JP2018005093A - Electrochromic display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic display element which maintains high transparency when decolored and is capable of displaying two types of information.SOLUTION: An electrochromic display element comprises a first substrate, a first electrode disposed on the first substrate, a second substrate disposed at a distance of the first electrode, a second electrode disposed on the second substrate, a first electrochromic layer disposed in contact with the first electrode, a second electrochromic layer disposed in contact with the second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrochromic layer and the second electrochromic layer both contain an electrochromic material that gets colored by oxidation reaction.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic display element.

  A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. The electrochromism is generally formed between two electrodes facing each other, and performs an oxidation-reduction reaction in a configuration in which an electrolyte layer capable of ion conduction is filled between the electrodes. When a reduction reaction occurs in the vicinity of one of the two electrodes facing each other, an oxidation reaction that is a reverse reaction occurs in the vicinity of the other electrode.

  An electrochemical device that utilizes the coloring / decoloring of an electrochromic compound that causes the phenomenon of electrochromism is called an electrochromic device. The electrochromic device has a memory effect, can adjust the color density by the applied voltage intensity, can be driven at a low voltage, and has high transparency when decolored. It is expected to be applied to various applications as an information display device that extracts information from transparent areas, and research and development are being conducted from material development to device design / process development.

Examples of material development for the information display device include those utilizing the chromic phenomenon of inorganic compounds, those utilizing organic low molecules, and those utilizing high molecular compounds. Among these, regarding organic compounds, various colors can be developed depending on the material structure, and the possibility of multicolor display is expected. Moreover, as a device design for the information display device, a method of patterning a drive electrode or an electrochromic dye can be considered.
For example, a display layer having an electrochromic layer that develops different colors such as yellow, cyan, and magenta is laminated, and a high aperture is obtained by switching three display electrodes with one TFT (Thin Film Transistor) electrode. A method for obtaining a full-color display image at a high rate has been proposed (see, for example, Patent Documents 1 and 2).

In addition, a method of displaying information by patterning an electrochromic layer by glow discharge has been proposed (see, for example, Patent Document 3).
In addition, by providing two working electrodes having an electrochromic layer and at least one counter electrode having a counter electrode reaction layer in the device, various technologies can be performed without using an active electrode such as a TFT. Has been proposed (see, for example, Patent Document 4).

  An object of this invention is to provide the electrochromic display element which can display two types of information, maintaining the high transparency at the time of decoloring.

The electrochromic display element 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 electrochromic layer provided in contact with the first electrode, and the second An electrochromic display element comprising: a second electrochromic layer provided in contact with the electrode; and an electrolyte layer disposed between the first electrode and the second electrode,
Each of the first electrochromic layer and the second electrochromic layer contains an electrochromic material that develops color by an oxidation reaction.

  ADVANTAGE OF THE INVENTION According to this invention, the electrochromic display element which can display two types of information can be provided, maintaining the high transparency at the time of decoloring.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the electrochromic display element of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the electrochromic display element of the present invention. FIG. 3 is a schematic view of a coating pattern of the first electrochromic layer of Examples 1 and 2. FIG. 4 is a schematic drawing of the coating pattern of the second electrochromic layer of Examples 1 and 2.

(Electrochromic display element)
An electrochromic display element according to 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 electrochromic layer provided in contact with the first electrode, and a second electrode provided in contact with the second electrode An electrochromic display element, and an electrolyte layer disposed between the first electrode and the second electrode,
Each of the first electrochromic layer and the second electrochromic layer contains an electrochromic material that develops color by an oxidation reaction.

The electrochromic display element of the present invention includes a display layer having an electrochromic layer that develops different colors, such as yellow, cyan, and magenta described in Patent Documents 1 and 2, and includes three TFT electrodes with one TFT electrode. In a method of obtaining a full color display image with a high aperture ratio by switching display electrodes, the use of an active electrode such as a TFT requires a large number of wirings in the substrate, which results in a decrease in transparency. As a result, it is based on the knowledge that it is difficult to adopt as a display device technology with high transmittance.
Further, in the method of displaying information by patterning the electrochromic layer by glow discharge described in Patent Document 3, the information to be displayed is fixed in one patterned pattern, and is matched with time and timing. There is a problem that two or more types of more useful information display such as providing information cannot be performed.
In addition, by providing two working electrodes having an electrochromic layer and at least one counter electrode having a counter electrode reaction layer in the device of Patent Document 4, various displays can be performed without using an active electrode such as a TFT. The technique that can be performed requires at least three electrodes in the device, leading to a decrease in transparency, and as a result, it is difficult to realize a display device with high transmittance.

Therefore, the electrochromic display element of the present invention includes a first substrate, a first electrode provided on the first substrate, and a second electrode provided at a distance from the first electrode. A substrate, a second electrode provided on the second substrate, a first electrochromic layer provided in contact with the first electrode, and provided in contact with the second electrode A second electrochromic layer, and an electrolyte layer disposed between the first electrode and the second electrode, wherein the first electrochromic layer and the second electrochromic layer are: In any case, by coloring by an oxidation reaction, even a device that displays information by patterning an electrochromic layer enables two types of information display while maintaining high transparency during decoloring.

  The first electrochromic layer is formed such that at least a part of the electrode part is exposed with respect to the first electrode, and the second electrochromic layer is at least partly with respect to the second electrode. It is preferable that the exposed electrode portion is formed so as to easily function as a counter electrode reaction material of the electrochromic layer.

A first counter electrode reaction layer that performs a reverse reaction electrically with the second electrochromic layer provided so as to be at least partially in contact with the first electrode;
A second counter electrode reaction layer that electrically reacts with the first electrochromic layer provided so that at least part of the second electrode is in contact with the second electrode. It is preferable from the viewpoint of improving the function as a counter electrode reaction material and improving driving characteristics.

It is preferable that the second electrochromic layer has a different coloring color with respect to the first electrochromic layer in terms of clearly displaying two types of information.
It is preferable that the second electrochromic layer is patterned in a different shape with respect to the first electrochromic layer from the viewpoint of clearly displaying two types of information.

  The first counter electrode reaction layer and the second counter electrode reaction layer preferably have a porous structure including conductive particles. As a result, the first and second counter electrode reaction layers can easily function as counter electrode reaction materials for the first and second electrochromic layers, and the first and second electrochromic layers can be easily filled with the electrolyte solution. Become.

  Hereinafter, each component of the electrochromic display element of the present invention will be described in detail.

<First electrochromic layer, second electrochromic layer>
Each of the first electrochromic layer and the second electrochromic layer contains an electrochromic material that develops color by an oxidation reaction.

-Electrochromic material that develops color by oxidation reaction-
As the electrochromic material that develops color by the oxidation reaction, for example, at least one selected from a radical polymerizable compound having triarylamine, a Prussian blue complex, and nickel oxide is used. Among these, a radically polymerizable compound having a triarylamine is particularly preferable.
When the first and second electrochromic layers are formed by polymerizing the radical polymerizable compound containing the triarylamine, the repeated drive (redox reaction) characteristics are good and the light durability is improved. It is advantageous in terms of superiority. In addition, the decolored state is transparent, and high coloration performance can be obtained by oxidation reaction.

  As the radically polymerizable compound having the triarylamine, a compound represented by the following general formula (1) is preferably used.

[General Formula 1]
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 1. At least one of A and B has a radical polymerizable functional group. The A is a structure represented by the following general formula 2, and is bonded to the B at any position of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .

[General formula 2]

[General formula 3]
However, in said general formula 2 and said general formula 3, R < ₁ > to R < ₂₁ > are all monovalent organic groups, and they may be the same or different, and among the monovalent organic groups, At least one is a radically polymerizable functional group.

-Monovalent organic group-
The monovalent organic group in the general formula 2 and the general formula 3 may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a substituent. An alkoxycarbonyl group, 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, a substituent; Optionally having a monoalkylaminocarbonyl group, optionally having a dialkylaminocarbonyl group, optionally having a monoarylaminocarbonyl group, optionally having a substituent. Diarylaminocarbonyl group, sulfonic acid group, alkoxysulfonyl group which may have a substituent, aryl which may have a substituent Xylsulfonyl group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, sulfonamide group, optionally substituted monoalkylaminosulfonyl group, substituted A dialkylaminosulfonyl group which may have a group, a monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have 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 aryl which may have a substituent Oxy group which may have a substituent alkylthio group 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 and light durability.

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 an alkyl group such as a halogen atom, a nitro group, a cyano group, 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. Group, aryl group such as phenyl group and naphthyl group, and aralkyl group 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 is capable of radical polymerization.
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 the general formula (i), X ₁ represents an arylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group, a —CON (R ₁₀₀₎ - group _{[R 100} is represents hydrogen, an alkyl group, an aralkyl group, 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 a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, And vinyl thioether group.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following general formula (ii).
In the general formula (ii), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, cyano. Group, nitro group, alkoxy group, —COOR ₁₀₁ group [R ₁₀₁ may have a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. An aryl group or CONR ₁₀₂ R ₁₀₃ (R ₁₀₂ and R ₁₀₃ may have a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aryl 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 the} general 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 of 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, and 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.

  Among 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 the general formula 1-1 to the general formula 1-3, R ₂₇ to R ₈₈ are all monovalent organic groups, which may be the same or different, and the monovalent organic group. At least one of them 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 formula 2 and the general formula 3.

  Examples of the compound represented by the general formula 1 and the general formula 1-1 to the general formula 1-3 include those shown below. The radical polymerizable compound having the triarylamine is not limited thereto.

[Exemplary Compound 1]

[Exemplary Compound 2]

[Exemplary Compound 3]

[Exemplary Compound 4]

[Exemplary Compound 5]

[Exemplary Compound 6]

[Exemplary Compound 7]

[Exemplary Compound 8]

[Exemplary Compound 9]

[Exemplary Compound 10]

[Exemplary Compound 11]

[Exemplary Compound 12]

[Exemplary Compound 13]

[Exemplary Compound 14]

[Exemplary Compound 15]

[Exemplary Compound 16]

[Exemplary Compound 17]

[Exemplary Compound 18]

[Exemplary Compound 19]

[Exemplary Compound 20]

[Exemplary Compound 21]

[Exemplary Compound 22]

[Exemplary Compound 23]

[Exemplary Compound 24]

[Exemplary Compound 25]

[Exemplary Compound 26]

[Exemplary Compound 27]

[Exemplary Compound 28]

[Exemplary Compound 29]

[Exemplary Compound 30]

[Exemplary Compound 31]

[Exemplary Compound 32]

[Exemplary Compound 33]

[Exemplary Compound 34]

[Exemplary Compound 35]

[Exemplary Compound 36]

[Exemplary Compound 37]

[Exemplary Compound 38]

[Exemplary Compound 39]

[Exemplary Compound 40]

  The radical polymerizable compound having a triarylamine structure includes a radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. It is preferable to have a cross-linked product obtained by cross-linking the product from the viewpoint of further improving the dissolution resistance and durability of the polymer.

Examples of the other radical polymerizable compound include a monofunctional radical polymerizable compound having one polymerizable functional group, a bifunctional radical polymerizable compound having two polymerizable functional groups, and 3 having 3 or more polymerizable functional groups. Examples of the functional polymerizable radical polymerizable compound, functional monomer, radical polymerizable oligomer, and the like. Among these, a radical polymerizable compound having 2 or more functional groups is particularly preferable.
The radical polymerizable functional group in the other radical polymerizable compound is the same as the radical polymerizable functional group in the radical polymerizable compound having the triarylamine, and among these, an acryloyloxy group and a methacryloyloxy group are particularly preferable. preferable.

  Examples of the monofunctional radically polymerizable compound include 2- (2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2- Ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate , Phenoxytetraethylene glycol Lumpur acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the bifunctional radical polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, and neopentyl glycol diacrylate. These may be used individually by 1 type and may use 2 or more types together.

Examples of the tri- or higher functional radical polymerizable compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, and caprolactone-modified trimethylolpropane. Triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol triacrylate, EO modified glycerol triacrylate, PO modified glycerol triacrylate, Tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hex Acrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate ( DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.
In the above, EO modification refers to ethyleneoxy modification, and PO modification refers to propyleneoxy modification.

Examples of the functional monomer include those substituted with fluorine atoms such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, and the like. No.-60503, JP-B-6-45770, acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl poly having 20 to 70 siloxane repeating units Examples thereof include vinyl monomers having a polysiloxane group such as dimethylsiloxane diethyl, acrylates and methacrylates. These may be used individually by 1 type and may use 2 or more types together.
Examples of the radical polymerizable oligomers include epoxy acrylate oligomers, urethane acrylate oligomers, and polyester acrylate oligomers.
The point that at least one of the radical polymerizable compound having the triarylamine and another radical polymerizable compound different from the radical polymerizable compound has two or more radical polymerizable functional groups forms a cross-linked product. To preferred.

The electrochromic layer containing the radical polymerizable compound having a triarylamine structure represented by the general formula (1) is formed by coating using a coating solution in which the composition is dissolved in a solvent, and then polymerized by light or heat. It is preferable to form an electrochromic layer as the film.
Examples of coating methods 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 average thickness of the said 1st and 2nd electrochromic layer, Although it can select suitably according to the objective, 0.2 to 5.0 micrometer is preferable.
When the average 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 the visibility may be easily lowered by coloring. .

<First counter electrode reaction layer, second counter electrode reaction layer>
The first counter electrode reaction layer is a layer that performs an electrical reverse reaction with the second electrochromic layer provided so as to be at least partially in contact with the first electrode.
The second counter electrode reaction layer is a layer that performs an electrical reverse reaction with the first electrochromic layer provided so as to be at least partially in contact with the second electrode.
The first counter electrode reaction layer and the second counter electrode reaction layer are electrochemically active layers that are not particularly accompanied by a large color change.
According to the first and second counter electrode reaction layers, the electrochemical reaction is stabilized by reverse reaction of the first and second electrochromic layers, and the potential difference required for the electrochromic reaction is reduced. Can be expected. For example, when the electrochromic layer is a reduction coloring type, the counter electrode is preferably a material that can undergo an oxidation reaction.
As a material used for the counter electrode reaction layer, any of an inorganic compound and an organic compound may be used similarly to the electrochromic layer.
The counter electrode reaction layer is an electrochromic material in which the change in the light absorption band in the visible light region accompanying the redox reaction is small (substantially no color change). Therefore, the same material as the electrochromic layer can be selected. .

It is preferable that the first counter electrode reaction layer and the second counter electrode reaction layer include conductive particles and have a porous structure.
The porous structure including the conductive particles refers to a porous structure having nanoscale irregularities such as a nanoparticle or a nanoporous structure.
Examples of the material constituting the porous structure containing the conductive particles include metal oxides from the viewpoint of transparency and conductivity.
Examples of the metal oxide include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, and oxidation. Examples thereof include calcium, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide are preferable from the viewpoint of electrical characteristics such as electrical conductivity and physical characteristics such as optical properties. Titanium oxide is more preferable.

As the shape of the metal oxide, metal oxide fine particles having an average primary particle diameter of 30 nm or less are preferable. As the average primary particle size is smaller, the light transmittance with respect to the metal oxide can be improved, and a shape having a larger surface area per unit volume (hereinafter referred to as “specific surface area”) is used. By having a large specific surface area, the electrochromic compound is more efficiently supported, and a multicolor display having an excellent display contrast ratio for color development and decoloration can be achieved. There is no restriction | limiting in particular in the specific surface area of a nanostructure, According to the objective, it can select suitably, 100 m < ² > / g or more is preferable.

  There is no restriction | limiting in particular as a formation method of the said 1st and 2nd counter electrode reaction layer, According to the objective, it can select suitably, For example, a vacuum evaporation method, sputtering method, an ion plating method etc. are mentioned. In addition, as long as the materials of the first and second counter electrode reaction layers can be applied and formed, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, and a wire bar coating. Printing methods such as dip coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reversal printing, and inkjet printing Can also be used.

<First substrate, second substrate>
The first and second substrates are not particularly limited as long as they are transparent materials capable of supporting each layer, and known organic materials and inorganic materials can be used as they are.
As said 1st and 2nd board | substrate, glass substrates, such as an alkali free glass, borosilicate glass, float glass, soda lime glass, can be used, for example.
As the first and second substrates, for example, resin substrates such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, and polyimide resin may be used. Good.
Among these, polycarbonate resin is preferable from the viewpoint of processability and transparency.
The surfaces of the first and second substrates may be coated with a transparent insulating layer, a UV cut layer, an antireflection layer or the like in order to improve water vapor barrier properties, gas barrier properties, ultraviolet resistance, and visibility. .

There is no restriction | limiting in particular as a shape of the said 1st and 2nd board | substrate, According to the objective, it can select suitably, For example, a rectangle or a round shape may be sufficient.
The first and second substrates may be a plurality of stacked layers. For example, by providing a structure in which an electrochromic display element is sandwiched between two glass substrates, it is possible to improve water vapor barrier properties and gas barrier properties. .

<First electrode, second electrode>
When one of the first electrode and the second electrode functions as a display electrode, the other functions as a counter electrode.
The display electrode is an electrode for controlling the potential with respect to the counter electrode and causing the electrochromic layer to develop color, and the counter electrode is for controlling the potential of the display electrode paired with the counter electrode and causing the electrochromic layer to develop color. Electrode.

  The material of the first electrode layer 12 and the second electrode layer 15 is preferably a transparent conductive oxide material, for example, indium oxide doped with tin (hereinafter referred to as “ITO”), fluorine And tin oxide doped with antimony (hereinafter referred to as “FTO”), tin oxide doped with antimony (hereinafter referred to as “ATO”), and the like. Among these, indium oxide formed by vacuum film formation (hereinafter referred to as “In oxide”), tin oxide (hereinafter referred to as “Sn oxide”), and zinc oxide (hereinafter referred to as “Zn oxide”). Inorganic materials comprising any one of the "oxides" are preferred.

The In oxide, Sn oxide, and Zn oxide are materials that can be easily formed by a sputtering method, and can obtain good transparency and electrical conductivity. Among these, InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO, and InZnO are particularly preferable. Furthermore, it is preferable that the electrode layer has a lower crystallinity. This is because if the crystallinity is high, the electrode layer is easily divided by thermoforming. From this point, IZO and AZO which show high conductivity with an amorphous film are preferable.

Further, a conductive metal thin film containing silver, gold, copper, and aluminum having transparency, a carbon film such as carbon nanotube and graphene, and a network electrode such as conductive metal, conductive carbon, and conductive oxide, or These composite layers are also useful. The network electrode is an electrode in which carbon nanotubes and other highly conductive non-permeable materials are formed in a fine network shape to provide transmittance. The network electrode is preferable because it is difficult to be divided during thermoforming.
Furthermore, it is more preferable that the electrode layer has a laminated structure of a network electrode and the conductive oxide, or a laminated structure of the conductive metal thin film and the conductive oxide. By using a laminated structure, the electrochromic layer can be colored and decolored without unevenness. The conductive oxide layer can also be formed by coating as nanoparticle ink. Specifically, the laminated structure of the conductive metal thin film and the conductive oxide is an electrode having both conductivity and transparency in a thin film laminated structure such as ITO / Ag / ITO.

  Examples of a method for manufacturing each of the first electrode and the second electrode include a vacuum deposition method, a sputtering method, and an ion plating method. In addition, as long as each material of the first electrode and the second electrode can be formed by coating, 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 And various printing methods.

The optical transmittance of the first and second electrodes is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 60% or more and less than 100%, more preferably 90% or more and less than 100%. . When the optical transmittance is 60% or more and less than 100%, display performance such as brightness and vividness is improved.
The average thickness of the first and second electrodes is not particularly limited and can be appropriately selected according to the purpose. In the case of an ITO electrode, it is preferably 10 nm or more and 300 nm or less.

<Electrolyte layer>
The electrolyte layer is for causing charge to move by moving ions between the first electrode and the second electrode, thereby causing a coloring / decoloring reaction of the electrochromic layer.

As the material of the electrolyte layer, 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.
Moreover, it is preferable to use the ionic liquid which combined the said cation component and the said anion component arbitrarily as a material of the said electrolyte layer.
Examples of the cationic component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, N- Examples include aromatic salts such as pyridinium derivatives such as methylpropylpyridinium salt, and aliphatic quaternary ammonium salts such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt. .
The anion component is preferably a compound containing fluorine in terms of stability in the atmosphere, 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.
It is also possible to dissolve the material of the electrolyte layer in a solvent and use it as an electrolyte solution to be 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, and polyethylene glycol. Alcohols or a mixed solvent thereof can be used.

Moreover, what can be formed in gel form and solid form is used for electrolyte solution. 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 forming a thin electrolyte layer containing a resin and an electrolyte material by evaporating the solvent or by evaporating the solvent, there is an advantage that a device can be manufactured at a low temperature and in a short time when using a photocurable resin. is there.

  There is no restriction | limiting in particular in the average thickness of the said electrolyte layer, Although it can select suitably according to the objective, 0.5 micrometer or more and 100 micrometers or less are preferable, and 1 micrometer or more and 50 micrometers or less are more preferable. When the average thickness is 0.5 μm or more and 100 μm or less, diffusion of electric charges can be prevented, and a good function as an electrolyte can be obtained.

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

-Insulating porous layer-
The insulating porous layer has a function of isolating the first electrode and the second electrode so as to be electrically insulated and retaining an electrolyte.
The material for the insulating porous layer is not particularly limited as long as it is porous, and an organic material, an inorganic material, or a composite thereof having high insulating properties and durability and excellent film forming properties is preferable.
As the method for forming the insulating porous layer, for example, a sintering method (using fine pores formed between particles by partially fusing polymer fine particles or inorganic particles by adding a binder or the like), extraction, etc. Method (after forming a constituent layer with a solvent-soluble organic or inorganic substance and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved in the solvent to obtain pores), foaming foaming method, good solvent and poor Examples include a phase change method in which a solvent is manipulated to phase-separate a mixture of polymers, and a radiation irradiation method in which various radiations are emitted to form pores.

-Deterioration prevention layer-
The deterioration preventing layer has a chemical reaction opposite to that of the electrochromic layer made of the electrochromic composition, and the first electrode and the second electrode are irreversibly oxidized / reduced by balancing electric charges. Corrosion and deterioration can be suppressed. The reverse chemical reaction means that the deterioration preventing layer functions as a capacitor in addition to oxidation / reduction.

  The material of the deterioration preventing layer is not particularly limited as long as it is a material that plays a role of preventing corrosion due to the irreversible oxidation-reduction reaction of the first electrode and the second electrode, and is appropriately selected depending on the purpose. For example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive metal oxide containing a plurality of them, or a semiconductive metal oxide can be used.

  The deterioration preventing layer can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive metal oxide fine particles or semiconductive metal oxide fine particles such as antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, etc., for example, acrylic, alkyd, isocyanate, urethane, epoxy By fixing to the second electrode with a binder such as phenol, a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer can be obtained.

  As the deterioration preventing layer, when the same conductive nanostructure or semiconducting nanostructure constituting the electrochromic composition is used, the manufacturing process of the first electrode and the electrochromic composition, and the second This is preferable because part of the manufacturing process of the electrode and the deterioration preventing layer can be shared.

-Protective layer-
The protective layer can protect the electrochromic display element from external stress and chemicals in the cleaning process, can also prevent leakage of the electrolyte, and can prevent electrochromic display elements such as moisture and oxygen in the atmosphere. In order to operate stably, it is possible to prevent entry of unnecessary objects.

There is no restriction | limiting in particular as average thickness of the said protective layer, Although it can select suitably according to the objective, 1 micrometer or more and 200 micrometers or less are preferable.
Examples of the material for the protective layer include ultraviolet curable resins and thermosetting resins, and specific examples include acrylic resins, urethane resins, and epoxy resins.

  The electrochromic display element of the present invention includes, for example, an electrochromic display, a large display board such as a stock price display board, a light control element such as an antiglare mirror, a light control glass, a low voltage driving element such as a touch panel key switch, a light It can be suitably used for switches, optical memories, electronic paper, electronic albums, information display devices that extract information from highly transparent areas, and the like.

  Here, FIG.1 and FIG.2 is a schematic sectional drawing of the electrochromic display element of this invention. However, FIG. 1 and FIG. 2 show an example of the electrochromic display element of the present invention, and the electrochromic display element of the present invention is not limited to the configuration of FIG. 1 and FIG.

As shown in FIG. 1, the electrochromic display element 10 of the present invention includes a first substrate 1a, a first electrode 2a provided on the first substrate 1a, a first electrochromic layer 3a, and a second substrate. The device includes an electrochromic layer 3b, an electrolyte layer 5, a second electrode 2b, and a second substrate 1b, and the electrolyte layer 5 is provided between the first electrode 2a and the second electrode 2b. The cells are configured by being pasted together in a state.
Both the first electrochromic layer 3a and the second electrochromic layer 3b contain an electrochromic material that develops color by an oxidation reaction.

In addition, as shown in FIG. 2, the electrochromic display element 20 of the present invention is spaced apart from the first substrate 1a, the first electrode 2a provided on the first substrate, and the first electrode. A second substrate 1b provided on the second substrate, a second electrode 2b provided on the second substrate, a first electrochromic layer 3a provided in contact with the first electrode, and the first electrode The second electrochromic layer 3b provided in contact with the second electrode, and the first counter electrode reaction layer 4a that performs an electrical reverse reaction with the second electrochromic layer provided so as to be at least partially in contact with the second electrode. And a second counter electrode reaction layer 4b that performs a reverse reaction electrically with the first electrochromic layer provided so that at least a part thereof is in contact with the second electrode, and between the two electrodes Pasted with electrolyte layer 5 on It has been the cell is configured.
Both the first electrochromic layer 3a and the second electrochromic layer 3b contain an electrochromic material that develops color by an oxidation reaction.

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

Example 1
In accordance with the following (1) to (4), an electrochromic display element 10 was produced in accordance with the configuration shown in FIG.

(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 having a monofunctional acrylate represented by the following structural formula (Exemplary Compound 2, electrochromic compound that exhibits blue color by oxidation): 70 parts by mass
IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanenone: 600 parts by mass

  The obtained electrochromic composition 1 is partially exposed in the shape of FIG. 3 on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode. First, a coated first electrochromic layer having an average thickness of 400 μm was irradiated with a UV irradiation apparatus (SPOT CURE, manufactured by Ushio Electric Co., Ltd.) for 60 seconds using a UV irradiation apparatus (SPOT CURE). Formed.

(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 having a monofunctional acrylate represented by the following structural formula (Exemplary Compound 40, electrochromic compound exhibiting blue-green color by oxidation): 70 parts by mass
IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanenone: 600 parts by mass

  The obtained electrochromic composition 2 is partially exposed in the shape of FIG. 4 on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. The coated film thus obtained was irradiated by an UV irradiation device (SPOT CURE, manufactured by USHIO INC.) For 60 seconds with a UV irradiation apparatus (SPOT CURE) to form a crosslinked second electrochromic layer having an average thickness of 400 μm. Formed.

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

(4) Bonding 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 second substrate was laminated on the surface of the electrolyte layer material for bonding.
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 10 was produced.

  Next, for the produced electrochromic display element 10 of Example 1, driving tests 1 and 2 were performed as follows. The results are shown in Table 1.

<Drive test 1>
The produced electrochromic display element was colored by applying a voltage of 3.0 V for 5 seconds so that the first electrode had a positive potential, and the state at that time was observed. Next, the electrodes were decolored by short-circuiting each other, and the state at that time was observed. The drive test 1 was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: The color development state of the first electrochromic layer was confirmed. Thereafter, the color was erased in less than 10 seconds due to a short circuit. ○: The colored state of the first electrochromic layer was confirmed. Then, it took 10 seconds or more due to a short circuit and the color disappeared. ×: The color development state of the first electrochromic layer could not be confirmed

<Drive test 2>
The produced electrochromic display element was colored by applying a voltage of 3.0 V for 5 seconds so that the second electrode had a positive potential, and the state at that time was observed. Next, the electrodes were decolored by short-circuiting each other, and the state at that time was observed. The driving test 2 was evaluated based on the following evaluation criteria.
[Evaluation criteria]
(Double-circle): The color development state of the 2nd electrochromic layer was confirmed. Thereafter, the color was erased in less than 10 seconds due to a short circuit. O: The color development state of the second electrochromic layer was confirmed. Then, it took 10 seconds or more due to a short circuit and the color disappeared. ×: The color development state of the second electrochromic layer could not be confirmed

(Comparative Example 1)
In Example 1, an electrochromic display element was produced in the same manner as in Example 1 except that the step (2) was not performed.
About the produced electrochromic display element, it carried out similarly to Example 1, and performed the drive tests 1 and 2. FIG. The results are shown in Table 1.

(Example 2)
In accordance with the following (1) to (6), an electrochromic display element 20 was produced in accordance with the configuration shown in FIG.

(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 having a monofunctional acrylate represented by the structural formula (Exemplary Compound 2, electrochromic compound that exhibits blue color by oxidation): 70 parts by mass IRGACURE184 (manufactured by BASF Japan Ltd.): 2 parts by mass -PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass-Cyclohexanenone: 600 parts by mass

  The obtained electrochromic composition 1 is partially exposed in the shape of FIG. 3 on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode. First, a coated first electrochromic layer having an average thickness of 400 μm is irradiated with a UV irradiation apparatus (SPOT CURE, manufactured by Ushio Electric Co., Ltd.) for 60 seconds using a UV irradiation apparatus (SPOT CURE). Formed.

(2) Formation of first counter electrode reaction layer on first electrode Titanium oxide fine particle dispersion (SP210, Showa Titanium Co., Ltd.) on the first electrode having the first electrochromic layer prepared in (1) above. A titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes to form a first counter electrode reaction layer.

(3) 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 having monofunctional acrylate represented by the structural formula (Exemplary Compound 40, electrochromic compound exhibiting blue-green color by oxidation): 70 parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 2 masses Parts PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 30 parts by mass Cyclohexanenon: 600 parts by mass

  The obtained electrochromic composition 2 is partially exposed in the shape of FIG. 4 on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. The coated film thus obtained was irradiated by an UV irradiation device (SPOT CURE, manufactured by USHIO INC.) For 60 seconds with a UV irradiation apparatus (SPOT CURE) to form a crosslinked second electrochromic layer having an average thickness of 400 μm. Formed.

(4) Formation of second counter electrode reaction layer on second electrode Titanium oxide fine particle dispersion (SP210, Showa Titanium Co., Ltd.) on the second electrode having the second electrochromic layer prepared in (3) above. A titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes to form a second counter electrode reaction layer.

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

(6) Bonding The electrolyte solution obtained in (5) above was applied onto 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 second substrate was laminated on the surface of the electrolyte layer material for bonding.
Immediately after bonding, the device was irradiated with UV (wavelength 250 nm) irradiation device (USHIO Inc., SPOT CURE) at 10 mW for 60 seconds to cross-link the electrolyte solution coating portion, and the electrochromic display of Example 2 Element 20 was produced.

  The produced electrochromic display elements were subjected to the driving tests 1 and 2 in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 2, an electrochromic display element was produced in the same manner as in Example 2 except that the step (3) was not performed.
The produced electrochromic display elements were subjected to the driving tests 1 and 2 in the same manner as in Example 1. The results are shown in Table 1.

From the results shown in Table 1, in Example 1, although it took 10 seconds or more to erase the color, it was possible to confirm the color development / decoloration of both the first electrochromic layer and the second electrochromic layer.
On the other hand, in Comparative Example 1, it was confirmed that the color development / decoloration of only the first electrochromic layer could be confirmed. This is due to the presence or absence of the second electrochromic layer on the second electrode.
In Example 2, it was possible to confirm the color development and decoloration of both the first electrochromic layer and the second electrochromic layer, and the decoloration was completed in less than 10 seconds. The result was better than 1. This is presumably because the introduction of the counter electrode reaction layer improved the function of the electrochromic layer as a counter electrode reaction material and improved the driving characteristics.
Further, in Comparative Example 2, the result of confirming the color development / decoloration of only the first electrochromic layer was the same reason as in Comparative Example 1.

  From the above results, even when a device that displays information by patterning the electrochromic layer was used, two types of information display could be performed without significantly reducing the high transparency during decoloring. That is, the present invention is extremely effective as a technique capable of realizing an electrochromic display element capable of switching display with high transmittance.

Aspects of the present invention are 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 electrochromic layer provided in contact with the first electrode;
A second electrochromic layer provided in contact with the second electrode;
An electrochromic display element having an electrolyte layer disposed between the first electrode and the second electrode,
Both the first electrochromic layer and the second electrochromic layer contain an electrochromic material that develops color by an oxidation reaction.
<2> The first electrochromic layer is formed such that at least a part of the electrode portion is exposed with respect to the first electrode, and the second electrochromic layer is formed with respect to the second electrode. The electrochromic display element according to <1>, wherein at least a part of the electrode part is exposed.
<3> a first counter electrode reaction layer that performs a reverse reaction electrically with the second electrochromic layer provided so that at least a part thereof is in contact with the first electrode;
<1> to <2> having a second counter electrode reaction layer that electrically reverse-reacts with the first electrochromic layer provided so as to be at least partially in contact with the second electrode The electrochromic display element according to any one of the above.
<4> The electrochromic display element according to <3>, wherein the first counter electrode reaction layer and the second counter electrode reaction layer include conductive particles and have a porous structure.
<5> The electrochromic display element according to any one of <1> to <4>, wherein the second electrochromic layer has a different coloring color with respect to the first electrochromic layer.
<6> The electrochromic display element according to any one of <1> to <5>, wherein the second electrochromic layer is patterned in a different shape with respect to the first electrochromic layer.
<7> The electrochromic display element according to any one of <1> to <6>, wherein the electrochromic material that develops color by the oxidation reaction is a radical polymerizable compound having a triarylamine.
<8> The electropolymeric display element according to <7>, wherein the radically polymerizable compound having the triarylamine is 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. At least one of A and B has a radical polymerizable functional group. The A is a structure represented by the following general formula 2, and is bonded to the B at any position of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
[General formula 2]
[General formula 3]
However, in said general formula 2 and said general formula 3, R < ₁ > to R < ₂₁ > are all monovalent organic groups, and they may be the same or different, and among the monovalent organic groups, At least one is a radically polymerizable functional group.
<9> The electrochromic display element according to any one of <1> to <8>, wherein the electrolyte layer contains an ionic liquid.
<10> The electrochromic display element according to any one of <1> to <9>, wherein an average thickness of the first and second electrochromic layers is 0.2 μm or more and 5.0 μm or less.

  According to the electrochromic display element described in any one of <1> to <10>, the conventional problems can be solved and the object of the present invention can be achieved.

DESCRIPTION OF SYMBOLS 1a 1st board | substrate 2a 1st electrode 3a 1st electrochromic layer 4a 1st counter electrode reaction layer 1b 2nd board | substrate 2b 2nd electrode 3b 2nd electrochromic layer 4b 2nd counter electrode reaction layer 5 Electrolyte Layer 10 Electrochromic display element 20 Electrochromic display element

JP 2012-128217 A JP 2012-137736 A JP 60-045226 A Special table 2011-515718 gazette

Claims (8)

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 electrochromic layer provided in contact with the first electrode;
A second electrochromic layer provided in contact with the second electrode;
An electrochromic display element having an electrolyte layer disposed between the first electrode and the second electrode,
The electrochromic display element, wherein both the first electrochromic layer and the second electrochromic layer contain an electrochromic material that develops color by an oxidation reaction.   The first electrochromic layer is formed such that at least a part of the electrode part is exposed with respect to the first electrode, and the second electrochromic layer is at least partly with respect to the second electrode. The electrochromic display element according to claim 1, wherein the electrode part is exposed so as to be exposed. A first counter electrode reaction layer that performs a reverse reaction electrically with the second electrochromic layer provided so as to be at least partially in contact with the first electrode;
3. The method according to claim 1, further comprising: a second counter electrode reaction layer that electrically reverse-reacts with the first electrochromic layer provided so that at least a part thereof is in contact with the second electrode. The electrochromic display element described in 1.   The electrochromic display element according to claim 3, wherein the first counter electrode reaction layer and the second counter electrode reaction layer include conductive particles and have a porous structure.   The electrochromic display element according to any one of claims 1 to 4, wherein the second electrochromic layer has a different coloring color with respect to the first electrochromic layer.   The electrochromic display element according to claim 1, wherein the second electrochromic layer is patterned in a different shape with respect to the first electrochromic layer.   The electrochromic display element according to any one of claims 1 to 6, wherein the electrochromic material that develops color by the oxidation reaction is a radical polymerizable compound having triarylamine. The electrochromic display element according to claim 7, wherein the radical polymerizable compound having the triarylamine is 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. At least one of A and B has a radical polymerizable functional group. The A is a structure represented by the following general formula 2, and is bonded to the B at any position of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
[General formula 2]
[General formula 3]
However, in said general formula 2 and said general formula 3, R < ₁ > to R < ₂₁ > are all monovalent organic groups, and they may be the same or different, and among the monovalent organic groups, At least one is a radically polymerizable functional group.