JPS6360368B2 - - Google Patents
Info
- Publication number
- JPS6360368B2 JPS6360368B2 JP14278880A JP14278880A JPS6360368B2 JP S6360368 B2 JPS6360368 B2 JP S6360368B2 JP 14278880 A JP14278880 A JP 14278880A JP 14278880 A JP14278880 A JP 14278880A JP S6360368 B2 JPS6360368 B2 JP S6360368B2
- Authority
- JP
- Japan
- Prior art keywords
- counter electrode
- ecd
- background plate
- electrode
- transparent electrode
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002265 redox agent Substances 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 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 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 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
- G02F1/155—Electrodes
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【発明の詳細な説明】
本発明は電気化学的酸化還元反応に基づく色の
着消色を利用したエレクトロクロミツク表示体
（以下、ECDと記す）に関し、特に対向電極の作
製方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic display (hereinafter referred to as ECD) that utilizes color change/decolorization based on an electrochemical redox reaction, and particularly relates to a method for manufacturing a counter electrode.
第１図は酸化タングステンを用いたECDの基
本構成を示した図である。１はガラス基板であり
内面には透明電極２がコーテイングされている。
３は蒸着された酸化タングステン薄膜である。４
は表示の背景となる白色の板であり、通常多孔質
のセラミツク材が用いられる。５はカーボンの対
極であり、プレス加工によつて作られる。６は対
極の集電体であり、Ti材が用いられている。７
は成形加工されたガラス容器であり、前面基板１
と接着し一体化する。８は表示セル内に封入され
た電解液であり、過塩素酸リチウムの1M／プ
ロピレンカーボネイト溶液である。このセルに於
て、表示極を負、対極を正にして電圧を印加する
と、WO3膜が青色に着色する。また、逆方向に
電圧を印加するとWO3膜が無色になり、表示が
消去される。 FIG. 1 is a diagram showing the basic configuration of an ECD using tungsten oxide. Reference numeral 1 denotes a glass substrate, and a transparent electrode 2 is coated on the inner surface.
3 is a deposited tungsten oxide thin film. 4
is a white plate that serves as the background of the display, and is usually made of porous ceramic material. 5 is the opposite electrode of carbon and is made by press working. Reference numeral 6 represents a current collector serving as a counter electrode, and Ti material is used. 7
is a molded glass container, and the front substrate 1
Glue and integrate with. 8 is an electrolytic solution sealed in the display cell, which is a 1M lithium perchlorate/propylene carbonate solution. In this cell, when a voltage is applied with the display electrode being negative and the counter electrode being positive, the WO 3 film is colored blue. Furthermore, when a voltage is applied in the opposite direction, the WO 3 film becomes colorless and the display disappears.
本発明はこのような基本構成をとるECDに於
て、対向電極の作製方法に改良を加えたものであ
る。即ち、従来プレス加工によつて板状に成形し
ていた対向電極に代つて、本発明では印刷、ハケ
塗り等が可能な対向電極材料を用い、これを背景
板と一体化したものである。 The present invention improves the method for manufacturing the counter electrode in an ECD having such a basic configuration. That is, instead of the counter electrode conventionally formed into a plate shape by press working, the present invention uses a counter electrode material that can be printed, painted with a brush, etc., and is integrated with the background plate.
