence of electric field, FI
Since (+) and FI (-) are equivalent, they are considered to coexist. 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 the state where the transmitted light intensity is 0 when the voltage is 0 in FIG.

【0009】また、 FI(+)及び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、フェリ誘電相で
は、反強誘電相と同様に強誘電相に見られる焼き付き現
象から逃れられる。
Further, FI (+) and FI (-) each have spontaneous polarization, as is clear from the molecular arrangement state, but in these coexisting states, the spontaneous polarizations cancel each other out, so the average spontaneous polarization is zero. Becomes For this reason, in the ferrielectric phase, like the antiferroelectric phase, it is possible to escape from the burn-in phenomenon that occurs in the ferroelectric phase.

【0010】フェリ誘電相に電場を印加していくと、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(+)又はFI
(-) と考えられる。なお、この場合、図2において、電
圧0Vと4Vとの間で連続的な透過光強度の変化ではな
く、階段状の透過光強度の変化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(+) 又は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
では上記の中間的な状態が必ず観測される液晶相をフェ
リ誘電相と、該相が最も広い液晶をフェリ誘電性液晶或
いはフェリ誘電性液晶組成物と呼ぶ。
When an electric field is applied to the ferrielectric phase, a region having an extinction position at a voltage lower than that at which the ferroelectric state is reached.
(Domain) appears. 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 FI (+) or FI
(-) it is conceivable that. In this case, in FIG. 2, not a continuous change in transmitted light intensity between voltages 0 V and 4 V, but a stepwise change in transmitted light intensity should be observed. However, continuous transmitted light intensity was observed in FIG. This is probably because the threshold voltage from FI (+) to FO (+) or from FI (-) to FO (-) is not clear. In the present invention, a liquid crystal phase in which the above intermediate state is always observed is called a ferri-dielectric phase, and a liquid crystal having the widest phase is called a ferri-dielectric liquid crystal or a ferri-dielectric liquid crystal composition.

【0011】さらに印加電圧を高くすると、電場の向き
に応じて安定な状態である強誘電相FO(+)又は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(+)又はFO(-)
である。この強誘電状態 FO(+)又はFO(-) では、フェリ
誘電状態 FI(+)又は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(+)及びFO(-) を明として使用できる。
When the applied voltage is further increased, the ferroelectric phase FO (+) or FO (-), which is in a stable state, undergoes a phase transition depending on the direction of the electric field. That is, FO (+) or FO (-) is the one in which the transmitted light intensity is saturated (the left and right flat portions) in FIG.
It is. It can be seen from FIG. 1 that in this ferroelectric state FO (+) or FO (-), a larger spontaneous polarization is developed than in the ferrielectric state FI (+) or FI (-). As described above, in the ferrielectric phase, the coexistence state of FI (+) and FI (-) is dark and the ferroelectric state is
FO (+) and FO (-) can be used as light.

【0012】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、フェリ誘電相では FI
(+)、FO(+) 、FO(-) 及び FI(-)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。しかしなが
ら、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。
In the conventional ferroelectric liquid crystal, switching between FO (+) and FO (-) was performed, whereas in the ferrielectric phase, FI was used.
It has a major feature of switching between four states of (+), FO (+), FO (-) and FI (-). However, all of the display principles utilize the birefringence of liquid crystal, and it is possible to manufacture a display element having a small viewing angle dependency.

【0013】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、すなわち、ヒステリシスの幅が狭い傾向
が強く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、フェリ誘電相の電圧による変
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、反強誘電相に比べて小さい傾
向を有し、この点からもフェリ誘電相はAM駆動に適し
た液晶相といえる。
As shown in FIG. 2, the ferrielectric phase generally has a small difference between the voltage changing from the ferrielectric state to the ferroelectric state and the voltage changing from the ferroelectric state to the ferrielectric state. The hysteresis width has a strong tendency to be narrow and has a property suitable for AM driving and gradation display in AM driving. In addition, the threshold voltage, which is the voltage that changes from the ferrielectric state to the ferroelectric state when the ferrielectric phase changes with voltage, tends to be smaller than that in the antiferroelectric phase. It can be said that the dielectric phase is a liquid crystal phase suitable for AM driving.

【0014】[0014]

【発明が解決しようとする課題】しかしながら、現在ま
で合成されたフェリ誘電相を有する液晶化合物、フェリ
誘電性液晶の数はきわめて少ない。更に、従来知られて
いたフェリ誘電相を有する液晶化合物、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、フェリ
誘電相の温度範囲、ヒステリシス、応答速度、しきい値
電圧の面で満足すべきものは見いだされていない。一般
にAM駆動素子における駆動電圧は低く、少なくとも10
V以下の印加電圧で高速に駆動できることが必要であ
る。この面から見た場合、従来得られていたフェリ誘電
性液晶単体は、10V以下の駆動電圧での応答性に問題が
あり、この面での改良が強く望まれている。本発明は、
この観点に立ってなされたものであり、AM駆動に好適
に使用できる低電圧駆動性に優れた、新しいフェリ誘電
性液晶組成物を与えるものである。
However, the number of liquid crystal compounds having a ferri-dielectric phase and ferri-dielectric liquid crystals synthesized so far is extremely small. Further, the liquid crystal compound having a ferri-dielectric phase and the ferri-dielectric liquid crystal simple substance known in the related art are considered to have a temperature range of the ferri-dielectric phase, a hysteresis, a response speed, and a threshold voltage in consideration of application to an AM driving element. Nothing satisfactory has been found. Generally, the driving voltage in the AM driving element is low, and at least 10
It is necessary to be able to drive at high speed with an applied voltage of V or less. From this point of view, the conventionally obtained ferrielectric liquid crystal alone has a problem in response at a drive voltage of 10 V or less, and improvement in this aspect is strongly desired. The present invention
The present invention has been made from this viewpoint, and provides a new ferrielectric liquid crystal composition excellent in low-voltage drivability that can be suitably used for AM driving.

