JPH0141970B2 - - Google Patents
Info
- Publication number
- JPH0141970B2 JPH0141970B2 JP10483781A JP10483781A JPH0141970B2 JP H0141970 B2 JPH0141970 B2 JP H0141970B2 JP 10483781 A JP10483781 A JP 10483781A JP 10483781 A JP10483781 A JP 10483781A JP H0141970 B2 JPH0141970 B2 JP H0141970B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- electrochromic
- counter electrode
- display device
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000004040 coloring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 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 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
- 230000002441 reversible effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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】
本発明はエレクトロクロミツク表示装置に関す
る。詳しくは、酸化タングステン膜をエレクトロ
クロミツク物質とし、イオン供給源を電解液とし
たエレクトロクロミツク表示装置において、活性
炭又はグラフアイトにシランカツプリング剤を含
有させ結着剤と共に成形した対極を用いたことを
特徴とする高信頼性エレクトロクロミツク表示装
置に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to electrochromic displays. Specifically, in an electrochromic display device in which a tungsten oxide film is used as an electrochromic substance and an ion supply source is an electrolytic solution, a counter electrode made of activated carbon or graphite containing a silane coupling agent and molded together with a binder is used. The present invention relates to a highly reliable electrochromic display device characterized by the following.
近年、エレクトロクロミツク物質、例えば三酸
化タングステン（WO3）等の遷移金属酸化物の
酸化還元反応による可逆的な発色・消色反応を利
用したエレクトロクロミツク表示装置が開発され
ている。第１図に、このような一般的なエレクト
ロクロミツク表示装置の構造を模型的に示す。 In recent years, electrochromic display devices have been developed that utilize reversible coloring and decoloring reactions caused by redox reactions of electrochromic materials, such as transition metal oxides such as tungsten trioxide (WO 3 ). FIG. 1 schematically shows the structure of such a general electrochromic display device.
透明ガラス基板１の内面に酸化スズ（SnO2）
や酸化インジウム（In2O3）等の透明導電膜２を
表示パターン例えば数字形状に形成し、この導電
膜２上にWO3等のエレクトロクロミツク物質層
３を被着する。ガラス基板１は容器状裏面基板７
と合せ、形成される空間内部にイオン供給源であ
る電解液８、多孔性白色基板４、対向電極５が収
納される。６は焦電体である。 Tin oxide (SnO 2 ) on the inner surface of transparent glass substrate 1
A transparent conductive film 2 made of indium oxide (In 2 O 3 ) or the like is formed in a display pattern, for example in the shape of numbers, and an electrochromic material layer 3 made of WO 3 or the like is deposited on the conductive film 2 . The glass substrate 1 is a container-shaped back substrate 7
In addition, an electrolytic solution 8 as an ion supply source, a porous white substrate 4, and a counter electrode 5 are housed inside the space formed. 6 is a pyroelectric substance.
従来の構成では対向電極は表示極と同じWO3
膜や第１図のような焦電体を含むグラフアイトの
圧縮成形体が用いられている。そして、このよう
な構成のエレクトロクロミツク表示装置において
は、WO3層３へ電解液８よりリチウムイオン
（Li+）又はプロトン（H+）が注入されることに
より（還元反応）、発生を生じ、また逆にエレク
トロクロミツク層からLi+又はH+が電解液中に拡
散放出することによつて（酸化反応）消色を行な
うものである。 In the conventional configuration, the counter electrode is the same WO 3 as the display electrode.
A graphite compression molded body containing a film or a pyroelectric material as shown in FIG. 1 is used. In an electrochromic display device having such a configuration, lithium ions (Li + ) or protons (H + ) are injected from the electrolytic solution 8 into the WO 3 layer 3 (reduction reaction), causing generation. , and conversely, decolorization is achieved by diffusing and releasing Li + or H + from the electrochromic layer into the electrolyte (oxidation reaction).
こうしたエレクトロクロミツク表示装置では、
適当な発色、消色応答速度を得るためには印加電
圧信号を約1.5V以上にしなければならず、この
ような電圧で長時間発色、消色サイクルを繰返す
につれて、対向電極表面の不活性化や電解質の分
解などにより反応電位の変化が生じ、発色が生じ
なくなつたり消え残りが生じたりするという欠点
がある。 In these electrochromic display devices,
In order to obtain appropriate coloring and decoloring response speeds, the applied voltage signal must be approximately 1.5V or more, and as the coloring and decoloring cycles are repeated for a long time with such a voltage, the surface of the counter electrode becomes inactivated. There is a drawback that the reaction potential changes due to decomposition of the electrolyte or the like, resulting in no color development or color remaining.
本発明は、このような欠点を除去した比較的低
電圧信号で速やかな発色・消色を呈するエレクト
ロクロミツク表示装置を提供するものである。 The present invention provides an electrochromic display device that eliminates these drawbacks and exhibits rapid coloring and decoloring with a relatively low voltage signal.
エレクトロクロミツク表示装置の発色・消色は
エレクトロクロミツク層、例えばWO3中への電
解液からのLi+もしくはH+の注入、WO3層内部
から電解液中への上記イオンの拡散放出により生
じるものであるが同時に対向電極側においても表
示極と逆の電気化学反応が生じている。即ち、こ
れら両電極における各反応は電気的に等量である
から表示極における発色・消色反応の速度は、対
向電極側の酸化、還元反応に大きく影響を受ける
ことになる。 Coloring and decoloring of electrochromic display devices is achieved by injecting Li + or H + from the electrolyte into the electrochromic layer, such as WO 3 , or by diffusing and releasing the above ions from inside the WO 3 layer into the electrolyte. However, at the same time, an electrochemical reaction opposite to that of the display electrode is also occurring on the counter electrode side. That is, since each reaction at these two electrodes is electrically equivalent, the speed of the coloring/decoloring reaction at the display electrode is greatly influenced by the oxidation/reduction reaction at the counter electrode.
前記した従来のエレクトロクロミツク表示装置
では、発色・消色の応答速度は実際には対向電極
における酸化、還元反応速度によつて決定されて
いる。 In the conventional electrochromic display device described above, the response speed of color development and decolorization is actually determined by the oxidation and reduction reaction rates at the counter electrode.
本発明はこの対向電極の酸化、還元反応の迅速
化をはかつたものであり、対向電極として活性炭
又はグラフアイトに次の構造式で表わされるシラ
ンカツプリング剤を好ましくは0.01〜５重量％含
有させ、結着剤と共に成形した電極を使用したも
のである。 The present invention aims to speed up the oxidation and reduction reactions of the counter electrode, and the counter electrode preferably contains 0.01 to 5% by weight of a silane coupling agent represented by the following structural formula in activated carbon or graphite. This uses electrodes molded together with a binder.
Ｒ：アルキル基、アルコキシ基、フエニル基、ビ
ニル基、エポキシ基を有する基又はアミノ基を
有する基。 R: a group having an alkyl group, an alkoxy group, a phenyl group, a vinyl group, an epoxy group, or a group having an amino group.
R′：アルキル基又は加水分解性基
Ｘ：加水分解性基
対向電極の活性炭又はグラフアイトに微量のシ
ランカツプリング剤を添加することにより界面の
接触電位に微妙な影響を与え明確な理由は不明で
あるが、発色、消色に必要な印加電圧が低下す
る。R': Alkyl group or hydrolyzable group However, the applied voltage required for color development and decolorization decreases.
以下に本発明の実施例を説明する。 Examples of the present invention will be described below.
透明ガラス基板１内面にIn2O3膜を表示パター
ンおよびリード部パターンに被着して透明導電膜
２を形成する。この透明導電膜２表示パターン上
にWO3を電子ビーム加熱法によりマスク蒸着し、
約3000Å厚のWO3層３を形成する。対向電極５
は活性炭と結着剤としてカルボキシメチルセルロ
ーズ（CMC）を４：１にて混合し、これにメチ
ルトリメトキシシラン0.5重量％添加し充分撹拌
混合した後、チタン網焦電体を挾んで1ton／cm2の
圧力で加圧成型した。電解液８はプロピレンカー
ボネートに１モル濃度の硼弗化リチウム
（LiBF4）を溶解したものを使用し、多孔性白色
基板４はアルミナセラミツク板を用いた。 A transparent conductive film 2 is formed by depositing an In 2 O 3 film on the display pattern and the lead pattern on the inner surface of the transparent glass substrate 1 . On this transparent conductive film 2 display pattern, WO 3 was vapor-deposited using an electron beam heating method using a mask.
Form a WO 3 layer 3 with a thickness of about 3000 Å. Counter electrode 5
Activated carbon and carboxymethyl cellulose (CMC) as a binder are mixed at a ratio of 4:1, 0.5% by weight of methyltrimethoxysilane is added to the mixture, and the mixture is thoroughly stirred and mixed, and then a titanium mesh pyroelectric material is sandwiched between the mixture and the mixture is heated at 1 ton/cm. Pressure molded at a pressure of 2 . The electrolytic solution 8 was prepared by dissolving 1 molar lithium borofluoride (LiBF 4 ) in propylene carbonate, and the porous white substrate 4 was an alumina ceramic plate.
