JPS6360430A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPS6360430A JPS6360430A JP61204055A JP20405586A JPS6360430A JP S6360430 A JPS6360430 A JP S6360430A JP 61204055 A JP61204055 A JP 61204055A JP 20405586 A JP20405586 A JP 20405586A JP S6360430 A JPS6360430 A JP S6360430A
- Authority
- JP
- Japan
- Prior art keywords
- counter electrode
- material layer
- electrode material
- component
- tungsten oxide
- 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
Links
- 239000007772 electrode material Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 27
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 37
- -1 tungsten oxide compound Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005611 electricity Effects 0.000 abstract description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 55
- 239000010408 film Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
この発明は、三酸化タングステンからなるエレクトロク
ロミック物質の電気化学的反応による色変化を利用して
各種ディスプレイ装置の表示を行うエレクトロクロミッ
ク表示素子に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrochromic display element that performs display on various display devices by utilizing color change caused by an electrochemical reaction of an electrochromic substance made of tungsten trioxide. .
［従来の技術］
この種エレクトロクロミンク表示素子は、たとえば図面
に示すように、透光性である表示側基板１の内面に透明
電極層２を介して三酸化タングステンからなるエレクト
ロクロミック物質層３を設けて所要パターンを構成する
セグメントに分画された表示極４とし、対向側基板５の
内面に電極層６を介して対極物質層７を設けて対向極８
とし、側基板１，５を両極４，８が対向する形で周辺部
にスペーサ９を介在して対向配置するとともに、上記両
極４，８間に電解液１０を封入した構造を備えている。[Prior Art] This type of electrochromic display element, as shown in the drawing, for example, has an electrochromic material layer 3 made of tungsten trioxide on the inner surface of a light-transmitting display side substrate 1 via a transparent electrode layer 2. A display electrode 4 is provided which is divided into segments constituting a required pattern, and a counter electrode material layer 7 is provided on the inner surface of the counter substrate 5 via an electrode layer 6 to form a counter electrode 8.
The side substrates 1 and 5 are arranged so that the poles 4 and 8 face each other with a spacer 9 interposed in the periphery thereof, and an electrolytic solution 10 is sealed between the poles 4 and 8.
図中、１１は両極４，８間に介在された背景材、１２は
リード端子、１３は電極層６と対向側のリード端子１２
とを電気的に接続する導電層、１４は絶縁保護膜である
。なお、対向側基板５を金属板にて構成することによっ
て対向極８の電極層６を省略した構造のものもある（文
献不詳）。In the figure, 11 is a background material interposed between the electrodes 4 and 8, 12 is a lead terminal, and 13 is a lead terminal 12 on the side opposite to the electrode layer 6.
14 is an insulating protective film. Note that there is also a structure in which the electrode layer 6 of the counter electrode 8 is omitted by constructing the counter substrate 5 from a metal plate (document unknown).
上記構成の表示素子では、対向極８を共通電極として所
要の表示極４に電圧を印加することにより、エレクトロ
クロミック物質である三酸化タングステンと対極物質と
の電解液を介した反応にて着色変化し、所要の表示がな
される。この着色変化は、たとえば電解液１０の電解質
がリチウム塩であるとき、次式で示される。In the display element with the above configuration, by applying a voltage to the required display electrodes 4 using the counter electrode 8 as a common electrode, the color changes due to the reaction between tungsten trioxide, which is an electrochromic material, and the counter electrode material via the electrolyte. Then, the required display is made. This color change is expressed by the following equation, for example, when the electrolyte of the electrolytic solution 10 is a lithium salt.
