JP7435006B2 - Electrochromic device, wearable device, and method for driving an electrochromic device - Google Patents

Description

The present invention relates to an electrochromic device, a wearable device, and a method for driving an electrochromic device.

The phenomenon in which a redox reaction occurs reversibly by applying a voltage and the color changes reversibly is called electrochromism, and a device that utilizes this electrochromism is an electrochromic device. Electrochromic devices have been extensively researched to date as they are applicable to a variety of uses.

Examples of electrochromic materials used in electrochromic devices include organic materials and inorganic materials. Electrochromic devices using organic materials are used in color display devices because they can produce various colors depending on their molecular structure. On the other hand, electrochromic devices using inorganic materials have been put into practical use as light control glasses and anti-glare mirrors, as applications that have the advantage of low color saturation.

In an electrochromic device, for example, an electrochromic material is formed between two opposing electrodes, and a redox reaction is performed in a state where an electrolyte layer capable of ion conduction is filled between the electrodes. A transparent electrode is often used for at least one of the electrodes in order to visually recognize the color.
Here, since electrochromic is an electrochemical phenomenon, the performance of the electrolyte layer (ion conductivity, etc.) affects the response speed and color memory effect. If the electrolyte layer is in a liquid state, in which the electrolyte is dissolved in a solvent, it is easy to obtain a fast response, but improvements by solidification or gelation are being considered in terms of element strength and reliability.
Furthermore, for electrochromic devices, a technique is known in which a voltage higher than the original drive voltage is applied for a short time at the start of voltage application in order to improve responsiveness (for example, see Patent Documents 1 and 2). .

The present invention has high responsiveness and uniformity of color density when performing color development/decolorization drive, as well as high strength and safety against external shocks, excellent durability when driven continuously for a long time, and consumption. The purpose of the present invention is to provide an electrochromic device that can suppress power consumption.

The electrochromic device of the present invention as a means for solving the above problems includes:
a first electrode;
a first auxiliary electrode formed in contact with the first electrode;
a second electrode;
a second auxiliary electrode that is in contact with the second electrode and formed such that the average distance from the first auxiliary electrode is 100 mm or less;
an electrochromic layer formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode;
A solid formed in contact with at least one of the first electrode, the second electrode, and the electrochromic layer, but not in contact with the first auxiliary electrode and the second auxiliary electrode. an electrolyte layer;
Control for applying a voltage to the electrochromic layer via the first electrode and the second electrode using at least one of the following drive patterns: a first drive pattern, a second drive pattern, and an initialization drive pattern. means and
Equipped with
The first driving pattern is a driving pattern for bringing the electrochromic layer into a first coloring state, and applies a first voltage pulse A for increasing the response speed of the electrochromic layer to bring the first coloring state. A drive pattern in which a first voltage pulse B lower than the first voltage pulse A is applied to form a first voltage pulse, and then a state in which no voltage is applied is maintained,
The second driving pattern is a driving pattern for forming a second coloring state having a lower color density than the first coloring state from the first coloring state, and is a driving pattern for increasing the response speed of the electrochromic layer. A second voltage pulse B higher than the second voltage pulse A, or a second voltage pulse B having the opposite polarity to the second voltage pulse A, for applying the second voltage pulse A and forming a second colored state. This is a driving pattern in which a voltage is applied and then a state in which no voltage is applied is maintained.
The initialization drive pattern is a drive pattern for forming an initial decolorized state, and includes an initialization voltage pulse A having a polarity opposite to that of the first voltage pulse A and for increasing the response speed of the electrochromic layer. This is a driving pattern in which an initializing voltage pulse B is applied or short-circuited to set the potential of the electrochromic layer to approximately 0 V in order to form an initial decolorized state.

According to the present invention, the responsiveness and uniformity of the coloring density when performing color development/decolorization driving, the strength and safety against external shocks, etc. are high, and the durability is excellent when driving continuously for a long time. At the same time, it is possible to provide an electrochromic device that can suppress power consumption.

FIG. 1 is a diagram showing current values measured using a potentiostat in an example of an electrochromic material capable of two-electron reaction. FIG. 2 is a diagram showing an example of a drive pattern in the first drive pattern. FIG. 3 is a diagram showing an example of a drive pattern in the second drive pattern. FIG. 4 is a diagram showing an example of a drive pattern in the initialization drive pattern. FIG. 5A is a schematic side view showing an example of the electrochromic device according to the first embodiment. FIG. 5B is a schematic top view showing an example of the electrochromic device according to the first embodiment. FIG. 6A is a schematic side view showing an example of an electrochromic device according to the second embodiment. FIG. 6B is a schematic top view showing an example of an electrochromic device according to the second embodiment. FIG. 7 is a schematic side view showing an example of an electrochromic device according to a third embodiment. FIG. 8 is a schematic side view showing an example of an electrochromic device according to the fourth embodiment. FIG. 9A is a schematic top view showing an example of an electrochromic device according to the fifth embodiment. FIG. 9B is a schematic top view showing another example of the electrochromic device according to the fifth embodiment. FIG. 9C is a schematic top view showing another example of the electrochromic device according to the fifth embodiment. FIG. 10 is a diagram showing the results of measuring the transmission spectrum in electrochromic device A. FIG. 11A is a diagram showing the light transmittance spectrum at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to increase the color density using the electrochromic device of Production Example 1. FIG. 11B is a diagram showing the transmittance spectrum at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to increase the coloring density using the electrochromic device of Production Example 1. FIG. 12A is a diagram showing the light transmittance spectrum at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to lower the coloring density using the electrochromic device of Production Example 1. FIG. 12B is a diagram showing the transmittance spectrum at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to lower the coloring density using the electrochromic device of Production Example 1. FIG. 13A is a diagram showing the light transmittance spectrum at the coloring peak wavelength of the oxidation-reactive electrochromic layer when performing initialization drive using the electrochromic device of Production Example 1. FIG. 13B is a diagram showing the transmittance spectrum at the coloring peak wavelength of the reduction-reactive electrochromic layer when performing initialization drive using the electrochromic device of Preparation Example 1. FIG. 14A is a diagram showing the light transmittance spectrum at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to increase the coloring density using the electrochromic device of Production Example 2. FIG. 14B is a diagram showing the transmittance spectrum at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to increase the coloring density using the electrochromic device of Production Example 2. FIG. 15 is a diagram showing another example of the drive pattern in the first drive pattern. FIG. 16 is a diagram showing another example of the drive pattern in the second drive pattern. FIG. 17 is a diagram showing another example of the drive pattern in the initialization drive pattern.

(Electrochromic device, method of driving an electrochromic device)
The electrochromic device of the present invention includes a first electrode, a first auxiliary electrode, a second electrode, a second auxiliary electrode, an electrochromic layer, a solid electrolyte layer, and a control means, It is preferable to have a measuring means, a support, a protective layer, and a deterioration prevention layer, and further have other means as necessary.
The method for driving an electrochromic device of the present invention provides an electrochromic device having a first electrode, a first auxiliary electrode, a second electrode, a second auxiliary electrode, an electrochromic layer, and a solid electrolyte layer. The method includes a control step of applying a voltage to the electrochromic layer according to a specific drive pattern, preferably includes a measurement step, and further includes other steps as necessary.

The method for driving an electrochromic device of the present invention can be suitably carried out using the electrochromic device of the present invention.
That is, the method for driving an electrochromic device of the present invention is implemented by the electrochromic device of the present invention. Therefore, through the description of the electrochromic device of the present invention, details of the method for driving the electrochromic device of the present invention will also be clarified.

Furthermore, in the electrochromic device of the present invention, the responsiveness and uniformity of coloring density when developing and decoloring, as well as the strength and safety against external impact, etc., are lower than those of conventional electrochromic devices. This is based on the knowledge that there may be problems with durability and increased power consumption when continuously driven for a long period of time.

An electrochromic device is driven to develop and fade color by applying a voltage between electrodes and injecting or releasing charges necessary for a redox reaction into an electrochromic layer. As the size of the electrochromic device increases, a voltage drop occurs due to the electrical resistance value of the transparent electrode, so the coloring density becomes thinner in areas far from the electrode contact portion (portion in contact with the electrode), which may cause density unevenness. Therefore, methods have been studied to reduce density unevenness by forming a correction electrical resistance distribution on the transparent electrode surface or by forming a metal auxiliary electrode. However, in these methods, there was a problem that the transparency of the electrochromic device became insufficient, resulting in a decrease in visibility.

Furthermore, as a technique for improving the responsiveness of an electrochromic device, as described above, a technique of applying a voltage higher than the original driving voltage for a short time at the start of voltage application, which is disclosed in Patent Documents 1 and 2, etc. It has been known.
However, in an electrochromic device that uses an electrolyte with excellent ion conductivity (such as an ionic liquid or a solution of an electrolyte dissolved in a solvent), ions are transmitted not only in the direction between the electrodes (vertical) but also in the direction of the electrolyte layer (horizontal). It's also easy to move. For this reason, only the area around the voltage application contact area (around the electrode) responds quickly, causing concentration unevenness, and there is a problem in that it is difficult to improve the response of the entire electrochromic device. In addition, in electrochromic devices that use a solid electrolyte layer that suppresses ion diffusion in the surface (lateral) direction of the electrolytic layer, there is a problem that the electrochromic layer tends to deteriorate when operated continuously for a long time due to the difficulty in ion diffusion. There is.

Further, in recent years, wearable devices have attracted attention as a next-generation application of electrochromic devices, and development is progressing. Batteries used in wearable devices are limited to small size from the viewpoints of lightness and safety, so wearable devices that can be driven with low power consumption are preferable. Furthermore, since wearable devices are used while being worn on the body, higher safety is required compared to other uses.

The electrochromic device of the present invention includes a first electrode, a first auxiliary electrode, a second electrode, a second auxiliary electrode, an electrochromic layer, a solid electrolyte layer, and a control means.
In the electrochromic device of the present invention, since the electrolyte layer is solid, it has high mechanical strength against external impacts and the like, and is highly safe because it does not cause problems such as liquid leakage.
Furthermore, since the electrolyte layer is solid, it is possible to obtain a memory effect in which the colored state and uncolored state are maintained for a certain period of time even when the power is turned off (no voltage is applied). Coloring density can be maintained even with intermittent application of voltage in the drive pattern or the second drive pattern. Therefore, in the electrochromic device of the present invention, power consumption can be suppressed, deterioration of the electrochromic layer due to continuous voltage application can be suppressed, and durability can be improved.

In addition, in the electrochromic device of the present invention, the second auxiliary electrode is formed such that the average distance from the first auxiliary electrode is 100 mm or less. That is, since the electrochromic device of the present invention has an average distance between auxiliary electrodes of 100 mm or less and has a solid electrolyte layer, it is possible to conduct (diffuse) ions efficiently and uniformly, so that it is possible to drive coloring and fading. It is possible to improve the uniformity of color density when performing this process.

Further, in the electrochromic device of the present invention, the electrochromic layer is in contact with at least one of the first electrode and the second electrode, and is in contact with the first auxiliary electrode and the second auxiliary electrode. is formed in a non-contact manner. Similarly, in the electrochromic device of the present invention, the solid electrolyte layer is in contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and the solid electrolyte layer is in contact with the first auxiliary electrode and the electrochromic layer. The second auxiliary electrode is formed in a non-contact manner. In other words, the first auxiliary electrode and the second auxiliary electrode are formed without contacting the electrochromic layer and the solid electrolyte layer. By doing this, even if the first auxiliary electrode and the second auxiliary electrode are made of a material that is easily ionized, such as a wiring material (metallic material), they will not deteriorate due to the electrochemical reaction of the electrochromic layer. can be prevented from happening.

Further, in the electrochromic device of the present invention, the control means controls the voltage application using at least one of the first drive pattern, the second drive pattern, and the initialization drive pattern. In these driving patterns, since voltage pulses are applied to increase the response speed of the electrochromic layer, it is possible to improve the responsiveness of the electrochromic layer when coloring/decoloring driving is performed.
A first driving pattern for bringing the electrochromic layer into a first coloring state (a state in which the coloring density is high), and a second driving pattern for bringing the electrochromic layer into a second coloring state (a state in which the coloring density is low). includes a pattern that maintains a state in which no voltage is applied (open circuit state, open circuit). Therefore, in the electrochromic device of the present invention, as described above, power consumption can be suppressed, and deterioration of the electrochromic layer due to continuous voltage application can be suppressed, and durability can be improved.

<First electrode, second electrode>
The materials for the first electrode and the second electrode are not particularly limited and can be selected as appropriate depending on the purpose, but transparent conductive oxide materials are suitable, such as tin-doped indium oxide (hereinafter referred to as (hereinafter referred to as "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), and antimony-doped tin oxide (hereinafter referred to as "ATO"). Among these, indium oxide (hereinafter referred to as "In oxide"), tin oxide (hereinafter referred to as "Sn oxide"), and zinc oxide (hereinafter referred to as "Zn oxide") formed by vacuum film formation are used. Preferred are inorganic materials containing any one of the following:
In oxide, Sn oxide, and Zn oxide are materials that can be easily formed into films by sputtering, and are also materials that provide good transparency and electrical conductivity. Among these, compositions containing InSnO, GaZnO, SnO, InO, ZnO, InZnO, and InZrO are particularly preferred.

Materials for the first electrode and the second electrode include transparent conductive metal thin films containing silver, gold, copper, and aluminum, carbon films such as carbon nanotubes, and graphene; Network electrodes such as conductive carbon and conductive oxides, or composites thereof are also preferred.
Here, the network electrode is an electrode in which carbon nanotubes or other highly conductive non-transparent materials are formed into a fine network to have transmittance. Furthermore, it is more preferable to laminate a network electrode and a conductive oxide, or to laminate a conductive metal thin film and a conductive oxide. By doing so, the electrochromic layer can be evenly colored and faded.
Note that the conductive oxide layer can also be formed by coating as a nanoparticle ink. Specifically, the laminated structure of a conductive metal thin film and a conductive oxide is an electrode that has both conductivity and transparency in a thin film laminated structure such as ITO/Ag/ITO. These electrode materials are used within a range where visibility reduction is acceptable.

