JP2017111389A - Electrochromic display element and manufacturing method of the same, and display, information apparatus, and electro-photochromic lens - Google Patents

Abstract

The present invention provides an electrochromic display element having good display quality that does not cause deterioration coloring even when it is repeatedly driven while ensuring prevention of light deterioration. A display substrate, a display electrode provided on the display substrate, an electrochromic layer provided in contact with the display electrode, a counter substrate provided to face the display substrate, A counter electrode provided on a counter substrate, and an electrolyte layer provided between the display substrate and the counter substrate, wherein the electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction, The electrolyte layer is an electrochromic display element containing an oxidizing agent. [Selection] Figure 1

Description

  The present invention relates to an electrochromic display element, a manufacturing method thereof, a display device, an information device, and an electrochromic light control lens.

  In recent years, so-called electronic paper has been actively developed as an information medium replacing paper. Display elements used for electronic paper include display elements using reflective liquid crystals, display elements using electrophoresis, display elements using toner migration, display elements using electrochromic compounds (electrochromic display elements), and the like. Is mentioned.

The electrochromic display element is a promising candidate for the next generation display element because it has a memory effect and can be driven at a low voltage, and is now an electrochromic display element from material development to device design. A wide range of research and development has been conducted.
The electrochromism phenomenon is a reversible phenomenon in which, when a voltage is applied to the electrochromic compound, the electrochromic compound causes an oxidation-reduction reaction to develop or decolor. The electrochromic display element can generate various types of colors by changing the structure of the electrochromic compound and utilizing the electrochromism phenomenon.

  For this reason, the electrochromic display element is also expected as a display element capable of multicolor display, and various proposals have been made (for example, see Patent Documents 1 to 4).

  On the other hand, in addition to the above-described electronic paper, electrochromic display elements are also being studied for application to light control elements such as light control lenses, light control windows, and antiglare mirrors. For example, an electrochromic dimming lens has been proposed in which a thin-film dimming function is formed on a single lens, which can be reduced in thickness and weight, and is low in cost and excellent in productivity (see, for example, Patent Document 5). .

  It is an object of the present invention to provide an electrochromic display element having good display quality that does not cause deterioration coloring even when it is repeatedly driven while ensuring prevention of light deterioration.

The electrochromic display element of the present invention as means for solving the above problems includes a display substrate, a display electrode provided on the display substrate, an electrochromic layer provided in contact with the display electrode, A counter substrate provided to face the display substrate, a counter electrode provided on the counter substrate, and an electrolyte layer provided between the display substrate and the counter substrate,
The electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction, and the electrolyte layer includes an oxidizing agent.

  ADVANTAGE OF THE INVENTION According to this invention, the electrochromic display element which has the favorable display quality which does not produce deterioration coloring even if it drives repeatedly, ensuring the light degradation prevention can be provided.

FIG. 1 is a schematic view showing an example of the structure of the electrochromic display element of the present invention. FIG. 2 is a schematic view showing an example of the structure of the electrochromic display element of the present invention. FIG. 3 is a schematic diagram showing an example of the information device of the present invention. FIG. 4 is a schematic view showing an example of the electrochromic light control lens of the present invention. FIG. 5 is a schematic view showing an example of eyeglasses using the electrochromic light control lens of the present invention.

(Electrochromic display element)
In the first embodiment, the electrochromic display element of the present invention includes a display substrate, a display electrode provided on the display substrate, an electrochromic layer provided in contact with the display electrode, and the display substrate. A counter substrate provided opposite to the counter substrate, a counter electrode provided on the counter substrate, and an electrolyte layer provided between the display substrate and the counter substrate, and having a white reflective layer It is preferable to have other members as required.
The electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction, and the electrolyte layer includes an oxidizing agent.

In the second embodiment, the electrochromic display element of the present invention includes a display substrate, a display electrode provided on the display substrate, a first electrochromic layer provided in contact with the display electrode, A counter substrate provided to face the display substrate; a counter electrode provided on the counter substrate; a second electrochromic layer provided in contact with the counter electrode; and the counter substrate And an electrolyte layer provided between the substrate and other members as required.
The first electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction,
The second electrochromic layer includes an electrochromic compound that develops color by a reduction reaction,
The electrolyte layer includes an oxidizing agent.