ＷＯ３＋ ｎＬ ｓ ＋ ｎ ｅ ＃ＬｉｎＷＯ３（
透明） （青 色）ところで、対向
極８の対極物質層７としては、従来より、真空蒸着やス
パッタリングなどの高真空下で行う薄膜形成方法にて被
着形成した三酸化タングステンの単独層、三酸化タング
ステン、タングステン酸鉄（Ｆｅ２Ｏ３・３ＷＯ，）、
三酸化マンガンの如き対極物質と結合剤および導電性粉
末を含む塗料の塗膜層、あるいは導電性粉末および結合
剤を含む塗膜層に活性炭素繊維を圧着したものなどが汎
用されている（特開昭５６−９１２２２号公報、同５７
−６８２６号公報、同５９−１９２２８２号公報など）
。またこれら以外にも、たとえば真空蒸着によって三酸
化タングステンを主体としてレニウムまたはマンガンを
含む層を形成したり（特開昭５４−４１７６０号公報）
、対向側基板にタングステン板を使用してその表面を酸
化する（特開昭５７−６４２８２号公報）ことも提案さ
れている。WO3+ nL s + ne #LinWO3(
(transparent) (blue) By the way, as the counter electrode material layer 7 of the counter electrode 8, conventionally, a single layer of tungsten trioxide, a tungsten trioxide layer deposited by a thin film forming method performed under high vacuum such as vacuum evaporation or sputtering, etc. Tungsten oxide, iron tungstate (Fe2O3.3WO,),
A coating layer of a paint containing a counter electrode material such as manganese trioxide, a binder and a conductive powder, or a coating layer containing a conductive powder and a binder with activated carbon fibers bonded to the coating layer are commonly used. Publication No. 56-91222, No. 57
-6826 publication, 59-192282 publication, etc.)
. In addition to these, for example, a layer containing rhenium or manganese mainly composed of tungsten trioxide may be formed by vacuum evaporation (Japanese Unexamined Patent Publication No. 54-41760).
It has also been proposed to use a tungsten plate as the opposing substrate and oxidize its surface (Japanese Patent Application Laid-Open No. 57-64282).
しかるに、エレクトロクロミック表示素子においては表
示特性上から表示極と対向極の電位の差が小さいことが
望ましく、このような観点からすれば、対極物質層７は
エレクトロクロミック物質層３と同じ電位のもの、つま
り三酸化タングステンの単独層であることが好ましい。However, in an electrochromic display element, it is desirable that the difference in potential between the display electrode and the counter electrode is small from the viewpoint of display characteristics, and from this point of view, the counter electrode material layer 7 should have the same potential as the electrochromic material layer 3. That is, a single layer of tungsten trioxide is preferable.
しかしながら、上記単独層を形成するには既述の如き真
空蒸着やスパッタリングなどの薄膜形成方法もしくは前
記提案の如きタングステン板の表面酸化方法を採用せざ
るを得ないが、前者の方法では装置的に大掛かりになる
とともに複雑な制御操作と長い処理時間を要して作業性
および量産性が悪くコスト高になり、とくに素子の大型
化に伴って対極物質層を大面積化する場合にコスト的な
不利がより顕著となり、かつピンホールなどの欠陥が生
じやすくなって安定した性状、特性のものを恒常的に得
にくいという問題がある。また、後者の方法では、基板
自体が非常に高価であり、しかも酸化膜厚の制御が困難
であることから、実用性に乏しい。However, in order to form the above-mentioned single layer, it is necessary to adopt a thin film forming method such as vacuum evaporation or sputtering as described above, or a surface oxidation method of a tungsten plate as proposed above, but the former method does not require much equipment. It becomes large-scale and requires complicated control operations and long processing time, resulting in poor workability and mass production, resulting in high costs, and is particularly disadvantageous in cost when increasing the area of the counter electrode material layer as the device becomes larger. There is a problem that defects such as pinholes are more likely to occur and it is difficult to consistently obtain stable properties and characteristics. Furthermore, in the latter method, the substrate itself is very expensive, and it is difficult to control the oxide film thickness, so it is not practical.
