JP2019191579A - Electrochromic element and method for manufacturing electrochromic element - Google Patents

Abstract

To provide an electrochromic element which can exhibit an excellent color production holding property and an excellent driving stability even under an atmosphere without requiring a strict sealing.SOLUTION: The electrochromic element includes: a first electrode 2a provided on a first substrate 1a; a second electrode 2b provided on a second substrate 1b provided opposite to the first electrode via a gap; a first electrochemical reaction layer provided in contact with the first electrode; a second electrochemical reaction layer provided in contact with the second electrode; and an electrolyte layer 4 disposed between the first and second electrodes. The first and second electrochemical reaction layers are made of a combination of a layer in a reversibly oxidizable state and a layer in a reversibly reducible state, and a formula of E1≥-0.8 V(vs.FC/FC) and E2≥-0.8 V(vs.FC/FC) is established when an oxidation-reduction potential of the first electrochemical reaction layer is defined as E1 and an oxidation-reduction potential of the second electrochemical reaction layer is defined as E2.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic device and a method for manufacturing an electrochromic device.

  When an electrochromic device is used for dimming or signage, it is necessary to maintain a colored state even in a low voltage application state or a non-application state, and thus high memory properties are required. In addition, since the outdoor environment of the electrochromic device is sufficiently assumed, it is desired to provide an electrochromic element that can be stably driven in the atmosphere for a long period of time. In particular, in an electrochromic device using an organic material system, it is difficult to ensure memory performance and stability in the atmosphere, which is an important issue.

For example, a viologen compound is mentioned as an electrochromic organic compound. This viologen compound is a compound that exhibits an electrochromic phenomenon in which a neutral state is a transparent state and color develops in a reduced state. However, viologen compounds that develop color in the reduced state immediately change to a decolored state due to oxidation when exposed to oxygen in the atmosphere, and it is difficult to operate stably unless the device is strictly sealed. There is a problem that there is.
In order to solve the above-mentioned problems, for example, a method has been proposed in which the instability of color development of a viologen compound is eliminated by using an organic solvent in the electrolyte layer and providing a polymer gel on the display electrode surface (for example, Patent Literature 1).
In addition, triarylamine compounds have been reported as electrochromic materials that are transparent in the neutral state and develop color in the oxidized state, and the triarylamine compound that develops color in the oxidized state exists stably regardless of oxygen in the atmosphere. Has been reported (for example, see Patent Document 2).

  An object of the present invention is to provide an electrochromic element that is excellent in color retention and driving stability even in the atmosphere without requiring strict sealing.

The electrochromic device of the present invention as a means for solving the above-described problems includes a first substrate, a first electrode provided on the first substrate, and a distance from the first electrode. A second substrate provided on the second substrate, a second electrode provided on the second substrate, a first electrochemical reaction layer provided in contact with the first electrode, and the second A first electrochemical reaction layer provided in contact with the first electrode, and an electrolyte layer disposed between the first electrode and the second electrode, and the first electrochemical reaction layer. And the second electrochemical reaction layer is a combination of a reversibly oxidizable layer and a reversibly reducible layer, the first electrochemical reaction layer and the second electrochemical reaction layer. At least one of the layers is an electrochromic layer, and the redox of the first electrochemical reaction layer When the potential E1, the oxidation-reduction potential of the second electrochemical reaction layer and E2, the following ^{formula, E1 ≧ -0.8V (vs.FC / FC} +), E2 ≧ -0.8V (vs.FC / FC ⁺ ).

  According to the present invention, it is possible to provide an electrochromic element that is excellent in color retention and driving stability even in the atmosphere without requiring strict sealing.

FIG. 1 is a schematic sectional view showing an example of the electrochromic device of the present invention.

(Electrochromic device)
The electrochromic device of the present invention includes a first substrate, a first electrode provided on the first substrate, and a second substrate provided at a distance from the first electrode. A second electrode provided on the second substrate; a first electrochemical reaction layer provided in contact with the first electrode; and a second electrode provided in contact with the second electrode. And an electrolyte layer disposed between the first electrode and the second electrode, wherein the first electrochemical reaction layer and the second electrochemical reaction layer are: It consists of a combination of a reversibly oxidizable layer and a reversibly reducible layer, and at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer , The redox potential of the first electrochemical reaction layer is E1, and the second electrochemical reaction is When the oxidation-reduction potential of the E2, the following ^{formula, E1 ≧ -0.8V (vs.FC / FC} +), E2 ≧ -0.8V (vs.FC / FC +), was filled, depending on further required Has other layers.

The electrochromic device of the present invention is based on the knowledge that the conventional technology of Patent Document 1 does not improve the durability of the material itself against oxygen, so that a great improvement cannot be expected depending on the degree of sealing. Is.
In addition, the electrochromic device of the present invention does not mention the counter electrode material that is paired with the reaction of the triarylamine compound and causes a reverse reaction in the prior art of Patent Document 2. In this case, as a general counter electrode material, studies have been made on metal oxides such as titanium oxide that show semiconducting properties, or materials in which a reducing material is supported on the surface of the metal oxide. However, since the metal oxide itself is photoactive, the driving stability under light irradiation may not be sufficiently secured. Furthermore, this is based on the finding that depending on the reducing material used, it is difficult to produce an electrochromic device having high stability in the atmosphere for the same reason as the viologen compound.

