JPS5878126A - Electrochromic display body - Google Patents

Abstract

PURPOSE:To prevent the consumption of water and the generation of oxygen in a display body contg. the diphthalocyanine complex of a rare earth element as an electrochromic material and to increase the responding speed of the display body by forming a reversibly and electrolytically oxidizable layer. CONSTITUTION:The titled display body is composed of an electrode layer A, a layer B of the diphthalocyanine complex of a rare earth element, an ionic conductive layer C, a reversibly and electrolytically oxidizable layer D and an electrode layer E. The layers A, E are made of SnO2, In2O3, Au, Ag, Al, electrically conductive resin or the like, and a transparent electrode is used as at least one of the layers. The layer C is made of Ta2O5 or the like contg. a small amount of water, and the layer D is made of Ir(OH)3, Ni(OH)2 or the like. By combining the oxidizable thin film as the layer D with other layers, the resulting display element has remarkably improved properties as compared to a conventional display element of this kind. For example, no water is consumed, no oxygen is generated, and the responding speed is increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic display (hereinafter abbreviated as ECD) K.

Electrochromism is a phenomenon in which a redox reaction occurs reversibly when a voltage is applied, and the substance reversibly develops or discolors. Color develops by applying and removing voltage.
An attempt was made to display the digits of an electronic hand counter among the digits of the hour hand using a repeating display element that was colorless.
The six examples that have been used for more than 15 years include a transparent electrode film (cathode), a tungsten trioxide thin film, and a tungsten trioxide thin film on a glass substrate.
All-solid-state electrochromic display elements are already known in which a surface insulating film such as silicon dioxide and an electrode film (anode) are sequentially laminated. When a voltage is applied to this display element, the tungsten trioxide (Wow) thin film is colored blue. Thereafter, when a reverse voltage is applied to this display element, the blue color of the W01 metal disappears and it becomes colorless.

As such an electrochromic material, a complex of 1% rare earth element has recently been reported, which is a sifthalodianine complex that can exhibit various colors.

However, even if a Shiftalodianine complex is laminated with a proton-conducting electrolyte (corresponding to the ion-conducting layer in the present invention) and sandwiched between a pair of electrodes to form an ECD, as reported in 9. According to their research, it has been found that there are the following drawbacks: 1. Although the mechanism by which the complex exhibits electrochromic behavior has not been elucidated in detail, The reaction formula for zero coloration, in which it was found that the trace amount of water that is released, controls the coloring and decolorization of the complex, is estimated as follows.

HmOjtH''+ OR- Complex - Cathode side complex 10aH+ l@ → [H complex] (Colorless) (Colored) Electrolyte - Anode side n0H--4-m&o+'*o proverb ↑1-2 Therefore, Jin's The disadvantages of ECD are that: (1) during the coloring reaction, the water content is consumed by an unfavorable side reaction of oxygen gas generation, and (2) water is not produced by the reverse decoloring reaction, so the repeated coloring Kd
The latter is 0%, which requires water supply from the atmosphere.
OW! However, this type of ECDK has the disadvantage that coloring reproducibility is affected by moisture in the atmosphere.

Therefore, it is an object of the present invention to eliminate such drawbacks and to produce a complex with 1 cc of such IcD.
It is with Jin who provides D.

According to the present invention, (6) electrode layer, (rare earth element Q-shiftthalocyanide complex, (Q) ion conductive layer, (2) reversibly electrolytically oxidizable layer, (to) electrode layer, and electrochromic An insert is provided.

When contaminating the present invention, [is required!] ! Depending on the situation, a substrate may be provided outside the electrode layer; in this case, for example, glass,
Strong and transparent materials such as ceramics and plastics are used.

The electrode layers of (2) and (g) are Inesa (mu0 layer), I
TO (1m indium K111m degree 8 crow 0 proverb Ofl
& 10 good transparency), indium saponide (IIl
*Os) Copper iodide, gold, platinum, palladium, aluminum, silver, conductive resin, etc. are used, but (4),
(2) At least the observation side electrode of the two layers O must be transparent. It is sufficient for the electrode layer to have a thickness of 0.01-0, Ss*, but if a thicker layer is desired, it may be thicker.

(Rare earth elements in the Moan layer include 8., Y%L1, Co,
Pr, Nd, Pa, 8ea, Nu, (ld,
Tb, Dy.

Contains He, Er, Tl1bYb%Lm.

(For the Q ion conductive layer, for example, saponified tantalum (Ta1on) containing a small amount of water, niobium oxide ()Jbs
Os), zirconium oxide (zros), titanium oxide (this), octium oxide (lifes), yttrium oxide (YsOs), lanthanum oxide (L phantom 0m3m
Silicon oxide (S0x), magnesium fluoride, zirconium phosphate, or supporting materials thereof, among which tantalum oxide is preferred.

These O substances are insulators for electrons, but conductors for protons (H) and hydrocyons (OH).