As a result, the electrochromic display element of the present invention is a conventional electrochromic display element, when one or more elements constituting the electrochromic display element are deteriorated by repeated driving of color development and decoloration many times. Coloring with a yellowish brown hue may occur, the original transparency of the decolored state is lost, and the display quality as an electrochromic display element is impaired. The degree of deterioration depends on the magnitude of the load applied to the electrochromic display element by driving, and is based on the knowledge that the higher the applied voltage, the easier the deterioration.
In addition, the present invention provides an electrochromic display element under air shut-off in order to prevent oxygen and moisture in the air from entering the electrochromic display element while ensuring prevention of light deterioration of the display element. An electrochromic display element may be manufactured. Compared to an electrochromic display element manufactured in the air, an electrochromic display element manufactured in such an environment is less likely to flow electric charge, and the voltage required to cause the electrochromic display element to emit and decolorize increases. There is a tendency that the above-described deterioration coloring occurs. As described above, oxygen and moisture contained in the electrochromic display element promote light deterioration and impair storage stability, while facilitating the color development by facilitating the flow of charge in the electrochromic display element. It is based on the knowledge that it is considered to be an element.

According to the electrochromic display elements according to the first and second embodiments, there is provided an electrochromic display element having good display quality that does not cause deterioration coloring even when repeatedly driven while ensuring prevention of light deterioration. be able to.
The electrochromic display element according to the first and second embodiments can be a transmissive display element and a reflective display element. In the transmissive display element, display characteristics with excellent transparency can be obtained, and reflection can be achieved. In the type display element, bright and clear display characteristics can be obtained.

[Electrochromic Display Element of First Embodiment]
The electrochromic display element according to the first embodiment will be described with reference to the drawings.
FIG. 1 is a schematic diagram illustrating an example of the electrochromic display element 20 according to the first embodiment.
As shown in FIG. 1, the electrochromic display element 20 includes a display substrate 1 and a display electrode 3, a counter substrate 2 and a counter electrode 4 provided to face each other with a space therebetween, and both electrodes ( An electrolyte layer 5 is provided between the display electrode 3 and the counter electrode 4).
The surface of the display electrode 3 has an electrochromic layer containing an electrochromic compound that develops color by an oxidation reaction. The electrochromic compound that develops color by the oxidation reaction is preferably a radically polymerizable compound having a triarylamine from the viewpoint of high driving durability and light durability.
It is preferable that an electrochromic layer 6 that is a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having triarylamine is formed on the surface of the display electrode 3.
In the electrochromic display element 20, the electrochromic layer 6 is colored on the surface of the display electrode 3 by an oxidation-reduction reaction. A protective layer 7 is formed on the counter electrode 4.
The white reflective layer 8 may be formed in contact with the electrochromic layer 6 or may be formed in contact with the protective layer 7.
In the case of a transmissive display element, the white reflective layer 8 need not be provided. In the present invention, a case having a white reflective layer is sometimes referred to as a reflective display element, and a case in which no white reflective layer is formed is sometimes referred to as a transmissive display element.
Although the white reflective layer 8 is shown in FIG. 1, the present invention includes the white reflective layer even if the white reflective layer is not provided. Although not shown, a deterioration preventing layer may be provided on the surface of the counter electrode 4.

<Display board>
The display substrate 1 is a substrate for supporting the display electrode and the electrochromic layer.
The material of the display substrate 1 is preferably a light-transmitting material, and examples thereof include glass and plastic films.

<Display electrode>
The display electrode 3 develops or decolors the electrochromic layer by a voltage generated between the electrode and the counter electrode. Since the color development in the electrochromic layer is determined by the magnitude of these voltages generated between the display electrode and the counter electrode, the color tone of each electrochromic layer changes depending on the voltage.
The material of the display electrode 3 is preferably a light-transmitting conductive material. Examples thereof include inorganic materials such as indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), and tin oxide doped with antimony (hereinafter referred to as ATO). Among these, InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO are particularly preferable.

<Counter substrate>
The counter substrate 2 is a substrate for supporting the counter electrode and the protective layer.
The material of the counter substrate 2 is preferably a light-transmitting material, and examples thereof include glass and plastic films.