In the present invention, the first electrochemical reaction layer and the second electrochemical reaction layer comprise a combination of a reversibly oxidizable layer and a reversibly reducible layer, At least one of the electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer, and the redox potential of the first electrochemical reaction layer is E1, and the redox potential of the second electrochemical reaction layer is E2. Then, the following expressions, E1 ≧ −0.8 V (vs. FC / FC ⁺ ), E2 ≧ −0.8 V (vs. FC / FC ⁺ ) are satisfied.
When the oxidation-reduction potentials E1 and E2 of the first and second electrochemical reaction layers satisfy −0.8 V (vs. FC / FC ⁺ ) or more, the first and second electric reactions are performed even in the atmosphere. The chemical reaction layer is not easily oxidized by oxygen and can exist stably in the atmosphere.
For example, it is known that a viologen compound has a redox potential at which one electron is reduced from a dicationic state in the vicinity of −0.9 V (vs. FC / FC ⁺ ). In this case, it is easy to be oxidized by oxygen present in the atmosphere, and as a result, a phenomenon is observed in which the viologen compound in a colored state is instantaneously reduced by one electron in the atmosphere to return to the dicationic state and disappear.
In addition, a compound having a triarylamine structure in which the redox potential between the neutral state and the radical cation state is in the vicinity of 0.3 V is not instantaneously oxidized and becomes a radical cation state even in the atmosphere. Both colored and decolored states can exist stably.
In the case of being composed of a compound having a neutral state and a radical cation state, such as a compound having a triarylamine structure, one of the first and second electrochemical reaction layers has a redox potential of 0.0 V ( vs. FC / FC ⁺ ) or more and less than 0.2 V (vs. FC / FC ⁺ ), and the other oxidation-reduction potential is 0.2 V or more (vs. FC / FC ⁺ ) 0.5 V (vs. FC / FC ⁺ ) or less is preferable.
The electrochemical reaction layer having an oxidation-reduction potential of 0.0 V (vs. FC / FC ⁺ ) or more and less than 0.2 V (vs. FC / FC ⁺ ) has a one-electron oxidized radical cation state that is very stable. It can be held for a long time in the radical cation state. When the oxidation-reduction potential is lower than this, the electrochemical reaction layer is gradually oxidized by oxygen over time even if the degree is small, and there is a concern that the stability in the neutral state is lowered.
An electrochemical reaction layer having a redox potential of 0.2 V or more (vs. FC / FC ⁺ ) and 0.5 V (vs. FC / FC ⁺ ) or less is relatively stable in both a neutral state and a radical cation state. Thereby, it becomes easy to change both states electrochemically. When the oxidation-reduction potential is higher than this, the neutral state stability of the electrochemical reaction layer is high, and it becomes difficult to realize a stable radical cation state.
Since the two electrochemical reaction layers have different redox potentials as described above, at least one of the first electrochemical reaction layer and the second electrochemical reaction layer can always be held in a radical cation state. Become.
In order to keep at least one of the first electrochemical reaction layer and the second electrochemical reaction layer always in a radical cation state, at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is oxidized. Process. The oxidation treatment will be described in the electrochromic device manufacturing method.

  It is preferable that the oxidation-reduction potential E1 of the first electrochemical reaction layer and the oxidation-reduction potential E2 of the second electrochemical reaction layer satisfy the following expression: | E1-E2 | <0.9V. When the potential difference between the redox potentials is less than 0.9 V, the driving voltage is also small, and the improvement in memory property (color retention time) due to the small energy difference between the color-decoloring states can be expected.

The first electrochemical reaction layer and the second electrochemical reaction layer are composed of an electrochemically active material capable of taking a radical cation state,
At least one of the first electrochemical reaction layer and the second electrochemical reaction layer is always in a radical cation state;
The redox potential between the neutral state and radical cation state of the first electrochemical reaction layer is E1 ′, and the redox potential between the neutral state and radical cation state of the second electrochemical reaction layer. Is E2 ′, satisfying the following formulas, E1 ′ ≧ −0.8 V (vs. FC / FC ⁺ ), E2 ′ ≧ −0.8 V (vs. FC / FC ⁺ ), does not contribute to the reaction. It is preferable from the viewpoint of expanding the material selectivity of the electrolytic solution.

  Here, the redox potential E1 between the neutral state and the radical cation state of the first electrochemical reaction layer, and the redox potential between the neutral state and the radical cation state of the second electrochemical reaction layer. Examples of the measuring method with E2 include an evaluation method by cyclic voltammetry.

  The electrochromic device of the present invention includes a first substrate, a first electrode provided on the first substrate, a second substrate spaced from the first electrode, A second electrode provided on the second substrate, a first electrochemical reaction layer provided in contact with the first electrode, and a second electrochemical reaction layer provided in contact with the second electrode And an electrolyte layer disposed between the first electrode and the second electrode, and further includes other layers as necessary.

<First substrate, second substrate>
The first substrate has a function of supporting the first electrode and the first electrochemical reaction layer.
The second substrate has a function of supporting the second electrode and the second electrochemical reaction layer.
As the substrate, a known organic material or inorganic material can be used as it is as long as it is a transparent material capable of supporting these layers.
Examples of the substrate include glass substrates such as alkali-free glass, borosilicate glass, float glass, and soda lime glass.
As the substrate, for example, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, or polyimide resin may be used. Note that the surface of the substrate may be coated with a transparent insulating layer, an antireflection layer, or the like in order to improve water vapor barrier properties, gas barrier properties, and visibility.
The shape of the substrate may be rectangular or round, and is not particularly limited. Moreover, even if it is a plane, it may take the spherical structure like a lens.

<First electrode and second electrode>
Any one or both of the first electrode and the second electrode may be transparent, and there is no particular limitation as long as it is a conductive material. Thereby, the coloring contrast can be further increased.

Examples of the transparent conductive material include indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), tin oxide doped with antimony (hereinafter referred to as ATO), and the like. Inorganic materials can be used. In particular, indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide), and zinc oxide (hereinafter referred to as In oxide) formed by vacuum film formation. It is preferable to use an inorganic material including any one of Zn oxide.
In oxides, Sn oxides, and Zn oxides are materials that can be easily formed by sputtering, have good transparency, and provide electrical conductivity. Particularly preferred materials are InSnO, GaZnO, SnO, In ₂ O ₃ , and ZnO.
In addition, carbon nanotubes with transparency and other highly conductive non-permeable materials such as Au, Ag, Pt, and Cu are formed in a fine network to improve conductivity while maintaining transparency. You may use the electrode which did.

  The thickness of each of the first electrode and the second electrode is adjusted so that an electrical resistance value necessary for the oxidation-reduction reaction of the electrochromic layer can be obtained. When ITO is used as the material for the first electrode and the second electrode, the thickness of each of the first electrode and the second electrode is preferably 50 nm to 500 nm, for example.

As a manufacturing method of each of the first electrode and the second electrode, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used.
There is no particular limitation as long as each material of the first electrode and the second electrode can be applied and formed. For example, spin coating method, casting method, micro gravure coating method, 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, flexographic printing method, offset printing method, reverse printing method, inkjet printing method Various printing methods such as these can be used.
In particular, when transparency is unnecessary, a metal plate such as titanium or zinc can also be used.
The optical transmittance of the transparent electrode is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60% or more and less than 100%, more preferably 90% or more and less than 100%. If the optical transmittance is less than 60%, the display image becomes dark, and the display performance such as brightness and vividness is inferior. The film thickness of the transparent electrode is not particularly limited, but is preferably 10 nm to 300 nm in the case of an ITO electrode.

