JPS62209421A - Electrochromic element - Google Patents

Abstract

PURPOSE:To improve the efficiency of complementary oxidation-reduction reaction to be generated between an oxidation coloring layer and reduction coloring layer when the voltage is impressed and to obtain an element which exhibits coloring performance of high density by constituting the oxidation coloring layer of an org. material and the reduction coloring layer of an inorg. material, disposing these two coloring layers to face each other and forming an electrolyte layer therebetween. CONSTITUTION:The inorg. reduction coloring layer 11 and the org. oxidation coloring layer 12 are formed on the surfaces of the thin films consisting of a lower electrode 10a and upper electrode 10b facing each other and the solid or semisolid electrolyte layer 12 is provided between these two coloring layers 11, 12. The circumference thereof is sealed with an epoxy resin 14. The inorg. reduction coloring layer refers to transition metallic oxides such as WO3, M0O3 and TiO2 or the mixture composed thereof and is formed on the surface of the lower electrode 10a. On the other hand, the org. oxidation coloring layer 12 is formed by forming the thin film of an electrochromic material such as polyaniline or polypyrrole on the surface of the upper electrode 10b by an electrolytic polymn. method or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to an electrochromic device and various display devices and light control devices using the same.

(Prior Art) An electrochromic device (hereinafter abbreviated as ECD), in which an electrochemical reaction is induced in the device by external voltage application, and its color and absorbance change reversibly,
Because it has many features not found in solid-state light emitting devices (LEDs) and liquid crystal devices (LCDs), it is being put to practical use as dimming devices and display devices in various industrial fields, including the electronics industry. ing.

The materials constituting the above ECD can be broadly classified into inorganic materials and organic materials, with the former being various transition metal oxides, and the latter being representative examples of conductive polymer films such as polyaniline, polypyrrole, and polythiophene. In recent years, various ECDs using these materials have been developed.

(Problems to be Solved by the Invention) The basic composition of the inorganic ECD made of the various transition metal oxides is ITO (In containing 5% by weight of SnOz).
A coloring layer made of various transition metal oxides, a dielectric layer, or a solid electrolyte is laminated in a thin film form between a pair of electrodes formed by forming a transparent thin film such as Z03).

Although the above-mentioned inorganic ECD has advantages such as being able to make the element smaller and thinner, and being highly durable and capable of stable operation over a long period of time, it also suffers from poor change in color density and absorbance when voltage is applied. It has also been pointed out that there is a problem with responsiveness. This is because no material for the oxidized coloring layer, such as WO3, suitable for the counter electrode of the reduction coloring layer has been found among inorganic materials. This is due to the difficulty in encapsulating it in layers or solid electrolytes.

On the other hand, the basic structure of an organic ECD is one in which the conductive polymer film, viologen derivative, etc. are laminated between a pair of thin film transparent electrodes made of the above-mentioned ITO, or they are sealed in a cell together with an electrolyte. be.

It has been pointed out that, although the above organic ECDs have better responsiveness than inorganic ECDs, there are problems with the durability of the elements, and there are concerns about stable operation over a long period of time. This is because no excellent material for the reduction color forming layer has been found in organic materials, and also because it is difficult to seal the electrolyte in the cell without leaking for a long period of time. Furthermore, conventionally, in order to seal an electrolyte in a cell, the inside of a tank containing the electrolyte and a hollow cell is evacuated, the cell is immersed in the electrolyte, and then the inside of the tank is returned to atmospheric pressure. , a method was adopted in which the electrolyte was injected into a vacuum cell using atmospheric pressure. However, this method also has the disadvantage that the cost of the obtained device increases because it requires time and effort to manufacture.

As described above, both types of elements have their own advantages and disadvantages, and at present neither of them can fully demonstrate the characteristics of ECD. Therefore, also these ECD
At present, satisfactory light control devices and display devices using the same have not been obtained.

In view of the above problems, the present inventors have repeatedly researched the characteristics of various ECDs, and have found that they have excellent responsiveness and a high color density when voltage is applied, resulting in a markedly rich contrast change when a reverse voltage is applied. We have discovered a new ECD with these characteristics and have completed the present invention.

Structure of the Invention (Means for Solving Problems) The second invention comprises a pair of electrodes, at least one of which is transparent, an organic oxidation color forming layer and an inorganic reduction layer formed opposite to each other between the pair of electrodes. The above-mentioned problem was solved by employing an electrochromic element comprising a coloring layer and a solid or semi-solid electrolyte layer formed between the two coloring layers.

The second invention also provides a pair of electrodes, at least one of which is transparent, an organic oxidation coloring layer and an inorganic reduction coloring layer formed opposite to each other between the pair of electrodes, and a layer formed between the two coloring layers. An electrochromic light control device is employed in which an electrochromic element comprising a solid or semi-solid electrolyte layer is formed on the surface of a substrate.

Furthermore, the present third invention provides a pair of electrodes, at least one of which is transparent, an organic oxidation coloring layer and an inorganic reduction coloring layer formed opposite to each other between the pair of electrodes, and a layer formed between the two coloring layers. An electrochromic display device is employed in which an electrochromic element comprising a solid or semi-solid electrolyte layer formed on the surface of a substrate is formed.

(Function) The oxidation coloring layer is made of an organic material, and the reduction coloring layer is made of an inorganic material, and by making these coloring layers face each other and forming an electrolytic layer between them, there is no interference between the two coloring layers when a voltage is applied. The efficiency of the complementary oxidation/reduction reactions that occur is improved. In addition, by composing the electrolytic layer with a solid or semi-solid material, it becomes easy to seal the electrolytic layer, and the element exhibits excellent responsiveness even when driven at low voltage, and exhibits high-concentration coloring performance. can get.

(Example) Hereinafter, the configuration of the ECD according to the second invention will be described in detail.

FIG. 1 shows the basic configuration of the ECD of the present invention,
An inorganic reduction coloring layer 11 and an organic oxidation coloring layer 12 are formed on the surface of the thin film composed of the lower electrode 10a and the upper electrode 10b facing each other. An electrolytic layer 13 is provided, and the periphery thereof is sealed with an epoxy resin 14.

Further, the lower electrode 10a and the upper electrode 10b are usually formed on the surface of a transparent glass 18 as a substrate by a thin film forming method such as an ion blasting method or a sputtering method.

Specifically, the inorganic reduction coloring layer 11 is Wo 3
, M o O 2 , T i O □ or a mixture thereof, which is formed on the surface of the lower mold 8iIOa by an EB (electron beam) evaporation method, an ion blasting method, a sputtering method, etc. It is.

In addition, this inorganic reduction coloring layer 11 has cations M''(M'' is H'',
A reversible coloring reaction is caused by the doping/dedoping reaction of
When 3 is used, it is assumed that the following reaction occurs.

WO3+2M"+X e-=MXWO:1 On the other hand, the organic oxidation coloring layer 12 specifically includes an electrochromic material such as polyaniline, polypyrrole, poly-N-alkylvirole, polythiophene, poly-3-alkylthiophene, etc. A thin film is formed on the surface of the upper electrode fob by an electrolytic polymerization method or a catalytic polymerization method, but the electrolytic polymerization method is preferably employed from the viewpoint of film formability and conductivity.

Next, the electrolytic layer 13 is a solid or semi-solid substance made of a molten mixture of an organic polymer and an electrolyte, and the organic polymer includes cellulose acetate, polyethylene oxide, polyvinyl acetate, Examples include polyvinyl butyral and polyvinylidene fluoride.

Also, the electrolyte is HCfO, HBF, or HPF.
, i.e., LiClO4, LiBF4,
In the present invention, LtPFh dissolved in a polar organic solvent such as propylene carbonate, sulfolane, acetonitrile, benzonitrile, nitrobenzene, nitromethane or dimethoxyethane is used.

Examples embodying the present invention will be described below along with the manufacturing method thereof.

[First example]

(Al The degree of vacuum inside the inorganic reduction coloring layer ion blating device is lXl0-
After evacuating until the vacuum level reaches 2.5 Torr, oxygen gas is introduced until the vacuum level inside the apparatus reaches 2.5
It was set to Xl0-'Torr.

Next, after discharging at a discharge output of 100 W using 13.56 MHz RF (high frequency), the ITO tablet was evaporated by EB ethane using an ion blating method.
A 2000 IT○ thin film layer was formed on a 1 mm thick soda lime glass substrate heated to 200°C. and,
Subsequently, the inside of the apparatus was made into a nitrogen gas atmosphere of IXl0-3 Torr, and WO was performed.

A W03 thin film layer with a thickness of 6000 was formed on the above ITO thin film by an EB evaporation method in which the tablet was evaporated with EB ethane.

(bl Organic oxidation coloring layer 1.0N H(1!04 aqueous solution and 1.0 molar concentration aniline hydrochloride crystal powder aqueous solution were mixed in an equal ratio to prepare an electrodeposition solution. Then, the above (a) An electrolytic polymerization method in which an ITO thin film layer with a thickness of 2,000 layers formed on a soda-lime glass substrate by the method of ) is used as an anode, and a carbon rod is used as a cathode, and both electrodes are immersed in the above electrodeposition solution and energized at room temperature. A green to dark blue polyaniline layer with a thickness of 4000 mm was formed on the ITO thin film of the anode.

The synthetic current density when carrying out the above electrolytic polymerization reaction is 10μ8~
It is preferably within the range of 5 mA/cnl, more preferably 5 mA/cnl.
It is 0 μA to 1 mA/cut. This combined current density is 1
0μA/co! The film formation rate is slow below 5 mA.
/ ad or more, there is a possibility that the formed thin film will be pulverized and its performance will deteriorate. The thickness of the polyaniline layer can be varied from 500 to 2
It can be controlled in the range of μm, but usually 2000 to 40 μm.
The film thickness must be controlled so that the complementary oxidation/reduction reaction with the inorganic reduction color forming layer proceeds smoothly from the viewpoint of preventing device deterioration due to gas generation and the like.

In addition, the electrolyte in the above electrodepositing solution was TeH instead of HCj704.
An inorganic acid such as Cl,, Hz SOa, HN O3 may be used in a range of 0.1 to 5N, and an aqueous solution of aniline sulfate with a concentration of 1 to 2 molar O, may be used instead of an aqueous solution of aniline hydrochloride. Alternatively, polyalinine may be precipitated.

Alternatively, polyalinine may be precipitated using an electrolytic solution in which 0.1 to 2 molar concentration of aniline is dissolved in an aqueous solution of these inorganic acids.

(C) Electrolytic layer Cellulose acetate was used as the organic polymer.

Moreover, LiBFa was used as an electrolyte. and 1 part by weight of cellulose acetate and 1 molar concentration of Li
Propylene carbonate-1-5 containing BFa,
A molten mixture was prepared by heating a mixture consisting of 5 parts by weight to 50-100'C.

Next, this semi-solid molten mixture was applied to the surface of the Wool i film layer of (a), and then the soda lime glass substrate laminated with the rTo electrode and polyaniline layer of (bl) was pressed onto the surface of the molten mixture. Furthermore, the surrounding area was sealed with epoxy resin.The cellulose acetate used was a product manufactured by Gyudon Kagaku Co., Ltd.

(d) Next, lead wires were attached to each of the pair of ITO electrodes to obtain an ECD.

A DC voltage (V) was applied to the ECD obtained as described above, and the optical density changed (Δ0.
D) was measured. In addition, as a comparative example, we measured the Δ0.0 of an ECD in which W O3 or polyaniline forms the coloring layer alone, and an all-solid-state ECD in which both coloring layers are made of W03/Ni0X. The ECD of this example has extremely large ΔQ and D (and is found to be an element with a large contrast change) compared to each of the above comparative examples.In addition, the ECD of this example has a solid or semi-solid electrolyte layer. Since a solid electrochromic material was used, there was no fear of liquid leakage, and the response was comparable to ECD using electrolyte.

[Second example]

(Al Inorganic reduction coloring layer An ITO thin film layer with a thickness of 2,000 layers was formed on a soda-lime glass substrate in the same manner as in the first embodiment, and then a W O'r layer with a thickness of 4,000 layers was formed on this ITO thin film. A thin film layer was formed.

(b) Organic oxidized coloring layer pyrrole and L i CI! Electrodeposition solutions consisting of propylene carbonate solutions each containing Oa at a 0.2 molar concentration were prepared. Then apply the above (
An ITO thin film layer formed in the same manner as a) is used as an anode,
Further, after using a carbon rod as a cathode and immersing them in the above-mentioned electrodeposition solution, electricity was passed between both electrodes at room temperature to form a polypyrrole layer of 4,000 layers on the ITO thin film on the anode side.

(Polyethylene oxide with an average molecular weight of 600,000 to 1,000,000 was used as the organic polymer for the C1 electrolytic layer.

Further, the electrolyte is the aforementioned LiBF. and 1 part by weight of polyethylene oxide and 1 molar concentration of LiBF4.
A mixed solution consisting of 5.5 parts by weight of propylene carbonate containing the above was heated at 50 to 100°C to prepare a molten mixture.

Next, as in the first embodiment, after applying this molten mixture to the surface of the W Ox thin film layer of (a), the I of (b) was applied.
A soda lime glass substrate laminated with a TO electrode and a polypyrrole layer was pressed onto the surface of the molten mixture, and the surrounding area was sealed with epoxy resin. The polyethylene oxide used was rPEo-34, manufactured by Seitetsu Kagaku Kogyo Co., Ltd.

(d+ ECD was obtained by attaching lead wires to the ITO electrodes of both of the above coloring layers.

When a direct current voltage was applied to this ECD and the change in absorption density (Δ0.0) with respect to the change in the applied voltage was measured, the Δ0.0 was extremely large, indicating that the device had a rich contrast change.

[Third Example]

(a) Inorganic reduction color forming layer An ITO thin film layer with a thickness of 2,000 thick was formed on a soda lime glass substrate in the same manner as in the first embodiment, and then a WOX thin film with a thickness of 6,000 thick was formed on this ITO thin film. was formed.

(bl Organic oxidation coloring layer 0, 5 molar concentration of thiophene and 0.2N AgC
A polythiophene layer having a thickness of 3000 nm was formed on the ITO thin film on the anode side by the method described above using an electrodeposition solution consisting of a nitrobenzene solution containing 10a.

(C) The organic polymer used in the electrolytic layer has an average degree of polymerization of 1300 to 1.
500 polyvinyl acetate. In addition, the electrolyte is the L
i BF 4.

A liquid mixture consisting of 1.3 parts by weight of propylene carbonate containing 1 part by weight of polyvinyl acetate and 1 molar concentration of LiBF is heated to 50 to 60°C to prepare a molten mixture,
As in the first embodiment, WO.

