JPH0433013B2 - - Google Patents
Info
- Publication number
- JPH0433013B2 JPH0433013B2 JP59114417A JP11441784A JPH0433013B2 JP H0433013 B2 JPH0433013 B2 JP H0433013B2 JP 59114417 A JP59114417 A JP 59114417A JP 11441784 A JP11441784 A JP 11441784A JP H0433013 B2 JPH0433013 B2 JP H0433013B2
- Authority
- JP
- Japan
- Prior art keywords
- counter electrode
- film
- electrode
- triphenylamine
- display
- 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 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 description 11
- 229960003351 prussian blue Drugs 0.000 description 11
- 239000013225 prussian blue Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- 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】
（技術分野）
この発明は電気化学的酸化還元反応を利用した
表示素子に関するもので、更に詳しくは可逆酸化
還元材料としてトリフエニルアミンの重合体皮膜
を形成した導電材料を対向電極として用いた耐湿
性を向上させたエレクトロクロミツク素子に関す
るものである。Detailed Description of the Invention (Technical Field) The present invention relates to a display element that utilizes an electrochemical redox reaction, and more specifically relates to a conductive material formed with a polymer film of triphenylamine as a reversible redox material. This invention relates to an electrochromic element with improved moisture resistance that is used as a counter electrode.
（従来技術）
電気化学的酸化還元反応を利用した表示素子は
多数提案されており、この内反射形エレクトロク
ロミツク素子としては例えば本出願人による特開
昭57−158282号公報に記載されているものがあ
る。(Prior Art) Many display elements that utilize electrochemical redox reactions have been proposed, and an internal reflection type electrochromic element is described, for example, in Japanese Patent Application Laid-Open No. 158282/1982 by the present applicant. There is something.
この公報に記載のエレクトロクロミツク素子
は、第４図に示すように構成されており、すなわ
ち透明基板１上に導電性透明電極２が設けられ、
この上に所定パターンを有するWO3薄膜より成
る表示極１３が設けられ、透明電極２のリード線
接続部および表示パターン部以外の部分にはSiO
皮膜のような絶縁性皮膜３が被着され、一方の背
面基板４上には対向電極５が設けられ、この対向
電極５はその周囲に塗布したスペーサ入りシール
用樹脂７を介して表示極１３と平行保持され、こ
れ等の表示極１３と対向電極５の間には光散乱板
６が設けられ注入口１５を介して電解質溶液９が
注入され、封止用接着剤８で注入口が封止されて
構成されている。このエレクトロクロミツク素子
は上記対向電極材料としてプルシアンブルー材料
を用いている。すなわち例えば布状のカーボン繊
維（日本カーボン(株)製）を使用し、各々0.01
〔Ｍ／〕の硫酸第２鉄およびフエリシアン化カ
リウムを含む溶液にカーボン繊維を浸漬し、見掛
けの表面積当り2.3mA／cm2の電流密度にて40秒間
電解還元を行ない、その表面にプルシアンブルー
皮膜を形成し、対向電極を作製した。第５図にこ
のようにして作成した対向電極の断面図を示す。
尚図面中１４はプルシアンプルー皮膜、１１は対
向電極用リード線、１２は対向電極用導電材料を
示す。 The electrochromic device described in this publication is constructed as shown in FIG. 4, that is, a conductive transparent electrode 2 is provided on a transparent substrate 1,
A display electrode 13 made of a WO 3 thin film having a predetermined pattern is provided on this, and a portion of the transparent electrode 2 other than the lead wire connection portion and the display pattern portion is made of SiO.
An insulating film 3 such as a film is applied, and a counter electrode 5 is provided on one back substrate 4. This counter electrode 5 is connected to a display electrode 13 via a spacer-containing sealing resin 7 applied around the counter electrode 5. A light scattering plate 6 is provided between the display electrode 13 and the counter electrode 5, an electrolyte solution 9 is injected through the injection port 15, and the injection port is sealed with a sealing adhesive 8. configured. This electrochromic device uses a Prussian blue material as the material for the counter electrode. That is, for example, using cloth-like carbon fiber (manufactured by Nippon Carbon Co., Ltd.), each 0.01
Carbon fibers were immersed in a solution containing ferric sulfate and potassium ferricyanide of [M/], and electrolytically reduced at a current density of 2.3 mA/cm 2 per apparent surface area for 40 seconds to form a Prussian blue film on the surface. A counter electrode was prepared. FIG. 5 shows a cross-sectional view of the counter electrode prepared in this manner.
