JPH06118396A - Liquid crystalline oligomer and liquid crystal display device using the same - Google Patents
Liquid crystalline oligomer and liquid crystal display device using the sameInfo
- Publication number
- JPH06118396A JPH06118396A JP27205992A JP27205992A JPH06118396A JP H06118396 A JPH06118396 A JP H06118396A JP 27205992 A JP27205992 A JP 27205992A JP 27205992 A JP27205992 A JP 27205992A JP H06118396 A JPH06118396 A JP H06118396A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- transparent
- oligomer
- display device
- crystal display
- 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
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 106
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 125000006850 spacer group Chemical group 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 230000004044 response Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000005264 High molar mass liquid crystal Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000005684 electric field Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical group 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- UOUILILVWRHZSH-UHFFFAOYSA-N dimethyl-tris[(dimethyl-$l^{3}-silanyl)oxy]silyloxysilicon Chemical compound C[Si](C)O[Si](O[Si](C)C)(O[Si](C)C)O[Si](C)C UOUILILVWRHZSH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010030 laminating Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- -1 siloxane chain Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ITWWXCLUKGZJRY-UHFFFAOYSA-N (4-octoxyphenyl) 4-pentylbenzoate Chemical compound C1=CC(OCCCCCCCC)=CC=C1OC(=O)C1=CC=C(CCCCC)C=C1 ITWWXCLUKGZJRY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
Abstract
(57)【要約】
【構成】 液晶性オリゴマーは下記式（１）で表され
る。
Ｚ（Ｘ−Ｙ）n （１）
（式中、ＺはＣ、Ｓｉ、Ｎ、Ｂ、Ｇｅを示し、Ｘはスペ
ーサーを示し、Ｙは液晶基を示し、ｎは３または４の整
数を示す。）また、液晶表示素子は、上記式（１）で表
される液晶性オリゴマーと、低分子液晶と、電解質とを
含有する混合膜を、少なくとも一方が透明な一対の導電
基材で挟着する。
【効果】 透明から不透明への転換が良好で、かつ透明
から不透明、不透明から透明のいずれの応答速度も速
い。
(57) [Summary] [Structure] The liquid crystal oligomer is represented by the following formula (1). Z (X-Y) n (1) (In the formula, Z represents C, Si, N, B, Ge, X represents a spacer, Y represents a liquid crystal group, and n represents an integer of 3 or 4. Further, in the liquid crystal display device, a mixed film containing a liquid crystalline oligomer represented by the above formula (1), a low molecular weight liquid crystal, and an electrolyte is sandwiched between a pair of conductive base materials, at least one of which is transparent. To do. [Effect] The conversion from transparent to opaque is good, and the response speed from transparent to opaque and from opaque to transparent is fast.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばＴＶ画面や一般
ＯＡ機器類、あるいは自動車に搭載して地図表示、案内
表示等の情報を表示する車載ナビゲーションのディスプ
レイ等に使用される液晶性オリゴマー及びそれを用いた
液晶表示素子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal oligomer for use in, for example, a TV screen, general office automation equipment, or an in-vehicle navigation display for displaying information such as map display and guidance display mounted on an automobile. The present invention relates to a liquid crystal display device using the same.
【０００２】[0002]
【従来の技術】通常の液晶表示素子は、数μｍの間隔に
固定した一対の導電基材間に液晶材料を注入することに
よって形成される。ところが、このような構成の液晶表
示素子では、大面積のディスプレイの作製が困難であ
る。また、液晶を封入した一対の透明導電基材には、そ
れぞれ偏光軸が互いに直行した偏向板を取り付ける必要
があるため、画面の明るさ、視野角等が不十分であっ
た。2. Description of the Related Art An ordinary liquid crystal display device is formed by injecting a liquid crystal material between a pair of conductive base materials fixed at intervals of several μm. However, it is difficult to manufacture a large-area display with the liquid crystal display device having such a configuration. In addition, since a pair of transparent conductive base materials in which liquid crystal is enclosed need to be equipped with polarizing plates whose polarization axes are perpendicular to each other, the brightness of the screen, the viewing angle, etc. are insufficient.
【０００３】また、従来の液晶表示素子では、強誘電性
液晶を用いる場合を除き、配向状態にメモリー性がない
ため、大画素数の表示画面用には製造歩留りの悪いＴＦ
Ｔ等を用いたアクティブマトリクス駆動が必要となり、
高価になるという問題があった。また、強誘電性液晶を
用いた場合には、１〜２μｍという極めて薄いセルギャ
ップ制御および液晶の均一な配向制御が必要なため、小
面積ですら満足な表示を得ることが困難であった。Further, in the conventional liquid crystal display device, except for the case where the ferroelectric liquid crystal is used, since the alignment state has no memory property, the TF having a low manufacturing yield is used for a display screen having a large number of pixels.
Active matrix drive using T etc. is required,
There was a problem of becoming expensive. Further, when a ferroelectric liquid crystal is used, it is difficult to obtain a satisfactory display even with a small area, because it is necessary to control the cell gap to be extremely thin at 1 to 2 μm and to control the uniform alignment of the liquid crystal.
