JPH10197907A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrochromic(EC) element of <=25% in the lower limit of transmittance by providing this element with the constitution obtd. by joining a pair of element substrates formed with EC layers and a pair of electrode layers holding these layers on the surfaces with sealing resins by disposing the forming surfaces of the respective layers opposite to each other. SOLUTION: This element is constituted by joining the EC elements (two) formed on the substrates with the sealing resins by disposing the element surfaces on the inner side. In this production process, a lower electrode layer 11, the EC layer 1 and an upper electrode layer 12 are first successively laminated on the one surface of the glass substrate 3. A lower electrode layer 21, the EC layer 2 and an upper electrode layer 22 are then successively laminated on the one surface of the other glass substrate 4. The substrates are stuck to each other with the sealing resins 5 by disposing the EC element formed on the glass substrate 3 and the EC element formed on the glass substrate 4 face to face. Conductive thin films or conductive paste, etc., are formed on the lower electrode layers 11, 21, upper electrode layers 12, 22, etc., exposed without being covered with the sealing resins 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic device used for controlling light quantity and displaying.

[0002]

2. Description of the Related Art A phenomenon in which an electrolytic oxidation or reduction reaction occurs reversibly when a voltage is applied, and the color reversibly turns on and off is called electrochromism. Using an electrochromic (hereinafter sometimes abbreviated as EC) substance that exhibits such a phenomenon, an EC element (hereinafter sometimes abbreviated as ECD) that can be turned on and off by applying voltage is made, and the ECD is controlled in light intensity. Attempts to use elements (for example, light control glass and anti-glare mirrors) and numerical display elements using 7 segments have been made for more than 20 years.

ECDs can be broadly classified into solution type, gel type, all solid type, etc. according to the material form of each layer constituting the ECD. Among them, all solid type ECDs are formed by laminating all layers in a thin film form. It is formed. Therefore, in the all-solid-state ECD,
The process of forming each layer on a separate device substrate and bonding both device substrates and the process of sealing the liquid material, such as when manufacturing a solution-type or gel-type ECD, are not necessary, and it is thought that the size can be easily increased. Have been.

[0004] For example, an ECD (special feature) in which a transparent electrode layer (cathode), a tungsten trioxide thin film layer (EC layer), an insulating layer such as silicon dioxide, and an electrode layer (anode) are sequentially laminated on a glass substrate. All-solid-state ECD
Also known as When a voltage (coloring voltage) is applied to the ECD, the tungsten trioxide (WO ₃ ) thin film layer is colored blue. Thereafter, when a reverse voltage (decoloring voltage) is applied to this ECD, the blue color of the WO ₃ thin film layer disappears, and the ECD becomes colorless. Although the mechanism of the discoloration is not elucidated in detail, it is understood that a small amount of water contained in the WO ₃ thin film layer and the insulating layer (ion conductive layer) controls the discoloration of the WO _3. I have.

[0005] The reaction formula for coloring is estimated as follows. Therefore, the disadvantages of such a display element include: (1) the contained water is consumed by an undesired side reaction such as generation of oxygen gas during the coloring reaction, and (2) water is generated by the reverse decoloring reaction. Therefore, it is necessary to replenish water from the atmosphere in order to repeat coloring. In particular, for the latter reason (2), this type of display element includes:
There is a disadvantage that the reproducibility of coloring is affected by atmospheric moisture.

[0006] Recently, the same amount of water has been produced by the decoloring reaction as the amount of water consumed by the coloring reaction, so that the coloring and decoloring can be repeated without the need for replenishment of water from the outside world, and the repetition is repeated. An all-solid-state EC device in which the coloring density is not affected by the outside world has been proposed (JP-A-52-7374).
No. 9). This display element is basically formed by sequentially laminating a transparent electrode film, an electrolytic reduction color-forming thin film (EC layer) such as WO ₃ , an electrolytic oxidizing thin film (EC layer) such as Cr ₂ O ₃ , and a counter electrode. It is. Also, according to the disclosure of the above publication,
When the voltage is released after coloring by applying a voltage, a phenomenon is seen in which the coloring gradually disappears due to spontaneous discharge, and this display element has a property that the coloring is preserved even after the voltage is released (this is called a memory property). It is necessary to provide an insulating film, for example, a thin film of silicon dioxide, magnesium fluoride, or the like at an arbitrary position between the transparent electrode and the counter electrode. According to Japanese Patent Publication No. 62-52845, this insulating film is
Although it is not a good conductor of electrons, it is a substance that can freely move protons and hydroxy ions, that is, it is presumed that it is an ion conductive substance. According to the disclosure of the above publication, it is most desirable that the insulating film, that is, the ionic conductive layer, is present between the electrolytic reduction color-forming thin film and the electrolytic oxidation color-forming thin film. It is alleged that it has been found that it is not necessary that both of the functional thin films have a color-forming property, and that either one of them has a color change such that a change can be recognized from the outside. At least one of the pair of electrode layers directly or indirectly sandwiching the EC layer must be transparent in order to make the coloration and decoloration of the EC layer appear to the outside. In particular, in the case of a transmission type ECD, both electrode layers must be transparent.

At present, as a transparent electrode layer material,
SnO ₂ , In ₂ O ₃ , ITO (a mixture of In ₂ O ₃ and SnO ₂ ), ZnO, etc. are known, but these materials have to be made thinner because of their relatively poor transparency. EC for other reasons
D is usually formed on an element substrate (for example, a glass plate or a plastic plate). In addition, the ECD is used by arranging a sealing substrate for protecting the element so as to face the element substrate depending on the use, and sealingly sealing the element with, for example, an epoxy resin.

[0008]

The upper limit of the transmittance of the ECD is about 80% when the color is erased and about 25% when the color is colored. If the lower limit of the transmittance is further reduced, for example, the application as a shutter is widened, so that it is required to realize a transmittance of 25% or less. However, for example, when the applied voltage is increased in order to lower the transmittance by coloring the ECD, if the applied voltage exceeds the limit voltage of the element, there is a problem that the ECD is peeled off and the film is broken. Also, EC
Even if the thickness of the layer is increased, the coloring density is saturated at a certain thickness or more, and the transmittance cannot be reduced below 25%. The present invention has been made in view of such conventional problems, and has as its object to provide an ECD in which the lower limit of the transmittance is 25% or less.

[0009]

Accordingly, the present invention firstly provides a device comprising: a pair of element substrates each having at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer formed on a surface thereof, with the surfaces on which the respective layers are formed facing each other; An electrochromic device (Claim 1) having a structure joined via a sealing resin is provided.

The present invention is also directed to a second aspect of the present invention in which an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed on a surface of an element substrate, and each layer forming surface is sealed with a sealing substrate via a sealing resin. Electrochromic device comprising a plurality of chromic devices joined together (Claim 2) "
I will provide a. In addition, the present invention relates to a third aspect of the present invention, wherein at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed on each layer forming surface of the first element substrate on which a pair of electrode layers sandwiching the electrochromic layer are formed. Each layer non-forming surface of the second element substrate formed on the surface is joined via a first sealing resin, and each layer forming surface of the second element substrate is further sealed by a sealing substrate via a second sealing resin. An electrochromic device (claim 3) having a sealed structure is provided.

[0011] The present invention is also directed to a fourth aspect of the present invention, wherein each layer forming surface of a first element substrate having at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer formed on a surface thereof is sealed by a sealing substrate via a first sealing resin. Sealing, and further sealing each layer forming surface of the second element substrate having formed thereon at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer with a non-bonding surface of the sealing substrate via a second sealing resin. An electrochromic device (Claim 4) having a structure formed by stopping.

[0012]

FIG. 1 shows a first embodiment according to the present invention.
1 is a schematic plan view and a schematic cross-sectional view of an ECD of FIG. The ECD according to the first embodiment of the present invention has a configuration in which two EC elements formed on an element substrate are bonded via a sealing resin with the element surface inside. The configuration of the EC element formed on the element substrate is as follows.
21, EC layers 1 and 2, and upper electrodes 12 and 22 are sequentially stacked. By applying a voltage between the lower electrode layer 11 and the upper electrode layer 12 of the EC layer 1 and between the lower electrode layer 21 and the upper electrode layer 22 of the EC layer 2, the EC layers 1 and 2 are turned off respectively. To color.

The connection between the electrode and the external wiring may be made by directly connecting the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 which are exposed without being covered with the sealing resin and the external wiring. A lower electrode layer 11 is provided on both end faces of the substrates 3 and 4.
21, when the upper electrode layers 12 and 22 are formed, an external electrode may be directly connected to an extraction electrode portion (not shown) of the EC element formed on the end face of the substrate due to a wraparound phenomenon. In addition, a conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) may be provided on the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered with the sealing resin and are exposed. A thin film or the like is provided, and the conductive thin film or the like is connected to an external wiring.

The lower electrode 11 of the EC layer 1 and the lower electrode 21 of the EC layer 2 are not electrically connected.
If the upper electrode 22 of the EC layer 2 is connected to an external power supply without making electrical contact, the transmittance can be controlled for each EC element, so that fine adjustment is possible. Also,
A conductive thin film or the like is formed from the lower electrode layer 11 of the EC layer 1 to the lower electrode layer 21 of the EC layer 2, and the upper electrode layer 12 of the EC layer 1 is formed.
To the upper electrode layer 22 of the EC layer 2.
Alternatively, a conductive thin film or the like is formed from the extraction electrode portion of the upper electrode layer 12 of the EC layer 1 to the extraction electrode portion of the upper electrode layer 22 of the EC layer 2, and an EC is formed from the extraction electrode portion of the lower electrode layer 11 of the EC layer 1. A conductive thin film or the like may be formed over the extraction electrode portion of the lower electrode layer 21 of the layer 2. in this case,
Although the transmittance cannot be controlled for each EC element, the number of wirings can be reduced.

A method for manufacturing an ECD according to the first embodiment of the present invention will be described. A lower electrode layer 11, an EC layer 1, and an upper electrode layer 12 are sequentially laminated on one surface of the glass substrate 3. Also,
A lower electrode layer 21, an EC layer 2, and an upper electrode layer 22 are sequentially laminated on one surface of another glass substrate 4 in the same manner as described above (FIG. 2). EC element formed on glass substrate 3 and glass substrate 4
The EC elements formed as described above are faced to each other as shown in FIG.

A conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) are formed on the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered with the sealing resin and are exposed. (Referred to as a thin film or the like). FIG.
FIG. 2 is a schematic plan view and a schematic sectional view of an ECD according to a second embodiment of the present invention. The ECD according to the second embodiment of the present invention has a configuration in which two or more sets of ECDs in which an EC element formed on an element substrate is sealed with a sealing substrate via a sealing resin are bonded. Between the lower electrode layer 11 and the upper electrode layer 12 of the EC layer 1;
When a voltage is applied between the lower electrode layer 21 and the upper electrode layer 22 of the EC layer 2, the EC layers 1 and 2 respectively color-disappear.

The connection between the electrode and the external wiring may be made by directly connecting the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are exposed without being covered with the sealing resin and the external wiring. A lower electrode layer 11 is provided on both end faces of the substrates 3 and 4.
21, when the upper electrode layers 12 and 22 are formed, an external electrode may be directly connected to an extraction electrode portion (not shown) of the EC element formed on the end face of the substrate due to a wraparound phenomenon. In addition, a conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) may be provided on the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered with the sealing resin and are exposed. A thin film or the like is formed, and the conductive thin film or the like is connected to an external wiring.

The lower electrode 11 of the EC layer 1 and the lower electrode 21 of the EC layer 2 are not electrically connected.
If the upper electrode 22 of the EC layer 2 is connected to an external power supply without making electrical contact, the transmittance can be controlled for each EC element, so that fine adjustment is possible. Also,
A conductive thin film or the like is formed from the lower electrode layer 11 of the EC layer 1 to the lower electrode layer 21 of the EC layer 2, and the upper electrode layer 12 of the EC layer 1 is formed.
To the upper electrode layer 22 of the EC layer 2.
Alternatively, a conductive thin film or the like is formed from the extraction electrode portion of the upper electrode layer 12 of the EC layer 1 to the extraction electrode portion of the upper electrode layer 22 of the EC layer 2, and an EC is formed from the extraction electrode portion of the lower electrode layer 11 of the EC layer 1. A conductive thin film or the like may be formed over the extraction electrode portion of the lower electrode layer 21 of the layer 2. in this case,
Although the transmittance cannot be controlled for each EC element, the number of wirings can be reduced.

A method for manufacturing an ECD according to the second embodiment of the present invention will be described. Lower electrode layers 11 and 21, EC layers 1 and 2 and upper electrode layer 1 are formed on one surface of glass substrates 3 and 4, respectively.
2 and 22 are sequentially laminated. The EC elements formed on the glass substrates 3 and 4 are sealed with the sealing glass substrate 6 via the sealing resin 5.
Seal with 6 '(FIG. 4). Next, two ECDs are bonded with a resin (FIG. 3).

A conductive thin film or a conductive paste and a conductive clip (hereinafter referred to as a conductive clip) are formed on the exposed lower electrode layers 11 and 21 and upper electrode layers 12 and 22 without being covered with the sealing resin. (Referred to as a thin film or the like). FIG.
3A and 3B are a schematic plan view and a schematic sectional view of an ECD according to a third embodiment of the present invention. In the ECD according to the third embodiment of the present invention, the EC element formed on the substrate 3 is sealed with the glass substrate 4 on which the EC element is formed via the sealing resin 5 and formed on the glass substrate 4. In this configuration, the EC element is sealed with a sealing substrate 6 via a sealing resin 5 '. By applying a voltage between the lower electrode layer 11 and the upper electrode layer 12 of the EC layer 1 and between the lower electrode layer 21 and the upper electrode layer 22 of the EC layer 2, the EC layers 1 and 2 are turned off respectively. To color.

The connection between the electrode and the external wiring may be made by directly connecting the lower electrode layers 11 and 12 and the upper electrode layers 21 and 22 that are exposed without being covered with the sealing resin and the external wiring. A lower electrode layer 11 is provided on both end faces of the substrates 3 and 4.
21, when the upper electrode layers 12 and 22 are formed, an external electrode may be directly connected to an extraction electrode portion (not shown) of the EC element formed on the end face of the substrate due to a wraparound phenomenon. In addition, a conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) may be provided on the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered with the sealing resin and are exposed. A thin film or the like is formed, and the conductive thin film or the like is connected to an external wiring.

The lower electrode 11 of the EC layer 1 and the lower electrode 21 of the EC layer 2 are not electrically connected.
If the upper electrode 22 of the EC layer 2 is connected to an external power supply without making electrical contact, the transmittance can be controlled for each EC element, so that fine adjustment is possible. Also,
A conductive thin film or the like is formed from the lower electrode layer 11 of the EC layer 1 to the lower electrode layer 21 of the EC layer 2, and the upper electrode layer 12 of the EC layer 1 is formed.
To the upper electrode layer 22 of the EC layer 2.
Alternatively, a conductive thin film or the like is formed from the extraction electrode portion of the upper electrode layer 12 of the EC layer 1 to the extraction electrode portion of the upper electrode layer 22 of the EC layer 2, and an EC is formed from the extraction electrode portion of the lower electrode layer 11 of the EC layer 1. A conductive thin film or the like may be formed over the extraction electrode portion of the lower electrode layer 21 of the layer 2. in this case,
Although the transmittance cannot be controlled for each EC element, the number of wirings can be reduced.

A method for manufacturing an ECD according to the third embodiment of the present invention will be described. Lower electrode layers 11 and 21, EC layers 1 and 2 and upper electrode layer 1 are formed on one surface of glass substrates 3 and 4, respectively.
2 and 22 are sequentially laminated. Formed on glass substrate 3
The EC element is sealed with a glass substrate 4 on which the EC element is formed via a sealing resin (FIG. 6). EC formed on glass substrate 4
The element is sealed with a sealing substrate 6 via a sealing resin 5 '.

A conductive thin film or a conductive paste and a conductive clip (hereinafter referred to as a conductive clip) are formed on the exposed lower electrode layers 11 and 21 and upper electrode layers 12 and 22 without being covered with the sealing resin. (Referred to as a thin film or the like). FIG.
9A and 9B are a schematic plan view and a schematic sectional view of an ECD according to a fourth embodiment of the present invention. In the ECD according to the fourth embodiment of the present invention, an EC element formed on a substrate 3 is sealed with a sealing substrate 6 via a sealing resin 5, and an EC element formed on a glass substrate 4 is further sealed. The configuration is such that the non-joining surface of the sealing substrate 6 is sealed via the resin 5 ′.

The lower electrode layer 11 and the upper electrode layer 12 of the EC layer 1
During this time, a voltage is applied between the lower electrode layer 21 and the upper electrode layer 22 of the EC layer 2 to cause the EC layers 1 and 2 to color-decolor, respectively. The connection between the electrode and the external wiring is performed by the lower electrode layers 11 and 12 and the upper electrode layer 2 which are exposed without being covered with the sealing resin.
1, 22 may be directly connected to the external wiring, or the lower electrode layers 11, 2 may be provided on both end surfaces of the substrates 3, 4, respectively.
1. When the upper electrode layers 12 and 22 are formed, an extraction electrode portion (not shown) of an EC element formed on the end face of the substrate due to a wraparound phenomenon may be directly connected to an external wiring. In addition, a conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) may be provided on the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered with the sealing resin and are exposed. A thin film or the like is formed, and the conductive thin film or the like is connected to an external wiring.

The lower electrode 11 of the EC layer 1 and the lower electrode 21 of the EC layer 2 are not electrically connected.
If the upper electrode 22 of the EC layer 2 is connected to an external power supply without making electrical contact, the transmittance can be controlled for each EC element, so that fine adjustment is possible. Also,
A conductive thin film or the like is formed from the lower electrode layer 11 of the EC layer 1 to the lower electrode layer 21 of the EC layer 2, and the upper electrode layer 12 of the EC layer 1 is formed.
To the upper electrode layer 22 of the EC layer 2.
Alternatively, a conductive thin film or the like is formed from the extraction electrode portion of the upper electrode layer 12 of the EC layer 1 to the extraction electrode portion of the upper electrode layer 22 of the EC layer 2, and an EC is formed from the extraction electrode portion of the lower electrode layer 11 of the EC layer 1. A conductive thin film or the like may be formed over the extraction electrode portion of the lower electrode layer 21 of the layer 2. in this case,
Although the transmittance cannot be controlled for each EC element, the number of wirings can be reduced.

A method for manufacturing an ECD according to the fourth embodiment of the present invention will be described. The lower electrode layers 11 and 21, the EC layer 1 and the upper electrode 12,
22 are sequentially laminated. The EC element formed on the glass substrate 3 is sealed with a sealing substrate 6 via a sealing resin 5. Further, the EC element formed on the glass substrate 4 is sealed on the non-joining surface of the sealing substrate 6 via the sealing resin 5 '.

A conductive thin film or a conductive paste and a conductive clip (hereinafter, referred to as a conductive clip) are applied to the lower electrode layers 11 and 21 and the upper electrode layers 12 and 22 that are not covered by the sealing resin layer and are exposed. (Referred to as a thin film or the like). Less than,
The materials used in ECD will be described. As the material of the transparent electrode, for example, SnO ₂ , In ₂ O ₃ , ITO, ZnO, or the like is used. If it is not necessary to be transparent, the electrode layer is formed of a metal material or carbon. As a metal material, for example,
Gold, silver, aluminum, chromium, tin, zinc, nickel, ruthenium, rhodium, stainless steel and the like are used. Even if the metal electrode layer has a low resistance based on the transparent electrode layer as described above, it has a much lower resistance.
Such an electrode layer is generally formed by a vacuum thin film forming technique such as vacuum deposition, ion plating, and sputtering. In the present invention, WO ₃ , MoO _3, a mixture thereof or the like is generally used for the electrolytic reduction color-forming thin film layer.

In the ionic conductive layer, for example, silicon oxide,
Tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, magnesium fluoride, and the like are used. The ionic conductive layer is an insulator for electrons, but is a good conductor for protons (H ⁺ ) and hydroxy ions (OH ⁻ ). E
Cations are required for the color-decoloring reaction of the C layer, and H ⁺ and Li ⁺
It must be contained in the EC layer and others. H ⁺ does not need to be an ion from the beginning, and it is sufficient that H + is generated when a voltage is applied, and thus water may be contained instead of H ⁺ . This water is very small and sufficient, and often discolors even water that naturally enters from the atmosphere.

Examples of the electrolytic oxidation color-forming thin film layer include oxide or iridium hydroxide, nickel, chromium, vanadium, ruthenium, rhodium and the like. When the patterned EC layer is an electrolytic reduction color-forming thin film layer, these electrolytic oxidation color-forming thin film layer materials may be dispersed in an ion conductive layer or a transparent electrode layer, or conversely, they may be dispersed. May be.

Other EC substances include, for example, metal oxides and sulfides such as titanium oxide, cobalt oxide, iron oxide, silicon oxide, lead oxide, copper oxide, iron sulfide, bismuth oxide, niobium sulfide, and hydroquinone. Derivatives, iron berlin derivatives, metal phthalocyanine derivatives (Co, Fe, Zn,
Nitrogen and Cu phthalocyanine derivatives), Prussian blue, Prussian blue-like compounds, indium nitride, tin nitride, zirconium chloride nitride, viologen-based organic EC materials, styryl-based organic EC materials, polyaniline, and the like can be used for the EC layer.

As other examples of the ionic conductive layer, a layer having ionic conductivity and adhesiveness can be used. For example, poly (2-acrylamido-2-methylpropanesulfonic acid), poly (styrene-sulfonic acid) ), A polymer comprising poly (ethylene-sulfonic acid), polyvinyl sulfonic acid, fluorinated copolymer, etc., (B) a first monomer (for example, vinyl sulfonic acid, sodium vinyl sulfonate, vinyl sulfonyl fluoride) ) And a second monomer (for example, vinylpyrrolidinone, butyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, cyclohexyl vinyl ether, isobutylene), (C) the first monomer and the second monomer (D) hydrophilic acrylate monomer (for example, Poly (ethylene oxide)
Dimethacrylate, ethoxytriethylene, glycol methacrylate, ethylene oxide-dimethylcyclohexane acrylate, hydroxypropyl acrylate, ethyl acrylate) and a sulfonic acid monomer (for example, 2-acrylamido-2-methylpropanesulfonic acid, styrene-sulfonic acid, ethylene- Sulfonic acid, vinyl sulfonic acid) and the like.

Further, a layer having ionic conductivity, EC property and adhesiveness can be used. For example, a material in which the EC substance is dispersed in the material of the layer having ionic conductivity and adhesiveness can be used. . Since the ECD is liable to be deteriorated as it is bare, it is used by being formed between two substrates. For example, when an ECD is formed on one substrate, the exposed ECD
The CD is sealed with a sealing resin and a sealing plate. Also, when each layer constituting the ECD is formed separately on two substrates,
The ECD is sealed by bonding two substrates together with the layer having ionic conductivity and adhesiveness and the layer having ionic conductivity, EC property and adhesiveness which constitute the ECD.

The sealing resin is preferably a transparent material such as an epoxy resin, a urethane resin, an acrylic resin, a vinyl acetate resin or a modified polymer, but is not limited thereto. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0035]

【Example】

[Embodiment 1] FIG. 1 is a schematic view of an ECD according to Embodiment 1, and a manufacturing process of the ECD according to Embodiment 1 will be described with reference to FIG. (1) ITO having a film thickness of about 200 nm as a lower electrode layer 11 on a glass substrate 3 by a vacuum evaporation method or an ion plating method.
Was formed. On top of this, a mixed film of iridium oxide and tin oxide with a thickness of about 150 nm, a tantalum oxide film with a thickness of about 500 nm and a tungsten oxide film with a thickness of about 500 nm are sequentially formed as an EC layer 1, and an upper electrode layer 12 is further formed thereon. About 200nm ITO
Was formed. (FIG. 2) (2) On the glass substrate 4, as in (1), as the lower electrode layer 21, an ITO having a thickness of about 200 nm, and as the EC layer 2, a mixed film of iridium oxide and tin oxide having a thickness of about 150 nm, about 500 nm A tantalum oxide film of about 500 nm and a tungsten oxide film of about 500 nm are sequentially formed, and an upper electrode layer 22 of about 200 nm of ITO is further formed thereon.
Was formed. (FIG. 2) (3) As shown in FIG. 1, the EC elements formed on the glass substrates 3 and 4 in the above (1) and (2) were bonded to each other with the sealing resin 5 so as to face each other ( (Fig. 1). (4) When the lower electrode layers 11 and 21 are formed on both end surfaces of the glass substrates 3 and 4, the thickness from the lead-out electrode portion (not shown) of the EC element formed by the wraparound phenomenon to the sealing resin. 50μm aluminum and 100
μm of copper was sequentially deposited to form a conductive thin film having a two-layer structure.

Similarly, when the upper electrode layers 12 and 22 are formed on both end surfaces of the glass substrates 3 and 4, sealing is performed from an extraction electrode portion (not shown) of the EC element formed by a wraparound phenomenon. Aluminum having a thickness of 50 μm and copper having a thickness of 100 μm were sequentially adhered to the resin to form a conductive thin film having a two-layer structure. (5) Attach a conductive clip to each of these conductive thin films with soldered wiring, and apply 1.3 V from the drive power supply.
When the voltage was applied, the ECD was colored blue. When a reverse voltage of 1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. 6% transmittance when colored, 6 when decolored
It was 0%.

In place of (4) and (5), the lower electrodes 11, 21 and the upper electrodes 12, 22 which are exposed without being covered with the sealing resin are electrically conductive thin films or conductive clips ( (Which may not be formed on the conductive thin film). [Embodiment 2] FIG. 3 is a schematic view of an ECD according to Embodiment 2, and a manufacturing process of the ECD according to Embodiment 2 will be described with reference to FIG. (1) ITO having a film thickness of about 200 nm as a lower electrode layer 11 on a glass substrate 3 by a vacuum evaporation method or an ion plating method.
Was formed. On top of this, a mixed film of iridium oxide and tin oxide with a thickness of about 150 nm, a tantalum oxide film with a thickness of about 500 nm and a tungsten oxide film with a thickness of about 500 nm are sequentially formed as an EC layer 1, and an upper electrode layer 12 is further formed thereon. About 200nm ITO
Was formed. The ECD was sealed with a sealing glass substrate 6 via a sealing resin 5. (FIG. 4) (2) The lower electrode layer 21 was formed on the glass substrate 4. On top of this, a mixed film of iridium oxide and tin oxide with a thickness of about 150 nm, tantalum oxide with a thickness of about 500 nm and about 500 nm as an EC layer 2
Was sequentially formed, and about 200 nm of ITO was further formed thereon as the upper electrode layer 22. The ECD was sealed with a sealing glass substrate 6 ′ via a sealing resin 5. (FIG. 4) (3) As shown in FIG. 3, the ECD manufactured in (1) and the ECD manufactured in (2) were bonded together with a sealing resin 5 (FIG. 3). (4) When the lower electrode layers 11 and 21 are formed on both end surfaces of the glass substrates 3 and 4, the thickness from the lead-out electrode portion (not shown) of the EC element formed by the wraparound phenomenon to the sealing resin. 50μm aluminum and 100
μm of copper was sequentially deposited to form a conductive thin film having a two-layer structure.

Similarly, when the upper electrode layers 12 and 22 are formed on both end surfaces of the glass substrates 3 and 4, sealing is performed from a lead-out electrode portion (not shown) of the EC element formed by a wraparound phenomenon. Aluminum having a thickness of 50 μm and copper having a thickness of 100 μm were sequentially adhered to the resin to form a conductive thin film having a two-layer structure. (5) When wiring is soldered to each of these conductive thin films and a voltage of 1.3 V is applied from a driving power source, the ECD
Was colored blue. When a reverse voltage of 1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. The transmittance at the time of coloring was 6%, and the transmittance at the time of decoloring was 60%.

In place of the parts (4) and (5), the lower electrodes 11, 21 and the upper electrodes 12, 22 which are exposed without being covered with the sealing resin are connected to the conductive thin film or the conductive clip ( (Which may not be formed on the conductive thin film). [Embodiment 3] FIG. 5 is a schematic view of an ECD according to a third embodiment, and a manufacturing process of the ECD according to the third embodiment will be described with reference to FIG. (1) ITO having a film thickness of about 200 nm as a lower electrode layer 11 on a glass substrate 3 by a vacuum evaporation method or an ion plating method.
Was formed. On top of this, a mixed film of iridium oxide and tin oxide with a thickness of about 150 nm, a tantalum oxide film with a thickness of about 500 nm and a tungsten oxide film with a thickness of about 500 nm are sequentially formed as an EC layer 1, and an upper electrode layer 12 is further formed thereon. About 200nm ITO
Was formed. (FIG. 2) (2) On the glass substrate 4, as in (1), as the lower electrode layer 21, an ITO having a thickness of about 200 nm, and as the EC layer 2, a mixed film of iridium oxide and tin oxide having a thickness of about 150 nm, about 500 nm A tantalum oxide film of about 500 nm and a tungsten oxide film of about 500 nm were sequentially formed, and about 200 nm of ITO was further formed as the upper electrode layer 22. (FIG. 2) (3) The EC element manufactured in (1) is sealed via the sealing resin 5 on the side of the ECD manufactured in (2) where the EC element is not formed, via the sealing resin 5 (FIG. 6). Formed on the glass substrate 4 in (2)
The EC element was sealed with a sealing substrate 6 via a sealing resin 5 '.
(FIG. 5) (4) Sealing from an extraction electrode portion (not shown) of the EC element formed by the wraparound phenomenon when the lower electrode layers 11 and 21 are formed on both end surfaces of the glass substrates 3 and 4 respectively. 50μm thick aluminum and 100
μm of copper was sequentially deposited to form a conductive thin film having a two-layer structure.

Similarly, when the upper electrode layers 12 and 22 are formed on both end surfaces of the glass substrates 3 and 4, sealing is performed from a lead-out electrode portion (not shown) of the EC element formed by a wraparound phenomenon. Aluminum having a thickness of 50 μm and copper having a thickness of 100 μm were sequentially adhered to the resin to form a conductive thin film having a two-layer structure. (5) When wiring is soldered to each of these conductive thin films and a voltage of 1.3 V is applied from a driving power source, the ECD
Was colored blue. When a reverse voltage of 1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. The transmittance at the time of coloring was 6%, and the transmittance at the time of decoloring was 60%.

Further, instead of the manufacturing process of (3), (2)
Of the EC element manufactured in the above process through a sealing resin 5 ′ and a sealing substrate 6.
Then, a step of sealing the EC element manufactured in (1) on the glass substrate 4 side of the ECD prepared in advance via the sealing resin 5 can be adopted. (FIG. 7) Further, the lower electrodes 11, 21 and the upper electrode 1, which are exposed without being covered with the sealing resin instead of part of (4) and (5).
A step of forming a conductive thin film or a conductive clip (which does not have to be formed on the conductive thin film) can be adopted in 2, 22. [Embodiment 4] FIG. 8 is a schematic view of an ECD according to a fourth embodiment, and a manufacturing process of the ECD according to the fourth embodiment will be described with reference to FIG. (1) ITO having a film thickness of about 200 nm as a lower electrode layer 11 on a glass substrate 3 by a vacuum evaporation method or an ion plating method.
Was formed. On top of this, a mixed film of iridium oxide and tin oxide with a thickness of about 150 nm, a tantalum oxide film with a thickness of about 500 nm and a tungsten oxide film with a thickness of about 500 nm are sequentially formed as an EC layer 1, and an upper electrode layer 12 is further formed thereon. About 200nm ITO
Was formed. (FIG. 2) (2) On the glass substrate 4, as in (1), as the lower electrode layer 21, an ITO having a thickness of about 200 nm, and as the EC layer 2, a mixed film of iridium oxide and tin oxide having a thickness of about 150 nm, about 500 nm A tantalum oxide film of about 500 nm and a tungsten oxide film of about 500 nm were sequentially formed, and about 200 nm of ITO was further formed as the upper electrode layer 22. (FIG. 2) (3) The EC element manufactured in (1) was sealed with a sealing substrate 6 via a sealing resin 5. Furthermore, EC produced in (2)
The device was sealed with a non-bonding surface of a sealing substrate 6 sealing the EC device manufactured in (1) via a sealing resin 5 '. (4) When the lower electrode layers 11 and 21 are formed on both end surfaces of the glass substrates 3 and 4, the thickness from the lead-out electrode portion (not shown) of the EC element formed by the wraparound phenomenon to the sealing resin. 50μm aluminum and 100
μm of copper was sequentially deposited to form a conductive thin film having a two-layer structure.

Similarly, when the upper electrode layers 12 and 22 are formed on both end surfaces of the glass substrates 3 and 4, sealing is performed from a lead-out electrode portion (not shown) of the EC element formed by a wraparound phenomenon. Aluminum having a thickness of 50 μm and copper having a thickness of 100 μm were sequentially adhered to the resin to form a conductive thin film having a two-layer structure. (5) When wiring is soldered to each of these conductive thin films and a voltage of 1.3 V is applied from a driving power source, the ECD
Was colored blue. When a reverse voltage of 1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. The transmittance at the time of coloring was 6%, and the transmittance at the time of decoloring was 60%.

Also, instead of a part of (4) and (5), a conductive thin film or a conductive clip ( (Which may not be formed on the conductive thin film). Comparative Example FIG. 10 is a schematic view of an ECD according to a comparative example.
(1) ITO having a film thickness of about 200 nm as a lower electrode layer 11 on a glass substrate 3 by a vacuum evaporation method or an ion plating method.
Was formed. On top of this, a mixed film of iridium oxide and tin oxide having a thickness of about 150 nm, a tantalum oxide film of about 500 nm and a tungsten oxide film of about 500 nm are sequentially formed as an EC layer 1, and an upper electrode layer 12 is further formed thereon. 200nm ITO
Was formed. (2) The ECD manufactured in the above (1) was sealed with the sealing resin 5 and the sealing substrate 6. (FIG. 7) (3) A thickness of 50 μm from the extraction electrode portion (not shown) of the EC element formed by the wraparound phenomenon when the lower electrode layer 11 is formed on both end surfaces of the glass substrate 3 to the sealing resin. Of aluminum and 100 μm of copper were sequentially deposited to form a conductive thin film having a two-layer structure.

Similarly, when the upper electrode layer 12 is formed on both end surfaces of the glass substrate 3, the upper electrode layer 12 is formed by a wraparound phenomenon.
Aluminum having a thickness of 50 μm and copper having a thickness of 100 μm were successively deposited from an extraction electrode portion (not shown) of the EC element to a sealing resin to form a conductive thin film having a two-layer structure. (4) When wiring is soldered to each of these conductive thin films and a voltage of 1.3 V is applied from a driving power supply, the ECD
Was colored blue. When a reverse voltage of 1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. The transmittance at the time of coloring was 25%, and the transmittance at the time of decoloring was 80%.

In place of (3) and (4), a conductive thin film or a conductive clip (on the conductive thin film) is applied to the lower electrode 11 and the upper electrode 12 which are exposed without being covered with the sealing resin. May be formed).

[0046]

As described above, according to the present invention, the EC
Since there are two or more EC elements in D, the transmittance is
It can be lowered sufficiently compared to CD. Further, setting the lower limit of the transmittance to 25% or less can be useful for, for example, a shutter.

[Brief description of the drawings]

FIG. 1A is a schematic plan view of an ECD according to a first embodiment of the present invention, FIG. 1B is a cross-sectional view taken along the line XX ′ in FIG.
(C) is a sectional view taken along the line YY 'of (a).

FIG. 2 is a schematic cross-sectional view showing an intermediate step of manufacturing an ECD according to Embodiments 1 and 3 according to the present invention.

3A is a schematic plan view of an ECD according to a second embodiment of the present invention, FIG. 3B is a cross-sectional view taken along the line XX ′ in FIG.
(C) is a sectional view taken along the line YY 'of (a).

FIG. 4 is a schematic cross-sectional view showing an intermediate step of ECD manufacturing according to a second embodiment of the present invention.

5A is a schematic plan view of an ECD according to a third embodiment of the present invention, FIG. 5B is a cross-sectional view taken along the line XX ′ in FIG.
(C) is a sectional view taken along the line YY 'of (a).

FIG. 6 is a schematic cross-sectional view showing a first halfway step of manufacturing an ECD according to the third embodiment of the present invention.

FIG. 7 is a schematic cross-sectional view showing a second halfway step of manufacturing an ECD according to the third embodiment of the present invention.

8A is a schematic plan view of an ECD according to a fourth embodiment of the present invention, FIG. 8B is a cross-sectional view taken along line XX ′ of FIG.
(C) is a sectional view taken along the line YY 'of (a).

FIG. 9 is a schematic cross-sectional view showing an intermediate step of ECD manufacturing according to a fourth embodiment of the present invention.

10A is a schematic plan view showing a conventional ECD (Comparative Example), and FIG. 10B is a cross-sectional view taken along line XX ′ of FIG. 10A.

[Explanation of symbols]

 1, 2, EC layer 3, 4, glass substrate 5, 5 ', sealing resin 6, 6', sealing glass substrate 11, lower electrode layer of EC layer 1 ..The upper electrode layer of EC layer 1 21... The lower electrode layer of EC layer 2 22... The upper electrode layer of EC layer 2

Claims (4)

[Claims] 1. A structure in which a pair of element substrates each having at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer formed on the surface thereof are joined to each other with a sealing resin in which the surfaces on which the respective layers are formed face each other. Characteristic electrochromic element. 2. An electrochromic device comprising a plurality of electrochromic elements in which at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed on the surface, and each layer forming surface of the element substrate is sealed with a sealing substrate via a sealing resin. Electrochromic element. 3. An electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed on the surface of each layer of the first element substrate on which at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed. Each layer non-formation surface of the second element substrate is joined via a first sealing resin, and each layer formation surface of the second element substrate is further sealed with a sealing substrate via a second sealing resin. An electrochromic device having a structure as follows. 4. A layer forming surface of a first element substrate on which at least an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed is sealed with a sealing substrate via a first sealing resin. It has a structure in which an electrochromic layer and a pair of electrode layers sandwiching the electrochromic layer are formed on the surface, and each layer forming surface of the second element substrate is sealed with a non-bonding surface of the sealing substrate via a second sealing resin. An electrochromic device, characterized in that: