JPH07258141A - 4-alkenyloxy-3,5-difluorobenzene derivative - Google Patents
4-alkenyloxy-3,5-difluorobenzene derivativeInfo
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- JPH07258141A JPH07258141A JP5177394A JP5177394A JPH07258141A JP H07258141 A JPH07258141 A JP H07258141A JP 5177394 A JP5177394 A JP 5177394A JP 5177394 A JP5177394 A JP 5177394A JP H07258141 A JPH07258141 A JP H07258141A
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は電気光学的液晶表示材料
として有用な、新規な4−アルケニルオキシ−3,5−
ジフルオロベンゼン誘導体である液晶性化合物、及びそ
れを含有する液晶組成物に関する。FIELD OF THE INVENTION The present invention relates to a novel 4-alkenyloxy-3,5-, which is useful as an electro-optical liquid crystal display material.
The present invention relates to a liquid crystal compound which is a difluorobenzene derivative, and a liquid crystal composition containing the same.
【0002】[0002]
【従来の技術】液晶表示素子は、時計、電卓をはじめと
して、各種測定機器、自動車用パネル、ワープロ、電子
手帳、プリンター、コンピューター、テレビ等に用いら
れるようになっている。液晶表示方式としては、その代
表的なものにTN(捩れネマチック)型、STN(超捩
れネマチック)型、DS(動的光散乱)型、GH(ゲス
ト・ホスト)型あるいはFLC(強誘電性液晶)等が知
られており、現在主流となっているのはTN型及びST
N型である。また駆動方式としても従来のスタティック
駆動からマルチプレックス駆動が一般的になり、さらに
単純マトリックス方式、最近ではアクティブマトリック
ス方式が実用化されている。これらのうち、アクティブ
マトリックス方式においては、非常に高画質の表示が可
能であり、視野角が広く、高精細化、カラー化が容易
で、動画表示も可能であるため、今後の液晶表示方式の
主流になると考えられている。2. Description of the Related Art Liquid crystal display devices have come to be used in watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and FLC (ferroelectric liquid crystal). ) Etc. are known, and currently mainstream is TN type and ST
It is N type. Also, as the drive system, the conventional static drive has become more common, and the multiplex drive is becoming more common, and the simple matrix system and recently the active matrix system have been put into practical use. Among these, the active matrix method can display a very high image quality, has a wide viewing angle, can easily achieve high definition and color, and can display moving images. It is believed to become mainstream.
【0003】このアクティブマトリックス表示方式に用
いられる液晶材料としては、通常の液晶表示と同様に、
種々の特性が要求されているが、特に、(1)比抵抗が
高く、電圧の保持率に優れること、(2)しきい値電圧
(Vth)が低いこと、(3)液晶相の温度範囲が広いこ
と等が重要である。As a liquid crystal material used in this active matrix display system, as in a normal liquid crystal display,
Various characteristics are required, but in particular, (1) high specific resistance and excellent voltage holding ratio, (2) low threshold voltage (V th ), (3) temperature of liquid crystal phase It is important that the range is wide.
【0004】通常、液晶表示におけるしきい値電圧(V
th)は式(a)Usually, the threshold voltage (V
th ) is the formula (a)
【0005】[0005]
【数1】 [Equation 1]
【0006】(式中、kは比例定数を、Kは弾性定数
を、Δεは誘電率異方性をそれぞれ表わす。)で表わさ
れるが、この式からわかるように、しきい値電圧を低く
するためには液晶材料の弾性定数を小さくするか、ある
いは誘電率異方性を大きくする必要がある。(In the formula, k is a proportional constant, K is an elastic constant, and Δε is a dielectric anisotropy.). As can be seen from this formula, the threshold voltage is lowered. Therefore, it is necessary to reduce the elastic constant of the liquid crystal material or increase the dielectric anisotropy.
【0007】しかしながら、誘電率異方性の大きい液晶
化合物は、極性の大きいものが多く、高い比抵抗値や電
圧保持率の液晶材料を得ることを困難にさせる傾向を有
する。そのため、こうした目的には弾性定数が小さい液
晶材料が必要である。However, many liquid crystal compounds having a large dielectric anisotropy have a large polarity, which tends to make it difficult to obtain a liquid crystal material having a high specific resistance value and a voltage holding ratio. Therefore, a liquid crystal material having a small elastic constant is required for such purpose.
【0008】弾性定数の小さい液晶材料としては、2環
性の化合物が挙げられる。しかしながら、2環性の化合
物は、添加により組成物の液晶相の上限温度を大幅に低
下させてしまう傾向を有するものが多い。Examples of the liquid crystal material having a small elastic constant include bicyclic compounds. However, many bicyclic compounds tend to significantly lower the maximum temperature of the liquid crystal phase of the composition when added.
【0009】そこで、液晶組成物の温度範囲を特に高温
域に拡大させるためには、3環性あるいは4環性の、液
晶相の上限温度の高い化合物を添加する必要がある。し
かしながら、このように上限温度の高い化合物は弾性定
数が大きいものが多く、添加により組成物のしきい値電
圧を大きく上昇させてしまう傾向を有する。Therefore, in order to extend the temperature range of the liquid crystal composition to a particularly high temperature range, it is necessary to add a tricyclic or tetracyclic compound having a high maximum liquid crystal phase temperature. However, many compounds having such a high maximum temperature have a large elastic constant, and the addition thereof tends to greatly increase the threshold voltage of the composition.
【0010】また、液晶相の温度範囲を狭くすることな
く、しきい値電圧を低下させる化合物として、一般式
(II)Further, as a compound which lowers the threshold voltage without narrowing the temperature range of the liquid crystal phase, the compound represented by the general formula (II)
【0011】[0011]
【化2】 [Chemical 2]
【0012】(式中、Rはアルキル基を表わす。)で表
わされる化合物等が知られている。(特開平2−233
626号公報に記載) しかしながら、この化合物の液晶相の上限温度はあまり
高くなく、添加による組成物の液晶相の上限温度の上昇
も、ほとんど期待できなかった。しかも融点が低くない
うえに、添加による組成物の融点の降下も少なく、さら
にネマチック相の低温域にスメクチック相を有するた
め、多量の添加により、低温域におけるネマチック相の
安定性に問題が生じ、添加量もかなり制限されていた。Compounds represented by the formula (wherein R represents an alkyl group) are known. (JP-A-2-233
However, the maximum temperature of the liquid crystal phase of this compound is not so high, and the increase of the maximum temperature of the liquid crystal phase of the composition due to the addition could hardly be expected. Moreover, the melting point is not low, the melting point of the composition is not much lowered by the addition, and since the nematic phase has a smectic phase in the low temperature region, the addition of a large amount causes a problem in the stability of the nematic phase in the low temperature region, The amount added was also quite limited.
【0013】上記のような一般式(II)で表わされる
化合物の欠点を補うため、本発明者らは一般式(II
I)In order to make up for the drawbacks of the compound represented by the general formula (II) as described above, the present inventors have proposed the general formula (II).