In the drawing, 14 indicates a Prussian blue film, 11 indicates a lead wire for the counter electrode, and 12 indicates a conductive material for the counter electrode.
上記プルシアンブルーは150℃以上で分解する
ことが知られており、したがつてエレクトロクロ
ミツク素子作製時、特にスペーサ７を介して表示
側基板と背面基板を平行に保持する工程におい
て、シール剤｛例えばエポキシ系の主剤LCB304
（EHC社製、商品名）：イミダゾール系硬化剤
2PZ（四国化成(株)製、商品名）＝25：２｝を含浸さ
せたガラス繊維あるいはアルミナ粉末などをスペ
ーサーに用い、表示側基板と背面基板を重ね合わ
せ150℃以下例えば130℃で１時間加圧接着する必
要がある。こうして得られた空セルに電解質溶液
（例えば１モル／LiClO4を添加したプロピレン
カーボネート）を注入し、電解質溶液の注入口１
５を接着剤８（スリーボンドTB2002：TB2103
＝100：８）で封止した。 It is known that the above-mentioned Prussian blue decomposes at temperatures above 150°C. Therefore, when manufacturing electrochromic devices, especially in the process of holding the display side substrate and the back substrate parallel to each other via the spacer 7, the sealant { For example, epoxy base material LCB304
(Manufactured by EHC, trade name): Imidazole curing agent
Using glass fiber or alumina powder impregnated with 2PZ (manufactured by Shikoku Kasei Co., Ltd., product name) = 25:2} as a spacer, the display side substrate and the back substrate are stacked and heated at 150℃ or less, for example, 130℃ for 1 hour. Needs to be pressure bonded. Inject an electrolyte solution (for example, propylene carbonate to which 1 mol/LiClO 4 has been added) into the empty cell obtained in this way, and then open the electrolyte solution injection port 1.
5 to adhesive 8 (Three Bond TB2002: TB2103
= 100:8).
（発明が解決しようとする問題点）
以上のようにして得られたエレクトロクロミツ
ク素子を60℃で95％相対湿度条件下で1000時間放
置し、表示性能を測定したところWO3表示極の
コントラストが低下するという問題が発生した。
この原因を調べてみると電解質溶液中の水分量が
放置前には0.2重量％であつたものが、放置後に
は10重量％と著しく増加し、これが原因でWO3
表示極が溶解し、膜厚がうすくなつたためと判明
した。さらに、この水分の増加は、シール剤７を
透過して侵入した水分によるものと判明した。(Problems to be Solved by the Invention) The electrochromic device obtained as described above was left at 60°C and 95% relative humidity for 1000 hours, and its display performance was measured.The contrast of the WO 3 display pole was A problem occurred in which the value decreased.
When we investigated the cause of this, we found that the water content in the electrolyte solution was 0.2% by weight before standing, but it increased significantly to 10% by weight after standing, and this was the cause of WO 3
It turned out that this was because the display electrode had melted and the film thickness had become thinner. Furthermore, it was found that this increase in moisture was due to moisture penetrating through the sealant 7 and entering.
従つて、この問題を解決するには透湿性の低い
シール剤の使用が望ましい。例えば半導体IC用
封止剤に使用されているようなエポキシ樹脂系主
剤と硬化剤の組合せを用いればよい。 Therefore, to solve this problem, it is desirable to use a sealant with low moisture permeability. For example, a combination of an epoxy resin base agent and a curing agent, such as those used in semiconductor IC encapsulants, may be used.
しかしこのようなシール剤は硬化温度が150℃
以上と高温になるため従来のプルシアンブルー対
極材料ではプルシアンブルーが分解あるいは脱落
するという問題があつた。すなわち前述の通り作
製したプルシアンブルー対極材料を180℃で１時
間加熱すると、加熱前後での反応電気量は、第３
図の破線ａに示すように約１／３に減少した。こ
れはプルシアンブルー（一般式Fe4〔Fe
（CN）6〕3・14.5H2OあるいはKFe〔Fe（CN）6・
1.9H2O）中の結晶水が蒸発し、その体積変化に
よりプルシアンブルーにひび割れが生じ導電材料
から脱落することおよびプルシアンブルの熱分解
による反応量の減少に由来すると考えられる。 However, the curing temperature of this type of sealant is 150℃.
Due to the high temperatures above, conventional Prussian blue counter electrode materials have had the problem that Prussian blue decomposes or falls off. In other words, when the Prussian blue counter electrode material prepared as described above is heated at 180°C for 1 hour, the amount of reaction electricity before and after heating is the third
As shown by the broken line a in the figure, it decreased to about 1/3. This is Prussian blue (general formula Fe 4 [Fe
(CN) 6 〕 3・14.5H 2 O or KFe [Fe(CN) 6・
This is thought to be due to the fact that crystal water in 1.9H 2 O) evaporates and the volume change causes Prussian blue to crack and fall off from the conductive material, and that the amount of reaction decreases due to thermal decomposition of Prussian blue.
WO3を対向電極に用いることも考えられるが、
初期還元を必要とするので第３電極を用いなけれ
ばならない。 It is also possible to use WO 3 as the counter electrode, but
Since initial reduction is required, a third electrode must be used.
この発明はこのような従来の問題点に着目して
なされたもので対向電極材料として還元状態で安
定なトリフエニルアミンの重合体を用い耐熱性を
向上させた対向電極材料を提供することにより上
記問題点を解決することを目的としている。 The present invention was made in view of these conventional problems, and by providing a counter electrode material with improved heat resistance using a polymer of triphenylamine, which is stable in a reduced state, as the counter electrode material, the above-mentioned problems can be solved. The purpose is to solve problems.
（発明の構成）
この発明の電気化学的酸化還元反応を利用した
エレクトロクロミツク表示素子は、トリフエニル
アミンの重合体皮膜を形成した導電材料を対向電
極として用いたことを特徴とするものである。(Structure of the Invention) The electrochromic display element using electrochemical redox reaction of the present invention is characterized in that a conductive material formed with a polymer film of triphenylamine is used as a counter electrode. .
トリフエニルアミンの重合体は、例えば本出願
人による特願昭59−68986号および同59−68987号
により提案したような４，4′，4″−トリハロゲノ
トリフエニルアミンを出発原料とし、これと金属
マグネシウムとによる中間体を経てジクロロニツ
ケルの如きニツケル触媒を用いて単独重合させる
かまたは４，4′−ジハロゲノベンゼンと共重合さ
せて得られる共重合体があり、高分子導電性材料
として用いられるものである。 The triphenylamine polymer uses 4,4',4''-trihalogenotriphenylamine as a starting material, as proposed in Japanese Patent Application No. 59-68986 and No. 59-68987 by the present applicant, for example. There are copolymers obtained by homopolymerization using a nickel catalyst such as dichloronickel through an intermediate between nickel and metallic magnesium, or by copolymerization with 4,4'-dihalogenobenzene, and are used as conductive polymer materials. It is used.
この発明のエレクトロクロミツク表示素子
（EC素子は、対向電極としてトリフエニルアミン
の重合体皮膜を形成した導電材料を用いた以外は
前記特開昭57−158282号公報に開示されたEC素
子と同様の構成を有する。対向電極は、例えばト
リフエニルアミンの重合体をバインダーと混練し
膜状とし、こね膜２枚を用いて例えばチタン
（Ti）網をはさみ、ホツトプレスした後焼成する
ことにより作製することができる。この場合の対
向電極材料としては上記Ti網以外には特開昭57
−157219号公報に開示したように種々の金属の
板、網、発泡体などあるいはカーボン繊維、不織
布などを用いることができる。 The electrochromic display element of the present invention (EC element is similar to the EC element disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 158282/1982, except that a conductive material on which a polymer film of triphenylamine is formed is used as a counter electrode. The counter electrode is prepared by, for example, kneading a triphenylamine polymer with a binder to form a film, sandwiching, for example, a titanium (Ti) mesh between two kneaded films, hot pressing, and then firing. In this case, the material for the counter electrode other than the above-mentioned Ti mesh can be
As disclosed in Japanese Patent No. 157219, various metal plates, nets, foams, carbon fibers, nonwoven fabrics, etc. can be used.
この発明において、シール用樹脂材料としては
硬化温度が高くても透湿性の低いエポキシ樹脂を
主剤とし硬化剤と組合せて用いるのが好ましい。 In this invention, as the sealing resin material, it is preferable to use an epoxy resin as a main ingredient, which has low moisture permeability even at a high curing temperature, in combination with a curing agent.
（発明の実施例） 以下この発明を図面に基づいて説明する。(Example of the invention) The present invention will be explained below based on the drawings.
