JPH09185043A - Liquid crystal element - Google Patents
Liquid crystal elementInfo
- Publication number
- JPH09185043A JPH09185043A JP34256195A JP34256195A JPH09185043A JP H09185043 A JPH09185043 A JP H09185043A JP 34256195 A JP34256195 A JP 34256195A JP 34256195 A JP34256195 A JP 34256195A JP H09185043 A JPH09185043 A JP H09185043A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal material
- composite film
- polycyclic
- film
- 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 160
- 239000000463 material Substances 0.000 claims abstract description 128
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 230000008961 swelling Effects 0.000 claims abstract description 14
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 24
- 230000004044 response Effects 0.000 abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 62
- 229920000642 polymer Polymers 0.000 description 44
- 238000002834 transmittance Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000007611 bar coating method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010330 laser marking Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- -1 methoxy, ethoxy, n-propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
Abstract
(57)【要約】
【課題】 耐熱性にすぐれ、とくに高温域で使用した際
に十分なコントラストを維持でき、かつ、透明状態／光
散乱状態間の応答時間の短い液晶素子を提供する。
【解決手段】 ３〜４個のベンゼン環またはシクロヘキ
サン環を骨格もつ液晶材料が、スポンジ状構造を有する
架橋高分子マトリクスの連続した孔内に充填されて、室
温から１５０℃の温度域における液晶材料の膨潤率が２
０％以下で、ドメイン径が４μｍ以下である複合膜を構
成し、その複合膜を一対の導電性基材で挟着した液晶素
子。
(57) Abstract: A liquid crystal element having excellent heat resistance, capable of maintaining a sufficient contrast particularly when used in a high temperature range, and having a short response time between a transparent state and a light scattering state. A liquid crystal material having 3 to 4 benzene rings or cyclohexane rings as a skeleton is filled in continuous pores of a crosslinked polymer matrix having a sponge-like structure, and the liquid crystal material in a temperature range of room temperature to 150 ° C. Swelling rate is 2
A liquid crystal element in which a composite film having a domain diameter of 4 μm or less is constituted by 0% or less, and the composite film is sandwiched between a pair of conductive base materials.
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、レーザマーキン
グや照明用調光素子、自動車用表示パネルに使用される
液晶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 device used for laser marking, a light control device for illumination, and a display panel for automobiles.
【０００２】[0002]
【従来の技術】ねじれネマティック（ＴＮ）方式、超ね
じれネマティック（ＳＴＮ）方式、強誘電性液晶（ＦＬ
Ｃ）方式等の液晶素子は、一般表示モードで電界印加に
よって起こる液晶の配列変化を可視化するために偏光子
を必要とする。しかし、当該偏光子による光のロスが５
０％以上あるため、光利用効率をあげるのが困難であっ
た。また、とくに照明装置の調光素子等、高温条件下で
使用される素子の場合は、偏光子の吸熱による素子の劣
化等の問題もあった。2. Description of the Related Art Twisted nematic (TN) system, super twisted nematic (STN) system, ferroelectric liquid crystal (FL)
A liquid crystal element of the C) type or the like requires a polarizer in order to visualize a change in alignment of liquid crystals caused by application of an electric field in a general display mode. However, the light loss due to the polarizer is 5
Since it is 0% or more, it is difficult to improve the light utilization efficiency. Further, particularly in the case of an element used under high temperature conditions such as a light control element of an illuminating device, there is a problem such as deterioration of the element due to heat absorption of the polarizer.
【０００３】これに対し、高分子マトリクスからなる担
体膜の連続した孔内に正の誘電率異方性（Δε＞０）を
もつ液晶材料を充填した構造、または高分子マトリクス
からなる担体膜中に、上記液晶材料を粒状に分散した構
造の複合膜を、一対の透明導電性基材で挟着した液晶素
子は、偏光子を必要としないため、光のロスが小さくな
り、光利用効率を向上することができる〔たとえばPoly
mer Preprints ，Japan Vol.37. (8) ，2450 (1988) 参
照〕。On the other hand, a structure in which a liquid crystal material having a positive dielectric anisotropy (Δε> 0) is filled in continuous holes of a carrier film made of a polymer matrix, or in a carrier film made of a polymer matrix In addition, the liquid crystal element in which the composite film having a structure in which the above liquid crystal material is dispersed in a granular form is sandwiched by a pair of transparent conductive substrates does not require a polarizer, so that the loss of light is reduced and the light utilization efficiency is improved. Can be improved (eg Poly
mer Preprints, Japan Vol.37. (8), 2450 (1988)].
【０００４】この液晶素子は、無電圧時には、液晶分子
が、当該液晶分子と高分子マトリクスとの界面の形状的
な規制（界面作用）を受けてランダムな状態にあるた
め、入射光が液晶材料内で散乱される。また、液晶材料
の見かけの屈折率と、高分子マトリクスの屈折率との差
が大きくなって、入射光が両者の界面で散乱される。そ
の結果、複合膜は不透明な状態となる。一方、一対の透
明導電性基材に電圧を印加すると、その印加電圧の強さ
に応じて、正の誘電率異方性をもつ液晶材料が電場方向
に配向し、配列の乱れが解消されるとともに、液晶材料
の見かけの屈折率と、高分子マトリクスの屈折率との差
が小さくなって、光の透過率が上昇し、最終的には透明
な状態に至るという電気光学効果を示す。In this liquid crystal element, when no voltage is applied, the liquid crystal molecules are in a random state due to the shape restriction (interfacial action) of the interface between the liquid crystal molecules and the polymer matrix. Scattered within. Further, the difference between the apparent refractive index of the liquid crystal material and the refractive index of the polymer matrix becomes large, and incident light is scattered at the interface between the two. As a result, the composite membrane becomes opaque. On the other hand, when a voltage is applied to the pair of transparent conductive base materials, the liquid crystal material having a positive dielectric anisotropy is oriented in the direction of the electric field according to the strength of the applied voltage, and the disorder of the alignment is eliminated. At the same time, the difference between the apparent refractive index of the liquid crystal material and the refractive index of the polymer matrix is reduced, the light transmittance is increased, and finally, the electro-optical effect is achieved in which the transparent state is achieved.
【０００５】[0005]
【発明が解決しようとする課題】上記複合膜を備えた従
来の液晶素子は、たとえば照明装置の調光素子等のよう
に、高温条件下で使用した際に、無電圧時（光散乱時）
の光の透過率が高くなって、コントラストが低下すると
いう問題があった。また、自動車用表示パネル、半導体
部品等に使用されるレーザマーキングへの適用を考慮し
た場合、実用可能な印加電圧において応答速度が遅い等
の問題があった。A conventional liquid crystal element provided with the above composite film is used under high temperature conditions such as a dimming element of a lighting device when no voltage is applied (when light is scattered).
However, there is a problem in that the light transmittance of is high and the contrast is low. Further, in consideration of application to laser marking used for automobile display panels, semiconductor parts, etc., there is a problem that the response speed is slow at a practically applied voltage.