I)
【0014】[0014]
【化3】 [Chemical 3]
【0015】(式中、RおよびR’はそれぞれアルキル
基を表わす。)で表わされる、4−アルコキシ−3,5
−ジフルオロベンセン系化合物を開発した。この一般式
(III)で表わされる化合物は、液晶相の温度範囲が
特に高温域まで大きく改善され、温度範囲の広い液晶組
成物を得ることが容易となったが、融点はあまり低くな
っておらず、低温域における充分な液晶相の温度範囲が
確保できなかった。4-alkoxy-3,5 represented by the formula: wherein R and R'each represent an alkyl group.
-Developed a difluorobenzene compound. The compound represented by the general formula (III) is greatly improved in the temperature range of the liquid crystal phase, particularly in the high temperature range, and it is easy to obtain a liquid crystal composition having a wide temperature range, but the melting point is too low. Therefore, a sufficient temperature range of the liquid crystal phase in the low temperature region could not be secured.
【0016】従って、液晶相の温度範囲が低温域から高
温域まで広く、添加により組成物のしきい値電圧を低下
させるような液晶化合物を得ることはかなり困難であっ
た。Therefore, it has been quite difficult to obtain a liquid crystal compound in which the temperature range of the liquid crystal phase is wide from the low temperature region to the high temperature region and the threshold voltage of the composition is lowered by the addition thereof.
【0017】[0017]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、以上の目的に応じ、融点が低く、広い温度
範囲でネマチック相を有し、添加により組成物のしきい
値電圧をほとんど上昇させることなく融点を降下させ、
しかも液晶相の上限温度を上昇させるような化合物を提
供し、また、その化合物を含有し、液晶相の温度範囲が
広く、且つしきい値電圧の低い液晶組成物を提供するこ
とにある。The problems to be solved by the present invention are, according to the above objects, a low melting point, a nematic phase in a wide temperature range, and a threshold voltage of the composition which is almost Without lowering the melting point,
Moreover, it is to provide a compound capable of increasing the maximum temperature of the liquid crystal phase, and to provide a liquid crystal composition containing the compound, having a wide temperature range of the liquid crystal phase and a low threshold voltage.
【0018】[0018]
【課題を解決するための手段】本発明は、上記課題を解
決するために、一般式(I)In order to solve the above-mentioned problems, the present invention has the general formula (I)
【0019】[0019]
【化4】 [Chemical 4]
【0020】(式中、R1は炭素原子数1〜12のアル
キル基または炭素原子数2〜12のアルケニル基を表わ
すが、好ましくは炭素原子数1〜10の直鎖状アルキル
基を表わし、さらに好ましくは炭素原子数1〜7の直鎖
状アルキル基を表わす。L及びMはそれぞれ独立的に、
単結合または−CH2CH2−を表わすが、少なくとも一
方は単結合を表わし、特に好ましくは共に単結合を表わ
す。R2は炭素原子数3〜12の直鎖状アルケニル基を
表わすが、好ましくは炭素原子数3〜7の直鎖状2−ア
ルケニル基を表わす。また、シクロヘキサン環はトラン
ス配置である。)で表わされる4−アルケニルオキシ−
3,5−ジフルオロベンゼン誘導体を提供する。(In the formula, R 1 represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, preferably a linear alkyl group having 1 to 10 carbon atoms, More preferably, it represents a linear alkyl group having 1 to 7 carbon atoms, L and M are each independently
A single bond or --CH 2 CH 2- , at least one of them represents a single bond, and particularly preferably both represent a single bond. R 2 represents a linear alkenyl group having 3 to 12 carbon atoms, preferably a linear 2-alkenyl group having 3 to 7 carbon atoms. The cyclohexane ring has a trans configuration. ) 4-alkenyloxy-
Provided is a 3,5-difluorobenzene derivative.
【0021】本発明の一般式(I)で表わされる化合物
において、好ましくは一般式(Ia)〜一般式(Id)In the compound represented by the general formula (I) of the present invention, the general formula (Ia) to the general formula (Id) are preferable.
【0022】[0022]
【化5】 [Chemical 5]
【0023】(式中、Raは炭素原子数1〜7の直鎖状
アルキル基を表わし、Rbは炭素原子数2〜7の直鎖状
アルケニル基を表わし、Rcは水素原子または炭素原子
数1〜4の直鎖状アルキル基を表わす。)で表わされる
化合物であり、特に好ましくは、一般式(Ia)で表わ
される化合物である。(In the formula, R a represents a linear alkyl group having 1 to 7 carbon atoms, R b represents a linear alkenyl group having 2 to 7 carbon atoms, and R c represents a hydrogen atom or a carbon atom. A compound represented by a linear alkyl group having 1 to 4 atoms), particularly preferably a compound represented by the general formula (Ia).
【0024】本発明の一般式(Ia)で表わされる化合
物は、例えば、以下の製造方法に従って製造することが
できる。The compound represented by the general formula (Ia) of the present invention can be produced, for example, according to the following production method.
【0025】[0025]
【化6】 [Chemical 6]
【0026】まず、2,6−ジフルオロフェノールを臭
素化して4−ブロモ−2,6−ジフルオロフェノールを
得る。これを、塩基存在下でヨウ化メチルと反応させ
て、式(IV)の4−メトキシ−1−ブロモ−3,5−
ジフルオロベンゼンを得る。First, 2,6-difluorophenol is brominated to obtain 4-bromo-2,6-difluorophenol. This is reacted with methyl iodide in the presence of a base to give 4-methoxy-1-bromo-3,5- of formula (IV).
Obtain difluorobenzene.
【0027】[0027]
【化7】 [Chemical 7]
【0028】(式中、Raは、前述と同じ意味を表わ
す。)次に、式(IV)の化合物をマグネシウムと反応
させてグリニヤール反応剤とし、これを一般式(Va)
で表わされる4−(トランス−4−アルキルシクロヘキ
シル)シクロヘキサノンと反応させる。反応後、脱水、
水素添加することにより中央のシクロヘキサン環の立体
配置による異性体混合物が得られる。これらを分割、ま
たは塩基により異性化させて、一般式(VIa)で表わ
される1−[トランス−4−(トランス−4−アルキル
シクロヘキシル)シクロヘキシル]−3,5−ジフルオ
ロ−4−メトキシベンゼンを得ることができる。(In the formula, R a has the same meaning as described above.) Next, the compound of the formula (IV) is reacted with magnesium to obtain a Grignard reactant, which is represented by the general formula (Va).
And reacted with 4- (trans-4-alkylcyclohexyl) cyclohexanone. After the reaction, dehydration,
Hydrogenation gives a mixture of isomers due to the configuration of the central cyclohexane ring. These are separated or isomerized with a base to obtain 1- [trans-4- (trans-4-alkylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene represented by the general formula (VIa). be able to.
