JPH0468608B2 - - Google Patents
Info
- Publication number
- JPH0468608B2 JPH0468608B2 JP60019186A JP1918685A JPH0468608B2 JP H0468608 B2 JPH0468608 B2 JP H0468608B2 JP 60019186 A JP60019186 A JP 60019186A JP 1918685 A JP1918685 A JP 1918685A JP H0468608 B2 JPH0468608 B2 JP H0468608B2
- Authority
- JP
- Japan
- Prior art keywords
- auxiliary electrode
- light transmittance
- variable light
- electrolyte
- electrochromic layer
- 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
- 238000002834 transmittance Methods 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 23
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 17
- 229960003351 prussian blue Drugs 0.000 claims description 17
- 239000013225 prussian blue Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 17
- 239000007772 electrode material Substances 0.000 description 16
- 230000005611 electricity Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920000547 conjugated polymer Polymers 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000327 poly(triphenylamine) polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- BUELGIDNGQQPTK-UHFFFAOYSA-N C(#N)[Co].[Fe] Chemical compound C(#N)[Co].[Fe] BUELGIDNGQQPTK-UHFFFAOYSA-N 0.000 description 1
- FSAYVKNORFJFQY-UHFFFAOYSA-N C(#N)[Ru].[Fe] Chemical compound C(#N)[Ru].[Fe] FSAYVKNORFJFQY-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000323 polyazulene Polymers 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000004793 poor memory Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
（産業上の利用分野）
この発明は、エレクトロクロミツク素子を用い
た大型の光透過度可変ガラス、特に透光性である
一対の電極のうち一方の電極表面上に酸化タング
ステンエレクトロクロミツク層を備え対向する電
極表面上にプルシアンブルーエレクトロクロミツ
ク層を備え、光透過度可変部分に関係しない部分
に酸化還元物質を有する補助電極を備え、両電極
間に極性溶媒を用いた電解質が封入されてなるエ
レクトロクロミツク素子を用いた光透過度可変ガ
ラスに関するものである。
（従来の技術）
発明者等は先にエレクトロクロミツク素子とし
て特開昭59−155833号公報において酸化タングス
テン（WO3）とプルシアンブルー（PB）をエレ
クトロクロミツク層として用いたエレクトロクロ
ミツク素子を提案した。この素子は作製した時点
ではWO3，PBともに酸化状態であり、同時発消
色を行うためにはどちらかを還元状態にする必要
がある。これを初期還元とよぶ。そのため一方の
エレクトロクロミツク層を還元する他方のエレク
トロクロミツク層表面上では電解質に含まれる不
純物が分解し、気泡を発生させるため、表示外観
を著しく損う。この欠点を解決するために、本出
願人は特開昭59−159134号公報において酸化還元
を可逆的に行う物質からなる補助電極を使用した
エレクトロクロミツク表示素子を提案した。この
表示素子を第３図に示す。第３図において１は第
１エレクトロクロミツク層または第１発色層、２
は第２エレクトロクロミツク層または第２発色
層、３は透明上基板、４は透明下基板、５は透明
電極、６はシール層、７は電解液、８は補助電
極、９は絶縁膜である。このように補助電極を用
いることによりこの種表示素子の前記欠点は解決
され、プルシアンブルー（PB）、鉄シアノコバル
ト錯体、鉄シアノルテニウム錯体、Ir2O3・NiO
などの補助電極材料により使用時のメモリー性の
向上を図ることができたが、この発明において意
図する大型透過度可変ガラスに適用した場合に以
下の２点について問題があつた。
(イ) 初期還元を行うには、補助電極のもつ単位重
量あたりの酸化電気量が不十分であたつた。
(ロ) 従来の補助電極材料では酸化反応に水が関与
しており、水の分解に伴う補助電極近傍でのエ
レクトロクロミツク層のメモリー性が劣るた
め、表示部周辺で色むらが発生した。
具体的には、代表的補助電極用酸化物質である
PBについてのべる。
科学的に合成したPB、導電材料としてアセチ
レンブラツク、結着剤としてポリテトラフルオロ
エチレン粉末を重量比で３：２：１の割合で混練
した酸化反応電極物質を用い、集電網として直径
0.1mmの太さを有すチタン網を用い、集電網をサ
ンドイツチ状に挟んだ厚さ0.8mmの補助電極を作
製した。この電極を電解液（プロピレンカーボネ
ート＋1.0重量％の水＋１モル／ｌ LiClO4）中
0.5mAで定電硫酸化を行なつたところ、補助電極
の酸化電気量は3.0クーロン／cm2であつた。
またPBの酸化反応電気量に対する電解液中水
分濃度の影響を、サイクリツクボルタモグラム測
定（電位範囲＋0.5V〜＋1.5V、掃引速度10mV／
sec）により調べ、その結果第４図に示す。この
場合の電解液はプロピレンカーボネート（PC）＋
１モル／lNaClO4である。
PBの酸化反応電気量は、電解液中水分濃度に
比例することからPBの酸化反応は電解液中に含
まれる少量の水分と深く関係しており、PB自身
の酸化反応とともに若干ではあるがPB表面上で
の水の分解反応も起つていることが判明した。そ
のため次式
２ H2Ｏ→O2＋4H+＋4e-
２ H2Ｏ→H2O2＋2H+＋2e-
で表わされるように、酸素あるいは過酸化水素が
発生し、補助電極近傍でのエレクトロクロミツク
層の色むらが発生したと考えられる。
従つて自動車用のミラー、サイドガラス、サン
ルーフ、サンバイザー、インスト用表示素子のよ
うに大型の光透過度可変ガラスにおいて、初期還
元とメモリー性保持のため補助電極が大きくな
り、またエレクトロクロミツク層周辺の色むらを
防止するため、補助電極とエレクトロクロミツク
層の周辺の間を必要以上に広くとつた結果、実効
光透過度可変部分の面積が狭くなるという問題点
があつた。
（問題点を解決するための手段）
この発明は上記従来の問題点に着目してなされ
たもので、補助電極用酸化還元物質として共役系
高分子材料を用いることにより上記問題点を解決
したものである。
すなわち、この発明の光透過度可変ガラスは、
上記のように補助電極用酸化還元物質として共役
系高分子材料を用いたことにより、実効光透過度
可変部分の面積を拡大するようにしたことを特徴
とするものである。
上記共役系高分子材料は、単位体積当りの酸化
電気量が多く、またその酸化反応は支持電解質中
陰イオンと反応し、電解液中水分量に影響を受け
ないという特徴がある。
この発明において補助電極用酸化還元物質とし
て用いられるかかる共役系高分子材料としては、
ポリアセチレン、ポリフエニレン、ポリトリフエ
ニルアミン、ポリピロール、ポリインドール、ポ
リアズレン、ポリチオフエン、ポリフラン、ポリ
ナフタレン、ポリアニリン、ポリフエニレンスル
フイド、ポリジアセチレン、ポリフエニレンオキ
シド、ポリフエニレンビニレンなどが挙げられ
る。
次に上記共役系高分子材料を用いて補助電極を
作製する方法を説明する。
上記ポリマーの粉末にアセチレンブラツク、グ
ラフアイト、白金、金などの導電性粉末とポリテ
トラフルオロエチレン粉末などの結着剤を所定量
添加し、三本ロールにて混練した後、プレスにり
シート状に成形体を作製する。この成形体２枚を
用意し、その間に白金、チタン、タンタル、タン
グステンなどの金網を挟み、ロールプレスにより
圧着することにより所定の形状、厚さに調整し、
その後150℃〜250℃で１時間〜２時間乾燥させて
補助電極を得る。
また他の作製方法として、フラン、ピロールお
よびチオフエンなどの複素環化合物を、電解重合
法によつて白金、カーボン繊維などの集電体上に
ポリマーを析出させる方法により補助電極が得ら
れる。電解重合条件を次の第１表に示す。
(Industrial Application Field) This invention relates to a large variable light transmittance glass using an electrochromic element, and in particular a tungsten oxide electrochromic layer on the surface of one of a pair of translucent electrodes. A Prussian blue electrochromic layer is provided on the surfaces of the electrodes facing each other, an auxiliary electrode containing a redox substance is provided in a portion not related to the light transmittance variable portion, and an electrolyte using a polar solvent is sealed between the two electrodes. This invention relates to a variable light transmittance glass using an electrochromic element. (Prior Art) The inventors previously described an electrochromic device using tungsten oxide (WO 3 ) and Prussian blue (PB) as an electrochromic layer in Japanese Patent Application Laid-open No. 155833/1983. Proposed. When this element is manufactured, both WO 3 and PB are in an oxidized state, and in order to perform simultaneous color development and decolorization, it is necessary to bring one of them into a reduced state. This is called initial reduction. Therefore, impurities contained in the electrolyte decompose on the surface of the other electrochromic layer that reduces one electrochromic layer and generate bubbles, which significantly impairs the appearance of the display. In order to solve this drawback, the present applicant proposed an electrochromic display element using an auxiliary electrode made of a substance that reversibly performs redox in Japanese Patent Laid-Open No. 59-159134. This display element is shown in FIG. In FIG. 3, 1 is the first electrochromic layer or first coloring layer, 2