The average thickness of the first electrode and the second electrode is not particularly limited and can be selected as appropriate depending on the purpose. Preferably, it is adjusted. Specifically, when ITO vacuum film formation is used as the material for the first electrode and the second electrode, the average thickness of the first electrode and the second electrode is preferably 20 nm or more and 500 nm or less, and 50 nm or more and 200 nm or less. The following are more preferred.
When the conductive oxide layer is formed by applying nanoparticle ink, the average thickness is preferably 0.2 μm or more and 5 μm or less. Further, the average thickness of the network electrode is preferably 0.2 μm or more and 5 μm or less.

Furthermore, when the electrochromic device is used as a light control mirror, either the first electrode or the second electrode may have a structure having a reflective function. In this case, it is preferable that the first electrode and the second electrode contain a metal material. Examples of the metal material include Pt, Ag, Au, Cr, rhodium, Al, or an alloy thereof, a laminated structure thereof, and a laminated structure with the metal oxide that is resistant to electrochemical reactions and has good durability. It will be done.

Note that the materials and average thicknesses of the first electrode and the second electrode may be the same or different.

The method for producing the first electrode and the second electrode is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a vacuum evaporation method, a sputtering method, an ion plating method, and the like. In addition, examples of methods that can form electrodes by applying the respective materials of the first electrode and the second electrode include a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, Roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet method Examples include various printing methods such as a printing method.

<First auxiliary electrode, second auxiliary electrode>
The first auxiliary electrode is formed in contact with the first electrode.
The second auxiliary electrode is formed so as to be in contact with the second electrode and have an average distance of 100 mm or less from the first auxiliary electrode. That is, the average distance between the first auxiliary electrode and the second auxiliary electrode is 100 mm or less. By doing so, it is possible to suppress the occurrence of unevenness in the color density in the electrochromic layer when performing the color development/decolorization drive, and it is possible to improve the uniformity of the color density.

The planar shapes of the first auxiliary electrode and the second auxiliary electrode are not particularly limited and can be appropriately selected depending on the purpose, for example, a linear shape, a curved shape, a point shape, etc. The planar shapes of the first auxiliary electrode and the second auxiliary electrode are shaped to match the shape of the electrochromic device, for example, when the electrochromic device is used as photochromic glasses (photochromic sunglasses) or a photochromic filter. It is preferable that
For example, when the electrochromic device of the present invention is used as photochromic glasses, the planes of the first auxiliary electrode and the second auxiliary electrode may Preferably, the shape is selected. When the lens part of the photochromic glasses has an elliptical shape, the planar shapes of the first auxiliary electrode and the second auxiliary electrode are, for example, different from the first auxiliary electrode in accordance with the shape of the side part of the lens part. It is preferable that the second auxiliary electrodes are shaped so as to face each other. In addition, if the photochromic glasses are frameless (rimless), the planar shape of the first auxiliary electrode and the second auxiliary electrode should be set to a dot shape, so that they can function as auxiliary electrodes. It is preferable that

Here, the average distance between the first auxiliary electrode and the second auxiliary electrode is the average distance between the first auxiliary electrode and the second auxiliary electrode (for example, the average distance between opposing ends). means.
When measuring the average distance between the first auxiliary electrode and the second auxiliary electrode, for example, when the planar shapes of the first auxiliary electrode and the second auxiliary electrode are linear or curved, , the shortest distance between the second auxiliary electrode and the second auxiliary electrode at any one point at the end of the first auxiliary electrode opposite to the second auxiliary electrode, It can be measured as the "distance" between Furthermore, the "distance" is also measured at any number of points other than the one point, and the average value of these "distances" is defined as the "average distance between the first auxiliary electrode and the second auxiliary electrode". can do.
It should be noted that the larger the number of arbitrary points, the better, and the arbitrary number of points should be selected so as not to include the shortest and longest among the plurality of "distances". This is preferable from the viewpoint of representing the average "distance" between the electrode and the second auxiliary electrode.
In addition, if the shapes of the first auxiliary electrode and the second auxiliary electrode are point-shaped (circular or elliptical), measure the average distance between the first auxiliary electrode and the second auxiliary electrode. In some cases, for example, the shortest distance between the center of the first auxiliary electrode and the center of the second auxiliary electrode can be set as "the average distance between the first auxiliary electrode and the second auxiliary electrode."
The average distance between the first auxiliary electrode and the second auxiliary electrode may be the average distance when viewed from above when the electrochromic layer and solid electrolyte layer are sufficiently thin.

The materials for the first auxiliary electrode and the second auxiliary electrode are not particularly limited and can be appropriately selected depending on the purpose, and the same materials as the first and second electrodes can be used. However, it is preferable to use a wiring material (metallic material) such as Au, Ag, Cu, Al, W, Ni, Wo, or Cr. In other words, in the electrochromic device of the present invention, it is preferable that the first auxiliary electrode and the second auxiliary electrode contain a metal material. By doing this, the electrical resistance of the first auxiliary electrode and the second auxiliary electrode can be made smaller, voltage pulses can be applied more efficiently, and the responsiveness and color density when performing color development/decolorization drive can be reduced. Uniformity can be further improved.
Further, the first auxiliary electrode and the second auxiliary electrode may have a single layer structure or a laminated structure. Furthermore, a coating film structure of metal particles or metal-coated particles may be used. Note that the electrochromic device of the present invention may further include an auxiliary electrode in addition to the first auxiliary electrode and the second auxiliary electrode.

In the electrochromic device of the present invention, it is preferable that the first auxiliary electrode is located on one side of the electrochromic layer, and the second auxiliary electrode is located on the other side opposite to the one side. By doing so, voltage pulses can be applied more efficiently, and the responsiveness and uniformity of color density when performing color development/decolorization driving can be further improved.

The average thickness of the first auxiliary electrode and the second auxiliary electrode is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 nm or more and 5,000 nm or less.

Further, the first auxiliary electrode and the second auxiliary electrode are formed so as not to contact the electrochromic layer and the solid electrolyte layer. By doing this, even if the first auxiliary electrode and the second auxiliary electrode are formed of a material that is easily ionized, such as the above-mentioned wiring material, they will not deteriorate due to the electrochemical reaction of the electrochromic layer. can be prevented.

<Electrochromic layer>
The electrochromic layer is formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode.

The electrochromic layer contains an electrochromic material and, if necessary, other components.
The electrochromic material is not particularly limited as long as it exhibits electrochromism, and can be appropriately selected depending on the purpose. Examples include inorganic electrochromic compounds, organic electrochromic compounds, conductive polymers, and the like.

The inorganic electrochromic compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, and the like.
The organic electrochromic compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include viologen, rare earth phthalocyanine, styryl, and the like.
Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, and derivatives thereof.

The electrochromic layer preferably has a structure in which conductive or semiconducting fine particles support an organic electrochromic compound. Specifically, it has a structure in which fine particles with a particle size of approximately 5 nm to 50 nm are bound to the electrode surface, and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, or silanol group is adsorbed on the surface of the fine particles. is preferred. With this structure, electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, so that the response can be improved compared to conventional electrochromic devices. Furthermore, since a transparent film can be formed as a display layer by using fine particles, a high color density of the electrochromic compound can be obtained.
Further, as the electrochromic layer, a plurality of types of organic electrochromic compounds can be supported on conductive or semiconducting fine particles. Furthermore, the conductive particles can also serve as conductivity as an electrode layer.

Examples of polymer-based and dye-based electrochromic compounds include azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, dipyridine-based, styryl-based, styryl spiropyran-based, spirooxazine-based, spirothiopyran-based, thioindigo-based, and tetrathiafulvalene. type, terephthalic acid type, triphenylmethane type, benzidine type, triphenylamine type, naphthopyran type, viologen type, pyrazoline type, phenazine type, phenylenediamine type, phenoxazine type, phenothiazine type, phthalocyanine type, fluorane type, fulgide type , low-molecular organic electrochromic compounds such as benzopyran-based and metallocene-based, and conductive polymer compounds such as polyaniline and polythiophene. These may be used alone or in combination of two or more.

The electrochromic material is preferably a compound capable of two-electron reaction. That is, it is preferable that the electrochromic layer contains a compound capable of two-electron reaction. Because the electrochromic layer contains a compound capable of two-electron reaction, when high voltage pulses such as first voltage pulse A, second voltage pulse A, and initialization voltage pulse A are applied, in addition to one-electron reaction, Two-electron reactions may also occur. If the electrochromic material is capable of a two-electron reaction, it can prevent the electrochromic material from absorbing excessive energy and decomposing when a high voltage pulse is applied, improving the durability of the electrochromic device. can.

Furthermore, the two-electron reaction that occurs in the electrochromic material can be observed and measured using a potentiostat. More specifically, as shown in FIG. 1, a compound in which two or more current value peaks (oxidation-reduction voltage) are detected when sweeping the voltage is considered an electrochromic material capable of two-electron reaction. be able to. Note that the vertical axis in FIG. 1 represents the current value, and the horizontal axis represents the potential with respect to the reference electrode.

Here, the electrochromic material that changes from a transparent state to a colored state upon oxidation preferably contains a triarylamine derivative having a radically polymerizable functional group represented by the following general formula (1).

Here, when n=2, m is 0, and when n=1, m is 0 or 1. At least one of A and B has a radically polymerizable functional group. A has a structure represented by the following general formula (2), and is bonded to B at any position from R ₁ to R ₁₅ . Note that R ₃ and R ₁₃ , R ₄ and R ₆ , and R ₁₀ and R ₁₁ may form a ring structure with an alkyl chain. Further, B has a structure represented by the following general formula (3), and is bonded to A at any position from R ₁₆ to R ₂₁ .

However, in the above general formulas (2) and (3), R ₁ to R ₂₁ are all monovalent organic groups, and may be the same or different, and each of R 1 to R 21 is a monovalent organic group. At least one of them is a radically polymerizable functional group.

Since the compound represented by the above general formula (1) is a compound capable of a two-electron reaction, it is possible to suppress the electrochromic material from absorbing excessive energy and decomposing, as described above, and the electrochromic device can improve the durability of
Further, when the electrochromic layer is formed of a polymer of a triarylamine derivative, it is advantageous in that the repeat drive (oxidation-reduction reaction) characteristics are good and the photodurability is excellent. In addition, it is transparent in the decolored state, and high-density coloring performance can be obtained through oxidation reaction.
Furthermore, it is more preferable to contain a crosslinked product obtained by crosslinking an electrochromic material containing a triarylamine derivative and another radically polymerizable compound different from this, since this further improves the dissolution resistance and durability of the polymer.

Here, a triarylamine derivative having a radically polymerizable functional group such as the above general formula (2) or general formula (3) will be explained.

<<Triarylamine derivative having radically polymerizable functional group>>
The monovalent organic groups in the above general formulas (2) and (3) each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a substituent. an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an amide group, Monoalkylaminocarbonyl group which may have a substituent, dialkylaminocarbonyl group which may have a substituent, monoarylaminocarbonyl group which may have a substituent, monoarylaminocarbonyl group which may have a substituent, Diarylaminocarbonyl group which may have an optional substituent, sulfonic acid group, alkoxysulfonyl group which may have an optional substituent, aryloxysulfonyl group which may have an optional substituent, alkylsulfonyl group which may have an optional substituent group, an arylsulfonyl group that may have a substituent, a sulfonamide group, a monoalkylaminosulfonyl group that may have a substituent, a dialkylaminosulfonyl group that may have a substituent, a substituent A monoarylaminosulfonyl group that may have a substituent, a diarylaminosulfonyl group that may have a substituent, an amino group, a monoalkylamino group that may have a substituent, a monoarylaminosulfonyl group that may have a substituent, a dialkylamino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an alkyl group which may have a substituent Examples include a good arylthio group and a heterocyclic group which may have a substituent.
Among these, from the viewpoint of stable operation and photodurability, alkyl groups, alkoxyl groups, hydrogen atoms, aryl groups, aryloxy groups, halogen groups, alkenyl groups, and alkynyl groups are particularly preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include methyl group, ethyl group, propyl group, and butyl group.
Examples of the aryl group include phenyl group and naphthyl group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. Examples of the alkoxy group include methoxy group, ethoxy group, and propoxy group.
Examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methoxyphenoxy group, and 4-methylphenoxy group.
Examples of the heterocyclic group include carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

Examples of substituents that are further substituted with the substituent include halogen atoms, alkyl groups such as nitro groups, cyano groups, methyl groups, and ethyl groups, alkoxy groups such as methoxy groups and ethoxy groups, and aryloxy groups such as phenoxy groups. , aryl groups such as phenyl group and naphthyl group, and aralkyl groups such as benzyl group and phenethyl group.

-Radical polymerizable functional group-
The radically polymerizable functional group is not particularly limited as long as it has a carbon-carbon double bond and is radically polymerizable, and can be appropriately selected depending on the purpose. Examples include a 1-substituted ethylene functional group represented by i) and a 1,1-substituted ethylene functional group represented by the following general formula (ii). Among these, acryloyloxy group and methacryloyloxy group are preferred.

In the general formula (i), X ₁ represents an arylene group which may have a substituent, an alkenylene group which may have a substituent, a -CO- group, a -COO- group, -CON )-group [R100 represents hydrogen, an alkyl group, an aralkyl group, or an aryl group. ], or represents a -S- group.

Examples of the arylene group in general formula (i) include a phenylene group and a naphthylene group which may have a substituent.
Examples of the alkenylene group include ethenylene group, propenylene group, and butenylene group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the aralkyl group include benzyl group, naphthylmethyl group, and phenethyl group. Examples of the aryl group include phenyl group and naphthyl group.
Specific examples of the 1-substituted ethylene functional group represented by general formula (i) include vinyl group, styryl group, 2-methyl-1,3-butadienyl group, vinylcarbonyl group, acryloyl group, and acryloyloxy group. , an acryloylamide group, a vinylthioether group, and the like.

In general formula (ii), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, a cyano group, a nitro group, alkoxy group, -COOR ₁₀₁ group [R ₁₀₁ is a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, an aryl group that may have a substituent, or CONR ₁₀₂ R ₁₀₃ (R ₁₀₂ and R ₁₀₃ are a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or an aryl group that may have a substituent) may be the same or different from each other)].
Moreover, _X2 represents the same substituent, single bond, or alkylene group as X1 in general formula (i). However, at least one of Y and X ₂ is an oxycarbonyl group, a cyano group, an alkenylene group, or an aromatic ring.