【0015】[0015]

【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) で表されるフェニルエステル化合物を、下
記一般式(2) で表されるフェリ誘電相を有する液晶化合
物に混合してなるフェリ誘電性液晶組成物。
Means for Solving the Problems That is, according to the present invention, a phenyl ester compound represented by the following general formula (1) is mixed with a liquid crystal compound having a ferrielectric phase represented by the following general formula (2). A ferrielectric liquid crystal composition comprising:

【0016】[0016]

【化2】 (式(1) 中のmは 3〜12の整数、nは 1〜11の整数、
X1, X2はH又はいずれか一方がF原子、AはH又は-CH3
基である。式(2) 中のRは炭素数 7〜12の直鎖アルキル
基、Y1, Y2はH又はいずれか一方がF原子、s は 2〜4
の整数、t は 2〜4の整数である。)
Embedded image (M in the formula (1) is an integer of 3 to 12, n is an integer of 1 to 11,
X 1 and X 2 are H or one of them is an F atom, A is H or --CH 3
Group. In formula (2), R is a straight-chain alkyl group having 7 to 12 carbon atoms, Y 1 and Y 2 are H or one of them is an F atom, and s is 2 to 4
, T is an integer from 2 to 4. )

【0017】本発明の一般式(1) で示されるフェニルエ
ステル化合物としては、AがH原子のとき、液晶相を有
しないことが望ましい。また、Aが CH3のときには、n
は 4〜8 が好ましい。
The phenyl ester compound represented by the general formula (1) of the present invention preferably has no liquid crystal phase when A is H atom. When A is CH 3 , n
Is preferably 4-8.

【0018】本発明のフェリ誘電性液晶組成物において
は、一般式(3) のsが4のとき、tが2〜4 の整数で、
Rの炭素数が 7〜12である液晶化合物、sが3のとき、
tが2〜4 の整数で、Rの炭素数が 9〜12である液晶化
合物、sが2のとき、tが2で、Rの炭素数が8、9で
ある液晶化合物が、フェリ誘電相を有するものとして好
ましい。一般式(1) で表されるフェニルエステル化合物
の混合量がフェリ誘電性液晶組成物の 1〜40モル%の範
囲、好ましくは10〜30モル%の範囲であり、特に少なく
とも温度0℃〜40℃の範囲、より好適には温度0℃〜50
℃の範囲でフェリ誘電相を示すフェリ誘電性液晶組成物
が好ましい。
In the ferrielectric liquid crystal composition of the present invention, when s in the general formula (3) is 4, t is an integer of 2 to 4,
A liquid crystal compound in which R has 7 to 12 carbon atoms, when s is 3,
A liquid crystal compound in which t is an integer of 2 to 4 and R has 9 to 12 carbon atoms, and when s is 2, a liquid crystal compound in which t is 2 and R has 8 and 9 carbon atoms is a ferrielectric phase Is preferred. The mixing amount of the phenyl ester compound represented by the general formula (1) is in the range of 1 to 40 mol%, preferably 10 to 30 mol% of the ferrielectric liquid crystal composition, and particularly at a temperature of 0 ° C. to 40 ° C. ℃ range, more preferably 0 ℃ ~ 50
A ferrielectric liquid crystal composition exhibiting a ferrielectric phase in the range of ° C is preferred.

【0019】また、該フェリ誘電性液晶組成物のフェリ
誘電相から強誘電相へ転移するときのしきい値電圧が 5
V/μm以下であること、特に 3V/μm以下であることが
好ましい。そして、本発明のフェリ誘電性液晶組成物
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挟持して、広い温
度範囲で好適に駆動できるアクティブマトリックス液晶
表示素子とでき、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。
Further, the threshold voltage at the time of transition from the ferrielectric phase to the ferroelectric phase of the ferrielectric liquid crystal composition is 5
It is preferably V / μm or less, and particularly preferably 3 V / μm or less. Further, the ferrielectric liquid crystal composition of the present invention can be sandwiched between substrates provided with non-linear active elements such as thin film transistors or diodes for each pixel to form an active matrix liquid crystal display element that can be suitably driven in a wide temperature range. , Driving a liquid crystal with a non-linear active element by two ferrielectric states and two ferroelectric states,
And switching to the intermediate state.

【0020】本発明において用いられる一般式(2) で示
されるフェリ誘電相を有する液晶化合物は、既に本発明
者らが示した方法によって簡便に製造することができる
(特開平4-198155号)。その概略は次の通りである。 (1) AcO-Ph(F)-COOH + SOCl2 → AcO-Ph(F)-COCl (2) (1) + R*OH → AcO-Ph(F)-COOR* (3) (2) + (PhCH2NH2) → HO-Ph(F)-COOR* (4) R'O-Ph-Ph-COOH + SOCl2 → R'O-Ph-Ph-COCl (5) (3) + (4) → 液晶化合物 式中のAcは、CH3CO-基、Phは1,4-フェニレン基、Ph(F)
は2-又は3-位にF置換していてもよい1,4-フェニレン
基、R*は光学活性アルコール残基、R'は直鎖アルキル基
をそれぞれ示す。
The liquid crystal compound having a ferrielectric phase represented by the general formula (2) used in the present invention can be easily produced by the method already shown by the present inventors (JP-A-4-198155). . The outline is as follows. (1) AcO-Ph (F) -COOH + SOCl 2 → AcO-Ph (F) -COCl (2) (1) + R * OH → AcO-Ph (F) -COOR * (3) (2) + (PhCH 2 NH 2 ) → HO-Ph (F) -COOR * (4) R'O-Ph-Ph-COOH + SOCl 2 → R'O-Ph-Ph-COCl (5) (3) + (4 ) → liquid crystal compound In the formula, Ac is a CH 3 CO- group, Ph is a 1,4-phenylene group, Ph (F)
Represents a 1,4-phenylene group which may be F-substituted at the 2- or 3-position, R * represents an optically active alcohol residue, and R ′ represents a linear alkyl group.