3 is a transparent upper substrate, 4 is a transparent lower substrate, 5 is a transparent electrode, 6 is a sealing layer, 7 is an electrolytic solution, 8 is an auxiliary electrode, and 9 is an insulating film. be. By using an auxiliary electrode in this way, the above-mentioned drawbacks of this type of display element are solved, and Prussian blue (PB), iron cyanocobalt complex, iron cyanoruthenium complex, Ir 2 O 3 ·NiO
Although it was possible to improve the memory property during use by using auxiliary electrode materials such as auxiliary electrode materials, there were problems with the following two points when applied to the large-scale variable transmittance glass intended in this invention. (a) The amount of oxidation electricity per unit weight of the auxiliary electrode was insufficient to carry out the initial reduction. (b) With conventional auxiliary electrode materials, water is involved in the oxidation reaction, and as water decomposes, the electrochromic layer near the auxiliary electrode has poor memory properties, resulting in uneven coloring around the display area. Specifically, it is a typical oxidizing material for auxiliary electrodes.
Talk about PB. An oxidation reaction electrode material made of scientifically synthesized PB, acetylene black as a conductive material, and polytetrafluoroethylene powder as a binder in a weight ratio of 3:2:1 is used.
An auxiliary electrode with a thickness of 0.8 mm was fabricated using titanium meshes with a thickness of 0.1 mm and sandwiching a current collector mesh in a sandwich pattern. This electrode was placed in an electrolyte (propylene carbonate + 1.0 wt% water + 1 mol/l LiClO 4 ).
When electrostatic sulfation was performed at 0.5 mA, the oxidation electricity amount of the auxiliary electrode was 3.0 coulombs/cm 2 . In addition, the influence of the water concentration in the electrolyte on the amount of electricity in the oxidation reaction of PB was measured by cyclic voltammogram measurement (potential range +0.5V to +1.5V, sweep rate 10mV/
sec), and the results are shown in Figure 4. The electrolyte in this case is propylene carbonate (PC) +
1 mol/l NaClO 4 . The amount of electricity in the oxidation reaction of PB is proportional to the water concentration in the electrolyte, so the oxidation reaction of PB is deeply related to the small amount of water contained in the electrolyte. It was also found that water decomposition reactions occur on the surface. Therefore , as expressed by the following equation: 2 H 2 O→ H 2 O 2 + 2H + +2e - , oxygen or hydrogen peroxide is generated and electrochromic reaction near the auxiliary electrode occurs. It is thought that uneven coloring of the layers occurred. Therefore, in large glass with variable light transmittance such as automobile mirrors, side glasses, sunroofs, sun visors, and instrument display elements, the auxiliary electrode has to be large for initial reduction and memory retention, and the area around the electrochromic layer has to be large. In order to prevent color unevenness, the space between the auxiliary electrode and the periphery of the electrochromic