JPH01232331A - Electrochromic display element - Google Patents

Abstract

PURPOSE:To improve the reliability of lead on opposed pole sides by making an opposed polar substrate of metal and integrally providing an opposed polar lead terminal on the opposed polar substrate. CONSTITUTION:The opposed polar substrate 5 is formed of stainless steel sheet (SUS304) whose thickness is 0.3mm and the opposed polar lead terminal 12 is integrally and directly formed on the outer peripheral end of the substrate 5. Therefore, the unstableness of the lead between the opposed polar lead terminal 12 and the opposed polar substrate 5 is removed. Then, a display element in which the lowering of injected electric amount caused by the passage of time in case of storage, etc., and the increase of resistance between the opposed polar lead terminals are a little can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrochromic display element, and more particularly to an electrical connection between a lead on the opposite electrode side, that is, an opposite electrode terminal, and an opposite electrode substrate. Regarding improvements.

[Conventional technology]

In order to cause the electrochromic substance in the display electrode of an electrochromic display element to cause a coloring reaction and exhibit its display function, it is necessary to supply electricity to the electrochromic display element from an external driving power source. The connection between this driving power source and the electrochromic display element is generally made by attaching lead terminals to the display electrode substrate of the electrochromic display element and connecting the lead terminals and the driving power source with lead wires. There is.

By the way, when attaching the lead terminals to the display electrode board as described above, it goes without saying that the lead terminals on the display electrode side (hereinafter referred to as "display lead terminals") are attached to the display electrode board, but recently, the work Due to gender, etc., the lead terminal on the opposite pole side (hereinafter referred to as the opposite pole side lead terminal)
As shown in FIG. (The display terminal is electrically insulated from the terminal It.)

The electrical connection (hereinafter referred to as lead) between the counter electrode lead terminal 12 attached to the display electrode substrate 1 and the counter electrode substrate 5 is made by applying a silver paste H4 to the counter electrode lead terminal 12 as shown in FIG. and the transparent conductive film 5b of the counter electrode substrate 5 (generally, the counter electrode substrate 5 is a glass plate 5a with a transparent conductive film 5b formed thereon). Jitsukai 60-685
Publication No. 20).

[Problems to be Solved by the Invention] However, when the silver paste 14 comes into contact with air, the silver is oxidized and the electrical conductivity is impaired, and the coefficient of thermal expansion is different from that of the resin spacer 10 made of synthetic resin such as polyester. As a result, cracks form in the applied silver base 4, making electrical conduction unstable, and over time, the amount of electricity that can be injected into the electrochromic material of the display electrode decreases, resulting in a decrease in color density. There was a problem.

As described above, in the conventional electrochromic display element, the lead between the counter electrode lead terminal 12 and the counter electrode substrate 5 is made by the silver paste 14, and therefore, the electrical conduction lacks stability, and the coloring density is The purpose of this study is to solve the problem that caused a decrease in the performance and improve the reliability of the opposing extreme lead.

[Means for Solving the Problems] In the present invention, a counter electrode substrate is made of metal, and a counter electrode lead terminal is integrally provided on the metal counter electrode substrate.

[Effect]

Since the opposite pole lead terminal and the opposite pole board are integrally provided, the leads between the opposite pole lead terminal and the opposite pole board will not become unstable, and the reliability of the lead on the opposite pole side is improved. do.

[Example] Figure 1 shows the first example of the electrochromic display element of the present invention.
FIG. 2 is a schematic perspective view and an enlarged cross-sectional view of essential parts of the embodiment;
2 is a schematic perspective view of a counter electrode substrate used in the electrochromic display element shown in FIG. 1. FIG.

In the figure, l is a display electrode substrate, and this display electrode substrate 1 is formed by forming a transparent conductive film 1b of ITO (indium tin oxide) on a transparent substrate la made of a transparent glass plate. A display electrode 3 is fabricated by forming an electrochromic material layer 2 on the transparent conductive film lb of the display electrode substrate 1.