Examples of the aryl group in general formula (ii) include phenyl group and naphthyl group.
Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the aralkyl group include benzyl group, naphthylmethyl group, and phenethyl group.
Specific examples of the 1,1-substituted ethylene functional group represented by general formula (ii) include α-acryloyloxy chloride group, methacryloyl group, methacryloyloxy group, α-cyanoethylene group, α-cyanoacryloyloxy group, α-cyanophenylene group, methacryloylamino group, etc.
In _addition , examples of substituents that are further substituted with the substituents related to these X ₁ , Examples include alkoxy groups such as, aryloxy groups such as phenoxy groups, aryl groups such as phenyl groups and naphthyl groups, and aralkyl groups such as benzyl groups and phenethyl groups.

Further, as the triarylamine derivative having a radically polymerizable functional group, compounds represented by the following general formulas (1-1) to (1-3) are preferable.
R ₂₇ to R ₈₈ in the following general formulas (1-1) to (1-3) are all monovalent organic groups, and may be the same or different, and at least one of them is It is a radically polymerizable functional group. Furthermore, R ₃₉ and R ₄₁ and R ₄₀ and R ₄₂ may form a cyclic structure. In addition, as the monovalent organic group and the radically polymerizable functional group, the same ones as in general formula (1) can be mentioned.

[General formula 1-1]

[General formula 1-2]

[General formula 1-3]

Specific examples of the compounds represented by the general formula (1) and the general formulas (1-1) to (1-3) include those shown below. The compounds represented by the general formulas (1-1) to (1-3) are not limited to these.

<<<Example Compound 1>>>

<<<Example Compound 2>>>

<<<Example Compound 3>>>

<<<Example Compound 4>>>

<<<Example Compound 5>>>

<<<Example Compound 6>>>

<<<<Example Compound 7>>>

<<<Example Compound 8>>>

<<<Exemplary Compound 9>>>

<<<<Example Compound 10>>>

<<<Example Compound 11>>>

<<<Example Compound 12>>>

<<<Example Compound 13>>>

<<<Example Compound 14>>>

<<<Example Compound 15>>>

<<<Example Compound 16>>>

<<<Example Compound 17>>>

<<<Example Compound 18>>>

<<<Example Compound 19>>>

<<<Example Compound 20>>>

<<<Example Compound 21>>>

<<<Example Compound 22>>>

<<<Example Compound 23>>>

<<<Example Compound 24>>>

<<<Example Compound 25>>>

<<<Example Compound 26>>>

<<<Example Compound 27>>>

<<<Example Compound 28>>>

<<<Example Compound 29>>>

<<<Example Compound 30>>>

<<<Example Compound 31>>>

<<<Example Compound 32>>>

<<<Example Compound 33>>>

<<<Example Compound 34>>>

<<<Example Compound 35>>>

<<<Example Compound 36>>>

<<<Example Compound 37>>>

<<<Example Compound 38>>>

<<<Example Compound 39>>>

<<<Example Compound 40>>>

-Other radically polymerizable compounds-
The other radically polymerizable compound refers to a compound that is different from the above triarylamine derivative having a radically polymerizable functional group and has at least one radically polymerizable functional group.
Examples of other radically polymerizable compounds include monofunctional, difunctional, trifunctional or higher functional radically polymerizable compounds, functional monomers, radically polymerizable oligomers, and the like. Among these, radically polymerizable compounds having two or more functionalities are particularly preferred.
The radically polymerizable functional group in other radically polymerizable compounds may be the same as the radically polymerizable functional group in the above-mentioned triarylamine derivative having a radically polymerizable functional group, but may include an acryloyloxy group and a methacryloyloxy group. is particularly preferred.

Examples of monofunctional radically polymerizable compounds include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2- Ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexylcarbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate , phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer and the like. These may be used alone or in combination of two or more.

Examples of difunctional radically polymerizable compounds include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, and neopentyl glycol diacrylate. These may be used alone or in combination of two or more.

Examples of the radically polymerizable compound having three or more functional groups include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, and caprolactone-modified trimethylolpropane triacrylate. Acrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, tris(acryloxyethyl ) Isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate Acrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified phosphoric triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used alone or in combination of two or more.
Note that here, EO modification means ethylene oxy modification, PO modification means propylene oxy modification, and ECH modification means epichlorohydrin modification.

Examples of functional monomers include those substituted with a fluorine atom such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, and 2-perfluoroisononylethyl acrylate; Acryloylpolydimethylsiloxaneethyl, methacryloylpolydimethylsiloxaneethyl, acryloylpolydimethylsiloxanepropyl, acryloylpolydimethylsiloxanebutyl, diacryloylpolydimethyl having 20 to 70 siloxane repeating units described in Publication No. 60503 and Japanese Patent Publication No. 6-45770 Examples include vinyl monomers having polysiloxane groups such as siloxane diethyl, acrylates, and methacrylates. These may be used alone or in combination of two or more.
Examples of radically polymerizable oligomers include epoxy acrylate oligomers, urethane acrylate oligomers, and polyester acrylate oligomers.

From the point of view of forming a crosslinked product, at least one of the above-mentioned triarylamine derivative having a radically polymerizable functional group and the other radically polymerizable compound has two or more radically polymerizable functional groups. preferable.

The content of the triarylamine derivative having a radically polymerizable functional group is not particularly limited and can be appropriately selected depending on the purpose, but it is 10% by mass or more and 100% by mass based on the total amount of the electrochromic composition. The following is preferable, and 30% by mass or more and 90% by mass or less is more preferable. When the above content is 10% by mass or more, the electrochromic function of the electrochromic layer is fully expressed, and the durability and color development sensitivity are good even when repeatedly used by applied voltage. Further, even if the above content is 100% by mass, the electrochromic function is exhibited, and in this case, the color development sensitivity to thickness can be made higher. Although it cannot be generalized because the required electrical properties differ depending on the process used, it is more preferable that the content is 30% by mass or more and 90% by mass or less, considering the balance between coloring sensitivity and repeated durability.

Electrochromic materials that change from a transparent state to a colored state upon reduction are not particularly limited and can be selected as appropriate depending on the purpose; Viologen-based compounds and dipyridine-based compounds are preferred, and for example, dipyridine-based compounds represented by the following general formula (4) are more preferred.

In the above general formula (4), R1 and R2 each independently represent either an alkyl group having 1 to 8 carbon atoms, which may have a substituent, or an aryl group, and also conductive fine particles described below. and semiconducting fine particles, at least one of R1 and R2 is COOH, PO(OH) ₂ , and Si(OC _k H _2k+1 ) ₃ (however, k has a substituent selected from 1 to 20). COOH, PO(OH) ₂ or Si(OC _k H _2k+1 ) ₃ added to at least one of R1 or R2 can contribute to the adsorption reaction.
In addition, in the above general formula (4), A, B, and C each independently represent any one of an alkyl group having 1 to 20 carbon atoms, an aryl group, and a heterocyclic group that may have a substituent. represent.
Furthermore, in the above general formula (4), X represents a monovalent anion. The monovalent anion is not particularly limited as long as it forms a stable pair with the cation moiety, and can be appropriately selected depending on the purpose. For example, Br ion (Br ^- ), Cl ion (Cl ^- ) , ClO ₄ ion (ClO ₄ ⁻ ), PF ₆ ion (PF ₆ ⁻ ), BF ₄ ion (BF ₄ ⁻ ), and the like.
In addition, in the above general formula (4), n, m, and l each independently represent 0, 1, or 2.

Also, the electrochromic device has two electrochromic layers, one electrochromic layer being a first electrochromic layer containing an electrochromic material capable of developing color in an oxidized state, and the other electrochromic layer comprising: Preferably, the second electrochromic layer comprises an electrochromic material capable of developing color in a reduced state. Details regarding this form will be described later.

As the metal complex-based and metal oxide-based electrochromic compounds, for example, inorganic electrochromic compounds such as titanium oxide, vanadium oxide, tungsten oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue can be used.

Metal complex-based and metal oxide-based electrochromic compounds can be formed by vacuum film formation, and vacuum evaporation, sputtering, ion plating, etc. are used. Furthermore, it is also possible to form it as a precursor solution or a fine particle layer, and the coating methods in that case include, for example, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, Wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Examples include various printing methods.

<<Other components in the electrochromic layer>>
Other components that may be included in the electrochromic layer are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, a polymerization initiator, conductive fine particles, semiconductive fine particles, and the like.

<<<Polymerization initiator>>>
The electrochromic layer preferably contains a polymerization initiator as necessary in order to efficiently advance the crosslinking reaction between the triarylamine derivative having a radically polymerizable functional group and another radically polymerizable compound.
Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, and the like, and among these, photopolymerization initiators are preferred from the viewpoint of polymerization efficiency.

The thermal polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples include 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(peroxy Peroxide initiators such as benzoyl)hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide; azobisisobutylnitrile, azobiscyclohexanecarbonitrile, azobisiso Examples include azo initiators such as methyl butyrate, azobisisobutyramidine hydrochloride, and 4,4'-azobis-4-cyanovaleric acid. These may be used alone or in combination of two or more.

The photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2- propyl)ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino Acetophenone or ketal photopolymerization initiators such as (4-methylthiophenyl)propan-1-one, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime; benzoin, benzoin methyl ether, Benzoin ether photopolymerization initiators such as benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether , acrylated benzophenone, benzophenone photoinitiators such as 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples include thioxanthone photopolymerization initiators such as. These may be used alone or in combination of two or more.

Other photoinitiators include, for example, ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl) Phenylphosphine oxide, bis(2,4-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compounds, triazine compounds, imidazole compounds, etc. Can be mentioned. These may be used alone or in combination of two or more.
Note that a compound having a photopolymerization promoting effect can be used alone or in combination with the photopolymerization initiator. Examples of such compounds include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, and 4,4'-dimethylaminobenzophenone. Examples include.

<<<Conductive fine particles or semiconducting fine particles>>>
The electrochromic material such as a viologen compound or a dipyridine compound is preferably supported on conductive fine particles or semiconductor fine particles in the electrochromic layer.
The conductive particles or semiconductor particles supporting the electrochromic material are not particularly limited and can be appropriately selected depending on the purpose, but metal oxides are preferably used.

Examples of metal oxide materials include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, Metal oxides whose main components are calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. Can be mentioned. These may be used alone or in combination of two or more.
Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide are selected from the viewpoint of electrical properties such as electrical conductivity and physical properties such as optical properties. At least one of the selected ones is preferable, and titanium oxide or tin oxide is particularly preferable since color display with excellent color development/decolorization response speed is possible.

In addition, the shape of the conductive fine particles or semiconducting fine particles is not particularly limited and can be appropriately selected depending on the purpose. ) is used. For example, when the fine particles are an aggregate of nanoparticles, they have a large specific surface area, so the electrochromic compound is supported more efficiently, and the display contrast ratio of color development and fading is excellent.
Although it is possible to form the layer of conductive fine particles or semiconductive fine particles by vacuum film formation, it is preferable to form the layer by coating as a particle dispersion paste from the viewpoint of productivity. Examples of coating methods include spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spray coating. Examples include various printing methods such as a method, a nozzle coating method, a gravure printing method, a screen printing method, a flexo printing method, an offset printing method, a reverse printing method, and an inkjet printing method.

When the electrochromic compound (material) of the general formula (4) is supported on at least one of the conductive fine particles and the semiconducting fine particles, the electrochromic compound (material) of the general formula (4) having a group contributing to the adsorption reaction is used. A chromic compound dissolved in a solvent can be easily adsorbed by bringing it into contact with conductive fine particles or semiconducting fine particles.
Although the adsorption treatment can be performed on the conductive fine particles and semiconductor fine particles before film formation, it is preferable to perform the adsorption treatment after forming the conductive fine particle and semiconductor fine particle layers by the various printing methods described above. This is because conductive fine particles and semiconductor fine particles that have adsorbed an electrochromic compound tend to have poor film forming properties. Examples of the method of bringing a solution of the electrochromic compound of general formula (4) dissolved in a solvent into contact with conductive fine particles or semiconductor fine particles include a spin coating method, a casting method, a microgravure coating method, a gravure coating method, Bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexo printing method, offset printing method, reversal Examples include various printing methods such as a printing method and an inkjet printing method.

The average thickness of the electrochromic layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.2 μm or more and 5.0 μm or less. When the average thickness of the electrochromic layer is 0.2 μm or more, the color density can be improved, and when it is 5.0 μm or less, manufacturing costs can be suppressed and transparency in the decolored state can be increased. Visibility can be improved.

The electrochromic layer is preferably formed by dissolving an electrochromic material in a solvent, coating it, and then polymerizing it with light or heat. Examples of coating methods include spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spray coating. Examples include various printing methods such as a method, a nozzle coating method, a gravure printing method, a screen printing method, a flexo printing method, an offset printing method, a reverse printing method, and an inkjet printing method.

<Solid electrolyte layer>
The solid electrolyte layer is in contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and is not in contact with the first auxiliary electrode and the second auxiliary electrode. It is formed.
The solid electrolyte layer is preferably formed as a film containing an electrolyte in a photo- or thermosetting resin. Furthermore, it is preferable to mix inorganic particles that control the layer thickness of the electrolyte layer.

The solid electrolyte layer is preferably a film that is coated on the electrochromic layer as a solution containing inorganic fine particles, a curable resin, and an electrolyte and then cured with light or heat. However, it is preferable to form a porous inorganic fine particle layer in advance. After that, a mixed solution of a curable resin and an electrolyte may be applied so as to penetrate into the inorganic fine particle layer, and then a film may be formed by curing with light or heat.
Furthermore, if the electrochromic layer is a layer in which an electrochromic compound is supported on conductive or semiconducting nanoparticles, after applying a solution containing a mixture of a curable resin and an electrolyte so as to permeate the electrochromic layer, It can also be formed as a film cured by light or heat.

As the electrolyte in the solid electrolyte layer, a liquid electrolyte such as an ionic liquid, a solution of a solid electrolyte in a solvent, etc. are used.
As the material for the electrolyte, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and supporting salts of acids and alkalis can be used. Specifically, _LiClO4 , _LiBF4 , _LiAsF6 , _LiPF6 , _LiCF3SO3 , LiCF3COO, KCl, _{NaClO3 ,} NaCl, _NaBF4 , NaSCN, _KBF4 , Mg _{( ClO4} ) ₂ , Mg( Examples include BF ₄ ) ₂ .