<Counter electrode>
The counter electrode 4 develops or decolors the electrochromic layer based on the voltage generated between the counter electrode 4 and the display electrode.
The material of the counter electrode 4 is not particularly limited as long as it is a conductive material. When a transmissive element is formed, examples of the light-transmitting conductive material include ITO, FTO, and zinc oxide. Is mentioned. In the case of constituting a reflective element, examples of the conductive metal material include zinc, platinum, and carbon.

<Electrochromic layer>
The electrochromic layer 6 includes an electrochromic compound that develops color by an oxidation reaction.
The electrochromic compound that develops color by the oxidation reaction contains a radical polymerizable compound having a triarylamine from the viewpoint of higher driving durability and light durability, and other than the radical polymerizable compound having the triarylamine It is preferable to contain other radically polymerizable compounds and fillers, more preferably a polymerization initiator, and further other components as necessary.

-Radical polymerizable compound having triarylamine-
The radical polymerizable compound having the triarylamine is important for imparting an electrochromic function having a redox reaction on the surface of the display electrode 3.
Examples of the radical polymerizable compound having a triarylamine include compounds 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, 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-
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.

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 radical polymerizable compound having the 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 formulas (1-1) to (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 the groups 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 (1).

  Examples of the compounds represented by the general formula (1) and the general formulas (1-1) to (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>

-Other radical polymerizable compounds-
Unlike the radical polymerizable compound having a triarylamine, the other radical polymerizable compound is a compound having at least one radical polymerizable functional group.
Examples of the other radical polymerizable compound include a monofunctional radical polymerizable compound, a bifunctional radical polymerizable compound, a trifunctional or higher functional radical polymerizable compound, a functional monomer, and a radical polymerizable oligomer. Among these, a bifunctional or higher radical polymerizable compound 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 group Call 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 radically polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, and the like. 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.
At least one of the radical polymerizable compound having the triarylamine and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine has two or more radical polymerizable functional groups. Is preferable from the viewpoint of forming a crosslinked product.
The content of the radical polymerizable compound having a triarylamine is preferably 10% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 90% by mass or less with respect to the total amount of the electrochromic composition.
When the content is 10% by mass or more, the electrochromic function of the electrochromic layer can be sufficiently exhibited, the durability is good by repeated use with applied voltage, and the color development sensitivity is good.
Even when the content is 100% by mass, an electrochromic function is possible. In this case, the color development sensitivity to the thickness is the highest. Contrary to this, the compatibility with the ionic liquid necessary for charge transfer may be lowered, and therefore, repeated use due to applied voltage causes deterioration of electrical characteristics due to decrease in durability. The required electrical characteristics differ depending on the process used, so it cannot be said unconditionally. However, when considering the balance between both the color development sensitivity and the repeated durability, the content is more preferably 30% by mass or more and 90% by mass or less.

-Polymerization initiator-
The electrochromic composition is necessary for efficiently proceeding with a crosslinking reaction between the radical polymerizable compound having the triarylamine and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine. Depending on the case, it is preferable to contain a polymerization initiator.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferable from the viewpoint of polymerization efficiency.
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-Butylcumyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide Peroxide initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azo initiators such as 4,4′-azobis-4-cyanovaleric acid, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy -Cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- ( acetophenone-based or ketal-based photopolymerization initiators such as o-ethoxycarbonyl) oxime; benzoin, benzoin methyl ester Benzoin ether photopolymerization initiators such as tellurium, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyl Benzophenone photopolymerization initiators such as phenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Examples include thioxanthone photopolymerization initiators such as dichlorothioxanthone.