In addition, in this example, the transparent substrate l of the display electrode substrate l
A protective film 4 made of a spread film of silicon oxide (S i O 2 ) for protecting the transparent conductive film is formed on the parts a and the transparent conductive film lb where the electrochromic material layer 2 is not formed. Although this protective film 4 is also a component of the display electrode 3, this protective film 4 is not necessarily necessary for the display function of the display electrode 3.

In this embodiment, the electrochromic material layer 2
is formed of 7 layers of tungsten oxide (WOi), and the electrochromic material layer 2 is formed of 7 layers of tungsten oxide (WOi).
It is formed so as to form one figure-eight-shaped digit by a collection of segments, and is arranged inside the element.

5 is a counter electrode substrate, and a counter electrode 7 is produced by forming a counter electrode material layer 6 on this counter electrode substrate 5.

The counter electrode substrate 5 is made of stainless steel T! Temporary A (SUS304
) and has a thickness of 0.31 mm, and a counter-pole lead terminal 12 is integrally provided on the outer peripheral edge of the counter-pole substrate 5. Note that this integrally provided means that the counter electrode substrate 5
This means that the opposite pole lead terminal 12 and the opposite pole lead terminal 12 are provided in metal-to-metal contact. It is also possible to create the pole board 5 and the opposite pole terminal 12 separately, and then weld them together by welding or using a low melting point alloy. And the above-mentioned opposite pole lead terminal 1
2 consists of a horizontal part 12a and a vertical part 12b, as is clear from FIG.
The vertical portion 12b projects vertically downward from the tip of the horizontal portion 12a.

Usually, the outer diameter of the counter electrode substrate 5 is made to be the same as the outer diameter of the spacer 10 or slightly larger than the outer diameter of the spacer IO, and the outer diameter of the display electrode substrate l is set so that the display electrode lead terminal 11 can be attached. Since the spacer IO and the counter electrode substrate 5 are manufactured to have a larger diameter than the spacer IO and the counter electrode substrate 5, the length of the horizontal portion 12a of the counter electrode lead terminal 12 is usually such that the tip of the horizontal portion 12a is the outer peripheral edge of the display electrode substrate 1. They are made to be in the same position.

In this embodiment, the opposite pole lead terminal 12
The width of both horizontal part 12a and vertical part 12b is 0,5ms+
It is.

The counter electrode material N6 is formed by using activated carbon fiber cloth as the counter electrode material and adhering and fixing it on the counter electrode substrate 5 with a conductive adhesive called carbon paste. It is arranged on the inside of the element so as to face the electrocomic material layer 2 of display 8ii3.

8 is 1 L i CI O4 in propylene carbonate
．． 0 mol/l? It is a liquid electrolyte in which water is added at a ratio of 1 part by volume to 100 parts by volume of propylene carbonate, and it is used together with the electrochromic material layer 2 and the counter electrode material layer 6 as well as the display electrode substrate 1 and the counter electrode substrate 5. is located between. Reference numeral 9 denotes a background material made of an ion-permeable polytetrafluoroethylene film containing a number of titanium dioxide, which is disposed between the electrochromic material layer 2 and the counter electrode material layer 6, and is white in color and has an opposite polarity. Although the polar material layer 6 is hidden to make it easier to visually recognize the change in coloring and fading of the electrochromic material layer 2, this is not necessarily necessary depending on the type of electrochromic material and the type of counter electrode material. Further, a polyester spacer 10 is interposed between the peripheral edge of the display electrode substrate 1 and the peripheral edge of the counter electrode substrate 5, and this spacer 10 is attached to the peripheral edge of the display electrode substrate 1 with an epoxy resin adhesive or the like. It is adhesively fixed to the periphery of the counter electrode substrate 5, and the electrochromic material layer 2, the electrolyte 8
, a background material 9, a counter electrode material layer 6, and other element contents are formed in a sealed chamber. In addition, the display lead terminal 11
consists of a clamping part and a vertical part extending below the clamping part, and the clamping part has an upper clamping piece and a lower clamping piece. The display electrode substrate 1 is attached to the display electrode substrate 1 so as to be sandwiched therebetween. And the first
As shown in the schematic perspective view of the entire part of the figure, a large number of display electrode lead terminals 11 are attached to the display electrode substrate 1, but the reason why a large number of display electrode lead terminals 11 are attached in this way is that This is because it is necessary to supply electricity to each segment of the chromic material layer 2 independently so that each segment can independently cause a coloring/decoloring reaction. Although not clearly shown in the drawings, the transparent conductive film 1b of the display electrode substrate 1 also connects the segments of the electrochromic material layer 2 so that electricity can be supplied independently to each segment of the electrochromic material layer 2. It is divided into multiple pieces depending on the number.