ECDの対極として良く知られているものは、
表示極と同様の酸化タングステン蒸着膜を用いる
ものである。しかし、これは対極側での分極も起
る為、対極の電位が安定せず定電圧駆動には不向
きである。そこで、これに代つて金属錯体とカー
ボンの混合物からなる対極が考えられた。これ
は、金属錯体の酸化還元電位が安定であること
と、分極が少ないことによつて通常の定電圧駆動
でも安定した表示効果が得られる為である。しか
し、現在の所この対極は金属錯体とカーボンの粉
末に結着材を加え、中に網状の集電体を挾んでプ
レス成形することによつて作られている。従つ
て、対極自体の厚みを１ｍ／ｍ以下に薄くでき
ず、また、製造上も芯材を挾んでプレス成形する
という量産向きでない問題点を含んでいる。そこ
で、本発明ではこのようなプレス成形による方法
に代つて、ハケ塗りや印刷塗布が可能な対極材料
を開発し、背景板と対極を一体化することに成功
した。 The well-known opposite of ECD is
A tungsten oxide vapor deposited film similar to that of the display electrode is used. However, since polarization also occurs on the opposite electrode side, the potential of the opposite electrode is unstable, making it unsuitable for constant voltage driving. Therefore, instead of this, a counter electrode made of a mixture of a metal complex and carbon was considered. This is because the oxidation-reduction potential of the metal complex is stable and the polarization is small, so that a stable display effect can be obtained even with normal constant voltage driving. However, at present, this counter electrode is made by adding a binder to metal complex and carbon powder, sandwiching a net-like current collector therein, and press-molding the mixture. Therefore, the thickness of the counter electrode itself cannot be reduced to 1 m/m or less, and there is also a problem in manufacturing that it is not suitable for mass production because the core material is sandwiched and press molded. Therefore, in the present invention, instead of such a press-forming method, we have developed a counter electrode material that can be coated by brushing or printing, and succeeded in integrating the background plate and the counter electrode.
本発明による対極材は黒鉛、アセチレンブラツ
ク、活性炭等の炭素材と結着材、あるいは、これ
に酸化還元剤としての金属錯体をさらに添加した
ものを用いる。結着材はエポキシ系の接着剤、フ
エノール系の接着剤などであるが、本発明ではセ
ルロース系の材料を用いる事によつて特に好結果
を得た。即ち、エポキシ系接着剤では硬化剤であ
るアミン系樹脂が電解液中に溶出し、ECDの応
答性を一層悪くしてしまつた。また、フエノール
系接着剤ではこれが電解液中に溶出し、電解液を
変色、変質させてしまつた。これに対し、セルロ
ース系の結着剤ではECDの応答性、寿命等に何
ら大きな変化はなく、これが電気化学的に安定な
材料である事が立証された。 The counter electrode material according to the present invention uses a carbon material such as graphite, acetylene black, activated carbon, etc. and a binder, or a material to which a metal complex as a redox agent is further added. The binder may be an epoxy adhesive or a phenol adhesive, but in the present invention, particularly good results were obtained by using a cellulose material. That is, in the case of epoxy adhesives, the amine resin, which is a curing agent, is eluted into the electrolyte, further worsening the responsiveness of ECD. Furthermore, in the case of phenol-based adhesives, this eluted into the electrolyte, causing discoloration and deterioration of the electrolyte. On the other hand, with cellulose-based binders, there was no significant change in ECD response, lifespan, etc., proving that this is an electrochemically stable material.
第２図は本発明による対極の構成を示した図で
ある。即ち、本発明ではECDの背景色となる背
景板９の裏側に前述した対極材料１０をハケ塗
り、あるいは、印刷塗布しこれに集電体１１を固
定するものである。ここに用いる背景板９は多孔
質のセラミツク、あるいは、多孔質のフツ素系樹
脂に白色の顔料TiO2をまぶしたものからなる。
また、集電体１１の固定は対極材料自身の固化に
よつても可能であるが、さらに、機械的強度をも
たせる為にはあらかじめ背景板にエポキシの接着
剤によつて部分的に接着させておくとよい。対極
材の塗布はこの上から行なうことが可能である。
さて、このようにして作られた対極は背景材が多
孔質である為、接着のアンカー効果も高まり強固
な接着となる。 FIG. 2 is a diagram showing the configuration of a counter electrode according to the present invention. That is, in the present invention, the above-described counter electrode material 10 is applied by brushing or printing on the back side of the background plate 9, which is the background color of the ECD, and the current collector 11 is fixed thereto. The background plate 9 used here is made of porous ceramic or porous fluororesin coated with white pigment TiO 2 .
