JPS645683B2 - - Google Patents
Info
- Publication number
- JPS645683B2 JPS645683B2 JP9037080A JP9037080A JPS645683B2 JP S645683 B2 JPS645683 B2 JP S645683B2 JP 9037080 A JP9037080 A JP 9037080A JP 9037080 A JP9037080 A JP 9037080A JP S645683 B2 JPS645683 B2 JP S645683B2
- Authority
- JP
- Japan
- Prior art keywords
- counter electrode
- electrode
- display
- carbon
- mixture
- 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 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000004698 iron complex Chemical class 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 α-methylstyrene (tetrahydrofuran) Chemical compound 0.000 description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000007740 vapor deposition 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】
従来より酸化還元反応によつて、発消色を起
す、エレクトロ・クロミツク（EC）表示体の開
発が積極的に進められている。しかしこの表示体
は表示効果の点できわめてすぐれているものの、
その長期安定性、信頼性の点で、いま一つ実用化
に致つていない。特にその中でも、EC表示体の
駆動条件の初期及び長期の経時変化は、対極の分
極特性に影響されるため、各種対極の検討報告が
なされている。例えば、対極にEC材と同一物質
を用いたり、或いは、炭素−鉄錯体混合物の、加
圧成型体を用いたりした例が報告されている。し
かしこれらの対極でも経時変化は不充分であり実
用化に至つていない。WO3対極の場合は、応答
性、分極特性に問題があり、Fe−錯体−カーボ
ン電極の場合には、非水溶ばい系電解液によるぼ
う潤により、機械的強度及び、実効電極面積の変
化等が生じるためと考えられる。本発明の表示体
は電解液中につけた時の圧粉体のぼう潤性を改良
する事により、機械的にも、電極実効面積的にも
極めて安定なEC表示体用対極を改良し、初期及
び長期の経時変化の少ない表示体を提供するもの
である。DETAILED DESCRIPTION OF THE INVENTION The development of electrochromic (EC) displays, which change color and fade through oxidation-reduction reactions, has been actively pursued. However, although this display body has excellent display effects,
In terms of long-term stability and reliability, it has not yet been put into practical use. Particularly among these, the initial and long-term changes in the driving conditions of the EC display are influenced by the polarization characteristics of the counter electrode, and therefore various reports have been made on studies of various counter electrodes. For example, examples have been reported in which the same material as the EC material is used for the counter electrode, or a pressure-molded body of a carbon-iron complex mixture is used. However, even at these opposite extremes, the changes over time are insufficient and have not been put into practical use. In the case of the WO 3 counter electrode, there are problems with response and polarization characteristics, and in the case of the Fe-complex-carbon electrode, there are problems such as changes in mechanical strength and effective electrode area due to depletion by the non-aqueous solute electrolyte. This is thought to be due to the occurrence of The display body of the present invention is an extremely stable counter electrode for an EC display body, which is extremely stable both mechanically and in terms of electrode effective area, by improving the burrability of the powder compact when immersed in an electrolytic solution. The present invention also provides a display body with little long-term change over time.
以下詳細な説明を実施例に基づいて行う。 A detailed explanation will be given below based on examples.
実施例 １
第１図は本実施例に用いたECセルの略図であ
る。ガラス基板１１上に設けられた、表示用透明
電極１２上に、蒸着によりWO3膜が設けられて
いる。膜の厚さは約2000Åである。スペース１４
中にはホウフツ化リチウムを支持電解質として含
む、ブロピレンカーボネート溶媒が満されてい
る。白色反射板としてのアルミナ板１６を挿入
し、対極と向き合う様にスペーサー１５を介し
て、セルが構成されている。Example 1 FIG. 1 is a schematic diagram of an EC cell used in this example. A WO 3 film is provided on a display transparent electrode 12 provided on a glass substrate 11 by vapor deposition. The thickness of the film is approximately 2000 Å. space 14
It is filled with a propylene carbonate solvent containing lithium borofluoride as a supporting electrolyte. A cell is constructed by inserting an alumina plate 16 as a white reflecting plate and interposing a spacer 15 so as to face the opposite electrode.