【０００４】一方、高分子骨格鎖にフレキシブルな炭素
骨格などのスペーサ部を介して、液晶化合物に相当する
部分を結合した側鎖型高分子液晶と、通常の低分子液晶
材料とを溶剤中に溶解した溶液を、透明電極板等の板状
またはフィルム状の一対の基材で挟着した液晶表示素子
（以下、高分子液晶／低分子液晶混合膜）が提案されて
いる（特開平２−１９３１１５号公報、特開平２−１２
７４９４号公報、Chem.Lett.,817(1989)、Polym.Prepri
nts,Japan 39(8)2373(1990) 等参照）。On the other hand, a side chain type polymer liquid crystal in which a portion corresponding to a liquid crystal compound is bonded to a polymer skeleton chain through a spacer portion such as a flexible carbon skeleton, and an ordinary low molecular weight liquid crystal material are placed in a solvent. A liquid crystal display device (hereinafter referred to as a polymer liquid crystal / low molecular liquid crystal mixed film) in which a dissolved solution is sandwiched between a pair of plate-shaped or film-shaped substrates such as transparent electrode plates has been proposed (JP-A-2- Japanese Laid-Open Patent Publication No. 193115, JP-A 2-12
7494, Chem. Lett., 817 (1989), Polym.Prepri
nts, Japan 39 (8) 2373 (1990) etc.).
【０００５】この高分子液晶／低分子液晶混合膜に、低
周波電場または直流電場を印加すると、当該混合膜中に
極微量存在するイオンが電場に付随した移動を起こし、
高分子液晶主鎖に衝突し液晶分子の配列を乱すことで、
混合膜の入射光を強く散乱する不透明な光散乱状態にな
る。次いで、高周波電場を印加すると、高分子液晶／低
分子液晶混合膜中の液晶分子が、電気光学効果によって
電場方向にホメオトロピック配向して、混合膜の入射光
を透過する透明な状態に転換する。さらに、上記混合膜
を用いた液晶表示素子では、上記両状態にて電場を除去
した際に、光散乱状態または透明状態を安定に保持する
メモリー性がある。When a low frequency electric field or a direct current electric field is applied to this polymer liquid crystal / low molecular weight liquid crystal mixed film, a very small amount of ions present in the mixed film cause a movement associated with the electric field,
By colliding with the polymer liquid crystal main chain and disturbing the alignment of liquid crystal molecules,
An opaque light-scattering state in which the incident light of the mixed film is strongly scattered is obtained. Then, when a high frequency electric field is applied, the liquid crystal molecules in the polymer liquid crystal / low molecular weight liquid crystal mixed film are homeotropically aligned in the electric field direction by the electro-optical effect, and are converted into a transparent state in which the incident light of the mixed film is transmitted. . Furthermore, the liquid crystal display device using the above mixed film has a memory property of stably holding the light scattering state or the transparent state when the electric field is removed in both the above states.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来の
高分子液晶／低分子液晶混合膜では、液晶性高分子の粘
性が高いため、透明から不透明への転換の応答速度、お
よび、不透明から透明への転換の応答速度が遅いという
問題があった。そこで、応答速度を速くするために、混
合膜中の高分子液晶の比率を下げることや、高分子液晶
の重合度（分子量）を下げることが考えられるが、この
場合、透明から不透明への転換の応答速度が極めて遅く
なるか、または転換しなくなるという問題が生じた。こ
の液晶表示素子では、低周波電場または直流電場を印加
した際に電場に付随して移動するイオンが高分子液晶主
鎖に衝突することで液晶分子の配列の乱れが起こるた
め、高分子液晶の比率や重合度が低いと移動したイオン
が主鎖に衝突する確率が小さくなる。したがって、液晶
配列の乱れが十分に起こらないため透明から不透明への
転換が悪化すると考えられる。この問題を解決するため
に、本発明者らは、側鎖型高分子液晶の主鎖を架橋した
ものを使用した液晶表示素子を発明した（特願平３−３
２７７２５号）。However, in the conventional polymer liquid crystal / low molecular weight liquid crystal mixed film, since the viscosity of the liquid crystal polymer is high, the response speed of conversion from transparent to opaque and the change from opaque to transparent. There was a problem that the response speed of conversion was slow. Therefore, in order to increase the response speed, it is possible to reduce the ratio of the polymer liquid crystal in the mixed film or the polymerization degree (molecular weight) of the polymer liquid crystal. In this case, the conversion from transparent to opaque There was a problem that the response speed of the was extremely slow or did not switch. In this liquid crystal display element, when a low-frequency electric field or a direct current electric field is applied, ions moving along with the electric field collide with the polymer liquid crystal main chain, causing disorder in the alignment of the liquid crystal molecules. If the ratio or the degree of polymerization is low, the probability that the migrated ions collide with the main chain becomes small. Therefore, it is considered that the transition from transparent to opaque deteriorates because the liquid crystal alignment is not sufficiently disturbed. In order to solve this problem, the present inventors have invented a liquid crystal display device using a side chain type polymer liquid crystal in which the main chain is crosslinked (Japanese Patent Application No. 3-3.
27725).