【0021】上記製造法について、以下に簡単に説明す
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
塩素化物(1) と光学活性アルコールとの反応によるエス
テル化である。(3) はエステル(2) の脱アセチル化であ
る。(4) はアルキルオキシビフェニルカルボン酸の塩素
化反応である。(5) はフェノール(3) と塩素化物(4) と
の反応による液晶の生成である。
The above manufacturing method will be briefly described below. (1) is a chlorination reaction of fluorine-substituted or unsubstituted p-acetoxybenzoic acid with thionyl chloride. (2) is esterification by reaction of the chlorinated compound (1) with an optically active alcohol. (3) is the deacetylation of ester (2). (4) is a chlorination reaction of alkyloxybiphenylcarboxylic acid. (5) is the formation of liquid crystal by the reaction of phenol (3) and chlorinated compound (4).

【0022】又、本発明で用いられるフェニルエステル
化合物は、本発明者らが既に明らかにした方法によって
容易に製造できる(特願平7-967497号)。その概略は次
の通りである。 (a) HO-Ph(X)-COOH + RCOCl → RCOO-Ph(X)-COOH (b) (a) + SOCl2 → RCOO-Ph(X)-COCl (c) (b) + ROH → RCOO-Ph(X)-COO-R 上記の式において、Phは1,4-フェニレン基、Ph(X) は2-
または3-位にF置換していてもよい1,4-フェニレン基、
Rは、不斉炭素を有していてもよい直鎖アルキル基を示
す。
Further, the phenyl ester compound used in the present invention can be easily produced by the method already disclosed by the present inventors (Japanese Patent Application No. 7-967497). The outline is as follows. (a) HO-Ph (X) -COOH + RCOCl → RCOO-Ph (X) -COOH (b) (a) + SOCl 2 → RCOO-Ph (X) -COCl (c) (b) + ROH → RCOO -Ph (X) -COO-R In the above formula, Ph is 1,4-phenylene group and Ph (X) is 2-
Or a 1,4-phenylene group which may be F-substituted at the 3-position,
R represents a linear alkyl group which may have asymmetric carbon.

【0023】上記製造法を簡単に説明すると次の通りで
ある。(a) はp-ヒドロキシ安息香酸と酸クロライドとの
反応によるエステルの生成である。(b) は (a)の塩化チ
オニルによる塩素化である。(c) は塩素化物(b) と直鎖
アルコール又は光学活性な2-アルカノール類との反応に
よるエステル化による目的物の生成である。
The above manufacturing method will be briefly described as follows. (a) is the formation of an ester by the reaction of p-hydroxybenzoic acid with an acid chloride. (b) is the chlorination of (a) with thionyl chloride. (c) is the formation of the desired product by esterification by reaction of the chlorinated compound (b) with a linear alcohol or an optically active 2-alkanol.

【0024】[0024]

【発明の効果】本発明は、新規なフェニルエステル化合
物とそれを混合してなる反強誘電性液晶組成物またはフ
ェリ誘電性液晶組成物を提供する事ができるものであ
る。そして、本発明により提供された新規な反強誘電性
液晶組成物は、広い温度範囲で反強誘電相を有し、かつ
高速応答を示し、そのため表示品質の高い反強誘電性液
晶表示素子を実現できる。また、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、広い温度範囲でフ
ェリ誘電相を有し、かつ高速応答を示し、ヒステリシス
がなく、そのため表示品質の高いアクティブマトリック
ス液晶表示素子を実現できる。
INDUSTRIAL APPLICABILITY The present invention can provide an antiferroelectric liquid crystal composition or a ferrielectric liquid crystal composition obtained by mixing a novel phenyl ester compound with it. Further, the novel antiferroelectric liquid crystal composition provided by the present invention has an antiferroelectric phase in a wide temperature range and exhibits a high-speed response, and therefore an antiferroelectric liquid crystal display device having high display quality can be obtained. realizable. In addition, the novel ferrielectric liquid crystal composition provided by the present invention has a ferrielectric phase in a wide temperature range, exhibits a high-speed response, and has no hysteresis, so that an active matrix liquid crystal display device having high display quality can be obtained. realizable.

【0025】[0025]

【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 下記の化学構造式で示されるフェリ誘電性液晶(2A)に、
下記の化学構造式で示されるフェニルエステル化合物(1
A)を15モル%混合し、液晶組成物を調整した。 1A : C3H7-COO-Ph(2F)-COO-CH2CH2CH3 (式(1) ; m=3, A=H, X1=H, X2=F, n=2) 2A : C9H19-O-Ph-Ph-COO-Ph(3F)-COO-C*H(CF3)(CH2)4OC2H5 (式(3) ; R=C9H19, Y1=H, Y2=F, s=4, t=2)
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. Example 1 In a ferrielectric liquid crystal (2A) represented by the following chemical structural formula,
Phenyl ester compound (1
15 mol% of A) was mixed to prepare a liquid crystal composition. 1A: C 3 H 7 -COO-Ph (2F) -COO-CH 2 CH 2 CH 3 (Formula (1); m = 3, A = H, X 1 = H, X 2 = F, n = 2) 2A: C 9 H 19 -O-Ph-Ph-COO-Ph (3F) -COO-C * H (CF 3 ) (CH 2 ) 4 OC 2 H 5 (Formula (3); R = C 9 H 19 , Y 1 = H, Y 2 = F, s = 4, t = 2)