【０００６】上記問題の原因を考察すると、高温条件下
でのコントラストの低下は、高分子マトリクスへの液晶
材料の溶け込み、すなわち液晶材料の高分子マトリクス
への膨潤にあると考えられる。つまり、低分子である液
晶材料が高分子の分子間に入り込んで膨潤すると、高分
子の屈折率が上昇する。その結果、ランダムな配向状態
にある液晶材料の見かけの屈折率との差が小さくなっ
て、両者の界面で入射光を散乱させる効果が低下し、そ
の分だけ、無電圧時の光の透過率が高くなって、コント
ラストが低下するのである。Considering the cause of the above problem, it is considered that the decrease in contrast under high temperature conditions is due to dissolution of the liquid crystal material into the polymer matrix, that is, swelling of the liquid crystal material into the polymer matrix. That is, when the liquid crystal material having a low molecular weight enters between the molecules of the polymer and swells, the refractive index of the polymer increases. As a result, the difference from the apparent refractive index of the liquid crystal material in the random alignment state becomes small, and the effect of scattering incident light at the interface between the two decreases, and the light transmittance when there is no voltage is reduced accordingly. Is higher and the contrast is lower.
【０００７】高温条件下における液晶材料の高分子への
溶け込みを防止するには、両者の相互作用（たとえば溶
解度パラメータ、相溶性等）を検討することも重要であ
るが、液晶材料自体の特性の検討、ならびに高分子自体
の特性の検討も必要となる。In order to prevent the liquid crystal material from melting into the polymer under high temperature conditions, it is important to study the interaction between them (eg, solubility parameter, compatibility, etc.). It is also necessary to study the properties of the polymer itself.
【０００８】液晶材料の側から、液晶材料の高分子への
溶け込みの原因を考察すると、分子量が大きい液晶材料
ほど、高温条件下で、高分子への溶け込みが少なくなる
ことが明らかとなった。つまり、液晶材料の全部または
一部を、より分子量の大きい液晶材料に置き換えると、
高温条件下での高分子への溶け込みを防いで、コントラ
ストの低下を抑制できることがわかった。この現象は、
組み合わされる高分子の種類によって、その程度に大小
はあるものの、通常、高分子マトリクスとして使用され
る各種の高分子においては、いずれも同様の傾向がみら
れる。また、無電圧時における光の散乱度合いを向上さ
せるには、液晶ドメインサイズの大きさをコントロール
することが有効であり、光の波長に極力近付けることが
重要である。さらに、液晶のドメインサイズを小さくす
ることは、応答速度の高速化につながる。Considering the cause of the dissolution of the liquid crystal material into the polymer from the side of the liquid crystal material, it became clear that the liquid crystal material having a higher molecular weight has less dissolution into the polymer under high temperature conditions. In other words, if you replace all or part of the liquid crystal material with a liquid crystal material with a higher molecular weight,
It was found that the decrease in contrast can be suppressed by preventing the polymer from melting under high temperature conditions. This phenomenon is
Although there are different sizes depending on the kinds of polymers to be combined, the same tendency is generally observed in various polymers used as a polymer matrix. Further, in order to improve the degree of light scattering when no voltage is applied, it is effective to control the size of the liquid crystal domain size, and it is important to control the size of light as close as possible to the wavelength of light. Further, reducing the domain size of the liquid crystal leads to higher response speed.
【０００９】この発明は、上記の課題に鑑みて上述の知
見に基づいてなされたもので、耐熱性に優れ、応答時間
が速く、室温から高温域で使用した際に十分なコントラ
ストを維持できる液晶素子を提供することを目的とす
る。The present invention has been made based on the above findings in view of the above problems, and has excellent heat resistance, a fast response time, and a liquid crystal capable of maintaining a sufficient contrast when used in a room temperature to a high temperature range. The purpose is to provide a device.
【００１０】[0010]
【課題を解決するための手段】発明者らは、上述の知見
を基に種々の液晶材料について検討した結果、室温から
１５０℃における透過率が１０％以下という優れたコン
トラストを有し、かつ、透明状態及び光散乱状態間の相
互変換の応答時間が１０ｍｓ以下である液晶素子を得る
ためには、室温から１５０℃の範囲内での液晶材料の膨
潤率が２０％以下で前記液晶材料のドメインサイズ径が
４μｍ以下である液晶が、本発明における液晶材料とし
て好適であることを見出した。The inventors have studied various liquid crystal materials based on the above findings, and as a result, have an excellent contrast that the transmittance from room temperature to 150 ° C. is 10% or less, and In order to obtain a liquid crystal device having a mutual conversion response time of 10 ms or less between a transparent state and a light scattering state, a swelling ratio of the liquid crystal material within a range of room temperature to 150 ° C. is 20% or less and a domain of the liquid crystal material is used. It has been found that a liquid crystal having a size diameter of 4 μm or less is suitable as the liquid crystal material in the present invention.
【００１１】すなわち本発明の液晶素子は、いわゆるス
ポンジ状構造を有する架橋された高分子マトリクスから
なる担体膜の連続した孔内に液晶材料を充填した構造を
なす複合膜を一対の導電性基材で挾着してなる液晶素子
であり、液晶材料として３〜４個のベンゼン環またはシ
クロヘキサン環を骨格に持つものを用い、かつ、室温か
ら１５０℃における前記液晶材料の膨潤率が２０％以下
であり、前記液晶材料のドメインサイズ径が０．５μｍ
以上４μｍ以下であることによって、本発明の目的を達
成することができる。That is, the liquid crystal device of the present invention comprises a pair of conductive base materials each having a composite film having a structure in which a liquid crystal material is filled in the continuous pores of a carrier film made of a cross-linked polymer matrix having a so-called sponge-like structure. A liquid crystal element having 3 to 4 benzene rings or cyclohexane rings in the skeleton as a liquid crystal material, and the swelling ratio of the liquid crystal material from room temperature to 150 ° C. is 20% or less. Yes, the domain size diameter of the liquid crystal material is 0.5 μm
When the thickness is 4 μm or less, the object of the present invention can be achieved.
【００１２】本発明の液晶素子における液晶相の多環式
液晶材料は、温度域が高いことから、通常の表示素子等
では余り使用されないが、特にレーザマーキング用や照
明用調光素子、自動車用表示パネル等の使用温度が１０
０℃以上に達する高温条件下での使用時には液晶相を示
し、かつ、その動作速度も十分に実用に供し得るもので
ある。The polycyclic liquid crystal material having a liquid crystal phase in the liquid crystal element of the present invention has a high temperature range, and thus is not used in a general display element or the like. However, it is particularly used for laser marking, lighting dimming element, and automobile. The operating temperature of the display panel etc. is 10
When used under high temperature conditions of 0 ° C. or higher, it exhibits a liquid crystal phase, and its operating speed can be sufficiently put to practical use.