この発明は、上述の事情に鑑みてなされたものであり、
対極物質層を極めて容易にかつ低コストで形成でき、し
かも注入電気量や応答速度などの表示特性面でもすぐれ
たエレクトロクロミック表示素子を提供することを目的
としている。This invention was made in view of the above circumstances,
The object of the present invention is to provide an electrochromic display element in which a counter electrode material layer can be formed extremely easily and at low cost, and which also has excellent display characteristics such as the amount of injected electricity and response speed.
［問題点を解決するための手段］
この発明者らは、上記目的を達成するために鋭意検討を
重ねた結果、対極物質層を分子内に特定成分を含む酸化
タングステン化合物にて構成した場合、該対極物質層が
上記酸化タングステン化合物の溶液のスピンコーティン
グや該溶液中への基板浸漬によって極めて容易に形成で
き、しかも従来の真空蒸着やスパッタリングなどによっ
て形成した三酸化タングステンの単独層からなる対極物
質層を有するものに比較して注入電気量や応答速度など
の表示性能面で遜色のないエレクトロクロミック表示素
子となることを見い出し、この発明をなすに至った。[Means for Solving the Problems] As a result of extensive studies to achieve the above object, the inventors found that when the counter electrode material layer is composed of a tungsten oxide compound containing a specific component in the molecule, The counter electrode material layer can be formed extremely easily by spin-coating a solution of the tungsten oxide compound or dipping the substrate in the solution, and furthermore, the counter electrode material is made of a single layer of tungsten trioxide formed by conventional vacuum evaporation, sputtering, etc. The present inventors have discovered that an electrochromic display element can be produced that is comparable in display performance, such as the amount of electricity injected and response speed, to those having layers, and this invention has been completed.
すなわち、この発明は、少なくとも表示側が透光性であ
る一対の基板が対向配置され、表示側基板の内面に三酸
化タングステンからなるエレクトロクロミンク物質層を
有する表示極が形成され、対向側基板の内面に対極物質
層を有する対向極が形成され、これら両極間に電解液が
封入されてなるエレクトロクロミック表示素子において
、上記対極物質層が分子内にＨ２Ｏ２成分とＨ２Ｏ成分
もしくはこれら同成分とＣＯ２成分を含む酸化タングス
テン化合物からなることを特徴とするエレクトロクロミ
ック表示素子に係る。That is, in the present invention, a pair of substrates having at least a light-transmitting side on the display side are disposed facing each other, a display electrode having an electrochromic substance layer made of tungsten trioxide is formed on the inner surface of the display side substrate, and the display electrode is formed on the inner surface of the display side substrate. In an electrochromic display element in which a counter electrode having a counter electrode material layer on the inner surface is formed and an electrolyte is sealed between these two electrodes, the counter electrode material layer contains H2O2 component and H2O component or these same components and CO2 component in the molecule. The present invention relates to an electrochromic display element characterized by being made of a tungsten oxide compound containing.
〔発明の構成・作用］
この発明において対向極の対極物質層を構成する酸化タ
ングステン化合物は、分子内にＨ２Ｏ□成分とＨ２Ｏ成
分を含むもの、ならびに上記同成分とともにＣＯ□成分
を含むもののいずれでもよく、これら各成分の含有量が
種々異なるものを包含するが、とくに下記一般式；
％式％
が０．１６〜３．５の範囲にある化合物が好適である。[Structure and operation of the invention] In the present invention, the tungsten oxide compound constituting the counter electrode material layer of the counter electrode may be one containing an H2O□ component and a H2O component in the molecule, or one containing a CO□ component in addition to the above-mentioned components. Generally, compounds having various contents of each of these components are included, but compounds having the following general formula; % formula % in the range of 0.16 to 3.5 are particularly suitable.