FIG. 3 shows a second diagram of the electrochromic display element of the present invention.
FIG. 4 is an enlarged sectional view of a main part showing an embodiment, and FIG. 4 is a schematic perspective view of a counter electrode substrate used in the electrochromic display element shown in FIG. 3.

In the second embodiment shown in FIG. 3, the counter electrode substrate 5 is a stainless steel plate (SUS304 plate) with a thickness of 0.31111 and is formed into a container shape with a flange, and the flange portion 51 is displayed. It is bonded to the transparent conductive film 1b at the peripheral edge of the polar substrate l using an adhesive I3 such as an epoxy resin adhesive. The adhesive 13 that bonds the transparent conductive film 1a of the display electrode substrate 1 and the flange portion 51 of the counter electrode substrate 5 also serves as an insulating material that insulates between them. The counter electrode lead terminal 12 first protrudes horizontally from a part of the outer peripheral end of the flange portion 51 at the periphery of the counter electrode substrate 5, and this horizontal portion 12a (see FIG. 4) is also attached to the transparent conductive film of the display electrode substrate l by adhesive. 1b and bent downward at a right angle at the tip of the horizontal part 12a to form the vertical part 12.
b. The width of the opposite electrode lead terminal 12 in the electrochromic display element of the second embodiment shown in FIG. 3 is the same as that of the first embodiment, and the other constituent members are This is similar to the case of display elements. That is, in the electrochromic display element of the second embodiment, the flange portion 51 at the periphery of the counter electrode substrate 5 is bonded to the periphery of the display electrode substrate 1 with the adhesive 13; Element contents such as an electrochromic material layer 2, an electrolyte 8, a background material 9, and a counter electrode material layer 6 are housed in the chamber formed by the main part of the display electrode substrate 1 and the counter electrode substrate 1. An electrochromic material layer 2, an electrolyte 8, a background material 9, a counter electrode material layer 6, etc. are arranged between the electrode 5 and the electrochromic material layer 5.

The following Table 1 shows the electrochromic display device according to the first embodiment of the present invention shown in FIG.
1.2 of the electrochromic display element of the example and the conventional electrochromic display element (conventional product) shown in FIG.
V indicates the amount of electricity injected during coloring for 0.6 seconds. All of the electrochromic display elements subjected to the above tests had a 15Il layer made of electrochromic material layer 2.
7D element with 7 ffi×30II11 digits (8-shaped digits) (in the drawing, to simplify the cylinder,
Only two digits are shown), and the number of samples tested was 10 for each electrochromic display element, and the test results are shown as average values for each electrochromic display element.

Table 1 As shown in Table 1 above, both the electrochromic display element of the first embodiment of the present invention and the electrochromic display element of the second embodiment each have a decrease in the amount of injected electricity due to storage of 0.3 sC. /d, which was as low as 0.2mC/cd, but in the conventional electrochromic display element (conventional product), the decrease in the amount of injected electricity due to storage was 2.4a+C.
It was large, /c-.

Table 2 shows the electrochromic display element of the first embodiment of the present invention shown in FIG. 1 used in the above test, the electrochromic display element of the second embodiment of the invention shown in FIG. The resistance between the opposite terminals of the conventional electrochromic display element (conventional product) shown in Fig.
In FIG. 1, the resistance between the opposing pole lead terminal 12 at the left end and the opposing pole lead terminal 12 at the right end in the right column is shown. The distance between the lead terminals is 47 mm, and the resistance between the lead terminals is measured on 10 samples of each electrochromic display element.
In the table, the measurement results are shown for each individual sample.

