JPH0693066B2 - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPH0693066B2 JPH0693066B2 JP60094726A JP9472685A JPH0693066B2 JP H0693066 B2 JPH0693066 B2 JP H0693066B2 JP 60094726 A JP60094726 A JP 60094726A JP 9472685 A JP9472685 A JP 9472685A JP H0693066 B2 JPH0693066 B2 JP H0693066B2
- Authority
- JP
- Japan
- Prior art keywords
- display
- electrode
- electrochromic display
- counter electrode
- solution
- 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.)
- Expired - Fee Related
Links
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は時計，家庭電化機器，案内表示，情報機器等の
各種表示素子として利用可能なエレクトロクロミック表
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 an electrochromic display element that can be used as various display elements for watches, home appliances, guide displays, information devices and the like.
従来の技術 液晶と比較してエレクトロクロミックディスプレイは視
角依存性がなく、色が明かるく鮮明であるという特徴が
ある。2. Description of the Related Art Compared to liquid crystal, electrochromic displays have the characteristics that they do not depend on the viewing angle and the colors are bright and clear.
エレクトロクロミック（EC）材料として用いられるもの
としては無機化合物のWO3で代表される金属酸化物のも
のと、有機化合物のビオローゲン誘導体で代表されるも
のがある。Materials used as electrochromic (EC) materials include metal oxides represented by WO 3 which is an inorganic compound and those represented by viologen derivatives which are organic compounds.
WO3は透明電極上に蒸着法などにより薄膜に形成されて
対極間に電解液や誘電体膜などが設けられることによっ
て素子が形成される。WO 3 is formed into a thin film on a transparent electrode by a vapor deposition method or the like, and an element is formed by providing an electrolytic solution or a dielectric film between the counter electrodes.
ビオローゲン誘導体の場合は水溶液中などに溶解した溶
液型として用いる場合と、高分子とブレンドあるいはコ
ンプレックス化して固体膜化して用いる場合がある。The viologen derivative may be used in the form of a solution dissolved in an aqueous solution or in the form of a solid film by blending or complexing with a polymer.
発明が解決しようとする問題点 これらの素子の実用上の問題は表示寿命と応答速度にあ
る。電極材料としてはIn2O3，In2O3−SnO2，SnO2のよう
な透明電極、特に対極材料としては白金，金，カーボ
ン，鉄錯体、遷移金属酸化物（例、WO3），遷移金属水
酸化物（例Ni(OH)2）などが用いられている。対極材料
に要求されることは、材料自信の電解液等に対する安定
性はもちろんのこと、表示極側の酸化還元反応の電荷量
と同じ電荷量を対極側で可逆的に供給できる材料という
ことである。対極側の電荷の供給や受取を早くするため
に、一般に対極の表面積を大きくして応答速度を早くし
ている。また、表示寿命という点では、対極の電位が駆
動時間に対して変位したり、電気化学的な反応により電
極材料が溶出したりして特性を劣化させている。Problems to be Solved by the Invention Practical problems of these devices are display lifetime and response speed. As the electrode material, transparent electrodes such as In 2 O 3 , In 2 O 3 —SnO 2 and SnO 2 are used, especially as the counter electrode material, platinum, gold, carbon, iron complex, transition metal oxide (eg WO 3 ), Transition metal hydroxides (eg Ni (OH) 2 ) are used. What is required of the counter electrode material is that it is a material that can reversibly supply the same charge amount as the charge amount of the redox reaction on the display electrode side to the counter electrode, as well as the stability of the material itself to the electrolytic solution. is there. In order to speed up the supply and reception of charges on the counter electrode side, the surface area of the counter electrode is generally increased to increase the response speed. Further, in terms of display life, the potential of the counter electrode is displaced with respect to the driving time, or the electrode material is eluted by an electrochemical reaction, which deteriorates the characteristics.
そこで本発明の目的は、EC材料の酸化還元反応時の電荷
移動の、表示極と対極側における速度をはやくし、かつ
可逆性を良くすることにより、エレクトロクロミック表
示素子の応答速度と表示寿命の改善をはかることであ
る。Therefore, an object of the present invention is to accelerate the speed of charge transfer during the redox reaction of an EC material on the display electrode and the counter electrode side, and improve the reversibility, thereby improving the response speed and display life of the electrochromic display device. It is to improve.