【0029】[0029]
【化8】 [Chemical 8]
【0030】(式中、Ra及びRcは前述と同じ意味を表
わし、Xは塩素原子、臭素原子、ヨウ素原子またはp−
トルエンスルホニル基等の脱離基を表わす。) さらに、一般式(VIa)の化合物を、臭化水素酸ある
いはヨウ化トリメチルシリル等により脱メチル化して、
一般式(VIIa)で表わされる4−[トランス−4−
(トランス−4−アルキルシクロヘキシル)シクロヘキ
シル]−2,6−ジフルオロフェノールとする。ここに
塩基存在下で、一般式(VIII)で表わされる化合物
と反応させることにより、一般式(Ia)の化合物を得
ることができる。(In the formula, R a and R c have the same meanings as described above, and X is a chlorine atom, a bromine atom, an iodine atom or p-
It represents a leaving group such as a toluenesulfonyl group. ) Further, the compound of the general formula (VIa) is demethylated with hydrobromic acid, trimethylsilyl iodide or the like,
4- [trans-4-represented by the general formula (VIIa)
(Trans-4-alkylcyclohexyl) cyclohexyl] -2,6-difluorophenol. The compound of the general formula (Ia) can be obtained by reacting with the compound of the general formula (VIII) in the presence of a base.
【0031】ここで、R2が1−アルケニル基の化合物
は、一般式(Ia)の化合物を強塩基で異性化させるこ
と等により得ることができる。また、R2が1あるいは
2−アルケニル基以外の化合物は、一般式(VIII)
の化合物に代えて、The compound wherein R 2 is a 1-alkenyl group can be obtained by isomerizing the compound of the general formula (Ia) with a strong base. Compounds in which R 2 is other than 1 or a 2-alkenyl group can be represented by the general formula (VIII)
Instead of the compound
【0032】[0032]
【化9】X−R2 (式中、R2及びXは前述と同じ意味を表わす。)を用
いることにより、同様にして製造することができる。By using X-R 2 (wherein R 2 and X have the same meanings as described above), the compound can be produced in the same manner.
【0033】本発明の一般式(Ib)で表わされる化合
物は、例えば、以下の製造方法に従って製造することが
できる。上記の一般式(Ia)で表わされる化合物の製
造方法において、一般式(Va)で表わされる化合物に
代えて、一般式(Vb)The compound represented by formula (Ib) of the present invention can be produced, for example, according to the following production method. In the method for producing a compound represented by the above general formula (Ia), a compound represented by the general formula (Vb) is used instead of the compound represented by the general formula (Va).
【0034】[0034]
【化10】 [Chemical 10]
【0035】(式中、Raは前述と同じ意味を表わ
す。)で表わされる4−(トランス−4−アルキルシク
ロヘキシル)シクロヘキサンエタナールを用いることに
より、一般式(Ib)の化合物を得ることができる。こ
こで一般式(Vb)の化合物は、例えば、以下の製造方
法に従って製造することができる。A compound of the general formula (Ib) can be obtained by using 4- (trans-4-alkylcyclohexyl) cyclohexaneethanal represented by the formula (wherein R a has the same meaning as described above). it can. Here, the compound of general formula (Vb) can be produced, for example, according to the following production method.
【0036】[0036]
【化11】 [Chemical 11]
【0037】(式中、Raは前述と同じ意味を表わ
す。) 即ち、一般式(Va)の化合物に、式(IXa)のウィ
ッティヒ反応剤を反応させ、酸処理を行う工程を2回繰
り返すことにより容易に得ることができる。(In the formula, R a has the same meaning as described above.) That is, the step of reacting the compound of the general formula (Va) with the Wittig reagent of the formula (IXa) and treating with acid is repeated twice. It can be easily obtained.
【0038】また、本発明の一般式(Ic)で表わされ
る化合物は、例えば、以下の方法に従って製造すること
ができる。前記の一般式(Ia)で表わされる化合物の
製造方法において、一般式(Va)で表わされる化合物
に代えて、一般式(Vc)The compound represented by the general formula (Ic) of the present invention can be produced, for example, according to the following method. In the method for producing the compound represented by the general formula (Ia), a compound represented by the general formula (Vc) is used instead of the compound represented by the general formula (Va).
【0039】[0039]
【化12】 [Chemical 12]
【0040】(式中、Raは前述と同じ意味を表わ
す。)で表わされる4−[2−(トランス−4−アルキ
ルシクロヘキシル)エチル]シクロヘキサノンを用いる
ことにより、一般式(Ic)の化合物を得ることができ
る。ここで一般式(Vc)で表わされる化合物は、例え
ば、以下の製造方法に従って製造することができる。By using 4- [2- (trans-4-alkylcyclohexyl) ethyl] cyclohexanone represented by the formula (wherein R a has the same meaning as described above), the compound of the general formula (Ic) can be obtained. Obtainable. The compound represented by the general formula (Vc) can be produced, for example, according to the following production method.
【0041】[0041]
【化13】 [Chemical 13]
【0042】(式中、Raは前述と同じ意味を表わ
す。) 即ち、トランス−4−アルキル−1−(2−ブロモエチ
ル)シクロヘキサンをグリニヤール反応剤とし、これを
シクロヘキサン−1,4−ジオンのモノエチレンアセタ
ールと反応させ、脱水、水素添加の後アセタールをはず
すことにより、一般式(Vc)の化合物を容易に得るこ
とができる。(In the formula, R a has the same meaning as described above.) That is, trans-4-alkyl-1- (2-bromoethyl) cyclohexane was used as a Grignard reaction agent, and this was converted into cyclohexane-1,4-dione. The compound of the general formula (Vc) can be easily obtained by reacting with monoethylene acetal, dehydrating and hydrogenating, and then removing the acetal.
【0043】[0043]
【化14】 [Chemical 14]
【0044】(式中、Raは前述と同じ意味を表わ
す。) あるいは、4−[2−[トランス−4−アルキルシクロ
ヘキシル]エチル]フェノールをルテニウム触媒等の存
在下に水素添加し、次いで水酸基を酸化しても得ること
ができる。(In the formula, R a has the same meaning as described above.) Alternatively, 4- [2- [trans-4-alkylcyclohexyl] ethyl] phenol is hydrogenated in the presence of a ruthenium catalyst or the like, and then hydroxyl group is added. It can also be obtained by oxidizing.
【0045】さらに、本発明の一般式(Id)で表わさ
れる化合物は、例えば、以下の製造方法に従って製造す
ることができる。Further, the compound represented by the general formula (Id) of the present invention can be produced, for example, according to the following production method.
【0046】[0046]
【化15】 [Chemical 15]
【0047】前記の一般式(Ia)で表わされる化合物
の製造方法において、一般式(Va)の化合物に代え
て、一般式(Vd)で表わされるビシクロヘキサン−
4,4’−ジオンのモノエチレンアセタールと反応さ
せ、脱水、水素添加の後アセタールをはずすことによ
り、式(X)の4−[トランス−4−(4−メトキシ−
3,5−ジフルオロフェニル)シクロヘキシル]シクロ
ヘキサノンを得る。In the method for producing the compound represented by the general formula (Ia), the compound represented by the general formula (Va) is replaced by bicyclohexane-containing compound represented by the general formula (Vd).