Examples of other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl). Phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compounds, triazine compounds, imidazole compounds, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
In addition, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like.
The content of the polymerization initiator is preferably 0.5 parts by mass or more and 40 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, an organic filler, an inorganic filler, etc. are mentioned.
Examples of the inorganic filler include metal powders such as copper, tin, aluminum, and indium; silicon oxide (silica), tin oxide, zinc oxide, titanium oxide, aluminum oxide (alumina), zirconium oxide, indium oxide, antimony oxide, Examples thereof include metal oxides such as bismuth oxide, calcium oxide, antimony-doped tin oxide (ATO) and tin-doped indium oxide, and metal fluorides such as tin fluoride, calcium fluoride, and aluminum fluoride. These may be used individually by 1 type and may use 2 or more types together. Among these, metal oxides are preferable from the viewpoint of transparency, stability, and surface treatment, and tin oxide doped with silica, alumina, and antimony (ATO) is particularly preferable.
Examples of the organic filler include resins such as polyester, polyether, polysulfide, polyolefin, silicone, and polytetrafluoroethylene, low molecular compounds such as fatty acids, and pigments such as phthalocyanine. These may be used individually by 1 type and may use 2 or more types together. Among these, a resin is preferable from the viewpoint of transparency and insolubility.

The average primary particle size of the filler is preferably 1 μm or less, and more preferably 10 nm or more and 1 μm or less. When the average primary particle size of the filler is 1 μm or less, coarse particles do not exist, the surface state of the resulting film is good, and the surface smoothness is excellent.
The content of the filler is preferably 0.3 parts by mass or more and 1.5 parts by mass or less, more preferably 0.6 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound. preferable.
When the content is 0.3 parts by mass or more, the filler addition effect is sufficiently obtained, the film forming property is good, and when it is 1.5 parts by mass or less, the ratio of the triarylamine compound is appropriate. Thus, good electrochemical characteristics of the produced electrochromic display element can be obtained.
The average thickness of the first electrochromic layer is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.4 μm or more and 10 μm or less.

<Deterioration prevention layer>
The deterioration preventing layer is provided in contact with the counter electrode.
The role of the deterioration preventing layer is to perform a chemical reaction opposite to that of the electrochromic layer and balance the electric charges to suppress corrosion and deterioration of the display electrode and the counter electrode due to an irreversible oxidation-reduction reaction. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.
The material of the deterioration preventing layer is not particularly limited as long as it plays a role of preventing corrosion due to irreversible oxidation-reduction reaction of the display electrode and the counter electrode, and can be appropriately selected according to the purpose. Antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used.
The deterioration preventing layer can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive 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, phenol, etc. By fixing to the counter electrode with this binder, it is possible to obtain a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer.

<Electrolyte layer>
The electrolyte layer 5 fills a space generated between the counter substrate and the display substrate surrounded by a wall member. The electrolyte layer 5 fills the space so that the electrochromic layer is included in the electrolyte layer. The electrolyte layer 5 moves electric charge between the display electrode and the counter electrode, and promotes color development or decoloration of the electrochromic layer.

As the electrolyte 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. As the ionic liquid, any substance that is generally studied and reported can be used. In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.
Examples of molecular structures include cation components such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, Examples thereof include aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salts, and aliphatic quaternary ammonium systems such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.
As the anion component, a compound containing fluorine is preferable 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.
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. Glycols, alcohols and mixed solvents thereof can be used.

The electrolyte layer 6 contains an oxidizing agent. When the electrolyte layer 6 contains an oxidizing agent, even when an electrochromic display element is produced under air shut-off in order to prevent photodegradation, the element can be well developed and decolored.
The oxidizing agent is not particularly limited as long as it can be dissolved in the electrolyte layer composition, and can be appropriately selected according to the purpose. Nitrogen compounds, cobalt complex compounds, halogen compounds, peroxosulfuric acid compounds, potassium nitrosodisulfonate compounds, permanganate compounds, manganese dioxide compounds, chromate compounds, lead tetraacetate compounds, peroxides Examples thereof include hydrogen compounds and organic peroxide compounds. These may be used individually by 1 type and may use 2 or more types together.
Among these, bromophenylaminium compounds and cobalt complex compounds are preferable, and tris (4-bromophenyl) aminium hexachloroantimonate, tris (2,2′-bipyridine) cobalt (III) tri (tetracyanoborate) , Tris (2,2′-bipyridine) cobalt (III) tri (hexafluorophosphate), tris (2,2′-bipyridine) cobalt (III) tri (trifluoromethanesulfonimide) are more preferable, and tris (4 -Bromophenyl) aminium hexachloroantimonate, tris (2,2'-bipyridine) cobalt (III) tri (trifluoromethanesulfonimide) are particularly preferred.
The content of the oxidizing agent in the electrolyte layer is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.3% by mass or more and 1.0% by mass or less. When the content is 0.1% by mass or more and 5% by mass or less, a sufficient addition effect can be obtained. The color development and decoloring of the element can be performed satisfactorily.

The electrolyte need not be a low-viscosity liquid, and can take various forms such as a gel, a polymer cross-linked type, and a liquid crystal dispersion type. By forming the electrolyte in a gel or solid state, advantages such as improved element strength and improved reliability can be obtained.
As a solidification method, it is preferable to hold the electrolyte and the solvent in a polymer. This is because high ionic conductivity and solid strength can be obtained.
Further, the polymer is preferably a photocurable resin. This is because the device can be manufactured at a low temperature and in a short time as compared with the method of thinning by thermal polymerization or evaporation of the solvent.

  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, 100 nm or more and 10 micrometers or less are preferable.

<White reflective layer>
The white reflective layer is for improving white reflectance in an electrochromic display element.
As the material for the white reflective layer, for example, titanium oxide particles are preferably used. The volume average particle size of the titanium oxide particles is preferably 200 nm to 3 μm, and more preferably 250 nm to 2 μm.

<Other members>
There is no restriction | limiting in particular as said other member, According to the objective, it can select suitably, For example, a protective layer, a sealing layer, a hard-coat layer, an antireflection layer etc. are mentioned.

[Electrochromic Display Element of Second Embodiment]
FIG. 2 shows an example of the structure of the electrochromic display element 21 of the second embodiment.
As shown in FIG. 2, the electrochromic display element includes a display substrate 1 and a display electrode 3, a counter substrate 2 and a counter electrode 4 provided to face each other at an interval, and both electrodes (displays). An electrolyte layer 5 is provided between the electrode 3 and the counter electrode 4).
The surface of the display electrode 3 has a first electrochromic layer 6 which is a polymer obtained by polymerizing an electrochromic composition containing the radical polymerizable compound having the triarylamine of the present invention. In the electrochromic display element, the first electrochromic layer 6 is colored by a redox reaction on the surface of the display electrode 3. A second electrochromic layer 9 containing an electrochromic compound that develops color by a reduction reaction is formed on the counter electrode 4. The second electrochromic layer 9 is colored by the oxidation-reduction reaction on the surface of the counter electrode 4.
Since each component in the electrochromic display element of the second embodiment is almost the same as that of the electrochromic display element of the first embodiment, only different components will be described.

<Second electrochromic layer>
The second electrochromic layer 9 carries an electrochromic compound in which the supported particle film develops color by a reduction reaction. Since the supported particle film adsorbs a single molecule of the electrochromic compound, electrons can be efficiently injected into the electrochromic compound using a large surface area. Therefore, the color density at the time of color development of the electrochromic compound can be increased, and the switching speed between color development and decoloration can be increased.

As the support particles constituting the support particle film, conductive fine particles or semiconductive fine particles are preferably used. The conductive fine particles and semiconductive fine particles are not particularly limited and may be appropriately selected depending on the intended purpose, but metal oxides are preferable.
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 of the metal oxide include calcium, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, and aluminosilicate. These may be used individually by 1 type and may use 2 or more types together.
Note that when a high response speed is required for color development and decoloration, any of titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide, or a mixture thereof. Is preferably used, and when titanium oxide is used, display with excellent response speed is possible.

The shape of the conductive fine particles and the semiconductive fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a shape having a large surface area (specific surface area) per unit volume. For example, when the conductive fine particles and the semiconductive fine particles are aggregates of nanoparticles, the electrochromic compound can be more efficiently supported because of the large specific surface area.
The electrochromic compound causes an oxidation-reduction reaction by a voltage generated between the display electrode 3 and the counter electrode 4, and develops or decolors (reversible reaction).
The average primary particle diameter of the supported particles is preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm. By setting the average primary particle size to 5 nm or more and 100 nm or less, the second electrochromic layer can be made a transparent layer. As a result, a vivid color is obtained at the time of color development, and a colorless and transparent state is obtained at the time of decoloration.