As shown in Table 2, in both the electrochromic display element of the first example of the present invention and the electrochromic display element of the second example, there was no increase in resistance between the opposing terminals due to storage. In the case of conventional electrochromic display elements (conventional products), there was an increase in resistance between opposing terminals due to storage, and this varied between samples, and some caused a large increase in resistance. .

As mentioned above, in the conventional electrochromic display element, since the lead between the counter electrode lead 12 and the counter electrode substrate 5 is established by the silver paste stitch 4, electrical conduction becomes unstable due to oxidation of the silver paste 14, etc. However, in the electrochromic display element of the present invention, the opposite electrode lead terminal 12 is integrated with the opposite electrode substrate 5. Therefore, there was no large decrease in the amount of electricity injected due to storage or a large increase in resistance between the opposite electrode lead terminals, which occurred in conventional electrochromic display elements.

In the above embodiment, the counter electrode substrate 5 is made of stainless steel (
SUS304) was used, but it is not limited to this.
Other stainless steels can be used, such as 5US316.5tlS430, or any corrosion-resistant metal such as titanium.

Further, in the embodiment, the counter electrode lead terminal 12 was not particularly subjected to surface treatment, but from the viewpoint of improving contact with the substrate to which the electrochromic display element is attached, surface treatment such as nickel plating may be performed.

In addition, although tungsten oxide was used as the electrochromic material of the display electrode in the example, [rO
, , MnOz, transition metal oxides, Prussian blue, tetrathiafulvalene derivatives, viologen derivatives, etc. can also be used. Further, in the embodiment, activated carbon fiber cloth was used as the counter electrode material, but the material is not limited thereto, and iron tungstate, Mn0r, MnO, etc. can also be used. Furthermore, the electrolyte is not limited to those exemplified in the examples, and any electrolyte, liquid or solid, can be used as long as the ionic species necessary for coloring and decoloring reactions can be transferred.

〔Effect of the invention〕

As explained above, in the present invention, the reliability of the lead on the opposite pole side is increased by making the opposite pole board 5 made of metal and integrally providing the opposite pole lead terminal 12 on the opposite pole board 5. Therefore, it was possible to provide an electrochromic display element in which the amount of electricity injected due to storage is reduced and the resistance between opposing lead terminals is less increased.

[Brief explanation of the drawing]

FIG. 1 shows the first diagram of the electrochromic display element of the present invention.
FIG. 1 is a schematic perspective view and an enlarged sectional view of essential parts of the embodiment. 2 is a schematic perspective view of a counter electrode substrate used in the electrochromic display element shown in FIG. 1. FIG. FIG. 3 is an enlarged sectional view of a main part showing a second embodiment of the electrochromic display element of the present invention. 4 is a schematic perspective view of a counter electrode substrate used in the electrochromic display element shown in FIG. 3. FIG. FIG. 5 is a schematic perspective view showing a conventional electrochromic display element and an enlarged sectional view of its essential parts. DESCRIPTION OF SYMBOLS 1...Display electrode substrate, 2...Electrochromic material layer, 5...Counter electrode substrate, 6...Counter electrode material layer, 8...Electrolyte, 12...Counter electrode terminal Dou 4 - Daijo Figure 1 Figure 2 ■...Display electrode substrate 2...Electrochromic material layer 5...Counter electrode substrate 6...Counter electrode material layer 8...Electrolyte ■2... Opposite pole lead terminal 3 Figure 4 Figure 5 Figure 12... Opposite pole lead end r-

Claims (1)

[Claims] (1) In an electrochromic display element in which at least an electrochromic material layer 2, an electrolyte 8, and a counter electrode material layer 6 are arranged between a display electrode substrate 1 and a counter electrode substrate 5, the counter electrode substrate 5 is made of metal. , and an electrochromic display element characterized in that a counter electrode lead terminal 12 is integrally provided on the counter electrode substrate 5.