Furthermore, the current collector 11 can be fixed by solidifying the counter electrode material itself, but in order to provide mechanical strength, it is possible to fix the current collector 11 by partially adhering it to the background plate with epoxy adhesive in advance. It's a good idea to leave it there. The counter electrode material can be applied from above.
Now, since the background material of the counter electrode made in this way is porous, the anchoring effect of the adhesion is enhanced, resulting in a strong adhesion.
第３図は本発明による背景板と対極を一体構成
した部分を用いたECDの様子を示した図である。
第１図と比較して明らかなように本発明では
ECDの構成が簡単となる為、組立が容易となる。
また、対極が印刷塗布となり薄く（0.2〜0.3mm）
なる為、ECD全体の厚みも薄くできる。 FIG. 3 is a diagram showing an ECD using a part in which a background plate and a counter electrode are integrated according to the present invention.
As is clear from the comparison with FIG.
Since the configuration of the ECD is simple, assembly is easy.
In addition, the counter electrode is printed and coated to make it thinner (0.2 to 0.3 mm).
Therefore, the overall thickness of the ECD can be reduced.
実施例
背景板に多孔質のアルミナセラミツクを用い、
この裏に活性炭粉末とカルボキシメチルセルロー
スナトリウムの混合物を水に溶いたものをハケ塗
りによつて塗布乾燥し、対極とした。集電体は
Ti線を用い、あらかじめセラミツク板にエポキ
シ接着剤にて部分接着固定した。次に、この一体
化された対極を用い第３図のECDを作製し、表
示性能、寿命等を調べた。このセルでは対極での
分極が殆んどない為、通常の定電圧駆動が可能で
あり、応答も書込、消去共に0.3秒台で速いこと
が確認された。メモリー性は24時間後でも褪色は
わずかであり充分であつた。また１秒の点滅によ
るエージング試験では107回以上を記録した。Example: Using porous alumina ceramic for the background plate,
A mixture of activated carbon powder and sodium carboxymethyl cellulose dissolved in water was applied to the back of the electrode by brushing and dried to serve as a counter electrode. The current collector is
Using Ti wire, parts were fixed in advance to a ceramic board with epoxy adhesive. Next, the ECD shown in Figure 3 was manufactured using this integrated counter electrode, and its display performance, lifespan, etc. were investigated. In this cell, there is almost no polarization at the opposite electrode, so normal constant voltage driving is possible, and the response was confirmed to be fast, on the order of 0.3 seconds for both writing and erasing. The memory property was sufficient with only slight fading even after 24 hours. In addition, in an aging test using 1-second flashes, more than 10 7 times were recorded.
他の実施例
背景板に多孔質のフツ素樹脂を使用し、前実施
例と同じ対極材によつて実験を行つた所、前に比
べて寿命の点で若干おちるが他は同様の性能を示
した。この実施例ではフツ素樹脂が0.2mm、印刷
対極の厚みが0.2mmであるので、従来のセラミツ
ク板（0.5mm）とプレス対極（1.5mm）を使用した
ものに比べECセルの内寸を1/5に減らすことがで
きる。さらに、他の実施例としては対極材料の組
成を変えたもの、例えば、酸化還元剤として鉄の
錯体を加えたもの、あるいは、活性炭に黒鉛粉末
を添加し導電性を改良したもの等を試みたが、結
果はほぼ最初の実施例と同等であり、本質的には
変らないことが明らかとなつた。Other Examples An experiment was conducted using a porous fluororesin for the background plate and the same counter electrode material as in the previous example.The lifespan was slightly lower than that of the previous example, but otherwise the performance was the same. Indicated. In this example, the thickness of the fluororesin is 0.2 mm and the thickness of the printed counter electrode is 0.2 mm, so the inner dimensions of the EC cell are 1 It can be reduced to /5. Furthermore, as other examples, attempts were made to change the composition of the counter electrode material, such as adding an iron complex as a redox agent, or adding graphite powder to activated carbon to improve conductivity. However, it became clear that the results were almost the same as in the first example and were essentially unchanged.