As the electrochromic compound that develops color by the reduction reaction, either an inorganic electrochromic compound or an organic electrochromic compound may be used.
Examples of the electrochromic compound that develops color by the reduction reaction include, for example, azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styrylspiropyran, and spirooxazine as dye-based and polymer-based electrochromic compounds. , Spirothiopyran, thioindigo, tetrathiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, Low molecular organic electrochromic compounds such as phthalocyanine, fluoran, fulgide, benzopyran, and metallocene; conductive polymers such as polyaniline and polythiophene Etc., and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, a viologen compound and a dipyridine compound are preferable because a necessary driving voltage can be suppressed to a low level.
There is no restriction | limiting in particular as average thickness of a said 2nd electrochromic layer, Although it can select suitably according to the objective, 500 nm or more and 3 micrometers or less are preferable.

(Method for manufacturing electrochromic display element)
According to a first aspect of the method for manufacturing an electrochromic display element of the present invention, a step of forming a display electrode on a display substrate, a step of forming an electrochromic layer that develops color by an oxidation reaction on the display electrode, A step of forming a counter electrode on the substrate, a step of forming a deterioration preventing layer or an electrochromic layer that develops color by a reduction reaction on the counter electrode, and bonding the display substrate and the counter substrate through an electrolyte layer And other steps as necessary.

  In the second embodiment, the method for producing an electrochromic display element according to the present invention includes a step of forming a display electrode on a display substrate, and a step of forming an electrochromic layer that develops color by an oxidation reaction on the display electrode. A step of forming a counter electrode on the substrate, a step of forming a deterioration preventing layer on the counter electrode, a step of forming a white reflective layer on the electrochromic layer that develops color by the oxidation reaction or the deterioration preventing layer, Including a step of bonding the display substrate and the counter substrate through an electrolyte layer, and further including other steps as necessary.

<Display electrode formation process>
An ITO film having a film thickness of about 100 nm and a surface resistance of about 200 Ω / □ is formed on the display substrate (for example, a glass substrate having a length of 40 mm and a width of 40 mm) by sputtering to form the display electrode 3. To do.
There is no restriction | limiting in particular as a film-forming method, According to the objective, it can select suitably, For example, other vacuum film-forming methods, such as a sputtering method and an ion plating method, are applicable.

<(First) Electrochromic Layer Formation Step>
On the display electrode, an electrochromic composition containing a radically polymerizable compound having triarylamine is applied by spin coating, spray coating, bead coating, blade coating, or an appropriate printing method. Then, the applied electrochromic composition is crosslinked by applying external energy.
Examples of the external energy include heat, light, and radiation. The heat energy is applied by heating from the coating surface side or the support side using a gas such as air, nitrogen, steam, various heat media, infrared rays, or electromagnetic waves. The heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. or higher and 170 ° C. or lower.
As the energy of the light, a UV irradiation light source such as a high pressure mercury lamp or a metal halide lamp having an emission wavelength mainly in ultraviolet light (UV) can be used, but it is visible according to the absorption wavelength of the radical polymerizable substance or the photopolymerization initiator. A light source can also be selected. Irradiation dose of UV is not particularly limited and may be appropriately selected depending on the intended purpose, 5 mW / cm ² or more 15,000 MW / cm ² or less.

<White reflective layer forming step>
A white reflective layer is formed when a reflective display element is manufactured.
A 2,2,3,3-tetrafluoropropanol (TFP) dispersion of titanium oxide particles and an aqueous polyurethane resin is applied onto the electrochromic layer by a spin coating method. Thereafter, annealing is performed at 120 ° C. for 10 minutes. Thereby, a white reflective layer is formed.

<Counter electrode formation process>
An ITO film having a film thickness of about 100 nm and a surface resistance of about 200 Ω / □ is formed on a counter substrate (for example, a glass substrate having a length of 40 mm and a width of 40 mm) by sputtering, thereby forming the counter substrate.
The film forming method is not limited to the sputtering method, and other vacuum film forming methods such as an ion plating method can be applied.
Next, a deterioration preventing layer or a second electrochromic layer is formed on the counter electrode.

<Deterioration prevention layer forming step>
On the counter electrode, for example, a dispersion of antimony tin oxide (ATO) is spin-coated and annealed at 120 ° C. for 10 minutes to form an ATO film.