【００１３】[0013]
【発明の実施の形態】この発明の液晶素子は、図１に示
すように、複合膜Ｌを、一対の導電基材Ｄ，Ｄで挟着す
ることで構成されている。BEST MODE FOR CARRYING OUT THE INVENTION As shown in FIG. 1, the liquid crystal element of the present invention is constituted by sandwiching a composite film L between a pair of conductive base materials D, D.
【００１４】複合膜Ｌとしては、図２(a)に示すよう
に、高分子マトリクスからなる担体膜Ｌ１の連続した孔
内に、液晶材料Ｌ２を充填した構造、または図２(b)に
示すように、高分子マトリクスからなる担体膜Ｌ３中
に、液晶材料Ｌ２を粒状に分散した構造のいずれかが採
用される。As the composite film L, as shown in FIG. 2 (a), a structure in which a liquid crystal material L2 is filled in the continuous holes of a carrier film L1 made of a polymer matrix, or shown in FIG. 2 (b). As described above, any of the structures in which the liquid crystal material L2 is dispersed in the carrier film L3 made of a polymer matrix in a granular form is adopted.
【００１５】複合膜を構成する液晶材料としては、３〜
４個のベンゼン環またはシクロヘキサン環を骨格にもつ
多環式液晶材料が使用される。ベンゼン環またはシクロ
ヘキサン環を骨格に５個以上もつものは、液晶相の温度
域が高すぎて、上記高温条件下でも液晶相を示さない
か、あるいは液晶相を示しても動作速度がきわめて遅い
ため、この発明には使用できない。室温から１５０℃の
範囲内における液晶の膨潤率が２０％以下で液晶のドメ
インサイズ径が４μｍ以下である液晶が使用される。ま
た、液晶材料は素子の使用温度で、ネマチック相、スメ
クチック相またはカイラルネマチック相を示す、正の誘
電率異方性を有する液晶材料が使用される。なお、高分
子の側からも、液晶材料の溶け込みを防止すべく、ガラ
ス転移温度Ｔｇが高くなるように架橋されている。この
発明によって、室温から１５０℃における光の透過率が
１０％以下で、室温から１５０℃における透過率が１０
％以下である液晶素子を実現することが可能となった。As the liquid crystal material constituting the composite film, 3 to
A polycyclic liquid crystal material having four benzene rings or cyclohexane rings in its skeleton is used. Those having five or more benzene rings or cyclohexane rings in the skeleton have too high a temperature range of the liquid crystal phase and do not show a liquid crystal phase even under the above high temperature condition, or even if they show a liquid crystal phase, the operation speed is extremely slow. , Cannot be used in this invention. A liquid crystal having a swelling ratio of 20% or less and a domain size diameter of 4 μm or less is used in the range of room temperature to 150 ° C. Further, as the liquid crystal material, a liquid crystal material having a positive dielectric anisotropy, which exhibits a nematic phase, a smectic phase, or a chiral nematic phase at a temperature at which the device is used, is used. The polymer is also cross-linked from the polymer side so that the glass transition temperature Tg becomes high in order to prevent the liquid crystal material from melting. According to the present invention, the light transmittance from room temperature to 150 ° C. is 10% or less and the light transmittance from room temperature to 150 ° C. is 10% or less.
It has become possible to realize a liquid crystal element having a ratio of not more than%.
【００１６】かかる多環式液晶材料としては、たとえば
一般式(1) 〜(11)：Examples of such polycyclic liquid crystal materials include those represented by the general formulas (1) to (11):
【００１７】[0017]
【化１】 Embedded image
【００１８】[0018]
【化２】 Embedded image
【００１９】〔上記各式中Ｒ1は、アルキル基またはア
ルコキシ基を示し、Ｒ2は、アルキル基、アルコキシ
基、シアノ基またはハロゲン原子を示す。〕で表される
ものがあげられる。上記各一般式において、Ｒ1，Ｒ2に
相当するアルキル基としては、たとえばメチル、エチ
ル、ｎ−プロピル、 iso−プロピル、ｎ−ブチル、イソ
ブチル、 sec−ブチル、tert−ブチル、ペンチル、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ウンデシ
ル、ドデシル等の、炭素数１〜１２のアルキル基があげ
られる。[In the above formulas, R 1 represents an alkyl group or an alkoxy group, and R 2 represents an alkyl group, an alkoxy group, a cyano group or a halogen atom. ] Is represented. In each of the above general formulas, examples of the alkyl group corresponding to R 1 and R 2 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, Examples thereof include alkyl groups having 1 to 12 carbon atoms such as heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
【００２０】またアルコキシ基としては、たとえばメト
キシ、エトキシ、ｎ−プロポキシ、ｎ−ブトキシ、ペン
チルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチ
ルオキシ、ノニルオキシ、デシルオキシ、ウンデシルオ
キシ、ドデシルオキシ等の、炭素数１〜１２のアルコキ
シ基があげられる。さらにハロゲン原子としては、ふっ
素、塩素、臭素、よう素があげられる。The alkoxy group has, for example, methoxy, ethoxy, n-propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc., and has 1 carbon atom. To 12 alkoxy groups. Further, examples of the halogen atom include fluorine, chlorine, bromine and iodine.
【００２１】かかる多環式液晶材料の具体的化合物とし
ては、これに限定されないが、たとえば、下記式(12)(1
3)で表されるものがあげられる。The specific compound of the polycyclic liquid crystal material is not limited to this, but may be, for example, one of the following formulas (12) (1)
The one represented by 3) is given.
【００２２】[0022]
【化３】 Embedded image
【００２３】これらはそれぞれ単独で使用される他、２
種以上を併用することもできる。多環式液晶材料の２種
以上の組み合わせの好適な例としては、たとえば式(12)
の多環式液晶材料と式(13)の多環式液晶材料の液晶材料
とを、重量比で３５：６５の割合で用いる組み合わせ等
があげられる。In addition to being used alone, 2
More than one species may be used in combination. Preferable examples of the combination of two or more kinds of polycyclic liquid crystal materials include compounds represented by the formula (12)
A combination of the polycyclic liquid crystal material (1) and the liquid crystal material of the polycyclic liquid crystal material (13) in a weight ratio of 35:65 can be used.
【００２４】上記多環式液晶材料の、全液晶材料中に占
める割合は、前記のように７０〜１００重量％に限定さ
れる。上記割合は、多環式液晶材料を２種以上併用する
場合には、その総量の、全液晶材料中に占める割合であ
る。つまりこの発明においては、複合膜を構成する液晶
材料の全量が、多環式液晶材料の１種または２種以上で
あってもよいが、これら多環式液晶材料と、通常の、よ
り低分子の液晶材料との、重量比７０：３０までの併用
系であってもよいのである。かかる併用系では、素子の
応答速度を向上できるという利点がある。The proportion of the above polycyclic liquid crystal material in the total liquid crystal material is limited to 70 to 100% by weight as described above. When two or more polycyclic liquid crystal materials are used in combination, the above ratio is the ratio of the total amount to all liquid crystal materials. That is, in the present invention, the total amount of the liquid crystal material forming the composite film may be one kind or two or more kinds of the polycyclic liquid crystal material, but these polycyclic liquid crystal materials and ordinary low molecular weight compounds may be used. It may be a combination system with the liquid crystal material of up to 70:30. Such a combined system has an advantage that the response speed of the element can be improved.
