JPH0564775B2 - - Google Patents
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- Publication number
- JPH0564775B2 JPH0564775B2 JP60255124A JP25512485A JPH0564775B2 JP H0564775 B2 JPH0564775 B2 JP H0564775B2 JP 60255124 A JP60255124 A JP 60255124A JP 25512485 A JP25512485 A JP 25512485A JP H0564775 B2 JPH0564775 B2 JP H0564775B2
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- JP
- Japan
- Prior art keywords
- membrane
- polymer
- cell
- composite membrane
- conductive
- 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
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電気化学的な酸化還元反応で可逆的に
変色する化合物を用いたエレクトロクロミツク素
子に関する。詳しくは、多孔質高分子膜中に導電
性高分子を重合した高分子複合膜を用いたエレク
トロクロミツク素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrochromic device using a compound that reversibly changes color through an electrochemical redox reaction. Specifically, the present invention relates to an electrochromic device using a polymer composite membrane in which a conductive polymer is polymerized into a porous polymer membrane.
導電性高分子のドーパントをドープすることに
よつて導電性高分子は光透過スペクトルや反射ス
ペクトルなどの光学的性質が変化することが知ら
れている。この現象を利用して、例えば、電圧を
印加して電気化学的にドープ、脱ドープした時の
印加電圧に応答する導電性高分子の光特性の変化
を利用した電圧応答性光機能素子が知られている
（特開昭59−129827）。
It is known that the optical properties of a conductive polymer, such as its light transmission spectrum and reflection spectrum, can be changed by doping the conductive polymer with a dopant. Utilizing this phenomenon, for example, voltage-responsive optical functional devices have been developed that utilize changes in the optical properties of conductive polymers that respond to the applied voltage when electrochemically doped and dedoped by applying a voltage. (Japanese Patent Application Laid-Open No. 129827, 1982).
導電性高分子の光透過性や色変化などを利用す
るためにはこれらの導電性高分子が薄膜状である
必要がある。また、素子としての機能を発揮させ
るためには金属板や導電性ガラス上にこれらの導
電性高分子を形成する必要がある。さらに、形成
された導電性高分子の膜は薄く、強度が弱く、取
扱が困難であり、電極との接合部が剥がれやすい
という問題を有している。
In order to take advantage of the light transmittance and color change of conductive polymers, these conductive polymers need to be in the form of a thin film. Further, in order to exhibit the function as an element, it is necessary to form these conductive polymers on a metal plate or conductive glass. Furthermore, the formed conductive polymer film is thin, has low strength, is difficult to handle, and has the problem that the bonded portion with the electrode is easily peeled off.
本発明の目的はこれらの問題を解決したエレク
トロクロミツク素子を提供することにある。 An object of the present invention is to provide an electrochromic device that solves these problems.
本発明者らはこれらの問題を解決すべく鋭意検
討し、本発明を完成した。
The present inventors conducted extensive studies to solve these problems and completed the present invention.
すなわち、本発明は、重合して導電性高分子を
形成する単量体を多孔質高分子膜中にて重合して
得られる高分子複合膜と電極からなるエレクトロ
クロミツク素子である。 That is, the present invention is an electrochromic device comprising an electrode and a polymer composite membrane obtained by polymerizing monomers that can be polymerized to form a conductive polymer in a porous polymer membrane.
本発明において用いる高分子複合膜は多孔質高
分子膜中に導電性高分子を重合形成したものであ
る。 The polymer composite membrane used in the present invention is formed by polymerizing a conductive polymer into a porous polymer membrane.
多孔質高分子膜としてはその孔径が0.001μｍ〜
1μｍのものが用いられる。その材質としては有
機化合物高分子や無機化合物高分子などがあげら
れ、例えば、ポリプロピレン、ポリエチレン、ポ
リ塩化ビニルなどの成形品、ガラスウールやシリ
コン処理紙などの成形物、これらの複合成形物な
どが示される。 As a porous polymer membrane, its pore diameter is 0.001 μm ~
1 μm is used. The materials include organic compound polymers and inorganic compound polymers, such as molded products such as polypropylene, polyethylene, and polyvinyl chloride, molded products such as glass wool and silicone-treated paper, and composite molded products of these. shown.
上記多孔質高分子膜の製造法については時に制
限はなく、例えば、熱可塑性樹脂と無機フイラー
の混合物を溶融製膜後延伸する方法、熱可塑性樹
脂と無機フイラーの混合物を溶融製膜後該フイラ
ーで溶剤で溶解抽出する方法などがある。また、
ガラスウールやセルロース繊維などを圧縮成形し
て膜状にすることでもかまわない。 There are no restrictions on the method for producing the porous polymer membrane, and examples include a method in which a mixture of a thermoplastic resin and an inorganic filler is melt-formed into a film and then stretched; There are methods such as dissolving and extracting with a solvent. Also,
It may also be made into a membrane by compression molding glass wool or cellulose fiber.