The ionic liquid is not particularly limited and can be appropriately selected depending on the purpose.
The organic ionic liquid preferably has a molecular structure that remains liquid in a wide temperature range including room temperature. In this case, the molecular structure preferably includes a cation component and an anion component.
Examples of the cation component include imidazole derivatives such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, N,N-methylpropylimidazole salt; N,N-dimethylpyridinium salt, N,N-methyl Examples include aromatic salts such as pyridinium derivatives such as propylpyridinium salt; aliphatic quaternary ammonium compounds such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.
The anion component is preferably a compound containing fluorine in terms of stability in the atmosphere, such as Br ion (Br ^- ), Cl ion (Cl ^- ), ClO ₄ ion (ClO ₄ ^- ), PF ₆ ion ( Examples include PF ₆ ⁻ ), BF ₄ ion (BF ₄ ⁻ ), TCB ion (tetracyanoborate), FSI ion (bis(fluorosulfonyl)imide), and TFSI ion (bis(trifluoromethylsulfonyl)imide). Ionic liquids formulated with a combination of these cationic and anionic components can be used.

Examples of the solvent in the solid electrolyte layer include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane. , polyethylene glycol, alcohols, or mixed solvents thereof.
Examples of the cured resin include photocurable resins such as acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, ethylene resins, melamine resins, and phenol resins, thermosetting resins, etc., but the compatibility with the electrolyte Materials with a high As the material having high compatibility with the electrolyte, for example, ethylene glycol derivatives such as polyethylene glycol and polypropylene glycol are preferable.
Further, as the cured resin, it is preferable to use a photocurable resin. By doing so, the element can be manufactured at a lower temperature and in a shorter time than with a method of forming a thin film by thermal polymerization or evaporating a solvent.

Preferred combinations for the solid electrolyte layer include, for example, a solid electrolyte layer formed of a solid solution of a matrix polymer containing oxyethylene chains or oxypropylene chains and an ionic liquid. That is, it is preferable that the solid electrolyte layer contains a solid solution of a matrix polymer and an ionic liquid. By doing so, by suppressing ion movement in the surface (lateral) direction of the electrolytic layer, in-plane concentration unevenness is reduced, and it is easy to achieve both hardness and high ionic conductivity. Moreover, by doing so, the solid electrolyte layer can be made to have a desired ionic conductivity by adjusting (controlling) the matrix structure.
Note that the ionic conductivity of the solid electrolyte layer is preferably 0.1 mS/cm or more and 50 mS/cm or less.

The inorganic fine particles in the solid electrolyte layer are not particularly limited as long as they can form a porous layer and hold the electrolyte and cured resin, and can be selected as appropriate depending on the purpose. From the viewpoint of reaction stability and visibility, materials with high insulation, transparency, and durability are preferred.
Examples of the inorganic fine particles include oxides or sulfides of silicon, aluminum, titanium, zinc, and tin, or mixtures thereof.

The size (average particle size) of the inorganic fine particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 nm or more and 10 μm or less, and more preferably 10 nm or more and 100 nm or less.

The average thickness of the solid electrolyte layer is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 5 μm or more and 500 μm or less, and more preferably 10 μm or more and 100 μm or less. When the average thickness of the solid electrolyte layer is within the above-mentioned preferable range, manufacturing costs can be suppressed while preventing current short-circuiting.

<Control means, control process>
The control means applies a voltage to the electrochromic layer via the first electrode and the second electrode using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern. It is a means of controlling.
In the control step, the electrochromic layer in the electrochromic device is controlled by at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern via a first electrode and a second electrode. This is a process of controlling the application of voltage.
The control means is not particularly limited and can be appropriately selected depending on the purpose, and for example, known integrated circuits such as a CPU (Central Processing Unit) and an FPGA (Field Programmable Gate Array) can be used. For example, the control means is provided in a pulse generator (voltage application device), and the control means can apply a voltage to the electrochromic layer via the pulse generator.

<<First drive pattern>>
The first driving pattern is a driving pattern for bringing the electrochromic layer into the first coloring state.
In the first drive pattern, a first voltage pulse A is applied to increase the response speed of the electrochromic layer, and a first voltage pulse B lower than the first voltage pulse A is applied to form a first colored state. is applied, and then a state in which no voltage is applied is maintained. By driving the electrochromic device of the present invention with the first driving pattern, it is possible to improve responsiveness when driving to increase the color density, and also has excellent durability and consumption when continuously driven for a long time. Electric power can be reduced.

The first voltage pulse A is a pulse for increasing the response speed of the electrochromic layer. The first voltage pulse A allows the amount of charge necessary for the redox reaction of the electrochromic layer to be injected into the electrochromic layer in a short time, thereby increasing the response speed. The energy applied to the electrochromic layer by the first voltage pulse A is preferably greater than the energy required to color the electrochromic layer.
By applying the first voltage pulse A, it is possible to improve the responsiveness when driving to increase the color density.

The first voltage pulse B is a pulse for forming the first colored state.
Here, the first coloring state means a state where the coloring density is higher than the second coloring state described later. In other words, a state of high color density is a state of low light transmittance (a state in which the electrochromic layer is deeply colored and does not allow much light to pass through).
The color density of the electrochromic device can be determined, for example, by measuring the transmittance spectrum at approximately the center of the color region using a panel module evaluation device LCD5200 (manufactured by Otsuka Electronics Co., Ltd.).

The first voltage pulse B is a lower pulse than the first voltage pulse A.
Here, a low pulse means that the energy applied (supplied) by the pulse is low. The energy applied by the pulse can be adjusted by controlling the average voltage, current amount, application time, etc., as described above. Note that hereinafter, the average voltage, current amount, and application time may be collectively referred to as "pulse characteristics."

When making the first voltage pulse B smaller than the first voltage pulse A, for example, making the average voltage in the first voltage pulse B smaller than the average voltage in the first voltage pulse A, This can be done by controlling the amount of current by making the voltage application time shorter than the voltage application time in the first voltage pulse A.
Here, the magnitude of the average voltage in each pulse means the magnitude (absolute value) of the average voltage at the same sign. For example, if 2V is greater than 1V, -2V is greater than -1V. Suppose that is larger. Note that the first voltage pulse A and the first voltage pulse B have the same sign (same polarity).

Furthermore, the first colored state that can be formed by applying the first voltage pulse B has a higher color density than the second colored state that will be described later. Therefore, for example, when the electrochromic device is already in the second color development state, the color density can be increased (deepened) by driving the electrochromic device according to the first drive pattern.

In the first drive pattern, a first voltage pulse B is applied, and then a state in which no voltage is applied is maintained. In other words, in the first drive pattern, after the first voltage pulse B is applied, the circuit of the electrochromic device is brought into an open circuit state. Since the electrochromic device of the present invention has a solid electrolyte layer, it exhibits a memory effect in which the colored state and decolored state are maintained for a certain period of time without applying a voltage. Concentration can be maintained.

Further, in the first drive pattern, it is preferable to repeat application of the first voltage pulse B and maintenance of a state in which no voltage is applied after application of the first voltage pulse B. By doing this, even if the electrochromic device is used continuously for a long time, power consumption can be suppressed, and deterioration of the electrochromic layer due to continuous voltage application can be suppressed, increasing durability. can be improved.

FIG. 2 is a diagram showing an example of a drive pattern in the first drive pattern.
In the example shown in FIG. 2, Pw1-1 corresponds to the first voltage pulse A, Pw2-1 corresponds to the first voltage pulse B, and Pw3-1 corresponds to a state in which no voltage is applied. In addition, the broken line part in FIG. 2 means the repeated part when applying the first voltage pulse B and maintaining the state in which no voltage is applied after applying the first voltage pulse B, and the part shown in the upper right corner of the broken line part The subscript l means the number of repetitions depending on the driving time.

FIG. 15 is a diagram showing another example of the drive pattern in the first drive pattern.
In the example shown in FIG. 15, unlike the example shown in FIG. 2, voltage is applied between Pw1-1 corresponding to the first voltage pulse A and Pw2-1 corresponding to the first voltage pulse B. The state Pw3-1-2 is maintained.
There is no particular restriction on the time to maintain the state Pw3-1-2 in which no voltage is applied, as long as the effect of increasing the response speed by applying the first voltage pulse A is not lost; It can be selected as appropriate.
In this way, in the first drive pattern, a state in which no voltage is applied may be maintained between the first voltage pulse A and the first voltage pulse B.

<<Second driving pattern>>
The second driving pattern is a driving pattern for forming a second coloring state, which has a lower color density than the first coloring state, from the first coloring state.
In the second drive pattern, a second voltage pulse A is applied to increase the response speed of the electrochromic layer, and a second voltage pulse B higher than the second voltage pulse A is applied to form a second colored state. Alternatively, a second voltage pulse B having a polarity opposite to that of the second voltage pulse A is applied, and then a state in which no voltage is applied is maintained. By driving the electrochromic device of the present invention with the second driving pattern, it is possible to improve the responsiveness when driving to reduce the color density, and it also has excellent durability and consumption when driven continuously for a long time. Electric power can be reduced.

The second voltage pulse A is a pulse for increasing the response speed of the electrochromic layer, and is a pulse lower than the second voltage pulse B described later, or a pulse of opposite polarity to the second voltage pulse.
By applying the second voltage pulse A, it is possible to inject the amount of charge necessary for the redox reaction of the electrochromic layer into the electrochromic layer in a short time, so when driving to reduce the color density. can improve responsiveness.

The second voltage pulse B is a pulse for forming a second colored state having a lower color density than the first colored state. Therefore, for example, when the electrochromic device is already in the first coloring state, the coloring density can be lowered (thinner) by driving the electrochromic device using the second drive pattern.

When making the second voltage pulse B smaller than the second voltage pulse A, contrary to the control in the first drive pattern, for example, the average voltage in the second voltage pulse B is made smaller than the average voltage in the second voltage pulse A. This can be done by controlling the amount of current by increasing the voltage, making the voltage application time in the second voltage pulse B longer than the voltage application time in the second voltage pulse A, and so on. Note that normally, the second voltage pulse A and the second voltage pulse B have the same sign, and the first voltage pulse A and the first voltage pulse B also have the same sign, but the polarity of the second voltage pulse A is reversed. A combination with different signs is also possible. That is, the second voltage pulse B may have the opposite polarity (opposite sign) to the second voltage pulse A. In this case, the second voltage pulse A may be a larger pulse than the second voltage pulse B, or may be a smaller pulse.

In the second drive pattern, similarly to the first drive pattern, the second voltage pulse B is applied, and thereafter, a state in which no voltage is applied is maintained. In other words, in the second drive pattern, after application of the second voltage pulse B, the circuit of the electrochromic device is brought into an open circuit state. Since the electrochromic device of the present invention has a solid electrolyte layer, it exhibits a memory effect in which the colored state and decolored state are maintained for a certain period of time without applying a voltage. Concentration can be maintained.

Further, in the second drive pattern, as in the first drive pattern, it is preferable to repeat application of the second voltage pulse B and maintenance of a state in which no voltage is applied after application of the second voltage pulse B. By doing this, even if the electrochromic device is used continuously for a long time, power consumption can be suppressed, and deterioration of the electrochromic layer due to continuous voltage application can be suppressed, increasing durability. can be improved.

FIG. 3 is a diagram showing an example of a drive pattern in the second drive pattern.
In the example shown in FIG. 3, Pw1-2 corresponds to the second voltage pulse A, Pw2-2 corresponds to the second voltage pulse B, and Pw3-2 corresponds to a state in which no voltage is applied. In addition, the broken line part in FIG. 3 means the repeated part when applying the second voltage pulse B and maintaining the state in which no voltage is applied after applying the second voltage pulse B. The subscript m means the number of repetitions depending on the driving time.

FIG. 16 is a diagram showing another example of the drive pattern in the second drive pattern.
In the example shown in FIG. 16, unlike the example shown in FIG. 3, voltage is applied between Pw1-2 corresponding to the second voltage pulse A and Pw2-2 corresponding to the second voltage pulse B. The state Pw3-2-2 is maintained.
There is no particular restriction on the time for maintaining the state Pw3-2-2 in which no voltage is applied, as long as the effect of increasing the response speed by applying the second voltage pulse A is not lost; It can be selected as appropriate.
In this way, in the second drive pattern, a state in which no voltage is applied may be maintained between the second voltage pulse A and the second voltage pulse B.

<<Initialization drive pattern>>
The initialization drive pattern is a drive pattern for forming an initial decolored state.
In the initialization drive pattern, an initialization voltage pulse A having a polarity opposite to that of the first voltage pulse A is applied to increase the response speed of the electrochromic layer, and then an initialization voltage pulse A is applied to form an initial decolorized state. , an initialization voltage pulse B is applied to bring the potential of the electrochromic layer to approximately 0V, or a short circuit is applied.

The initialization voltage pulse A has a polarity opposite to that of the first voltage pulse A and the second voltage pulse A described above. Here, the term "reverse polarity" means that the sign is opposite. For example, when the average voltage of the first voltage pulse is a positive voltage, the average voltage of the initialization voltage pulse is a negative voltage.
By applying the initialization voltage pulse A, it is possible to improve the responsiveness when driving to initialize the color density.

The initialization voltage pulse B is a pulse that brings the potential of the electrochromic layer to approximately 0V to form an initial decolored state. Here, setting the potential to approximately 0V means bringing the potential close to 0V so that the electrochromic layer can be returned to its initial decolored state (eg, transparent state).
The initialization voltage pulse B can be applied, for example, by applying a voltage pulse of approximately 0V.
Further, in the initialization drive pattern, the control means may short-circuit the first electrode and the second electrode in order to bring the potential of the electrochromic layer to approximately 0V. The short circuit based on the initialization drive pattern can be performed, for example, by the control means connecting the first electrode and the second electrode.

FIG. 4 is a diagram showing an example of a drive pattern in the initialization drive pattern.
In the example shown in FIG. 4, Pw4 corresponds to initialization voltage pulse A, and Pw5 corresponds to initialization voltage pulse B. In addition, the broken line part in FIG. 4 means the repeated part when the application of the initialization voltage pulse A and the application of the initialization voltage pulse B are repeated, and the subscript n in the upper right of the broken line part is the repetition part according to the driving time. means the number of times.