layer is made wider than necessary, resulting in the problem that the area of the effective light transmittance variable portion becomes narrower. (Means for Solving the Problems) This invention has been made by focusing on the above-mentioned conventional problems, and solves the above-mentioned problems by using a conjugated polymer material as a redox substance for an auxiliary electrode. It is. That is, the variable light transmittance glass of this invention is
As described above, by using a conjugated polymer material as the redox substance for the auxiliary electrode, the area of the effective light transmittance variable portion is expanded. The conjugated polymer material has a large amount of oxidation electricity per unit volume, and its oxidation reaction reacts with anions in the supporting electrolyte and is not affected by the amount of water in the electrolyte. In this invention, such conjugated polymer materials used as redox substances for auxiliary electrodes include:
Examples include polyacetylene, polyphenylene, polytriphenylamine, polypyrrole, polyindole, polyazulene, polythiophene, polyfuran, polynaphthalene, polyaniline, polyphenylene sulfide, polydiacetylene, polyphenylene oxide, polyphenylene vinylene, and the like. Next, a method for producing an auxiliary electrode using the above conjugated polymer material will be explained. A predetermined amount of conductive powder such as acetylene black, graphite, platinum, and gold and a binder such as polytetrafluoroethylene powder are added to the above polymer powder, kneaded with three rolls, and then pressed into a sheet. A molded body is produced. Two pieces of this molded body are prepared, a wire mesh made of platinum, titanium, tantalum, tungsten, etc. is sandwiched between them, and they are pressed together using a roll press to adjust the shape and thickness to the desired shape.
Thereafter, it is dried at 150° C. to 250° C. for 1 hour to 2 hours to obtain an auxiliary electrode. As another manufacturing method, an auxiliary electrode can be obtained by depositing a polymer of a heterocyclic compound such as furan, pyrrole, and thiophene on a current collector such as platinum or carbon fiber by electrolytic polymerization. The electrolytic polymerization conditions are shown in Table 1 below.
【表】
以上述べた共役系高分子材料のうち、空気中で
安定で、酸化反応開始電位が＋1.0V〔VSAg／
AgCl〕以下の材料が望ましい。
前記共役系高分子材料より成る補助電極材料
は、酸化体、還元体ともに安定であり、耐熱性
（150℃以上）、耐湿性に優れ、単位体積あたりの
反応電気量が多く、還元体としてセル作製が容易
であるなどの特徴を示す。
（実施例）
次にこの発明を実施例により説明する。
実施例
第２表１〜３に示す酸化反応物質を用い形状１
cm×１cm×厚さ0.8mmの補助電極材料を作製した。
但し、ポリトリフエニルアミンとプルシアンブル
ーについては、夫々の粉末に導電材料としてアセ
チレンブラツク、結着剤としてポリテトラフルオ
ロエチレンを、ポリトリフエニルアミンについて
は６：３：１の重量比、プルシアンブルーについ
ては３：２：１の重量比で混合し、三本ロールに
て混練した後、プレスにてシート状の成形体を作
製した。この成形体２枚の間にチタン網を挟み、
ロールプレスにより圧着して、乾燥することによ
り上記形状の補助電極材料を得た。またポリ３−
メチルチオフエンおよびポリピロールについて
は、夫々のモノマーを第１表に示した電解重合条
件下でカーボン繊維より成る集電体上に電解重合
法により各ポリマーを析出させて同じ形状の補助
電極材料を得た。
これ等の補助電極材料の単位体積当りの酸化反
応電気量を測定し、第２表に示す。比較のため第
２表の４に示す物質を用いて実施例と同様の方法
で補助電極材料を得た。第２表の結果からこの発
明における共役系高分子材料を用いた作製したNo.