本発明に用いる導電性高分子は、ピロール、チ
オフエン、フラン、アニリンなどの酸化剤により
導電性高分子となる単量体から得られるものであ
る。 The conductive polymer used in the present invention is obtained from a monomer that becomes a conductive polymer with an oxidizing agent such as pyrrole, thiophene, furan, or aniline.
ここに用いる酸化剤としては種々のものがあげ
られ、無機酸、過酸化物、ルイス酸などが有効に
用いられる。 Various oxidizing agents can be used here, and inorganic acids, peroxides, Lewis acids, etc. are effectively used.
導電性高分子を多孔質高分子膜中に重合する方
法としては、多孔質高分子膜を隔壁として上記単
量体と酸化剤を接触せしめる方法が好ましい。 As a method for polymerizing a conductive polymer into a porous polymer membrane, a method is preferred in which the monomer is brought into contact with an oxidizing agent using the porous polymer membrane as a partition wall.
酸化剤を適当な溶剤、例えば、水、アルコール
類、ハロゲン化炭化水素類、ニトロ化炭化水素類
などに溶解し、この溶液と上記単量体のガスを、
必要に応じ窒素、ヘリウムなどの不活性ガスで希
釈し、多孔質高分子膜を隔壁として、第１図に示
すような装置を用いて接触することでよい。 An oxidizing agent is dissolved in a suitable solvent such as water, alcohols, halogenated hydrocarbons, nitrated hydrocarbons, etc., and this solution and the above monomer gas are mixed together.
If necessary, the mixture may be diluted with an inert gas such as nitrogen or helium, and brought into contact using a device as shown in FIG. 1, using a porous polymer membrane as a partition.
図において、１は酸化剤溶液用セル、２は多孔
質高分子膜の隔壁、３は単量体のガス用セルであ
り、ａ，ｂは酸化剤溶液出入口、ｃ，ｄは単量体
ガス入出口である。 In the figure, 1 is a cell for oxidizing solution, 2 is a partition wall of a porous polymer membrane, 3 is a cell for monomer gas, a and b are oxidizing solution inlets and outlets, and c and d are monomer gas cells. It is the entrance and exit.
この接触処理は連続的に行うこともできる。 This contact treatment can also be carried out continuously.
ここで用いる酸化剤溶液の濃度としては特に制
限はないが、0.001〜5mol／、好ましくは、
0.01〜1mol／が適当である。また、接触処理
の時間、温度についても特に制限はなく、所望の
重合体量になるように適宜決めればよいが、通
常、室温にて１〜100分が適当である。 There is no particular restriction on the concentration of the oxidizing agent solution used here, but 0.001 to 5 mol/, preferably,
A suitable amount is 0.01 to 1 mol/. Further, there are no particular restrictions on the time and temperature of the contact treatment, and they may be determined as appropriate to obtain the desired amount of polymer, but usually 1 to 100 minutes at room temperature is appropriate.
得られた膜をエタノールやアンモニア性エタノ
ールなどで洗浄することによつてドーパントを含
まない高分子複合膜が得れらる。この複合膜は強
靭で柔軟性があり、取り扱いが容易である。さら
に、通常は導電性高分子の厚い膜は黒色であるの
に対し、この高分子複合膜は厚い膜であつても導
電性高分子の有する鮮やかな色をしている。 By washing the obtained membrane with ethanol, ammoniacal ethanol, etc., a polymer composite membrane containing no dopant can be obtained. This composite membrane is tough, flexible, and easy to handle. Furthermore, while thick films of conductive polymers are usually black in color, this polymer composite film has the vivid color of conductive polymers even though it is a thick film.
本発明のエレクトロクロミツク素子は上記によ
り得られる複合膜と対向電極を電解質を介在して
対向させることにより得られる。 The electrochromic device of the present invention can be obtained by placing the composite membrane obtained above and a counter electrode facing each other with an electrolyte interposed therebetween.
対向電極として、ニツケル、白金、導電性ガラ
スなどを用いることができる。 As the counter electrode, nickel, platinum, conductive glass, etc. can be used.
電解質は溶液としてあるいは固体電解質として
複合膜と対向電極の間に介在させるが、多孔質の
複合膜自体に含浸させるだけでもよい。 The electrolyte is interposed between the composite membrane and the counter electrode as a solution or a solid electrolyte, but it may also be simply impregnated into the porous composite membrane itself.
また、ドーパントとがドープされる前の高分子
複合膜は絶縁体に近いものが多いので、高分子複
合膜上に金属を蒸着したり、導電性ペーストなど
を塗布しておくことが好ましい。 Moreover, since many polymer composite films are similar to insulators before being doped with a dopant, it is preferable to vapor-deposit a metal or coat a conductive paste on the polymer composite film.
電解質としては、過塩素酸塩、ホウフツ化塩、
ヘキサフルオロリン酸塩、塩化物、臭化物、ヨウ
化物などの無機塩、アルキルベンゼンスルホン酸
塩、アミノ酸塩などの有機塩が用いられる。 As electrolytes, perchlorate, borofusate,
Inorganic salts such as hexafluorophosphate, chloride, bromide, and iodide, and organic salts such as alkylbenzene sulfonate and amino acid salts are used.
電解質の溶剤としては、ベンゾニトリル、アセ
トニトリル、プロピレンカーボネート、テトラヒ
ドロフラン、水などが用いられるが、特に限定さ
れるものではない。 As the electrolyte solvent, benzonitrile, acetonitrile, propylene carbonate, tetrahydrofuran, water, etc. are used, but the solvent is not particularly limited.
このように構成されたセルは対向電極間に電圧
を印加することによつてエレクトロクロミズムを
示す。 A cell configured in this manner exhibits electrochromism by applying a voltage between opposing electrodes.
セルの例を第２図に示した。図において、４は
対向電極、５は電解質を含浸した高分子複合膜、
６は４に対向する電極、７はスイツチ、８は電池
および９は８と逆の極性を有する電池である。 An example of a cell is shown in FIG. In the figure, 4 is a counter electrode, 5 is a polymer composite membrane impregnated with electrolyte,
6 is an electrode opposite to 4, 7 is a switch, 8 is a battery, and 9 is a battery having a polarity opposite to that of 8.
以下、本発明例により本発明を説明する。 The present invention will be explained below using examples.
実施例 １
第１図に示す装置の隔壁２として平均孔径0.4μ
ｍ、厚さ20μｍのエチレン・２−メチルペンテン
共重合体多孔質高分子膜（三井東圧化学(株)製）を
用い、酸化剤溶液用セル１に無水塩化第二鉄飽和
クロロホルム溶液を入れ、単量体のガス用セル３
にチオフエンを飽和した窒素ガスをゆつくりと導
入して、10分間重合した。その後、膜２を取り出
してエタノールで洗浄し、さらにアンモニア性エ
タノールで洗浄した。得られた複合膜は赤色を呈
しており、その酸化剤溶液用セル側の電気伝導度
は10-9s／cmであつた。この複合膜の酸化剤溶液
用セル側に金を蒸着し、0.5mol／過塩素酸リ
チウムのアセトニトリル溶液に30分間浸漬した後
に取り出して、ネサガラスを対向電極として第２
図に示すようなエレクトロクロミズム素子のセル
を組み立てた。Example 1 The average pore diameter of the partition wall 2 of the device shown in Fig. 1 is 0.4μ.
Using an ethylene/2-methylpentene copolymer porous polymer membrane (manufactured by Mitsui Toatsu Chemical Co., Ltd.) with a thickness of 20 μm, an anhydrous ferric chloride saturated chloroform solution was placed in the oxidizing agent solution cell 1. , monomer gas cell 3
Nitrogen gas saturated with thiophene was slowly introduced into the solution, and polymerization was carried out for 10 minutes. Thereafter, the membrane 2 was taken out and washed with ethanol, and further washed with ammoniacal ethanol. The resulting composite membrane was red in color, and its electrical conductivity on the oxidant solution cell side was 10 -9 s/cm. Gold was vapor-deposited on the oxidant solution cell side of this composite membrane, immersed in an acetonitrile solution containing 0.5 mol/lithium perchlorate for 30 minutes, taken out, and placed on the second electrode using Nesa glass as a counter electrode.
An electrochromic device cell as shown in the figure was assembled.
このセルの複合膜側をアノード、ネサガラスを
カソードとして両電極間に4Vの電圧を印加した
ところ、複合膜は赤色から青色に変わつた。次い
で、印加電圧を−2Vにしたところ、複合膜は青
色から赤色に戻つた。 When a voltage of 4V was applied between the two electrodes, with the composite membrane side of this cell as the anode and Nesaglass as the cathode, the composite membrane turned from red to blue. Next, when the applied voltage was changed to -2V, the composite film returned from blue to red.
実施例 ２
多孔質高分子膜として、オリプラスチツク(株)製
のポリプロピレンを主とする厚さ25μｍの多孔質
高分子膜“ジユラガード2500”（商標、最大孔径
0.4×0.04μｍ）を用い、また、チオフエンに代え
てセレノフエンを用いる外は実施例１と同様にし
て、エレクトロクロミズム素子のセルを得た。な
お、複合膜の色は赤色であり、その電気伝導度は
10-9s／cmであつた。Example 2 As a porous polymer membrane, a 25 μm thick porous polymer membrane “Jyuragard 2500” (trademark, maximum pore diameter
A cell for an electrochromic device was obtained in the same manner as in Example 1, except that selenophene was used in place of thiophene. The color of the composite membrane is red, and its electrical conductivity is
It was 10 -9 s/cm.
このセルの複合膜剤をアノード、ネサガラスを
カソードとして両電極間に5Vの電圧を印加した
ところ、複合膜は赤色から青色に変わつた。次い
で、印加電圧を−2Vにしたところ、複合膜は青
色から赤色に戻つた。 When a voltage of 5V was applied between the electrodes of this cell, using the composite membrane material as the anode and Nesaglass as the cathode, the composite membrane turned from red to blue. Next, when the applied voltage was changed to -2V, the composite film returned from blue to red.
本発明のエレクトロクロミズム素子は、電圧応
答性光スイツチや色スイツチあるいは光メモリー
として使用することができるものであり、組み込
まれている複合膜は強靭で安定していいるため、
素子としての安定性が極めて優れている。
The electrochromic device of the present invention can be used as a voltage-responsive optical switch, color switch, or optical memory, and the incorporated composite film is strong and stable.
It has extremely high stability as an element.
第１図は本発明に用いられる高分子複合膜を製
造するのに適した製造装置の１例の概念図、第２
図は本発明のエレクトロクロミツク素子を組み込
んだセルの１例の概念図である。
１は酸化剤溶液用セル、２は多孔質高分子膜の
隔壁、３は単量体のガラス用セルであり、ａ，ｂ
は酸化剤溶液出入口、ｃ，ｄは単量体ガラス出入
口である。また、４は対向電極、５は電解質を含
浸した高分子複合膜、６は４に対向する電極、７
はスイツチ、８は電池および９は８と逆の極性を
有する電池である。
Figure 1 is a conceptual diagram of an example of a manufacturing apparatus suitable for manufacturing the polymer composite membrane used in the present invention;
The figure is a conceptual diagram of an example of a cell incorporating the electrochromic device of the present invention. 1 is a cell for an oxidizing agent solution, 2 is a partition wall of a porous polymer membrane, and 3 is a cell for monomer glass;
is an oxidizing agent solution inlet/outlet, and c and d are monomer glass inlets and outlets. Further, 4 is a counter electrode, 5 is a polymer composite membrane impregnated with an electrolyte, 6 is an electrode opposite to 4, and 7
is a switch, 8 is a battery, and 9 is a battery with opposite polarity to 8.
Claims (1)
孔質高分子膜中にて重合して得られる高分子複合
膜と電極からなるエレクトロクロミツク素子。1. An electrochromic device consisting of a polymer composite membrane obtained by polymerizing monomers that can be polymerized to form a conductive polymer in a porous polymer membrane and an electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60255124A JPS62115426A (en) | 1985-11-15 | 1985-11-15 | Electrochromic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60255124A JPS62115426A (en) | 1985-11-15 | 1985-11-15 | Electrochromic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62115426A JPS62115426A (en) | 1987-05-27 |
| JPH0564775B2 true JPH0564775B2 (en) | 1993-09-16 |
Family
ID=17274421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60255124A Granted JPS62115426A (en) | 1985-11-15 | 1985-11-15 | Electrochromic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62115426A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2631709B1 (en) * | 1988-05-20 | 1991-10-18 | Commissariat Energie Atomique | CONDUCTIVE COMPOSITE COLOR FILTERS AND THEIR MANUFACTURING METHOD |
| EP0385523A1 (en) * | 1989-02-20 | 1990-09-05 | SOLVAY (Société Anonyme) | Process for preparing electrically conductible polymers derived from 3-alkylthiophenes and electrical devices containing them |
| DE19824185A1 (en) * | 1998-05-29 | 1999-12-02 | Bayer Ag | Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives in combination with a lithium niobate counter electrode |
| DE19824215A1 (en) * | 1998-05-29 | 1999-12-02 | Bayer Ag | Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives in the electrochromic and ion-storing functional layers |
| JP2008203740A (en) * | 2007-02-22 | 2008-09-04 | Nissan Motor Co Ltd | Dimmer element and dimmer device |
-
1985
- 1985-11-15 JP JP60255124A patent/JPS62115426A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62115426A (en) | 1987-05-27 |
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