そして、このような酸化タングステン化合物からなる対
極物質層を形成するには、原料となる酸化タングステン
化合物をイソプロピルアルコールなどのアルコールもし
くは水に好ましくは０．１〜５９’／ｍｌの範囲で溶解
し、この溶液を対向側基板の導電性表面にスピンコード
するか、または該溶液中に上記基板を浸漬したのち、１
００〜３００°Ｃ程度の温度で加熱処理すればよい。In order to form a counter electrode material layer made of such a tungsten oxide compound, the tungsten oxide compound as a raw material is dissolved in alcohol such as isopropyl alcohol or water preferably in a range of 0.1 to 59'/ml, After spin-coding this solution onto the conductive surface of the opposite substrate or immersing the substrate in the solution,
The heat treatment may be performed at a temperature of about 00 to 300°C.
ここで、上記基板としては、ガラス板やセラミック板な
どの表面にインジウム−スズ複合酸化物膜（以下、ＩＴ
Ｏ膜という）の如き透明導電膜を蒸着するか、もしくは
金、白金などの箔状物を圧着して導電層を形成したもの
、ならびにＡＪ、Ｎｉ。Here, as the above-mentioned substrate, an indium-tin composite oxide film (hereinafter, IT
A conductive layer is formed by vapor-depositing a transparent conductive film such as O film, or by press-bonding a foil-like material such as gold or platinum, as well as AJ and Ni.
Ｃｕ％Ｔｉなどの金属板が使用される。A metal plate such as Cu%Ti is used.
また、上記原料となる酸化タングステン化合物は、一般
に金属タングステンまたは炭化タングステンと過酸化水
素との反応にて合成されるもので、通常は前記一般式で
示されるＸが０〜０．２５、ｙが０．０５〜１．０．２
が０．１６〜４．０の範囲にある化合物である。なお、
原料の酸化タングステン化合物に含まれるＨ２Ｏ成分は
対極物質層形成時の加熱処理にて一部蒸散するため、上
記２の値は対極物質層としての酸化タングステン化合物
における前記した好適な２の値よりも大きくなっている
。In addition, the tungsten oxide compound used as the above raw material is generally synthesized by the reaction of metallic tungsten or tungsten carbide with hydrogen peroxide, and usually, X shown in the above general formula is 0 to 0.25, and y is 0.05-1.0.2
is a compound in which the value is in the range of 0.16 to 4.0. In addition,
Since the H2O component contained in the raw material tungsten oxide compound is partially evaporated during the heat treatment during the formation of the counter electrode material layer, the above value 2 is higher than the above-mentioned preferred value 2 for the tungsten oxide compound used as the counter electrode material layer. It's getting bigger.
かくして形成される対極物質層の厚みは２，０００〜１
０，０ＯＯＡ程度とするのがよい。The thickness of the counter electrode material layer thus formed is 2,000 to 1
It is preferable to set it to about 0.0OOA.
一方、この発明の表示素子における表示極は、従来と同
様構成であり、ガラス板などの透光性基板の一面に設け
られたＩＴＯ膜などの透明電極層上に、真空蒸着やスパ
ッタリングなどの簿膜形成方法によって三酸化タングス
テンを２，０００〜ａ、ｏｏｏＸ程度の厚みに被着して
エレクトロクロミック物質層とすればよい。On the other hand, the display electrode in the display element of the present invention has the same structure as the conventional one, and is formed by vacuum deposition, sputtering, etc. on a transparent electrode layer such as an ITO film provided on one surface of a light-transmitting substrate such as a glass plate. Depending on the film forming method, tungsten trioxide may be deposited to a thickness of about 2,000 to 1,000 mm to form an electrochromic material layer.
