JPH01144491A - Liquid crystal material - Google Patents
Liquid crystal materialInfo
- Publication number
- JPH01144491A JPH01144491A JP62303741A JP30374187A JPH01144491A JP H01144491 A JPH01144491 A JP H01144491A JP 62303741 A JP62303741 A JP 62303741A JP 30374187 A JP30374187 A JP 30374187A JP H01144491 A JPH01144491 A JP H01144491A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- optically active
- crystal material
- carboxylic acid
- reacting
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 20
- -1 2-metylbutyloxy Chemical group 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 230000010287 polarization Effects 0.000 abstract description 11
- 230000002269 spontaneous effect Effects 0.000 abstract description 11
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004990 Smectic liquid crystal Substances 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 abstract description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000002140 halogenating effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000005264 High molar mass liquid crystal Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- DSADESJTZDXCPN-UHFFFAOYSA-N 3-hydroxy-4-phenylbenzoic acid Chemical compound OC1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 DSADESJTZDXCPN-UHFFFAOYSA-N 0.000 description 1
- HZBABTUFXQLADL-UHFFFAOYSA-N 4-Heptyloxyphenol Chemical compound CCCCCCCOC1=CC=C(O)C=C1 HZBABTUFXQLADL-UHFFFAOYSA-N 0.000 description 1
- PWRCOONECNWDBH-UHFFFAOYSA-N 4-prop-2-enoxyphenol Chemical compound OC1=CC=C(OCC=C)C=C1 PWRCOONECNWDBH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XXDKRMQJHKMZPC-UHFFFAOYSA-N octan-2-yl 4-methylbenzenesulfonate Chemical compound CCCCCCC(C)OS(=O)(=O)C1=CC=C(C)C=C1 XXDKRMQJHKMZPC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は強誘電性カイラルスメクチック液晶材料に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a ferroelectric chiral smectic liquid crystal material.
（従来の技術）
現在、液晶表示素子としてはＴ Ｎ （Ｔｗｉｓｔｅｄ
Ｎｅｍａｔｉｃ）型表示方式が最も広く用いられている
。(Prior Art) Currently, T N (Twisted
The nematic type display method is most widely used.
しかし、ＴＮＮ型表示示式は応答速度の点で発光型表示
素子（エレクトロルミネッセンス、プラズマデイスプレ
ィなど）と比較して劣るという問題がある。そして、こ
の点における改善は種々試みられているが、大幅な改善
の可能性はほとんど残っていない。However, the TNN type display has a problem in that it is inferior to light emitting type display elements (electroluminescence, plasma display, etc.) in terms of response speed. Various attempts have been made to improve this point, but there remains little possibility of significant improvement.
このため、ＴＮ型表未方式に代わる別の液晶表示方式の
開発が不可欠である。そうした試みの一つとして強誘電
性液晶を利用した表示方式がある（Ｎ、Ａ、Ｃ１ａｒｋ
ｅｔ ａｌ、；Ａｐｐｌｉｄｅ Ｐｈｙｓ、 Ｌｅｔ
ｔ、、 ３８゜８９９（１９８０））、この方式は強誘
電性液晶のカイラルスメクチックＣ相（以下、ＳＣ本相
と記す）又はカイラルスメクチックＨ相（以下、ＳＨ零
相と記す）などを利用するものである。こうした強誘電
性液晶を用いた表示素子においては、実用上、室温付近
でＳａｔ相やＳＨ本相を示すことが望ましい。Therefore, it is essential to develop another liquid crystal display method to replace the TN type. One such attempt is a display system using ferroelectric liquid crystals (N, A, C1ark).
et al,;Apply Phys, Let
38°899 (1980)), this method utilizes the chiral smectic C phase (hereinafter referred to as SC main phase) or chiral smectic H phase (hereinafter referred to as SH zero phase) of ferroelectric liquid crystal. It is something. In a display element using such a ferroelectric liquid crystal, it is practically desirable that the display element exhibits a Sat phase or an SH main phase near room temperature.
また、強誘電性液晶を用いた表示素子において、応答時
間で、回転粘性係数η及び自発分極Ｐｓとの間には、一
般に
の関係がある（Ｎ、Ａ、ＣＩａｒｋ ｅｔ ａｌ、；１
ｂｉｄ、） ＊なお、０式でＥは印加電圧（ただし、し
きい値電圧Ｅｃ＜＜Ｅ）である、０式から明らかなよう
に、応答速度を速くするためには１回転粘性係数が小さ
く、かつ自発分極が大きいことが必要である。In addition, in display elements using ferroelectric liquid crystals, there is a general relationship between the rotational viscosity coefficient η and the spontaneous polarization Ps in response time (N, A, CIark et al.; 1
bid, ) *In the formula 0, E is the applied voltage (however, the threshold voltage Ec<<E).As is clear from the formula 0, in order to increase the response speed, the one-turn viscosity coefficient must be small. , and the spontaneous polarization is required to be large.
しかし、現状の強誘電性液晶化合物のうち、室温付近で
安定なＳｃ末相を呈し、かつ回転粘性係数が小さく自発
分極が大きい材料はない０例えば、Ｓｃ本和の温度域が
広く、自発分極の大きい強誘電性カイラルスメクチック
液晶化合物として、 Ｓ−（＋）−ｐ−（１−メチル−
へブチルオキシ）−フェニル−４゛−アルコキシ−４−
ビフェニルカルボキシレート、アルコキシフェニル−４
’−５−（＋）−ｐ−（１−メチル−へブチルオキシ）
−４−ビフェニルカルボキシレートなどが知られている
（Ｔ、Ｉｎｕｋａｉ ａｔ ａｌ、；Ｍｏｌ。However, among the current ferroelectric liquid crystal compounds, there is no material that exhibits a stable Sc terminal phase near room temperature, has a small rotational viscosity coefficient, and has a large spontaneous polarization. S-(+)-p-(1-methyl-
hebutyloxy)-phenyl-4'-alkoxy-4-
Biphenylcarboxylate, alkoxyphenyl-4
'-5-(+)-p-(1-methyl-hebutyloxy)
-4-biphenylcarboxylate and the like are known (T, Inukai at al,; Mol.
Ｃｒｙｓｔ、 Ｌｉｑ、 Ｃｒｙｓｔ、、 １４１．２
５１（１９８８））が、これらの化合物はＳ＋ｊ相が室
温よりかなり高温域にあり、しかも回転粘性係数が大き
いため充分速い応答速度が得られていない。Cryst, Liq, Cryst, 141.2
51 (1988)), but in these compounds, the S+j phase is in a much higher temperature range than room temperature, and the rotational viscosity coefficient is large, so that a sufficiently fast response speed cannot be obtained.
一方、高分子化合物のうちでは、粘性が低いポリシロキ
サンの存在が知られている。これは、シロキサン結合回
りの内部回転障害が小さく、例えばアルキル鎖と比較す
ると高分子鎖の屈曲性が大きいためと考えられる。On the other hand, among polymer compounds, it is known that polysiloxanes have low viscosity. This is thought to be because internal rotational hindrance around the siloxane bond is small and the flexibility of the polymer chain is greater than, for example, an alkyl chain.
こうした知見をもとにして、高分子液晶でもシロキサン
鎖を主鎖骨格とする側鎖型高分子液晶について研究が行
われている０例えば、主鎖がアクリル重合体である高分
子液晶と比較すると、主鎖がシロキサン共重合体である
高分子液晶はスメクチック相の温度域が低温域に広がり
（Ｈ，Ｆｉｎｋｅｌ−ｍａｎｎ ｅｔ ａｌ、；Ｍａｋ
ｒｏｍｏｌ、Ｃｈｅｍ、、Ｒａｐｉｄ Ｃｏｍｍｕｎ、
、ユ。Based on these findings, research is being conducted on side-chain polymer liquid crystals that have siloxane chains as their main chain skeleton.0For example, compared to polymer liquid crystals whose main chain is an acrylic polymer, In polymer liquid crystals whose main chain is a siloxane copolymer, the temperature range of the smectic phase expands to a low temperature range (H, Finkel-mann et al.; Mak
romol, Chem, Rapid Commun,
, Yu.
３１（＋９８０）） 、粘性パラメータが１７２０とい
う結果が得られティる（Ｈ，Ｐｒａｎｏｔｏ ｅｔ ａ
ｌ、；Ｍｏ１．Ｃｒ７ｓｔ、Ｌｉｑ。31 (+980)), and the viscosity parameter is 1720 (H, Pranoto et al.
l,;Mo1. Cr7st, Liq.
Ｃｒｙｓ’ｌ、 ９８，２９９（１９８３）） 、 シ
かし、これらの高分子液晶ではシロキサン結合が主鎖骨
格となっているため、回転粘性係数を小さくすることに
も限度がある。Crys'l, 98, 299 (1983)) However, since these polymeric liquid crystals have siloxane bonds as the main chain skeleton, there is a limit to how low the rotational viscosity coefficient can be made.
更に、強誘電性液晶セルでは、耐メカニカルシ百ツクに
対する問題もまだ解決されていない。Furthermore, in ferroelectric liquid crystal cells, the problem of mechanical shock resistance has not yet been solved.
（発明が解決しようとする問題点）
本発明は上記問題点を解決するためになされたものであ
り、ＳＣ末相の温度域が低温域で広く。(Problems to be Solved by the Invention) The present invention has been made to solve the above problems, and the temperature range of the SC terminal phase is wide in the low temperature range.
かつ小さい回転粘性係数と大きい自発分極を有し応答速
度が速い液晶材料を提供することを目的とする。Another object of the present invention is to provide a liquid crystal material that has a small rotational viscosity coefficient, a large spontaneous polarization, and a fast response speed.
［発明の構成］
（問題点を解決するための手段と作用）本発明の液晶材
料は、一般式（Ｉ）
Ｈ３
（（１）式中、ｍはＯ〜５の整数、ｎは２〜１０の整数
を示し、ＯＲは光学活性を有するアルコキシ基又はアラ
ルキルオキシ基を示す）
で表わされる少なくとも１種を含有することを特徴とす
るものである。[Structure of the invention] (Means and effects for solving the problems) The liquid crystal material of the present invention has the general formula (I) H3 (in formula (1), m is an integer of 0 to 5, and n is 2 to 10 is an integer of , and OR represents an alkoxy group or an aralkyloxy group having optical activity.
一般式（Ｉ）の例としては、ｍ＝１、ｎ＝２〜ｌＯの整
数で、ＯＲが光学活性２−メチルブトキシ基であるもの
、ｍ＝１、ｎ＝２〜１０の整数で、ＯＲが光学活性１−
メチルへブチルオキシ基であるもの、ｍ＝２．ｎ＝２〜
１０の整数で、ＯＲが光学活性１−メチルブトキシ基で
あるもの、ｍ＝２、ｎ＝２〜１０の整数で、ＯＲが光学
活性１−メチルへブチルオキシ基であるもの、ｍ＝３、
ｎ＝２〜８の整数テ、ＯＲが光学活性２−メチルブトキ
シ基であるもの、ｍ＝３、ｎ＝２〜１０の整数で、ＯＲ
が光学活性１−メチルへブチルオキシ基であるもの、ｍ
＝４、ｎ＝２〜６の整数で、ＯＲが光学活性２−メチル
ブトキシ基であるものｌｍ＝４、ｎ＝２〜６の整数で、
ＯＲが光学活性１−メチルへブチルオキシ基であるも
の、ｍ＝５、ｎ＝２〜４の整数で、ＯＲが光学活性２−
メチルブトキシ基であるもの、ｍ＝５．ｎ＝＝２〜４の
整数で、 ＯＲが光学活性ｌ−メチルへブチルオキシ基
であるものが挙げられる。Examples of general formula (I) include m = 1, n = an integer of 2 to 1O, and OR is an optically active 2-methylbutoxy group, m = 1, n = an integer of 2 to 10, and OR is optically active 1-
methylhebutyloxy group, m=2. n=2~
An integer of 10 and OR is an optically active 1-methylbutoxy group, m = 2, n = an integer of 2 to 10 and OR is an optically active 1-methylhebutyloxy group, m = 3,
n = an integer of 2 to 8, OR is an optically active 2-methylbutoxy group, m = 3, n = an integer of 2 to 10, OR
is an optically active 1-methylhebutyloxy group, m
= 4, n = an integer of 2 to 6, and OR is an optically active 2-methylbutoxy group lm = 4, n = an integer of 2 to 6,
OR is an optically active 1-methylhebutyloxy group, m = 5, n = an integer from 2 to 4, and OR is an optically active 2-
methylbutoxy group, m=5. Examples include those in which n is an integer of 2 to 4, and OR is an optically active l-methylhebutyloxy group.
これらの化合物は液晶状態で強誘電性を示す。These compounds exhibit ferroelectricity in a liquid crystal state.
また、アルキル基と比較して内部回転障害が小さく屈曲
性が大きいポリシロキシル基が分子末端に導入されてい
るので、ポリシロキシル鎖を主鎖骨格とする高分子液晶
よりも更に回転粘性係数が小さくなり、しかも自発分極
が大きい、このため、室温付近に安定なＳｃ求相を呈し
、かつ応答速度が速い実用的な強誘電性液晶材料を提供
でき、更には耐メカニカルショ゛ツクにも優れた液晶表
示素子を提供することができる。In addition, since a polysiloxyl group, which has less internal rotational hindrance and greater flexibility than an alkyl group, is introduced at the end of the molecule, the rotational viscosity coefficient is even smaller than that of a polymer liquid crystal whose main chain skeleton is a polysiloxyl chain. In addition, it has a large spontaneous polarization, which makes it possible to provide a practical ferroelectric liquid crystal material that exhibits stable Sc phase attraction near room temperature and has a fast response speed, as well as a liquid crystal display with excellent mechanical shock resistance. element can be provided.
これらの化合物は単独で、又は２種以上混合して用いら
れる。また、これらの強誘電性液晶と。These compounds may be used alone or in combination of two or more. Also, with these ferroelectric liquid crystals.
単独では強誘電性液晶とならない化合物とを混合しても
、強誘電性を示す液晶材料として用いることができる。Even when mixed with a compound that does not produce a ferroelectric liquid crystal by itself, it can be used as a liquid crystal material exhibiting ferroelectric properties.
次に、一般式（Ｉ）の化合物の製造方法を次頁に示す反
応式を参照して説明する。Next, a method for producing the compound of general formula (I) will be explained with reference to the reaction formula shown on the next page.
ＣＨ，、：ＣＨ（ＣＨ２墳ｏ−＠−ＯＨ■ 兜
■Ｃ）１．７ＣＨ−（ＣＨ２７０舎０−Ｃ−＠−＠−
ＯＲ＠Ｈ３
すなわ・ち、ピリジン中で光学活性アルコール■と重板
のｐ−トルエンスルホン酸クロライドとを反応させて、
光学活性ｐ−トルエンスルホン酸アルキルエステル■を
生成させる０次に、エタノール水溶液中、アルカリ存在
下にｐ−）ルエンスルホン酸アルキルエステル■と４−
ヒドロキシビフェニル−４−カルボン酸とを加熱して、
光学活性４°−フルキルオキシビフェニル−４−カルボ
ン酸■を生成させる。つづいて、光学活性４°−フルキ
ルオキシビフェニル−４−カルボン酸■と塩化チオニル
などのハロゲン化剤とを反応させて、光学活性４−フル
キルオキシビフェニル−４−カルボン酸ハロゲン化物■
を生成させる。CH,,:CH(CH2 mound o-@-OH■ Kabuto
■C) 1.7CH-(CH270 building 0-C-@-@-
OR@H3 In other words, by reacting optically active alcohol ■ with heavy p-toluenesulfonic acid chloride in pyridine,
Next, in an aqueous ethanol solution in the presence of an alkali, p-)toluenesulfonic acid alkyl ester ■ and 4-
By heating hydroxybiphenyl-4-carboxylic acid,
Optically active 4°-furkyloxybiphenyl-4-carboxylic acid (2) is produced. Next, optically active 4°-furkyloxybiphenyl-4-carboxylic acid (■) is reacted with a halogenating agent such as thionyl chloride to form optically active 4-flukyloxybiphenyl-4-carboxylic acid halide (■).
to generate.
次いで、アルケニルオキシフェノール■と光学活性４−
アルキルオキシビフェニル−４−カルボン酸ハロゲン化
物■とを反応させて、光学活性４−アルケニルオキシフ
ェニル−４１−フルキルオキシビフェニル−４−カルボ
ン酸エステル■を生成させる。Next, alkenyloxyphenol ■ and optically active 4-
The optically active 4-alkenyloxyphenyl-41-furkyloxybiphenyl-4-carboxylic acid ester (2) is produced by reacting with the alkyloxybiphenyl-4-carboxylic acid halide (1).
更に、白金触媒下で、光学活性４−アルケニルオキシフ
ェニル−４゛−アルキルオキシビフェニル−４−カルボ
ン酸エステル■とトリメチルジメチルポリシロキサンと
を反応させて、光学活性４−（トリメチルシリルジメチ
ルボリシロキンルアルキルオキシ）フェニル−４’−（
アルキルオキシ）ビフェニル−４−カルボン酸エステル
ＣＩ）を生成させる。Furthermore, optically active 4-alkenyloxyphenyl-4'-alkyloxybiphenyl-4-carboxylic acid ester ■ and trimethyldimethylpolysiloxane were reacted under a platinum catalyst to form optically active 4-(trimethylsilyldimethylbolysilokinerualkyl). oxy)phenyl-4'-(
alkyloxy)biphenyl-4-carboxylic acid ester CI) is produced.
（実施例） 以下、本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
実施例１
以下のようにして光学活性４−（３−ペンタメチルジシ
ロキシプロピルオキシ）フェニル−４’−（１−メチル
へプチルオ午シ）ビフェニル−４−カルボン酸エステル
（（１） 式において、ＯＲが１−メチルへブチルオキ
シ基、ｍ＝１．ｎ＝３の化合物）を製造した。Example 1 Optically active 4-(3-pentamethyldisiloxypropyloxy)phenyl-4'-(1-methylheptyloxy)biphenyl-4-carboxylic acid ester ((1) in the formula: A compound in which OR is a 1-methylhebutyloxy group and m=1.n=3 was produced.