【0026】液晶相の同定は、テクスチャー観察、コノ
スコープ像の観察、DSC(示差走差熱量計)の測定および
層法線方向と強誘電状態の光軸方向の間に消光位を持つ
領域(ドメイン)の存在の確認、即ち中間状態(FI(±))
の観測により行なった。コノスコープ像の観察はフェリ
誘電相の観察に有力な手段である。コノスコープ像の観
察は文献に従った(J. Appl. Phys. 31. 793(1992))。通
常の平行配向セルによるテクスチャー観察、コノスコー
プ観察及びDSC測定、及び中間状態の観測即ち層法線
方向と強誘電状態の光軸方向の間に消光位を持つ領域
(ドメイン)の存在が認められたことなどにより、本実
施例の液晶組成物の相系列を決定した。結果を表1に示
した。
The liquid crystal phase is identified by texture observation, conoscopic image observation, DSC (differential differential scanning calorimeter) measurement, and a region having an extinction position between the layer normal direction and the optical axis direction of the ferroelectric state ( Confirmation of existence of domain), that is, intermediate state (FI (±))
Was observed. Observation of a conoscopic image is a powerful means for observing a ferrielectric phase. Observation of the conoscopic image was according to the literature (J. Appl. Phys. 31. 793 (1992)). Ordinary parallel alignment cell texture observation, conoscopic observation and DSC measurement, and intermediate state observation, that is, the existence of a region (domain) having an extinction position between the layer normal direction and the ferroelectric state optical axis direction is recognized. Based on the above, the phase series of the liquid crystal composition of this example was determined. The results are shown in Table 1.

【0027】次に得られたフェリ誘電性液晶の光学応答
を調べた。セルは以下の手順で作製した。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−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。
Next, the optical response of the obtained ferrielectric liquid crystal was examined. The cell was produced by the following procedure. Insulating film (SiO 2 ;
A glass substrate with an ITO electrode (thickness: 50 nm) was coated with polyimide (thickness: about 80 nm), and only one of the pair of glass substrates was rubbed. A pair of glass substrates were bonded together via a spacer having a particle diameter 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 was in an isotropic phase, and the liquid crystal was injected into the test cell by a capillary phenomenon. Thereafter, the liquid crystal was gradually cooled at a rate of 1 ° C./min to parallel align the liquid crystal.

【0028】次に、30℃においてテストセルに±10V,
50mHz の三角波電圧を印加し駆動を行い、透過光変化を
調べた。透過光強度の最低を 0%、透過光強度の最高を
100%として、フェリ誘電相から強誘電相へ相転移する
ときに透過光強度が90%となる電圧をしきい値電圧I 、
強誘電相からフェリ誘電相へ相転移するときに透過光強
度が90%となる電圧をしきい値電圧IIと定義してしきい
値電圧を測定した。また、8V, 周波数10Hzのパルス電圧
を印加して透過光強度が90%変化するに要する時間を応
答時間と定義して応答時間を測定した。結果を表2に示
した。
Next, at 30 ° C., ± 10 V was applied to the test cell,
A triangular wave voltage of 50 mHz was applied and driving was performed, and changes in transmitted light were investigated. The minimum transmitted light intensity is 0% and the maximum transmitted light intensity is
Assuming 100%, the threshold voltage I
The threshold voltage was measured with the threshold voltage II defined as the voltage at which the transmitted light intensity becomes 90% when the phase transition from the ferroelectric phase to the ferrielectric phase occurs. The response time was measured by defining the time required for a 90% change in transmitted light intensity when a pulse voltage of 8 V and a frequency of 10 Hz was applied. The results are shown in Table 2.

【0029】実施例2〜5 実施例1で用いたフェリ誘電性液晶(2A)に、下記の化学
構造式で示されるフェニルエステル化合物(1B, 1C, 1D,
1E)をそれぞれ15モル%混合し、液晶組成物を調整し
た。 1B : C5H11-COO-Ph(2F)-COO-CH2(CH2)5CH3 (式(1) ; m=5, A=H, X1=H, X2=F, n=6) 1C : C7H15-COO-Ph(2F)-COO-CH2(CH2)7CH3 (式(1) ; m=7, A=H, X1=H, X2=F, n=8) 1D : C5H11-COO-Ph(2F)-COO-CH2(CH2)3CH3 (式(1) ; m=5, A=H, X1=H, X2=F, n=4) 1E : C7H15-COO-Ph(2F)-COO-CH2(CH2)3CH3 (式(1) ; m=7, A=H, X1=H, X2=F, n=4)
Examples 2 to 5 The ferrielectric liquid crystal (2A) used in Example 1 was prepared by adding the phenyl ester compound (1B, 1C, 1D,
1E) was mixed in an amount of 15 mol% to prepare a liquid crystal composition. 1B: C 5 H 11 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 5 CH 3 (equation (1); m = 5, A = H, X 1 = H, X 2 = F, n = 6) 1C: C 7 H 15 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 7 CH 3 (Formula (1); m = 7, A = H, X 1 = H, X 2 = F, n = 8) 1D: C 5 H 11 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 3 CH 3 (Formula (1); m = 5, A = H, X 1 = H, X 2 = F, n = 4) 1E: C 7 H 15 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 3 CH 3 (Formula (1); m = 7, A = H, X 1 = H, X 2 = F, n = 4)

【0030】実施例6 実施例1で用いたフェリ誘電性液晶(2A)に、下記の化学
構造式で示されるフェニルエステル化合物(1G)を20モル
%混合し、液晶組成物を調整した。 1F : C9H19-COO-Ph(2F)-COO-CH2(CH2)5CH3 (式(1) ; m=9, A=H, X1=H, X2=F, n=6) 実施例2〜6の組成物について、液晶相の同定、その他
の物性測定を実施例1と同様にした結果を表1、2に示
した。
Example 6 A liquid crystal composition was prepared by mixing 20 mol% of the phenyl ester compound (1G) represented by the following chemical structural formula with the ferrielectric liquid crystal (2A) used in Example 1. 1F: C 9 H 19 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 5 CH 3 (Formula (1); m = 9, A = H, X 1 = H, X 2 = F, n = 6) With respect to the compositions of Examples 2 to 6, the results of making the identification of the liquid crystal phase and the other physical property measurements the same as in Example 1 are shown in Tables 1 and 2.