(C) As for Nil, if the manufacturing method is devised, it will not necessarily be in the above example 4, and other liquid electrolytes...
For example, acids such as sulfuric acid and hydrochloric acid or their aqueous solutions, aqueous alkaline solutions such as sodium hydroxide and potassium hydroxide, solid strong acids such as sodium chloride, lithium chloride, potassium chloride, and lithium sulfate. Aqueous electrolyte solution, ■ Bovine solid gel electrolyte...For example, an electrolyte aqueous solution is mixed with a gelling agent such as polyvinylflucol, CMC.
, gelatinized with agar, gelatin, etc. 94 tons < p-tson + urine! Il! (Mixed at a molar ratio of 12:l)) ■ Solid electrolyte...For example, HUP, 1-M5OssNalZr,! QIP
Os s %N@1+zZr@S4x P@-go@
*, Na5YStaOxs Rklm f41
1b etc. ■ Water or ion-containing synthetic resin solid...
...For example, methacryl #/-hydroxyethyl and 2
-A copolymer of acrylic 7-mido with 2-methylpropanesulfonic acid, a hydrous vinyl polymer such as a hydrous methyl methacrylate copolymer, a hydrous polyester, etc. can also be used.

(C) When the layer is liquid or semi-solid gel (powder layer and (2)
Although it is sandwiched between layers and exists in a round shape, in the case of water or ion-containing synthetic resin solid O, the adhesive layer of the layer (2) may also be used, and this method is described by Ganto Motoyama. For details, see the specification of Japanese Patent Application No. 1856-98404.
A C@O thickness of about 0.1 to 1000 μm is sufficient.

(For the purpose of making the Q layer thinner or to solve the problem of liquid leakage and to make it round, it is preferable to use a so-called solid insulator of 0.
It is possible to do 0Jl+aK.

(C) jl a transmission ■ If you wish to use QECD,
It must be as transparent as possible.

(b) As a layer that can be reversibly electrolytically oxidized, nickel hydroxide, ruthenium hydroxide, hydroxide, etc. are useful.

These hydroxides cannot be formed in layers by vacuum evaporation.
Therefore, it is recommended to first vapor-deposit the corresponding metal and then anodize it in an acid or alkali aqueous solution to convert it into the desired hydroxide, or to laminate it all together and then apply an AC voltage in the atmosphere. It may be converted into the desired hydroxide by anodic oxidation.

(2) ~ (The oxidant layer may be patterned as necessary, or a patterned ion and electron insulating layer may be formed between any layers, such as silicon oxide, aluminized titanium, and zirconium oxide, which do not contain water. Bismuth oxide, octthium oxide, tantalum pentoxide, yttrium oxide, aluminum oxide, magnesium oxide, cerium oxide, galvanized chromium oxide, niobium oxide, calcium oxide, heptimony oxide, magnesium fluoride,
Various polymeric insulating materials such as lithium fluoride, calcium fluoride, neodymium fluoride, cerium fluoride, lanthanum fluoride, silicon nitride, epoxy resin, EV, parylene resist, etc. may be inserted.

The drawing is a sectional view of an ECD showing an embodiment of the present invention.

8 is a transparent substrate such as glass, and on this substrate 8, sequentially,
Transparent electrode such as indium oxide E% Oxidation color forming thin film D1 with an optical thickness of 50 OA made of iridium hydroxide Optical thickness 15000 made of tantalum oxide containing a small amount of water
The ion conductive thin film C of A, the reduction coloring thin film B1 having an optical thickness of 75 GOA and made of a lutetium siphthalodianine complex, and the transparent electrode system of indium oxide are superimposed.

The transparent electrode layer, the iridium hydroxide thin film D1, the tantalum oxide thin film C1, the complex thin film B1, and the transparent electrode layer are each formed by a known thin film forming technique such as vapor deposition. The thickness of each thin film is not limited to the above-mentioned values, but can be selected from a wide range above and below the above value.In order to increase the degree of color development, the thickness of the iridium hydroxide layer must be thickened to increase the % and memory properties. To increase this, it is recommended to thicken the tantalum oxide. Of course, if nickel hydroxide or a mixture thereof is used instead of the above-mentioned iridium hydroxide, the structure may be the same as above. The same applies to ionically conductive substances such as zirconium oxide in molybdenum oxide. Furthermore, the positional relationship between the oxidizing thin film and the reduction coloring thin film B with respect to the substrate can be reversed. In this way, oxidizing thin films such as iridium hydroxide and nickel hydroxide are used together.

The 0ECD of the present invention has dramatically improved performance compared to the conventional ECDK.

For example, it has advantages such as no water consumption, no oxygen generation, and fast response speed.

[Brief explanation of the drawing]

The drawing is a sectional view of an ECD showing an embodiment of the present invention. [Explanation of symbols of main parts] M...Electrode 1...Lutetium siphthalodianine complex C...Tantalum oxide D as an ion conductive layer...Iridium hydroxide as a reversibly electrolytically oxidizable layer E... Electrode applicant: Nippon Kogaku Kogyo Co., Ltd.? Yasuinaka - Sendryoichi''

Claims (1)

[Scope of Claims] An electrochromic film comprising: (2) an electrode layer; (B) a Shiftalodianine complex of a rare earth element; (0 ion conductive layer); (B) a reversibly electrolytically oxidizable layer; Demonstration.