Ｓ−（＋）−２−オクタツール１００ｇ （０，７８８
ｍａｌ）を乾燥ピリジン５００１に溶解し、系内の温度
が１０℃以上にならないようにしながら、ｐ−）ルエン
スルホン酸クロライド２９３ ｇ （１，５８３ｍｏｌ
）を加え、 ３時間攪拌した。これに水５００１を加え
て２時間攪拌した後、エーテル５００ｏ＋１で抽出し、
８Ｎ塩酸で洗浄し、更に中性になるまで水洗した。エ
ーテルを留去することにより、残留物として光学活性ｐ
ｉミルエンスルホン−１−メチルへブチルエステル１６
４ ｇを得た。S-(+)-2-octatool 100g (0,788
293 g (1,583 mol
) and stirred for 3 hours. After adding water 5001 to this and stirring for 2 hours, it was extracted with ether 500o+1,
It was washed with 8N hydrochloric acid and further washed with water until it became neutral. By distilling off the ether, the optically active p
i Millenesulfone-1-methylhebutyl ester 16
4 g was obtained.
一方、４′−ヒドロキシビフェニル−４−カルボン酸５
０ ｇ （０，２３４ｍｏ１）、エタノール８００＋ｌ
Ｉｌ、５０％水酸化ナトリウム水溶液 １００ｍ１を混
合攪拌しておき、これに上記光学活性Ｐ−トルエンスル
ポン酸−１−メチルヘプチルエステル８５．７ｇ （０
，２８０ａ＋ｏｌ）を注入して８０℃で６時間加熱攪拌
した。エタノールの大部分を留去し、水２！；Ｌを加え
て攪拌した後、６Ｎ塩酸で酸性化し、析出物をろ取し、
エタノールで再結晶を縁り返して、光学活性４−（１−
メチルへブチルオキシ）ビフェニル−４−カルボン酸を
得た。この反応ではワルデン反転が起っていると考えら
れるので、生成した光学活性４−（１−メチルへブチル
オキシ）ビフェニル−４−カルボン酸はＲ体であると推
定される。On the other hand, 4'-hydroxybiphenyl-4-carboxylic acid 5
0 g (0,234 mo1), ethanol 800+l
Il, 100 ml of 50% aqueous sodium hydroxide solution was mixed and stirred, and 85.7 g of the above optically active P-toluenesulfonic acid-1-methylheptyl ester (0
, 280a+ol) and heated and stirred at 80° C. for 6 hours. Most of the ethanol is distilled off and water is removed! ; After adding L and stirring, acidify with 6N hydrochloric acid and collect the precipitate by filtration.
The optically active 4-(1-
Methylhebutyloxy)biphenyl-4-carboxylic acid was obtained. Since Walden inversion is thought to occur in this reaction, the optically active 4-(1-methylhebutyloxy)biphenyl-4-carboxylic acid produced is presumed to be in the R form.
次に、上記光学活性４’−（１−メチルへブチルオキシ
）ビフェニル−４−カルボン酸２．５ｇと塩化千オニル
５０ｆｆ１１とを８０℃で２時間加熱攪拌した後、塩化
チオニルを留去し、光学活性４’−（１−メチルへブチ
ルオキシ）ビフェニル−４−カルボン酸クロライドを得
た。これをテトラヒドロフラン３０ｆｆ１１に溶解し、
そこに４−アリルオキシフェノール１．３ｇをテトラヒ
ドロフラン２５０！１に溶解したものを滴下し、室温で
２時間攪拌した。これにトルエン２００ｍ ｌ ヲ加え
て中性になるまで攪拌した後、トルエンを溶離液として
カラムクロマトグラフィーにより濃縮した後、エタノー
ルと酢酸エチルを用いて再結晶を行ない、光学活性４−
アリルオキシフェニル−４′＝（１−メチルヘプチルオ
キシ
ボン酸エステル１．８ｇを得た。Next, 2.5 g of the optically active 4'-(1-methylhebutyloxy)biphenyl-4-carboxylic acid and 50 ff11 of 1,000 onyl chloride were heated and stirred at 80°C for 2 hours, and thionyl chloride was distilled off. Active 4'-(1-methylhebutyloxy)biphenyl-4-carboxylic acid chloride was obtained. Dissolve this in 30ff11 of tetrahydrofuran,
A solution of 1.3 g of 4-allyloxyphenol dissolved in 250:1 of tetrahydrofuran was added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. After adding 200ml of toluene and stirring until the mixture became neutral, it was concentrated by column chromatography using toluene as an eluent, and recrystallized using ethanol and ethyl acetate.
1.8 g of allyloxyphenyl-4'=(1-methylheptyloxybonylate) was obtained.