【0031】[0031]

【表1】 相 系 列 成分 モル比 液晶 2A Cr(*1)SCγ*(89)SA(91)I 実施例1 Cr(*1)SCγ*(73)SA(85)I 2A/1A =85/15 〃 2 Cr(*1)SCγ*(70)SA(79)I 2A/1B =85/15 〃 3 Cr(*1)SCγ*(70)SA(78)I 2A/1C =85/15 〃 4 Cr(*1)SCγ*(72)SA(81)I 2A/1D =85/15 〃 5 Cr(*1)SCγ*(71)SA(80)I 2A/1E =85/15 〃 6 Cr(*1)SCγ*(64)SA(73)I 2A/1F =80/20 Crは結晶相、SCγ* はフェリ誘電相、SAはスメクチック
A相、Iは等方相を示し、また、相系列中の()内の数
字は転移温度(℃)を示す。なお、(*1)は、DSC(下限温
度 -50℃) によって、融点が確認されなかったことを示
す。
[Table 1] Phase series Component Molar ratio Liquid crystal 2A Cr (* 1) SCγ * (89) SA (91) I Example 1 Cr (* 1) SCγ * (73) SA (85) I 2A / 1A = 85 / 15〃 2 Cr (* 1) SCγ * (70) SA (79) I 2A / 1B = 85/15 〃 3 Cr (* 1) SCγ * (70) SA (78) I 2A / 1C = 85/15 〃 4 Cr (* 1) SCγ * (72) SA (81) I 2A / 1D = 85/15 〃 5 Cr (* 1) SCγ * (71) SA (80) I 2A / 1E = 85/15 〃 6 Cr (* 1) SCγ * (64) SA (73) I 2A / 1F = 80/20 Cr is crystalline phase, SCγ * is ferrielectric phase, SA is smectic A phase, I is isotropic phase, and The numbers in parentheses in the phase series indicate the transition temperature (° C). In addition, (* 1) indicates that the melting point was not confirmed by DSC (minimum temperature -50 ° C).

【0032】[0032]

【表2】 しきい値電圧 (V/μm) 応答時間 測定温度 I II (μ秒) (℃) 液晶 3A 1.5 1.4 88 30 実施例1 1.2 1.2 70 30 〃 2 1.4 1.4 70 30 〃 3 1.4 1.4 71 30 〃 4 1.4 1.4 31 30 〃 5 1.4 1.4 80 30 〃 6 1.0 1.0 30 30 [Table 2] Threshold voltage (V / μm) Response time Measurement temperature I II (μsec) (℃) Liquid crystal 3A 1.5 1.4 88 30 Example 1 1.2 1.2 70 30 〃 2 1.4 1.4 70 30 〃 3 1.4 1.4 71 30 〃 4 1.4 1.4 31 30 〃 5 1.4 1.4 80 30 〃 6 1.0 1.0 30 30

【0033】実施例7 下記の化学構造式で示されるフェリ誘電性液晶(2B)に、
上記の実施例5で得たフェニルエステル化合物(1C)を20
モル%混合し、液晶組成物を調整した。 2B : C9H19-O-Ph-Ph-COO-Ph(3F)-COO-C*H(CF3)(CH2)3OC2H5 (式(2) ; R=C9H19, Y1=H, Y2=F, s=3, t=2) 液晶相の同定、その他の物性測定を実施例1と同様にし
た結果を表3、4に示した。
Example 7 A ferrielectric liquid crystal (2B) represented by the following chemical structural formula was added:
The phenyl ester compound (1C) obtained in Example 5 above was used in 20
A mol% was mixed to prepare a liquid crystal composition. 2B: C 9 H 19 -O-Ph-Ph-COO-Ph (3F) -COO-C * H (CF 3 ) (CH 2 ) 3 OC 2 H 5 (Formula (2); R = C 9 H 19 , Y 1 = H, Y 2 = F, s = 3, t = 2) The results of identification of the liquid crystal phase and other physical property measurements performed in the same manner as in Example 1 are shown in Tables 3 and 4.

【0034】実施例8、9および参考例1 実施例7で用いたフェリ誘電性液晶(2B)に、下記の化学
構造式で示されるフェニルエステル化合物(1G, 1H, 1I)
をそれぞれ25モル%混合し、液晶組成物を調整した。 1G : C9H19-COO-Ph(2F)-COO-CH2(CH2)7CH3 (式(1) ; m=9, A=H, X1=H, X2=F, n=8) 1H : C10H21-COO-Ph(2F)-COO-CH2(CH2)7CH3 (式(1) ; m=10, A=H, X1=H, X2=F, n=8) 1I : C10H21-COO-Ph(2F)-COO-CH2(CH2)9CH3 (式(1) ; m=10, A=H, X1=H, X2=F, n=10) 液晶相の同定、その他の物性測定を実施例1と同様にし
た結果を表3、4に示した。参考例1においては、スメ
クチックA相が存在しなかった。
Examples 8 and 9 and Reference Example 1 In the ferrielectric liquid crystal (2B) used in Example 7, a phenyl ester compound (1G, 1H, 1I) represented by the following chemical structural formula was added.
Were mixed in an amount of 25 mol% to prepare a liquid crystal composition. 1G: C 9 H 19 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 7 CH 3 (Formula (1); m = 9, A = H, X 1 = H, X 2 = F, n = 8) 1H: C 10 H 21 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 7 CH 3 (Formula (1); m = 10, A = H, X 1 = H, X 2 = F, n = 8) 1I: C 10 H 21 -COO-Ph (2F) -COO-CH 2 (CH 2 ) 9 CH 3 (Formula (1); m = 10, A = H, X 1 = H, X 2 = F, n = 10) Tables 3 and 4 show the results of identification of the liquid crystal phase and other physical property measurements performed in the same manner as in Example 1. In Reference Example 1, the smectic A phase was not present.