問題点を解決するための手段 本発明は上記目的を達成するもので、少なくとも一方が
透明な二枚の基板のいずれか一方に設けられた表示極
と、前記表示極に相対向して他方基板に設けられた対極
と、前記基板間に充填された溶液又は電解液を備え、前
記溶液又は電解液が少なくとも支持電解質と溶媒を含み
さらに電解重合性モノマーを添加したことを特徴とする
エレクトロクロミック表示素子を提供するものである。Means for Solving the Problems The present invention achieves the above object, and a display electrode provided on either one of two substrates, at least one of which is transparent, and the other substrate facing the display electrode. An electrochromic display comprising a counter electrode provided on the substrate and a solution or an electrolytic solution filled between the substrates, the solution or the electrolytic solution containing at least a supporting electrolyte and a solvent, and further containing an electropolymerizable monomer. It provides an element.
作用 本発明はエレクトロクロミック表示素子の溶液又は電解
液中に電解重合性モノマーを添加することにより、表示
極，対極におけるEC材料の酸化還元反応の電荷移動速度
をはやくし、可逆性をよくすることができる。本発明の
電解重合性モノマーとしては、酸化重合タイプと還元重
合タイプのものがあり、前者についてはアニリンやフェ
ノールのようなベンゼン環にアミノ基あるいは水酸基を
有するもの、ピロールやチオフエンのようなヘテロ環を
有するもの、その他のタイプとしてジベンゾクラウンエ
ーテル等が好適である。一方後者についてはビニルピリ
ジンのようなビニル基を有するものが好適である。Effect The present invention accelerates the charge transfer rate of the redox reaction of the EC material at the display electrode and the counter electrode by adding the electropolymerizable monomer to the solution or the electrolytic solution of the electrochromic display element, and improves the reversibility. You can The electropolymerizable monomer of the present invention includes an oxidative polymerization type and a reduction polymerization type. For the former, those having an amino group or a hydroxyl group in the benzene ring such as aniline and phenol, and a heterocycle such as pyrrole and thiophene. And other types such as dibenzocrown ether are preferable. On the other hand, the latter is preferably one having a vinyl group such as vinyl pyridine.
実施例 以下に本発明の実施例を図面を用いて説明する。第１図
は本発明の一実施例におけるエレクトロクロミック表示
素子の断面図を示す。図中の１と４は基板で、ガラスか
プラスチックが用いられる。２は表示極で、In2O3，SnO
2，In2O3−SnO2等の化合物が用いられる。５は対極でIn
2O3,,SnO2，In2O3−SnO2化合物あるいは金属が用いられ
る。７は表示可能物質で、８は封着材である。本実施例
の表示可能物質７としては、EC材料，支持電解質，溶媒
に加えて電解重合性モノマーを添加している。Embodiments Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view of an electrochromic display device according to an embodiment of the present invention. In the figure, 1 and 4 are substrates, and glass or plastic is used. 2 is a display electrode, In 2 O 3 , SnO
A compound such as 2 , In 2 O 3 —SnO 2 is used. 5 is the opposite pole, In
2 O 3 , SnO 2 , In 2 O 3 —SnO 2 compound or metal is used. Reference numeral 7 is a displayable substance, and 8 is a sealing material. As the displayable substance 7 of this embodiment, an electropolymerizable monomer is added in addition to the EC material, supporting electrolyte, and solvent.
EC材料として１式にしめすようなスチリル類似化合物の
色素を用い、支持電解質としてテトラブチルアンモニウ
ムパークロレイト、溶媒としてアセトニトリルを用い
た。濃度はそれぞれ0.03,0.3M/lである。A dye of styryl-like compound as shown in Formula 1 was used as an EC material, tetrabutylammonium perchlorate was used as a supporting electrolyte, and acetonitrile was used as a solvent. The concentrations are 0.03 and 0.3 M / l, respectively.
電解重合性モノマーとしては、ピロールを用いて、1Mol
/lの濃度で含ませた。この素子の表示特性を測定したと
ころ、電解重合モノマーを添加しないものに比較して、
発色濃度が光吸収率（550nm）で10％ほど高くなり、か
つ飽和濃度に達するまでの時間が２倍ほどはやくなっ
た。また消色速度についても同じく２倍程度はやくなっ
た。応答速度がはやくなるのは電解質中にモノマーを含
ませることにより電解質の電気抵抗が見かけ上小さくな
るためと思われる。 Pyrrole was used as the electropolymerizable monomer, and 1 mol
It was included at a concentration of / l. When the display characteristics of this element were measured, it was compared with that without addition of the electropolymerized monomer,
The color density was increased by about 10% in terms of light absorptivity (550 nm), and the time required to reach the saturation density was about twice as fast. In addition, the erasing speed was also doubled. The reason for the faster response speed is considered to be that the electric resistance of the electrolyte is apparently reduced by including the monomer in the electrolyte.
第２の実施例として前記実施例の電解重合性モノマーの
かわりに同じく酸化重合性のチオフエン，アニリンにつ
いて第１図に示す表示素子を用いて表示特性を測定した
ところ同様に応答速度の改善がみられた。効果としては
ピロールが最も良く、チオフェン，アニリンの順であっ
た。As a second example, instead of the electrolytically polymerizable monomer of the above example, the same characteristics of oxidatively polymerizable thiophene and aniline were measured by using the display element shown in FIG. Was given. Pyrrole was the most effective, followed by thiophene and aniline.
第３の実施例として、実施例１と同じEC材料を用い、電
解重合性モノマーとして還元重合反応を行うビニールピ
リジンを0.1mol/l添加した。As a third example, the same EC material as in Example 1 was used, and 0.1 mol / l of vinylpyridine, which was used as an electrolytically polymerizable monomer, for a reduction polymerization reaction was added.
電解重合性モノマーを含まない素子と含む素子とで、連
続発色の表示寿命試験を60℃下で行ったところ電解重合
性モノマーを含まない表示素子の寿命は約2000Hであっ
たが、含むものは、3000H以上あることが確認された。
寿命がくる評価は初期濃度の80％とした。印加電圧は表
示極２と対極５間に1.3Vの直流を印加した。最終的な劣
化の状態は電圧印加を行っても発色現象を示さなくな
る。When the display life test of continuous color development was performed at 60 ° C. with the element containing no electropolymerizable monomer and the element containing it, the life of the display element containing no electropolymerizable monomer was about 2000 H, but the one containing , It was confirmed that it was over 3000H.
The evaluation of the life expectancy was set to 80% of the initial concentration. As the applied voltage, a direct current of 1.3 V was applied between the display electrode 2 and the counter electrode 5. The final deteriorated state does not show a color development phenomenon even when a voltage is applied.
第４の実施例における表示素子の断面図を第２図に示
す。基板１上に設けられた表示極２上に蒸着法によりWO
3膜のようなEC膜３を設けたものを用い、電解液９とし
て溶媒をプロピレンカーボネート、支持電解質としてLi
ClO4を1mol/lの濃度で溶解し、電解重合性モノマーとし
てチオフェンを0.5mol/lの濃度で添加した。表示素子と
しての特性を測定したところ、応答速度で1.5倍、発消
色のくり返し回数で２倍程度の改善が確認された。FIG. 2 shows a sectional view of the display element in the fourth embodiment. The WO is formed on the display electrode 2 provided on the substrate 1 by the vapor deposition method.
Using an EC membrane 3 such as 3 membranes, the solvent is propylene carbonate as the electrolyte 9 and Li as the supporting electrolyte.
ClO 4 was dissolved at a concentration of 1 mol / l, and thiophene was added at a concentration of 0.5 mol / l as an electropolymerizable monomer. When the characteristics of the display device were measured, it was confirmed that the response speed was improved by 1.5 times, and the number of times of repeated coloring and erasing was improved by about 2 times.
かかる素子を100時間以上連続して発色させると図に示
すような重合膜（ポリチオフェン膜）６が対極５上に析
出される。このポリチオフェン膜のような重合膜６が形
成されることにより応答速度と表示寿命がさらに改善さ
れる。When such an element is continuously colored for 100 hours or more, a polymerized film (polythiophene film) 6 as shown in the figure is deposited on the counter electrode 5. By forming the polymer film 6 such as the polythiophene film, the response speed and the display life are further improved.
応答速度がはやくなるのは、EC材料あるいは需解液成分
と表示極２あるいは対極５の電極である透明電極（In2O
3，SnO2,ITO）などとの電荷移度速度よりも、重合膜を
介した場合の方がはやくなることと、電解液中にモノマ
ーを含ませることにより、電解液の電気抵抗が見かけ上
小さくなるためと思われる。The response speed becomes faster when the transparent electrode (In 2 O) which is the electrode of the EC material or the liquid electrolyte solution and the electrode of the display electrode 2 or the counter electrode 5 is used.
3 , SnO 2 , ITO), etc., and the electric resistance of the electrolyte is apparently faster than that with a polymer film, and the presence of a monomer in the electrolyte causes the electrolyte to have a higher electric resistance. It seems that it becomes smaller.
また、重合膜を形成することにより電極の表面が安定化
されて、表示極２や対極５の腐食を防止できるし、ある
いはEC材料の酸化還元反応に対応して、電解重合反応の
酸化還元反応を逆反応として利用することにより、付可
逆な化学反応を減らすことができて表示寿命が改善でき
る。In addition, by forming a polymerized film, the surface of the electrode is stabilized and corrosion of the display electrode 2 and the counter electrode 5 can be prevented, or in response to the redox reaction of the EC material, the redox reaction of the electrolytic polymerization reaction is performed. By using as a reverse reaction, the reversible chemical reaction can be reduced and the display life can be improved.
発明の効果 以上要するに本発明は少なくとも一方が透明な二枚の基
板に表示極と対極とを相対向するごとく設け、かかる基
板間に溶液又は電解液を充填し、この溶液又は電解液が
少なくとも支持電解質と溶媒を含みさらに電解重合性モ
ノマーを添加したことを特徴とするエレクトロクロミッ
ク表示素子を提供するもので、表示特性の応答速度と表
示寿命の改善が図れる。In summary, the present invention provides at least one transparent substrate on which two display electrodes and a counter electrode are provided so as to face each other, and a solution or an electrolytic solution is filled between the substrates, and the solution or the electrolytic solution is at least supported. The present invention provides an electrochromic display device including an electrolyte and a solvent, and further containing an electropolymerizable monomer, and can improve the response speed of display characteristics and the display life.
第１図及び第２は本発明の一実施例におけるエレクトロ
クロミック表示素子の断面図である。 １……基板、２……表示極、３……EC膜（WO3膜）、４
……基板、５……対極、６……重合膜（ポリチオフェン
膜）、７……表示可能物質、８……封着材、９……電解
液。1 and 2 are cross-sectional views of an electrochromic display device according to an embodiment of the present invention. 1 ... Substrate, 2 ... Display electrode, 3 ... EC film (WO 3 film), 4
…… Substrate, 5 …… Counter electrode, 6 …… Polymerized film (polythiophene film), 7 …… Displayable substance, 8 …… Sealing material, 9 …… Electrolyte.
Claims (3)
れか一方に設けられた表示極と、前記表示極に相対向し
て他方基板に設けられた対極と、前記基板間に充填され
た溶液又は電解液を備え、前記溶液又は電解液が少なく
とも支持電解質と溶媒を含みさらに電解重合性モノマー
を添加したことを特徴とするエレクトロクロミック表示
素子。1. A display electrode provided on at least one of two transparent substrates, a counter electrode provided on the other substrate opposite to the display electrode, and a space between the substrates. An electrochromic display device comprising a solution or an electrolytic solution, wherein the solution or the electrolytic solution contains at least a supporting electrolyte and a solvent, and an electrolytically polymerizable monomer is further added.
ものであることを特徴とする特許請求の範囲第１項記載
のエレクトロクロミック表示素子。2. The electrochromic display element according to claim 1, wherein the electropolymerizable monomer is one that undergoes an oxidative polymerization reaction.
ものであることを特徴とする特許請求の範囲第１項記載
のエレクトロクロミック表示素子。3. The electrochromic display element according to claim 1, wherein the electropolymerizable monomer is one that undergoes a reduction polymerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094726A JPH0693066B2 (en) | 1985-05-02 | 1985-05-02 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094726A JPH0693066B2 (en) | 1985-05-02 | 1985-05-02 | Electrochromic display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61252535A JPS61252535A (en) | 1986-11-10 |
| JPH0693066B2 true JPH0693066B2 (en) | 1994-11-16 |
Family
ID=14118117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60094726A Expired - Fee Related JPH0693066B2 (en) | 1985-05-02 | 1985-05-02 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693066B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031422A1 (en) * | 2007-09-05 | 2009-03-12 | Kuraray Co., Ltd. | Method for manufacturing electrochromic display device |
| WO2014018472A1 (en) | 2012-07-23 | 2014-01-30 | The University Of Connecticut | Electrochromic copolymers from precursors, method of making, and use thereof |
| US10323178B2 (en) | 2014-05-16 | 2019-06-18 | The University Of Connecticut | Color tuning of electrochromic devices using an organic dye |
-
1985
- 1985-05-02 JP JP60094726A patent/JPH0693066B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61252535A (en) | 1986-11-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |