JPS6084533A - Electrochromic display element - Google Patents

Electrochromic display element

Info

Publication number
JPS6084533A
JPS6084533A JP58193721A JP19372183A JPS6084533A JP S6084533 A JPS6084533 A JP S6084533A JP 58193721 A JP58193721 A JP 58193721A JP 19372183 A JP19372183 A JP 19372183A JP S6084533 A JPS6084533 A JP S6084533A
Authority
JP
Japan
Prior art keywords
counter electrode
display element
electrode
polytetrafluoroethylene powder
electrochromic 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.)
Pending
Application number
JP58193721A
Other languages
Japanese (ja)
Inventor
Osamu Ishida
修 石田
Akira Kawakami
章 川上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maxell Ltd
Original Assignee
Hitachi Maxell Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Maxell Ltd filed Critical Hitachi Maxell Ltd
Priority to JP58193721A priority Critical patent/JPS6084533A/en
Publication of JPS6084533A publication Critical patent/JPS6084533A/en
Pending legal-status Critical Current

Links

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
    • G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • 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
    • 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
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

PURPOSE:To enable formation of a uniform counter electrode independently and to prevent its cracking by using a polytetrafluoroethylene powder as the binder of a counter electrode material and a conductive agent for the counter electrode. CONSTITUTION:A display electrode 2 made of an electrochromic display element having resistance, as shown in the table, is formed on a display electrode plate 1 obtained by forming transparent conductive film 1b made of ITO on a glass plate 1a. A counter electrode 4 is composed, e.g., of 50pts.wt. Fe3(WO4)3, 50pts. wt. carbon paste, and a polytetrafluoroethylene powder in pts.wt., as shown in the table, and they are pulverized and mixed with a high speed mixer, and formed into an about 0.2mm. thick sheet. The electrode 4 has a background material 6 and it is bonded to a counter electrode base 3 through a transparent conductive film 3b.

Description

【発明の詳細な説明】 に係り、対向電極の単独形成を可能ならしめ、それによ
ってエレクトロクロミック表示素子製造の作業性を改善
するとともに、均一でヒビ割れのない対向電極を得てエ
レクトロクロミック表示素子の品質向上をはかることを
目的とする。[Detailed Description of the Invention] According to the present invention, it is possible to form a counter electrode independently, thereby improving workability in manufacturing an electrochromic display element, and obtaining a uniform and crack-free counter electrode to produce an electrochromic display element. The purpose is to improve the quality of

（１） 従来、エレクトロクロミック表示素子の対向電極は、タ
ングステン酸鉄（Ｆ　８２　（ＷＯ４　）　３　）、二
酸化マンガン（ＭｎＯ２）などの対向極材料、カーボン
ペースト（カーボンを少量のエポキシ樹脂でペースト化
したもの）およびプロピレンカーボネートからなる泥状
混合物を導電性ガラスなどの対向極基板上にへヶで塗布
し、加熱してプロピレンカーボネートを除去するととも
にエポキシ樹脂を硬化させることによって形成されてい
た。(1) Conventionally, the counter electrode of an electrochromic display element has been made of counter electrode materials such as iron tungstate (F 82 (WO4) 3 ), manganese dioxide (MnO2), carbon paste (carbon paste made by pasting carbon with a small amount of epoxy resin), etc. The epoxy resin was formed by applying a mud-like mixture consisting of propylene carbonate and propylene carbonate onto a counter electrode substrate such as conductive glass, and heating to remove the propylene carbonate and harden the epoxy resin.

しかしながら、上記泥状混合物より得られる対向電極は
可撓性がなく、単独では自己保持できないので必ず基板
を必要とし、かつ均一な厚みの皮膜をつくりがたく、し
かもヒビ割れが発生しやすいため、対向電極の抵抗が高
くなり、表示極の着色、消色の応答速度を低下させる原
因となっていた。However, the counter electrode obtained from the above muddy mixture is not flexible and cannot be self-supported by itself, so it always requires a substrate, and it is difficult to form a film with a uniform thickness, and cracks are likely to occur. The resistance of the counter electrode becomes high, which causes a decrease in the response speed for coloring and decoloring the display electrode.

本発明は上述した従来技術の欠点を解消するもので、対
向電極の対向極材料と導電助剤との結着剤としてポリテ
トラフルオルエチレン粉末を用いることによって対向電
極の単独形成を可能ならしく２） め、それによってエレクトロクロミック表示素子製造の
作業性を改善するとともに、均一でかつヒビ割れのない
対向電極が得られるようにしてエレクトロクロミック表
示素子の品質向上をはかったものである。The present invention solves the above-mentioned drawbacks of the prior art, and by using polytetrafluoroethylene powder as a binder between the counter electrode material of the counter electrode and the conductive additive, it is possible to form the counter electrode independently. 2) This improves the workability of manufacturing electrochromic display elements, and improves the quality of electrochromic display elements by making it possible to obtain uniform and crack-free counter electrodes.

対向電極の対向極材料としては、たとえばＦｅ２　（Ｗ
Ｏ４）３、ＭｎＯ２、ＭｏＯ３、ＫＦｅ２（ＣＮ）ｓ　
、ＷＯ３などが用いられ、導電助剤としてはたとえばカ
ーボンが用いられる。このカーボンは作業性などの関係
から通常カーボンペースト（カーボンを少量のエポキシ
樹脂でペースト化したもの）として使用に供される。こ
のカーボンペースト中のエポキシ樹脂も結着作用を有す
るが、このエポキシ樹脂はポリテトラフルオルエチレン
粉末の結着作用に悪影響を及ぼすことがなく、したがっ
て本発明の実施に際して障害とならない。なお、本発明
においては、ポリテトラフルオルエチレン粉末の結着作
用に悪影響を及ぼさないものであれば、上記エポキシ樹
脂はもとより、他の結着作用を有する物質が含まれてい
てもよい。As the counter electrode material of the counter electrode, for example, Fe2 (W
O4)3, MnO2, MoO3, KFe2(CN)s
, WO3, etc., and carbon, for example, is used as the conductive aid. This carbon is usually used as a carbon paste (carbon paste made with a small amount of epoxy resin) for reasons such as workability. Although the epoxy resin in this carbon paste also has a binding effect, this epoxy resin does not adversely affect the binding effect of the polytetrafluoroethylene powder, and therefore does not pose an obstacle to the implementation of the present invention. In addition, in the present invention, in addition to the above-mentioned epoxy resin, other substances having a binding effect may be included as long as they do not adversely affect the binding effect of the polytetrafluoroethylene powder.

（３） 対向電極の形成は、対向極材料、カーボンペーストおよ
びポリテトラフルオルエチレン粉末の混合物をロールに
よってシート化することにより行なわれる。シートの厚
みはどのようなエレクトロクロミック表示素子をつくる
かによっても異なるが、通常０．１〜０．５１１ＩＩ１
１にされる。(3) The counter electrode is formed by rolling a mixture of the counter electrode material, carbon paste, and polytetrafluoroethylene powder into a sheet. The thickness of the sheet varies depending on what kind of electrochromic display element is made, but is usually 0.1 to 0.511II1.
Becomes 1.

対向極材料、カーボンペーストおよびポリテトラフルオ
ルエチレン粉末の混合は高速ミキサーで破砕混合するの
が好ましい。ポリテトラフルオルエチレン粉末の使用量
としては対向極材料とカーボンペースト（重量的にはほ
とんどカーボンであると考えられる）との合計１００重
量部に対して５〜３０重量部の範囲が好ましい。なお、
通常、対向極材料とカーボンペーストとの割合は重量比
で１８１にされるので、混合物中の各成分の割合は、通
常、対向極材料５０重量部、カーボンペースト５０重量
部およびポリテトラフルオルエチレン粉末５〜３０重量
部である。The counter electrode material, carbon paste, and polytetrafluoroethylene powder are preferably mixed by crushing with a high-speed mixer. The amount of polytetrafluoroethylene powder to be used is preferably in the range of 5 to 30 parts by weight based on the total of 100 parts by weight of the counter electrode material and carbon paste (which is considered to be mostly carbon in terms of weight). In addition,
Usually, the ratio of the counter electrode material to the carbon paste is 181 by weight, so the ratio of each component in the mixture is usually 50 parts by weight of the counter electrode material, 50 parts by weight of the carbon paste, and polytetrafluoroethylene. The powder is 5 to 30 parts by weight.

次に実施例をあげて本発明を説明する。Next, the present invention will be explained with reference to Examples.