By reacting with 4,4'-dione monoethylene acetal, dehydration and hydrogenation to remove the acetal, 4- [trans-4- (4-methoxy-) of the formula (X) is obtained.
3,5-difluorophenyl) cyclohexyl] cyclohexanone is obtained.
【0048】[0048]
【化16】 [Chemical 16]
【0049】(式中、n、mはそれぞれ1以上の整数を
表わすが、n+m≦10である。)次いで、式(X)の
化合物に、式(IXa)のウィッティヒ反応剤をn回反
応させ、さらに式(IXb)のウィッティヒ反応剤を反
応させることにより、側鎖の任意の位置に二重結合を有
する一般式(VId)で表わされる化合物を得る。ここ
で、m≧2の場合、シス体が主として得られるが、これ
らはp−トルエンスルフィン酸等の触媒あるいは増感剤
の存在下に光照射するなど通常の方法により、トランス
体に異性化することが可能である。(In the formula, n and m each represent an integer of 1 or more, and n + m ≦ 10.) Then, the compound of the formula (X) is reacted with the Wittig reagent of the formula (IXa) n times. Further, by reacting with a Wittig reagent of the formula (IXb), a compound represented by the general formula (VId) having a double bond at any position of the side chain is obtained. Here, when m ≧ 2, cis isomers are mainly obtained, but these are isomerized to trans isomers by a usual method such as light irradiation in the presence of a catalyst such as p-toluenesulfinic acid or a sensitizer. It is possible.
【0050】この一般式(VId)の化合物を脱メチル
化、アルケニル化することによって、本発明の一般式
(Id)で表わされる化合物を容易に得ることができ
る。斯くして製造された一般式(I)で表わされる化合
物の代表例を第1表に掲げる。By demethylating and alkenylating the compound of the general formula (VId), the compound of the general formula (Id) of the present invention can be easily obtained. Table 1 shows typical examples of the compounds represented by the general formula (I) thus produced.
【0051】[0051]
【表1】 [Table 1]
【0052】(表中、Crは結晶相を、Nはネマチック
相を、Iは等方性液体相をそれぞれ表わす。) 第1表から、本発明の一般式(I)で表わされる化合物
は融点が低く、しかも高い温度までネマチック液晶相を
示すことが明らかである。これに対し、第1表中の(N
o.1)の化合物の類似構造を有する一般式(III−
1)(In the table, Cr represents a crystalline phase, N represents a nematic phase, and I represents an isotropic liquid phase.) From Table 1, the compound represented by the general formula (I) of the present invention has a melting point. It is clear that the liquid crystal exhibits a nematic liquid crystal phase at a low temperature and a high temperature. On the other hand, (N in Table 1
o. The compound of the general formula (III-) having a similar structure to the compound of 1)
1)
【0053】[0053]
【化17】 [Chemical 17]
【0054】の化合物と比較すると、ネマチック相上限
温度(TN-I)はほとんど変わらないにもかかわらず、
融点においては、一般式(III−1)の化合物が5
5.5℃であるのに対し、(No.1)の化合物は2
3.2℃であり、本願発明の化合物が30℃以上も低
い。従って、通常の母体液晶に添加した場合に、液晶相
の温度範囲を大きく拡大することが可能である。Compared with the compound of (1), although the maximum temperature of the nematic phase (T NI ) is almost unchanged,
At the melting point, the compound of the general formula (III-1) is 5
It is 5.5 ° C, whereas the compound of (No. 1) is 2
The temperature is 3.2 ° C., and the compounds of the present invention are as low as 30 ° C. or higher. Therefore, when added to a normal host liquid crystal, the temperature range of the liquid crystal phase can be greatly expanded.
【0055】本発明の一般式(I)で表わされる化合物
は、他のネマチック液晶化合物との混合物の状態で、T
N型あるいはSTN型といった電界効果型表示セルの材
料として、組成物のしきい値電圧をほとんど上昇させる
ことなく、液晶相の温度範囲を拡大する目的に使用する
ことができ、アクティブマトリックス駆動用液晶材料の
構成成分として特に適している。The compound represented by the general formula (I) of the present invention is T in the state of a mixture with other nematic liquid crystal compounds.
As a material for N-type or STN-type field effect display cells, it can be used for the purpose of expanding the temperature range of the liquid crystal phase without substantially increasing the threshold voltage of the composition, and is used as an active matrix driving liquid crystal. It is particularly suitable as a constituent of the material.
【0056】この組成物中において、一般式(I)で表
わされる化合物と混合して使用することのできるネマチ
ック液晶化合物の好ましい代表例としては、例えば、4
−置換安息香酸4−置換フェニルエステル、4−置換シ
クロヘキサンカルボン酸4−置換フェニルエステル、4
−置換シクロヘキサンカルボン酸4’−置換ビフェニリ
ルエステル、4−(4−置換シクロヘキサンカルボニル
オキシ)安息香酸4−置換フェニルエステル、4−(4
−置換シクロヘキシル)安息香酸4−置換フェニルエス
テル、4−(4−置換シクロヘキシル)安息香酸4−置
換シクロヘキシルエステル、4,4’−置換ビフェニ
ル、1−(4−置換フェニル)−4−置換シクロヘキサ
ン、4,4’−置換ビシクロヘキシル、4,4”−置換
テルフェニル、1−(4’−置換ビフェニリル)−4−
置換シクロヘキサン、1−(4−置換シクロヘキシル)
−4−(4−置換フェニル)シクロヘキサン、4,4”
−置換テルシクロヘキサン、2−(4−置換フェニル)
−5−置換ピリミジン、2−(4’−置換ビフェニリ
ル)−5−置換ピリミジンなどを挙げることができる。In this composition, a preferable representative example of the nematic liquid crystal compound which can be used by mixing with the compound represented by the general formula (I) is, for example, 4
-Substituted benzoic acid 4-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4-substituted phenyl ester, 4
-Substituted cyclohexanecarboxylic acid 4'-substituted biphenylyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4-substituted phenyl ester, 4- (4
4-substituted cyclohexyl) benzoic acid 4-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4-substituted cyclohexyl ester, 4,4′-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4,4'-substituted bicyclohexyl, 4,4 "-substituted terphenyl, 1- (4'-substituted biphenylyl) -4-
Substituted cyclohexane, 1- (4-substituted cyclohexyl)
-4- (4-substituted phenyl) cyclohexane, 4,4 "
-Substituted tercyclohexane, 2- (4-substituted phenyl)
Examples thereof include -5-substituted pyrimidine and 2- (4'-substituted biphenylyl) -5-substituted pyrimidine.