上述の如く、本発明によればカーボンに酸化還
元剤を混合したので、酸化還元電位が安定となり
又、分極の発生も低減されることにより定電圧駆
動でも安定した表示が得られるという効果を有し
ており、さらに結着材を混合してハケ塗りや印刷
塗布が可能となつたので製造工程も容易となるば
かりでなく、背景板と対向電極が一体化されるの
でECDの総厚も薄くすることが可能となり薄型
のエレクトロクロミツク表示体を提供できるとい
う優れた効果を有している。 As described above, according to the present invention, since a redox agent is mixed with carbon, the redox potential becomes stable and the occurrence of polarization is reduced, so that stable display can be obtained even when driven at a constant voltage. Furthermore, it is now possible to mix a binder and apply by brush or print, which not only simplifies the manufacturing process, but also reduces the total thickness of the ECD because the background plate and counter electrode are integrated. This has the excellent effect of making it possible to provide a thin electrochromic display.
第１図は従来のECDの基本構成を示した図で
ある。第２図は本発明による背景板と対極が一体
化された部品を示した図である。第３図は背景板
と対極を一対とする部品を用いたECDの構成図
である。
図中の番号、１……前面ガラス板、２……透明
電極、３……EC蒸着膜、４……白色セラミツク
板、５……対極、６……集電体、７……背面ガラ
ス容器、８……電解液、９……多孔質背景板、１
０……対極材料、１１……集電体。
FIG. 1 is a diagram showing the basic configuration of a conventional ECD. FIG. 2 is a diagram showing a component in which a background plate and a counter electrode are integrated according to the present invention. FIG. 3 is a configuration diagram of an ECD using a pair of parts including a background plate and a counter electrode. Numbers in the diagram: 1...Front glass plate, 2...Transparent electrode, 3...EC vapor deposited film, 4...White ceramic plate, 5...Counter electrode, 6...Current collector, 7...Back glass container , 8... Electrolyte, 9... Porous background plate, 1
0... Counter electrode material, 11... Current collector.
Claims (1)
クトロクロミツク物質と、前記透明電極に対向し
て配設された対向電極と前記透明電極と前記対向
電極との間に配設された背景板とを有してなるエ
レクトロクロミツク表示体において、前記対向電
極がカーボンと酸化還元剤と結着材からなり、前
記背景板の前記透明電極と対向する面と反対の面
上に形成されたことを特徴とするエレクトロクロ
ミツク表示体。1. A transparent electrode, an electrochromic material formed on the transparent electrode, a counter electrode disposed opposite to the transparent electrode, and a background plate disposed between the transparent electrode and the counter electrode. In the electrochromic display, the counter electrode is made of carbon, a redox agent, and a binder, and is formed on a surface of the background plate opposite to the surface facing the transparent electrode. An electrochromic display body featuring:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14278880A JPS5766423A (en) | 1980-10-13 | 1980-10-13 | Electrochromic display body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14278880A JPS5766423A (en) | 1980-10-13 | 1980-10-13 | Electrochromic display body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5766423A JPS5766423A (en) | 1982-04-22 |
| JPS6360368B2 true JPS6360368B2 (en) | 1988-11-24 |
Family
ID=15323613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14278880A Granted JPS5766423A (en) | 1980-10-13 | 1980-10-13 | Electrochromic display body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5766423A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58189616A (en) * | 1982-04-30 | 1983-11-05 | Asahi Glass Co Ltd | Electrochromic display |
-
1980
- 1980-10-13 JP JP14278880A patent/JPS5766423A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5766423A (en) | 1982-04-22 |
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| JPS61241734A (en) | Electrochemical display element |