【００２５】ただしこの併用系では、多環式液晶材料の
割合が、上記のように７０重量％以上に限定される。こ
れは、多環式液晶材料の割合が７０重量％を下回った場
合、相対的に、より低分子の通常の液晶材料の割合が多
くなるため、とくに高温条件下で、かかる液晶材料の高
分子への溶け込みによる、素子のコントラストの低下が
発生するからである。However, in this combined system, the proportion of the polycyclic liquid crystal material is limited to 70% by weight or more as described above. This is because when the proportion of the polycyclic liquid crystal material is less than 70% by weight, the proportion of the normal liquid crystal material having a lower molecular weight becomes relatively large, and therefore, especially under high temperature conditions, the polymer of the liquid crystal material becomes high. This is because the contrast of the device is lowered due to the melting into the element.
【００２６】なお上記併用系における、多環式液晶材料
の割合は、素子の耐熱性を考慮すると、上記範囲内でも
特に８０〜１００重量％の範囲内が好ましく、とくに９
０〜１００重量％の範囲内がより一層好ましい。多環式
液晶材料と併用される他の液晶材料としては、現在一般
に用いられている、２個のベンゼン環またはシクロヘキ
サン環を骨格にもつ通常の液晶材料の中から、素子の使
用温度で多環式液晶材料と同じ液晶相を示す、正の誘電
率異方性を有する液晶材料の１種または２種以上があげ
られる。The proportion of the polycyclic liquid crystal material in the above-mentioned combined system is preferably within the range of 80 to 100% by weight, particularly 9 in view of the heat resistance of the device.
The range of 0 to 100% by weight is even more preferable. As other liquid crystal materials used in combination with the polycyclic liquid crystal material, there are selected from among ordinary liquid crystal materials having two benzene rings or a cyclohexane ring as a skeleton, which are generally used at present, at the operating temperature of the device. One or more kinds of liquid crystal materials exhibiting the same liquid crystal phase as the formula liquid crystal material and having positive dielectric anisotropy can be given.
【００２７】かかる液晶材料の具体的化合物としては、
これに限定されないが、たとえば、下記式(a)(b)で表さ
れるものがあげられる。Specific compounds of the liquid crystal material include:
Although not limited to this, examples thereof include those represented by the following formulas (a) and (b).
【００２８】[0028]
【化４】 Embedded image
【００２９】多環式液晶材料と、上記他の液晶材料との
組み合わせの好適な例としては、例えば前記式(12)で表
される多環式液晶材料と、式(a) および(b) で表される
他の液晶材料とを、重量比で７０：１５：１５の割合で
用いる組み合わせ等があげられる。なお液晶材料には、
表示をカラー化するために、従来公知の各種２色性色素
を配合することもできる。かかる２色性色素の具体例と
しては、たとえばアゾ系化合物やアントラキノン系化合
物等があげられる。かかる２色性色素は、液晶材料に対
して０．０１〜１重量％程度の割合で添加される。Preferable examples of the combination of the polycyclic liquid crystal material and the above-mentioned other liquid crystal material include, for example, the polycyclic liquid crystal material represented by the above formula (12) and the formulas (a) and (b). Another liquid crystal material represented by is used in a ratio of 70:15:15 by weight, and the like. The liquid crystal material includes
In order to color the display, various conventionally known dichroic dyes may be added. Specific examples of such dichroic dyes include azo compounds and anthraquinone compounds. The dichroic dye is added in a proportion of about 0.01 to 1% by weight with respect to the liquid crystal material.
【００３０】上記液晶材料とともに複合膜を構成する担
体膜の材料である、高分子マトリクスとしては、可視光
に対する透明性の高いものが好ましく、たとえば（メ
タ）アクリル系樹脂、スチレン系樹脂、エポキシ系樹
脂、ウレタン系樹脂等が好適に使用される。かかる高分
子は、液晶材料の溶け込みを防止するため、前述したよ
うに、ガラス転移温度Ｔｇが高いことが好ましく、その
ために架橋されているのが望ましい。The polymer matrix, which is the material of the carrier film forming the composite film together with the above liquid crystal material, is preferably one having high transparency to visible light, for example, (meth) acrylic resin, styrene resin, epoxy resin. Resin, urethane resin, etc. are preferably used. Such a polymer preferably has a high glass transition temperature Tg, as described above, in order to prevent the liquid crystal material from melting, and therefore it is desirable that the polymer be crosslinked.
【００３１】エポキシ系樹脂、ウレタン系樹脂はとも
に、分子中に官能基を有する硬化性樹脂であって、通常
は液状を呈し、複合膜の形成時に、空気中の酸素、湿
気、加熱あるいは硬化剤や触媒の添加等によって架橋さ
れて、硬化される。一方、（メタ）アクリル系樹脂、ス
チレン系樹脂は熱可塑性樹脂であって、通常は架橋構造
をとらないが、分子中に官能基（たとえばＯＨ基）を導
入しておき、複合膜の形成時に、この官能基と反応する
複数の官能基（たとえばイソシアネート基）を有する架
橋剤を添加すれば、架橋させることができる。架橋剤
は、高分子中の官能基と、架橋剤の官能基が当量となる
ように、添加量を調整するのが好ましい。Both the epoxy resin and the urethane resin are curable resins having a functional group in the molecule and are usually in a liquid state. When forming a composite film, oxygen, moisture in the air, heating or a curing agent is used. It is cross-linked and hardened by adding a catalyst or the like. On the other hand, the (meth) acrylic resin and the styrene resin are thermoplastic resins and usually do not have a cross-linking structure, but a functional group (for example, OH group) is introduced into the molecule to form a composite film during formation. By adding a cross-linking agent having a plurality of functional groups (for example, an isocyanate group) that reacts with this functional group, cross-linking can be achieved. The amount of the crosslinking agent added is preferably adjusted so that the functional groups in the polymer and the functional groups of the crosslinking agent are equivalent.
【００３２】上記のように架橋されて高いガラス転移温
度Ｔｇとなった高分子を用いた複合膜は、上記のように
液晶材料の溶け込み防止効果にすぐれるだけでなく、相
分離構造がより一層明確化するとともに、高温条件下で
の複合膜の強度低下を効果的に防止できるという利点も
ある。複合膜の膜厚は、十分な光散乱を得るために、可
視光の波長以上である必要がある。ただし、あまりに厚
さが大なるときは、素子の駆動電圧が高くなりすぎると
いう問題があるたは、実際上は１０〜３０μｍ程度、と
くに１５〜２５μｍ程度が適当である。The composite film using the polymer cross-linked to have a high glass transition temperature Tg as described above is not only excellent in the effect of preventing the liquid crystal material from melting, but also has a further phase separation structure. There is also an advantage that the strength of the composite film can be effectively prevented from being deteriorated under a high temperature condition while being clarified. The film thickness of the composite film needs to be not less than the wavelength of visible light in order to obtain sufficient light scattering. However, when the thickness is too large, there is a problem that the driving voltage of the element becomes too high. However, in practice, about 10 to 30 μm, particularly about 15 to 25 μm is appropriate.
