JPH11316395A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the ratio of the light transmittance at the time of decoloring to that at the time of coloring, i.e., a switching ratio larger and a life longer by a first juncture which electrically connects both of a first lower electrode layer and a second lower electrode layer and a second juncture which electrically connects both of a first upper electrode layer and a second upper electrode layer. SOLUTION: The lower electrode layer 11 of an electrochromic layer 1 and the lower electrode layer 21 of an electrochromic layer 2 are common in the juncture which is an electrode take-out port. The upper electrode layer 12 of the electrochromic layer 1 and the upper electrode layer 22 of the electrochromic layer 2 are common in the juncture of electricity. Voltage is impressed on the common juncture of the lower electrode layers and the common juncture of the upper electrode layers, by which both of the electrochromic layer 1 and the electrochromic layer 2 are simultaneously colored and decolored. As a result, the electrochromic element having the larger transmitted light quantity at the time of coloring and decoloring, i.e., switching ratio, than the element having just one set of the electrochromic layer 1 is obtd.

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 light quantity control, display and optical switches.

[0002]

2. Description of the Related Art When a voltage is applied to a substance, a phenomenon in which an electrolytic oxidation or electrolytic reduction reaction occurs reversibly and a color or a color disappears reversibly is called electrochromism. By using an electrochromic substance exhibiting this phenomenon, an electrochromic element that can be turned on and off by a voltage operation is manufactured, and the electrochromic element is formed by using a light amount control element (for example, a light control glass or an anti-glare mirror) or a 7-segment. Attempts to use it for numerical display elements have been made for more than 20 years.

[0003] Electrochromic devices can be roughly classified into a solution type, a gel type, an all solid type, and the like, depending on the material form of each layer constituting the electrochromic device. All are formed by laminating in a thin film shape. Therefore, not only is the all-solid-state electrochromic device easy to increase in size, but also, as in the case of producing a solution-type or gel-type electrochromic device, each layer is formed on a separate substrate and the two substrates are bonded to each other. Since there is no need for a step or a step of sealing a liquid or gel material, the productivity is excellent.

For example, a transparent electrode layer (cathode), a tungsten trioxide thin film layer (electrochromic layer), a silicon dioxide thin film layer (insulating layer), and an electrode layer (anode) are sequentially laminated on a glass substrate. An all-solid-state electrochromic device is described in JP-B-52-46098. Voltage (coloring voltage) applied to this electrochromic device
Is applied, the tungsten trioxide (WO ₃ ) thin film layer is colored blue. Thereafter, when a voltage having a reverse polarity (decoloring voltage) is applied to the electrochromic element, the blue color of the tungsten trioxide thin film layer disappears, and the electrochromic element returns to colorless. Although the mechanism of the coloration and discoloration is not elucidated in detail, a small amount of water contained in the tungsten trioxide thin film layer and the insulating layer (ion conductive layer) controls the coloration and discoloration of the tungsten trioxide thin film layer. Is understood.

[0005] The reaction formula for coloring is estimated as follows. ^{_{H 2 O → H + + OH}} - (WO 3 layer = ^{_{cathode) WO 3 + nH + + ne}} - → HnWO 3 colorless blue colored (insulating layer = ^{anode) OH - → (1/2) H} 2 O + (1 / 4) O ₂ ↑ + e ^- Therefore, such a display element has (1) a coloring reaction.
A side reaction called oxygen gas generation occurs, and this oxygen gas is released from the inside of the film. Therefore, the property that the contained water is consumed by this side reaction, and (2) the oxygen that becomes the material is degraded by the reverse decolorization reaction Since it does not exist inside the film, it has a property that water is not generated. For this reason, there is a disadvantage that water inside the film is consumed for coloring and decoloring, and that replenishment of water from the atmosphere is required for repeated coloring and decoloring. In particular, for the latter reason (2), this type of device has the disadvantage that the reproducibility of the coloring is affected by atmospheric moisture.

[0006] In order to solve the above disadvantages, a coloring reaction is used.
The same amount of water is consumed by the decolorization reaction
Coloration without the need for external water supply
The color can be repeated, and the repeated coloring density
All-solid-state electrochromic element not affected by the outside world
This is described in JP-A-52-73749. This element
The element basically consists of a transparent electrode layer as an electrode,
Tungsten trioxide thin film layer as rochromic layer
Such as chromium oxide (Cr _TwoO_Three)film
And a counter electrode are successively stacked.
It consists of layers.

[0007] Also, in Japanese Patent Laid-Open Publication No. 52-73749, a DC power supply is connected to the electrode and the counter electrode of the element, and after applying a DC voltage to color the element, the connection with the DC power supply is cut. In the case, a phenomenon is seen in which the coloring gradually disappears due to spontaneous discharge, but by providing a thin film such as an insulating layer such as silicon dioxide or magnesium fluoride at an arbitrary position between the transparent electrode and the other electrode, It is described that a property of retaining coloring even after the voltage is released (this property is referred to as a memory property) is imparted to this element. Tokiko Sho 62-528
No. 45 speculates that this insulating layer is not a good conductor of electrons, but may be a layer of a substance that can freely move protons and hydroxy ions, that is, an ion conductive substance. Furthermore, Japanese Patent Publication No. 62-52845 discloses that it is most desirable that an insulating layer, that is, an ionic conductive layer, is disposed between an electrolytic reduction color-forming thin film layer and an electrolytic oxidation color-forming thin film layer.
In addition, it is described that both the electrolytic reduction color-forming thin film layer and the electrolytic oxidation color-forming thin film layer do not need to be color-forming, and it is sufficient if one of them is discolored so that a change can be recognized from the outside. .

[0008] Electrochromic element
A pair of electrodes directly or indirectly sandwiching the
Light is incident on the decolorized electrochromic layer,
Is to extract the emitted light to the outside of the device, so at least
One electrode must be transparent. In particular, transmission-type
In the case of a lectrochromic element, both electrodes must be transparent.
I have to.

[0009] Currently, as a transparent electrode layer material,
SnO_Two, In_TwoO_Three, ITO (In_TwoO_ThreeAnd SnO_TwoMixture), ZnO etc
However, these materials have relatively high light absorption.
Therefore, the film thickness must be reduced to obtain the required transmittance.
However, the electrochromic element is not
Film or plastic board)
Is common.

[0010] A voltage is applied to the pair of electrodes from an external power supply
The extraction electrode, which is the connection part with the external wiring,
Provide. If a transparent electrode layer is used as the electrode,
Since the electrode layer has high resistance to external wiring, the transparent electrode
Low resistance take-out electrodes overlaid (ie, in contact)
Is often provided. Normally, the transparency is located at the edge of the substrate surface.
A low-resistance electrode section is provided in a strip around the bright electrode layer (for example,
For example, attach a metal clip or use a low-resistance metal material.
Or by vacuum thin film forming technology
And a low-resistance extraction electrode.

In addition, depending on the application, an electrochromic element is provided with a sealing substrate for protecting the element facing the element substrate, and hermetically sealed using, for example, an epoxy resin, an acrylic resin, a urethane resin, or the like. Used.

[0012]

As described above, the all-solid-state electrochromic device has characteristics such as excellent color erasing and erasing characteristics and the possibility of increasing the size. However, the ratio of the light transmittance at the time of erasing to the time of coloring, that is, the switching ratio is at a satisfactory level for normal use, but the conventional switching ratio is not sufficient to further expand the use range. There was a problem.

Conventionally, there is known a method of increasing the driving voltage to increase the coloring density in order to improve the switching ratio. However, when the driving voltage is increased beyond the limit voltage, the element is peeled off and the element is destroyed. In addition, excessively increasing the drive voltage without causing film peeling or destruction leads to shortening of the device life. Further, in order to improve the switching ratio, a method of increasing the thickness of the electrochromic layer to increase the coloring concentration is also known. However, the coloring concentration surely increases up to a certain film thickness. At a film thickness of, the coloring concentration is saturated.

The present invention has been made in view of such conventional problems, and provides a long-life electrochromic device having a large ratio of light transmittance at the time of erasing to coloring, that is, a switching ratio. Aim.

[0015]

In order to solve the above-mentioned problems, the present invention firstly provides an "electrochromic element, wherein a first substrate and a first lower electrode which are sequentially arranged on the first substrate in a laminated manner. A first electrochromic member having a layer, a first electrochromic layer, and a first upper electrode layer,
A second substrate and a second electrochromic member having a second lower electrode layer, a second electrochromic layer, and a second upper electrode layer, which are sequentially arranged in a stacked form on the second substrate, and an end of the electrochromic element The portion comprises a first connection portion and a second connection portion, the first electrochromic member and the second electrochromic member facing the first upper electrode layer surface and the second upper electrode layer surface sealing resin And the first connection portion is connected to both the first lower electrode layer and the second lower electrode layer, and the second connection portion is connected to the first upper electrode layer and the second upper electrode layer. An electrochromic device (Claim 1) characterized by being electrically connected to both.

Secondly, in an electrochromic device, a substrate, an electrochromic layer laminated on the substrate, a pair of electrode layers sandwiching the substrate, and a sealing member joined via a sealing resin. A plurality of electrochromic members having a substrate and a plurality of connection portions at the ends of the electrochromic element, the plurality of connection portions being electrically connected to the electrode layer, wherein the plurality of electrochromic members are provided on the surface of the substrate. Or the sealing substrate surface, the substrate surface or the sealing substrate surface facing and all bonded and integrated via an adhesive, the connection portion is electrically connected to two or more electrode layers An electrochromic device (claim 2). "

Third, in the electrochromic device, a plurality of electrochromic members each having a substrate, an electrochromic layer laminated on the substrate, and a pair of electrode layers sandwiching the substrate are provided. Comprising a plurality of sealing substrates, and a plurality of connection portions at the ends of the electrochromic element where electrical connection with the electrode layer is made, wherein the plurality of electrochromic members and the sealing substrate are the substrate Each layer forming surface and each layer non-forming surface, as well as the respective layer forming surface of the substrate and the sealing substrate surface, are all joined and integrated via a sealing resin, and at least one connection portion is formed by two. An electrochromic device (claim 3), which is electrically connected to the above-mentioned electrode layer, is provided.

Fourth, in the electrochromic element, the number of substrates, two or more and two or more electrochromic layers arranged in a stacked manner on the substrate, and one more layer than the electrochromic layer A thin-film portion having an electrode layer, and a plurality of connection portions at the end of the electrochromic element, which are electrically connected to the electrode layer. Each of the electrochromic layers has two electrode layers. A layer closest to the substrate surface of the thin film portion and a layer farthest from the substrate surface each include an electrode layer, and at least one connection portion is electrically connected to two or more electrode layers. An electrochromic device (Claim 4) is provided.

Fifth, "the number of the connection portions is two, and when a certain DC voltage is applied between the two connection portions, all the electrochromic layers are colored, and a certain reverse polarity DC voltage is applied. 5. An electrochromic layer according to claim 2, wherein all the electrochromic layers are decolored when the voltage is applied.
The present invention provides an electrochromic device (claim 5).

Sixth, in the electrochromic device, a first substrate, a first lower electrode layer, a first electrochromic layer, and a first upper electrode layer, which are sequentially stacked on the first substrate, are formed. Having a first electrochromic member, a second substrate, a second lower electrode layer, a second electrochromic layer, a second upper electrode layer, which are sequentially arranged in a stacked state on the second substrate, and joined via a sealing resin. A second electrochromic member having a sealed substrate, comprising a first connection portion and a second connection portion at an end of the electrochromic element, wherein the first electrochromic member and the second electrochromic member are Each layer forming surface of the first substrate and the non-layer forming surface of the second substrate are opposed to each other and joined via a sealing resin, and the first connection portion is a two-layer electrode layer of the total of four electrode layers. Electrically connected to The second connection portion is electrically connected to the remaining two electrode layers, and when a constant DC voltage is applied between the first connection portion and the second connection portion, the first electrochromic layer and An electrochromic device characterized in that both the second electrochromic layer and the second electrochromic layer are colored, and when a DC voltage having a certain reverse polarity is applied, both the first electrochromic layer and the second electrochromic layer are decolorized. Item 6) is provided.

Seventh, "the connection portion, the first connection portion, and the second connection portion have a conductive thin film or conductive paste and a conductive clip. An electrochromic device according to any one of claims 3, 4, 5, and 6 (claim 7) ".

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, one electrochromic element has two or more sets of electrochromic layers, and the number of connection portions of electrodes is one set of one electrochromic layer. The feature is that it is not different from the time of the element in which it is. The electrochromic layer commonly used in the following description is composed of a multilayer thin film layer, and there are two types as viewed from the lamination order. The first is a type in which an electrolytic oxidation color-forming thin film layer, an ion conductive layer, and an electrolytic reduction color-forming thin film layer are sequentially stacked. The second is an electrolytic reduction color-forming layer, an ion conductive layer, and an electrolytic oxidation color-forming thin film layer in that order. It is a type that is laminated.

Hereinafter, embodiments of the electrochromic device of the present invention will be described with reference to the drawings, but the present invention is not limited to these drawings. As an example of the first embodiment of the present invention, an electrochromic device having two sets of electrochromic layers will be described. 2
Each set of electrochromic layers is sandwiched between a pair of electrode layers. The electrode layer closer to the glass substrate is a lower electrode, and the other electrode is an upper electrode. In FIG. 1, each of the electrochromic layers is denoted by 1 and 2, respectively. The lower electrode layers are denoted as 11, 21 and the upper electrode layers are denoted as 12, 22. Of the layers constituting the electrochromic layer, a layer in contact with the lower electrode layer is formed so as to be an electrolytic oxidation coloring thin film layer, and a layer closer to the upper electrode is formed as an electrolytic reduction coloring thin film layer. Of course, on the contrary, a layer in contact with the lower electrode layer may be formed so as to be an electrolytic reduction color-forming thin film layer, and a layer closer to the upper electrode may be formed as an electrolytic oxidation color-forming thin film layer. The lower electrode layer 11 of the electrochromic layer 1 and the lower electrode layer 21 of the electrochromic layer 2 have a common connection portion as an electrode outlet, and the upper electrode layer 12 of the electrochromic layer 1 The upper electrode layer 22 of the layer 2 has a common electrode connection. By applying a voltage to the connection portion of the common lower electrode layer and the connection portion of the common upper electrode layer, the electrochromic layer 1 and the electrochromic layer 2 are simultaneously colored. Therefore, an electrochromic element having a larger transmission light amount ratio, ie, a switching ratio at the time of color erasing and erasing, than an electrochromic element having only one set of electrochromic layers can be obtained. Furthermore, since the present electrochromic device has a common connection portion between the electrode layers of the two electrochromic layers, the number of connection portions is the same as that of a device having only one set of electrochromic layers.

The method for producing an electrochromic device of the present invention can be, for example, the following method. The lower electrode layer 11 is formed on one surface of the glass substrate 3. An electrochromic layer 1 is formed thereon, and an upper electrode layer 12 is further formed. A lower electrode layer 21, an electrochromic layer 2, and an upper electrode layer 22 are formed on one surface of another glass substrate 4 in the same manner as described above. Here, when the two substrates are bonded to each other, the extraction portions of the lower electrode layers 11 and 21 of the two substrates are close to each other, and the extraction portions of the upper electrode layers 12 and 22 of the two substrates are A lower electrode layer and an upper electrode layer of two element substrates are formed so as to be close to each other. Formed in this way, the two upper electrode lead portions of the two electrochromic layers are electrically connected to one connection portion, and the two lower electrode lead portions are electrically connected to the other connection portion. I do. (Corresponding to claim 1) Further, two sets of electrochromic elements may be manufactured, and then two electrochromic elements may be bonded and integrated. Also in this case, the upper electrode layer and the lower electrode layer for each electrochromic element are configured such that when they are bonded, the lead-out portion of the electrode is electrically connected to the common connection portion. Further, one of the two sets of electrochromic elements in the former stage is not sealed with the sealing substrate, and each layer forming surface of the unsealed electrochromic element and the sealed electrochromic element. May be bonded together to be integrated. Also in this case, the upper electrode layer and the lower electrode layer for each electrochromic element are configured such that when they are bonded, the lead-out portion of the electrode is electrically connected to the common connection portion. (Corresponding to claim 3) As shown in FIG. 5, of the layers constituting the electrochromic layer 1, the layer in contact with the lower electrode layer is formed by the electrolytic oxidation coloring thin film layer and the layer constituting the electrochromic layer 2 is formed by the upper part. The layer in contact with the electrode may be an electrolytic oxidation color-forming thin film layer. In this case, the first connection portion for electrically connecting the lead portion of the lower electrode layer 11 and the lead portion of the upper electrode layer 22 is electrically connected to the lead portion of the upper electrode layer 12 and the lead portion of the lower electrode layer 21. Is formed in advance. Also in this case, by applying a voltage between the first connection portion and the second connection portion, the electrochromic layer 1 and the electrochromic layer 2 are simultaneously colored. (Corresponding to claim 1) Further, it is possible to adopt a form in which two sets of electrochromic elements are manufactured and then both elements are bonded together to be integrated. Also in this case, the upper electrode layer and the lower electrode layer for each electrochromic element are configured such that when they are bonded, the lead-out portion of the electrode is electrically connected to the common connection portion. (Corresponding to claim 2) Further, one of the two sets of electrochromic elements in the former stage is not sealed with the sealing substrate, and each layer forming surface of the unsealed electrochromic element and the electrochromic element of the sealed electrochromic element are not sealed. It may be integrated with a substrate by bonding. Also in this case, the upper electrode layer and the lower electrode layer for each electrochromic element are configured such that when they are bonded, the lead-out portion of the electrode is electrically connected to the common connection portion. (Corresponding to Claim 3) An electrochromic device according to a second embodiment of the present invention will be described by taking an electrochromic device having two sets of electrochromic layers as an example as described above. In FIG. 3, two sets of electrochromic layers 1 and 2 are sandwiched by a pair of electrode layers, respectively. However, the entire electrode layer is shared by the two sets of electrochromic layers, and the connection part is electrically connected. It is connected to the. In addition, the electrode layers 11 and 21 that do not share the entire electrode layer share a connection portion that is electrically connected. In this case, the constituent layers of the respective electrochromic layers adjacent to the shared electrode layer are unified as both the electrolytic reduction color-forming thin film layer and both the electrolytic oxidation color-forming thin film layers. With such a configuration, the electrochromic layer 1 and the electrochromic layer 2 are formed by applying a DC voltage to the connection portion of the electrode layer 12 where the entire electrode layer is shared and the connection portion of the electrodes 11 and 21. Colors at the same time and decolors at the same time.
Therefore, an electrochromic device having a larger change width of color erasing and discoloring than an electrochromic device having only one set of electrochromic layers can be obtained. Furthermore, since the electrode layers of the electrochromic layers 1 and 2 or the connection portions of the electrode layers are common, the number of connection portions is the same as in the case of an element having only one electrochromic layer. (Claim 4
Correspondence) The above-described method for manufacturing an electrochromic element includes, for example, the following method. The lower electrode layer 11 is formed on one surface of the element substrate 3. An electrochromic layer 1 is formed thereon, and an upper electrode layer 12 is further formed.
At this time, the electrochromic layer 1 is of a type in which the electrolytic reduction coloring layer is in contact with the upper electrode layer. The electrochromic layer 2 is further formed on the upper electrode layer 12. At this time, the electrochromic layer 2
Is a type in which the electrolytic reduction coloring layer is in contact with the upper electrode layer. Further, a lower electrode layer 21 is formed thereon.
At this time, a common connection portion is provided for the lower electrode layer 11 and the lower electrode layer 21, and a connection portion for the upper electrode layer 12 is further provided. By forming in this way, two sets of electrochromic layers can be simultaneously colored by applying a constant DC voltage to these connection portions.

Hereinafter, the materials used in the electrochromic device will be described. As a material of the electrode and the counter electrode, for example, a transparent electrode material such as SnO ₂ , In ₂ O ₃ , ITO (a mixture of In ₂ O ₃ and SnO ₂ ), and ZnO is preferably used. Depending on the use conditions, a metal material or carbon is used. As the metal material, gold, silver, aluminum, chromium, tin, zinc, nickel, ruthenium, rhodium, stainless steel and the like are preferably used, but are not limited thereto. The metal electrode layer has the advantage that it has much lower resistance than the electrode layer formed from the transparent electrode material as described above. Such electrode layers are generally vacuum deposited,
It is formed by a vacuum thin film forming technique such as ion plating and sputtering.

[0026] WO is used for the electrolytic reduction coloring layer._Three, MoO_ThreeMa
Or a mixture thereof is preferably used.
It is not limited to them. Oxide oxide
Iodine, tantalum oxide, titanium oxide, aluminum oxide,
Niobium oxide, zirconium oxide, hafnium oxide, oxidation
Lanthanum, magnesium fluoride, etc. are preferably used
However, the present invention is not limited to these.

[0027] The ionic conductive layer is an insulator for electrons.
But the proton (H⁺) And hydroxy ions (OH^-)
Is a good conductor. Electrochromic layer attachment
A cation is required for the decolorization reaction, and H⁺And Li⁺The
It must be contained in the trochromic layer and the like. H
⁺Does not have to be ions from the beginning;
H when⁺And therefore H⁺instead of
May contain water. This water is very little and enough
Water, which often enters naturally from the atmosphere
Decolorize.

[0028] Electrolytic oxidation coloring thin film layer
Indium, iridium hydroxide, nickel oxide, nickel hydroxide
Kel, chromium oxide, chromium hydroxide, vanadium oxide, water
Vanadium oxide, ruthenium oxide, ruthenium hydroxide,
Rhodium oxide, rhodium hydroxide, etc. are preferably used.
However, the present invention is not limited to these. Other elements
As a trochromic substance, for example, titanium oxide, acid
Cobalt oxide, iron oxide, silicon oxide, lead oxide, copper oxide, sulfuric acid
Metal oxides such as iron fossil, bismuth oxide, niobium sulfide, and gold
Genus sulfide, hydroquinone derivative, iron berlinate
Derivatives, metal phthalocyanine derivatives (Co, Fe, Zn, Ni,
Each phthalocyanine derivative of Cu), Prussian blue, P
Lucian blue-like compound, indium nitride, silicon nitride
Size, zirconium nitride chloride, viologen-based organic elect
Rochromic material, styryl organic electrochromic
Material, polyaniline, etc. in the electrochromic layer
Can be used.

[0029] Other examples of ion conductive layers include ion
Conductive and adhesive layers can be used.
(A) Poly (2-acrylamido-2-methylpro
Pansulfonic acid), poly (styrene-sulfonic acid),
Li (ethylene-sulfonic acid), polyvinyl sulfonic acid,
A polymer consisting of a fluorinated copolymer, etc., (B) a first monomer
Body (eg, vinyl sulfonic acid, vinyl sulfonic acid nato)
Lium, vinylsulfonyl fluoride) and a second monomer (eg
For example, vinyl pyrrolidinone, butyl vinyl ether,
Tyl vinyl ether, isopropyl vinyl ether,
(Co-hexyl vinyl ether, isobutylene)
Coalescence, (C) the first monomer and the second monomer
Copolymer with sodium lensulfonate, (D) hydrophilic
Acrylate monomers (eg, poly (ethyleneoxy)
C) dimethacrylate, ethoxytriethylene, glyco
Methacrylate, ethylene oxide-dimethyl cycle
Rohexane acrylate, hydroxypropyl acryle
Acid, ethyl acrylate) and sulfonic acid monomer (for example,
For example, 2-acrylamide-2-methylpropane sulfone
Acid, styrene-sulfonic acid, ethylene-sulfonic acid,
And a layer composed of a copolymer with sulfonic acid.

Since the electrochromic element is liable to be deteriorated as it is bare, it is used by being sealed between two substrates. For example, when an electrochromic element is formed on one substrate, the exposed electrochromic element is sealed with a sealing resin and a sealing substrate. As the sealant, for example, a transparent material such as an epoxy resin, a urethane-based resin, an acrylic resin, a vinyl acetate-based resin, and a modified polymer is preferably used, 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.

[0031]

EXAMPLES Example 1 (1) An ITO film was formed as an electrode 11 on a glass substrate 3. On top of that, a mixed film of iridium oxide and tin oxide (electrolytic oxidation coloring thin film layer) as an electrochromic layer 1,
A first electrochromic member was manufactured by forming a tantalum oxide film (ion conductive layer) and a tungsten oxide film (electrolytic reduction coloring thin film layer) in this order, and further forming an ITO film as an upper electrode layer 12 thereon. (FIG. 1 (b-1)) (2) An ITO film as the lower electrode layer 21 and a mixed film of iridium oxide and tin oxide, a tantalum oxide film, a tungsten oxide as the electrochromic layer 2 on the glass substrate 4 as in (1). A film is formed and ITO is used as the upper electrode layer 22.
A film was formed to produce a second electrochromic member. (FIG. 1 (b-2)) (3) The substrate of the above (1) and (2) is pulled out of the upper electrode layer 12 of the first electrochromic member with the epoxy resin 5, as shown in FIG. 1 (a). And the leading portion of the lower electrode layer 11 of the first electrochromic member and the leading portion of the lower electrode layer 21 of the second electrochromic member are close to each other. Then, it was bonded by sealing. (4) A gold paste 6 is applied to each end where the lead-out portions of the adjacent electrodes are present, and both lead-out portions are made conductive, and a clip is held between the glass substrate 3 and the glass substrate 4 while being in contact with the gold paste layer. 7 was attached, and a pair of connection parts was produced. (FIG. 1 (a)) (5) Of the pair of connecting portions, the connecting portion connected to the electrode layer in contact with the tungsten oxide film (electrolytic reduction coloring thin film layer) is connected to the cathode of an external DC power supply; When the connection part connected to the electrode layer in contact with the mixed film of iridium oxide and tin oxide (electrolytic oxidation color-forming thin film layer) is connected to the anode of an external DC power supply and a voltage of 1.3 V is applied, the electrochromic device becomes Colored blue. When a 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%. Example 2 (1) An ITO film was formed as a lower electrode layer 11 on a glass substrate 3. A mixed film of iridium oxide and tin oxide (electrolytic chromogenic thin film layer), a tantalum oxide film (ionic conductive layer), and a tungsten oxide film (electrolytic reduction chromogenic thin film layer) are sequentially formed thereon as the electrochromic layer 1. Then, an ITO film was further formed thereon as the upper electrode layer 12 to produce a first electrochromic member. (FIG. 5 (b-
1)) (2) An ITO film as the lower electrode layer 21 on the glass substrate 4, a tungsten oxide film (electrolytic reduction coloring thin film layer), a tantalum oxide film (ion conductive layer), iridium oxide and tin oxide as the electrochromic layer 2 Are sequentially formed, and the upper electrode layer 22 is formed.
As a result, an ITO film was formed to produce a second electrochromic member. (FIG. 5 (b-2)) (3) Using the epoxy resin 5, the above-mentioned substrates (1) and (2) are pulled out from the upper electrode layer 12 of the first electrochromic member as shown in FIG. 5 (a). And the leading portion of the lower electrode layer 21 of the first electrochromic member is close to the leading portion of the lower electrode layer 21 of the second electrochromic member. Then, it was bonded by sealing. (4) A gold paste 6 is applied to each end where the lead-out portions of the adjacent electrodes are present, and both lead-out portions are made conductive, and a clip is held between the glass substrate 3 and the glass substrate 4 while being in contact with the gold paste layer. 7 was attached, and a pair of connection parts was produced. (FIG. 5 (a)) (5) Of the pair of connecting portions, the connecting portion connected to the electrode layer in contact with the tungsten oxide film (electrolytic reduction coloring thin film layer) is connected to the cathode of an external DC power supply; When the connection part connected to the electrode layer in contact with the mixed film of iridium oxide and tin oxide (electrolytic oxidation color-forming thin film layer) is connected to the anode of an external DC power supply and a voltage of 1.3 V is applied, the electrochromic device becomes Colored blue. When a 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%. Example 3 (1) As shown in FIG. 2, a lower electrode layer 1 was formed on a glass substrate 3.
As No. 1, an ITO film was formed. A mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film were sequentially formed thereon as the electrochromic layer 1, and an ITO film was further formed thereon as the upper electrode layer 12.
Next, the element was sealed with the sealing glass substrate 8 and the epoxy resin 5 to produce a first electrochromic member. (2) The lower electrode layer 21 was formed on the glass substrate 4. A mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film were sequentially formed thereon as the electrochromic layer 2, and an ITO film was further formed thereon as the upper electrode layer 22. Next, the element was sealed with the sealing glass substrate 9 and the epoxy resin 5 to produce a second electrochromic member. (3) As shown in FIG. 2, the first electrochromic member and the second electrochromic member have a lead portion of the upper electrode 12 of the first electrochromic member and a lead portion of the upper electrode 22 of the second electrochromic member. Then, the lead portion of the lower electrode 11 and the lead portion of the lower electrode 21 were adhered with the epoxy resin 5 so as to be close to each other. (4) A gold paste 6 is applied to each end where a lead-out portion of an adjacent electrode is present, so that both lead-out portions are conducted, and the glass substrate 3 and the sealing substrate 9 are sandwiched while being in contact with the gold paste layer. The clip 7 was attached, and a pair of connection portions was produced. (FIG. 2) (5) Of the pair of connection portions, the connection portion connected to the electrode layer in contact with the tungsten oxide film is connected to the cathode of the external DC power supply, and is in contact with the mixed film of iridium oxide and tin oxide. When the other connection part connected to the electrode layer was connected to the anode of the external DC power supply and a voltage of 1.3 V was applied, the electrochromic element was colored blue. When a voltage of -1.3 V was applied to this device, the blue color disappeared and the device returned to transparent. 6% transmittance when colored, 60 when decolored
%Met. Example 4 (1) As shown in FIG. 3, a lower electrode layer 1 was formed on a glass substrate 3.
1 was formed. A mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film were sequentially formed thereon as the electrochromic layer 1, and an ITO film was further formed as the upper electrode layer 12 on the tungsten oxide film. On the ITO film, a tungsten oxide film, a tantalum oxide film, and a mixed film of iridium oxide and tin oxide are sequentially formed as the electrochromic layer 2, and an ITO film as the lower electrode layer 21 is formed on the mixed film of iridium oxide and tin oxide. Was formed. At this time, the pattern of the lower electrode layer 21 was determined such that the lead portion of the lower electrode layer 21 was close to the lead portion of the lower electrode layer 11. (2) The element was sealed with the sealing glass substrate 8 and the epoxy resin 5. (3) A gold paste 6 is applied to each end where a lead-out portion of an adjacent electrode is present, so that both lead-out portions are conducted, and the glass substrate 3 and the sealing substrate 8 are sandwiched while being in contact with the gold paste layer. The clip 7 was attached, and a pair of connection portions was produced. (FIG. 3) (4) Of the pair of connecting portions, the connecting portion connected to the electrode layer in contact with the tungsten oxide film is connected to the cathode of the external DC power supply, and is in contact with the mixed film of iridium oxide and tin oxide. When the other connection part connected to the electrode layer was connected to the anode of an external direct power supply and a voltage of 1.3 V was applied, both of the electrochromic layers 1 and 2 were colored blue.
When a DC voltage of -1.3 V was applied to this device, the blue color disappeared, and the electrochromic device returned to transparent. The transmittance at the time of coloring was 6%, and the transmittance at the time of decoloring was 60%. Example 5 (1) As shown in FIG. 6, a lower electrode layer 1 was formed on a glass substrate 3.
1 was formed. A mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film are sequentially formed thereon as an electrochromic layer 1, and an ITO film is further formed thereon as an upper electrode layer 12, thereby forming a first electrochromic member. Was prepared. (2) A lower electrode layer 21 is formed on a glass substrate 4, and a mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film are sequentially formed thereon as an electrochromic layer 2, and a further upper portion is formed thereon. As the electrode layer 22
An ITO film was formed. The surface on which each layer of the glass substrate 4 was formed and the sealing glass substrate 9 were bonded to each other with an epoxy resin 5 to produce a second electrochromic member. (3) As shown in FIG. 6, the first electrochromic member and the second electrochromic member are formed such that the lead-out portion of the upper electrode 12 of the first electrochromic member and the lead-out portion of the upper electrode 22 of the second electrochromic member. Then, the respective layers forming surface of the first electrochromic member and the respective non-layer forming surfaces of the glass substrate 4 are bonded to each other with the epoxy resin 5 so that the leading portion of the lower electrode 11 and the leading portion of the lower electrode 21 are close to each other. . (4) A gold paste 6 is applied to each end where the lead-out portions of the adjacent electrodes exist, so that both lead-out portions are conducted, and the glass substrate 3 and the sealing substrate 9 are sandwiched while being in contact with the gold paste layer. The clip 7 was attached, and a pair of connection portions was produced. (FIG. 6) (5) Of the pair of connection portions, the connection portion connected to the electrode layer in contact with the tungsten oxide film is connected to the cathode of the external DC power supply, and is in contact with the mixed film of iridium oxide and tin oxide. When the other connection part connected to the electrode layer was connected to the anode of an external DC power supply and a voltage of 1.3 V was applied, both of the electrochromic layers 1 and 2 were colored blue. When a DC voltage of -1.3 V was applied to this device, the blue color disappeared and the electrochromic device returned to transparent. The transmittance at the time of coloring was 6%, and the transmittance at the time of decoloring was 60%.

As described above, in the first to fifth embodiments, the gold paste is used as the relay electrode for electrical connection between the lead portion of each electrode and the clip, but instead of the gold paste, a conductive film formed by a vacuum thin film forming technique is used. Needless to say, good results can be obtained by using a thin film. Comparative Example (1) As shown in FIG.
As No. 1, an ITO film was formed. A mixed film of iridium oxide and tin oxide, a tantalum oxide film, and a tungsten oxide film are sequentially formed as an electrochromic layer on the ITO film, and an ITO is further formed as an upper electrode layer 12 on the tungsten oxide film.
A film was formed. (2) The substrate (1) was sealed with the epoxy resin 5 and the sealing glass substrate 8. (3) A gold paste is applied to the end of the sealed element where the electrode lead-out portion exists, so that both lead-out portions are conducted, and the glass substrate 3 and the sealing substrate 8 are sandwiched while being in contact with the gold paste layer. A clip was attached, and a pair of connection portions was produced. (FIG. 4) (4) Of the pair of connecting portions, the connecting portion connected to the electrode layer in contact with the tungsten oxide film is connected to the cathode of the external DC power supply, and is in contact with the mixed film of iridium oxide and tin oxide. When the other connection part connected to the electrode layer was connected to the anode of the external DC power supply and a voltage of 1.3 V was applied, the electrochromic element was colored blue. When a DC voltage of -1.3 V was applied to this device, the blue color disappeared, and the electrochromic device returned to transparent. The transmittance at the time of coloring was 25%, and the transmittance at the time of decoloring was 80%.

[0033]

As described above, the electrochromic device of the present invention has a very large transmittance change ratio, that is, a switching ratio. Therefore, light amount control, displays, optical switches, etc., which cannot be applied with conventional electrochromic devices. It can be applied to the field and the range of application is expanded.

Further, the electrochromic device according to the present invention can be driven for coloring and decoloring only by providing the same number of connection parts as the conventional electrochromic device, so that the device structure is simple and the life is long. And cost performance is high.

[Brief description of the drawings]

FIG. 1 is a diagram showing a structure of an electrochromic device of Example 1 of the present invention. (Corresponding to claims 1 and 7)

FIG. 2 is a diagram illustrating a structure of an electrochromic device according to a third embodiment of the present invention. (Claims 2, 5, and 7)

FIG. 3 is a diagram showing a structure of an electrochromic device of Example 4 of the present invention. (Corresponding to claims 4, 5, and 7)

FIG. 4 is a diagram showing a structure of a conventional electrochromic device (comparative example).

FIG. 5 is a diagram showing a structure of an electrochromic device of Example 2 of the present invention. (Corresponding to claim 1)

FIG. 6 is a diagram showing a structure of an electrochromic device of Example 5 of the present invention. (Corresponding to claims 3, 5, 6, 7)

[Explanation of symbols]

Reference Signs List 1 electrochromic layer 2 electrochromic layer 11 lower electrode layer of electrochromic layer 1 12 upper electrode layer of electrochromic layer 1 21 lower electrode layer of electrochromic layer 2 22 upper electrode layer of electrochromic layer 2 3 glass substrate 4 glass substrate 5 Epoxy resin 6 Gold paste 7 Clip 8 Sealing glass substrate
9 sealing glass substrate

Claims (7)

[Claims] 1. An electrochromic device comprising: a first substrate; a first lower electrode layer, a first electrochromic layer, and a first upper electrode layer sequentially arranged on the first substrate in a stacked state. An electrochromic member, a second substrate and a second electrochromic member having a second lower electrode layer, a second electrochromic layer, and a second upper electrode layer, which are sequentially arranged in a stacked state on the second substrate, A first connection portion and a second connection portion are provided at an end of the electrochromic element, and the first electrochromic member and the second electrochromic member face the first upper electrode layer surface and the second upper electrode layer surface. The first connection portion is both the first lower electrode layer and the second lower electrode layer, and the second connection portion is the first upper electrode layer and the Second Electrochromic device, characterized in that electrical connection with both of the electrode layers have been made. 2. An electrochromic device, comprising: a substrate; an electrochromic layer laminated on the substrate; and a pair of electrode layers sandwiching the electrochromic layer and a sealing substrate joined via a sealing resin. A plurality of electrochromic members, and a plurality of connection portions at an end of the electrochromic element, the plurality of connection portions being electrically connected to the electrode layer. The stop substrate surface, the substrate surface or the sealing substrate surface is opposed to the bonding surface and all are bonded and integrated via an adhesive, and the connection portion is electrically connected to two or more of the electrode layers. Characteristic electrochromic element. 3. An electrochromic device, comprising: a plurality of electrochromic members each having a substrate, an electrochromic layer laminated on the substrate, and a pair of electrode layers sandwiching the substrate; A plurality of connection portions electrically connected to the electrode layer at the ends of the electrochromic element, wherein the plurality of electrochromic members and the sealing substrate form each layer of the substrate. The surface and each layer non-formed surface as well as the respective layer formed surface of the substrate and the sealing substrate surface are all joined and integrated via a sealing resin, and at least one connection portion is two or more of the connecting portions. An electrochromic device electrically connected to an electrode layer. 4. An electrochromic device, comprising: a substrate; two or more types of electrochromic layers arranged in a stacked manner on the substrate; a total of two or more electrochromic layers; and one more electrode layer than the electrochromic layer. And a plurality of connecting portions electrically connected to the electrode layer at the end of the electrochromic element,
Each of the electrochromic layers is sandwiched between two of the electrode layers, a layer closest to the substrate surface of the thin film portion and a layer farthest from the substrate surface are each composed of an electrode layer, and at least one of the connection portions is two or more. An electrochromic device electrically connected to said electrode layer. 5. The method according to claim 1, wherein the number of the connection portions is two. When a certain DC voltage is applied between the two connection portions, all the electrochromic layers are colored, and when a certain reverse DC voltage is applied, all the electrochromic layers are colored. The electrochromic element according to any one of claims 2, 3, and 4, wherein the electrochromic layer of (1) is decolorized. 6. An electrochromic device, comprising: a first substrate; a first lower electrode layer, a first electrochromic layer, and a first upper electrode layer, which are sequentially stacked on the first substrate. An electrochromic member, a second substrate, and a second lower electrode layer, a second electrochromic layer, and a second upper electrode layer, which are sequentially stacked on the second substrate, and a seal bonded to the second upper electrode layer via a sealing resin. A second electrochromic member having a stop substrate, and a first connection portion and a second connection portion at an end of the electrochromic element, wherein the first electrochromic member and the second electrochromic member are the first substrate. Each layer forming surface and each layer non-forming surface of the second substrate are opposed to each other and joined via a sealing resin, and the first connection portion is electrically connected to two of the four electrode layers. Connected to the front The second connection part is electrically connected to the remaining two electrode layers, and when a constant DC voltage is applied between the first connection part and the second connection part, the first electrochromic layer and the second electrochromic layer are connected. An electrochromic device characterized in that both the chromic layer and the chromic layer are colored, and when a DC voltage having a certain reverse polarity is applied, both the first electrochromic layer and the second electrochromic layer are decolorized. 7. The method according to claim 1, wherein said connecting portion, said first connecting portion, and said second connecting portion have a conductive thin film or conductive paste and a conductive clip.
The electrochromic device according to any one of 4, 5, and 6.