<Second electrochromic layer forming step>
First, a carrier particle, that is, a dispersion of titanium oxide is applied on the counter electrode by a spin coating method. Thereafter, an annealing process is performed at 120 ° C. for 15 minutes so that the counter electrode, the supported particles, and the supported particles are partially bonded. This forms a supported particle film.
Thereafter, 2,2,3,3-, containing 1% by mass of electrochromic compound 4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide on the supported particle film. A tetrafluoropropanol (TFP) solution is applied by spin coating, and an annealing treatment is performed at 120 ° C. for 10 minutes. Thus, a second electrochromic layer composed of the titanium oxide particle film and the electrochromic compound is formed.

<Lamination process>
The laminating process is performed in a glove box substituted with argon gas.
A counter substrate formed with up to the deterioration preventing layer or the second electrochromic layer, a display substrate formed up to the (first) electrochromic layer, or a display substrate formed up to the white reflective layer, a counter electrode and a display electrode Are bonded with the electrolyte layer sandwiched between them.
Specifically, for example, a spherical resin bead having a volume average particle size of 30 μm is sprayed in advance on one side of the display substrate side or the counter substrate side, and then both substrates are bonded together, and the outer periphery is partially bonded, and then bonded. The precursor material of the electrolyte layer is injected into the gap between the combined counter substrate side and display substrate side. Thereafter, ultraviolet light is irradiated for 2 minutes from the display electrode side by a high pressure mercury lamp. Since the precursor material can be photopolymerized and phase-separated by irradiation with ultraviolet light, an electrolyte layer can be formed between both substrates. The ultraviolet light having a center wavelength of 365 nm and an intensity of 50 mW / cm ² can be used.
As an example of a method for preparing the precursor material of the electrolyte layer, first, a propylene carbonate solution of tetrabutylammonium perchlorate (Tetra Butyl Ammonium Perchlorate: TBAP) is used, and a molar concentration of TBAP is about 20 mol / Adjust to L. Thereafter, a mixture of a liquid crystal composition for PNLC (Polymer Network Liquid Crystal), a monomer composition, and a polymerization initiator is mixed into the solution. Thereafter, the molar concentration of TBAP in the propylene carbonate solution is adjusted again to be about 0.04 mol / L. On the other hand, 0.5 mass% of tris (4-bromophenyl) aminium hexachloroantimonate is added as an oxidizing agent. Thereafter, in order to regulate the thickness of the electrolyte layer to be produced, true spherical resin beads having a volume average particle diameter of 30 μm are dispersed in the propylene carbonate solution at a concentration of 0.2% by mass. Thus, it can be set as the precursor material of an electrolyte layer.

(Display device)
The display device of the present invention, the electrochromic display element of the present invention,
A VRAM (first storage means) for storing display data;
And a display controller that controls the electrochromic display element based on the display data, and further includes other means as necessary.

(Information equipment)
The information device of the present invention includes the display device of the present invention and a control device for controlling information displayed on the display device, and further includes other means as necessary.

Hereinafter, the case where the electrochromic display element of the present invention is applied to an electronic book reader will be described.
The electrochromic display element is not limited to an electronic book reader, and can be applied to any information device including a display device such as an electronic advertisement, a mobile personal computer, and a portable terminal.

FIG. 3 shows an example of a schematic structure of the electronic book reader 100.
The electronic book reader 100 includes a display device 101, a main controller 102, a ROM (second storage means) 103, a RAM (third storage means) 104, a flash memory (fourth storage means) 105, a character generator 106, an interface. 107 is included. The display device 101 includes a display panel 111 with a touch panel, a touch panel driver 112, a display controller 113, and a VRAM (first storage means) 114.
In the structure shown in FIG. 3, the character generator 106 is provided outside the display device 101, but the character generator 106 may be provided inside the display device 101. The display panel 111 may not include a touch panel. If there is other input means, the display panel 111 may be provided with other input means. When the display panel 111 does not include a touch panel, the touch panel driver 112 is not necessary.
The arrows shown in FIG. 3 represent typical signals and information flows, and do not represent all the connection relationships of the blocks.