【0035】[0035]

【表3】 相 系 列 成分 モル比 液晶 2B Cr(40)SCγ*(SA(103)I 実施例7 Cr(*1)SCγ*(72)SA(83)I 2B/1C =80/20 〃 8 Cr(*1)SCγ*(64)SA(75)I 2B/1G =75/25 〃 9 Cr(*1)SCγ*(55)SA(79)I 2B/1H =75/25 参考例1 Cr(*1)SCγ*(50)I 2B/1I =75/25 表中の記載は表5と同じである。[Table 3] Phase series component Molar ratio Liquid crystal 2B Cr (40) SCγ * (SA (103) I Example 7 Cr (* 1) SCγ * (72) SA (83) I 2B / 1C = 80 / 20〃 8 Cr (* 1) SCγ * (64) SA (75) I 2B / 1G = 75/25 〃 9 Cr (* 1) SCγ * (55) SA (79) I 2B / 1H = 75/25 Reference Example 1 Cr (* 1) SCγ * (50) I 2B / 1I = 75/25 The descriptions in the table are the same as those in Table 5.

【0036】[0036]

【表4】 しきい値電圧 (V/μm) 応答時間 測定温度 I II (μ秒) (℃) 液晶 3B 1.3 1.2 101 30 実施例7 1.1 1.0 58 30 〃 8 1.1 1.1 23 30 〃 9 1.4 1.4 61 30 参考例1 1.3 1.3 54 30 [Table 4] Threshold voltage (V / μm) Response time Measurement temperature I II (μsec) (℃) Liquid crystal 3B 1.3 1.2 101 30 Example 7 1.1 1.0 58 30 〃 8 1.1 1.1 23 30 〃 9 1.4 1.4 61 30 Reference example 1 1.3 1.3 54 30

【0037】実施例10、11 実施例1で用いたフェリ誘電性液晶(2A)に、下記の化学
構造式で示されるフェニルエステル化合物(1J, 1K)を20
モル%混合し、液晶組成物を調整した。 1J : C9H19-COO-Ph-COO-CH2(CH2)7CH3 (式(1) ; m=9, A=H, X1=H, X2=H, n=8) 1K : C5H11-COO-Ph-COO-CH2(CH2)3CH3 (式(1) ; m=5, A=H, X1=H, X2=H, n=4)
Examples 10 and 11 To the ferrielectric liquid crystal (2A) used in Example 1, the phenyl ester compound (1J, 1K) represented by the following chemical structural formula was added.
A mol% was mixed to prepare a liquid crystal composition. 1J: C 9 H 19 -COO-Ph-COO-CH 2 (CH 2 ) 7 CH 3 (Formula (1); m = 9, A = H, X 1 = H, X 2 = H, n = 8) 1K: C 5 H 11 -COO-Ph-COO-CH 2 (CH 2 ) 3 CH 3 (Formula (1); m = 5, A = H, X 1 = H, X 2 = H, n = 4)

【0038】実施例11、12 次の化学構造式で表されるフェリ誘電性液晶(2C, 2D)
に、フェニルエステル化合物(E1)をそれぞれ20モル%混
合し、液晶組成物を調整した。 2C : C9H19-O-Ph-Ph-COO-Ph-COO-C*H(CF3)(CH2)4OC2H5 (式(2) ; R=C9H19, Y1=H, Y2=H, s=4, t=2) 2D : C8H17-O-Ph-Ph-COO-Ph(3F)-COO-C*H(CF3)(CH2)2OC2H5 (式(2) ; R=C8H17, Y1=H, Y2=F, s=2, t=2) 実施例10〜12で調製した液晶組成物について、液晶
相の同定、その他の物性測定を実施例1と同様にした結
果を表5、6に示した。
Examples 11 and 12 Ferrielectric liquid crystal (2C, 2D) represented by the following chemical structural formula
A phenyl ester compound (E1) was mixed with each of 20 mol% to prepare a liquid crystal composition. 2C: C 9 H 19 -O-Ph-Ph-COO-Ph-COO-C * H (CF 3 ) (CH 2 ) 4 OC 2 H 5 (Formula (2); R = C 9 H 19 ,, Y 1 = H, Y 2 = H, s = 4, t = 2) 2D: C 8 H 17 -O-Ph-Ph-COO-Ph (3F) -COO-C * H (CF 3 ) (CH 2 ) 2 OC 2 H 5 (Formula (2); R = C 8 H 17 , Y 1 = H, Y 2 = F, s = 2, t = 2) Liquid crystal compositions prepared in Examples 10 to 12 Table 5 and 6 show the results obtained by making the same as Example 1 with respect to the identification and the other physical property measurements.

【0039】[0039]

【表5】 相 系 列 成分 モル比 実施例10 Cr(*1)SCγ*(62)SA(72)I 2A/1J =80/20 〃 11 Cr(*1)SCγ*(55)SA(72)I 2A/1K =80/20 〃 12 Cr(*1)SCγ*(60)SA(80)I 2C/1F =80/20 〃 13 Cr(*1)SCγ*(70)SA(85)I 2D/1F =80/20 液晶 2C Cr(41)SCγ*(95)SA(103)I 液晶 2D Cr(58)SCγ*(104)SA(108)I 表中の記載は表1と同じである。[Table 5] Phase series Component Molar ratio Example 10 Cr (* 1) SCγ * (62) SA (72) I 2A / 1J = 80/20 〃 11 Cr (* 1) SCγ * (55) SA (72 ) I 2A / 1K = 80/20 〃 12 Cr (* 1) SCγ * (60) SA (80) I 2C / 1F = 80/20 〃 13 Cr (* 1) SCγ * (70) SA (85) I 2D / 1F = 80/20 Liquid crystal 2C Cr (41) SCγ * (95) SA (103) I Liquid crystal 2D Cr (58) SCγ * (104) SA (108) I The description in the table is the same as in Table 1. .

【0040】[0040]

【表6】 しきい値電圧 (V/μm) 応答時間 測定温度 I II (μ秒) (℃) 実施例10 1.4 1.1 50 30 〃 11 1.1 1.1 59 30 〃 12 1.1 1.1 48 30 〃 13 2.2 1.5 75 30 液晶 2C 1.8 1.7 165 50 液晶 2D 1.2 1.2 33 50 [Table 6] Threshold voltage (V / μm ) Response time Measurement temperature I II (μsec) (℃) Example 10 1.4 1.1 50 30 〃 11 1.1 1.1 59 30 〃 12 1.1 1.1 48 30 〃 13 2.2 1.5 75 30 LCD 2C 1.8 1.7 165 50 LCD 2D 1.2 1.2 33 50

【0041】実施例14 次の化学構造式で表されるフェリ誘電性液晶(2E)に、フ
ェニルエステル化合物(1F)を15モル%混合し、液晶組成
物を調整した。 2E : C9H19-O-Ph-Ph-COO-Ph(2F)-COO-C*H(CF3)(CH2)4OC2H5 (式(2) ; R=C8H17, Y1=F, Y2=H, s=4, t=2)
Example 14 A liquid crystal composition was prepared by mixing 15 mol% of a phenyl ester compound (1F) with a ferrielectric liquid crystal (2E) represented by the following chemical structural formula. 2E: C 9 H 19 -O-Ph-Ph-COO-Ph (2F) -COO-C * H (CF 3 ) (CH 2 ) 4 OC 2 H 5 (Formula (2); R = C 8 H 17 , Y 1 = F, Y 2 = H, s = 4, t = 2)

【0042】実施例15、16 実施例1で用いたフェリ誘電性液晶(2A)に、下記の化学
構造式で示されるフェニルエステル化合物(1L, 1M)を10
モル%混合し、液晶組成物を調整した。 1L : C9H19-COO-Ph(2F)-COO-C*H(CH3)(CH2)4CH3 (式(1) ; m=9, A=CH3, X1=H, X2=F, n=5) 1M : C9H19-COO-Ph(2F)-COO-C*H(CH3)(CH2)5CH3 (式(1) ; m=9, A=CH3, X1=H, X2=F, n=6) 実施例14〜16で調製した液晶組成物について、液晶
相の同定、その他の物性測定を実施例1と同様にした結
果を表7、8に示した。
Examples 15 and 16 To the ferrielectric liquid crystal (2A) used in Example 1, the phenyl ester compound (1L, 1M) represented by the following chemical structural formula was added.
A mol% was mixed to prepare a liquid crystal composition. 1L: C 9 H 19 -COO-Ph (2F) -COO-C * H (CH 3 ) (CH 2 ) 4 CH 3 (Formula (1); m = 9, A = CH 3 ,, X 1 = H, X 2 = F, n = 5) 1M: C 9 H 19 -COO-Ph (2F) -COO-C * H (CH 3 ) (CH 2 ) 5 CH 3 (Formula (1); m = 9, A = CH 3 , X 1 = H, X 2 = F, n = 6) For the liquid crystal compositions prepared in Examples 14 to 16, the results of identifying the liquid crystal phase and measuring other physical properties were the same as in Example 1. The results are shown in Tables 7 and 8.

【0043】[0043]

【表7】 相 系 列 成分 モル比 実施例14 Cr(*1)SCγ*(56)SA(72)I 2E/1F =85/15 液晶 2E Cr(3) SCγ*(68)SA(87)I 実施例15 Cr(*1)SCγ*(68)SA(75)I 2A/1L =90/10 〃 16 Cr(*1)SCγ*(73)SA(74)I 2A/1M =90/10 表中の記載は表1と同じである。[Table 7] Phase series Component Molar ratio Example 14 Cr (* 1) SCγ * (56) SA (72) I 2E / 1F = 85/15 Liquid crystal 2E Cr (3) SCγ * (68) SA (87) I Example 15 Cr (* 1) SCγ * (68) SA (75) I 2A / 1L = 90/10 〃 16 Cr (* 1) SCγ * (73) SA (74) I 2A / 1M = 90/10 The description in the table is the same as in Table 1.

【0044】[0044]

【表8】 しきい値電圧 (V/μm) 応答時間 測定温度 I II (μ秒) (℃) 実施例14 0.9 0.9 61 30 液晶 2E 1.2 1.2 33 50 実施例15 1.1 1.1 56 30 〃 16 1.2 1.2 61 30 [Table 8] Threshold voltage (V / μm) Response time Measurement temperature I II (μsec) (℃) Example 14 0.9 0.9 61 30 Liquid crystal 2E 1.2 1.2 33 50 Example 15 1.1 1.1 56 30 〃 16 1.2 1.2 61 30

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

【図1】フェリ誘電相の分子配列を示す図である。FI
(+), FI(-)はフェリ誘電状態、FO(+), FO(-)は強誘電状
態を表す。
FIG. 1 is a diagram showing a molecular arrangement of a ferrielectric phase. FI
(+) And FI (-) indicate a ferrielectric state, and FO (+) and FO (-) indicate a ferroelectric state.

【図2】フェリ誘電相の三角波に対する光学応答を表
す。
FIG. 2 shows an optical response of a ferrielectric phase to a triangular wave.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 冨山 照予 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 Teruyo Toyama 22nd Wadai, Tsukuba, Ibaraki Pref. Mitsubishi Gas Chemical Company, Ltd.

Claims (14)