この構成は従来のものと差はないが、本発明の
特徴である所の対極１７は以下にして作られてい
る。THF中でα−メチルスチレンのリビングテ
トラマー（テトラ・ヒドロフラン）を合成し、こ
れを架橋剤として、スチレンのアニオン重合によ
り、リビングポリスチレンを作る。これにポリメ
タクリル酸メチルのTHF溶液を加え、低温で重
合反応を行わせる。粘度が上昇した時、炭素粉末
（活性炭やアセチレンブラツク）及び鉄錯体を添
加し反応を進行させ、ゲル状高分子中にカーボン
−鉄錯体を分散せしめる。この後メタノールで重
合体を沈澱させ、それを加圧成型して対極とす
る。この時電極リード用として対極中にメツシユ
状になつた部分を持つステンレスよりなるリード
１８を作つてある。 Although this configuration is no different from the conventional one, the counter electrode 17, which is a feature of the present invention, is made as follows. A living tetramer of α-methylstyrene (tetrahydrofuran) is synthesized in THF, and living polystyrene is produced by anionic polymerization of styrene using this as a crosslinking agent. A THF solution of polymethyl methacrylate is added to this, and a polymerization reaction is carried out at a low temperature. When the viscosity increases, carbon powder (activated carbon or acetylene black) and an iron complex are added to advance the reaction and the carbon-iron complex is dispersed in the gel-like polymer. Thereafter, the polymer is precipitated with methanol and molded under pressure to form a counter electrode. At this time, a lead 18 made of stainless steel and having a mesh-like portion in the counter electrode is prepared as an electrode lead.
このECセルに電圧約1.0〜1.2Vで反転パルス駆
動を行つた所、106回以上の発消色のくり返しに
対しても何ら外観上の変化が見られなかつた。又
放置中に於ける駆動条件（印加電圧の大きさ）の
変化も極めてわずかで、経時変化による問題点も
解消された。又応答スピードも改良された。特に
従来のポリエチレンバインダー対極に比べ、機械
的強度も大きく、特に従来のものでみられた、ぼ
う潤現象もなくなつていた。 When this EC cell was subjected to inversion pulse driving at a voltage of about 1.0 to 1.2 V, no change in appearance was observed even after repeated color development and fading more than 10 6 times. Further, the change in driving conditions (magnitude of applied voltage) during storage was extremely small, and problems caused by changes over time were also resolved. The response speed has also been improved. In particular, compared to the conventional polyethylene binder counter electrode, the mechanical strength was greater, and the swelling phenomenon observed with the conventional electrode was also eliminated.
実施例 ２
実施例１に於いて、対極としてカーボン及び鉄
錯体混合物中に10〜20wt％のエポキシ樹脂（重
合度の低いもの）を添加し、さらに架橋剤とし
て、テトラ、エチルアミンを少量添加し、充分撹
拌し、その後ステンレスメツシユを挿入して、板
状に成形し、80℃で加熱重合させて、エポキシ樹
脂を架橋重合させたものを使用した。Example 2 In Example 1, 10 to 20 wt% of epoxy resin (low degree of polymerization) was added to the carbon and iron complex mixture as a counter electrode, and a small amount of tetra and ethylamine was added as a crosslinking agent. After sufficient stirring, a stainless steel mesh was inserted, the mixture was molded into a plate, and the mixture was heated and polymerized at 80° C. to crosslink and polymerize the epoxy resin.
その結果、従来の対極に比べ、駆動条件の経時
変化が少なく、応答スピードも改良された。又ぼ
う潤性、強度的にもすぐれた対極材が得られた。 As a result, compared to conventional counter electrodes, there are fewer changes in driving conditions over time and response speed is improved. A counter electrode material with excellent moisture resistance and strength was also obtained.
以上架橋構造を持つ高分子により支持された対
極は従来の対極に比べ良好な結果をもたらした。 The counter electrode supported by a polymer with a crosslinked structure gave better results than the conventional counter electrode.