上述の如き対向極および表示極を有するこの発明のエレ
クトロクロミック表示素子は、対極物質層の酸化タング
ステン化合物とエレクトロクロミック物質層の三酸化タ
ングステンとが非常に近似した成分であってほぼ同じ電
位を示すことから、後述実施例と比較例の表示素子の特
性比較にて示されるように、対極物質層が三酸化タング
ステン ゛の蒸着層からなる表示素子に対して遜色のな
いすぐれた表示特性を発揮する。In the electrochromic display element of the present invention having a counter electrode and a display electrode as described above, the tungsten oxide compound of the counter electrode material layer and the tungsten trioxide of the electrochromic material layer are very similar components and exhibit approximately the same potential. Therefore, as shown in the comparison of characteristics of the display elements of Examples and Comparative Examples described below, the counter electrode material layer exhibits excellent display characteristics comparable to those of display elements made of a vapor-deposited layer of tungsten trioxide. .
なお、表示極と対向極との間に封入される電解液として
は、一般にＬｉＣｌ０＜などのリチウム塩をプロピレン
カーボネートなどの非水系溶媒に溶解したもの、または
これに少量の水を添加したものが使用される。また背景
材は、対向極を隠蔽してそれ自身の色調を表示の背景色
とするもので、三酸化チタンなどの顔料とポリテトラフ
ルオルエチレン粉末との混合物のシート状成形物を使用
するか、あるいは顔料と電解液とのゲル体をスクリーン
印刷法などで対向極上に塗着形成する。The electrolytic solution sealed between the display electrode and the counter electrode is generally one in which a lithium salt such as LiCl0 is dissolved in a non-aqueous solvent such as propylene carbonate, or one in which a small amount of water is added. used. The background material is one that hides the opposing electrode and uses its own color as the background color of the display, and may be a sheet-shaped molded product of a mixture of pigments such as titanium trioxide and polytetrafluoroethylene powder. Alternatively, a gel body of a pigment and an electrolytic solution is applied and formed on the opposing top using a screen printing method or the like.
この発明のエレクトロクロミック表示素子は、表示極の
エレクトロクロミック物質層が三酸化タングステンから
なるものにおいて、対向極の対極物質層が分子中に特定
成分を含有する酸化タングステン化合物にて構成された
ものであり、この対極物質層の形成にあたり、上記酸化
タングステン化合物の溶液を基板上にスピンコーティン
グするか、もしくは該溶液中へ基板を浸漬する手段を採
用でき、従来の三酸化タングステンの単独層からなる対
極物質層の如き真空蒸着やスパッタリングによる層形成
に比較して、作業性が著しく改善されるとともに、簡単
な装置構成によって同時に大量の層形成を短時間で行う
ことが可能であって、製造コストが大幅に低減されると
いう利点があり、しかも注入電気量や応答特性などの表
示特性面でも上記の三酸化タングステンの単独層からな
る対極物質層を設けた表示素子に対して全く遜色のない
性能を具備する。In the electrochromic display element of the present invention, the electrochromic material layer of the display electrode is made of tungsten trioxide, and the counter electrode material layer of the counter electrode is made of a tungsten oxide compound containing a specific component in the molecule. In forming this counter electrode material layer, it is possible to spin-coat a solution of the above-mentioned tungsten oxide compound on the substrate or to immerse the substrate in the solution. Compared to forming material layers by vacuum evaporation or sputtering, workability is significantly improved, and a large amount of layers can be formed simultaneously in a short time with a simple equipment configuration, reducing manufacturing costs. It has the advantage of being significantly reduced, and in terms of display characteristics such as the amount of injected electricity and response characteristics, it has a performance that is completely comparable to the above-mentioned display element with a counter electrode material layer consisting of a single layer of tungsten trioxide. Be equipped.
〔実施例］ 以下、この発明の実施例を比較例とともに示す。〔Example] Examples of the present invention will be shown below along with comparative examples.
゛実施例１
前記一般式中のＸが０．０８〜０゜２５、ｙが０．０５
〜１．０．２が３〜４である酸化タングステン化合物（
ｘ＋ ３Ｆ ＋ Ｚに幅があるのは合成時のばらつきに
よる）を水中に１．５９／ｍｅの濃度で溶解した溶液を
、予め一面側にＩＴＯ膜からなる厚さ２．００ＯＡの電
極層が蒸着形成された透明ガラス製の対向側基板（縦２
５朋、横１８０調、厚さ１．１制）の該電極層上に回転
数３，０００ ｒｐｍにてスピンコードし、乾燥後、１
２Ｏ℃にて６０分間の加熱処理を施して厚さ５．５０
ＯＡの対極物質層を形成し、対向極を構成した。この対
極物質層を分析したところ、前記一般式におけるＸが０
．０８〜０．２５、ｙが０．０５〜１．０．２が０．１
６〜３．５である酸化タングステン化合物から構成され
ていた。゛Example 1 In the above general formula,
~1.Tungsten oxide compound where 0.2 is 3 to 4 (
x + 3F + Z has a wide range due to variations during synthesis), dissolved in water at a concentration of 1.59/me, and an electrode layer of 2.00 OA thick made of ITO film was deposited on one side in advance. Opposite substrate made of transparent glass (vertical 2
5 mm, width 180 scale, thickness 1.1 scale) was spin-coded on the electrode layer at a rotation speed of 3,000 rpm, and after drying,
Heat treated at 20℃ for 60 minutes to a thickness of 5.50
A counter electrode material layer of OA was formed to constitute a counter electrode. Analysis of this counter electrode material layer revealed that X in the general formula is 0.
．． 08-0.25, y is 0.05-1.0.2 is 0.1
It was composed of a tungsten oxide compound having a molecular weight of 6 to 3.5.
一方、予め一面側に厚さ２，０ＯＯＡのＩＴＯ膜からな
る所定パターンの透明電極層と厚さ５．００ＯＡのＳｉ
Ｏ２保護膜が蒸着された透明ガラス製の表示側基板（縦
２７Ｂ、横１８５ｆｌ、厚さ１．１露）の上記透明電極
とに、フォトレジストのマスクを用いて三酸化タングス
テンを真空蒸着して厚さ５゜０００Ａの所定パターンの
エレクトロクロミック物質層を形成し、表示極を構成し
た。On the other hand, a transparent electrode layer with a predetermined pattern made of an ITO film with a thickness of 2,000 OA and a Si layer with a thickness of 5.00 OA on one side in advance.
Using a photoresist mask, tungsten trioxide was vacuum-deposited on the transparent electrode of the transparent glass display side substrate (length: 27B, width: 185 fl, thickness: 1.1 dew) on which the O2 protective film was deposited. An electrochromic material layer having a predetermined pattern with a thickness of 5.000 Å was formed to constitute a display electrode.
そして、上記側基板を表示極と対向極とが向かい合う形
で周辺部に厚さＩＢのポリエステル樹脂製方形環状スペ
ーサを介在して対向配置して接着剤にて固定するととも
に、その際上記両極間に酸化チタン１００重量部とポリ
テトラフルオルエチレン１００重量部とからなる厚さ０
．３ ｒｒｒｍのシート状の背景材を挾み込み、さらに
１モル濃度のＬｉＣｌＯ４を溶解したプロピレンカーボ
ネートからなる電解液５ｍｅを内部に封入し、図面で示
す構造のエレクトロクロミック表示素子を作製した。Then, the side substrates are arranged facing each other with a display electrode and a counter electrode facing each other with a polyester resin rectangular annular spacer having a thickness of IB interposed at the periphery and fixed with adhesive, and at this time, the display electrode and the counter electrode are fixed with an adhesive. 0 thickness consisting of 100 parts by weight of titanium oxide and 100 parts by weight of polytetrafluoroethylene.
．． A sheet-like background material of 3 rrrm was inserted, and an electrolytic solution 5me made of propylene carbonate in which 1 molar concentration of LiClO4 was dissolved was sealed inside to produce an electrochromic display element having the structure shown in the drawing.
実施例２
原料の酸化タングステン化合物として荊記一般式のＸが
０、ｙが０．０５〜１． Ｏ１２が３〜４であるものを
使用した以外は実施例１と同様にしてエレクトロクロミ
ック表示素子を作製した。なお、この素子の対極物質層
の酸化タングステン化合物は前記一般式中のＸがＯ％ｙ
が０．０５〜１．０．２が０．１６〜３であった。Example 2 As a raw material tungsten oxide compound, X in the general formula of Jingji is 0 and y is 0.05 to 1. An electrochromic display element was produced in the same manner as in Example 1 except that an element having O12 of 3 to 4 was used. Note that in the tungsten oxide compound of the counter electrode material layer of this element, X in the above general formula is O%y.
was 0.05-1.0.2 was 0.16-3.
比較例１
対極物質層を三酸化タングステンの真空蒸着によって形
成した厚さ５．５０ＯＡの層とした以外は実施例１と同
様にしてエレクトロクロミック表示素子を作製した。Comparative Example 1 An electrochromic display element was produced in the same manner as in Example 1, except that the counter electrode material layer was a layer having a thickness of 5.50 OA formed by vacuum evaporation of tungsten trioxide.
実施例３
対向側基板としてＡｌ板（縦２５謂、横１８０酎、厚さ
１削）をトリクレン洗浄後に６０°Ｃの酸性フッ化アン
モニウム溶液中で２分間処理して乾燥させたものを使用
するとともに、スピンコードにて形成する対極物質層の
厚さを５，０ＯＯＡとした以外は、実施例１と同様にし
てエレクトロクロミック表示素子を作製した。なお、こ
の素子の対極物質層の酸化タングステン化合物は、前記
一般式中（Ｄｘｂｉｏ、０８〜０．２５、ｙが０．０５
〜１．０ 。Example 3 As the opposing substrate, an Al plate (length: 25 cm, width: 180 cm, thickness: 1 cut) was cleaned with trichloride, treated in an acidic ammonium fluoride solution at 60°C for 2 minutes, and dried. At the same time, an electrochromic display element was produced in the same manner as in Example 1, except that the thickness of the counter electrode material layer formed by spin cord was 5.0 OOA. Note that the tungsten oxide compound of the counter electrode material layer of this element has the formula (Dxbio, 08 to 0.25, y is 0.05) in the above general formula.
~1.0.
２が０．１６〜３．５であった。2 was 0.16 to 3.5.
実施例４
対向側基板として実施例３と同様のＡｌ板を使用してス
ピンコードによる対極物質層の厚さを５゜０００Ａとし
た以外は実施例２と同様にしてエレクトロクロミック表
示素子を作製した。なお、この素子の対極物質層の酸化
タングステン化合物は、前記一般式中のＸが０、ｙが０
０５〜１．０．２が０．１６〜３であった。Example 4 An electrochromic display element was produced in the same manner as in Example 2, except that the same Al plate as in Example 3 was used as the opposite substrate and the thickness of the counter electrode material layer was 5°000A by spin cord. . In addition, the tungsten oxide compound of the counter electrode material layer of this element has a structure in which X in the general formula is 0 and y is 0.
05-1.0.2 was 0.16-3.
比較例２
対向側基板として実施例３と同様のＡＩ！板を使用して
真空蒸着による対極物質層の厚さを５．００ＯＡとした
以外は比較例１と同様にしてエレクトロクロミック表示
素子を作製した。Comparative Example 2 The same AI as in Example 3 was used as the opposing substrate! An electrochromic display element was produced in the same manner as in Comparative Example 1 except that a plate was used and the thickness of the counter electrode material layer was 5.00 OA by vacuum deposition.
上記実施例および比較例の各表示素子について、−１，
２Ｖの電圧を０．５秒間印加したときの注入電気量、な
らびに＋１．２Ｖの電圧を印加して表示が消えるまでの
時間で表わされる応答速度を測定したところ、下表の結
果が得られた。For each display element of the above example and comparative example, -1,
We measured the amount of electricity injected when a voltage of 2V was applied for 0.5 seconds, and the response speed expressed by the time until the display disappeared after applying a voltage of +1.2V, and the results shown in the table below were obtained. .