FIG. 17 is a diagram showing another example of the drive pattern in the initialization drive pattern.
In the example shown in FIG. 17, unlike the example shown in FIG. 4, a state Pw3- where no voltage is applied between Pw4 corresponding to the initialization voltage pulse A and Pw5 corresponding to the initialization voltage pulse B is shown. Maintain 3.
There is no particular restriction on the time to maintain the state Pw3-3 in which no voltage is applied, as long as the effect of increasing the response speed by applying the initialization voltage pulse A is not lost, and it may vary depending on the purpose. can be selected as appropriate.
In this way, in the initialization drive pattern, a state in which no voltage is applied may be maintained between the initialization voltage pulse A and the initialization voltage pulse B.
Similarly, in the initialization drive pattern, a state in which no voltage is applied may be maintained from the time the initialization voltage pulse A is applied until the short circuit is made.

That is, in the present invention, between the first voltage pulse A and the first voltage pulse B, between the second voltage pulse A and the second voltage pulse B, and between the initializing voltage pulse A and the initializing voltage pulse B, The state in which no voltage is applied may be maintained during at least one of the period from the time when the initialization voltage pulse A is applied until the short circuit is made. By doing so, the electrochromic layer can be changed from an redox state in which an excessive reaction such as a two-electron reaction occurs to a stable state, thereby improving durability.

Further, in the first drive pattern and the second drive pattern described above, it is preferable that the first voltage pulse B and the second voltage pulse B are 1.23V or less. In this way, by setting the average voltage of the first voltage pulse B and the second voltage pulse B, which may be repeatedly applied, to 1.23 V or less, which is the decomposition voltage of water, the presence in the electrochromic layer and the solid electrolyte layer can be reduced. Drive deterioration due to moisture content can be suppressed.

<Measurement means, measurement process>
The electrochromic device of the present invention preferably has a measuring means for measuring the open circuit voltage between the first electrode and the second electrode. Note that the measuring step can be suitably performed using a measuring means.

When the electrochromic device has a measuring means, the control means controls the first voltage pulse B and the first voltage pulse B according to the measured open-circuit voltage when maintaining a state in which no voltage is applied in the first drive pattern and the second drive pattern. Preferably, the pulse characteristics of the second voltage pulse B are changed. By doing this, when repeating the application of the first voltage pulse B or the second voltage pulse B and the maintenance of the state in which no voltage is applied after the application of the pulse, the open circuit voltage that can develop the desired density can be adjusted at any time. Since the color density can be controlled, the controllability of the color density can be improved.
Here, the pulse characteristics refer to parameters that can control the characteristics (shapes) of the pulses, such as the average voltage, current amount, and application time in the first voltage pulse B and the second voltage pulse B, as described above.

<Support>
The electrochromic device of the present invention preferably has a support.
The support supports the first electrode, the electrochromic layer, the solid electrolyte layer, the second electrode, the first auxiliary electrode, the second auxiliary electrode, the control means, etc.
The support is not particularly limited and can be appropriately selected depending on the purpose. For example, a well-known light-transmitting material (organic material or inorganic material) can be used.

Examples of the light-transmitting material include glass substrates such as alkali-free glass, borosilicate glass, float glass, and soda-lime glass. Further, as the light-transmitting material, for example, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, polyimide resin, etc. may be used.
Further, the surface of the support 1 may be coated with a transparent insulating layer, an antireflection layer, etc. in order to improve water vapor barrier properties, gas barrier properties, and visibility. Note that when the electrochromic device is a reflective display device that is visible from one side, the support disposed on the non-visible side does not need to be transparent.

The average thickness of the support is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 0.1 mm or more and 2.0 mm or less. When the average thickness of the support is 0.1 mm or more, it is possible to suppress deformation of the support and the electrochromic device to improve handling, and when it is 2.0 mm or less, weight and manufacturing cost can be suppressed. Can be done.

<Protective layer>
Preferably, the electrochromic device of the present invention has a protective layer.
The term "protective layer" refers to a layer formed to physically and chemically protect the side surfaces of an electrochromic device.
The protective layer can be formed by, for example, applying an ultraviolet curable or thermosetting insulating resin so as to cover the side surfaces and/or the top surface, and then curing it.

Moreover, as the protective layer, it is more preferable to use a protective layer in which a cured resin and an inorganic material are laminated. By forming the protective layer into a laminated structure with an inorganic material, the barrier properties of the electrochromic device against oxygen and water can be improved.
The inorganic material is preferably a material with high insulation, transparency, and durability, and specific examples include oxides or sulfides of silicon, aluminum, titanium, zinc, and tin, or mixtures thereof. can be mentioned. A protective layer containing these materials can be easily formed by a vacuum film forming process such as sputtering or vapor deposition.

The average thickness of the protective layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 μm or more and 10 μm or less. In addition, the protective layer may be formed after processing, such as when molding the support.

<Deterioration prevention layer>
The electrochromic device of the present invention preferably has a deterioration prevention layer.
The deterioration prevention layer reversely reacts with the electrochromic layer, balances the charges, and suppresses corrosion and deterioration of the second electrode due to irreversible redox reactions. By having an electrochromic device with a deterioration prevention layer, the repeat stability of the electrochromic device is improved. Note that the reverse reaction includes not only the case where the deterioration prevention layer undergoes oxidation-reduction, but also the case where the deterioration prevention layer acts as a capacitor.

The material for the deterioration prevention layer is not particularly limited as long as it can prevent corrosion due to irreversible redox reactions of the first electrode and the second electrode, and can be appropriately selected depending on the purpose.
As a material for the deterioration prevention layer, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconducting metal oxide containing a plurality of these can be used. Furthermore, if coloring of the anti-deterioration layer is not a problem, the same electrochromic material can be used.
Among these, when producing an electrochromic device as an optical element such as a lens that requires transparency, it is preferable to use a highly transparent material as the deterioration prevention layer.

As the highly transparent material, it is preferable to use n-type semiconductor oxide fine particles (n-type semiconductor metal oxide). As the n-type semiconducting metal oxide, titanium oxide, tin oxide, zinc oxide, compound particles containing a plurality of them, or a mixture thereof can be used, which have a primary particle size of 100 nm or less. Furthermore, when using n-type semiconductor oxide fine particles as a deterioration prevention layer, it is preferable that the electrochromic layer is a material that changes color due to an oxidation reaction. By doing so, the n-type semiconductor metal oxide is easily reduced (electron injection) at the same time as the electrochromic layer undergoes an oxidation reaction, and the driving voltage can be reduced. In such a form, a particularly preferred electrochromic material is a triarylamine derivative having a radically polymerizable functional group represented by the general formula (1).

On the other hand, examples of materials for the highly transparent p-type semiconductor layer as the deterioration prevention layer include organic materials having nitroxyl radicals (NO radicals), and more specifically, 2,2,6,6 Examples include derivatives of -tetramethylpiperidine-N-oxyl (TEMPO) and polymer materials of derivatives.

When the p-type semiconductor layer is used as a deterioration prevention layer, it is preferable that the electrochromic layer is a material that changes color due to a reduction reaction. By doing so, the p-type semiconductor metal oxide is easily oxidized at the same time as the electrochromic layer undergoes a reduction reaction, and the driving voltage can be reduced. In such a form, a particularly preferred electrochromic material is a dipyridine compound represented by the general formula (4).

Furthermore, in the electrochromic device of the present invention, an electrochromic layer having an absorption band in the visible range in an oxidized state is formed on one of the surfaces of the first electrode or the second electrode, and the surface of the other electrode is Preferably, an electrochromic layer having an absorption band in the visible range in a reduced state is formed, also serving as a prevention layer. By simultaneously driving the oxidation-colored electrochromic layer and the reduction-colored electrochromic layer, a high coloring density can be obtained and the driving voltage can be reduced.

That is, the electrochromic device of the present invention has two electrochromic layers, one electrochromic layer is a first electrochromic layer containing an electrochromic material capable of developing color in an oxidized state, and the other electrochromic Preferably, the layer is a second electrochromic layer comprising an electrochromic material capable of developing color in a reduced state. By doing so, the oxidation-colored electrochromic layer and the reduction-colored electrochromic layer can be driven simultaneously, and a high coloring density can be obtained, and the driving voltage can be reduced.

The electrochromic compound used in the oxidation-colored electrochromic layer and having an absorption band in the visible range in an oxidized state preferably contains a radically polymerizable compound having a triarylamine represented by the above general formula (1). Further, the electrochromic compound used in the reduction colored electrochromic layer and having an absorption band in the visible range in a reduced state preferably contains a dipyridine compound represented by the above general formula (4). By doing this, these materials have a low redox reaction potential and a stable redox reaction state, and it is possible to easily adjust light absorption (i.e. color) by changing the molecular structure. . In particular, by adjusting two types of light absorption, it is possible to realize a black display showing broad light absorption.

Note that, as the deterioration prevention layer, a deterioration prevention function can be imparted to the solid electrolyte layer by mixing a deterioration prevention layer material into the solid electrolyte layer.

The method for forming the deterioration prevention layer is not particularly limited and can be appropriately selected depending on the purpose, such as vacuum evaporation, sputtering, and ion plating.
In addition, if the material of the deterioration prevention layer can be formed by coating, for example, spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method. , various printing methods such as slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, and inkjet printing method can also be used. .

[Applications of electrochromic device]
The use of the electrochromic device of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but it can be suitably used as a light control device, for example.
Examples of the light control device (electrochromic light control device) using the electrochromic device of the present invention include light control glasses, anti-glare mirrors, light control glass, etc. Among these, the light control device which is a wearable device Glasses are particularly suitable.

In photochromic glasses (photochromic sunglasses), which are wearable devices, the batteries used are limited to small size from the viewpoint of light weight and safety, so the photochromic part (electrochromic layer) can be driven with low power consumption. is preferred. Furthermore, since wearable devices are used while being worn on the body, higher safety is required compared to other uses.
Wearable devices using the electrochromic device of the present invention have high strength and safety against external shocks, have excellent durability when operated continuously for long periods of time, and can suppress power consumption, making them extremely useful as wearable devices. It has excellent performance. Further, the wearable device of the present invention has high responsiveness and uniformity of color density when performing color development/decolorization drive, and is therefore particularly suitable for use as photochromic glasses.

(Method for manufacturing electrochromic device)
Examples of methods for manufacturing the electrochromic device of the present invention include, but are not limited to, the methods shown below.
The method for manufacturing the electrochromic device of the present invention includes, for example, forming a first electrode and a first auxiliary electrode on a first support, and forming a second electrode on which an electrochromic layer is formed on the first electrode. a step of manufacturing a second member in which a second electrode and a second auxiliary electrode are formed on a second support; and a step of manufacturing the first member and the second member. It is preferable to include a step of bonding the two with a solid electrolyte layer in between to produce an electrochromic device, and a step of connecting a control means (drive circuit) to the produced electrochromic device.

In another example, the method for manufacturing the electrochromic device of the present invention includes the steps of forming a first electrode and a first auxiliary electrode on a first support; forming an electrochromic layer; forming a solid electrolyte layer on the electrochromic layer; forming a second electrode and a second auxiliary electrode on the solid electrolyte layer; It is preferable to include a step of forming a protective layer on the electrode layer to produce an electrochromic element, and a step of connecting a control means (drive circuit) to the produced electrochromic element. In this method, since there is no bonding step, productivity can be improved.

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
Note that the number, position, shape, etc. of the following constituent members are not limited to this embodiment, and can be set to a preferable number, position, shape, etc. for implementing the present invention.

<First embodiment>
FIG. 5A is a schematic side view showing an example of the electrochromic device according to the first embodiment. FIG. 5B is a schematic top view showing an example of the electrochromic device according to the first embodiment.
As shown in FIGS. 5A and 5B, the electrochromic device 10 includes a first transparent support 11, a first transparent electrode 12 as a first electrode, an electrochromic layer 13, and a solid electrolyte layer 14. , it has a second transparent electrode 15 as a second electrode and a second transparent support 16 in this order. Further, the electrochromic device 10 has a first auxiliary electrode 18 on the first transparent electrode 12, a second auxiliary electrode 19 on the second transparent electrode 15, and has an electrochromic layer 13 and a solid electrolyte layer. It has a protective layer 17 that seals 15. In addition, the electrochromic device 10 has a drive circuit 50 as a control means connected to the first auxiliary electrode 18 and the second auxiliary electrode 19.
Furthermore, in the electrochromic device 10, the first transparent electrode 12 and the second transparent electrode 15 are located so as to partially overlap the protective layer 17. By doing this, the inorganic material transparent electrode can suppress oxygen and moisture permeation through the redox reaction layer (electrochromic layer, anti-degradation layer, electrolyte layer). The reliability (eg, drive stability, mechanical strength, etc.) of the device 10 can be improved. This also applies to the second embodiment, third embodiment, fourth embodiment, and fifth embodiment described below.

Furthermore, in the electrochromic device 10, the average distance between the first auxiliary electrode 18 and the second auxiliary electrode 19 is 100 mm or less. Furthermore, in the electrochromic device 10, the first auxiliary electrode 18 and the second auxiliary electrode 19 are provided so as not to come into contact with the electrochromic layer 13 and the solid electrolyte layer 14 (non-contact).

In the electrochromic device 10, a drive circuit 50 connects the first auxiliary electrode 18 and the second auxiliary electrode 19 with at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern. By applying a voltage according to the above, the electrochromic layer 13 undergoes an oxidation-reduction reaction due to the exchange of electric charges, thereby making it possible to develop and erase color.

<<Method for manufacturing an electrochromic device according to the first embodiment>>
The method for manufacturing the electrochromic device 10 of the first embodiment includes the steps of forming a first transparent electrode 12 on a first transparent support 11, and forming a first transparent electrode 12 on one side of the end of the first transparent electrode 12. a step of forming one auxiliary electrode 18; a step of laminating the electrochromic layer 13 in contact with the surface of the first transparent electrode 12; and a step of forming the second transparent electrode 15 on the second transparent support 16. a step of forming a second auxiliary electrode 19 on one side of the end of the second transparent electrode 15; and a step of forming a solid electrolyte layer between the first transparent support 11 and the second transparent support 16. 14 is formed and then cured, and further includes a step of sealing the outer peripheral portion with a protective layer 17, and a step of connecting a drive circuit 50 to the first auxiliary electrode 18 and the second auxiliary electrode 19.