このようにして作成したエレクトロクロミツク
表示装置に−1.0ボルト（0.2秒）で書込み、＋1.0
ボルト（0.2秒）で消去の寿命試験を行なつた所、
９×106サイクルを経過しても、表示、消去に何
ら異常を認めなかつた。なお、−1.0ボルト（0.2
秒）で従来の−1.5ボルト（0.5秒）電圧印加と同
等の表示コントラストが得られており、従来より
も低電圧で表示動作が可能となり、この低電圧化
により、高速応答化、長寿命化が可能となつた。 The electrochromic display device created in this way is written with -1.0 volts (0.2 seconds) and +1.0 volts (0.2 seconds) is written.
After performing an erase life test using volts (0.2 seconds),
Even after 9×10 6 cycles, no abnormality was observed in display or erasure. In addition, -1.0 volt (0.2
The same display contrast as the conventional voltage application of -1.5 volts (0.5 seconds) can be obtained, and display operation can be performed with lower voltage than before, and this lower voltage results in faster response and longer life. became possible.
本発明に使用可能なシランカツプリング剤は、
濃度の条件を最適に選べばきわめて多種類のもの
が対象となるが、代表的な例を次に示す。 Silane coupling agents that can be used in the present invention include:
If the concentration conditions are optimally selected, a wide variety of substances can be targeted, but typical examples are shown below.
●メチルトリメトキシシラン
CH3Si（OCH3）3
●ｎ−プロピルトリエトキシシラン
CH3CH2CH2Si（OEt）3
●アミノプロピルトリメトキシシラン
H2NCH2CH2CH2Si（OCH3）3
上述の如く、本発明によれば活性炭又はグラフ
アイトにシランカツプリング剤を含有させ且つ結
着剤と共に成形された対向電極を用いたので、従
来より低電圧で且つ従来と同様のコントラストの
表示動作（発色・消色）が可能となつた。また、
前述の低電圧化により長時間の発色・消色サイク
ルを繰返しても、対向電極表面の不活性化や電解
質の分解などにより、発色が生じなくなつたり消
え残りが生じたりするという従来の欠点を防止で
きる。●Methyltrimethoxysilane CH 3 Si (OCH 3 ) 3 ●n-Propyltriethoxysilane CH 3 CH 2 CH 2 Si (OEt) 3 ●Aminopropyltrimethoxysilane H 2 NCH 2 CH 2 CH 2 Si (OCH 3 ) 3 As described above, according to the present invention, since a counter electrode made of activated carbon or graphite containing a silane coupling agent and molded together with a binder is used, display operation can be performed at a lower voltage than before and with the same contrast as before. (color development/decolorization) is now possible. Also,
Due to the lower voltage mentioned above, even if the coloring/decoloring cycle is repeated for a long time, the conventional disadvantage is that coloring stops occurring or color remains due to deactivation of the counter electrode surface or decomposition of the electrolyte. It can be prevented.
従つて、長寿命のエレクトロクロミツク表示装
置が実現できるものである。 Therefore, a long-life electrochromic display device can be realized.
第１図は従来例および本発明に係わるエレクト
ロクロミツク表示装置の断面図を示す。
FIG. 1 shows cross-sectional views of electrochromic display devices according to the prior art and the present invention.
Claims (1)
クロミツク物質を介して配置される表示電極と、
該表示電極と対向して配置された対向電極とを有
するエレクトロクロミツク表示装置において、前
記対向電極が、活性炭又はグラフアイトに以下の
一般式で表わされるシランカツプリング剤を含有
させ且つ結着剤と共に成形されたことを特徴とす
るエレクトロクロミツク表示装置。 Ｒ：アルキル基、アルコキシ基、フエニル基、ビ
ニル基、エポキシ基を有する基又はアミノ基を
有する基 R′：アルキル基又は加水分解性基 Ｘ：加水分解性基[Scope of Claims] 1. An electrochromic material, a display electrode disposed via the electrochromic material,
In an electrochromic display device having a counter electrode disposed opposite to the display electrode, the counter electrode comprises activated carbon or graphite containing a silane coupling agent represented by the following general formula, and a binder. An electrochromic display device characterized in that it is molded with. R: a group having an alkyl group, an alkoxy group, a phenyl group, a vinyl group, an epoxy group, or a group having an amino group R': an alkyl group or a hydrolyzable group X: a hydrolyzable group
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10483781A JPS587127A (en) | 1981-07-03 | 1981-07-03 | electrochromic display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10483781A JPS587127A (en) | 1981-07-03 | 1981-07-03 | electrochromic display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS587127A JPS587127A (en) | 1983-01-14 |
| JPH0141970B2 true JPH0141970B2 (en) | 1989-09-08 |
Family
ID=14391466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10483781A Granted JPS587127A (en) | 1981-07-03 | 1981-07-03 | electrochromic display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS587127A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018091910A (en) * | 2016-11-30 | 2018-06-14 | 株式会社カネカ | Electrochromic dimmer |
-
1981
- 1981-07-03 JP JP10483781A patent/JPS587127A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS587127A (en) | 1983-01-14 |
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