【００３３】複合膜は、たとえば次に示す３つの方法で
形成される。 i)たとえば前記（メタ）アクリル系樹脂やスチレン系樹
脂等の熱可塑性樹脂を使用する場合には、当該樹脂と液
晶材料とを適当な溶媒に溶解または分散させた塗布液
を、一方の導電基材Ｄの表面に塗布し、溶媒を蒸発させ
て、高分子と液晶材料とを相分離させる（いわゆる溶媒
蒸発法）。その後他方の導電基材を１ｋｇ／ｃｍ2の圧
力で重ね合わす。そうすると、図１(a) に示す構造の複
合膜が得られる。またこの際、上記樹脂として官能基を
有するものを使用するとともに、塗布液に架橋剤を添加
しておくと、透明体マトリクスを構成する高分子が架橋
される。The composite film is formed, for example, by the following three methods. i) For example, when a thermoplastic resin such as the (meth) acrylic resin or styrene resin is used, a coating solution obtained by dissolving or dispersing the resin and the liquid crystal material in a suitable solvent is used as one conductive group. It is applied to the surface of the material D, the solvent is evaporated, and the polymer and the liquid crystal material are phase-separated (so-called solvent evaporation method). Then, the other conductive base material is superposed at a pressure of 1 kg / cm 2 . Then, a composite film having the structure shown in FIG. 1 (a) is obtained. At this time, when a resin having a functional group is used as the resin and a cross-linking agent is added to the coating liquid, the polymer constituting the transparent matrix is cross-linked.
【００３４】ii)またエポキシ系樹脂、ウレタン系樹脂
等の熱硬化性樹脂を使用する場合には、硬化前の液状の
樹脂と液晶材料と、さらに必要に応じて硬化剤または触
媒とを、適当な溶媒に溶解または分散させた溶液を、２
枚の導電基材Ｄ間に注入し、さらに必要に応じて加熱す
る。そうすると、高分子中に液晶材料が粒状に分散され
た、図１(b)に示す構造の複合膜が形成される。Ii) When a thermosetting resin such as an epoxy resin or a urethane resin is used, a liquid resin before curing, a liquid crystal material and, if necessary, a curing agent or a catalyst are appropriately used. The solution dissolved or dispersed in various solvents is 2
It is injected between the conductive base materials D of one sheet, and further heated if necessary. Then, a composite film having a structure shown in FIG. 1 (b) in which the liquid crystal material is dispersed in the polymer in a granular form is formed.
【００３５】iii)さらに重合相分離法においては、（メ
タ）アクリル系樹脂やスチレン系樹脂等の熱可塑性樹脂
の前駆体（プレポリマー）であるモノマーやオリゴマー
と、液晶材料、重合開始剤および、さらに必要に応じて
架橋剤とを混合した溶液を、２枚の導電基材Ｄ間に注入
し、紫外線もしくは熱により重合および架橋反応させる
と、高分子と液晶材料が相分離することにより、図２
(a) に示す構造の複合膜が形成される。Iii) Further, in the polymerization phase separation method, a monomer or oligomer which is a precursor (prepolymer) of a thermoplastic resin such as a (meth) acrylic resin or a styrene resin, a liquid crystal material, a polymerization initiator, and Further, if necessary, a solution mixed with a crosslinking agent is injected between the two conductive base materials D, and polymerized and crosslinked by ultraviolet rays or heat to cause phase separation between the polymer and the liquid crystal material. Two
A composite film having the structure shown in (a) is formed.
【００３６】導電基材Ｄとしては、基材の表面に導電膜
を形成したものがあげられる。基材としては、ガラス板
等の、液晶素子の基材として従来より使用されている種
々の基材が使用可能であるが、重くかつ割れやすいとい
うガラス板の欠点を解消して、軽量でしかも丈夫な素子
を得るには、プラスチックフィルムやプラスチック板
が、基材として好適に使用される。Examples of the conductive base material D include those having a conductive film formed on the surface of the base material. As the base material, various base materials conventionally used as a base material of a liquid crystal element such as a glass plate can be used, but the disadvantage of the glass plate, which is heavy and easy to break, is eliminated, and it is lightweight and In order to obtain a durable element, a plastic film or a plastic plate is preferably used as the base material.
【００３７】プラスチックフィルムとしては、たとえば
耐熱性、実用的強度、光学的均一性などにすぐれたポリ
エチレンテレフタレート（ＰＥＴ）フィルムやポリエー
テルスルホン（ＰＥＳ）フィルム等があげられる。プラ
スチックフィルムの厚みは、これに限定されるものでは
ないが、５０〜５００μｍ程度が好ましい。プラスチッ
ク板としては、たとえば各種アクリル樹脂板、ポリカー
ボネート板、ポリスチレン板等の、光学的特性にすぐれ
たプラスチック板が好適に使用される。プラスチック板
の厚みは、これに限定されるものではないが０．５〜３
mm程度が好ましい。Examples of the plastic film include polyethylene terephthalate (PET) film and polyether sulfone (PES) film which are excellent in heat resistance, practical strength and optical uniformity. The thickness of the plastic film is not limited to this, but is preferably about 50 to 500 μm. As the plastic plate, for example, various acrylic resin plates, polycarbonate plates, polystyrene plates, and other plastic plates having excellent optical characteristics are preferably used. The thickness of the plastic plate is not limited to this, but is 0.5 to 3
mm is preferable.
【００３８】基材の表面に形成される導電膜としては、
ＩＴＯ（インジウム−チン−オキサイド）やＳｎＯ2等
の透明導電材料からなる透明導電膜が好適に使用され
る。透明導電膜は、真空蒸着法や反応性スパッタリング
法により形成される他、上記透明導電材料を含むインク
を基材上に塗布あるいは印刷して形成することもでき
る。この発明の液晶素子を、たとえば表示装置や各種の
イルミネーション等に使用する場合には、その表示パタ
ーンに合わせて、液晶層を、個別に駆動される複数のセ
グメントに分割すべく、上記導電膜を、エッチング等に
よって、上記セグメントに対応する所定の形状にパター
ン化するとともに、各セグメント毎に個別の駆動電圧を
印加できるように、駆動回路を接続すればよい。As the conductive film formed on the surface of the base material,
A transparent conductive film made of a transparent conductive material such as ITO (Indium-Tin-Oxide) or SnO 2 is preferably used. The transparent conductive film may be formed by a vacuum deposition method or a reactive sputtering method, or may be formed by applying or printing an ink containing the transparent conductive material on a substrate. When the liquid crystal element of the present invention is used in, for example, a display device or various illuminations, the conductive film is used to divide the liquid crystal layer into a plurality of individually driven segments in accordance with the display pattern. The electrodes may be patterned into a predetermined shape corresponding to the segments by etching or the like, and a drive circuit may be connected so that an individual drive voltage can be applied to each segment.
【００３９】また、素子を反射型とする場合には、一方
の導電基材Ｄの裏面に、金属薄膜等からなる反射膜を形
成するか、一方の導電基材Ｄの導電膜を金属薄膜で形成
して反射膜を兼ねさせればよい。When the element is of a reflective type, a reflective film made of a metal thin film or the like is formed on the back surface of one conductive base material D, or the conductive film of one conductive base material D is made of a metal thin film. It may be formed so that it also serves as a reflection film.
【００４０】[0040]
【実施例】以下にこの発明を、実施例、比較例に基づい
て説明する。 実施例１ 多環式液晶材料としての、前記式(12)で表される化合物
と、式(13)で表される化合物とを、重量比で２０：８０
の割合で配合した混合液晶材料〔ネマチック相→等方相
転移温度１９０℃〕７０重量部と、アクリル系樹脂〔帝
国化学社製の商品名ＷＳ０２３〕２５重量部とを、架橋
剤としてのポリイソシアネート５重量部とともに、溶媒
としての１，２−ジクロロエタン中に溶解して、溶質濃
度が２０％の塗布液を作製した。The present invention will be described below with reference to examples and comparative examples. Example 1 A compound represented by the formula (12) and a compound represented by the formula (13) as a polycyclic liquid crystal material were mixed at a weight ratio of 20:80.
70 parts by weight of a mixed liquid crystal material [nematic phase → isotropic phase transition temperature 190 ° C.] and 25 parts by weight of an acrylic resin [trade name WS023 manufactured by Teikoku Kagaku] as a crosslinking agent. Along with 5 parts by weight, it was dissolved in 1,2-dichloroethane as a solvent to prepare a coating solution having a solute concentration of 20%.
【００４１】つぎにこの塗布液を、ＩＴＯコートガラス
基材の、ＩＴＯ膜上に、バーコート法によって塗布し、
２５℃、１気圧の空気中で溶媒を蒸発させて、図２(a)
に示す構造を有する、厚み１７μｍの複合膜を形成し
た。つぎに、上記複合膜を、ガラス基材ごと１００℃に
加熱して、複合膜中に残留する溶媒を除去するととも
に、高分子マトリクスの架橋を完了させた。そして上記
複合膜上に、前記と同じＩＴＯコートガラス基材を、Ｉ
ＴＯ膜が複合膜と接するように重ね合わせた後、約１kg
／cm2の圧力をかけて密着させて、液晶素子を作製し
た。Next, this coating solution was applied onto the ITO film of the ITO-coated glass substrate by the bar coating method,
After evaporating the solvent in air at 25 ° C and 1 atm, see Fig. 2 (a).
A 17 μm-thick composite film having the structure shown in FIG. Next, the composite film was heated to 100 ° C. together with the glass substrate to remove the solvent remaining in the composite film and complete the crosslinking of the polymer matrix. Then, on the above composite film, the same ITO coated glass substrate as above
Approximately 1 kg after stacking so that the TO film contacts the composite film
A liquid crystal element was produced by applying a pressure of / cm 2 and bringing them into close contact.
【００４２】実施例２ 混合液晶材料に代えて、前記式(12)で表される多環式液
晶材料〔ネマチック相→等方相転移温度２１９℃〕７０
重量部を使用したこと以外は、実施例１と同様にして液
晶素子を作製した。Example 2 Instead of the mixed liquid crystal material, a polycyclic liquid crystal material represented by the above formula (12) [nematic phase → isotropic phase transition temperature 219 ° C.] 70
A liquid crystal device was produced in the same manner as in Example 1 except that the parts by weight were used.
【００４３】実施例３ 実施例１で使用したのと同じ混合液晶材料７０重量部
と、二成分触媒硬化型のウレタン系樹脂〔武田薬品社製
の商品名Ａ５０〕２５重量部とを、触媒としてのポリイ
ソシアネート５重量部とともに、溶媒としてのジクロロ
メタン中に溶解して、溶質濃度が２０％の塗布液を作製
した。つぎにこの塗布液を、ＩＴＯコートガラス基材
の、ＩＴＯ膜上に、バーコート法によって塗布し、２５
℃、１気圧の空気中で溶媒を蒸発させるとともにウレタ
ン系樹脂を架橋、硬化させて、図２(b) に示す構造を有
する、厚み１７μｍの複合膜を形成した。つぎに、上記
複合膜を、ガラス基材ごと１００℃に加熱して、複合膜
中に残留する溶媒を除去するとともに、高分子マトリク
スの架橋を完了させた。そして上記複合膜上に、前記と
同じＩＴＯコートガラス基材を、ＩＴＯ膜が複合膜と接
するように重ね合わせた後、約１kg／cm2の圧力をかけ
て密着させて、液晶素子を作製した。Example 3 70 parts by weight of the same mixed liquid crystal material as used in Example 1 and 25 parts by weight of a two-component catalyst-curing urethane resin [trade name A50 manufactured by Takeda Pharmaceutical Co., Ltd.] were used as catalysts. Was dissolved in dichloromethane as a solvent together with 5 parts by weight of polyisocyanate to prepare a coating solution having a solute concentration of 20%. Next, this coating solution is applied onto the ITO film of the ITO-coated glass substrate by the bar coating method,
The solvent was evaporated in air at 1 ° C. and the urethane resin was crosslinked and cured to form a composite film having a thickness of 17 μm and having a structure shown in FIG. 2 (b). Next, the composite film was heated to 100 ° C. together with the glass substrate to remove the solvent remaining in the composite film and complete the crosslinking of the polymer matrix. Then, the same ITO-coated glass substrate as described above was superposed on the composite film so that the ITO film was in contact with the composite film, and then a pressure of about 1 kg / cm 2 was applied to adhere them to produce a liquid crystal element. .
【００４４】実施例４ 実施例１で使用したのと同じ混合液晶材料７０重量部
と、エポキシ系樹脂〔油化シェルエポキシ社製の商品名
エピコート１００１〕３０重量部とを、硬化剤としての
ジエチルアミンの当量重量部とともに、溶媒としてのジ
クロロメタン中に溶解して、溶質濃度が２０％の塗布液
を作製した。Example 4 70 parts by weight of the same mixed liquid crystal material as used in Example 1 and 30 parts by weight of an epoxy resin [trade name Epicoat 1001 manufactured by Yuka Shell Epoxy Co.] were used as a curing agent for diethylamine. Was dissolved in dichloromethane as a solvent to prepare a coating solution having a solute concentration of 20%.