【0057】このうち、アクティブマトリックス駆動用
としては、4,4’−置換ビフェニル、1−(4−置換
フェニル)−4−置換シクロヘキサン、4,4’−置換
ビシクロヘキシル、4,4”−置換テルフェニル、1−
(4’−置換ビフェニリル)−4−置換シクロヘキサ
ン、1−(4−置換シクロヘキシル)−4−(4−置換
フェニル)シクロヘキサン、4,4”−置換テルシクロ
ヘキサン等が好ましく、1−(4−置換フェニル)−4
−置換シクロヘキサン、1−(4’−置換ビフェニリ
ル)−4−置換シクロヘキサン、1−(4−置換シクロ
ヘキシル)−4−(4−置換フェニル)シクロヘキサン
が適している。Of these, for active matrix driving, 4,4'-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4,4'-substituted bicyclohexyl, 4,4 "-substituted Terphenyl, 1-
(4′-Substituted biphenylyl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane, 4,4 ″ -substituted tercyclohexane and the like are preferable, and 1- (4-substituted Phenyl) -4
Suitable are -substituted cyclohexane, 1- (4'-substituted biphenylyl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane.
【0058】本発明の一般式(I)の化合物の効果は、
後述の実施例にも示したが、以下の例からも明らかであ
る。ネマチック液晶材料として、特にアクティブマトリ
ックス用として好適な母体液晶(A)The effects of the compound of the general formula (I) of the present invention are as follows:
Although shown in Examples below, it is clear from the following examples. A host liquid crystal (A) suitable as a nematic liquid crystal material, particularly for an active matrix
【0059】[0059]
【化18】 [Chemical 18]
【0060】(式中、シクロヘキサン環はトランス配置
を表わし、「%」は「重量%」を表わす。)は、11
6.7℃以下ネマチック相を示し、低温で放置して結晶
化させた後にその融点を測定したところ、約11℃であ
り、これを用いて作製したTNセル(セル厚8.0μ
m)のしきい値電圧(Vth)は2.43Vであった。(Wherein the cyclohexane ring represents the trans configuration and "%" represents "% by weight") is 11
A nematic phase of 6.7 ° C. or less was exhibited, and the melting point was measured after the crystallization was performed by leaving it at a low temperature. The melting point was about 11 ° C., and a TN cell (cell thickness 8.0 μ
The threshold voltage (V th ) of m) was 2.43V.
【0061】この母体液晶(A)85重量%及び第1表
中の(No.1)の化合物15重量%からなる液晶組成
物(M−1)を調製した。この(M−1)のネマチック
相の上限温度(TN-I)は121.0℃と大きく上昇し
た。また、同様にして融点を測定したところ、−5℃と
大きく低下した。さらに、これを用いて作製したTNセ
ル(セル厚7.7μm)のしきい値電圧(Vth)は、
2.53Vとその上昇をわずかに抑えることができた。
さらにこの組成物の比抵抗は1012Ωcm以上と大き
く、このセルの電圧保持率は非常に高かった。A liquid crystal composition (M-1) comprising 85% by weight of the base liquid crystal (A) and 15% by weight of the compound (No. 1) in Table 1 was prepared. The upper limit temperature (T NI ) of the nematic phase of (M-1) was significantly increased to 121.0 ° C. Further, when the melting point was measured in the same manner, it was significantly lowered to -5 ° C. Furthermore, the threshold voltage (V th ) of a TN cell (cell thickness 7.7 μm) manufactured using this is
It could be suppressed to 2.53V and its rise slightly.
Further, the specific resistance of this composition was as large as 10 12 Ωcm or more, and the voltage holding ratio of this cell was very high.
【0062】以上の結果から、本発明の一般式(〓)で
表わされる化合物は、ネマチック液晶相を示す母体液晶
に添加することにより、しきい値電圧(Vth)をほとん
ど上昇させることなく、しかも液晶相の温度範囲を低温
域にも高温域にも拡大できる効果を有することが明らか
である。From the above results, the compound represented by the general formula (〓) of the present invention was added to the host liquid crystal exhibiting a nematic liquid crystal phase, and the threshold voltage (V th ) was hardly increased, Moreover, it is clear that it has the effect of expanding the temperature range of the liquid crystal phase to both low and high temperatures.
【0063】[0063]
【実施例】以下に本発明の実施例を示し、本発明を更に
説明する。しかしながら、本発明はこれらの実施例に限
定されるものではない。EXAMPLES The present invention will be further described below by showing Examples of the present invention. However, the invention is not limited to these examples.
【0064】なお、相転移温度の測定は温度調節ステー
ジを備えた偏光顕微鏡及び示差走査熱量計(DSC)を
併用して行った。また、化合物の構造は核磁気共鳴スペ
クトル(1H−NMR)、質量スペクトル(MS)等に
より確認した。NMRにおけるCDCl3は溶媒を表わ
し、sは1重線、dは2重線、tは3重線、mは多重線
を表わし、Jはカップリング定数を表わす。MSにおけ
るM+は親ピークを表わす。 (参考例) 1−[トランス−4−(トランス−4−
プロピルシクロヘキシル)シクロヘキシル]−3,5−
ジフルオロ−4−メトキシベンゼンの合成(1−a)
4−ブロモ−2,6−ジフルオロアニソールの合成The phase transition temperature was measured by using a polarization microscope equipped with a temperature adjusting stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum ( 1 H-NMR), mass spectrum (MS) and the like. In NMR, CDCl 3 represents a solvent, s represents a singlet, d represents a doublet, t represents a triplet, m represents a multiplet, and J represents a coupling constant. M + in MS represents the parent peak. (Reference example) 1- [trans-4- (trans-4-
Propylcyclohexyl) cyclohexyl] -3,5-
Synthesis of difluoro-4-methoxybenzene (1-a)
Synthesis of 4-bromo-2,6-difluoroanisole
【0065】[0065]
【化19】 [Chemical 19]
【0066】市販の2,6−ジフルオロフェノール1
8.0gをジクロロメタン100ml及びピリジン1
1.0gに溶解し、5℃で冷却した。冷却後、攪拌下で
臭素27gを30分間で滴下した。反応終了後、亜硫酸
水素ナトリウム水溶液を加えて過剰の臭素を分解し、有
機層を分離し、水層から反応生成物をジクロロメタンで
抽出し、有機相を合わせた。有機相を水、飽和食塩水で
洗浄し、無水硫酸ナトリウムで脱水乾燥した後、溶媒を
溜去して、4−ブロモ−2,6−ジフルオロフェノール
の粗結晶28.6gを得た。Commercially available 2,6-difluorophenol 1
8.0 g of dichloromethane 100 ml and pyridine 1
It was dissolved in 1.0 g and cooled at 5 ° C. After cooling, 27 g of bromine was added dropwise over 30 minutes with stirring. After the reaction was completed, an aqueous sodium hydrogen sulfite solution was added to decompose excess bromine, the organic layer was separated, the reaction product was extracted from the aqueous layer with dichloromethane, and the organic phases were combined. The organic phase was washed with water and saturated brine, dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain 28.6 g of crude 4-bromo-2,6-difluorophenol crystals.
【0067】次に、上記で得た4−ブロモ−2,6−ジ
フルオロフェノール28.6gをアセトン150mlに
溶解し、炭酸カリウム28gを加えた。ここにヨウ化メ
チル29.1gを滴下し、還流下で1時間加熱攪拌した
後、稀塩酸を加えて酸性とし、アセトンを減圧下で溜去
して、反応生成物を酢酸エチルで抽出した。有機層を
水、飽和食塩水で洗浄し、無水硫酸ナトリウムで脱水乾
燥した後、溶媒を溜去して、得られた粗生成物を減圧下
で蒸留(92〜93℃/23mmHg)して、4−ブロ
モ−2,6−ジフルオロアニソール26.9gを得た。
(1−b) 1−[トランス−4−(トランス−4−
プロピルシクロヘキシル)シクロヘキシル]−3,5−
ジフルオロ−4−メトキシベンゼンの合成Next, 28.6 g of 4-bromo-2,6-difluorophenol obtained above was dissolved in 150 ml of acetone, and 28 g of potassium carbonate was added. Methyl iodide (29.1 g) was added dropwise thereto, and the mixture was heated with stirring under reflux for 1 hour, acidified by adding dilute hydrochloric acid, acetone was distilled off under reduced pressure, and the reaction product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dehydrated and dried over anhydrous sodium sulfate, the solvent was distilled off, and the obtained crude product was distilled under reduced pressure (92 to 93 ° C./23 mmHg), 26.9 g of 4-bromo-2,6-difluoroanisole was obtained.
(1-b) 1- [trans-4- (trans-4-
Propylcyclohexyl) cyclohexyl] -3,5-
Synthesis of difluoro-4-methoxybenzene
【0068】[0068]
【化20】 [Chemical 20]
【0069】上記(1−a)で得た4−ブロモ−2,6
−ジフルオロアニソール26.9gを、テトラヒドロフ
ラン(THF)140mlに溶解した。この溶液を、マ
グネシウム3.5gのTHF10ml懸濁液に、穏やか
な還流が続く温度に保ちながら滴下し、さらに1時間加
熱攪拌した。反応終了後、室温まで放冷し、これに4−
(トランス−4−プロピルシクロヘキシル)シクロヘキ
サノン26.8gのTHF140ml懸濁液を30分間
で滴下し、さらに3時間攪拌した。反応終了後、稀塩酸
を加え、反応生成物を酢酸エチルで抽出した。溶媒を溜
去した後、抽出物をトルエン200mlに溶解し、硫酸
1mlを加え、110℃で1時間攪拌した。反応終了
後、反応生成物を室温で放冷し、飽和炭酸水素ナトリウ
ム水溶液、水、飽和食塩水で順次洗浄し、無水硫酸ナト
リウムで脱水乾燥した後、溶媒を溜去して、1−[4−
(トランス−4−プロピルシクロヘキシル)シクロヘキ
セン−1−イル]−3,5−ジフルオロ−4−メトキシ
ベンゼンの粗結晶39.6gを得た。4-Bromo-2,6 obtained in the above (1-a)
26.9 g of difluoroanisole were dissolved in 140 ml of tetrahydrofuran (THF). This solution was added dropwise to a suspension of 3.5 g of magnesium in 10 ml of THF while maintaining the temperature at which gentle reflux continued, and the mixture was further stirred with heating for 1 hour. After the reaction was completed, the reaction mixture was allowed to cool to room temperature, and 4-
A suspension of 26.8 g of (trans-4-propylcyclohexyl) cyclohexanone in 140 ml of THF was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. After completion of the reaction, dilute hydrochloric acid was added and the reaction product was extracted with ethyl acetate. After the solvent was distilled off, the extract was dissolved in 200 ml of toluene, 1 ml of sulfuric acid was added, and the mixture was stirred at 110 ° C for 1 hour. After completion of the reaction, the reaction product was allowed to cool at room temperature, washed successively with saturated aqueous sodium hydrogencarbonate solution, water and saturated brine, dried over anhydrous sodium sulfate, and evaporated to remove the solvent, 1- [4 −
39.6 g of crude crystals of (trans-4-propylcyclohexyl) cyclohexen-1-yl] -3,5-difluoro-4-methoxybenzene were obtained.
【0070】上記で得た1−[4−(トランス−4−プ
ロピルシクロヘキシル)シクロヘキセン−1−イル]−
3,5−ジフルオロ−4−メトキシベンゼンの全量を酢
酸エチル400mlに溶解し、パラジウム−炭素4.0
gを加え、常圧の水素雰囲気下、室温で4時間接触還元
した。反応終了後、触媒を濾別し、溶媒を溜去して、1
−[4−(トランス−4−プロピルシクロヘキシル)シ
クロヘキシル]−3,5−ジフルオロ−4−メトキシベ
ンゼンの粘ちゅうな油状物を得た。これをエタノールか
ら再結晶させて、白色結晶37.4gを得た。 NMR:δ=0.84〜0.95(t,3H),1.0
〜2.34(m,14H),3.88(s,3H),
7.26(d,J=8Hz,2H) MS:m/e=350(M+) (1−c) 2,6−ジフルオロ−4−[トランス−
4−(トランス−4−プロピルシクロヘキシル)シクロ
ヘキシル]フェノールの合成1- [4- (trans-4-propylcyclohexyl) cyclohexen-1-yl] -obtained above
The total amount of 3,5-difluoro-4-methoxybenzene was dissolved in 400 ml of ethyl acetate, and palladium-carbon 4.0 was added.
g was added, and catalytic reduction was carried out at room temperature for 4 hours in a hydrogen atmosphere at normal pressure. After the reaction was completed, the catalyst was filtered off, the solvent was distilled off, and 1
A viscous oil of-[4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene was obtained. This was recrystallized from ethanol to obtain 37.4 g of white crystals. NMR: δ = 0.84 to 0.95 (t, 3H), 1.0
~ 2.34 (m, 14H), 3.88 (s, 3H),
7.26 (d, J = 8 Hz, 2H) MS: m / e = 350 (M + ) (1-c) 2,6-difluoro-4- [trans-
Synthesis of 4- (trans-4-propylcyclohexyl) cyclohexyl] phenol
【0071】[0071]
【化21】 [Chemical 21]
【0072】上記(1−b)で得た、1−[トランス−
4−(トランス−4−プロピルシクロヘキシル)シクロ
ヘキシル]−3,5−ジフルオロ−4−メトキシベンゼ
ン27.2gを酢酸560mlに溶解した。溶解後、4
8%臭化水素酸800mlを加え、8時間加熱還流し
た。反応終了後、放冷し、反応液を水にあけ、反応生成
物をトルエンで抽出した。抽出後、水層が中性になるま
で水で洗浄し、無水硫酸ナトリウムで脱水乾燥し、溶媒
を溜去して得られた粗結晶を、ヘキサンから再結晶させ
て、2,6−ジフルオロ−4−[トランス−4−(トラ
ンス−4−プロピルシクロヘキシル)シクロヘキシル]
フェノール18.4gを得た。 (実施例1) 1−[トランス−4−(トランス−4
−プロピルシクロヘキシル)シクロヘキシル]−3,5
−ジフルオロ−4−アリルオキシベンゼン(第1表中の
No.1の化合物)の合成1- [trans-obtained in the above (1-b)
2- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene (27.2 g) was dissolved in 560 ml of acetic acid. After dissolution 4
800 ml of 8% hydrobromic acid was added, and the mixture was heated under reflux for 8 hours. After completion of the reaction, the mixture was allowed to cool, the reaction solution was poured into water, and the reaction product was extracted with toluene. After extraction, the aqueous layer was washed with water until neutral, dehydrated and dried over anhydrous sodium sulfate, and the crude crystals obtained by distilling off the solvent were recrystallized from hexane to give 2,6-difluoro- 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl]
18.4 g of phenol was obtained. (Example 1) 1- [trans-4- (trans-4
-Propylcyclohexyl) cyclohexyl] -3,5
-Synthesis of difluoro-4-allyloxybenzene (Compound No. 1 in Table 1)
【0073】[0073]
【化22】 [Chemical formula 22]
【0074】上記参考例で得た2,6−ジフルオロ−4
−[トランス−4−(トランス−4−プロピルシクロヘ
キシル)シクロヘキシル]フェノール1.5gのTHF
15ml懸濁液を、水素化ナトリウム0.14gのTH
F15ml懸濁液中に滴下し、1時間室温で攪拌した。
さらに、臭化アリル0.61gのTHF10ml溶液を
滴下し、さらに3時間加熱還流した。反応終了後、放冷
し、反応液に水を加え、反応生成物をトルエンで抽出し
た。抽出液を、水及び飽和食塩水で洗浄した後、溶媒を
溜去して、シリカゲルカラムクロマトグラフィー(ヘキ
サン/酢酸エチル)を用いて精製して、さらにエタノー
ルから再結晶させて、1−[トランス−4−(トランス
−4−プロピルシクロヘキシル)シクロヘキシル]−
3,5−ジフルオロ−4−アリルオキシベンゼンの白色
結晶1.1gを得た。 相転移温度(℃):23.2(Cr→I)、154.5
(N−I) NMR:δ=0.87(m,5H),0.98〜1.1
6(m,4H),1.74(m,4H),1.85
(m,4H),2.36(tt,J=12,1.5H
z,1H),4.59(d,J=6Hz,2H),5.
24(d,J=10Hz,1H),5.35(dd,J
=17,1.5Hz,1H),6.0〜6.1(m,1
H),6.7(m,2H) MS:376(M+) (実施例2) 液晶組成物の調製2,6-difluoro-4 obtained in the above reference example
-[Trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenol 1.5 g THF
A 15 ml suspension was prepared by adding 0.14 g of sodium hydride to TH.
It was added dropwise to F15 ml suspension and stirred at room temperature for 1 hour.
Further, a solution of 0.61 g of allyl bromide in 10 ml of THF was added dropwise, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the mixture was allowed to cool, water was added to the reaction solution, and the reaction product was extracted with toluene. The extract was washed with water and saturated brine, the solvent was evaporated, the product was purified by silica gel column chromatography (hexane / ethyl acetate), and recrystallized from ethanol to give 1- [trans. -4- (trans-4-propylcyclohexyl) cyclohexyl]-
1.1 g of white crystals of 3,5-difluoro-4-allyloxybenzene were obtained. Phase transition temperature (° C): 23.2 (Cr → I), 154.5
(N-I) NMR: δ = 0.87 (m, 5H), 0.98 to 1.1
6 (m, 4H), 1.74 (m, 4H), 1.85
(M, 4H), 2.36 (tt, J = 12, 1.5H
z, 1H), 4.59 (d, J = 6Hz, 2H), 5.
24 (d, J = 10 Hz, 1H), 5.35 (dd, J
= 17, 1.5 Hz, 1H), 6.0-6.1 (m, 1
H), 6.7 (m, 2H) MS: 376 (M + ) (Example 2) Preparation of liquid crystal composition
【0075】[0075]
【化23】 [Chemical formula 23]
【0076】(式中、シクロヘキサン環はトランス配置
を表わし、「%」は「重量%」を表わす。)からなる母
体液晶(A)を調製したところ、116.7℃以下でネ
マチック(N)相を示した。また、低温で放置して結晶
化させた後、融点を測定したところ、約11℃であっ
た。また、これを用いて作製したTNセルのしきい値電
圧(Vth)は以下の通りであった。(Wherein the cyclohexane ring represents a trans configuration and "%" represents "% by weight"), a matrix liquid crystal (A) was prepared, and a nematic (N) phase was obtained at a temperature of 116.7 ° C or lower. showed that. Further, when the melting point was measured after being left to crystallize at a low temperature, it was about 11 ° C. Further, the threshold voltage (V th ) of the TN cell manufactured using this was as follows.
【0077】 N相の上限温度(TN-I) 116.7℃ 融点 約11℃ しきい値電圧(Vth) 2.43V この母体液晶(A)85重量%及び実施例1で得られた
(No.1)の化合物15重量%からなる液晶組成物
(M−1)を調製した。この(M−1)のN相の上限温
度(TN-I)、融点は以下の通りであった。Maximum temperature of N phase (T NI ) 116.7 ° C. Melting point about 11 ° C. Threshold voltage (V th ) 2.43 V 85% by weight of this host liquid crystal (A) and obtained in Example 1 (No. A liquid crystal composition (M-1) containing 15% by weight of the compound of 1) was prepared. The maximum temperature (T NI ) and melting point of the N phase of this (M-1) were as follows.
【0078】 N相の上限温度(TN-I) 121.0℃ 融点 約−5℃ しきい値電圧(Vth) 2.53V このように(No.1)の化合物は、組成物のTN-Iを
大きく上昇させることができ、しかもしきい値電圧をほ
とんど上昇させていないことが明らかである。 (比較例1)母体液晶(A)85重量%及び(No.
1)の化合物の類似構造を有する式(II−1)Maximum temperature of N phase (T NI ) 121.0 ° C. Melting point about −5 ° C. Threshold voltage (V th ) 2.53 V Thus, the compound of (No. 1) has T NI of the composition. It is clear that the threshold voltage can be greatly increased and the threshold voltage is hardly increased. (Comparative Example 1) 85% by weight of the base liquid crystal (A) and (No.
Formula (II-1) having a similar structure to the compound of 1)
【0079】[0079]
【化24】 [Chemical formula 24]
【0080】の化合物15重量%からなる液晶組成物
(M−2)を調製した。この(M−2)のTN-I、融点
及び同様にして測定したVthは以下の通りであった。 N相の上限温度(TN-I) 112.8℃ 融点 約 6℃ しきい値電圧(Vth) 2.27V このように(M−1)と比較すると、Vthは低下したも
のの、TN-Iも大きく低下してしまい、また融点もあま
り降下しなかった。 (比較例2)母体液晶(A)85重量%及び(No.
1)の化合物の類似構造を有する一般式(III−1)A liquid crystal composition (M-2) containing 15% by weight of the compound of the above was prepared. The T NI , melting point and V th measured in the same manner of this (M-2) were as follows. Upper limit temperature of N-phase (T NI ) 112.8 ° C. Melting point of about 6 ° C. Threshold voltage (V th ) 2.27 V As described above, although V th is lower than that of (M-1), T NI is also The melting point was greatly lowered, and the melting point was not lowered so much. (Comparative Example 2) 85% by weight of the base liquid crystal (A) and (No.
The compound of the general formula (III-1) having a similar structure to the compound of 1)
【0081】[0081]
【化25】 [Chemical 25]
【0082】の化合物15重量%からなる液晶組成物
(M−3)を調製した。この(M−3)のTN-I、融点
及び同様にして測定したVthは以下の通りであった。 N相の上限温度(TN-I) 124.3℃ 融点 約 2℃ しきい値電圧(Vth) 2.55V このように(M−1)と比較すると、TN-Iはほとんど
変わらなかったが、融点は大きく上昇してしまい、Vth
もやや上昇してしまった。A liquid crystal composition (M-3) consisting of 15% by weight of the compound of was prepared. The T NI , melting point, and V th measured in the same manner of this (M-3) were as follows. Upper limit temperature of N phase (T NI ) 124.3 ° C. Melting point about 2 ° C. Threshold voltage (V th ) 2.55 V Thus, when compared with (M-1), T NI was almost unchanged, but melting point Greatly increases, and V th
It has risen slightly.
【0083】[0083]
【発明の効果】本発明に係わる一般式(I)で表わされ
る化合物は、実施例に示したように工業的にも容易に製
造でき、熱、光、水等に対し、化学的に安定である。ま
た、ネマチック液晶として現在汎用されている母体液晶
との相溶性にも優れている。しかも、添加により、組成
物のしきい値電圧(Vth)をあまり上昇させることな
く、液晶相の温度範囲を低温域にも高温域にも拡大させ
ることが可能である。従って、温度範囲が広く、かつ低
電圧駆動が要求される各種液晶表示素子、特にアクティ
ブマトリックス駆動用の液晶材料として非常に有用であ
る。INDUSTRIAL APPLICABILITY The compound represented by the general formula (I) according to the present invention can be easily produced industrially as shown in Examples and is chemically stable against heat, light, water and the like. is there. Further, it is also excellent in compatibility with the host liquid crystal that is currently widely used as a nematic liquid crystal. Moreover, the addition makes it possible to extend the temperature range of the liquid crystal phase to a low temperature region and a high temperature region without raising the threshold voltage (V th ) of the composition so much. Therefore, it is very useful as various liquid crystal display elements having a wide temperature range and required to be driven at a low voltage, particularly as a liquid crystal material for active matrix driving.
Claims (6)
アルケニル基を表わし、L及びMはそれぞれ独立的に、
単結合または−CH2CH2−を表わすが、少なくとも一
方は単結合を表わし、R2は炭素原子数3〜12のアル
ケニル基を表わし、シクロヘキサン環の2つの置換基は
トランス配置である。)で表わされる化合物。1. A compound represented by the general formula (I): (In the formula, R 1 represents an alkyl group or an alkenyl group having 1 to 12 carbon atoms, L and M are each independently,
A single bond or --CH 2 CH 2- , at least one of which represents a single bond, R 2 represents an alkenyl group having 3 to 12 carbon atoms, and the two substituents on the cyclohexane ring are in the trans configuration. ) The compound represented by.
載の一般式(I)で表わされる化合物。2. The compound represented by the general formula (I) according to claim 1, wherein L and M are both single bonds.
ルケニル基である請求項2記載の一般式(I)で表わさ
れる化合物。3. The compound represented by the general formula (I) according to claim 2, wherein R 2 is a linear 2-alkenyl group having 3 to 7 carbon atoms.
キル基である請求項3記載の一般式(I)で表わされる
化合物。4. The compound represented by the general formula (I) according to claim 3, wherein R 1 is a linear alkyl group having 1 to 10 carbon atoms.
ル基である請求項4記載の一般式(I)で表わされる化
合物。5. The compound represented by the general formula (I) according to claim 4, wherein R 1 is a linear alkyl group having 1 to 7 carbon atoms.
る化合物を含有する液晶組成物。6. A liquid crystal composition containing a compound represented by the general formula (I) according to claim 1.
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JP05177394A JP3632772B2 (en) | 1994-03-23 | 1994-03-23 | 4-alkenyloxy-3,5-difluorobenzene derivatives |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6183822B1 (en) * | 1998-07-15 | 2001-02-06 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Polymerizable mesogenic fluorophenylenes |
EP1840185A1 (en) * | 2004-12-10 | 2007-10-03 | Adeka Corporation | Liquid crystal composition |
WO2015093193A1 (en) * | 2013-12-16 | 2015-06-25 | Dic株式会社 | Alkenyl ether compound and liquid crystal composition using same |
CN106459767A (en) * | 2014-07-31 | 2017-02-22 | Dic株式会社 | Nematic liquid crystal composition |
-
1994
- 1994-03-23 JP JP05177394A patent/JP3632772B2/en not_active Expired - Fee Related
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6183822B1 (en) * | 1998-07-15 | 2001-02-06 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Polymerizable mesogenic fluorophenylenes |
EP1840185A1 (en) * | 2004-12-10 | 2007-10-03 | Adeka Corporation | Liquid crystal composition |
EP1840185A4 (en) * | 2004-12-10 | 2009-01-07 | Adeka Corp | Liquid crystal composition |
US7618554B2 (en) | 2004-12-10 | 2009-11-17 | Adeka Corporation | Liquid crystal composition |
WO2015093193A1 (en) * | 2013-12-16 | 2015-06-25 | Dic株式会社 | Alkenyl ether compound and liquid crystal composition using same |
JP5862996B2 (en) * | 2013-12-16 | 2016-02-16 | Dic株式会社 | Alkenyl ether compound and liquid crystal composition using the same |
KR20160055924A (en) | 2013-12-16 | 2016-05-18 | 디아이씨 가부시끼가이샤 | Alkenyl ether compound and liquid crystal composition using same |
CN105849075A (en) * | 2013-12-16 | 2016-08-10 | Dic株式会社 | Alkenyl ether compound and liquid crystal composition using same |
JPWO2015093193A1 (en) * | 2013-12-16 | 2017-03-16 | Dic株式会社 | Alkenyl ether compound and liquid crystal composition using the same |
US9822301B2 (en) | 2013-12-16 | 2017-11-21 | Dic Corporation | Alkenyl ether compound and a liquid crystal composition using the same |
CN106459767A (en) * | 2014-07-31 | 2017-02-22 | Dic株式会社 | Nematic liquid crystal composition |
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