Further, in another example of the method for manufacturing the electrochromic device 10 of the first embodiment, the step of forming the first transparent electrode 12 on the first transparent support 11 and the step of forming the first transparent electrode 12 on the first transparent support 11 are performed. A step of forming a first auxiliary electrode 18 on one side of the end portion, a step of laminating an electrochromic layer 13 in contact with the surface of the first transparent electrode 12, and a step of forming a solid electrolyte layer 14 on the electrochromic layer 13. A process of post-curing and laminating the second transparent electrode 15, a process of forming a second auxiliary electrode 19 on one side of the end of the second transparent electrode 15, and a process of laminating the cured resin on the second transparent electrode 15. a step of forming a second transparent support 16 consisting of a second transparent support 16; a step of further sealing the outer periphery with a protective layer 17; and a step of connecting a drive circuit 50 to the first auxiliary electrode 18 and the second auxiliary electrode 19. including.

<Second embodiment>
FIG. 6A is a schematic side view showing an example of an electrochromic device according to the second embodiment. FIG. 6B is a schematic top view showing an example of an electrochromic device according to the second embodiment.
As shown in FIGS. 6A and 6B, the electrochromic device 20 of the second embodiment has a deterioration prevention layer 21 formed in contact with the solid electrolyte layer 14 and the second transparent electrode 15. This is different from the electrochromic device 10 according to the first embodiment.
In this second embodiment, a deterioration prevention layer 21 is formed to prevent deterioration of the second transparent electrode 15 due to electrochemical reactions. Thereby, the electrochromic device 20 according to the second embodiment can further improve the repeatability characteristics compared to the electrochromic device 10 according to the first embodiment.

<Third embodiment>
FIG. 7 is a schematic side view showing an example of an electrochromic device according to a third embodiment.
As shown in FIG. 7, the electrochromic device 30 of the third embodiment has the following points: the second transparent support 16 is omitted, and a protective layer 17 is formed on the second transparent electrode 15. , is different from the electrochromic device 20 according to the second embodiment.
The protective layer 17 formed on the second transparent electrode 15 may be made of the same material as the protective layer 17 formed on the side surface of the electrochromic device 10, or may be made of a different material. It may be formed of. Since the electrochromic device 30 of the third embodiment is formed from one support (first transparent support 11), the electrochromic device can be made thinner and can be produced at low cost.

<Fourth embodiment>
FIG. 8 is a schematic side view showing an example of an electrochromic device according to the fourth embodiment.
As shown in FIG. 8, the electrochromic device 40 according to the fourth embodiment is different from the electrochromic device according to the third embodiment in that the positional relationship between the electrochromic layer 13 and the deterioration prevention layer 21 is reversed. This is different from the device 30.
In the electrochromic device 40 of the fourth embodiment, although the positional relationship of each layer is different from the other embodiments, a voltage is applied between the first transparent electrode 12 and the second transparent electrode 15. As a result, similarly to other embodiments, the electrochromic layer 13 can undergo an oxidation-reduction reaction by transferring and receiving charges, and can develop and erase color.

<Fifth embodiment>
FIG. 9A is a schematic top view showing an example of an electrochromic device according to the fifth embodiment.
The electrochromic device 60 of the fifth embodiment is different from the electrochromic device 20 of the second embodiment in the shape of the electrochromic device. More specifically, the electrochromic device 60 of the fifth embodiment is an example in which the planar shape of the electrochromic device 20 of the second embodiment is changed to an elliptical shape. The electrochromic device 60 of the fifth embodiment can be suitably used as a lens for photochromic glasses, for example.
In the example shown in FIG. 9A, the first auxiliary electrode 18 and The second auxiliary electrodes 19 are shaped to face each other. Thus, in the electrochromic device of the present invention, the first auxiliary electrode and the second auxiliary electrode may have a curved shape.
Note that the electrochromic device 60 according to the fifth embodiment, like the electrochromic device 20 according to the second embodiment, includes the first transparent electrode 12, the second transparent electrode 15, and the drive circuit 50. It can be assumed that the

FIG. 9B is a schematic top view showing another example of the electrochromic device according to the fifth embodiment.
An electrochromic device 60a shown in FIG. 9B is an example in which the length and arrangement of the first auxiliary electrode 18 and the second auxiliary electrode 19 are changed in the electrochromic device 60 shown in FIG. 9A. As shown in FIG. 9B, in the fifth embodiment, the first auxiliary electrode 18 and the second auxiliary electrode 19 include an electrochromic reaction region (electrochromic layer 13, solid electrolyte layer 14, deterioration prevention layer 21). It may be located in a part of the periphery of the side.

FIG. 9C is a schematic top view showing another example of the electrochromic device according to the fifth embodiment.
The electrochromic device 60b shown in FIG. 9C has the shapes of the first auxiliary electrode 18 and the second auxiliary electrode 19 in the electrochromic device 60 shown in FIG. 9A changed from a curved shape to a point shape (elliptical shape). This is an example. As shown in FIG. 9C, in the electrochromic device of the present invention, the first auxiliary electrode and the second auxiliary electrode are dot-shaped as long as the size and arrangement are such that they can function as auxiliary electrodes. be able to.
Since the first auxiliary electrode 18 and the second auxiliary electrode 19 are small, the electrochromic device 60b can be suitably used as a lens for frameless (rimless) photochromic glasses, for example.

Examples of the present invention will be described below, but the present invention is not limited to these Examples in any way.

(Preparation example 1)
<Production of electrochromic device A>
In Manufacturing Example 1, an example of manufacturing the electrochromic device 20 shown in FIGS. 6A and 6B will be described. Note that the electrochromic device A produced in Production Example 1 can also be used as a light control device.

<<Formation of first electrode and electrochromic layer>>
A glass substrate of 50 mm x 50 mm and an average thickness of 0.7 mm was prepared as the first transparent support 11.
The first transparent electrode 12 was formed by forming an ITO film with an average thickness of about 100 nm on a 50 mm x 40 mm area on the first transparent support 11 by sputtering. The sheet resistance of the first transparent electrode 12 was 40Ω/□.
Furthermore, an AgPdCu alloy film (manufactured by Furuya Metal Co., Ltd.) was formed into a film with an average thickness of about 100 nm on the end portion of the first transparent electrode 12 in a 40 mm x 2 mm area and a 5 mm x 2 mm area by sputtering. One auxiliary electrode 18 was formed.

Next, polyethylene diacrylate (PEG400DA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (IRG184, manufactured by BASF), a compound represented by the following structural formula A, and a compound represented by the structural formula B and 2-butanone were mixed in a mass ratio (20:1:14:6:400) to prepare a solution. Then, the prepared solution was applied and cured by ultraviolet irradiation in a nitrogen atmosphere to form an oxidation-reactive electrochromic layer 13 in an electrochromic reaction area (40 mm x 40 mm) on the surface of the ITO film. The average thickness of the electrochromic layer 13 was 1.3 μm.
In addition, the reaction potential of structural formula A is Ag/Ag+reference electrode measurement (0.55 vs SHE), and the average value of the peak in one-electron reaction is +0.33V, and the average value of the peak in two-electron reaction is +0. 53V, and the compound of structural formula A is a compound capable of two-electron reaction. Furthermore, the reaction potential of structural formula B is measured by Ag/Ag+reference electrode (0.55 vs SHE), and the average value of the peak in one-electron reaction is +0.36V, and the average value of the peak in two-electron reaction is +0. 95V, and the compound of structural formula B is a compound capable of two-electron reaction.

[Structural formula A]

[Structural formula B]

<<Formation of second electrode and deterioration prevention layer>>
A second transparent support 16 having the same shape as the first transparent support 11 is prepared, and in the same manner as the first transparent electrode 12 and the first auxiliary electrode 18, the second transparent electrode 15 and the second Auxiliary electrode 19 was formed.
Next, a thickener is added to a tin oxide particle dispersion (methanol dispersion, solid content mass 50%, average particle size: 18 nm), applied by screen printing, and annealed at 120°C for 15 minutes. A nanostructured semiconductor material consisting of a film of tin oxide particles having an average thickness of about 3.5 μm was formed in an electrochromic reaction region (40 mm×40 mm) on the surface of an ITO film.

Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 2.0% by mass of an electrochromic compound represented by the following structural formula C was applied by spin coating, and then annealed at 120°C for 10 minutes. By doing this, a reduction-reactive electrochromic layer that also served as the deterioration prevention layer 21 was formed by being supported (adsorbed) on the tin oxide particle film.

[Structural formula C]

Subsequently, a SiO ₂ fine particle dispersion (silica solid content concentration 24.8% by mass, polyvinyl alcohol 1.2% by mass, and water 74% by mass) having an average primary particle size of 20 nm was spin-coated on the electrochromic layer 13. , an insulating inorganic fine particle layer having an average thickness of 2 μm was formed.

<<Formation and bonding of solid electrolyte layer>>
On the surface of the insulating inorganic fine particle layer on the second transparent support 16, polyethylene dimethacrylate (molecular weight 600), a photopolymerization initiator (IRG184, manufactured by BASF), and an electrolyte (1-ethyl-3-methylimidazo An electrolyte solution was prepared by mixing lium (bis(fluorosulfonyl)imide) at a mass ratio (50:5:45).Next, the prepared electrolyte solution was applied to an electrochromic reaction area (40 mm x 40 mm). Further, a UV curing resin (TB3035B manufactured by ThreeBond Holdings Co., Ltd.) is applied to the outer periphery of the resin, bonded to the electrochromic layer 13 surface on the first transparent support 11 under reduced pressure, and cured by ultraviolet (UV) irradiation. In this way, the solid electrolyte layer 14 and the protective layer 17 were formed.The film thicknesses of the solid electrolyte layer 14 and the protective layer 17 were set to an average thickness of 50 μm by controlling the bonding gap, and the electrochromic element was A was produced. Note that the average distance between the first auxiliary electrode 18 and the second auxiliary electrode 19 in the electrochromic device A was 40 mm.

<<Drive circuit connection>>
A drive circuit 50 was connected to the first auxiliary electrode 18 and the second auxiliary electrode 19 of the electrochromic device A, and an electrochromic device A as shown in FIGS. 6A and 6B was manufactured. The drive circuit 50 was connected so that the first auxiliary electrode 18 of the first transparent support 11 had a positive polarity, and the second auxiliary electrode 19 of the second transparent support 16 had a negative polarity. Further, as the drive circuit 50, Modulab Xm solartron analytical (manufactured by Toyo Technica Co., Ltd.) was used.

<Color development test>
Subsequently, a color development test was conducted to confirm the color development characteristics of the produced electrochromic device A.
First, in order to investigate the coloring peak wavelength of the oxidation-reactive electrochromic layer and the coloring peak wavelength of the reduction-reactive electrochromic layer in electrochromic device A, in a stable state where a voltage of -1.2V was continuously applied. The transmission spectrum was measured. A panel module evaluation device LCD5200 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure the transmittance spectrum.

FIG. 10 is a diagram showing the results of measuring the transmission spectrum in electrochromic device A. As shown in FIG. 10, the coloring peak wavelength of the oxidation-reactive electrochromic layer in electrochromic device A was around 495 nm. Further, the coloring peak wavelength of the reduction-reactive electrochromic layer was around 610 nm. Note that in FIG. 10, the vertical axis represents the transmittance spectrum, and the horizontal axis represents the wavelength.

<<Drive by first drive pattern>>
Next, using the electrochromic device A that has been returned to the decolorized state, the electrochromic reaction area center is (the central part of the electrochromic layer), and the time required for the colored state of the oxidation-reactive or reduction-reactive electrochromic layer to stabilize was measured as an index of responsiveness. The results are shown in Table 1 and FIGS. 11A and 11B. Note that the colored state of the electrochromic device A was defined as a stable state when a voltage of -1.2V was applied.

As shown in Table 1, in the drive patterns P01 to P04 corresponding to the examples of the present invention, it takes 35 minutes for both the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer to respond to color development. It is less than seconds. On the other hand, in the drive pattern R01 corresponding to the comparative example of the present invention, the first voltage pulse A (Pw1-1) is not applied, and the time until the color response occurs is 180 seconds or more. From this, it was found that responsiveness could be improved by driving the electrochromic device using the first drive pattern in the present invention.
In addition, in the evaluation of Table 1, in the case of an oxidation-reactive electrochromic layer, the time from application of the driving voltage until the transmittance at the coloring peak wavelength of 495 nm becomes stable at about 13% or less was evaluated. . Similarly, in the evaluation of Table 1, in the case of a reduction-reactive electrochromic layer, after applying the first voltage pulse B, until the transmittance at the coloring peak wavelength of 610 nm becomes stable at about 23% or less, Time was evaluated.

Furthermore, although the drive patterns P01 to P04 include patterns in which no voltage is applied and the open circuit state is maintained, visual observation shows that there is no unevenness in the coloring state, and the coloring density is maintained even in the open circuit state. I was sure that.

FIG. 11A is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to increase the color density using the electrochromic device A of Preparation Example 1. . FIG. 11B is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to increase the coloring density using the electrochromic device A of Preparation Example 1. . Note that in FIGS. 11A and 11B, the vertical axis represents the transmittance spectrum, and the horizontal axis represents the time after starting the application of the drive voltage.
As shown in FIGS. 11A and 11B, it was found that the responsiveness of the electrochromic layer could be improved in drive patterns P01 to P04.

<<Drive by second drive pattern>>
Next, while the electrochromic device A is coloring under the driving conditions (second driving pattern) that reduce the coloring density shown in Table 2 below, the transmittance spectrum at the center of the electrochromic reaction region is measured, and the oxidation reactivity or The time required for the colored state of the reduction-reactive electrochromic layer to stabilize was measured as an index of responsiveness. The results are shown in Table 2 and FIGS. 12A and 12B. Note that the colored state of the electrochromic device A was defined as a stable state (a state in which the coloring density was reduced to a predetermined density by the second drive pattern) when −1.0 V was applied. Further, the initial colored state (the initial colored state before driving by the second drive pattern, and the state where the color density is high) was a state in which −1.6 V was applied for 20 seconds.

As shown in Table 2, in the drive patterns P05 and P06 corresponding to the examples of the present invention, it takes 50 minutes for both the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer to respond to color development. seconds. On the other hand, in the drive pattern R02 corresponding to the comparative example of the present invention, the second voltage pulse A (Pw1-2) is not applied, and the time until the color response occurs is 120 seconds or more. From this, it was found that responsiveness could be improved by driving the electrochromic device using the second drive pattern in the present invention.
In addition, in the evaluation of Table 2, in the case of an oxidation-reactive electrochromic layer, the time from application of the driving voltage until the transmittance at the coloring peak wavelength of 495 nm becomes stable at about 55% or more was evaluated. . Similarly, in the evaluation of Table 2, in the case of a reduction-reactive electrochromic layer, the time from application of the driving voltage until the transmittance at the coloring peak wavelength of 610 nm reaches a stable level of about 63% or more is evaluated. did.

Furthermore, although driving patterns P05 and P06 include patterns in which no voltage is applied and the open circuit state is maintained, visual observation shows that the coloring state is uniform and the coloring density is maintained even in the open circuit state. I was sure that.

FIG. 12A is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to lower the coloring density using the electrochromic device A of Preparation Example 1. . FIG. 12B is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to lower the coloring density using the electrochromic device A of Preparation Example 1. . Note that in FIGS. 12A and 12B, the vertical axis represents transmittance, and the horizontal axis represents time after starting application of the drive voltage.
As shown in FIGS. 12A and 12B, it was found that the responsiveness of the electrochromic layer could be improved in drive patterns P05 and P06.

<<Drive using initialization drive pattern>>
Next, while driving the electrochromic device A under the driving conditions (initialization drive pattern) for initializing the color density of the electrochromic device shown in Table 3 below, the transmittance spectrum at the center of the electrochromic reaction region was measured. The time taken until the colored state of the oxidation-reactive or reduction-reactive electrochromic layer was initialized was measured as an index of responsiveness. The results are shown in Table 3 and FIGS. 13A and 13B. Further, the initial colored state (the colored state before driving according to the initialization drive pattern, in which the electrochromic device is coloring) was a state in which −1.6 V was applied for 20 seconds.

As shown in Table 3, in drive patterns P07 and P08 corresponding to the examples of the present invention, it takes time for both the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer to respond to initialization. It takes less than 6 seconds. On the other hand, in the drive pattern R03 corresponding to the comparative example of the present invention, the initialization voltage pulse A (Pw4) is not applied, and the time until the initialization response is made is 6 seconds or more. From this, it was found that responsiveness can be improved by driving the electrochromic device using the initialization drive pattern according to the present invention.
In addition, in the evaluation of Table 3, in the case of an oxidation-reactive electrochromic layer, the time from the application of the initialization driving voltage until the transmittance at the coloring peak wavelength of 495 nm becomes stable at about 80% or more is determined. evaluated. Similarly, in the evaluation of Table 3, in the case of a reduction-reactive electrochromic layer, the time from application of the initialization drive voltage until the transmittance at the coloring peak wavelength of 610 nm reaches a stable value of about 80% or more was evaluated.

FIG. 13A is a diagram showing a temporal change in light transmittance at a coloring peak wavelength of an oxidation-reactive electrochromic layer when performing initialization drive using electrochromic device A of Production Example 1. FIG. 13B is a diagram showing a temporal change in light transmittance at the coloring peak wavelength of the reduction-reactive electrochromic layer when performing initialization drive using the electrochromic device A of Preparation Example 1. Note that in FIGS. 13A and 13B, the vertical axis represents transmittance, and the horizontal axis represents time after starting application of the drive voltage.
As shown in FIGS. 13A and 13B, it was found that the responsiveness of the electrochromic layer could be improved in drive patterns P07 and P08.

<Durability evaluation>
Next, under the conditions of light exposure (38000 Lux, 30°C environment) using a light exposure device Q-sun (Xe-1, manufactured by Q-LAB), the driving conditions (first The electrochromic device A was continuously driven for color development for a total of 50 hours using a drive pattern (corresponding to the drive pattern and the initialization drive pattern), and then was driven for decolorization. Durability was evaluated by measuring the change in transmittance in the decolored state under these conditions. When the electrochromic device was exposed to light, the first transparent support 11 was irradiated with light. In addition, in drive patterns P09 and P10, continuous driving was performed for 50 hours by repeating Pw2-1 and Pw3-1 (400 seconds in total) 450 times. The measurement results are shown in Table 4.

As shown in Table 4, in drive patterns P09 and P10 corresponding to Examples of the present invention, the decolorization transmittance decrease after continuous driving was small, and it was found that the electrochromic layer was less likely to be colored and deteriorated. From this, it was found that by driving the electrochromic device according to the initialization drive pattern according to the present invention, the durability when continuously driven for a long time can be improved. Furthermore, since the drive patterns P09 and P10 corresponding to the embodiments of the invention include Pw3-1 in which no voltage is applied and the circuit is in an open circuit state, it is difficult to drive continuously for a long time. Power consumption can be suppressed.

(Preparation example 2)
<Production of electrochromic device B>
In Production Example 2, an electrochromic device B having an electrochromic reaction area (100 mm x 100 mm) was produced in the same manner as Production Example 1 except for the size of the support, the size of the film formed, and the resistance of the electrodes.

<<Formation of first electrode and electrochromic layer>>
A glass substrate of 110 mm x 110 mm and an average thickness of 0.7 mm was prepared as the first transparent support 11.
The first transparent electrode 12 was formed by forming an ITO film with an average thickness of about 200 nm on a 110 mm x 100 mm area on the first transparent support 11 by sputtering. The sheet resistance of the first transparent electrode 12 was 15Ω/□.
Furthermore, an AgPdCu alloy film (manufactured by Furuya Metal Co., Ltd.) was formed into a film with an average thickness of about 100 nm on the end portion of the first transparent electrode 12 in a 100 mm x 2 mm area and a 5 mm x 2 mm area by sputtering. One auxiliary electrode 18 was formed.
Next, an oxidation-reactive electrochromic layer 13 having the same composition as in Preparation Example 1 was formed in the electrochromic reaction area (100 mm x 100 mm) on the surface of the ITO film.

<<Formation of second electrical and deterioration prevention layer>>
A second transparent support 16 having the same shape as the first transparent support 11 is prepared, and in the same manner as the first transparent electrode 12 and the first auxiliary electrode 18, the second transparent electrode 15 and the second Auxiliary electrode 19 was formed.
Next, a tin oxide particle film is formed in the electrochromic reaction area (100 mm x 100 mm) on the ITO film surface, and a reduction-reactive electrochromic compound having the same composition as in Preparation Example 1 is supported (adsorbed) on the tin oxide particle film. In this way, a reduction-reactive electrochromic layer that also served as the deterioration prevention layer 21 was formed.

<<Formation and bonding of solid electrolyte layer>>
On the surface of the insulating inorganic fine particle layer on the second transparent support 16, an electrolyte solution prepared in the same manner as in Preparation Example 1 is applied to the electrochromic reaction area (100 mm x 100 mm), and the outer periphery is further UV cured. A resin (TB3035B manufactured by ThreeBond Holdings Co., Ltd.) is applied, bonded to the electrochromic layer 13 surface on the first transparent support 11 under reduced pressure, and cured by ultraviolet (UV) irradiation to form the solid electrolyte layer 14, A protective layer 17 was formed. The film thicknesses of the solid electrolyte layer 14 and the protective layer 17 were set to have an average thickness of 50 μm by controlling the bonding gap, and electrochromic device B was produced. Note that the average distance between the first auxiliary electrode 18 and the second auxiliary electrode 19 in the electrochromic element B was 100 mm.

<<Drive circuit connection>>
A drive circuit 50 was connected to the first auxiliary electrode 18 and the second auxiliary electrode 19 of the electrochromic device B, and an electrochromic device B as shown in FIGS. 6A and 6B was produced. The drive circuit 50 was connected so that the first auxiliary electrode 18 of the first transparent support 11 had a positive polarity, and the second auxiliary electrode 19 of the second transparent support 16 had a negative polarity.

<<Drive by first drive pattern>>
Next, using the electrochromic device B that has been returned to the decolorized state, the electrochromic reaction area center is Transmittance spectra were measured at two points: the part, and the end 5 mm (a position 5 mm from the auxiliary electrode of the substrate on which the electrochromic layer was formed, and the central part in the short axis direction where no auxiliary electrode was formed). The time taken for the colored state of the oxidation-reactive or reduction-reactive electrochromic layer to stabilize was measured as an index of responsiveness. The results are shown in Table 5 and FIGS. 14A and 14B. Note that the colored state of the electrochromic device B was defined as a stable state when a voltage of -1.2V was applied.

As shown in Table 5, in the drive patterns P11 and P12 corresponding to the examples of the present invention, it takes 60 minutes for both the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer to respond to color development. seconds. On the other hand, in drive patterns R05 and R06 corresponding to comparative examples of the present invention, the first voltage pulse A (Pw1-1) is not applied, and the time until color response occurs is 180 seconds or more. From this, it was found that responsiveness could be improved by driving the electrochromic device using the first drive pattern in the present invention.
In addition, in the evaluation of Table 5, in the case of an oxidation-reactive electrochromic layer, after applying the driving voltage until the fluctuation in the transmittance at the coloring peak wavelength of 495 nm becomes stable for 10 seconds becomes 1% or less. Time was evaluated. Similarly, in the evaluation of Table 5, in the case of a reduction-reactive electrochromic layer, after applying the driving voltage, until the change in transmittance at the coloring peak wavelength of 610 nm becomes stable for 10 seconds becomes 1% or less. The time was evaluated.

Furthermore, although the driving patterns P11 and P12 include patterns in which no voltage is applied and the open circuit state is maintained, visual observation shows that the coloring state is uniform and the coloring density is maintained even in the open circuit state. I was sure that.
In addition, there was no problem in which the density in the center became thinner than in the ends due to a voltage drop between the center and the ends of the electrochromic reaction region, and the color density was highly uniform.

FIG. 14A is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the oxidation-reactive electrochromic layer when driving to increase the coloring density using electrochromic device B of Preparation Example 2. . FIG. 14B is a diagram showing temporal changes in light transmittance at the coloring peak wavelength of the reduction-reactive electrochromic layer when driving to increase the color density using the electrochromic device B of Preparation Example 2. . Note that in FIGS. 14A and 14B, the vertical axis represents the transmittance spectrum, and the horizontal axis represents the time after starting the application of the drive voltage.
As shown in FIGS. 14A and 14B, it was found that in drive patterns P11 to P12, the responsiveness of the electrochromic layer could be improved, and the difference in responsiveness between the center and edge of the electrochromic reaction region was small. .

(Preparation example 3)
<Production of electrochromic device C>
In Production Example 3, an electrochromic device C having an electrochromic reaction area (150 mm x 150 mm) was produced in the same manner as Production Example 1 except for the following points. Electrochromic device C corresponds to a comparative example of the present invention.

A glass substrate of 160 mm x 160 mm and an average thickness of 0.7 mm was prepared as the first transparent support 11.
The first transparent electrode 12 was formed by forming an ITO film with an average thickness of about 100 nm on a 160 mm x 150 mm area on the first transparent support 11 by sputtering. The sheet resistance of the first transparent electrode 12 was 15Ω/□.
Furthermore, an AgPdCu alloy film (manufactured by Furuya Metal Co., Ltd.) was formed into a film with an average thickness of about 100 nm on the end portion of the first transparent electrode 12 in a 150 mm x 2 mm area and a 5 mm x 2 mm area by sputtering. One auxiliary electrode 18 was formed.
A second transparent support 16 on which a second transparent electrode 15 and a second auxiliary electrode 19 were formed using the same procedure was prepared, and the electrode surfaces were made to face each other, and the outer periphery of the electrochromic reaction area (150 mm x 150 mm) was prepared. A UV curable resin (TB3035B manufactured by ThreeBond Holdings Co., Ltd.) was formed as a protective layer with a thickness of 120 μm and a gap of 120 μm. Note that a hole was formed in a part of the protective layer as an injection port for an electrochromic solution, and after injecting the electrochromic solution described below under vacuum, the hole was again plugged with a UV curing resin.

<Electrochromic solution>
The following three components were dissolved in propylene carbonate, and then filtered (pore size: 0.2 μm).
・40mM 1,1'-Diheptyl-4,4'-bipyridinium Dibromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
・40mM 5,10-Dihydro-5,10-dimethylphenazine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・0.1M Tetrabutylammonium Tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.)

A driving circuit 50 was connected to the first auxiliary electrode 18 and the second auxiliary electrode 19 of the electrochromic device C, which was prepared by bonding supports together, to produce an electrochromic device C corresponding to a comparative example of the present invention. . The drive circuit 50 was connected so that the first auxiliary electrode 18 of the first transparent support 11 had a positive polarity, and the second auxiliary electrode 19 of the second transparent support 16 had a negative polarity. Note that the average distance between the first auxiliary electrode 18 and the second auxiliary electrode 19 in the electrochromic element C was 150 mm.

The coloring characteristics of the obtained electrochromic device C were confirmed.
Specifically, under the driving conditions of driving patterns P11 and R05 in Table 5, while coloring the electrochromic device C, the electrochromic reaction area center and the edge 5 mm (from the auxiliary electrode of the substrate on which the electrochromic layer was formed) Transmittance spectra were measured at two points: 5 mm position and the center in the short axis direction where no auxiliary electrode was formed. The coloring peak wavelength of electrochromic device C was 605 nm.

As a result of the above measurement, in driving pattern R05, the 5 mm edge of the electrochromic layer was colored and the transmittance (605 nm) was 30%, but the central part of the electrochromic reaction area was not colored (coloring density did not rise).
Further, in Pw3-1 (open circuit) of the drive pattern P11, it was confirmed that the coloring of the end 5 mm of the electrochromic layer was discolored. Therefore, when the electrochromic device C corresponding to the comparative example of the present invention is driven with a drive pattern that includes an open circuit state in order to save power, the electrochromic device C becomes colored and disappears even when no voltage is applied. It was found that the memory effect of retaining the color state for a certain period of time could not be achieved, and the color density could not be maintained.

As described above, the electrochromic device of the present invention includes a first electrode, a first auxiliary electrode formed in contact with the first electrode, a second electrode, and a second electrode. A second auxiliary electrode that is in contact with the first auxiliary electrode and formed such that the average distance with the first auxiliary electrode is 100 mm or less, and a second auxiliary electrode that is in contact with at least one of the first electrode and the second electrode. , and the formed electrochromic layer and at least one of the first electrode, the second electrode, and the electrochromic layer without contacting the first auxiliary electrode and the second auxiliary electrode. is in contact with the formed solid electrolyte layer and the electrochromic layer through the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode. and a control means for controlling application of a voltage using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern.
Further, in the electrochromic device of the present invention, the first driving pattern is a driving pattern for bringing the electrochromic layer into a first coloring state, and the first voltage pulse A is for increasing the response speed of the electrochromic layer. This is a driving pattern in which a first voltage pulse B lower than the first voltage pulse A is applied to form a first coloring state, and then a state in which no voltage is applied is maintained.
Further, in the electrochromic device of the present invention, the second driving pattern is a driving pattern for forming a second coloring state having a lower color density than the first coloring state from the first coloring state, A second voltage pulse B higher than the second voltage pulse A, or the second voltage, for applying a second voltage pulse A for increasing the response speed of the electrochromic layer and forming a second colored state. This is a drive pattern in which a second voltage pulse B having the opposite polarity to the pulse A is applied, and then a state in which no voltage is applied is maintained.
In addition, in the electrochromic device of the present invention, the initialization drive pattern is a drive pattern for forming an initial decolorized state, the polarity is opposite to that of the first voltage pulse A, and the response of the electrochromic layer is Apply an initialization voltage pulse A to increase the speed, then apply an initialization voltage pulse B to bring the potential of the electrochromic layer to approximately 0 V or short circuit to form an initial bleached state. This is a driving pattern.
As a result, the electrochromic device of the present invention has high responsiveness and uniformity of color density when performing color development/decolorization driving, and high strength and safety against external shocks, and when operated continuously for a long time. It has excellent durability and can reduce power consumption.

Examples of aspects of the present invention are as follows.
<1> A first electrode,
a first auxiliary electrode formed in contact with the first electrode;
a second electrode;
a second auxiliary electrode that is in contact with the second electrode and formed such that an average distance from the first auxiliary electrode is 100 mm or less;
An electrochromic device formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode. layer and
In contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and in non-contact with the first auxiliary electrode and the second auxiliary electrode. , a formed solid electrolyte layer,
Control of applying a voltage to the electrochromic layer via the first electrode and the second electrode using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern. a control means for performing;
Equipped with
The first driving pattern is the driving pattern for bringing the electrochromic layer into the first coloring state, and applying a first voltage pulse A for increasing the response speed of the electrochromic layer; The driving pattern is to apply a first voltage pulse B lower than the first voltage pulse A to form a first coloring state, and then maintain a state in which no voltage is applied;
The second driving pattern is the driving pattern for forming a second coloring state from the first coloring state with a lower color density than the first coloring state, and the second driving pattern is a driving pattern for forming a second coloring state having a lower color density than the first coloring state, A second voltage pulse B higher than the second voltage pulse A, or a second voltage pulse A for forming the second colored state by applying a second voltage pulse A for increasing the speed; The drive pattern is such that a second voltage pulse B of opposite polarity is applied, and then a state in which no voltage is applied is maintained;
The initialization drive pattern is the drive pattern for forming an initial decolorized state, and has a polarity opposite to the first voltage pulse A, and is an initialization drive pattern for increasing the response speed of the electrochromic layer. The driving pattern is to apply a voltage pulse A, and then apply an initialization voltage pulse B to bring the potential of the electrochromic layer to approximately 0 V to form an initial decolored state, or to short-circuit the electrochromic layer.
This is an electrochromic device characterized by the following.
<2> The control means, in at least one of the first drive pattern and the second drive pattern,
Applying the first voltage pulse B and maintaining a state in which the voltage is not applied after applying the first voltage pulse B, or
The electrochromic device according to <1>, wherein application of the second voltage pulse B and maintenance of a state in which the voltage is not applied after application of the second voltage pulse B are repeated.
<3> The electrochromic device according to any one of <1> to <2>, wherein the first auxiliary electrode and the second auxiliary electrode contain a metal material.
<4> The first auxiliary electrode is located on one side of the electrochromic layer, and the second auxiliary electrode is located on the other side opposite to the one side, <1> to <3. The electrochromic device according to any one of the above.
<5> The electrochromic device according to any one of <1> to <4>, wherein the average voltage of the first voltage pulse B and the second voltage pulse B is 1.23 V or less.
<6> Further comprising a measuring means for measuring an open circuit voltage between the first electrode and the second electrode,
When the control means maintains a state in which the voltage is not applied in the first drive pattern and the second drive pattern, the first voltage pulse B and The electrochromic device according to any one of <1> to <5>, wherein the pulse characteristics of the second voltage pulse B are changed.
<7> The electrochromic device according to any one of <1> to <6>, wherein the solid electrolyte layer includes a solid solution of a matrix polymer and an ionic liquid.
<8> The electrochromic device according to any one of <1> to <7>, wherein the electrochromic layer contains a compound capable of two-electron reaction.
<9> The electrochromic device has two of the electrochromic layers,
one of the electrochromic layers is a first electrochromic layer containing an electrochromic material capable of developing color in an oxidized state;
The electrochromic device according to any one of <1> to <8>, wherein the other electrochromic layer is a second electrochromic layer containing an electrochromic material capable of developing color in a reduced state.
<10> Between the first voltage pulse A and the first voltage pulse B, between the second voltage pulse A and the second voltage pulse B, and between the initialization voltage pulse A and the initialization voltage pulse B. According to any one of <1> to <9> above, the state in which no voltage is applied is maintained during at least one of the period between the application of the initialization voltage pulse A and the period from application of the initialization voltage pulse A until short circuiting. It is an electrochromic device.
<11> A wearable device comprising the electrochromic device according to any one of <1> to <10>.
<12> The wearable device according to <11>, wherein the wearable device has a shape of glasses.
<13> A first electrode,
a first auxiliary electrode formed in contact with the first electrode;
a second electrode;
a second auxiliary electrode that is in contact with the second electrode and formed such that an average distance from the first auxiliary electrode is 100 mm or less;
An electrochromic device formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode. layer and
In contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and in non-contact with the first auxiliary electrode and the second auxiliary electrode. , a formed solid electrolyte layer, and the electrochromic layer in an electrochromic device comprising:
A control step of applying voltage via the first electrode and the second electrode using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern,
The first driving pattern is the driving pattern for bringing the electrochromic layer into the first coloring state, and applying a first voltage pulse A for increasing the response speed of the electrochromic layer; The driving pattern is to apply a first voltage pulse B lower than the first voltage pulse A to form a first coloring state, and then maintain a state in which no voltage is applied;
The second driving pattern is the driving pattern for forming a second coloring state from the first coloring state with a lower color density than the first coloring state, and the second driving pattern is a driving pattern for forming a second coloring state having a lower color density than the first coloring state, A second voltage pulse B higher than the second voltage pulse A, or a second voltage pulse A for forming the second colored state by applying a second voltage pulse A for increasing the speed; The drive pattern is such that a second voltage pulse B of opposite polarity is applied, and then a state in which no voltage is applied is maintained;
The initialization drive pattern is the drive pattern for forming an initial decolorized state, and has a polarity opposite to that of the first voltage pulse A, and is an initialization drive pattern for increasing the response speed of the electrochromic layer. The driving pattern is to apply a voltage pulse A, and then apply an initialization voltage pulse B to bring the potential of the electrochromic layer to approximately 0 V to form an initial decolored state, or to short-circuit the electrochromic layer.
A method for driving an electrochromic device is characterized in that:

The electrochromic device according to any one of <1> to <10>, the wearable device according to any one of <11> to <12>, and the method for driving an electrochromic device according to <13> Accordingly, various problems in the prior art can be solved and the object of the present invention can be achieved.

Japanese Patent Application Publication No. 2016-218364 Japanese Patent Application Publication No. 9-211497

10 Electrochromic device according to the first embodiment 11 First transparent support 12 First transparent electrode (first electrode)
13 Electrochromic layer 14 Solid electrolyte layer 15 Second transparent electrode (second electrode)
16 Second transparent support 18 First auxiliary electrode 19 Second auxiliary electrode 20 Electrochromic device according to second embodiment 21 Deterioration prevention layer (second electrochromic layer)
30 Electrochromic device according to third embodiment 40 Electrochromic device according to fourth embodiment 50 Drive circuit (an example of control means)

Claims (10)

a first electrode;
a first auxiliary electrode formed in contact with the first electrode;
a second electrode;
a second auxiliary electrode that is in contact with the second electrode and formed such that an average distance from the first auxiliary electrode is 100 mm or less;
An electrochromic device formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode. layer and
In contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and in non-contact with the first auxiliary electrode and the second auxiliary electrode. , a formed solid electrolyte layer,
Control of applying a voltage to the electrochromic layer via the first electrode and the second electrode using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern. a control means for performing;
Measuring means for measuring an open circuit voltage between the first electrode and the second electrode;
An electrochromic device comprising :
The first driving pattern is the driving pattern for bringing the electrochromic layer into a first coloring state,
After applying the first voltage pulse A for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied ,
After that, after applying a first voltage pulse B lower than the first voltage pulse A for forming the first coloring state, the driving pattern maintains a state in which no voltage is applied ;
The second driving pattern is the driving pattern for forming a second coloring state having a lower color density than the first coloring state from the first coloring state,
After applying the second voltage pulse A for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied ,
Thereafter, a second voltage pulse B higher than the second voltage pulse A or a second voltage pulse B having the opposite polarity to the second voltage pulse A was applied to form the second colored state. The driving pattern maintains a state in which no voltage is applied after that,
The initialization drive pattern is the drive pattern for forming an initial decolorized state,
After applying an initialization voltage pulse A having a polarity opposite to the first voltage pulse A and for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied;
Thereafter, the driving pattern is to apply an initialization voltage pulse B that brings the potential of the electrochromic layer to approximately 0 V or to short-circuit the electrochromic layer in order to form an initial decolored state;
The control means includes:
Immediately after the application of the first voltage pulse B or immediately after the application of the second voltage pulse B, the first voltage is determined according to the open-circuit voltage measured by the measuring means when maintaining the state in which the voltage is not applied. applying a first voltage pulse B' and a second voltage pulse B' in which pulse characteristics of the pulse B and the second voltage pulse B are changed;
In at least one of the first drive pattern and the second drive pattern, applying the first voltage pulse B' and maintaining a state in which the voltage is not applied after applying the first voltage pulse B', or repeating the application of the second voltage pulse B' and the maintenance of the state in which the voltage is not applied after the application of the second voltage pulse B';
An electrochromic device characterized by: The electrochromic device of claim 1, wherein the first auxiliary electrode and the second auxiliary electrode include a metallic material. According to any one of claims 1 to 2, the first auxiliary electrode is located on one side of the electrochromic layer, and the second auxiliary electrode is located on the other side opposite to the one side. electrochromic device. The electrochromic device according to any one of claims 1 to 3, wherein the average voltage of the first voltage pulse B and the second voltage pulse B is 1.23V or less. 5. An electrochromic device according to any one of claims 1 to 4, wherein the solid electrolyte layer comprises a solid solution of a matrix polymer and an ionic liquid. The electrochromic device according to any one of claims 1 to 5, wherein the electrochromic layer contains a compound capable of two-electron reaction. the electrochromic device has two of the electrochromic layers;
one of the electrochromic layers is a first electrochromic layer containing an electrochromic material capable of developing color in an oxidized state;
7. The electrochromic device according to claim 1, wherein the other electrochromic layer is a second electrochromic layer containing an electrochromic material capable of developing color in a reduced state. A wearable device comprising the electrochromic device according to claim 1. The wearable device according to claim 8, wherein the wearable device has a shape of glasses. a first electrode;
a first auxiliary electrode formed in contact with the first electrode;
a second electrode;
a second auxiliary electrode that is in contact with the second electrode and formed such that an average distance from the first auxiliary electrode is 100 mm or less;
An electrochromic device formed in contact with at least one of the first electrode and the second electrode, but not in contact with the first auxiliary electrode and the second auxiliary electrode. layer and
In contact with at least one of the first electrode, the second electrode, and the electrochromic layer, and in non-contact with the first auxiliary electrode and the second auxiliary electrode. , a formed solid electrolyte layer, and the electrochromic layer in an electrochromic device comprising:
A control step of applying voltage via the first electrode and the second electrode using at least one of a first drive pattern, a second drive pattern, and an initialization drive pattern;
A method for driving an electrochromic device, the method comprising: measuring an open circuit voltage between the first electrode and the second electrode;
The first driving pattern is the driving pattern for bringing the electrochromic layer into a first coloring state,
After applying the first voltage pulse A for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied,
After that, after applying a first voltage pulse B lower than the first voltage pulse A for forming the first coloring state, the driving pattern maintains a state in which no voltage is applied;
The second driving pattern is the driving pattern for forming a second coloring state having a lower color density than the first coloring state from the first coloring state,
After applying the second voltage pulse A for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied,
After that, after applying a second voltage pulse B higher than the second voltage pulse A or a second voltage pulse B having the opposite polarity to the second voltage pulse A for forming the second colored state. , the driving pattern maintaining a state in which no voltage is applied;
The initialization drive pattern is the drive pattern for forming an initial decolorized state,
After applying an initialization voltage pulse A having a polarity opposite to the first voltage pulse A and for increasing the response speed of the electrochromic layer, maintaining a state in which no voltage is applied;
Thereafter, the driving pattern is to apply an initialization voltage pulse B that brings the potential of the electrochromic layer to approximately 0 V or to short-circuit the electrochromic layer in order to form an initial decolored state;
The control step includes:
Immediately after the application of the first voltage pulse B or immediately after the application of the second voltage pulse B, the first voltage is determined according to the open circuit voltage measured in the measurement step when maintaining the state in which the voltage is not applied. applying a first voltage pulse B' and a second voltage pulse B' in which pulse characteristics of the pulse B and the second voltage pulse B are changed;
In at least one of the first drive pattern and the second drive pattern, applying the first voltage pulse B' and maintaining a state in which the voltage is not applied after applying the first voltage pulse B', or repeating the application of the second voltage pulse B' and the maintenance of the state in which the voltage is not applied after the application of the second voltage pulse B';
A method for driving an electrochromic device, characterized in that:

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