【００４５】つぎにこの塗布液を、ＩＴＯコートガラス
基材の、ＩＴＯ膜上に、バーコート法によって塗布し、
２５℃、１気圧の空気中で溶媒を蒸発させるとともにウ
レタン系樹脂を架橋、硬化させて、図２(b) に示す構造
を有する、厚み１７μｍの複合膜を形成した。つぎに、
上記複合膜を、ガラス基材ごと１００℃に加熱して、複
合膜中に残留する溶媒を除去するとともに、高分子マト
リクスの架橋を完了させた。そして上記複合膜上に、前
記と同じＩＴＯコートガラス基材を、ＩＴＯ膜が複合膜
と接するように重ね合わせた後、約１kg／cm2の圧力を
かけて密着させて、液晶素子を作製した。Next, this coating solution was applied onto the ITO film of the ITO-coated glass substrate by the bar coating method,
The solvent was evaporated in air at 25 ° C. and 1 atm, and the urethane resin was crosslinked and cured to form a composite film having a thickness of 17 μm and having a structure shown in FIG. 2 (b). Next,
The composite membrane was heated to 100 ° C. together with the glass substrate to remove the solvent remaining in the composite membrane and complete the crosslinking of the polymer matrix. Then, the same ITO-coated glass substrate as described above was superposed on the composite film so that the ITO film was in contact with the composite film, and then a pressure of about 1 kg / cm 2 was applied to adhere them to produce a liquid crystal element. .
【００４６】実施例５ 前記式(12)で表される多環式液晶材料〔ネマチック相→
等方相転移温度２１９℃〕と、前記式(a) で表される通
常の液晶材料〔ネマチック相→等方相転移温度１９０
℃〕と、同じく前記式(b) で表される通常の液晶材料
〔ネマチック相→等方相転移温度１８０℃〕とを、重量
比で７０：１０：２０の割合で配合した混合液晶材料７
０重量部を使用したこと以外は、実施例１と同様にして
液晶素子を作製した。Example 5 Polycyclic liquid crystal material represented by the above formula (12) [nematic phase →
Isotropic phase transition temperature of 219 ° C.] and an ordinary liquid crystal material represented by the formula (a) [nematic phase → isotropic phase transition temperature of 190]
C.] and a normal liquid crystal material [nematic phase → isotropic phase transition temperature 180 ° C.] also represented by the above formula (b) at a weight ratio of 70:10:20.
A liquid crystal element was produced in the same manner as in Example 1 except that 0 part by weight was used.
【００４７】比較例１ 式(12)で表される多環式液晶材料と、式(a) および(b)
で表される通常の液晶材料の割合を５５：３０：１５と
した混合液晶材料７０重量部を使用したこと以外は、実
施例１と同様にして液晶素子を作製した。上記各実施
例、比較例の液晶素子について、以下の各試験を行い、
その特性を評価した。Comparative Example 1 A polycyclic liquid crystal material represented by the formula (12) and the formulas (a) and (b)
A liquid crystal element was produced in the same manner as in Example 1 except that 70 parts by weight of the mixed liquid crystal material in which the ratio of the ordinary liquid crystal material represented by the above was set to 55:30:15 was used. For each of the above-mentioned Examples and Comparative Examples, the following tests were carried out,
Its properties were evaluated.
【００４８】液晶材料の膨潤率測定 屈折率計のプリズムの表面に、実施例、比較例の液晶素
子で使用したのと同じ高分子の薄膜（膜厚３μｍ）を形
成し、その上に、実施例、比較例の液晶素子で使用した
のと同じ液晶材料を塗布して、複合膜における透明体マ
トリクスと液晶材料の界面のモデルを作製し、このモデ
ルを６０〜１２０℃に加熱した際の屈折率変化を測定し
て、図３に実線で示すようにプロットした。また上記液
晶材料単独および高分子単独の屈折率変化も測定して、
図３に二点鎖線（液晶材料）および破線（高分子）で示
すようにプロットした。そして、液晶材料単独の屈折率
変化曲線と高分子単独の屈折率変化曲線との、所定温度
における差（たとえば１２０℃の場合は図中符号ａ）
と、モデルの屈折率変化曲線と高分子単独の屈折率変化
曲線との、所定温度における差（たとえば１２０℃の場
合は図中符号ｂ）を求め、下記計算式により、所定温度
における膨潤率（％）を計算した。 Measurement of swelling ratio of liquid crystal material On the surface of the prism of the refractometer, a thin film (thickness of 3 μm) of the same polymer as used in the liquid crystal elements of Examples and Comparative Examples was formed, and the measurement was performed thereon. The same liquid crystal material as that used in the liquid crystal elements of Examples and Comparative Examples was applied to prepare a model of the interface between the transparent matrix and the liquid crystal material in the composite film, and this model was refracted when heated to 60 to 120 ° C. The rate change was measured and plotted as shown by the solid line in FIG. Further, by measuring the change in the refractive index of the liquid crystal material alone and the polymer alone,
Plots are shown in FIG. 3 as indicated by a two-dot chain line (liquid crystal material) and a broken line (polymer). Then, the difference between the refractive index change curve of the liquid crystal material alone and the refractive index change curve of the polymer alone at a predetermined temperature (for example, in the case of 120 ° C., symbol a in the figure).
And the difference in the refractive index change curve of the model and the refractive index change curve of the polymer alone at a predetermined temperature (for example, in the case of 120 ° C., symbol b in the figure), the swelling ratio at the predetermined temperature ( %) Was calculated.
【００４９】[0049]
【数１】 [Equation 1]
【００５０】そして、温度と膨潤率との関係を図４にプ
ロットした。図４の結果より、実施例１〜５で使用した
液晶材料はいずれも、比較例１で使用した液晶材料に比
べて、高温条件下での高分子への膨潤が少ないことが確
認された。コントラストの温度特性測定 実施例、比較例の液晶素子の、複合膜を挟む一対の透明
導電膜間に、矩形波状の駆動電圧（周波数２００Ｈｚ、
電圧１００Ｖ）を印加した状態におけるHe−Neレーザー
光（波長６３３nm）の透過率（ＯＮ時透過率）と、電圧
を印加していない状態における上記He−Neレーザー光
（波長６３３nm）の透過率（ＯＦＦ時透過率）とを、雰
囲気温度６０〜１４０℃の条件下で測定し、下記計算式
により、コントラストを計算した。The relationship between temperature and swelling ratio was plotted in FIG. From the results of FIG. 4, it was confirmed that all of the liquid crystal materials used in Examples 1 to 5 had less swelling to the polymer under high temperature conditions than the liquid crystal material used in Comparative Example 1. Contrast temperature characteristic measurement In the liquid crystal elements of Examples and Comparative Examples, a rectangular-wave drive voltage (frequency: 200 Hz, between a pair of transparent conductive films sandwiching the composite film).
Transmittance of He-Ne laser light (wavelength 633 nm) (transmittance at the time of ON) when a voltage of 100 V) is applied, and transmittance of the He-Ne laser light (wavelength 633 nm) when a voltage is not applied (wavelength of 633 nm). The transmittance at OFF) was measured under the condition of an ambient temperature of 60 to 140 ° C., and the contrast was calculated by the following calculation formula.