After coating the surface of the thin film layer, the soda lime glass substrate laminated with the ITO electrode and polythiophene layer (b) was pressed onto the surface of the molten mixture, and the periphery was roughly sealed with epoxy resin. The polyvinyl acetate used was a product manufactured by Denki Kagaku Kogyo Co., Ltd. [Sakunor 5N-1ON J].

(dl ECD was obtained by attaching lead wires to the ITO electrodes of both of the above-mentioned full color layers.

It should be noted that the change in contrast of this ECD at Δ0.0 was extremely large, similar to the 0ECD of the first example and the second example.

[Fourth embodiment]

(al) The structures of the inorganic reduction coloring layer and the organic oxidation coloring layer are the same as those of the first embodiment.

(b) Electrolyte layer The organic polymer used was Denka Lac-500HJ (polyvinyl acetate with an average degree of polymerization of 850) manufactured by Denki Kagaku Kogyo Co., Ltd. The electrolyte was the above-mentioned LiBFn.

Since the above polymer is commercially available as a methanol solution with a solid content of 52%, the solvent was first evaporated in a vacuum chamber.

Next, 1 part by weight of this polyvinyl acetate and 1 molar concentration of L
i B F 4 containing propylene carbonate 1
A mixed solution consisting of parts by weight was prepared, and WO was prepared using the method described above.
After resin sealing was performed between the three thin film layers and the polyaniline layer, lead wires were attached to both electrodes to obtain an ECD. This ECD also showed an extremely large change in contrast, similar to each of the examples described above.

[Fifth example]

This example differs from the first example only in the structure and manufacturing method of the electrolytic layer.

The organic polymer used was polyvinyl butyral manufactured by Denki Kagaku Kogyo Co., Ltd. (“Denka Butyral #4000-2J”).
).

1 part by weight of this polyvinyl butyral and 1 molar concentration of Li
A liquid mixture consisting of 3 parts by weight of propylene carbonate containing BF4 was applied to the surface of the WOa thin film layer, and then placed on a hot press and heated to 100°C. Next, a soda lime glass substrate on which an ITO electrode and a polyaniline layer were laminated was brought into contact with the surface of the molten mixture and press-bonded, and then lead wires were attached to both electrodes, respectively.

[Sixth Example]

This embodiment differs from the fifth embodiment only in the structure of the electrolytic layer.

The organic polymer used was polyvinylidene fluoride. A mixed solution consisting of 1 part by weight of polyvinylidene fluoride and 2 parts by weight of propylene carbonate containing 1 molar concentration of L i B Fa was prepared, and a mixture was prepared between the WO3 thin film layer and the polyaniline layer by the method of the fifth embodiment. After press-bonding the electrodes, lead wires were attached to both electrodes.

In addition, each ECD of the fifth and sixth embodiments is also 0EC of each of the above-mentioned embodiments.
Similar to D, an extremely large change in contrast was observed.

Note that the present invention is not limited to the first to sixth embodiments described above, and may be embodied, for example, as follows without departing from the gist thereof.

■ As electrolytes, the above Li CII Oa, Li
P F h may be used, and the aforementioned sulfolane, acetonitrile, benzonitrile, nitrobenzene, nitromethane, dimethoxyecune, etc. may be used as the polar organic solvent.

(2) Instead of WO, other transition metals such as MoO2 and Tie□ may be used to form the reduction coloring layer. Further, another type of ion blating method, sputtering method, vacuum evaporation method, etc. may be used to form the reduction coloring layer.

(2) An oxidized coloring layer may be formed using an organic electrochromic material such as poly-N-alkylpyrrole or poly-IJ-3-furkylthiophene.

■ If necessary, one of the opposing electrodes can be replaced with TiO2 or S.
Transparent materials such as nOz, or Au%Ag, P
It may be made of an opaque material such as T.

Next, an embodiment in which the second invention is embodied in a sunroof with a dimming function for an automobile will be described.

[Seventh Example]

As shown in Fig. 2, a sunroof is attached to the roof of a car for the purpose of giving a sense of openness to the interior of the car and adjusting the brightness inside the car. The main parts of 17 are a transparent glass 18 shown in FIG. 3 and an ECD formed on the surface using this transparent glass 18 as a substrate.
It is I.

Both electrodes of this ECD 1 are connected to lead wires 19a, respectively.
, 19b to the battery power supply.

Further, as shown in FIG. 4, the ECD 1 uses a transparent glass 18 for a sunroof as a substrate, and an ITO lower electrode 10a, an inorganic reduction coloring layer 11, an electrolytic layer 13, and an organic oxidation coloring layer 14 are sequentially laminated on the surface thereof. , ITO upper electrode 10b
and a protection J'W20 made of transparent glass. Note that the periphery of this electrolytic layer 13 is sealed with an epoxy resin 14.

The ECDl of this example uses the same electrochromic material as that of the first example of the first invention,
It was obtained by a similar manufacturing method.

That is, the sunroof transparent glass 18 is made of soda-lime glass with a thickness of 6 mm, and a lower electrode 10a made of an ITO thin film layer with a thickness of 2000 mm is formed on the surface of this substrate by the ion-blating method.

In addition, the inorganic reduction coloring layer 11 has a film thickness of 6000 mm.
The ITo lower electrode 102 is made of three thin film layers and is formed using an EB evaporation method in which a WO2 tablet is evaporated using an EB evaporator.
formed on the surface.

On the other hand, the protective layer 20 made of transparent glass is also made of soda-lime glass with a thickness of 1 mm, and the upper electrode 10 made of an ITOI film layer with a thickness of 2000 mm is placed on the surface of this as a substrate.
b is formed by the ion blating method. Then, on the surface of this upper electrode 10b, an organic oxidation coloring layer 12 consisting of a green to dark blue polyaniline layer with a film thickness of 4000 mm is provided.
is formed. This organic oxidation coloring film 12 is 1.0
The above-mentioned upper electrode 10b immersed in an electrolyte solution in which a normal HC10a aqueous solution and a 1.0 molar concentration aniline hydrochloride crystal powder aqueous solution are mixed in an equal ratio is used as an anode, and a carbon rod is used as a cathode between both electrodes. This was obtained by applying electricity to the

Next, the electrolytic layer 13 is made of propylene carbonate 5 containing 1 part by weight of cellulose acetate and 1 molar concentration of LiBF4.
．． After applying a mixture obtained by heating and melting a liquid mixture consisting of 5 parts by weight to the surface of the WO thin film layer, the polyaniline layer on the surface of the upper electrode 10b is pressed onto the surface of the molten mixture, and the surrounding area is further sealed with an epoxy resin 14. This is what I did.

In addition, each of the pair of ITO electrodes has one lead wire.
93.19b is attached.

When sunlight or the like is irradiated onto the sunroof with dimming function 17 having the above configuration, when a DC voltage is applied between the above-mentioned electrodes 10a and 10b, the inorganic reduction color development F in the ECD 1 is applied.
At the interface between JII and the electrolytic layer 15, Li is doped/dedoped, and the organic oxidized color forming layer 12 and the electrolytic layer 13
A reversible coloring reaction occurs due to the doping/undoping of BF,-anions at the interface with the BF, - anion, and the transmittance of light entering the interior of the vehicle from the outside changes reversibly. Therefore, for example, a switch equipped with a voltage transformation mechanism is installed on the instrument panel, and when this switch is operated, the ECD
By appropriately adjusting the voltage applied to 1, it becomes possible to arbitrarily set the amount of light incident on the interior of the vehicle. Moreover, since the ECDl of this embodiment has an extremely large optical density change (Δ0.D) and high responsiveness, it is possible to quickly and significantly change the brightness inside the vehicle interior.

Further, by incorporating an optical sensor into the circuit and providing a mechanism that can automatically adjust the applied voltage, the driver is freed from the trouble of operating the switches.

Furthermore, the sunroof with dimming function 17 of this embodiment also has the following effects.

■ By coloring ECD, it is possible to improve the design of automobiles.

■ It is possible to prevent the deterioration and fading of automobile interior parts caused by ultraviolet rays.

■ Privacy can be maintained from large vehicles with high vehicle height.

Next, an embodiment in which the second invention is embodied in an anti-glare mirror for an automobile will be described.

[Eighth Example]

The main parts of the anti-glare mirror 21 are a transparent glass 18 shown in FIG. 5 and an ECD 1 formed on the surface of the transparent glass 18 as a substrate. Lead wires 19a and 19b are attached to both electrodes of this ECD 1, respectively, and are connected to a battery power source.

Further, as shown in FIG. 6, the ECD 1 has an ITO lower electrode 10a, an inorganic reduction coloring layer 11, an electrolytic layer 13, an organic oxidation coloring layer 13, and an ITO lower electrode 10a, an inorganic reduction coloring layer 11, an electrolytic layer 13, and an organic oxidation coloring layer 10a, which are successively laminated on the surface of a transparent glass 18 for an anti-glare mirror as a substrate, as shown in FIG. Layer 12, ITO upper electrode 10b
and a protective layer 20 made of transparent glass. Note that this electrolytic layer 13 is sealed with epoxy resin. And a protective RWM made of the above transparent glass.
A thin film of metal such as aluminum is formed on one of the three or five sides of the mirror 20 by vacuum evaporation or sputtering to form a mirror surface that reflects incident light from the front.
ECD 1 of this example was obtained using the same electrochromic material as that of the second example of the first invention and by the same manufacturing method.

That is, the transparent glass 18 for the anti-glare mirror is made of soda lime glass with a thickness of 1.5 mm, and a lower electrode 10a made of an ITOil film with a thickness of 2000 mm is formed on the surface of this substrate. Further, on the surface of this [TO thin film, an inorganic reduction color forming layer 11 consisting of a WO□ thin film layer having a thickness of 4000 is formed by the EB evaporation method described above.

On the other hand, the glass plate 11N20 made of transparent glass is soda lime glass with a thickness of 1 fi, and a thin aluminum film is formed on the b side thereof by vacuum evaporation.

Further, using this protective layer 20 as a substrate, an upper electrode 10b made of an ITO thin film layer having a thickness of 2000 is formed on three sides thereof by an ion-blating method. and,
On the surface of this upper electrode 10b, an organic oxidized coloring layer 12 made of polypyrrole with a thickness of 4000 is formed. This organic oxidation coloring layer 12 is composed of pyrrole and LiCI.
The upper electrode 10 is immersed in an electrodeposition solution consisting of a propylene carbonate solution each containing O4 at a 0.2 molar concentration.
This was obtained by using b as an anode and a carbon rod as a cathode and passing current between the two electrodes.

Next, the electrolytic layer 13 is formed by heating and melting a liquid mixture consisting of 1 part by weight of polyethylene oxide and 5.5 parts by weight of propylene carbonate containing 1 molar concentration of LiBFa. After coating the layer surface, an opposing polypyrrole layer was pressed onto the surface of the molten mixture.

Further, each electrode IQa, 10b has a single lead wire 19.
a and 19b are attached.

When the anti-glare mirror 21 having the above structure is illuminated by headlights of a vehicle behind at night, both the electrodes 10a and 10b
When a DC voltage is applied between them, Li" is doped/dedoped at the interface between the electrolytic N13 sealed with the epoxy resin 14 in ECD1 and the inorganic oxidative coloring layer 11, and the electrolytic FIJ13 and the organic oxidative coloring layer 11 are doped/dedoped. BF at the interface with 12, -
Doping/dedoping of anions causes a reversible coloring reaction, and the light transmittance of ECDl changes reversibly. Therefore, the amount of the heptadrite reflected by the mirror surface made of the aluminum thin film vacuum-deposited on the surface of the protective layer 20 also changes reversibly.

Therefore, by installing a switch equipped with a voltage transformation mechanism on the instrument panel, for example, and adjusting the voltage applied to the ECD1 as appropriate by operating this switch, it is possible to arbitrarily set the amount of light reflected from the headlights on the mirror surface. Become. Moreover, since the ECD I of this example has an extremely large optical density change (Δ0.0) and high responsiveness, it is possible to quickly set an arbitrary reflectance with a good balance between anti-glare effect and rearward visibility. It becomes possible to set.

In addition, by incorporating an optical sensor into the circuit and providing a mechanism that can automatically adjust the applied voltage, the driver is freed from the trouble of operating the switches.

Note that the second invention is not limited to the seventh embodiment described above, and may be embodied as follows, for example, without departing from the gist thereof.

(2) The above-mentioned LiC1tO4 and LiPF6 may be used as the electrolyte, and the above-mentioned polar organic solvent.

Sulfolane, acetonitrile, benzonitrile, nitromenzene, nitromethane or dimethoxyethane may also be used. Furthermore, polyvinyl acetate, polyvinyl butyral, or polyvinylidene fluoride may be used as the organic polymer.

(2) Instead of WO, other transition metals such as MoO3 and TiO2 may be used to form the reduction coloring layer. Further, another type of ion blating method, sputtering method, vacuum evaporation method, etc. may be used to form the reduction coloring layer.

(2) The oxidized coloring layer may be formed using an electrochromic material such as poly-N-alkylpyrrole, polythiophene, or poly-3-alkylthiophene.

■ In the case of an anti-glare mirror, one of the opposing electrodes is made of Ti.
Transparent materials such as 0z, 5nOz, or Au, A
It may also be an opaque material such as Pt, Pt, etc. Also, A
If Pt is used, the aluminum vapor deposition film on the back surface may be unnecessary.

■ Inorganic glass or heat-resistant plastic material other than soda-lime glass may be used as the substrate material.

Furthermore, the electrochromic light control device of the second invention can be widely applied not only to the above-mentioned sunroofs and anti-glare mirrors, but also to places where light control is required, such as windows of automobiles, aircraft, railway vehicles, and buildings. .

Next, a description will be given of an embodiment in which the third invention is embodied in a display device for an automobile.

[Ninth embodiment]

The display device of this embodiment displays various information such as vehicle speed and engine rotational speed by having a display section made of a transparent thin film layer installed on the windshield of an automobile color or emit light when necessary.

FIG. 7 shows the basic configuration of this display device. That is, the display section 23 of this display device includes an ECD 1 formed on the surface of a substrate made of transparent glass 18, and an electroluminescent element 2 (hereinafter referred to as
It is a transparent thin film layer formed by laminating two layers (abbreviated as ELD). The substrate is then attached to a part of the windshield 22 of an automobile as shown in FIG. Further, this display unit 23 is connected to a battery power source via a lead wire and a control circuit (not shown), and when a DC voltage is applied, the ECD
1 is activated, and when a high frequency AC voltage is applied, ELD 2 is activated.

Next, the details of the configuration of this display device will be explained along with its manufacturing method. First, the ECD 1 was obtained using the same electrochromic and mink materials as those of the first embodiment of the first invention and by the same manufacturing method.

That is, the transparent glass 18 serving as the substrate is soda lime glass with a thickness of 1 s, and the lower electrode 1 formed on the surface thereof.
0a is the film thickness 20 obtained by ion blating method
00 ITO''M membrane.

Then, patterns such as numbers, letters, figures, etc. are formed on this lower mold +11Oa.

In addition, the inorganic reduction color forming layer 11 formed on the surface of this ITO thin film has a film thickness of 6000 W obtained by the EB evaporation method.
The electrolyte layer 13 formed on the surface of the OzWJ film contains 1 part by weight of cellulose acetate and 1 mole of cellulose acetate. Mt degree LiB
After applying a mixture obtained by heating and melting a mixture consisting of 5.5 parts by weight of propylene carbonate containing F4 to the surface of the WO3 thin film layer, the opposing polyaniline layer is pressed onto the surface of the molten mixture, and the surrounding area is covered with epoxy. It is sealed with resin 14.

Furthermore, an organic oxidation coloring layer 12 and an upper electrode 10b are sequentially laminated on the surface thereof, and the upper electrode 10b is an ITO thin film having a thickness of 2000 mm, like the lower electrode 10a. Further, the organic oxidation coloring layer 12 is 1.0N HC.
l0. A green to dark blue polyaniline film with a thickness of 4000 mm was formed on the surface of the upper electrode 10b using an electrodeposition solution prepared by mixing an aqueous solution and an aqueous solution of aniline hydrochloride crystal powder at an equal ratio of 1.0 molar. It is a layer.

On the other hand, the above I? , 1. The IJ 2 is made of an electroluminescent material laminated on the surface of the upper electrode 10b of the ECD 1. That is, an insulating layer 25 made of Ta and O3 is formed on the surfaces of the upper electrode 10b and the counter electrode 24.
are respectively formed, and a light emitting layer 26 of ZnS containing a trace amount of Mn is formed between the double insulating layers 25. In addition, a protective layer 20 of transparent glass is provided on the other surface of the counter electrode 24.
is attached.゛This ELD 2 has a light emitting layer 2 when a high frequency AC voltage is applied between the upper electrode 10b and the counter electrode 24.
6 is an element that emits yellow-orange light (emission peak wavelength=5850), and is manufactured by using a combination of high-frequency sputtering and EB evaporation in a high-frequency sputtering apparatus.

The display section 23 having the above configuration is attached to a part of the windshield 22 via an adhesive applied to the back surface of the substrate. Further, each electrode 10a, 10b, 2 of this display section 23
A lead wire connected to a control circuit is attached between the four.

Therefore, when driving in the daytime, if a DC voltage is applied to this display section 23, the ECD 1 is activated and a reversible coloring reaction occurs, and the display section 23 of the windshield 22 displays the vehicle speed and engine as shown in FIG. Various information such as rotation speed is displayed. In addition, as mentioned above, this ECDl has an extremely large change in optical density (Δ0.D) and high responsiveness. By appropriately adjusting the voltage applied to the display section 23, it becomes possible to quickly and arbitrarily set the brightness of the display section 23 according to the external brightness.

Further, by incorporating an optical sensor into the circuit and providing a mechanism that can automatically adjust the applied voltage, the driver is freed from the trouble of operating the switches.

Further, when driving at night, by applying a high frequency AC voltage, the ELD 2 emits light and various information is displayed on the display section 23 of the windshield 22.

Since the display section 23 is attached to a part of the windshield 22, the driver can visually check various information without moving his/her line of sight, which is extremely convenient. Furthermore, since the parts other than the displayed numbers and letters are transparent, the driver's view of the road ahead is not obstructed.

Note that the third invention is not limited to the above-mentioned embodiments, and may be embodied as follows, for example, without departing from the gist thereof.

■ The above LiCff0. as an electrolyte. , LiPF6 may be used, and the above-mentioned sulfolane, acetonitrile, benzonitrile, nitrobenzene, nitromethane, dimethoxyethane, etc. may be used as the polar organic solvent. Furthermore, polyethylene oxide, polyvinyl acetate, polyvinyl butyral, or polyvinylidene fluoride may be used as the organic polymer.

■ M o O *, T as an inorganic reduction color forming layer of ECD
Transition metals such as iOz may also be used. Further, another type of ion blating method, sputtering method, vacuum evaporation method, etc. may be used to form the reduction coloring layer.

■ Polypyrrole, poly-N-alkylvirole, polythiophene, poly-3 as an organic oxidation coloring layer for ECD.
- Organic electrochromic materials such as alkylthiophenes may be used.

■ Other electroluminescent materials can also be used in ELDs.

■ Inorganic glass or heat-resistant plastic material other than soda-lime glass may be used as the substrate material.

(2) The display section may be constructed by replacing the arrangement of the ECD and ELD. Further, the display section may be composed only of the ECD.

Further, the electrochromic display device of the third invention can be widely applied as a display device for aircraft, railway vehicles, or various industrial equipment.

Effects of the Invention As detailed above, the electrochromic element of the present invention can obtain an extremely large contrast change due to the high coloring density when voltage is applied, and also has a solid or semi-solid state in the electrolyte layer. Since it uses an electrochromic material, there is no fear of liquid leakage, and it has high responsiveness, making it an excellent invention that can be applied to a wide range of applications.

In addition, the electrochromic light control device of the second invention has excellent responsiveness and uses an element with high color density when voltage is applied, so it exhibits the effect of quickly obtaining any desired light transmittance. This is an excellent invention.

Furthermore, since the electrochromic display device of the third invention has excellent responsiveness and uses elements with high color density when voltage is applied, information of any brightness can be displayed quickly. This is an excellent invention that demonstrates the following.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view showing the structure of the ECD of the present invention. Further, Figs. 2 to 4 show an embodiment of the second invention, Fig. 2 is a perspective view of the mounting part of the sunroof with dimming function, Fig. 3 is a plan view of the main part, and Fig. 4 is the ECD. FIG. 3 is a schematic cross-sectional view of the configuration. Fig. 5.6 shows another embodiment of the second invention, Fig. 5 is a sectional view of the main part of the anti-glare mirror, and Fig. 6 is an EC
FIG. 3 is a schematic cross-sectional view of the configuration of D. Furthermore, FIGS. 7 to 9 show an embodiment of the third invention, in which FIG. 7 is a schematic sectional view of the structure of the display section, FIG. 8 is a perspective view of the display section attached to the windshield, and FIG. FIG. 9 is also a front view of the display section. 1. ECD, 10. Electrode, 11. Inorganic reduction coloring layer, 12. Organic oxidation coloring layer, 13. Electrolytic layer. Patent applicant Yutaka 1) Synthesis Co., Ltd. Toyota Central Research Institute Co., Ltd. Representative Patent Attorney On 1) Hironobu Figure 5 Figure 6 Figure 7 Figure 1 (Ja Figure 8

Claims (1)

[Claims] 1. A pair of electrodes (10a, 10
b), an organic oxidation coloring layer (12) and an inorganic reduction coloring layer (11) formed opposite to each other between the pair of electrodes (10a, 10b), and both coloring layers (12, 11). An electrochromic device comprising a solid or semi-solid electrolytic layer (13) formed in between. 2. The electrochromic device according to claim 1, wherein the organic oxidation coloring layer (12) is one selected from the group consisting of polyaniline, polypyrrole, and polythiophene. 3. The inorganic reduction coloring layer (11) is WO_3, MoO
The electrochromic device according to claim 1, which is any one selected from the group consisting of _3 and TiO_2 or a mixture thereof. 4. The electrolyte in the electrolytic layer (13) is LiClO_4,
The electrochromic device according to claim 1, which is one selected from the group consisting of LiBF_4 and LiPF_6. 5. A pair of electrodes (10a, 10
b), an organic oxidation coloring layer (12) and an inorganic reduction coloring layer (11) formed opposite to each other between the pair of electrodes (10a, 10b), and both coloring layers (12, 11). An electrochromic light control device in which an electrochromic element (1) comprising a solid or semi-solid electrolyte layer (13) formed in between is formed on the surface of a substrate. 6. The electrochromic light control device according to claim 5, wherein the organic oxidation coloring layer (12) is one selected from the group consisting of polyaniline, polypyrrole, and polythiophene. 7. The inorganic reduction coloring layer (11) is WO_3, MoO
The electrochromic light control device according to claim 5, which is any one selected from the group consisting of _3 and TiO_2 or a mixture thereof. 8. The electrolyte in the electrolytic layer (13) is LiClO_4,
The electrochromic light control device according to claim 5, which is one selected from the group consisting of LiBF_4 and LiPF_6. 9. A pair of transparent electrodes (10a, 10b), an organic oxidation coloring layer (12) and an inorganic reduction coloring layer (11) formed opposite to each other between the pair of electrodes (10a, 10b).
) and a solid or semi-solid electrolyte layer (13) formed between the two coloring layers (12, 11), an electrochromic element (1) is formed on the surface of a substrate. 10, the organic oxidation coloring layer (12) is polyaniline;
The electrochromic display device according to claim 9, which is any one selected from the group consisting of polypyrrole and polythiophene. 11. The inorganic reduction color forming layer (11) is WO_3, Mo
The electrochromic display device according to claim 9, which is any one selected from the group consisting of O_3 and TiO_2 or a mixture thereof. 12. The electrolyte in the electrolytic layer (13) is LiClO_4
10. The electrochromic display device according to claim 9, which is one selected from the group consisting of , LiBF_4, and LiPF_6. 13. The electrochromic display device according to claim 9, wherein an electroluminescent element (2) is integrally formed on the surface of the electrochromic element (1).