【特許請求の範囲】[Claims] 【請求項1】 下記一般式(1) で表されるフェニルエス
テル化合物を、下記一般式(2) で表されるフェリ誘電相
を有する液晶化合物に混合してなるフェリ誘電性液晶組
成物。 【化1】 (式(1) 中のmは 3〜12の整数、nは 1〜11の整数、
X1, X2はH又はいずれか一方がF原子、AはH又は-CH3
基である。式(2) 中のRは炭素数 7〜12の直鎖アルキル
基、Y1, Y2はH又はいずれか一方がF原子、s は 2〜4
の整数、t は 2〜4の整数である。)
1. A ferrielectric liquid crystal composition obtained by mixing a phenyl ester compound represented by the following general formula (1) with a liquid crystal compound having a ferrielectric phase represented by the following general formula (2). Embedded image (M in the formula (1) is an integer of 3 to 12, n is an integer of 1 to 11,
X 1 and X 2 are H or one of them is an F atom, A is H or --CH 3
Group. In formula (2), R is a straight-chain alkyl group having 7 to 12 carbon atoms, Y 1 and Y 2 are H or one of them is an F atom, and s is 2 to 4
, T is an integer from 2 to 4. )
【請求項2】 該一般式(1) で示される化合物が、液晶
相を有しないことを特徴とする請求項1記載のフェニル
エステル化合物。
2. The phenyl ester compound according to claim 1, wherein the compound represented by the general formula (1) has no liquid crystal phase.
【請求項3】 該一般式(1) のAが CH3のとき、nは 4
〜8 の整数である請求項1記載のフェニルエステル化合
物。
3. When A in the general formula (1) is CH 3 , n is 4
The phenyl ester compound according to claim 1, which is an integer of -8.
【請求項4】 該一般式(2) のsが4のとき、tが2〜
4 の整数、Rの炭素数が 7〜12である請求項1記載のフ
ェリ誘電性液晶組成物。
4. When s in the general formula (2) is 4, t is 2 to
The ferrielectric liquid crystal composition according to claim 1, wherein the integer of 4 and the carbon number of R are 7 to 12.
【請求項5】 該一般式(2) のsが3のとき、tが2〜
4 の整数で、Rの炭素数が 9〜12である請求項1記載の
フェリ誘電性液晶組成物。
5. When s in the general formula (2) is 3, t is 2 to
The ferrielectric liquid crystal composition according to claim 1, wherein R is an integer of 4 and has 9 to 12 carbon atoms.
【請求項6】 該一般式(2) のsが2のとき、Rの炭素
数が8、9である請求項1記載のフェリ誘電性液晶組成
物。
6. The ferrielectric liquid crystal composition according to claim 1, wherein when s in the general formula (2) is 2, the carbon number of R is 8 or 9.
【請求項7】 該一般式(2) のsが2のとき、tが2で
である請求項1記載のフェリ誘電性液晶組成物。
7. The ferrielectric liquid crystal composition according to claim 1, wherein when s in the general formula (2) is 2, t is 2.
【請求項8】 該一般式(1) で表されるフェニルエステ
ル化合物の混合量がフェリ誘電性液晶組成物の 1〜40モ
ル%の範囲である請求項1記載のフェリ誘電性液晶組成
物。
8. The ferrielectric liquid crystal composition according to claim 1, wherein the amount of the phenyl ester compound represented by the general formula (1) mixed is in the range of 1 to 40 mol% of the ferrielectric liquid crystal composition.
【請求項9】 該一般式(1) で表されるフェニルエステ
ル化合物の混合量がフェリ誘電性液晶組成物の10〜30モ
ル%の範囲である請求項1記載のフェリ誘電性液晶組成
物。
9. The ferrielectric liquid crystal composition according to claim 1, wherein the amount of the phenyl ester compound represented by the general formula (1) mixed is in the range of 10 to 30 mol% of the ferrielectric liquid crystal composition.
【請求項10】 該フェリ誘電性液晶組成物が、少なく
とも温度0℃〜40℃の範囲でフェリ誘電相である請求項
1記載のフェリ誘電性液晶組成物。
10. The ferrielectric liquid crystal composition according to claim 1, wherein the ferrielectric liquid crystal composition has a ferrielectric phase at least at a temperature of 0 ° C. to 40 ° C.
【請求項11】 該フェリ誘電性液晶組成物のフェリ誘
電相から強誘電相へ転移するときのしきい値電圧が 5V/
μm以下である請求項1記載のフェリ誘電性液晶組成
物。
11. The threshold voltage when the ferrielectric liquid crystal composition transitions from the ferrielectric phase to the ferroelectric phase is 5 V /
The ferrielectric liquid crystal composition according to claim 1, having a thickness of not more than μm.
【請求項12】 該フェリ誘電性液晶組成物のフェリ誘
電相から強誘電相へ転移するときのしきい値電圧が 3V/
μm以下である請求項1記載のフェリ誘電性液晶組成
物。
12. The threshold voltage when the ferrielectric liquid crystal composition transitions from the ferrielectric phase to the ferroelectric phase is 3 V /
The ferrielectric liquid crystal composition according to claim 1, having a thickness of not more than μm.
【請求項13】 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請求
項1記載のフェリ誘電性液晶を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
13. An active matrix liquid crystal display device comprising a ferri-dielectric liquid crystal according to claim 1 sandwiched between substrates provided with a non-linear active device such as a thin film transistor or a diode for each pixel.
【請求項14】 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う請求項13
記載のアクティブマトリックス液晶表示素子。
14. Driving a liquid crystal using a non-linear active element with two ferrielectric states and two ferroelectric states,
And switching to an intermediate state thereof.
An active matrix liquid crystal display device as described in the above.
JP8133540A 1995-06-12 1996-05-28 Ferrielectric liquid crystal composition and liquid crystal display element Pending JPH0959640A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8133540A JPH0959640A (en) 1995-06-12 1996-05-28 Ferrielectric liquid crystal composition and liquid crystal display element

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7-144721 1995-06-12
JP14472195 1995-06-12
JP8133540A JPH0959640A (en) 1995-06-12 1996-05-28 Ferrielectric liquid crystal composition and liquid crystal display element

Publications (1)

Publication Number Publication Date
JPH0959640A true JPH0959640A (en) 1997-03-04

Family

ID=26467863

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8133540A Pending JPH0959640A (en) 1995-06-12 1996-05-28 Ferrielectric liquid crystal composition and liquid crystal display element

Country Status (1)

Country Link
JP (1) JPH0959640A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002532613A (en) * 1998-12-11 2002-10-02 クラリアント ゲーエムベーハー Ferroelectric active matrix display with wide operating temperature range

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002532613A (en) * 1998-12-11 2002-10-02 クラリアント ゲーエムベーハー Ferroelectric active matrix display with wide operating temperature range

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