タングステン酸鉄（Ｆｅ２　（ＷＯ４）３）５０重（４
） 置部、カーボンペースト５０重量部およびポリテトラフ
ルオルエチレン粉末を第１表に示す量（重量部で表示）
とし、これを高速ミキサーで破砕混合し、該混合物をロ
ールで厚さ０．２１ＩＩＩｌｌのシートにし、得られた
対向電極を用いて、第１図に示すようなエレクトロクロ
ミック表示素子を製造した。Iron tungstate (Fe2 (WO4)3) 50 weight (4
) 50 parts by weight of carbon paste and polytetrafluoroethylene powder in the amounts shown in Table 1 (expressed in parts by weight)
This was crushed and mixed using a high-speed mixer, and the mixture was rolled into a sheet with a thickness of 0.21IIII. Using the obtained counter electrode, an electrochromic display element as shown in FIG. 1 was manufactured.

第１図において１は表示極基板で、この表示極基板１は
ガラス板よりなる透明基板１ａにＩＴＯの透明導電膜１
ｂを形成してなるものである。２はエレクトロクロミッ
ク物質よりなる表示極で、この表示極２は上記表示極基
板１の透明導電膜ｌｂ上に形成され、素子内部側に配置
されている。そして、本実施例においては、この表示極
２を構成するエレクトロクロミック物質としてＷＯ３が
用いられている。３は対向極基板で、この対向極基板３
はガラス基板３ａ上にＩＴＯの透明導電膜３ｂを形成し
た導電性ガラスよりなるものである。本実施例では、こ
の対向極基板３も上記表示極基板１と同様に透明に形成
されているが、対向極基板３は透明でなくてもよい、４
は前記のように単独でシー（５） ト状に形成された対向電極で、この対向電極４は対向極
基板３との密着性をよくするためカーボンペースト５に
よって対向極基板３の透明導電膜３ｂに接着されている
。そして、この対向電極４は前記表示極２と対向するよ
うに素子内部側に配置されている。In FIG. 1, 1 is a display electrode substrate, and this display electrode substrate 1 has a transparent conductive film of ITO on a transparent substrate 1a made of a glass plate.
b. Reference numeral 2 denotes a display electrode made of an electrochromic substance, and this display electrode 2 is formed on the transparent conductive film lb of the display electrode substrate 1, and is disposed inside the device. In this embodiment, WO3 is used as the electrochromic material constituting the display electrode 2. 3 is a counter electrode substrate, and this counter electrode substrate 3
is made of conductive glass with a transparent conductive film 3b of ITO formed on a glass substrate 3a. In this embodiment, the counter electrode substrate 3 is also formed transparent like the display electrode substrate 1, but the counter electrode substrate 3 may not be transparent.
is a counter electrode formed singly in the form of a sheet (5) as described above, and this counter electrode 4 is coated with a transparent conductive film of the counter electrode substrate 3 using carbon paste 5 in order to improve adhesion to the counter electrode substrate 3. It is glued to 3b. The counter electrode 4 is arranged inside the device so as to face the display electrode 2.

６は上記表示極２と対向電極４との間に配置された背景
材で、この背景材６は二酸化チタンを分散含有させたイ
オン透過性のポリテトラフルオルエチレン膜よりなるも
のである。７はプロピレンカーボネートにＬ　Ｉ　Ｃ１
ｏ４を１．０モル／１溶解させ、水をプロピレンカーボ
ネート１００容量部に対して２容量部の割合で添加した
液状の電解質であり、８は表示極基板１と対向極基板３
との間の周辺部を封止する樹脂製のスペーサである。A background material 6 is disposed between the display electrode 2 and the counter electrode 4, and the background material 6 is made of an ion-permeable polytetrafluoroethylene film containing titanium dioxide dispersed therein. 7 is L I C1 to propylene carbonate
It is a liquid electrolyte in which 1.0 mol/1 O4 is dissolved and water is added at a ratio of 2 parts by volume to 100 parts by volume of propylene carbonate, and 8 is a display electrode substrate 1 and a counter electrode substrate 3.
This is a resin spacer that seals the peripheral area between the two.

前記シート作製時のＮ易さと、該シートを対向電極とし
て用いたエレクトロクロミック表示素子の抵抗を第１表
に示す。Table 1 shows the ease of N during production of the sheet and the resistance of an electrochromic display element using the sheet as a counter electrode.

（６） 第１表 （注）　ＰＴＦＥ量とはポリテトラフルオルエチレン粉
末の量である。(6) Table 1 (Note) The amount of PTFE is the amount of polytetrafluoroethylene powder.

第１表に示す結果から明らかなように、ポリテトラフル
オルエチレン粉末をＦ１１１２　（ＷＯ４）３とカーボ
ンペーストとの合計１００重量部に対して５重量部以上
使用するとシート化が容易になり、また３０重量部を超
えると素子抵抗が高くなる。As is clear from the results shown in Table 1, using 5 parts by weight or more of polytetrafluoroethylene powder per 100 parts by weight of F1112 (WO4)3 and carbon paste facilitates sheeting. If it exceeds 30 parts by weight, the element resistance will increase.

（７） 実施例では、対向電極の対向極材料としてＦｅ２（ＷＯ
４）３を用いた場合を示したが、本発明はそれのみに限
られることなく、たとえばＭｎＯ２、ＭｎＯ３、ＫＰＯ
３（ＣＮ）６、ＷＯ３などを対向電極の対向極材料とし
て用いる場合にも適用される。(7) In the example, Fe2 (WO
4) Although the case where 3 is used is shown, the present invention is not limited thereto, and for example, MnO2, MnO3, KPO
This also applies to cases where 3(CN)6, WO3, etc. are used as the counter electrode material of the counter electrode.

また、実施例では表示極を構成するエレクトロクロミッ
ク物質としてＷＯ３を用いたが、それに代えてたとえば
１ｒ０２、ＭｎＯ３などの遷移金属酸化物、プルシャン
ブルー、テトラチアフルバレン誘導体、ビオロゲン誘導
体などを用いてもよい。さらに電解質も実施例に例示の
ものに限られることなく、着色、消色反応に必要なイオ
ン種が移動可能なものであれば液体、固体を問わずどの
ような系でもよい。Further, in the examples, WO3 was used as the electrochromic substance constituting the display electrode, but instead, transition metal oxides such as 1r02 and MnO3, Prussian blue, tetrathiafulvalene derivatives, viologen derivatives, etc. may be used. good. Furthermore, the electrolyte is not limited to those exemplified in the examples, but any type of system, whether liquid or solid, may be used as long as the ionic species necessary for coloring and decoloring reactions can be transferred.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明に係るエレクトロクロミック表示素子の
一例を示す断面図である。 ２・・・表示極、　４・・・対向電極、　７・・・電解
質（８）FIG. 1 is a sectional view showing an example of an electrochromic display element according to the present invention. 2... Display electrode, 4... Counter electrode, 7... Electrolyte (8)

Claims (2)

【特許請求の範囲】[Claims] （１）表示極、対向電極および電解質を有してなるエレ
クトロクロミック表示素子において、対向電極の対向極
材料と導電助剤との結着剤としてポリテトラフルオルエ
チレン粉末を用いたことを特徴とするエレクトロクロミ
ック表示素子。(1) An electrochromic display element comprising a display electrode, a counter electrode, and an electrolyte, characterized in that polytetrafluoroethylene powder is used as a binder between the counter electrode material of the counter electrode and the conductive additive. electrochromic display element. （２）ポリテトラフルオルエチレン粉末の使用量が対向
極材料と導電助剤との合計１００重量部に対して５〜３
０重量部である特許請求の範囲第１項記載のエレクトロ
クロミック表示素子。(2) The amount of polytetrafluoroethylene powder used is 5 to 3 parts by weight per 100 parts by weight of the counter electrode material and conductive additive.
The electrochromic display element according to claim 1, which contains 0 parts by weight.
JP58193721A 1983-10-17 1983-10-17 Electrochromic display element Pending JPS6084533A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58193721A JPS6084533A (en) 1983-10-17 1983-10-17 Electrochromic display element

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58193721A JPS6084533A (en) 1983-10-17 1983-10-17 Electrochromic display element

Publications (1)

Publication Number Publication Date
JPS6084533A true JPS6084533A (en) 1985-05-13

Family

ID=16312686

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58193721A Pending JPS6084533A (en) 1983-10-17 1983-10-17 Electrochromic display element

Country Status (1)

Country Link
JP (1) JPS6084533A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012501008A (en) * 2008-08-28 2012-01-12 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド Electrochromic devices

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012501008A (en) * 2008-08-28 2012-01-12 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド Electrochromic devices

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