【０００７】しかし、この高分子液晶を架橋すると高分
子液晶の分子量が大きくなることは避けられず、混合膜
の粘度が増加し応答速度が遅くなるという問題があっ
た。そこで、本発明の目的は、上記技術的課題を解決
し、透明から不透明への転換が良好で、応答速度の速い
液晶表示素子を提供することである。However, when the polymer liquid crystal is crosslinked, the molecular weight of the polymer liquid crystal is inevitably increased, and there is a problem that the viscosity of the mixed film increases and the response speed becomes slow. Therefore, it is an object of the present invention to solve the above technical problems and to provide a liquid crystal display device having a good conversion from transparent to opaque and a high response speed.
【０００８】[0008]
【課題を解決するための手段および作用】上記課題を解
決するために、本発明者らは、液晶表示素子の透明から
不透明への転換が架橋した高分子液晶の主鎖構造におけ
る交差部分に起因すると考え、このような主鎖が交差し
た形の最も小さい構成としての液晶性オリゴマーについ
て種々検討した結果、本発明を完成するに到った。In order to solve the above problems, the inventors of the present invention have proposed that the conversion of a liquid crystal display device from transparent to opaque is caused by an intersection in the main chain structure of a crosslinked polymer liquid crystal. In view of this, various studies have been conducted on the liquid crystal oligomer having the smallest configuration in which the main chains intersect with each other, and as a result, the present invention has been completed.
【０００９】すなわち、本発明の液晶性オリゴマーは、
下記式（１）で表されることを特徴とする。 Ｚ（Ａ−Ｙ）n （１） （式中、ＺはＣ、Ｓｉ、Ｎ、Ｂ、Ｇｅを示し、Ａはスペ
ーサーを示し、Ｙは液晶基を示し、ｎは３または４の整
数を示す。）この液晶性オリゴマーは、上記式（１）
中、Ｚで示された結合手にスペーサーを介して液晶基が
３または４個結合したものである。この式（１）で表さ
れる液晶性オリゴマーによれば、混合膜中において、イ
オンがスペーサーに衝突した場合、液晶基の配列を素早
くしかも確実に乱すことができる。That is, the liquid crystal oligomer of the present invention is
It is characterized by being expressed by the following formula (1). Z (A-Y) n (1) (In the formula, Z represents C, Si, N, B, and Ge, A represents a spacer, Y represents a liquid crystal group, and n represents an integer of 3 or 4. This liquid crystalline oligomer has the above formula (1).
Among these, 3 or 4 liquid crystal groups are bonded to a bond represented by Z through a spacer. According to the liquid crystal oligomer represented by the formula (1), when the ions collide with the spacer in the mixed film, the alignment of the liquid crystal groups can be disturbed quickly and reliably.
【００１０】また、本発明の液晶表示素子は、上記式
（１）で表される液晶性オリゴマーと、低分子液晶と、
電解質とを含有する混合膜を、少なくとも一方が透明な
一対の導電基材で挟着したことを特徴とする。この液晶
表示素子の動作は、液晶性オリゴマーの液晶基間に低分
子液晶が入り込み配列した場合（透明状態）および液晶
性オリゴマーがイオンにより乱され、それに伴って液晶
性オリゴマーの液晶基および低分子液晶がランダムな配
向をする場合（不透明状態）を双安定的に交替すること
で行われる。その際、これら２つの状態の変換における
分子運動が液晶表示素子の応答速度に直接関連してい
る。そして、透明から不透明への転換は、液晶性オリゴ
マーの運動が、また不透明から透明への転換は液晶性オ
リゴマーの液晶基の運動がそれぞれ速度を律していると
考えられる。したがって、混合膜の構成成分として架橋
した高分子液晶に代えて液晶性オリゴマーを用いること
で、混合膜の粘度増加することなく、透明から不透明状
態への転換を良好にするとともに、透明から不透明状態
および不透明から透明状態への応答速度も向上すること
ができる。The liquid crystal display device of the present invention comprises a liquid crystalline oligomer represented by the above formula (1), a low molecular weight liquid crystal, and
A mixed film containing an electrolyte is sandwiched between a pair of conductive base materials, at least one of which is transparent. The operation of this liquid crystal display device is such that when a low-molecular liquid crystal enters and is arranged between the liquid crystal groups of the liquid crystal oligomer (transparent state), the liquid crystal oligomer is disturbed by ions, and accordingly, the liquid crystal group and the low molecular weight of the liquid crystal oligomer are When the liquid crystal has a random orientation (opaque state), bistable alternation is performed. In that case, the molecular motion in the conversion of these two states is directly related to the response speed of the liquid crystal display device. It is considered that the movement of the liquid crystalline oligomer controls the speed in the transition from transparent to opaque, and the movement of the liquid crystal group in the liquid crystalline oligomer controls the speed in the transition from opaque to transparent. Therefore, by using the liquid crystalline oligomer instead of the cross-linked polymer liquid crystal as a constituent of the mixed film, it is possible to improve the conversion from the transparent state to the opaque state without increasing the viscosity of the mixed film, and to improve the transparent state to the opaque state. Also, the response speed from the opaque to the transparent state can be improved.
【００１１】図１に示すように、上記式（１）で表され
る液晶性オリゴマーは、液晶基２が一点で結合した構造
を有している。すなわち、この液晶性オリゴマーは、図
中Ｚで示したＣ、Ｓｉ、Ｎ、Ｂ、Ｇｅ等の結合手が３つ
以上ある原子に液晶基２がスペーサー１を介して結合し
たものである。同図（Ａ）はスペーサー１を介してＺに
結合した液晶基２が３つ有するもの、同図（Ｂ）はこの
液晶基２が４つ有するものを示している。As shown in FIG. 1, the liquid crystalline oligomer represented by the above formula (1) has a structure in which liquid crystal groups 2 are bonded at one point. That is, the liquid crystal oligomer is one in which the liquid crystal group 2 is bonded via the spacer 1 to an atom having three or more bonds such as C, Si, N, B, and Ge shown by Z in the figure. The figure (A) shows what has three liquid crystal groups 2 linked to Z through the spacer 1, and the figure (B) shows what has four liquid crystal groups 2.
【００１２】スペーサー１としては、例えば、下記式
（２）で表されるメチレン鎖、下記式（３）で表される
シロキサン鎖あるいは下記式（４）で表されるこれらの
共重合体等が使用可能である。The spacer 1 is, for example, a methylene chain represented by the following formula (2), a siloxane chain represented by the following formula (3), or a copolymer thereof represented by the following formula (4). It can be used.
【００１３】[0013]
【化１】 [Chemical 1]
【００１４】（式中、ｍ、ｍ′は、１〜２０の整数であ
る。）液晶基２としては、例えば、下記式（５）（６）
で表される基が使用される他、任意の液晶基が使用可能
である。(In the formula, m and m ′ are integers of 1 to 20.) As the liquid crystal group 2, for example, the following formulas (5) and (6) are used.
In addition to the group represented by, any liquid crystal group can be used.
【００１５】[0015]
【化２】 [Chemical 2]
【００１６】（式中、ＲはＣＮ基、ＯＣＨ3 基等の置換
基を示す。）上記各成分より構成される本発明の液晶性
オリゴマーとしては、例えば、下記式（７）〜（２２）
で表される化合物があげられる。(In the formula, R represents a substituent such as a CN group and an OCH 3 group.) Examples of the liquid crystalline oligomer of the present invention composed of the above components include, for example, the following formulas (7) to (22).
The compound represented by
【００１７】[0017]
【化３】 [Chemical 3]
【００１８】[0018]
【化４】 [Chemical 4]
【００１９】[0019]
【化５】 [Chemical 5]
【００２０】[0020]
【化６】 [Chemical 6]
【００２１】本発明の上記式（１）で表される液晶性オ
リゴマーは、例えば、所望の液晶性オリゴマーの合成原
料を、トルエン等の溶媒に溶解し、塩化白金酸触媒下で
還流することで合成することができる。具体的には、テ
トラキス（ジメチルシロキシ）シラン〔Ｓｉ（Ｏ−Ｓｉ
（ＣＨ3 ）2 Ｈ）4 〕０．０１モルと、末端にアリル基
を持つ下記式（ａ）の液晶基０．０４モルとをトルエン
に溶解し、塩化白金酸触媒下で還流することで、下記式
（ｂ）の液晶性オリゴマーを合成することができる。The liquid crystalline oligomer represented by the above formula (1) of the present invention can be obtained by, for example, dissolving a raw material for synthesis of a desired liquid crystalline oligomer in a solvent such as toluene and refluxing it under a chloroplatinic acid catalyst. Can be synthesized. Specifically, tetrakis (dimethylsiloxy) silane [Si (O-Si
0.01 mol of (CH 3 ) 2 H) 4 ] and 0.04 mol of a liquid crystal group of the following formula (a) having an allyl group at the terminal are dissolved in toluene and refluxed under a chloroplatinic acid catalyst. A liquid crystal oligomer of the following formula (b) can be synthesized.
【００２２】[0022]
【化７】 [Chemical 7]
【００２３】（式中、Ｙは液晶基を示し、Ｐ、Ｐ’は１
〜２０の整数である。）また、本発明の液晶表示素子に
おける低分子液晶としては、通常用いられる各種低分子
液晶を用いることができ、単独または２種以上混合して
使用することができるが、液晶性オリゴマーと混合した
状態でスメクチック相を示すように混合系を選択する必
要がある。液晶性オリゴマーと低分子液晶の混合割合
は、特に限定されないが、重量比で１／９〜７／３程度
が好ましい。液晶性オリゴマーの割合が上記範囲より少
ないとイオンの衝突する確率が小さくなり透明から不透
明への転換が起こり難しくなり、逆に上記範囲より多い
場合は素子の応答速度が遅くなるおそれがある。(Wherein Y represents a liquid crystal group and P and P ′ are 1
Is an integer of -20. As the low-molecular liquid crystal in the liquid crystal display device of the present invention, various low-molecular liquid crystals that are commonly used can be used, and they can be used alone or in combination of two or more kinds, but they are mixed with a liquid crystalline oligomer. It is necessary to select a mixed system so as to exhibit a smectic phase in the state. The mixing ratio of the liquid crystal oligomer and the low molecular weight liquid crystal is not particularly limited, but a weight ratio of about 1/9 to 7/3 is preferable. When the proportion of the liquid crystalline oligomer is less than the above range, the probability of collision of ions becomes small, and it becomes difficult to switch from transparent to opaque. On the contrary, when it exceeds the above range, the response speed of the device may be slowed.
【００２４】電解質としては、混合膜を形成する際に使
用する溶媒に可溶なものであれば種々の化合物が使用で
きるが、特に下記式（２３）で表される四級アンモニウ
ム塩が好適な電解質としてあげられる。As the electrolyte, various compounds can be used as long as they are soluble in the solvent used for forming the mixed film, but a quaternary ammonium salt represented by the following formula (23) is particularly preferable. It is given as an electrolyte.
【００２５】[0025]
【化８】 [Chemical 8]
【００２６】（式中、Ｒ1 、Ｒ2 、Ｒ3 およびＲ4 は、
それぞれ同一または異なって、メチル、エチル、プロピ
ル、イソプロピル、ブチル、ペンチル、ヘキシル基等の
アルキル基を示し、Ｘは、Ｃｌ、Ｂｒ、Ｉ、ＣｌＯ4 、
ＰＦ4 またはＢＦ4 等を示す。）この電解質は、単独ま
たは２種以上混合して使用することができ、液晶性オリ
ゴマーと低分子液晶の混合膜に対して０．１〜１重量％
程度の割合で含有させることができる。混合膜は、この
電解質に起因したイオンにより、確実かつ再現性よく透
明から不透明への変化を生じさせることができる。(Wherein R 1 , R 2 , R 3 and R 4 are
Each is the same or different and represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups, and X is Cl, Br, I, ClO 4 ,
Indicates PF 4 or BF 4 . ) This electrolyte can be used alone or as a mixture of two or more kinds, and is 0.1 to 1% by weight based on the mixed film of the liquid crystalline oligomer and the low molecular liquid crystal.
It can be contained in a certain ratio. The mixed film can cause a change from transparent to opaque reliably and reproducibly by the ions derived from the electrolyte.
【００２７】また、混合膜には、液晶表示素子をカラー
表示タイプにするため、従来公知の各種２色性色素を配
合することもできる。混合膜には、導電基材間の距離を
一定に保持すべく、ガラス製、セラミックス製、プラス
チック製等の従来公知のスペーサ材を含有することもで
きる。混合膜を挟着する一対の導電基材としては、例え
ば、ガラス、プラスチック板、プラスチックフィルム
（ポリエチレンテレフタレート（ＰＥＴ）、ポリエーテ
ルサルホン（ＰＥＳ）等）等の基材の表面に、ＩＴＯ
（インジウム・チン・オキサイド）やＳｎＯ2 等の導電
膜を蒸着法、スパッタリング法あるいは塗布法等で形成
したものがあげられる他、通常の液晶表示素子に用いら
れる透明導電ガラスやフィルムも使用できる。Further, in the mixed film, various conventionally known dichroic dyes can be blended in order to make the liquid crystal display element a color display type. The mixed film may contain a conventionally known spacer material such as glass, ceramics, or plastic in order to keep the distance between the conductive base materials constant. As a pair of conductive base materials for sandwiching the mixed film, for example, ITO is formed on the surface of a base material such as glass, a plastic plate, a plastic film (polyethylene terephthalate (PET), polyether sulfone (PES), etc.).
In addition to those obtained by forming a conductive film such as (indium / tin / oxide) or SnO 2 by a vapor deposition method, a sputtering method, a coating method or the like, a transparent conductive glass or film used in a usual liquid crystal display element can be used.
【００２８】本発明の液晶表示素子は、図２に示すよう
に、上記各成分を適当な溶媒に溶解し、スペーサ材４と
ともに混合した後乾燥してペースト状の混合液晶材料５
を得た後、この混合液晶材料５を２枚の導電基材６，６
間に挟んでラミネートロール３，３によってラミネート
処理して混合膜７を形成することで製造できる。また、
本発明の液晶表示素子は、従来同様に一方の導電基材の
表面に、上記各成分を適当な溶媒に溶解または分散した
溶液を塗布し、乾燥固化させた混合膜を形成した後、こ
の混合膜上にもう一方の導電基材を重ね合わせて製造す
ることができる。なお、本発明の各成分を適当な溶媒に
溶解した塗布液を導電基材上に塗布する方法として、バ
ーコート法、スピンコート法、プレーコート法、ローラ
コート法等の従来公知のコート法を採用することができ
る。In the liquid crystal display device of the present invention, as shown in FIG. 2, the above components are dissolved in an appropriate solvent, mixed with the spacer material 4 and dried, and then the paste-like mixed liquid crystal material 5 is mixed.
Then, the mixed liquid crystal material 5 is added to the two conductive substrates 6 and 6.
It can be manufactured by sandwiching it and laminating with the laminating rolls 3 to form the mixed film 7. Also,
The liquid crystal display device of the present invention is formed by applying a solution obtained by dissolving or dispersing each of the above components in a suitable solvent onto the surface of one of the conductive base materials in the same manner as in the prior art, and forming a mixed film by drying and solidifying, and then mixing the mixed film. It can be manufactured by superimposing another conductive substrate on the film. As a method for applying a coating solution in which each component of the present invention is dissolved in a suitable solvent onto a conductive substrate, a conventionally known coating method such as a bar coating method, a spin coating method, a precoating method, or a roller coating method is used. Can be adopted.
【００２９】その他、この発明の要旨を変更しない範囲
で種々の設計変更を施すことが可能である。In addition, various design changes can be made within the scope of the present invention.