上表から明らかなように、分子内に特定の成分を含む酸
化タングステン化合物からなる対極物質層を有するこの
発明のエレクトロクロミック表示素子（実施例１〜４）
は、三酸化タングステンの蒸着層からなる対極物質層を
有する従来構成の表示素子に比較して、注入電気量や応
答速度などの表示特性において同等以上の性能を備える
ことが判る。As is clear from the above table, the electrochromic display element of the present invention (Examples 1 to 4) has a counter electrode material layer made of a tungsten oxide compound containing a specific component in the molecule.
It can be seen that the display element has the same or better performance in terms of display characteristics such as the amount of injected electricity and the response speed, compared to a display element having a conventional configuration having a counter electrode material layer made of a vapor-deposited layer of tungsten trioxide.
図面はエレクトロクロミック表示素子の構造例を示す断
面図である。The drawing is a sectional view showing a structural example of an electrochromic display element.
Claims (2)
向配置され、表示側基板の内面に三酸化タングステンか
らなるエレクトロクロミツク物質層を有する表示極が形
成され、対向側基板の内面に対極物質層を有する対向極
が形成され、これら両極間に電解液が封入されてなるエ
レクトロクロミツク表示素子において、上記対極物質層
が分子内にＨ＿２Ｏ＿２成分とＨ＿２Ｏ成分もしくはこ
れら両成分とＣＯ＿２成分を含む酸化タングステン化合
物からなることを特徴とするエレクトロクロミック表示
素子。(1) A pair of substrates whose display side is translucent at least are placed opposite each other, a display electrode having an electrochromic material layer made of tungsten trioxide is formed on the inner surface of the display side substrate, and a counter electrode is formed on the inner surface of the opposing substrate. In an electrochromic display element in which a counter electrode having a material layer is formed and an electrolyte is sealed between these two electrodes, the counter electrode material layer contains an H_2O_2 component, a H_2O component, or both of these components and a CO_2 component in the molecule. An electrochromic display element characterized by being made of a tungsten oxide compound.
・ｘＣＯ＿２・ｙＨ＿２Ｏ＿２・ｚＨ＿２Ｏで表わされ
るｘが０〜０．２５、ｙが０．０５〜１．０、ｚが０．
１６〜３．５の化合物である特許請求の範囲第（１）項
記載のエレクトロクロミツク表示素子。(2) The tungsten oxide compound has the following general formula; WO_3
・x expressed as xCO_2・yH_2O_2・zH_2O, where x is 0 to 0.25, y is 0.05 to 1.0, and z is 0.
The electrochromic display element according to claim (1), which is a compound of 16 to 3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61204055A JPS6360430A (en) | 1986-08-30 | 1986-08-30 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61204055A JPS6360430A (en) | 1986-08-30 | 1986-08-30 | Electrochromic display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6360430A true JPS6360430A (en) | 1988-03-16 |
Family
ID=16484000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61204055A Pending JPS6360430A (en) | 1986-08-30 | 1986-08-30 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6360430A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851439A (en) * | 1993-08-25 | 1998-12-22 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Coloring layer composition for chromatic device and method of producing chromatic device by using same |
| JP2012128457A (en) * | 2012-03-23 | 2012-07-05 | Stanley Electric Co Ltd | Aperture optical element for camera and manufacturing method thereof |
-
1986
- 1986-08-30 JP JP61204055A patent/JPS6360430A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851439A (en) * | 1993-08-25 | 1998-12-22 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Coloring layer composition for chromatic device and method of producing chromatic device by using same |
| JP2012128457A (en) * | 2012-03-23 | 2012-07-05 | Stanley Electric Co Ltd | Aperture optical element for camera and manufacturing method thereof |
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