第１図はこの発明の一実施例のEC素子の断面
を示すもので、対向電極５としてトリフエニルア
ミンの重合体皮膜を形成した導電材料を用いた以
外は第３図につき説明したと同様の構成により成
る。即ち第１図において１は透明基板、２は導電
性透明電極、３は絶縁性皮膜、４は背面基板、５
は対向電極、６は光散乱板、７はスペーサ入りシ
ール樹脂、８は封止用樹脂、９は電解質溶液、１
３はWO3薄膜を示す。また第２図ａおよびｂは
第１図のEC素子の対向電極の断面図および平面
図、１０はトリフエニルアミンの重合体皮膜、１
１は対向電極用リード線、１２は対向電極用導電
材料を示す。 FIG. 1 shows a cross section of an EC element according to an embodiment of the present invention, which is similar to that described in FIG. 3 except that a conductive material on which a triphenylamine polymer film is formed is used as the counter electrode 5. Consists of configuration. That is, in FIG. 1, 1 is a transparent substrate, 2 is a conductive transparent electrode, 3 is an insulating film, 4 is a back substrate, and 5 is a transparent substrate.
is a counter electrode, 6 is a light scattering plate, 7 is a sealing resin with a spacer, 8 is a sealing resin, 9 is an electrolyte solution, 1
3 indicates a WO 3 thin film. 2a and b are a cross-sectional view and a plan view of the counter electrode of the EC element in FIG. 1, 10 is a triphenylamine polymer film, 1
1 is a lead wire for the counter electrode, and 12 is a conductive material for the counter electrode.
実施例 １
第１図に示す構造のエレクトロクロミツク素子
をつくつた。但し透明基板１、背面基板４はガラ
ス、透明電極２はSnO2、絶縁性皮膜３はSiOの
蒸着膜、光散乱板６は多孔質アルミナ基板、電解
質溶液９は１モル／ LiClO4を添加したプロ
ピレンカーボネートを用いた。Example 1 An electrochromic device having the structure shown in FIG. 1 was manufactured. However, the transparent substrate 1 and the back substrate 4 were made of glass, the transparent electrode 2 was made of SnO 2 , the insulating film 3 was a deposited SiO film, the light scattering plate 6 was a porous alumina substrate, and the electrolyte solution 9 was made of 1 mol/LiClO 4 added. Propylene carbonate was used.
対向電極はポリ（４，4′，4″−トリフエニルア
ミン）７重量部、アセチレンブラツク２重量部お
よびテフロン粉末１重量部を充分に混練し、
50μmの膜状とし、この膜を２枚用いてチタン
（Ti）網をはさみ、100℃にてホツトプレスを行
なつた。その後250〜300℃にて１時間以上焼成
し、対向電極として用いた。 The counter electrode was prepared by thoroughly kneading 7 parts by weight of poly(4,4',4''-triphenylamine), 2 parts by weight of acetylene black, and 1 part by weight of Teflon powder.
A 50 μm film was formed, two sheets of this film were sandwiched between titanium (Ti) nets, and hot pressing was performed at 100°C. Thereafter, it was fired at 250 to 300°C for more than 1 hour and used as a counter electrode.
このように構成された対向電極は透湿性の低い
エポキシ樹脂の硬化条件、180℃、１時間の熱処
理を行つても第３図の実線ｂで示されるように反
応電気量の減少は見られなかつた。 Even when the counter electrode configured in this way was subjected to heat treatment at 180°C for 1 hour under the curing conditions of an epoxy resin with low moisture permeability, no decrease in the amount of reaction electricity was observed, as shown by the solid line b in Figure 3. Ta.
またシール用樹脂材料としては主剤：エピコー
ト828 100重量部、硬化剤：C11AZiNE（四国化成
工業(株)製）を用いた。 In addition, as the resin material for sealing, a base agent: 100 parts by weight of Epicoat 828 and a curing agent: C 11 AZiNE (manufactured by Shikoku Kasei Kogyo Co., Ltd.) were used.
このようにして構成したエレクトロクロミツク
素子を先に述べた従来例と同様な60℃で95％相対
湿度条件下で1000時間放置し、表示性能を測定し
たところ、WO3表示極のコントラストには何の
影響もなかつた。この際、電解液中の水分は、
0.2重量％から0.9重量％に増加したのみであつ
た。 The electrochromic device constructed in this way was left for 1000 hours under the same conditions as the conventional example at 60°C and 95% relative humidity, and its display performance was measured. There was no effect. At this time, the water in the electrolyte is
It only increased from 0.2% by weight to 0.9% by weight.
実施例 ２
対向電極として、ポリ（４，4′，4″−トリフエ
ニルアミン）をエタノール中に分散させ、これに
カーボンブラツクおよびポリアクリル酸ナトリウ
ムの水溶液を混合し、懸濁液を作成した。この液
中にカーボン繊維を浸した後、風乾し、更に180
℃にて２時間真空乾燥を行ない、対向電極をつく
つた。この際、カーボン繊維からのリード線は白
金ペーストにて、白金線を取りつけて利用した。
このようにして作製した対向電極を用い、他は実
施例１と同様にしてEC素子を作製したところ同
様に耐久性に優れたEC素子を作製することがで
きた。Example 2 As a counter electrode, poly(4,4',4''-triphenylamine) was dispersed in ethanol, and carbon black and an aqueous solution of sodium polyacrylate were mixed therein to prepare a suspension. After soaking the carbon fiber in this solution, air dry it and further
Vacuum drying was performed at ℃ for 2 hours to prepare a counter electrode. At this time, the lead wire from the carbon fiber was used by attaching a platinum wire with platinum paste.
An EC element was produced using the counter electrode thus produced and in the same manner as in Example 1, and an EC element with excellent durability was also produced.
（発明の効果）
以上説明してきたように、この発明によれば、
反射形エレクトロクロミツク素子において対向電
極をトリフエニルアミンの重合体皮膜を形成した
導電材料で作製したことにより第３電極を用いず
に耐久性が著しく向上したという効果が得られ
る。(Effect of the invention) As explained above, according to this invention,
By making the counter electrode in a reflective electrochromic device from a conductive material coated with a polymer film of triphenylamine, it is possible to obtain the effect of significantly improved durability without using a third electrode.
第１図はこの発明の一例のエレクトロクロミツ
ク表示素子の断面図、第２図ａはこの発明に用い
られる対向電極の断面図、第２図ｂは第２図ａの
対向電極の平面図、第３図はこの発明に用いられ
る対向電極と従来の対向電極の電気量の熱処理時
間による変化を示す線図、第４図は従来のエレク
トロクロミツク表示素子の断面図、第５図は従来
の対向電極の断面図である。
１…透明基板、２…導電性透明電極、３…絶縁
性皮膜、４…背面基板、５…対向電極、６…光散
乱板、７…スペーサ入りシール用樹脂またはスペ
ーサ、８…封止用樹脂、９…電解質溶液、１０…
トリフエニルアミンの重合体膜、１１…対向電極
用リード線、１２…対向電極用導電材料、１３…
WO3薄膜、１４…プルシアンブルー皮膜、１５
…注入口。
FIG. 1 is a sectional view of an electrochromic display element as an example of the present invention, FIG. 2a is a sectional view of a counter electrode used in the invention, FIG. 2b is a plan view of the counter electrode of FIG. 2a, FIG. 3 is a diagram showing the change in the amount of electricity of the counter electrode used in the present invention and the conventional counter electrode depending on the heat treatment time, FIG. 4 is a cross-sectional view of a conventional electrochromic display element, and FIG. FIG. 3 is a cross-sectional view of a counter electrode. DESCRIPTION OF SYMBOLS 1... Transparent substrate, 2... Conductive transparent electrode, 3... Insulating film, 4... Back substrate, 5... Counter electrode, 6... Light scattering plate, 7... Sealing resin with spacer or spacer, 8... Sealing resin , 9...electrolyte solution, 10...
Triphenylamine polymer film, 11... Lead wire for counter electrode, 12... Conductive material for counter electrode, 13...
WO 3 thin film, 14...Prussian blue film, 15
...Inlet.
Claims (1)
ロクロミツク表示素子において、トリフエニルア
ミンの重合体で形成した導電材料を対向電極とし
て用いたことを特徴とするエレクトロクロミツク
表示素子。1. An electrochromic display element using an electrochemical redox reaction, characterized in that a conductive material made of a triphenylamine polymer is used as a counter electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59114417A JPS60258519A (en) | 1984-06-06 | 1984-06-06 | Electrochromic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59114417A JPS60258519A (en) | 1984-06-06 | 1984-06-06 | Electrochromic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60258519A JPS60258519A (en) | 1985-12-20 |
| JPH0433013B2 true JPH0433013B2 (en) | 1992-06-01 |
Family
ID=14637176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59114417A Granted JPS60258519A (en) | 1984-06-06 | 1984-06-06 | Electrochromic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60258519A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH065344B2 (en) * | 1984-12-07 | 1994-01-19 | 理化学研究所 | Multicolor display element and multicolor display device |
-
1984
- 1984-06-06 JP JP59114417A patent/JPS60258519A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60258519A (en) | 1985-12-20 |
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