JP2512568B2 - Method for manufacturing electrochromic display device - Google Patents
Method for manufacturing electrochromic display deviceInfo
- Publication number
- JP2512568B2 JP2512568B2 JP1273016A JP27301689A JP2512568B2 JP 2512568 B2 JP2512568 B2 JP 2512568B2 JP 1273016 A JP1273016 A JP 1273016A JP 27301689 A JP27301689 A JP 27301689A JP 2512568 B2 JP2512568 B2 JP 2512568B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- layer
- electrolyte layer
- display device
- voltage
- 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 - Lifetime
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はエレクトロクロミツク（以下、ECという。）
表示装置の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is electrochromic (hereinafter referred to as EC).
The present invention relates to a method for manufacturing a display device.
（従来の技術） 従来のEC表示装置は電解質層の形状によつて固体系と
溶液系に分類されるが、後者の場合液漏れなどの欠点が
有り、取り扱い易さの点からは前者の開発が望まれてい
る。このようなEC表示装置を作製する場合、一般にEC層
と電解質層は別々に形成される。すなわち、電極上にEC
層を積層した後、さらに電解質層を積層し、対向電極で
挾ことにより作製される。このためEC層と電解質層の間
に明確な界面が存在することにより、電荷の移動が妨げ
られる。またEC層を積層した段階でEC層に酸素や水分が
吸着するためEC反応に悪影響を及ぼすことがある。(Prior Art) Conventional EC display devices are classified into a solid type and a solution type depending on the shape of the electrolyte layer, but in the latter case, there are drawbacks such as liquid leakage, and the former development is easier to handle. Is desired. When manufacturing such an EC display device, the EC layer and the electrolyte layer are generally formed separately. Ie EC on the electrode
After stacking the layers, an electrolyte layer is further stacked and sandwiched by the counter electrode to prepare the layer. Therefore, the existence of a clear interface between the EC layer and the electrolyte layer hinders the transfer of charges. Further, when the EC layers are laminated, oxygen and water are adsorbed to the EC layers, which may adversely affect the EC reaction.
こうした欠点を改良する試みとして、予め高分子電解
質中にモノマーを溶解した後、両側を電極で挾み、電圧
印加することによりEC層を形成する方法が特開昭63−29
1037号公報に示されている。この方法によれば電解質層
とEC層の界面が均質であるため、電荷移動の妨げや他物
質の吸着が起こらない。しかしこの方法では高分子電解
質全体にモノマーを溶解させるため、電解重合生成物が
作用電極のみならず対向電極側にも生成し、表示性能が
悪い。As an attempt to improve such a drawback, a method of previously forming a EC layer by dissolving a monomer in a polymer electrolyte, sandwiching both sides with electrodes, and applying a voltage is disclosed in JP-A-63-29.
No. 1037 publication. According to this method, since the interface between the electrolyte layer and the EC layer is uniform, the charge transfer is not hindered and other substances are not adsorbed. However, in this method, since the monomer is dissolved in the entire polymer electrolyte, an electrolytic polymerization product is generated not only on the working electrode but also on the counter electrode side, and the display performance is poor.
（発明が解決しようとする課題） 本発明の目的は、上記欠点に鑑み、表示性能のすぐれ
たEC表示装置を得ることができる製造方法を提供するこ
とにある。(Problem to be Solved by the Invention) An object of the present invention is to provide a manufacturing method capable of obtaining an EC display device having excellent display performance in view of the above-mentioned drawbacks.
（課題を解決するための手段） 本発明で使用される電解重合性モノマーは、電圧を印
加することにより電解重合し、EC層を形成しうるもので
あればよく、たとえばチオフエン、アニリン、ο−ジア
ルコキシベンゼン等があげられる。(Means for Solving the Problem) The electropolymerizable monomer used in the present invention may be any one that can be electropolymerized by applying a voltage to form an EC layer, for example, thiophene, aniline, ο- Examples thereof include dialkoxybenzene.
ο−ジアルコキシベンゼンは、その重合体が無色と有
色の間で変化し、コントラストも高いので透過型のEC表
示装置を作製することができる。ο−ジアルコキシベン
ゼンとしては、たとえばο−ジメトキシベンゼン、ο−
ジエトキシベンゼン、ο−ジプロポキシベンゼン等があ
げられる。The polymer of o-dialkoxybenzene changes between colorless and colored and has a high contrast, so that a transmissive EC display device can be manufactured. Examples of ο-dialkoxybenzene include ο-dimethoxybenzene and ο-
Examples thereof include diethoxybenzene and o-dipropoxybenzene.
本発明で使用される高分子電解質は、無機電解質とそ
の無機電解質を解離固溶化できる有機高分子とから形成
される。例えば過塩素酸リチウム、ホウフツ酸テトラエ
チルアンモニウム、ヨウ化リチウム等の無機電解質とポ
リビニルアルコール、ポリビニルブチラール、ポリエチ
レンオキサイドなどの有機高分子を、両者を溶解し得る
溶媒に溶解した後溶媒を除去することによつて得られ
る。The polymer electrolyte used in the present invention is formed of an inorganic electrolyte and an organic polymer capable of dissociating and solidifying the inorganic electrolyte. For example, after dissolving the inorganic electrolyte such as lithium perchlorate, tetraethylammonium borohydride, lithium iodide and the like and the organic polymer such as polyvinyl alcohol, polyvinyl butyral and polyethylene oxide in a solvent capable of dissolving them, the solvent is removed. You can get it.
本発明で使用される電極は表示装置として用いるた
め、少なくとも一方は透明である必要がある。このよう
な透明電極としては、例えば酸化インジウム、酸化錫、
酸化チタンなどの半導体薄膜、金、銀などの金属薄膜、
これらの薄膜が蒸着などによりガラスやポリエチレンテ
レフタレート等のプラスチツクフイルムに積層されたも
のが挙げられる。Since the electrodes used in the present invention are used as a display device, at least one of them needs to be transparent. Examples of such a transparent electrode include indium oxide, tin oxide,
Semiconductor thin films such as titanium oxide, metal thin films such as gold and silver,
An example is one in which these thin films are laminated on a plastic film such as glass or polyethylene terephthalate by vapor deposition or the like.
本発明においては、電解重合性モノマーが含浸された
高分子電解質層（ａ）と電解重合性モノマーが含浸され
ていない高分子電解質層（ｂ）を２個の電極間に挾持す
るのであるが、積層方法及び挾持方法は任意の方法が採
用されてよく、たとえば、電解重合性モノマーと高分
子電解質を両者を溶解しうる有機溶媒に溶解し、一方の
電極上に塗布乾燥して高分子電解質層（ａ）を形成した
後、高分子電解質を溶解しうる有機溶媒に溶解し、高分
子電解質層（ａ）上に塗布乾燥して高分子電解質（ｂ）
を形成し、さらにその上に他の電極を圧着する方法、
同様にして一方の電極上に高分子電解質層（ａ）を形成
し、他方の電極に高分子電解質層（ｂ）を形成し、両者
を圧着する方法等があげられる。In the present invention, the polymer electrolyte layer (a) impregnated with the electropolymerizable monomer and the polymer electrolyte layer (b) not impregnated with the electropolymerizable monomer are sandwiched between two electrodes. Any method may be adopted for the stacking method and the sandwiching method. For example, a polymer electrolyte layer is prepared by dissolving an electrolytically polymerizable monomer and a polymer electrolyte in an organic solvent capable of dissolving both, coating and drying on one electrode. After forming (a), the polymer electrolyte is dissolved in an organic solvent capable of dissolving the polymer electrolyte, and the polymer electrolyte layer (a) is coated and dried to obtain the polymer electrolyte (b).
To form and then crimp another electrode on it,
Similarly, a method in which the polymer electrolyte layer (a) is formed on one electrode, the polymer electrolyte layer (b) is formed on the other electrode, and both are pressure-bonded can be mentioned.
次に、電極間に重合電圧を印加し、上記電解重合性モ
ノマーを電解重合し、電極と高分子電解質層（ａ）の間
にEL層を形成する。重合電圧及び電圧の印加時間は重合
状態によつて適宜決定されればよいが、一般に重合電圧
は３〜10Vで１〜10分印加されるのが好ましい。尚、電
圧を印加した側の電極がEC表示装置として使用する際に
作用電極となる。Next, a polymerization voltage is applied between the electrodes to electrolytically polymerize the above-mentioned electrolytically polymerizable monomer to form an EL layer between the electrode and the polymer electrolyte layer (a). The polymerization voltage and the application time of the voltage may be appropriately determined depending on the polymerization state, but in general, the polymerization voltage is preferably 3 to 10 V and applied for 1 to 10 minutes. The electrode to which the voltage is applied becomes the working electrode when it is used as an EC display device.
（実施例） 次に本発明の実施例を説明する。(Example) Next, the Example of this invention is described.
実施例１ 1gのシアノエチルポバールと0.1gのEt4NBF4を4mlのア
セトニトリルに溶かして高分子電解質とした。この高分
子電解質にο−ジメトキシベンゼン0.2mlをよく溶か
し、透明作用電極（ガラス基板上に酸化インジウムと酸
化錫を蒸着したもの）上に塗布乾燥した。さらにο−ジ
メトキシベンゼンを含まない高分子電解質をその上に塗
布し、対向電極（ポリエチレンテレフタレートフイルム
上に酸化インジウムと酸化錫を蒸着したもの）ではさみ
乾燥させた。両電極間に4Vの電圧を３分間印加して、作
用極側にポリο−ジメトキシベンゼンの青色重合体を生
成させた。このセルに−３〜3Vの電圧を繰り返し印加す
ると重合体の色は無色−青色の間で繰り返し変化した。Example 1 1 g of cyanoethyl poval and 0.1 g of Et 4 NBF 4 were dissolved in 4 ml of acetonitrile to obtain a polymer electrolyte. 0.2 ml of o-dimethoxybenzene was well dissolved in this polymer electrolyte, and the solution was applied onto a transparent working electrode (a glass substrate on which indium oxide and tin oxide were deposited) and dried. Further, a polyelectrolyte containing no o-dimethoxybenzene was applied thereon, and sandwiched and dried with a counter electrode (a polyethylene terephthalate film having indium oxide and tin oxide deposited thereon). A voltage of 4 V was applied between both electrodes for 3 minutes to form a blue polymer of poly (o-dimethoxybenzene) on the working electrode side. When a voltage of -3 to 3 V was repeatedly applied to this cell, the color of the polymer repeatedly changed between colorless and blue.
比較例１ 実施例１において、電解質層をο−ジメトキシベンゼ
ンを含んだ高分子電解質１層のみにした以外は、実施例
と全く同じにECセルを作製した。Comparative Example 1 An EC cell was prepared in exactly the same manner as in Example 1, except that only one polymer electrolyte layer containing o-dimethoxybenzene was used as the electrolyte layer.
このセルに−３〜3Vの電圧を繰り返し印加すると、負電
圧印加の際に対向電極側の未反応モノマーが重合して、
薄青色を示した。このため電圧変化による色変化はあま
り顕著ではなかつた。When a voltage of -3 to 3 V is repeatedly applied to this cell, unreacted monomers on the counter electrode side are polymerized when a negative voltage is applied,
It exhibited a light blue color. Therefore, the color change due to the voltage change was not so remarkable.
（発明の効果） 本発明の構成は上述の通りであるから、EC層と電解質
層は一体に形成され、かつEC層と電解質層の界面は均質
になつており、電圧をかけた際の電荷の移動がスムーズ
で色変化が鮮明である。又、EC層は電解質層と作用電極
間に形成され、対向電極側に形成されることがないので
表示性能がすぐれている。(Effect of the invention) Since the constitution of the present invention is as described above, the EC layer and the electrolyte layer are integrally formed, and the interface between the EC layer and the electrolyte layer is uniform, and the charge when a voltage is applied is applied. The movement is smooth and the color changes are clear. Further, since the EC layer is formed between the electrolyte layer and the working electrode and is not formed on the counter electrode side, the display performance is excellent.
Claims (1)
解質層（ａ）と、電解重合性モノマーが含浸されていな
い高分子電解質層（ｂ）を２個の電極間に挾持し、電極
間に重合電圧を印加し、上記電解重合性モノマーを電解
重合し、電極と高分子電解質層（ａ）の間にエレクトロ
クロミツク層を形成することを特徴とするエレクトロク
ロミツク表示装置の製造方法。1. A polymer electrolyte layer (a) impregnated with an electropolymerizable monomer and a polymer electrolyte layer (b) not impregnated with an electropolymerizable monomer are sandwiched between two electrodes to provide a space between the electrodes. A method of manufacturing an electrochromic display device, characterized in that a polymerization voltage is applied to the film to electrolytically polymerize the above-mentioned electropolymerizable monomer to form an electrochromic layer between the electrode and the polymer electrolyte layer (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1273016A JP2512568B2 (en) | 1989-10-19 | 1989-10-19 | Method for manufacturing electrochromic display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1273016A JP2512568B2 (en) | 1989-10-19 | 1989-10-19 | Method for manufacturing electrochromic display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03132724A JPH03132724A (en) | 1991-06-06 |
| JP2512568B2 true JP2512568B2 (en) | 1996-07-03 |
Family
ID=17521987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1273016A Expired - Lifetime JP2512568B2 (en) | 1989-10-19 | 1989-10-19 | Method for manufacturing electrochromic display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2512568B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2009031422A1 (en) * | 2007-09-05 | 2010-12-09 | 株式会社クラレ | Method for manufacturing electrochromic display element |
| WO2009038033A1 (en) * | 2007-09-19 | 2009-03-26 | Kuraray Co., Ltd. | Electrochromic display device and method for manufacturing the same |
| 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 |
| US10732476B2 (en) * | 2018-05-14 | 2020-08-04 | Nokia Solutions And Networks Oy | Electrochromic cell |
-
1989
- 1989-10-19 JP JP1273016A patent/JP2512568B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03132724A (en) | 1991-06-06 |
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