【００３０】[0030]
【実施例】以下に本発明を、実施例および比較例に基づ
いて説明する。まず、上記式（１）で表される本発明の
液晶性オリゴマーの合成例を示す。合成例１ テトラキス（ジメチルシロキシ）シラン〔Ｓｉ（Ｏ−Ｓ
ｉ（ＣＨ3 ）2 Ｈ）4〕０．０１モルと、下記式（ｃ）
で表される化合物０．０４モルをトルエンに溶解し、塩
化白金酸触媒下で還流することで下記式（７）で表され
る液晶性オリゴマーを合成した。EXAMPLES The present invention will be described below based on Examples and Comparative Examples. First, a synthesis example of the liquid crystalline oligomer of the present invention represented by the above formula (1) will be shown. Synthesis Example 1 Tetrakis (dimethylsiloxy) silane [Si (OS)
i (CH 3 ) 2 H) 4 ] 0.01 mol and the following formula (c)
A liquid crystal oligomer represented by the following formula (7) was synthesized by dissolving 0.04 mol of the compound represented by the following in toluene and refluxing under a chloroplatinic acid catalyst.
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】そして、合成原料及び得られた液晶性オリ
ゴマーのＩＲ分析を行った。この結果について、図３
に、テトラキス（ジメチルシロキシ）シラン、図４に、
上記式（ｃ）で表される化合物、図５に、得られた液晶
性オリゴマーをそれぞれ示した。図４において、テトラ
キス（ジメチルシロキシ）シランに見られるＳｉ−Ｈの
吸収（２１３４cm-1）が、図５において、消失してお
り、代わって、図３に見られた液晶基末端の−ＣＮの吸
収（２２３０cm-1付近）が見られる。このことからテト
ラキス（ジメチルシロキシ）シランの４つのＳｉＨに液
晶基がヒドロシリル化反応により結合し上記式（７）の
液晶性オリゴマーが合成できたことを確認した。合成例２ 上記式（ｃ）の化合物に代えて、下記式（ｄ）で表され
る化合物を用いた以外は同様にして、下記式（９）で表
される液晶性オリゴマーを合成した。Then, IR analysis was performed on the synthetic raw materials and the obtained liquid crystalline oligomer. This result is shown in FIG.
, Tetrakis (dimethylsiloxy) silane, in FIG.
The compound represented by the above formula (c) and the obtained liquid crystal oligomer are shown in FIG. 5, respectively. In FIG. 4, the absorption of Si—H (2134 cm −1 ) found in tetrakis (dimethylsiloxy) silane disappears in FIG. 5, and instead of —CN at the terminal of the liquid crystal group seen in FIG. Absorption (around 2230 cm -1 ) is seen. From this, it was confirmed that the liquid crystal group was bonded to four SiHs of tetrakis (dimethylsiloxy) silane by a hydrosilylation reaction to synthesize the liquid crystal oligomer of the above formula (7). Synthesis Example 2 A liquid crystal oligomer represented by the following formula (9) was synthesized in the same manner except that the compound represented by the following formula (d) was used instead of the compound of the above formula (c).
【００３３】そして、合成原料及び得られた液晶性オリ
ゴマーのＩＲ分析を行ったところ、テトラキス（ジメチ
ルシロキシ）シランの４つのＳｉＨに液晶基がヒドロシ
リル化反応により結合し上記式（９）の液晶性オリゴマ
ーが合成できたことを確認した。An IR analysis of the synthetic raw material and the obtained liquid crystalline oligomer was carried out. As a result, a liquid crystal group was bonded to four SiHs of tetrakis (dimethylsiloxy) silane by a hydrosilylation reaction, and the liquid crystallinity of the above formula (9) was obtained. It was confirmed that the oligomer could be synthesized.
【００３４】[0034]
【化１０】 [Chemical 10]
【００３５】次に、本発明の液晶表示素子の実施例およ
び比較例について、以下に説明する。実施例１ 合成例１で得た上記式（７）で表される液晶性オリゴマ
ーを２８重量部、低分子液晶材料として４−ｎ−ペンチ
ルベンゾイックアシッド−４′−ｎ−オクチルオキシフ
ェニルエステルを２８重量部と低分子液晶（メルクジャ
パン社製の型番「Ｅ３１ＬＶ」）の混合成分を４４重量
部、電解質としてテトラエチルアンモニウムブロマイド
を液晶材料総量に対して０．０５重量％、および球状ス
ペーサ材（ベンゾグアナミン樹脂製、粒径１０μｍ）を
適当量のジクロロメタンに溶解し、攪拌した後乾燥させ
て、ペースト状混合液晶材料を製造した。Next, examples and comparative examples of the liquid crystal display device of the present invention will be described below. Example 1 28 parts by weight of the liquid crystalline oligomer represented by the above formula (7) obtained in Synthesis Example 1, and 4-n-pentylbenzoic acid-4'-n-octyloxyphenyl ester as a low molecular weight liquid crystal material. 44 parts by weight of a mixed component of 28 parts by weight and a low-molecular liquid crystal (model number "E31LV" manufactured by Merck Japan Ltd.), 0.05 wt% of tetraethylammonium bromide as an electrolyte with respect to the total amount of the liquid crystal material, and a spherical spacer material (benzoguanamine). A resin, particle size 10 μm) was dissolved in an appropriate amount of dichloromethane, stirred and dried to produce a pasty mixed liquid crystal material.
【００３６】つぎに、上記液晶混合材料を一対のＩＴＯ
／ＰＥＳ（住友ベークライト社製、厚さ１００μｍ）間
に挟み、図２で示したロールラミネート処理し、液晶表
示素子を作製した。実施例２ 液晶性オリゴマーを、合成例２で得た上記式（９）で表
される液晶性オリゴマーを用いたことの他、上記実施例
１と同様にして液晶表示素子を作製した。比較例１ 液晶性オリゴマーに代え、下記式（２４）で表される側
鎖型高分子液晶を用いたことの他、上記実施例１と同様
にして液晶表示素子を作製した。Next, the above liquid crystal mixed material is used as a pair of ITO.
/ PES (Sumitomo Bakelite Co., Ltd., thickness 100 μm), and the roll lamination treatment shown in FIG. 2 was performed to produce a liquid crystal display element. Example 2 A liquid crystal display device was produced in the same manner as in Example 1 except that the liquid crystal oligomer represented by the above formula (9) obtained in Synthesis Example 2 was used as the liquid crystal oligomer. Comparative Example 1 A liquid crystal display device was produced in the same manner as in Example 1 except that a side chain type polymer liquid crystal represented by the following formula (24) was used instead of the liquid crystal oligomer.
【００３７】[0037]
【化１１】 [Chemical 11]
【００３８】比較例２ 重合度４のポリメチルヒドロシロキサンに対して５０％
当量の液晶基をグラフト重合し、下記式（２５）で表さ
れる高分子液晶を合成した。 Comparative Example 2 50% with respect to polymethylhydrosiloxane having a degree of polymerization of 4
An equivalent amount of liquid crystal group was graft-polymerized to synthesize a polymer liquid crystal represented by the following formula (25).
【００３９】[0039]
【化１２】 [Chemical 12]
【００４０】さらに、この高分子液晶を１００℃で熱処
理を行い残留するＳｉ−Ｈどうしを以下のように化学反
応させて結合し、架橋した側鎖型高分子液晶を作製し
た。 Ｓｉ−Ｈ → Ｓｉ−ＯＨ → Ｓｉ−Ｏ−Ｓｉ そして、液晶性オリゴマーに代え、この架橋した側鎖型
高分子液晶を用いたことの他、上記実施例１と同様にし
て液晶表示素子を作製した。Further, this polymer liquid crystal was heat-treated at 100 ° C., and the remaining Si—H were chemically reacted with each other as follows to bond them to prepare a crosslinked side chain polymer liquid crystal. Si-H->Si-OH-> Si-O-Si Then, a liquid crystal display device was produced in the same manner as in Example 1 except that this crosslinked side chain type polymer liquid crystal was used instead of the liquid crystal oligomer. did.
【００４１】上記実施例および比較例で得られた液晶表
示素子について、以下の応答性試験を行った。応答性試験 実施例および比較例で得た液晶表示素子に、Ｈｅ−Ｎｅ
レーザー光（波長６３３ｎｍ）を照射しつつ、室温下、
交流１ＫＨｚ、６０Ｖの駆動電圧を印加し、液晶表示素
子における不透明時の透過率を０％、透明時の透過率を
１００％として、Ｈｅ−Ｎｅレーザー光の透過率が１０
％から９０％に達するまでの時間を計測して、不透明か
ら透明への応答時間とした。また同様にして、室温下、
直流６０Ｖの駆動電圧を印加し、Ｈｅ−Ｎｅレーザー光
の透過率が９０％から１０％に達するまでの時間を計測
して、透明から不透明への応答時間とした。The liquid crystal display elements obtained in the above-mentioned Examples and Comparative Examples were subjected to the following responsiveness test. Responsiveness test He-Ne
While irradiating laser light (wavelength 633 nm), at room temperature,
When a driving voltage of 60 V is applied at an alternating current of 1 KHz, the transmittance of He—Ne laser light is 10% when the transmittance of the liquid crystal display element when opaque is 0% and the transmittance when transparent is 100%.
% To 90% was measured and taken as the response time from opaque to transparent. Similarly, at room temperature,
A drive voltage of DC 60 V was applied, and the time required for the transmittance of He—Ne laser light to reach from 90% to 10% was measured, which was taken as the response time from transparent to opaque.
【００４２】この結果を表１に示す。The results are shown in Table 1.
【００４３】[0043]
【表１】 [Table 1]
【００４４】表１より、重合度４で架橋していない高分
子液晶を使用した液晶表示素子（比較例１）では透明か
ら不透明への転換が起こらなかった。液晶性オリゴマー
を使用した液晶表示素子（実施例１，２）は、いずれも
重合度４で架橋した高分子液晶を使用した液晶表示素子
（比較例２）に比べて、不透明から透明および透明から
不透明ともに応答速度が速くなっていることが確認でき
た。From Table 1, in the liquid crystal display device (Comparative Example 1) using the polymer liquid crystal which was not crosslinked at the polymerization degree of 4, the conversion from transparent to opaque did not occur. The liquid crystal display devices using liquid crystalline oligomers (Examples 1 and 2) were both opaque to transparent and transparent, as compared with the liquid crystal display device using a liquid crystal polymer having a degree of polymerization of 4 (Comparative Example 2). It was confirmed that both the opacity and the response speed were faster.
【００４５】[0045]
【発明の効果】以上のように、本発明の液晶表示素子
は、液晶性オリゴマーを用いて混合膜を構成することに
より、従来型の側鎖型高分子液晶のように重合度を大き
くしたり架橋させたりしなくても、透明から不透明への
転換を良好に行うことができる。また混合膜中の液晶性
オリゴマー自体の分子量が小さいため液晶基の運動性を
阻害することなく、応答速度の速い液晶表示素子が得ら
れる。As described above, in the liquid crystal display device of the present invention, by forming a mixed film using a liquid crystal oligomer, the degree of polymerization can be increased like a conventional side chain type polymer liquid crystal. The conversion from transparent to opaque can be satisfactorily performed without crosslinking. Further, since the molecular weight of the liquid crystalline oligomer itself in the mixed film is small, a liquid crystal display device having a fast response speed can be obtained without inhibiting the mobility of the liquid crystal group.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の液晶性オリゴマーの構造を示す模式図
である。FIG. 1 is a schematic view showing a structure of a liquid crystalline oligomer of the present invention.
【図２】液晶表示素子の製造におけるラミネート法を示
す概略図である。FIG. 2 is a schematic view showing a laminating method in manufacturing a liquid crystal display element.
【図３】液晶性オリゴマーの合成原料のＩＲ分析を示す
グラフである。FIG. 3 is a graph showing IR analysis of a raw material for synthesizing a liquid crystalline oligomer.
【図４】液晶性オリゴマーの合成原料のＩＲ分析を示す
グラフである。FIG. 4 is a graph showing IR analysis of a raw material for synthesizing a liquid crystalline oligomer.
【図５】液晶性オリゴマーのＩＲ分析を示すグラフであ
る。FIG. 5 is a graph showing IR analysis of a liquid crystalline oligomer.
１ スペーサー ２ 液晶基 ３ ラミネートロール ４ スペーサ材 ５ 液晶材料 ６ 導電基材 ７ 混合膜 1 Spacer 2 Liquid Crystal Base 3 Laminating Roll 4 Spacer Material 5 Liquid Crystal Material 6 Conductive Base Material 7 Mixed Film
Claims (2)
液晶性オリゴマー。 Ｚ（Ａ−Ｙ）n （１） （式中、ＺはＣ、Ｓｉ、Ｎ、Ｂ、Ｇｅを示し、Ａはスペ
ーサーを示し、Ｙは液晶基を示し、ｎは３または４の整
数を示す。）1. A liquid crystalline oligomer represented by the following formula (1). Z (A-Y) n (1) (In the formula, Z represents C, Si, N, B, and Ge, A represents a spacer, Y represents a liquid crystal group, and n represents an integer of 3 or 4. .)
と、低分子液晶と、電解質とを含有する混合膜を、少な
くとも一方が透明な一対の導電基材で挟着したことを特
徴とする液晶表示素子。2. A mixed film containing a liquid crystalline oligomer represented by the above formula (1), a low molecular weight liquid crystal, and an electrolyte is sandwiched between a pair of conductive base materials, at least one of which is transparent. Liquid crystal display device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27205992A JPH06118396A (en) | 1992-10-09 | 1992-10-09 | Liquid crystalline oligomer and liquid crystal display device using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27205992A JPH06118396A (en) | 1992-10-09 | 1992-10-09 | Liquid crystalline oligomer and liquid crystal display device using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06118396A true JPH06118396A (en) | 1994-04-28 |
Family
ID=17508530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27205992A Pending JPH06118396A (en) | 1992-10-09 | 1992-10-09 | Liquid crystalline oligomer and liquid crystal display device using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06118396A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997036908A1 (en) * | 1996-03-29 | 1997-10-09 | The Secretary Of State For Defence | Liquid crystal materials and devices |
| WO2014088362A1 (en) * | 2012-12-07 | 2014-06-12 | 전북대학교산학협력단 | Liquid crystal compound having fourth generation dendron structure and method for preparing same |
| WO2017204515A1 (en) * | 2016-05-23 | 2017-11-30 | 주식회사 엘지화학 | Novel liquid crystal compound and use thereof |
-
1992
- 1992-10-09 JP JP27205992A patent/JPH06118396A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997036908A1 (en) * | 1996-03-29 | 1997-10-09 | The Secretary Of State For Defence | Liquid crystal materials and devices |
| GB2326418A (en) * | 1996-03-29 | 1998-12-23 | The Secretary Of State For Defence | Siloxane liquid crystal materials and devices |
| US6277451B1 (en) | 1996-03-29 | 2001-08-21 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal materials and devices |
| WO2014088362A1 (en) * | 2012-12-07 | 2014-06-12 | 전북대학교산학협력단 | Liquid crystal compound having fourth generation dendron structure and method for preparing same |
| WO2017204515A1 (en) * | 2016-05-23 | 2017-11-30 | 주식회사 엘지화학 | Novel liquid crystal compound and use thereof |
| TWI648377B (en) * | 2016-05-23 | 2019-01-21 | Ｌｇ化學股份有限公司 | New liquid crystal compound and its use |
| US10954444B2 (en) | 2016-05-23 | 2021-03-23 | Lg Chem, Ltd. | Liquid crystal compound and use thereof |
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