１，２および３の補助電極材料は、従来のPBを
用いて得たNo.４の補助電極材料に比較して３倍以
上の酸化反応電気量を示した。[Table] Among the conjugated polymer materials mentioned above, they are stable in air and have an oxidation reaction initiation potential of +1.0V [VSAg/
AgCl] The following materials are desirable. The auxiliary electrode material made of the conjugated polymer material is stable in both the oxidant and the reductant, has excellent heat resistance (150°C or higher) and moisture resistance, has a large amount of reaction electricity per unit volume, and can be used as the reductant in cells. It exhibits characteristics such as easy production. (Example) Next, the present invention will be explained with reference to an example. Example Shape 1 using the oxidation reactants shown in Table 2 1 to 3
An auxiliary electrode material measuring cm x 1 cm x 0.8 mm in thickness was prepared.
However, for polytriphenylamine and Prussian blue, acetylene black is used as a conductive material in each powder, polytetrafluoroethylene is used as a binder, and a weight ratio of 6:3:1 is used for polytriphenylamine, and for Prussian blue. were mixed at a weight ratio of 3:2:1, kneaded using three rolls, and then pressed into a sheet-like molded body. A titanium net is sandwiched between these two molded bodies,
The auxiliary electrode material having the above shape was obtained by pressure bonding using a roll press and drying. Also poly 3-
For methylthiophene and polypyrrole, each polymer was deposited by electrolytic polymerization on a current collector made of carbon fiber under the electrolytic polymerization conditions shown in Table 1 to obtain auxiliary electrode materials of the same shape. . The oxidation reaction electricity amount per unit volume of these auxiliary electrode materials was measured and shown in Table 2. For comparison, auxiliary electrode materials were obtained in the same manner as in the examples using the substances shown in 4 in Table 2. From the results in Table 2, No. 1 was prepared using the conjugated polymer material of this invention.
The auxiliary electrode materials No. 1, 2, and 3 exhibited three times or more the amount of electricity for the oxidation reaction compared to the auxiliary electrode material No. 4 obtained using conventional PB.
【表】
次に補助電極材料を第２表のNo.１〜３と同様に
作製した、厚さ0.8mm、長さ300mmの補助電極を、
周辺部に２本設置した第１図に示す400mm×400mm
サイズの４種類の大型光透過度可変ガラスを次の
ようにして作製した。このガラスの第１図におけ
るＡ−Ａ線に沿つて切断した端部の拡大断面を第
２図に示す。先ず400mm×400mm×厚さ3.5mmの上
基板ガラス３上に、常法により厚さ3000〓に
SnO2をスパツターして透明電極５を設け、この
上に第１エレクトロクロミツク層としてWO3膜
１を4000〓真空蒸着で形成し、もう一方の同じサ
イズで同様にして透明電極５を被着した下基板ガ
ラス４の電極５上に第２エレクトロクロミツク層
としてPB膜２を3000〓電着形成した。これらの
２枚の基板間にPC＋2.0重量％の水＋１モル／
lLiClO4の電解液７と、集電網８−３上に酸化反
応物質８−２が被着した補助電極材料を厚さ0.1
mmのポリプロピレン不織布から成る絶絶カバー８
−１で被覆して成る補助電極を挟持し、シール材
としてシリコンゴムとエポキシ樹脂を用いて第１
図に示すように、シール幅を補助電極部15mm、非
補助電極部20mmとして厚さ１mmのシール層６でシ
ールし、光透過度可変ガラスを得た。
比較例
補助電極材料を第２表のNo.４と同様に作成し、
実施例と同様に光透過度可変ガラスを得た。
尚これらの光透過度可変ガラスにおいて、補助
電極に要求される酸化反応電気量は600クーロン
以上であることから、上記補助電極を、前記の如
く周辺部に長さ300mmで２本設置した場合には、
第２図に示す補助電極の幅l1と補助電極と表示極
の間隔l2は次の第３表のようにきまる。[Table] Next, auxiliary electrodes with a thickness of 0.8 mm and a length of 300 mm were prepared in the same manner as Nos. 1 to 3 in Table 2.