次いで，光学活性４−アリルオキシフェニル−４′−（
１−メチルヘプチルオキシ
ボン酸エステル１．５ ｇとペンタメチルジシロキサン
０．５ｇとをテトラヒドロフランに溶解し、白金触媒（
東芝シリコーン社製、Ｐｔ−Ｃａｔ．−２） ０．０２
５ ｇを加え，４５℃で６時間攪拌した．テトラヒドロ
フランを留去した後、トルエンを溶離液としてカラムク
ロマトグラフィーによりＷｉｌｌし、エタノールＧ酢酸
エチルを用いて再結晶を行い、最終目的物である光学活
性４−（３−ペンタメチルジシロキシプロビルオキシ）
フェニル−４’−（１−メチルへブチルオキシ）ビフェ
ニル−４−カルボン酸エステル １．０ｇを得た。Next, optically active 4-allyloxyphenyl-4'-(
1.5 g of 1-methylheptyloxyboxylic acid ester and 0.5 g of pentamethyldisiloxane were dissolved in tetrahydrofuran, and a platinum catalyst (
Manufactured by Toshiba Silicone Co., Ltd., Pt-Cat. -2) 0.02
5 g was added and stirred at 45°C for 6 hours. After distilling off tetrahydrofuran, column chromatography was performed using toluene as an eluent, and recrystallization was performed using ethanol G and ethyl acetate to obtain the final target product, optically active 4-(3-pentamethyldisiloxypropyloxy). )
1.0 g of phenyl-4'-(1-methylhebutyloxy)biphenyl-4-carboxylic acid ester was obtained.
比較例
以下のようにして４−へブチルオキシフェニル−４’−
（１−メチルへブチルオキシ）ビフェニル−４−カルポ
ン酸エステルを製造した。Comparative Example 4-hebutyloxyphenyl-4'-
(1-Methylhebutyloxy)biphenyl-4-carboxylic acid ester was produced.
実施例１と同様にして得た光学活性４°−（１−メチル
へブチルオキシ）ビフェニル−４−カルボン酸２、５ｇ
と塩化チオニル５０ｎ＋１とを８０″Ｃで２時間加熱攪
拌した．塩化チオニルを留去し、光学活性４°−（１−
メチルへブチルオキシ）ビフェニル−４−カルボン酸ク
ロライドを得た。これを乾燥ピリジン３０ｍｌに溶解し
、そこへ４−へプチルオギシフェノール１、９ｇを乾燥
ピリジン２０ｍｌに溶解したものを滴下し、室温で２時
間攪拌した．水１文を加えて攪拌した後、６Ｎ塩酸で酸
性化した．析出物をろ取し、充分水洗した後、乾燥した
トルエンを溶離液としてカラムクロマトグラフィーによ
りｅ縮し、エタノールと酢酸エチルを用いて再結晶を行
い，最終目的物である光学活性４−へブチルオキシフェ
ニル−４’−（１−メチルへブチルオキシ）ビフェニル
−４−カルボン酸エステル２．８ｇを得た。2.5 g of optically active 4°-(1-methylhebutyloxy)biphenyl-4-carboxylic acid obtained in the same manner as in Example 1
and thionyl chloride 50n+1 were heated and stirred at 80"C for 2 hours. Thionyl chloride was distilled off and optically active 4°-(1-
Methylhebutyloxy)biphenyl-4-carboxylic acid chloride was obtained. This was dissolved in 30 ml of dry pyridine, and a solution of 1.9 g of 4-heptyloxyphenol dissolved in 20 ml of dry pyridine was added dropwise thereto, followed by stirring at room temperature for 2 hours. After adding one liter of water and stirring, the mixture was acidified with 6N hydrochloric acid. The precipitate was collected by filtration, thoroughly washed with water, and then condensed by column chromatography using dried toluene as an eluent, and recrystallized using ethanol and ethyl acetate to obtain the final target product, optically active 4-hebutyl. 2.8 g of oxyphenyl-4'-(1-methylhebutyloxy)biphenyl-4-carboxylic acid ester was obtained.
上記実施例１及び比較例で得られた強銹電性液晶化合物
について、相転移温度、自発分極及び回転粘性係数を調
べた結果を第１表に示す。なお、自発分極Ｐｓ及び回転
粘性係数ηは、透明電極にポリイミドを塗布して表面を
ラビングして平行配向処理を施した後、電極間隔２ｇｍ
のセルを組立て，それぞれの液晶化合物を注入してモノ
ドメインを作製し、三角波型“界を印加して測定した．
測定温度は実施例１の場合５０．０°Ｃ，比較例の場合
７５、０℃とした。Table 1 shows the results of examining the phase transition temperature, spontaneous polarization, and rotational viscosity coefficient of the strongly galvanic liquid crystal compounds obtained in Example 1 and Comparative Example. In addition, the spontaneous polarization Ps and the rotational viscosity coefficient η are determined when the electrode spacing is 2 g after applying polyimide to the transparent electrode and performing parallel alignment treatment by rubbing the surface.
A cell was assembled, each liquid crystal compound was injected to create a monodomain, and a triangular wave type field was applied to perform measurements.
The measurement temperature was 50.0°C in Example 1 and 75.0°C in Comparative Example.
第１表
実施例２
いずれも本発明に係る液晶化合物である以下の３種をそ
れぞれ３５％、３５％、 ３０％の割合で混合して液晶
材料を調製した。Table 1 Example 2 A liquid crystal material was prepared by mixing the following three liquid crystal compounds according to the present invention in proportions of 35%, 35%, and 30%, respectively.
この液晶材料は１０〜６０°Ｃの広い温度域でＳｅ２相
を示し、それ以上の温度でＳＡ相を示し、７５℃で等方
性液体となった。また、この液晶材料の自発分極の大き
さは５０°Ｃで５０ ｎ Ｃ／ ｃ ｒｔｒ ２と非常
に大きく１回転粘性係数も５０℃で８．ＯＸ ｔｏ−’
ｋｇ／ ｍ−ｓと低いものであった。This liquid crystal material exhibited a Se2 phase over a wide temperature range of 10 to 60°C, an SA phase at higher temperatures, and became an isotropic liquid at 75°C. Furthermore, the spontaneous polarization of this liquid crystal material is as large as 50 nC/crtr2 at 50°C, and the one-turn viscosity coefficient is 8. OX to-'
It was as low as kg/m-s.
実施例３
いずれも本発明に係る液晶化合物である以下の４種をそ
れぞれ３０％、２０％、２５％、２５％の割合で混合し
て液晶材料を調製した。Example 3 A liquid crystal material was prepared by mixing the following four types of liquid crystal compounds according to the present invention in proportions of 30%, 20%, 25%, and 25%, respectively.
この液晶材料は８〜７２℃の広い温度域でＳｃ本相を示
し、それ以上の温度でＳＡ相を示し、８０℃で等方性液
体となった。また、この液晶材料の自発分極の大きさは
５０℃で８２ｎＣ／ｃｍ２と非常に大きく、回転粘性係
数も５０℃テ０．７Ｘ １０４ｋｇ／ ｒａ−ｓと低い
ものであった。更に、この液晶材料を用いた液晶セルは
外部応力に対しても配向の乱れが少なくメカニカルショ
ックに対する耐性も優れていた。This liquid crystal material exhibited an Sc main phase over a wide temperature range of 8 to 72°C, an SA phase at higher temperatures, and became an isotropic liquid at 80°C. Further, the spontaneous polarization of this liquid crystal material was extremely large at 82 nC/cm2 at 50°C, and the rotational viscosity coefficient was as low as 0.7×104 kg/ra-s at 50°C. Furthermore, a liquid crystal cell using this liquid crystal material had less disturbance in orientation even when subjected to external stress, and had excellent resistance to mechanical shock.
［発明の効果］
以と詳述したように本発明の液晶材料は室温付近の広い
温度域でＳｅ２相を示し、かつ自発分極が大きいだけで
なく回転粘性係数が小さく、ひいては実用的なスイッチ
ング動作が良好で応答速度が速く、更に耐メカニカルシ
ョックにも優れた液晶表示素子を提供することができる
。[Effects of the Invention] As detailed below, the liquid crystal material of the present invention exhibits the Se2 phase in a wide temperature range around room temperature, and not only has a large spontaneous polarization but also a small rotational viscosity coefficient, and has practical switching operation. Accordingly, it is possible to provide a liquid crystal display element that has good performance, fast response speed, and excellent mechanical shock resistance.
出願人代理人 弁理士 鈴江武彦Applicant's agent: Patent attorney Takehiko Suzue
Claims (3)
数を示し、ＯＲは光学活性を有するアルコキシ基又はア
ラルキルオキシ基を示す） で表わされる少なくとも１種を含有することを特徴とす
る液晶材料。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula (I), m is an integer from 0 to 5, n is an integer from 2 to 10, and OR is an optically active An alkoxy group or an aralkyloxy group having the following.
ることを特徴とする特許請求の範囲第１項記載の液晶材
料。(2) The liquid crystal material according to claim 1, wherein OR is an optically active 1-methylheptyloxy group.
ことを特徴とする特許請求の範囲第１項記載の液晶材料
。(3) The liquid crystal material according to claim 1, wherein OR is an optically active 2-methylbutyloxy group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62303741A JP2513742B2 (en) | 1987-12-01 | 1987-12-01 | Liquid crystal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62303741A JP2513742B2 (en) | 1987-12-01 | 1987-12-01 | Liquid crystal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01144491A true JPH01144491A (en) | 1989-06-06 |
| JP2513742B2 JP2513742B2 (en) | 1996-07-03 |
Family
ID=17924713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62303741A Expired - Lifetime JP2513742B2 (en) | 1987-12-01 | 1987-12-01 | Liquid crystal material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513742B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0291080A (en) * | 1988-08-13 | 1990-03-30 | Hoechst Ag | Organosylylalkyl-or sylylalkenyl-compound, its production and use thereof in liquid crystal mixture |
| JPH0334987A (en) * | 1989-06-22 | 1991-02-14 | Consortium Elektrochem Ind Gmbh | Derivative of benzoate silide,its manufacture inter- mediate product and its manufacture, liyuid crystal display device containing new compound |
| JPH0348688A (en) * | 1989-06-22 | 1991-03-01 | Consortium Elektrochem Ind Gmbh | Silylated benzoic acid derivative, preparation thereof, and liquid crystal display device containing same |
| US5399290A (en) * | 1991-12-06 | 1995-03-21 | Consortium Fur Elektrochemische Industrie Gmbh | Liquid crystals with (polysila) alkyl wing groups |
| US5486311A (en) * | 1993-09-15 | 1996-01-23 | National Science Council | Optically erasable read-and-write liquid crystal/side-chain liquid crystalline polymer composition and method of making recordation on the same |
| US5498368A (en) * | 1993-09-10 | 1996-03-12 | Dow Corning Limited | Liquid crystal devices |
| US5547604A (en) * | 1993-01-30 | 1996-08-20 | Dow Corning Limited | Liquid crystal siloxanes |
| WO2003040812A1 (en) * | 2001-11-08 | 2003-05-15 | Qinetiq Limited | Liquid crystal compounds, liquid crystal mixtures containing them and liquid crystal devices |
| JP2009533720A (en) * | 2006-04-17 | 2009-09-17 | ダウ・コーニング・コーポレイション | Bistable ferroelectric liquid crystal device |
| CN113956889A (en) * | 2021-09-27 | 2022-01-21 | 苏州大学 | Colored polysilsesquioxane liquid crystal film and preparation method and application thereof |
| WO2025069643A1 (en) * | 2023-09-29 | 2025-04-03 | 富士フイルム株式会社 | Liquid crystal composition, cured product, film, and compound |
-
1987
- 1987-12-01 JP JP62303741A patent/JP2513742B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348684A (en) * | 1988-08-13 | 1994-09-20 | Hoechst Aktiengesellschaft | Organosilylalkyl or organosilylalkenyl compounds, process for preparing them and their use in liquid-crystalline mixtures |
| JPH0291080A (en) * | 1988-08-13 | 1990-03-30 | Hoechst Ag | Organosylylalkyl-or sylylalkenyl-compound, its production and use thereof in liquid crystal mixture |
| USRE35462E (en) * | 1989-06-22 | 1997-02-25 | Consortium Fur Elekochemische Ind. Gmbh | Silylated benzoic acid derivatives |
| US5106530A (en) * | 1989-06-22 | 1992-04-21 | Consortium Fur Elektrochemische Ind. | Silylated benzoic acid derivatives |
| JPH0348688A (en) * | 1989-06-22 | 1991-03-01 | Consortium Elektrochem Ind Gmbh | Silylated benzoic acid derivative, preparation thereof, and liquid crystal display device containing same |
| JPH0334987A (en) * | 1989-06-22 | 1991-02-14 | Consortium Elektrochem Ind Gmbh | Derivative of benzoate silide,its manufacture inter- mediate product and its manufacture, liyuid crystal display device containing new compound |
| US5399290A (en) * | 1991-12-06 | 1995-03-21 | Consortium Fur Elektrochemische Industrie Gmbh | Liquid crystals with (polysila) alkyl wing groups |
| US5547604A (en) * | 1993-01-30 | 1996-08-20 | Dow Corning Limited | Liquid crystal siloxanes |
| US5498368A (en) * | 1993-09-10 | 1996-03-12 | Dow Corning Limited | Liquid crystal devices |
| US5486311A (en) * | 1993-09-15 | 1996-01-23 | National Science Council | Optically erasable read-and-write liquid crystal/side-chain liquid crystalline polymer composition and method of making recordation on the same |
| WO2003040812A1 (en) * | 2001-11-08 | 2003-05-15 | Qinetiq Limited | Liquid crystal compounds, liquid crystal mixtures containing them and liquid crystal devices |
| JP2009533720A (en) * | 2006-04-17 | 2009-09-17 | ダウ・コーニング・コーポレイション | Bistable ferroelectric liquid crystal device |
| CN113956889A (en) * | 2021-09-27 | 2022-01-21 | 苏州大学 | Colored polysilsesquioxane liquid crystal film and preparation method and application thereof |
| WO2025069643A1 (en) * | 2023-09-29 | 2025-04-03 | 富士フイルム株式会社 | Liquid crystal composition, cured product, film, and compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2513742B2 (en) | 1996-07-03 |
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