【００５１】 コントラスト＝ＯＮ時透過率／ＯＦＦ時透過率 そして、温度とコントラストとの関係を図５にプロット
した。図５の結果より、実施例１〜５の液晶素子はいず
れも、比較例１の液晶素子に比べて、高温条件下でのコ
ントラストの低下が少ないことから、耐熱性にすぐれた
ものであることが確認された。Contrast = ON Transmittance / OFF Transmittance Then, the relationship between temperature and contrast is plotted in FIG. From the results shown in FIG. 5, all of the liquid crystal elements of Examples 1 to 5 are excellent in heat resistance, as compared with the liquid crystal element of Comparative Example 1, because the decrease in contrast under high temperature conditions is small. Was confirmed.
【００５２】応答速度の測定 上記液晶素子の一対の透明電極膜に１００Ｖのステップ
電圧を印加したときに、その透過率が飽和透過率の９０
％に到達するまでの時間を、光散乱状態から透明状態へ
の応答時間τon、逆に印加電圧０Ｖにしたときに、その
透過率が飽和透過率の１０％に減衰するまでの時間を透
明状態から光散乱状態への応答時間τoffとして、それ
ぞれ測定した。その結果を表１に示す。液晶ドメイン径の測定 光学顕微鏡により平均粒径を求めた。その結果を表１に
示す。 Measurement of Response Speed When a step voltage of 100 V was applied to the pair of transparent electrode films of the liquid crystal element, the transmittance thereof was 90% of the saturated transmittance.
%, The response time from the light scattering state to the transparent state is τ on , and conversely, when the applied voltage is 0 V, the time until the transmittance decays to 10% of the saturated transmittance is transparent. The response time τ off from the state to the light scattering state was measured. Table 1 shows the results. Measurement of liquid crystal domain diameter The average particle diameter was determined by an optical microscope. Table 1 shows the results.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【発明の効果】以上、詳述したようにこの発明の液晶素
子によれば、複合膜を構成する液晶材料は、室温から１
５０℃の温度域において、透過率が１０％で、膨潤率が
２０％以下で、ドメイン径が４μｍ以下であるものを使
用しているので、使用温度が１００℃以上に達する高温
条件下でも、液晶材料の高分子マトリクス中への膨潤が
発生しない。したがってこの発明の液晶素子は、耐熱性
にすぐれ、とくに高温域で使用した際に十分なコントラ
ストを維持でき、たとえば照明装置の調光素子等、従来
は適用不可能であった、より高温領域への液晶素子の利
用可能性を拡大できるという、特有の作用効果を奏する
ものである。As described above in detail, according to the liquid crystal element of the present invention, the liquid crystal material forming the composite film is from room temperature to 1
In the temperature range of 50 ° C., the transmittance is 10%, the swelling ratio is 20% or less, and the domain diameter is 4 μm or less. Therefore, even under high temperature conditions where the operating temperature reaches 100 ° C. or more, Swelling of the liquid crystal material into the polymer matrix does not occur. Therefore, the liquid crystal element of the present invention is excellent in heat resistance and can maintain a sufficient contrast particularly when used in a high temperature range. The liquid crystal display device of the present invention has a unique function and effect that the availability of the liquid crystal device can be expanded.
【図１】この発明の液晶素子の層構成を示す断面図であ
る。FIG. 1 is a sectional view showing a layer structure of a liquid crystal element of the present invention.
【図２】同図(a)(b)はいずれも、この発明の液晶素子を
構成する複合膜の構造を示す断面図である。2 (a) and 2 (b) are sectional views showing the structure of a composite film constituting the liquid crystal element of the present invention.
【図３】この発明の実施例、比較例における、高分子へ
の液晶材料の膨潤率を求めるための基礎データを示すグ
ラフである。FIG. 3 is a graph showing basic data for obtaining a swelling ratio of a liquid crystal material to a polymer in Examples and Comparative Examples of the present invention.
【図４】この発明の実施例、比較例における、高分子へ
の液晶材料の膨潤率と温度との関係を示すグラフであ
る。FIG. 4 is a graph showing the relationship between the swelling ratio of a liquid crystal material to a polymer and the temperature in Examples and Comparative Examples of the present invention.
【図５】この発明の実施例、比較例における、素子のコ
ントラストと温度との関係を示すグラフである。FIG. 5 is a graph showing the relationship between the contrast of the device and the temperature in the example of the present invention and the comparative example.
Ｄ 導電基材 Ｌ 複合膜 Ｌ１ 担体膜 Ｌ２ 液晶材料 Ｌ３ 担体膜 D Conductive Base Material L Composite Film L1 Carrier Film L2 Liquid Crystal Material L3 Carrier Film
Claims (2)
膜の連続した多孔内に液晶材料を充填した構造をなす複
合膜を一対の導電性基材で挾着してなる液晶素子におい
て、前記液晶材料が３〜４個のベンゼン環またはシクロ
ヘキサン環を骨格を持つ多環式液晶材料を７０重量％以
上含み、かつ、室温から１５０℃における前記液晶材料
の膨潤率が２０％以下であり、前記液晶材料のドメイン
サイズ径が０．５μｍ以上４μｍ以下であることを特徴
とする液晶素子。1. A liquid crystal device comprising a carrier film made of a crosslinked polymer matrix, and a composite film having a structure in which liquid crystal material is filled in continuous pores of a carrier film, sandwiched between a pair of conductive base materials. The material contains 70% by weight or more of a polycyclic liquid crystal material having a skeleton of 3 to 4 benzene rings or cyclohexane rings, and the swelling ratio of the liquid crystal material at room temperature to 150 ° C. is 20% or less, A liquid crystal element, wherein the domain size diameter of the material is 0.5 μm or more and 4 μm or less.
シクロヘキサン環を骨格に持つ多環式液晶材料と２個の
ベンゼン環またはシクロヘキサン環を骨格にもつ他の液
晶材料からなり、かつ、素子の使用温度で多環式液晶材
料と同じ液晶相を示す、正の誘電率異方性を有する液晶
材料である請求項１記載の液晶素子。2. A liquid crystal material comprising a polycyclic liquid crystal material having 3 to 4 benzene rings or cyclohexane rings in its skeleton and another liquid crystal material having two benzene rings or cyclohexane rings in its skeleton, and The liquid crystal device according to claim 1, which is a liquid crystal material having a positive dielectric constant anisotropy, which exhibits the same liquid crystal phase as the polycyclic liquid crystal material at the operating temperature of the device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34256195A JPH09185043A (en) | 1995-12-28 | 1995-12-28 | Liquid crystal element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34256195A JPH09185043A (en) | 1995-12-28 | 1995-12-28 | Liquid crystal element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09185043A true JPH09185043A (en) | 1997-07-15 |
Family
ID=18354715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34256195A Pending JPH09185043A (en) | 1995-12-28 | 1995-12-28 | Liquid crystal element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09185043A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550181B2 (en) | 1999-01-08 | 2009-06-23 | Dai Nippon Printing Co., Ltd. | Information recording medium |
-
1995
- 1995-12-28 JP JP34256195A patent/JPH09185043A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550181B2 (en) | 1999-01-08 | 2009-06-23 | Dai Nippon Printing Co., Ltd. | Information recording medium |
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