400mm x 400mm shown in Figure 1 with two installed around the periphery
Large variable light transmittance glasses of four sizes were produced as follows. FIG. 2 shows an enlarged cross-section of the end of this glass taken along line A--A in FIG. 1. First, on the upper substrate glass 3 of 400 mm x 400 mm x 3.5 mm thickness, the thickness was 3000 mm by the usual method.
A transparent electrode 5 is provided by sputtering SnO 2 , and a WO 3 film 1 is formed thereon as a first electrochromic layer by vacuum evaporation at a thickness of 4000 mm, and another transparent electrode 5 of the same size is deposited in the same manner. On the electrode 5 of the lower substrate glass 4, a PB film 2 was electrodeposited in a thickness of 3000 mm as a second electrochromic layer. Between these two substrates, PC + 2.0 wt% water + 1 mol/
The electrolyte 7 of lLiClO 4 and the auxiliary electrode material with the oxidation reactant 8-2 deposited on the current collecting network 8-3 are coated to a thickness of 0.1
Zettai cover 8 made of mm polypropylene non-woven fabric
-1, and using silicone rubber and epoxy resin as a sealing material, the first
As shown in the figure, the sealing width was set to 15 mm for the auxiliary electrode part and 20 mm for the non-auxiliary electrode part, and the glass was sealed with a sealing layer 6 having a thickness of 1 mm to obtain a variable light transmittance glass. Comparative example: The auxiliary electrode material was prepared in the same manner as No. 4 in Table 2,
A variable light transmittance glass was obtained in the same manner as in the example. In addition, in these glasses with variable light transmittance, the oxidation reaction electricity required for the auxiliary electrode is 600 coulombs or more, so when two auxiliary electrodes are installed at the periphery as described above with a length of 300 mm, teeth,
The width l 1 of the auxiliary electrode and the distance l 2 between the auxiliary electrode and the display electrode shown in FIG. 2 are determined as shown in Table 3 below.
【表】
以上のようにNo.１〜３の補助電極材料を用いた
実施例の光透過度可変ガラスと、No.４の補助電極
材料を用いた比較例の光透過度可変ガラスを比較
すると実施例のものは第１図に示す光透過度可変
部分Ａの面積が著しく増加しており、特にNo.１の
補助電極材料を用いた実施例の光透過度可変ガラ
スでは、表示面積が、比較例の光透過度可変ガラ
スの光透過度可変部分面積約290mm×360mmから約
350mm×360mmと約20％増加した。
（発明の効果）
以上説明してきたように、この発明の光透過度
可変ガラスは、補助電極用酸化還元物質として共
役系高分子材料を用いたことにより、単位体積あ
たりの反応電気量が著しく増加し、またその酸化
反応は支持電解質中陰イオンと反応し、電解液中
の水分量に影響をうけないため、実効光透過度可
変部分面積を著しく増加させることができるとい
う効果が得られる。[Table] As shown above, when comparing the variable light transmittance glass of Examples using auxiliary electrode materials No. 1 to 3 and the variable light transmittance glass of Comparative Example using auxiliary electrode material No. 4, In the example, the area of the variable light transmittance portion A shown in FIG. The variable light transmittance area of the comparative example glass with variable light transmittance ranges from approximately 290 mm x 360 mm to approx.
The size increased by approximately 20% to 350mm x 360mm. (Effects of the Invention) As explained above, in the variable light transmittance glass of the present invention, the amount of reaction electricity per unit volume is significantly increased by using a conjugated polymer material as the redox substance for the auxiliary electrode. Moreover, since the oxidation reaction reacts with anions in the supporting electrolyte and is not affected by the amount of water in the electrolyte, the effective light transmittance variable partial area can be significantly increased.
第１図は一例の大型光透過度可変ガラスの平面
図、第２図は第１図のＡ−Ａ線に沿つて切断した
光透過度可変ガラスの端部の拡大断面図、第３図
は特開昭59−159134号公報に開示されたエレクト
ロクロミツク表示素子の断面図、第４図はPBの
酸化反応電気量と電解液中の水分濃度との関係を
示す線図である。
１……第１エレクトロクロミツク層、２……第
２エレクトロクロミツク層、３……上基板、４…
…下基板、５……透明電極、６……シール層、７
……電解液、８……補助電極、９……絶縁膜。
Fig. 1 is a plan view of an example of a large variable light transmittance glass, Fig. 2 is an enlarged sectional view of the end of the variable light transmittance glass cut along line A-A in Fig. 1, and Fig. 3 is a plan view of an example of a large variable light transmittance glass. FIG. 4, which is a sectional view of an electrochromic display element disclosed in Japanese Patent Application Laid-open No. 59-159134, is a diagram showing the relationship between the amount of electricity in the oxidation reaction of PB and the water concentration in the electrolyte. DESCRIPTION OF SYMBOLS 1...First electrochromic layer, 2...Second electrochromic layer, 3...Upper substrate, 4...
... lower substrate, 5 ... transparent electrode, 6 ... sealing layer, 7
. . . Electrolyte, 8 . . . Auxiliary electrode, 9 . . . Insulating film.
Claims (1)
表面上に酸化タングステンエレクトロクロミツク
層を備え、対向する電極表面上にプルシアンブル
ーエレクトロクロミツク層を備え、光透過度可変
部分に関係しない部分に酸化還元物質を有する補
助電極を備え、両電極間に極性有機溶媒を用いた
電解質が封入されてなるエレクトロクロミツク素
子を用いた光透過度可変ガラスにおいて、補助電
極用酸化還元物質として共役系高分子材料を用い
たことを特徴とする光透過度可変ガラス。1 Of a pair of translucent electrodes, a tungsten oxide electrochromic layer is provided on the surface of one electrode, a Prussian blue electrochromic layer is provided on the surface of the opposing electrode, and is not related to the light transmittance variable portion. Conjugated as a redox substance for the auxiliary electrode in a variable light transmittance glass using an electrochromic element, which is equipped with an auxiliary electrode that has a redox substance in its part, and an electrolyte using a polar organic solvent is sealed between the two electrodes. A variable light transmittance glass characterized by using a polymeric material.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60019186A JPS61179422A (en) | 1985-02-05 | 1985-02-05 | Glass having variable light transmittance |
| US06/810,687 US4801195A (en) | 1985-01-29 | 1985-12-19 | Variable light transmittance glass board functional as electrochromic cell |
| EP85116655A EP0189601B1 (en) | 1985-01-29 | 1985-12-30 | Variable light transmittance glass board functional as electrochromic cell |
| DE8585116655T DE3586126D1 (en) | 1985-01-29 | 1985-12-30 | PANEL WITH VARIABLE TRANSMISSION REALIZED AS AN ELECTROCHROME CELL. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60019186A JPS61179422A (en) | 1985-02-05 | 1985-02-05 | Glass having variable light transmittance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61179422A JPS61179422A (en) | 1986-08-12 |
| JPH0468608B2 true JPH0468608B2 (en) | 1992-11-02 |
Family
ID=11992303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60019186A Granted JPS61179422A (en) | 1985-01-29 | 1985-02-05 | Glass having variable light transmittance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61179422A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030040039A (en) | 2001-11-14 | 2003-05-22 | 가부시키가이샤 유야마 세이사쿠쇼 | medicine feeder |
| JP2003154845A (en) * | 2001-11-20 | 2003-05-27 | Kyowa Sangyo Kk | Sun visor for vehicles |
| FR2960558B1 (en) * | 2010-05-27 | 2012-06-08 | Essilor Int | METHOD FOR MANUFACTURING AN ELECTROCHROME ARTICLE |
| FR2963936B1 (en) * | 2010-08-17 | 2012-08-31 | Essilor Int | METHOD FOR MANUFACTURING AN ELECTROCHROME ARTICLE |
| JP6808363B2 (en) * | 2015-07-02 | 2021-01-06 | キヤノン株式会社 | Electrochromic elements and their driving methods, as well as optical filters, lens units, imaging devices and window materials |
-
1985
- 1985-02-05 JP JP60019186A patent/JPS61179422A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61179422A (en) | 1986-08-12 |
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