JPH0193719A - Electrochromic display device - Google Patents

Abstract

PURPOSE:To three-dimensionally show a variable color function to improve the display effect by setting the thickness of an electrolyte layer to 2-10mm and changing a second electrochromic color developing layer in accordance with the change of color of a first electrochromic color developing layer. CONSTITUTION:Transparent conductive films 2 and 21 are formed on inside surfaces facing each other of a pair of glass substrates 1 and 11 and first and second electrochromic color developing layers 3 and 31 are formed on these transparent conductive films facing each other and an electrolyte layer 4 having 2-10mm thickness is provided between them. Power is supplied to the electrolyte layer 4 and electrochromic layers 3 and 31 are allowed to face each other to develop, discolor or extinguish color. For example, the second color developing layer 31 is transparent or has light red when the first color developing layer 3 has red and the second color developing layer 31 has deep blue when the first color developing layer 3 is transparent or has blue. Consequently, three-dimensional variable color display with blue in the rear and red in the front is possible.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrochromic display device, and more particularly to an electrochromic display device in which a variable color effect is displayed three-dimensionally to enhance the display effect.

[Prior Art] A conventional electrochromic display device includes a pair of transparent substrates facing each other in parallel, transparent conductive films formed on the inner surfaces of the pair of transparent substrates, and a transparent conductive film formed on one of the transparent conductive films. A device comprising an electrochromic coloring layer and an electrolyte layer sealed between a pair of transparent substrates is known (Japanese Unexamined Patent Publication No. 84028/1983).

[Problems to be Solved by the Invention] In this conventional display device, the electrochromic coloring layer is one layer, and the electrolyte layer is small, about 0.1 to 2 mm, so that the display remains flat.

The present invention has been made in view of the above-mentioned viewpoints, and an object of the present invention is to provide an electrochromic display device that exhibits a variable color effect in a three-dimensional manner and enhances the display effect.

[Means for Solving the Problems] The electrochromic display device of the present invention includes: a pair of transparent substrates facing each other in parallel; a pair of transparent conductive films respectively formed on the mutually facing inner surfaces of the transparent substrates; , a first electrochromic coloring layer formed on one of the pair of transparent conductive films, a second electrochromic coloring layer formed on the other transparent conductive film, and between the transparent substrate. An electrochromic display device comprising: an electrolytic solution layer made of an encapsulated electrolytic solution, wherein the electrolytic solution layer has a thickness of 2 mm to 10 mm, and the first electrochromic coloring layer has a first coloring layer; , transparent and a second coloring layer, and the second electrochromic coloring layer is transparent when the first electrochromic coloring layer exhibits the first coloring; If the first electrochromic color forming layer exhibits one of transparent and second coloring, a second dark bamboo color is darker than the first color. It is characterized by showing.

As the transparent substrate, a conventionally used transparent plate-like member such as glass or plastic can be used. In order to seal an electrolyte between the transparent substrates, it is desirable to use a pair of transparent substrates having the same size, curvature, and other external shapes. As this transparent substrate, for example, a plate made of soda glass, reinforced glass, reinforced plastic, or the like can be used.

The transparent conductive film is a light-transmitting electrode that supplies power to the electrochromic coloring layer and electrolyte layer, which are electrochromic materials, to develop, change color, or decolorize the electrochromic material. This transparent conductive film can be formed using ITO (indium tin oxide) or the like by a vapor deposition method, a sputtering method, or the like. This film thickness is usually ITO
It is about 5°O to 3000 people for the membrane.

In the present invention, two electrochromic coloring layers, first and second, are each formed on the inner surface of each transparent substrate.

The first electrochromic coloring layer has a first coloring layer;
The transparent color and the second color can be mutually changed. The second electrochromic coloring layer is transparent when the first electrochromic coloring layer exhibits the first coloring;
and if the first electrochromic film exhibits one of transparent and second coloring, it has a color darker than the first color. This shows the second dark and young color. That is, in a certain electric field state, one electrochromic coloring layer disposed on one of the front and rear surfaces is strongly colored, and in another electric field state, the other electrochromic coloring layer disposed on the other surface is strongly colored. .

For example, the first electrochromic color-forming layer may be a polythenylene film, and may change between red and blue. In this case, the second electrochromic film is a tungsten oxide (WO3) film, which can change to be transparent when the color is red and dark blue when the color is blue.

An electrochromic coloring layer made of polythenylene (polythiophene) or the like can be formed on a predetermined electrode by electrolytic oxidative polymerization. Such electrolytic oxidation Φ combination can be performed in an inert gas atmosphere of N2 or ArS.

In this case, it is easy to increase the area, and the layer can be uniformly colored, changed color, or decolored. Note that this film thickness can be approximately 1000 to 4000 people. Also W
The coloring layer made of O3 or the like can be formed by a vapor deposition method, a sputtering method, a spray method, an anodic oxidation method, etc. as in the conventional method.

The thickness of this coloring layer can be about 1,000 to 4,000 layers.

For the electrolyte layer, acetonitrile or propylene carbonate is used as a solvent, and lithium tetrafluoroborate (L i BFa ) or lithium barchlorate (L
A type of non-aqueous electrolyte having iC or 04) as an electrolyte can be used. The thickness of the electrolyte layer is 2 mm to 10 mm. This is because if the thickness is less than 2 mm, the three-dimensional variable color effect will be small, and if it exceeds 10 mm, the liquid resistance will increase and the response will be slow. The thickness can be selected within this range depending on the type of electrolyte to be sealed and the degree of three-dimensional effect.

Note that the electrochromic display device of the present invention usually has a predetermined electric circuit including electrode lead wires and a power source.

[Effects of the Invention] In the present invention, the first electrochromic coloring layer changes mutually between the 11F color and one of transparent and 2′W colors. The second electrochromic coloring layer exhibits one of transparent when the first electrochromic coloring layer exhibits the first coloring, and a first light coloring that is lighter than the first coloring, When the chromic coloring layer exhibits one of transparent and second coloring, it exhibits second degree deep coloring, which is darker than the first color. Also, the thickness of the electrolyte layer is 2 to 10 m.
It is as large as m.

Therefore, in certain electric field conditions, one electrochromic coloring layer placed on one of the front and back surfaces will be strongly colored, and in other electric field conditions, the other electrochromic coloring layer placed on the other side will be strongly colored. do. Therefore, in this device, the variable color effect can be made to appear three-dimensionally, and the display effect can be enhanced.

Based on the above, when this device is used as an emergency display such as a warning lamp in a car, for example, the blue display in normal conditions will move backwards and be noticeable to the driver (or change to red in abnormal conditions). At the same time, you can make the color develop in front of you.

This effectively makes the driver aware of the abnormality.

[Example] Hereinafter, the present invention will be explained with reference to an example. FIG. 1 is an explanatory sectional view of the electrochromic display device of this embodiment.

This display device includes a pair of first and second transparent substrates 1.11 facing each other in parallel, and a pair of first and second transparent substrates formed on the opposing inner surfaces of the pair of transparent substrates 1.11. a conductive film 2.21, a first electrochromic coloring layer 3 made of polythenylene formed on the first transparent conductive film 2,
A second layer made of WO3 formed on the second transparent conductive film 21
Electrochromic coloring layer 31 and a pair of transparent substrates 1
．． An electrolytic solution layer 4 made of an electrolytic solution sealed between 11 and 11, an inner peripheral end sealing member 5 having a spacer and sealing function, and a lead wire connected to each transparent S electrical film 2.21 via a solder 7. 6 and.

As the transparent substrate 1.11, a glass substrate with a wall thickness of 1.1 mm was used. The transparent substrate 1.11 has a cell gap of approximately 7 due to the peripheral end sealing member 5 formed of epoxy resin.
It is said to be mm.

As the transparent conductive film 2.21, a [TO film having a sheet resistance of 10 Ω/hole and a film thickness of about 30,002 mm formed by a sputtering method was used.

As the first electrochromic coloring layer 3, a polychenylene film with an Ill thickness of about 4000 was used. This coloring layer 4 is prepared by preparing an electrolytic solution in which 0.1 M (mol/L) lithium tetrafluoroborate (L+BF4) and 0.2 M (mol/L) chenylene are dissolved in dehydrated acetonitrile as a solvent. , and a transparent conductive film 2 (
The first transparent substrate 1 on which the display electrode (display electrode) is formed and the counter electrode plate are immersed, and in that state, a current of about 1 mA/cm2 is passed in a nitrogen atmosphere so that the display electrode side becomes the positive electrode, and the desired thickness is obtained. A polythenylene film was formed by electrolytic oxidation polymerization. At this time, a voltage of 8 to 10 volts is applied.

As the second electrochromic coloring layer 31, a thin film having a thickness of about 3,000 O3 was used.

This coloring layer 31 was formed by vapor deposition.

As electrolytic solution 4, propylene carbonate was used as a solvent, and IM (mol/L) lithium tetrafluoroborate (LiBF4) was dissolved therein. The thickness of the electrolyte layer 5 is about 7 mm.

Note that in the display device, the pair of transparent conductive films 2.21 are electrically connected to a power source via terminals and lead wires 6.

At this time, the thickness of the electrolyte layer 4 is 2 mm to 1'Omm Pi! The relationship between the film thicknesses of the polythenylene film 3 and the WO3 film 31 is such that the amount of electricity required for the polythenylene film to change between red and black, while the WO3 film changes between transparent and blue. Set the amount of electricity that changes to a small value. Then, when backlight (white light) is applied from the WO3 film 31 side and viewed from the polythenylene B#:83 side, the polythenylene film 3
When -1.5V is applied to the side, the polythenylene film 3 is colored red, the WO3 film 31 becomes transparent, and the hand side is colored red as a whole. On the other hand, when +1.5 is applied, the polythenylene film 3 is colored bluish, the WO3 film 31 becomes completely blue, and the blue color of the rear WO3 film 31 is deep and clearly visible as a whole.

Therefore, in this display device, it has become possible to display three-dimensional variable colors in which blue is colored at the rear and red is colored at the front. This display device is extremely useful when used as an emergency display such as a warning lamp in an automobile or the like.

[Brief explanation of the drawing]

FIG. 1 is a partially illustrative sectional view of an electrochromic display device according to this embodiment. 1.11... Glass substrate 2.21... Transparent conductive film 3... First electrochromic coloring layer 31... Second electrochromic coloring layer 4... Electrolyte layer 5... Seal member 6...Lead wire 7...Solder patent applicant Toyota Motor Vehicles Co., Ltd. agent
Patent Attorney Okawa Deishin 0 "Blue"

Claims (5)

[Claims] (1) A pair of transparent substrates facing each other in parallel, a pair of transparent conductive films formed on the mutually opposing inner surfaces of the transparent substrates, and a transparent conductive film formed on one of the pair of transparent conductive films. an electrochromic coloring layer formed on a transparent conductive film, a second electrochromic coloring layer formed on another transparent conductive film, and an electrolytic solution layer made of an electrolytic solution sealed between the transparent substrates. A chromic display device, wherein the electrolytic solution layer has a thickness of 2 mm to 10 mm, and the first electrochromic coloring layer mutually changes between a first color and one of transparent and second color, When the first electrochromic coloring layer exhibits the first coloring, the second electrochromic coloring layer exhibits one of transparent and first light coloring that is lighter than the first coloring, and An electrochromic display device characterized in that when the electrochromic coloring layer exhibits either transparency or the second coloring, it exhibits a second deep coloring that is darker than the one color. (2) A patent in which the first electrochromic coloring layer is a polythienylene film that changes between red and blue, and the second electrochromic coloring layer is a tungsten oxide film that changes between transparent and dark blue. An electrochromic display device according to claim 1. (3) The electrochromic display device according to claim 2, wherein the polythenylene film is formed by electrolytic oxidative polymerization. (4) The electrochromic display device according to claim 2, wherein the second electrochromic coloring layer is formed by a vapor deposition method, a sputtering method, a spray method, or an anodic oxidation method. (5) The electrolyte is lithium tetrafluoroborate (L) using acetonitrile or propylene carbonate as a solvent.
iBF_4) or lithium perchlorate (LiClO
The electrochromic display device according to claim 1, which is a type of non-aqueous electrolyte formed by dissolving _4).