<First electrochemical reaction layer, second electrochemical reaction layer>
The first electrochemical reaction layer and the second electrochemical reaction layer are made of an electrochemically active material, and the first electrochemical reaction layer and the second electrochemical reaction layer can be reversibly oxidized. It is necessary that at least one of the first electrochemical reaction layer and the second electrochemical reaction layer be an electrochromic layer.
The electrochemical reaction layer having a reversibly oxidizable state specifically refers to a layer containing a compound corresponding to the following characteristics.
-Compound having reversibly oxidizable state-
It is a compound that can donate one or more electrons with respect to the target compound, has electron acceptability after electron donation, and can return to the initial compound after electron acceptance.
In addition, the electrochemical reaction layer having a reversibly reducible state specifically refers to a layer containing a compound corresponding to the following characteristics.
It is a compound that can accept one or more electrons with respect to the target compound, has an electron donating property after electron acceptance, and can return to the initial compound after electron donation.

It is preferable that at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer that develops color depending on the radical cation state, and the first electrochemical reaction layer and the second electrochemical reaction It is more preferable that only one of the layers is an electrochromic layer from the viewpoint of improving display quality in the case where it is desired to clearly display a target color display such as a signage application.
In the case of adopting such an electrochemical reaction layer configuration, for example, a counter electrode electrical reaction layer that performs an electrochemical reaction without causing a large color change can be used. These electrochemical reaction layers can be expected to have the effect of stabilizing each electrochemical reaction by carrying out the reverse reaction of the electrochromic layer and reducing the potential difference required for the electrochromic reaction. For example, when the electrochromic layer is an oxidation coloring type, the counter electrode is preferably a material capable of a reduction reaction.

As a material used for the electrochemical reaction layer, either an inorganic compound or an organic compound may be used. The electrochemical reaction layer can be regarded as an electrochromic material with a small change in the light absorption band in the visible light region due to the oxidation-reduction reaction (substantially no color change), so select the same material as the electrochromic layer be able to.
Examples of the method for forming the electrochemical reaction layer include a vacuum deposition method, a sputtering method, and an ion plating method. Also, spin coating method, casting method, micro gravure coating method, 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 Various printing methods such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can also be used.

  The electrochromic layer indicates that containing an electrochromic material, and any of an inorganic electrochromic compound and an organic electrochromic compound may be used as the electrochromic material. Moreover, the conductive polymer known by showing electrochromism can also be used.

Examples of the inorganic electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide. Examples of the organic electrochromic compound include viologen, rare earth phthalocyanine, and styryl.
Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, or derivatives thereof.
Specifically, azobenzene compounds, anthraquinone compounds, diarylethene compounds, dihydroprene compounds, dipyridine compounds, styryl compounds, styryl spiropyran compounds, spirooxazine compounds as polymer-based and dye-based electrochromic compounds , Spirothiopyran compounds, thioindigo compounds, tetrathiafulvalene compounds, terephthalic acid compounds, triphenylmethane compounds, triarylamine compounds, naphthopyran compounds, viologen compounds, pyrazoline compounds, phenazine compounds, phenylenediamine Compounds, phenoxazine compounds, phenothiazine compounds, phthalocyanine compounds, fluoran compounds, fulgide compounds, benzopyran compounds, metallocene compounds Low molecular weight organic electrochromic compound of the compounds such as, polyaniline, and the like conductive polymer compounds such as polythiophene.

  Among these, it is preferable to include a compound having a triarylamine skeleton, and a radical polymerizable compound having a triarylamine skeleton represented by the following general formula and having a triarylamine having a radical polymerizable functional group is particularly preferable. preferable.

  When the electrochromic layer contains a compound having a triarylamine skeleton represented by the following general formula 1, it is advantageous in that the repeated driving (oxidation-reduction reaction) characteristics are good and the light durability is excellent. In addition, the decolored state is transparent, and high coloration performance can be obtained by oxidation reaction.

[General Formula 1]
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 1. A has a structure represented by the following general formula 2, and is bonded to B at any position of R ₁ to R ₁₅ . 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 .

[General formula 2]

[General formula 3]
However, R ₁ to R ₂₁ are all monovalent organic groups, which may be the same or different, and at least one of the monovalent organic groups is a radical polymerizable functional group.

-Monovalent organic group-
As the monovalent organic group in the general formula 2 and the general formula 3, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or an alkoxycarbonyl group which may have a substituent. An aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an amide group, and a substituent. A monoalkylaminocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a monoarylaminocarbonyl group which may have a substituent, a diarylaminocarbonyl which may have a substituent Group, sulfonic acid group, alkoxysulfonyl group which may have a substituent, aryloxysulfo which may have a substituent Group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, sulfonamide group, optionally substituted monoalkylaminosulfonyl group, substituent A dialkylaminosulfonyl group optionally having a substituent, a monoarylaminosulfonyl group optionally having a substituent, a diarylaminosulfonyl group optionally having a substituent, an amino group, and a substituent. A monoalkylamino group which 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, and a substituent An alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, Alkylthio group which may have a substituent, which may have a substituent arylthio group, and a heterocyclic group which may have a substituent.
Among these, an alkyl group, an alkoxy group, a hydrogen atom, an aryl group, an aryloxy group, a halogen atom, an alkenyl group, and an alkynyl group are particularly preferable from the viewpoint of stable operation.

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

  Examples of the substituent further substituted with the substituent include, for example, a halogen atom, a nitro group, a cyano group, an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group Aryl groups such as phenyl group and naphthyl group, and aralkyl groups such as benzyl group and phenethyl group.

-Radically polymerizable functional group-
The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and can be radically polymerized.
Examples of the radical polymerizable functional group include a 1-substituted ethylene functional group and a 1,1-substituted ethylene functional group shown below.

(1) As 1-substituted ethylene functional group, the functional group represented by the following general formula (i) is mentioned, for example.
However, in general formula (i), X ₁ is an arylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group, —CON (R ₁₀₀ ) -Group [R ₁₀₀ represents hydrogen, an alkyl group, an aralkyl group or an aryl group. Or -S- group.

Examples of the arylene group of the general formula (i) include a phenylene group and a naphthylene group which may have a substituent.
Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group.
Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.

  Specific examples of the radical polymerizable functional group represented by the general formula (i) include vinyl group, styryl group, 2-methyl-1,3-butadienyl group, vinylcarbonyl group, acryloyloxy group, acryloylamide group, vinyl Examples include thioether groups.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following general formula (ii).
However, in general formula (ii), Y is 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, an alkoxy group, a —COOR ₁₀₁ group [R ₁₀₁ is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl which may have a substituent. 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 that may have a substituent. Represents a group and may be the same or different from each other. X ₂ represents the same substituent, single bond, and alkylene group as X _{1 in} formula (i). Provided that at least one oxycarbonyl group in Y and X _2, a cyano group, an alkenylene group, an aromatic ring.

Examples of the aryl group represented by the general formula (ii) include a phenyl group and a 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 a benzyl group, a naphthylmethyl group, and a phenethyl group.

  Specific examples of the radical polymerizable functional group represented by the general formula (ii) include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, And a methacryloylamino group.

In addition, examples of the substituent further substituted with the substituent for X ₁ , X ₂ , and Y include, for example, a halogen atom, a nitro group, a cyano group, a methyl group, an alkyl group such as an ethyl group, a methoxy group, and an ethoxy group. And aryloxy groups such as a phenoxy group, aryl groups such as a phenyl group and a naphthyl group, and aralkyl groups such as a benzyl group and a phenethyl group.

  Of the radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly preferable.

  Preferred examples of the radically polymerizable compound having a triarylamine include compounds represented by the following general formulas 1-1 to 1-3.

[General Formula 1-1]

[General Formula 1-2]

[General Formula 1-3]

In General Formula 1-1 to General Formula 1-3, R ₂₇ to R ₈₈ are all monovalent organic groups, which may be the same or different, and are at least one of the monovalent organic groups. One is a radically polymerizable functional group.
Examples of the monovalent organic group and the radical polymerizable functional group include the same as those in the general formulas 2 and 3.

  Examples of the compounds represented by the general formula 1 and the general formulas 1-1 to 1-3 include those shown below. The radically polymerizable compound having a triarylamine is not limited to these.

  Furthermore, an electrochromic material (composition) comprising a radical polymerizable compound having a triarylamine structure represented by the above general formula 1 and another radical polymerizable compound different from the radical polymerizable compound having a triarylamine structure is provided. Having a cross-linked product is preferable in that the dissolution resistance and durability of the polymer are further improved. Examples of other radical polymerizable compounds to be mixed with the composition include compounds having a diarylamine structure (diarylamine compounds), (meth) acrylate compounds, di (meth) acrylate compounds, tri (meth) acrylate compounds, and ethylene oxide groups. (Meth) acrylate compounds containing ethylene, di (meth) acrylate compounds containing ethylene oxide groups, tri (meth) acrylate compounds containing ethylene oxide groups, and the like.

The electrochromic layer containing the compound having the triarylamine skeleton represented by the general formula 1 is composed of a compound having the triarylamine skeleton represented by the general formula 1, another radical polymerizable compound, and, if necessary, other It is preferable to form an electrochromic layer as a polymerized film by light or heat after coating and forming using a coating solution in which a composition containing components is dissolved in a solvent.
Other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, polymerization initiator, solvent, plasticizer, leveling agent, sensitizer, dispersant, surfactant, antioxidant And fillers.

  Examples of the coating method include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spray coating. And various printing methods such as a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method.

There is no restriction | limiting in particular as thickness of an electrochemical reaction layer, Although it can select suitably according to the objective, 0.2 to 5.0 micrometer is preferable.
When the thickness is less than 0.2 μm, it may be difficult to obtain a color density, and when it exceeds 5.0 μm, the manufacturing cost increases, and visibility may easily decrease due to haze or coloring. is there.

  The electrochromic element (cell) of the present invention has a structure in which a display substrate and a counter substrate are bonded together with a space. An electrolyte layer containing an electrolyte layer material is disposed inside the cell (for example, filled with an electrolytic solution).

<Electrolyte layer>
The electrolyte layer is for causing charge to move by moving ions between the display electrode and the counter electrode, thereby causing a coloring / decoloring reaction of the electrochromic layer.
As the electrolyte layer material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts can be used.
Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg ( BF ₄ ) _{2 and the} like.

An ionic liquid can also be used. In particular, organic ionic liquids include compounds having a molecular structure that show a liquid state in a wide temperature range including room temperature.
Examples of molecular structures showing such a liquid state include, as a cation component, imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt; N, N -Pyridinium derivatives such as dimethylpyridinium salt, N, N-methylpropylpyridinium salt, aromatic salts, or tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, triethylhexylammonium salt; aliphatic quaternary ammonium And salt of the system.
On the other hand, the anion component is preferably a compound containing fluorine in terms of stability in the atmosphere, and examples thereof include BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{− and the} like. . An ionic liquid formulated by a combination of these cationic components and anionic components can be used.
These electrolyte layer materials can be dissolved in a solvent and used as an electrolytic solution, and used for the electrolyte layer.

  Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, Examples thereof include alcohols or mixed solvents thereof.

An electrolytic solution that can be formed into a gel or solid is used. This is also preferable from the viewpoints of improving element strength, improving reliability, and preventing color diffusion.
As a solidification method, it is preferable to hold an electrolyte and a solvent in a resin (polymer). This is because solid strength can be obtained while maintaining high ionic conductivity. Furthermore, as the resin (polymer), a photocurable resin (photocurable resin) is preferable. Compared to the method of thinning the electrolyte layer containing the resin and electrolyte layer material by evaporating the thermal polymerization or solvent, the device can be manufactured at a low temperature and in a short time when using a photocurable resin. There are advantages.
As described above, the electrolytes can be used alone or in combination.
The thickness of the electrolyte layer is preferably 0.5 μm or more and 100 μm or less, and more preferably 1 μm or more and 50 μm or less. When the thickness of the electrolyte layer is thicker than 50 μm, electric charges are easily diffused. Moreover, when the thickness of the electrolyte layer is thinner than 1 μm, it is difficult to maintain the function as an electrolyte.

<Other layers>
There is no restriction | limiting in particular as another layer, According to the objective, it can select suitably, For example, an insulating porous layer, a protective layer, etc. are mentioned.

-Insulating porous layer-
The insulating porous layer has a function of holding the electrolyte while isolating the first electrode and the second electrode so as to be electrically insulated.
The material of the insulating porous layer is not particularly limited as long as it is transparent and porous. However, it is an organic or inorganic material having high insulation and durability and excellent film forming properties, or a composite thereof. It is preferable to use a body.

-Protective layer-
The role of the protective layer is to protect the device from external stresses and chemicals in the cleaning process, to prevent electrolyte leakage, and to prevent the entry of unnecessary substances such as moisture and oxygen in the atmosphere for stable operation of the electrochromic device For example.
There is no restriction | limiting in particular as average thickness of a protective layer, Although it can select suitably according to the objective, 1 micrometer or more and 200 micrometers or less are preferable.
As a material of the protective layer, for example, an ultraviolet curable resin or a thermosetting resin can be used, and examples thereof include an acrylic resin, a urethane resin, and an epoxy resin.

  Here, the electrochromic device of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of an electrochromic element 10 of the present invention. The electrochromic device 10 of FIG. 1 includes a first substrate 1a, a first electrode 2a provided on the first substrate, and a first electrode 2a spaced from the first electrode 2a. The second substrate 1b, the second electrode 2b provided on the second substrate, the first electrochemical reaction layer 3a provided in contact with the first electrode 2a, and the second electrode 2b. A second electrochemical reaction layer 3b provided, and an electrolyte layer 4 disposed between the first electrode 2a and the second electrode 2b.

(Method for manufacturing electrochromic device)
The method for manufacturing an electrochromic device of the present invention is a method for manufacturing the electrochromic device of the present invention, which includes an oxidation treatment step, and further includes other steps as necessary.

<Oxidation process>
The oxidation treatment step is a step of oxidizing at least one of the first electrochemical reaction layer and the second electrochemical reaction layer.
By oxidizing at least one of the first electrochemical reaction layer and the second electrochemical reaction layer, the radical cation state of at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is changed. Can be held.
As the oxidation treatment, for example, a method of obtaining an electrochemical reaction layer in a radical cation state by arranging electrodes having electrical conductivity such as a metal foil facing each other through an electrolytic solution and applying a voltage, etc. It is done.

  The method for producing the electrochromic device is not particularly limited except that the oxidation treatment is performed. For example, a method in which a first electrode and a first electrochemical reaction layer are formed on a first substrate, The second electrode and the second electrochemical reaction layer formed on the second substrate are prepared, and are manufactured by pasting them together via the electrolyte layer. When the electrolyte layer can be cured by light or heat, it can be cured after bonding. In order to prevent intrusion of moisture, oxygen, or the like, the outer periphery of the element may be sealed.

  Since the electrochromic device of the present invention is an all-solid device with excellent decolorization response, for example, an electrochromic display, a large display plate such as a stock price display plate, a light control lens, a light control window, a light shielding filter, It can be suitably used for dimming elements such as anti-glare mirrors, low-voltage driving elements such as touch panel key switches, optical switches, optical memories, electronic paper, and electronic albums.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, examples in which the first electrochromic layer was used as the first electrochemical reaction layer and the second electrochromic layer was used as the second electrochemical reaction layer were shown.

(Example 1)
An electrochromic element was fabricated according to the following (1) to (5) based on the configuration shown in FIG.

(1) Formation of first electrochromic layer on first electrode In order to form a first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the following structural formula (electrochromic compound exhibiting green color by oxidation): 70 parts by mass

[Diarylamine compound]
IRGACURE184 (manufactured by BASF Japan KK): 2 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 1 having a bifunctional acrylate represented by the following structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass

[Triarylamine Compound 1]
IRGACURE184 (manufactured by BASF Japan KK): 2 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

(3) Preparation of electrolyte solution An electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (Merck): 50 parts by mass

(4) Oxidation treatment of first electrochromic layer The electrolyte solution obtained in (3) was applied on the first substrate. Here, since the electrochromic layer has a porous structure, the electrolyte layer material sufficiently penetrates to the first electrode interface.
Next, the substrate for color processing was superimposed on the surface of the electrolyte layer so that the first substrate and the electrode faced each other, and temporary bonding was performed. In this state, a voltage of 3.0 V was applied for 5 seconds so that the first electrode had a positive potential, and the first electrochromic layer was oxidized to change to a colored state. Finally, the first substrate on which the temporary bonding was performed and the substrate for color treatment were peeled off.

(5) Bonding The electrolyte solution obtained in (3) was applied to the first electrochromic layer provided on the first substrate oxidized in (4). Here, since the electrochromic layer has a porous structure, the electrolyte layer material sufficiently penetrates to the first electrode interface.
Next, the second electrochromic layer provided on the second substrate was laminated on the surface of the electrolyte layer material and bonded.
Immediately after bonding, the device was irradiated with a UV (wavelength 250 nm) irradiation device (USHIO INC., SPOT CURE) at 10 mW for 60 seconds to crosslink the electrolyte solution coating portion, and the electrochromic of Example 1 A display element was produced.

  Next, the driving test 1 and the driving test 2 were performed as follows for the produced electrochromic device of Example 1. The results are shown in Table 3.

<Driving test 1: Color retention test>
The produced electrochromic element was connected to an external power source so that the second electrode was at a positive potential, and a voltage was applied so that a constant current of 0.7 mA flowed for 10 seconds. By this work, color development driving (color development of the second electrochromic layer, decoloration of the first electrochromic layer) was attempted. Next, the first electrode and the second electrode are changed to the open state, and the color retention time of the second electrochromic layer (the time until the absorbance of the absorption peak becomes 1/3 from the initial value) is recorded. Evaluation was performed based on the following evaluation criteria.
[Evaluation criteria]
A: Driven by voltage application and color retention time is 10 minutes or longer. O: Driven by voltage application and color retention time is less than 10 minutes. X: Not driven even by voltage application.

<Driving test 2: Decolorization driving test>
The produced electrochromic element was connected to an external power source so that the second electrode was at a positive potential, and a voltage was applied so that a constant current of 0.7 mA flowed for 10 seconds.
Next, after the first electrode and the second electrode are opened, and the colored state (coloring of the second electrochromic layer, decoloring of the first electrochromic layer) is maintained for 5 minutes, this time, Is connected to an external power source so that the electrode becomes positive potential, and a voltage is applied so that a constant current of 0.7 mA flows for 10 seconds (color development of the first electrochromic layer, second electrochromic layer). The chromic layer was decolored), the state at that time was observed, and evaluated according to the following evaluation criteria.
[Evaluation criteria]
◎: Decoloring drive is completed in less than 10 seconds due to short circuit ○: Decoloring drive is completed in 10 seconds or more due to short circuit ×: Decoloring drive is not completed even when short-circuited, and the second electrochromic layer remains unerased There has occurred

(Example 2)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation apparatus (USHIO Inc., SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 2 having a bifunctional acrylate represented by the following structural formula (electrochromic compound that exhibits yellow color by oxidation): 70 parts by mass

[Triarylamine Compound 2]
IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of Example 2 was produced in the same manner as (3) to (5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Example 3)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation apparatus (USHIO Inc., SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the following structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass

[Triarylamine Compound 3]
IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Thereafter, an electrochromic device of Example 3 was produced in the same manner as (3) to (5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

Example 4
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation apparatus (USHIO Inc., SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of Example 4 was produced like (3)-(5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Example 5)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation apparatus (USHIO Inc., SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of Example 5 was produced like (3)-(5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Example 6)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of Example 6 was produced like (3)-(5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Example 7)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 4 having a monofunctional acrylate represented by the following structural formula (electrochromic compound that exhibits blue color by oxidation): 70 parts by mass

[Triarylamine Compound 4]
IRGACURE184 (manufactured by BASF Japan KK): 2 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of Example 7 was produced like (3)-(5) of Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Example 8)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of second electrochemical reaction layer on second electrode In order to form the second electrochemical reaction layer on the second electrode, a tin oxide dispersion having the following composition was prepared. .
[composition]
Tin oxide fine particles: 45 parts by mass HW140SF (manufactured by DIC Corporation): 49 parts by mass Tetrafluoropropanol: 906 parts by mass

  The obtained tin oxide dispersion was spin-coated on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode, and annealed at 90 ° C. for 15 minutes. Thus, a tin oxide particle film was formed.

(3) Preparation of electrolyte solution An electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (Merck): 50 parts by mass

(4) Bonding The electrolyte solution obtained in (3) was applied to the first electrochromic layer provided on the first substrate. Here, since the first electrochromic layer has a porous structure, the electrolyte layer material sufficiently penetrates to the first electrode interface.
Next, the second electrochemical reaction layer provided on the second substrate was superposed on the surface of the electrolyte layer material and bonded.
Immediately after the bonding, the device was irradiated with a UV (wavelength 250 nm) irradiation device (USHIO Corporation, SPOT CURE) at 10 mW for 60 seconds to crosslink the electrolyte solution coating portion, and the electrochromic of Example 8 An element was produced.
About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

Example 9
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of second electrochemical reaction layer on second electrode In order to form the second electrochemical reaction layer on the second electrode, a tin oxide dispersion having the following composition was prepared. .
[composition]
Tin oxide fine particles: 45 parts by mass HW140SF (manufactured by DIC Corporation): 49 parts by mass Tetrafluoropropanol: 906 parts by mass

  The obtained tin oxide dispersion was spin-coated on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode, and annealed at 90 ° C. for 15 minutes. Thus, a tin oxide particle film was formed.

(3) Preparation of electrolyte solution An electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (Merck): 50 parts by mass

(4) Bonding The electrolyte solution obtained in (3) was applied to the first electrochromic layer provided on the first substrate. Here, since the first electrochromic layer has a porous structure, the electrolyte layer material sufficiently penetrates to the first electrode interface.
Next, the second electrochemical reaction layer provided on the second substrate was superposed on the surface of the electrolyte layer material and bonded.
Immediately after the bonding, the device was irradiated with a UV (wavelength 250 nm) irradiation device (USHIO Corporation, SPOT CURE) at 10 mW for 60 seconds to crosslink the electrolyte solution coating portion, and the electrochromic of Example 8 An element was produced.
About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 1)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

(3) Preparation of electrolyte solution An electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA having bifunctional acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (Merck): 50 parts by mass

(4) Bonding The electrolyte solution obtained in (3) was applied to the first electrochromic layer provided on the first substrate. Here, since the first electrochromic layer has a porous structure, the electrolyte layer material sufficiently penetrates to the first electrode interface.
Next, the second electrochromic layer provided on the second substrate was superposed on the surface of the electrolyte layer and bonded together.
Immediately after bonding, the device was irradiated with a UV (wavelength 250 nm) irradiation device (USHIO INC., SPOT CURE) at 10 mW for 60 seconds to crosslink the electrolyte solution coating portion, and the electrochromic of Comparative Example 1 An element was produced.
About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 2)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound that exhibits green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 2 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 3)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound exhibiting green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied by an inkjet printing method in a solid shape of 30 mm × 30 mm on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. did.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 3 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 4)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 4 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 5)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 was applied to an ITO glass substrate (4
(0 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) was applied in a solid shape of 30 mm × 30 mm by an inkjet printing method.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 5 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 6)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of first electrochromic layer on first electrode In order to form a second electrochromic layer on the first electrode, an electrochromic composition 1 having the following composition was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 1 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode in a solid shape of 30 mm × 30 mm by an inkjet printing method. Applied.
The obtained coating film was irradiated at 10 mW for 60 seconds with a UV irradiation device (USHIO Corporation, SPOT CURE) to form a crosslinked first electrochromic layer having an average thickness of 1.0 μm.

(2) Formation of second electrochromic layer on second electrode In order to form an electrochromic layer on the second electrode, an electrochromic composition 2 having the following composition was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 6 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 7)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an ITO glass substrate (40 mm × 40 mm, 40 mm × 40 mm, A titanium oxide fine particle dispersion (SP210, manufactured by Showa Titanium Co., Ltd.) was spin-coated on a 0.7 mm thickness and an ITO film thickness of about 100 nm, and a titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes.
Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 2% by mass of a viologen compound represented by the following structural formula, which is an electrochromic compound that develops a blue color, was dropped, immersed for 1 minute, and then 10 ° C. at 120 ° C. The first electrochromic layer having an average thickness of 1.0 μm was formed by performing an annealing treatment for a minute.

[Viologen compound]

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 1 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting brown color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 7 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 8)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an ITO glass substrate (40 mm × 40 mm, 40 mm × 40 mm, A titanium oxide fine particle dispersion (SP210, manufactured by Showa Titanium Co., Ltd.) was spin-coated on a 0.7 mm thickness and an ITO film thickness of about 100 nm, and a titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes.
Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 2% by mass of the viologen compound represented by the above structural formula, which is an electrochromic compound that develops a blue color, was dropped, immersed for 1 minute, and then 10 ° C. at 120 ° C. The first electrochromic layer having an average thickness of 1.0 μm was formed by performing an annealing treatment for a minute.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Triarylamine compound 2 having a bifunctional acrylate represented by the above structural formula (electrochromic compound exhibiting yellow color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-Bifunctional acrylate PEG400DA (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 8 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 9)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an ITO glass substrate (40 mm × 40 mm, 40 mm × 40 mm, A titanium oxide fine particle dispersion (SP210, manufactured by Showa Titanium Co., Ltd.) was spin-coated on a 0.7 mm thickness and an ITO film thickness of about 100 nm, and a titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes.
Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 2% by mass of the viologen compound represented by the above structural formula, which is an electrochromic compound that develops a blue color, was dropped, immersed for 1 minute, and then 10 ° C. at 120 ° C. The first electrochromic layer having an average thickness of 1.0 μm was formed by performing an annealing treatment for a minute.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
Triarylamine compound 3 having a monofunctional acrylate represented by the above structural formula (electrochromic compound exhibiting magenta color development by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass Bifunctional PEG400DA having acrylate (polyethylene glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass • Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 is formed on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode by an inkjet printing method in a solid shape of 30 mm × 30 mm. Applied.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

  Then, the electrochromic element of the comparative example 9 was produced like (3)-(4) of the comparative example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

(Comparative Example 10)
The electrochromic device having the configuration shown in FIG. 1 was produced by the following procedure.

(1) Formation of the first electrochromic layer on the first electrode In order to form the first electrochromic layer on the first electrode, an ITO glass substrate (40 mm × 40 mm, 40 mm × 40 mm, A titanium oxide fine particle dispersion (SP210, manufactured by Showa Titanium Co., Ltd.) was spin-coated on a 0.7 mm thickness and an ITO film thickness of about 100 nm, and a titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes.
Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 2% by mass of the viologen compound represented by the above structural formula, which is an electrochromic compound that develops a blue color, was dropped, immersed for 1 minute, and then 10 ° C. at 120 ° C. The first electrochromic layer having an average thickness of 1.0 μm was formed by performing an annealing treatment for a minute.

(2) Formation of 2nd electrochromic layer on 2nd electrode In order to form a 2nd electrochromic layer on a 2nd electrode, the electrochromic composition 2 of the composition shown below was prepared.
[composition]
-Diarylamine compound represented by the above structural formula (electrochromic compound exhibiting green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass-PEG400DA (polyethylene glycol di) having a bifunctional acrylate Acrylate, manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanone: 600 parts by mass

The obtained electrochromic composition 2 was applied to an ITO glass substrate (4
(0 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) was applied in a solid shape of 30 mm × 30 mm by an inkjet printing method.
The obtained coating film was irradiated with a UV irradiation apparatus (SPUS CURE, manufactured by Ushio Electric Co., Ltd.) at 10 mW for 60 seconds to form a crosslinked second electrochromic layer having an average thickness of 1.0 μm.

Then, the electrochromic element of the comparative example 10 was produced like (3)-(4) of the comparative example 1.
About the produced electrochromic element, it carried out similarly to Example 1, and performed the drive tests 1-2. The results are shown in Table 3.

Next, Table 1 shows the configurations of the devices prepared in Examples and Comparative Examples, and the oxidation-reduction potential of the electrochromic layer as each electrochemical reaction layer. The oxidation-reduction potential was measured as follows.
Table 2 shows the presence or absence of a reversibly oxidizable state and a reversibly oxidizable state of each of the first electrochemical reaction layer and the second electrochemical reaction layer of the fabricated device.

<Measurement of redox potential>
The cell was assembled using the following members, and cyclic voltammetry was performed under the following measurement conditions to measure the oxidation-reduction potential.
-Cell member-
Working electrode: Pt electrode Counter electrode: Pt wire Reference electrode: Ag / Ag ⁺ (Internal electrolyte 0.1 M tetrabutylammonium perchlorate (TBAP) + 0.05 M silver nitrate acetonitrile solution)
Solution: 0.1M TBAP acetonitrile solution (dissolvable is dichloromethane solution) -Measurement conditions-
Sweep speed: 0.05 V / s
Sweep range: -0.3 to + 1.0V
The potential at which two peaks obtained from the VI curve obtained by the above measurement are Ea and Eb, and (Ea + Eb) / 2 = E was taken as the redox potential with Ag / Ag ⁺ reference.
Next, the oxidation-reduction potential of ferrocene was measured under the same conditions, and the value obtained with the ferrocene was used as a reference for the potential (0 V. vs Fc / Fc ⁺ ).
When tin oxide was used as the electrochemical reaction layer, CV was measured using an ITO electrode on which a solid film of tin oxide was formed as the working electrode because tin oxide did not dissolve in the solution. Since the redox potential may not be obtained with a clear peak during measurement of the solid film, the intermediate value between the reduction start potential and the oxidation end potential is defined as the redox potential in the present invention.
In addition, when using other electrochemical reaction layers that are not soluble in the solution other than tin oxide, the oxidation-reduction potential may be measured by the same method.

* “−” As a result of the decoloring driving test in Table 3 indicates that measurement is impossible.

From the result of the driving test 1, Examples 1 to 9 were able to be driven for color development and could maintain the color retention state for a long time. First, the reason why color development is possible is that one electrochemical reaction layer was oxidized before being bonded. Thereby, when an oxidation reaction occurs in one electrochemical reaction layer, it is considered that a reduction reaction can occur in the other electrochemical reaction layer.
In addition, ΔE is related to the color retention time, and in Examples 1 to 6, ΔE was as small as 0.1 to 0.3 V, and good results were shown. With regard to the erasing drive in the driving test 2, the larger the ΔE, the better the result. However, as far as the results of Examples 1 to 6 are seen, the erasing drive within 10 seconds if it is about 0.1 to 0.3V. Showed results that could be completed.
Next, in Example 7, although the result of the driving test 2 was good, the color retention of the driving test 1 was slightly insufficient. This is considered to be related to ΔE being as large as 0.5V.
In Comparative Examples 1 to 6, all of the first electrochemical reaction layer and the second electrochemical reaction layer of the present invention are reversibly oxidizable and reversibly reducible. It does not meet the requirement of “composed of a combination of layers”, color development cannot be performed in driving test 1, and one electrochemical reaction layer needs to be oxidized in advance (in a radical cation state) I was able to confirm that there is.
Next, in Comparative Examples 7 to 10, sufficient color retention and decoloring driving could not be performed. First, it can be considered that the color retention is low because ΔE is large.
In addition, regarding the decoloring drive, since the viologen compound is used in one electrochemical reaction layer, the viologen compound has been spontaneously decolored due to the influence of oxygen during the color development for 5 minutes. It is probable that driving was not completed.

  From the above results, it was possible to realize a device excellent in color retention and driving stability even in the atmosphere by controlling the oxidation-reduction potential of the electrochemical reaction layers provided on both electrodes. That is, the present invention is extremely effective as a technique capable of realizing an electrochromic device having excellent color retention and driving stability even in the air without requiring strict sealing.

As an aspect of this invention, it is as follows, for example.
<1> a first substrate;
A first electrode provided on the first substrate;
A second substrate spaced from the first electrode;
A second electrode provided on the second substrate;
A first electrochemical reaction layer provided in contact with the first electrode;
A second electrochemical reaction layer provided in contact with the second electrode;
An electrolyte layer disposed between the first electrode and the second electrode;
Have
The first electrochemical reaction layer and the second electrochemical reaction layer comprise a combination of a reversibly oxidizable layer and a reversibly reducible layer,
At least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer;
Assuming that the redox potential of the first electrochemical reaction layer is E1, and the redox potential of the second electrochemical reaction layer is E2, the following formula, E1 ≧ −0.8 V (vs. FC / FC ⁺ ), The electrochromic device satisfies E2 ≧ −0.8 V (vs. FC / FC ⁺ ).
<2> The oxidation-reduction potential E1 of the first electrochemical reaction layer and the oxidation-reduction potential E2 between the second electrochemical reaction layers are expressed by the following equation: | E1-E2 | <0.9V The electrochromic device according to <1>, which satisfies the above.
<3> The first electrochemical reaction layer and the second electrochemical reaction layer are composed of an electrochemically active material capable of taking a radical cation state,
At least one of the first electrochemical reaction layer and the second electrochemical reaction layer is always in a radical cation state;
The redox potential between the neutral state and radical cation state of the first electrochemical reaction layer is E1 ′, and the redox potential between the neutral state and radical cation state of the second electrochemical reaction layer. Is E2 ′, <1> to <2 satisfying the following expressions: E1 ′ ≧ −0.8 V (vs. FC / FC ⁺ ), E2 ′ ≧ −0.8 V (vs. FC / FC ⁺ ) The electrochromic device according to any one of the above.
<4> Any one of <1> to <3>, wherein at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer that develops color depending on a radical cation state. This is an electrochromic device.
<5> The electrochromic device according to any one of <1> to <4>, wherein only one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer.
<6> The electrochromic layer according to any one of <1> to <5>, wherein the electrochromic layer includes a compound having a triarylamine skeleton represented by the following general formula 1.
[General Formula 1]
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 1. A has a structure represented by the following general formula 2, and is bonded to B at any position of R ₁ to R ₁₅ . 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 .
[General formula 2]
[General formula 3]
However, R ₁ to R ₂₁ are all monovalent organic groups, which may be the same or different, and at least one of the monovalent organic groups is a radical polymerizable functional group.
<7> The electro according to <6>, wherein the compound having a triarylamine skeleton represented by the general formula 1 is any one of compounds represented by the following general formula 1-1 to general formula 1-3. It is a chromic element.
[General Formula 1-1]
[General Formula 1-2]
[General Formula 1-3]
However, in General Formula 1-1 to General Formula 1-3, R ₂₇ to R ₈₈ are all monovalent organic groups, which may be the same or different from each other. At least one of them is a radically polymerizable functional group.
<8> A method for producing an electrochromic device for producing the electrochromic device according to any one of <1> to <6>,
An electrochromic device manufacturing method comprising an oxidation treatment step of oxidizing at least one of a first electrochemical reaction layer and a second electrochemical reaction layer.

  According to the electrochromic device according to any one of <1> to <7> and the method for producing an electrochromic device according to <8>, the conventional problems are solved and the object of the present invention is achieved. be able to.

DESCRIPTION OF SYMBOLS 1a 1st board | substrate 2a 1st electrode 3a 1st electrochemical reaction layer 1b 2nd board | substrate 2b 2nd electrode 3b 2nd electrochemical reaction layer 4 Electrolyte layer 10 Electrochromic element

JP-A-1-231028 Japanese Patent Laid-Open No. 2006-038572

Claims (7)

A first substrate;
A first electrode provided on the first substrate;
A second substrate spaced from the first electrode;
A second electrode provided on the second substrate;
A first electrochemical reaction layer provided in contact with the first electrode;
A second electrochemical reaction layer provided in contact with the second electrode;
An electrolyte layer disposed between the first electrode and the second electrode;
Have
The first electrochemical reaction layer and the second electrochemical reaction layer comprise a combination of a reversibly oxidizable layer and a reversibly reducible layer,
At least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer;
Assuming that the redox potential of the first electrochemical reaction layer is E1, and the redox potential of the second electrochemical reaction layer is E2, the following formula, E1 ≧ −0.8 V (vs. FC / FC ⁺ ), An electrochromic element satisfying E2 ≧ −0.8 V (vs. FC / FC ⁺ ).   The redox potential E1 of the first electrochemical reaction layer and the redox potential E2 between the second electrochemical reaction layers satisfy the following expression: | E1-E2 | <0.9V. 1. The electrochromic device according to 1. The first electrochemical reaction layer and the second electrochemical reaction layer are composed of an electrochemically active material capable of taking a radical cation state,
At least one of the first electrochemical reaction layer and the second electrochemical reaction layer is always in a radical cation state;
The redox potential between the neutral state and radical cation state of the first electrochemical reaction layer is E1 ′, and the redox potential between the neutral state and radical cation state of the second electrochemical reaction layer. Is E2 ′, the following formulas are satisfied: E1 ′ ≧ −0.8 V (vs. FC / FC ⁺ ), E2 ′ ≧ −0.8 V (vs. FC / FC ⁺ ) An electrochromic device according to any one of the above.   4. The electrochromic device according to claim 1, wherein at least one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer that develops color depending on a radical cation state. 5.   5. The electrochromic device according to claim 1, wherein only one of the first electrochemical reaction layer and the second electrochemical reaction layer is an electrochromic layer. The electrochromic device according to any one of claims 1 to 5, wherein the electrochromic layer includes a compound having a triarylamine skeleton represented by the following general formula 1.
[General Formula 1]
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 1. A has a structure represented by the following general formula 2, and is bonded to B at any position of R ₁ to R ₁₅ . 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 .
[General formula 2]
[General formula 3]
However, R ₁ to R ₂₁ are all monovalent organic groups, which may be the same or different, and at least one of the monovalent organic groups is a radical polymerizable functional group. An electrochromic device manufacturing method for manufacturing the electrochromic device according to any one of claims 1 to 6,
The manufacturing method of the electrochromic element characterized by including the oxidation process process of oxidizing at least any one of a 1st electrochemical reaction layer and a 2nd electrochemical reaction layer.