以上述べたように本発明によれば、架橋反応可
能な高分子と、カーボンと鉄錯体との混合物とを
混合し、架橋構造中にカーボンと鉄錯体との混合
物をバインドしたので、カーボンと鉄錯体との混
合物が強固に保持され且つ均一に分散され、外的
条件による対極の経時変化を防止し、安定した減
極効果が得られる。さらに、電解液との接触によ
る“対極のぼう潤現象”が防止でき、酸化還元反
応による経時変化（電解液との接触面積の変化や
亀裂の発生など）をおさえて長期に安定した駆動
を可能とするエレクトロクロミツク表示体が提供
できる。 As described above, according to the present invention, a crosslinkable polymer and a mixture of carbon and an iron complex are mixed, and the mixture of carbon and iron complex is bound in the crosslinked structure. The mixture with the complex is firmly held and uniformly dispersed, preventing the counter electrode from changing over time due to external conditions, and providing a stable depolarization effect. Furthermore, it prevents the "counter electrode swelling phenomenon" caused by contact with the electrolyte, and suppresses changes over time due to oxidation-reduction reactions (changes in contact area with the electrolyte, cracks, etc.), enabling stable driving over a long period of time. An electrochromic display body can be provided.
第１図は本発明によるECセルの略図を示す。
１１：表示側基板ガラス、１２：ネサ透明電
極、１３：WO3蒸着膜、１４：電解液、１５：
スペーサー、１６：白色反射板、１７：対極、１
８：リード取り出し電極、１９：下部基板ガラ
ス、２０：保護用SiO2膜。
FIG. 1 shows a schematic diagram of an EC cell according to the invention. 11: Display side substrate glass, 12: Nesa transparent electrode, 13: WO 3 vapor deposited film, 14: Electrolyte, 15:
Spacer, 16: White reflector, 17: Counter electrode, 1
8: Lead extraction electrode, 19: Lower substrate glass, 20: Protective SiO 2 film.
Claims (1)
板の内面に形成された表示用電極と、他方の基板
に近接して配設された対極とを有したエレクトロ
クロミツク表示体の製造方法において、架橋剤
と、架橋反応可能な高分子と、カーボンと鉄錯体
との混合物とを混合し、前記高分子を架橋反応さ
せた後、所定形状の対極を形成することを特徴と
するエレクトロクロミツク表示体の製造方法。1. Method for manufacturing an electrochromic display in which an electrolytic solution is sandwiched between a pair of substrates, a display electrode formed on the inner surface of one substrate, and a counter electrode disposed close to the other substrate. In the electrochromic system, a crosslinking agent, a polymer capable of crosslinking reaction, and a mixture of carbon and an iron complex are mixed, and after crosslinking the polymer, a counter electrode of a predetermined shape is formed. Method for manufacturing a Tsuku display body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9037080A JPS5716424A (en) | 1980-07-02 | 1980-07-02 | Electrochromic display body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9037080A JPS5716424A (en) | 1980-07-02 | 1980-07-02 | Electrochromic display body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5716424A JPS5716424A (en) | 1982-01-27 |
| JPS645683B2 true JPS645683B2 (en) | 1989-01-31 |
Family
ID=13996664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9037080A Granted JPS5716424A (en) | 1980-07-02 | 1980-07-02 | Electrochromic display body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5716424A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4849781B2 (en) * | 2003-06-16 | 2012-01-11 | 富士通株式会社 | Display device and electrodeposition type display device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610352B2 (en) * | 1972-12-13 | 1981-03-07 | ||
| FR2321751A1 (en) * | 1975-08-04 | 1977-03-18 | Raychem Corp | MATERIALS OF HIGH ELECTRICAL RESISTANCE AT HIGH TEMPS. - comprise crystalline thermoplastic (co)polymer and conducting filler used for heating elements |
| GB1595198A (en) * | 1976-10-15 | 1981-08-12 | Raychem Corp | Ptc compositions and devices comprising them |
| JPS561920A (en) * | 1979-06-19 | 1981-01-10 | Matsushita Electric Ind Co Ltd | Electrochromic display device |
-
1980
- 1980-07-02 JP JP9037080A patent/JPS5716424A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5716424A (en) | 1982-01-27 |
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