The display panel 111 with a touch panel includes a drive circuit for individually driving the electrochromic display element 20 according to the first embodiment, the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer 29. Including. The drive circuit includes a drive element layer 34, and the drive element layer 34 has a plurality of drive elements corresponding to each counter electrode 33. The display panel 111 drives a drive element corresponding to the selected pixel based on the pixel selection signal output from the display controller 113, and applies a predetermined voltage to the selected pixel. The pixel selection signal is a signal that designates the vertical position and the horizontal position of the selected pixel. Further, based on the color designation signal output from the display controller 113, the display panel 111 applies a predetermined voltage to the corresponding display electrode according to the designated color. Based on signals such as a pixel selection signal and a color designation signal, the display panel 111 displays a moving image, a still image, or the like.
The display panel 111 outputs a signal based on the touch position to the touch panel driver 112 when the user touches the touch panel.
Since the display panel 111 includes the electrochromic display element 20 of the present invention, high-definition full color display (multicolor display) can be realized while maintaining high white reflectance and high contrast ratio. . Actually, even after displaying and erasing a full-color image alternately 1,000 times, no special change was observed in the display state of the image.

Further, the display panel 111 can switch between color development and color erasure at high speed. Actually, the time required from the start of driving to image acquisition and the time required to erase the acquired image were about 500 mm seconds.
In addition, since the display panel 111 has excellent light resistance, the display panel 111 has high fastness to light such as sunlight and room light, and can maintain a highly visible image display even when light is irradiated for a long time. In fact, even after standing for about 30 minutes after displaying a full-color image, there was no change in the appearance of the image, and blurring of the image could not be recognized.
A VRAM (first storage unit) 114 stores display data for displaying a moving image or a still image on the display panel 111. The display data individually corresponds to a plurality of pixels included in the display panel 111. Therefore, the display data includes display color information corresponding to each pixel.
The display controller 113 reads display data stored in a VRAM (first storage means) 114 at predetermined timings, and displays display colors of a plurality of pixels included in the display panel 111 according to the display data. Control individually. The display controller 113 outputs to the display panel 111 a pixel selection signal for specifying a pixel to be colored and a color designation signal for specifying a color.
The touch panel driver 112 outputs position information corresponding to the position touched by the user on the display panel 111 to the main controller 102.
The main controller 102 includes a RAM (third storage means) 104, a flash memory (fourth storage means) 105, a character generator 106, an interface 107, in accordance with a program stored in a ROM (second storage means) 103. Each unit such as the VRAM (first storage unit) 114 is controlled in an integrated manner.

For example, when the power is turned on by the user, the main controller 102 reads the initial menu screen data from the ROM (second storage means) 103 and refers to the character generator 106 to convert the initial menu screen data into dot data. And the dot data is transferred to a VRAM (first storage means) 114. As a result, the initial menu screen is displayed on the display panel 111. At this time, a list of contents stored in the flash memory 105 is displayed on the display panel 111. When one of the menus on the display panel 111 is selected by the user and the display portion is touched, the main controller 102 acquires the selection content of the user based on the position information from the touch panel driver 112.
When the user designates the content and requests to view the content, the main controller 102 reads the electronic data of the content from the flash memory (fourth storage means) 105, refers to the character generator 106, The electronic data is converted into dot data, and the dot data is transferred to a VRAM (first storage means) 114.
When the user requests to purchase content via the Internet, the main controller 102 connects to a predetermined purchase site via the interface 107 and functions as a normal browser. When the information from the purchase site is displayed on the display panel 111 and the user purchases the content, electronic data of the content is downloaded. The main controller 102 stores the electronic data of the content in the flash memory (fourth storage means) 105.

A ROM (second storage means) 103 stores various programs described in codes readable by the main controller 102 and various data necessary for executing the programs.
A RAM (third storage means) 104 is a working memory.
The flash memory (fourth storage means) 105 stores electronic data of books as contents.
The character generator 106 stores dot data corresponding to various character data.
The interface 107 controls connection with an external device. The interface 107 can connect a memory card, a personal computer, and a public line. The connection to the personal computer and the public line can be either wired or wireless.

  According to the electronic book reader 100, since the electrochromic display element of the present invention is applied to a touch panel, it is excellent in transparency, and a vivid color can be obtained. Even so, clear display characteristics can be obtained.

(Electrochromic light control lens)
The electrochromic light control lens of the present invention includes a lens and a thin film light control function unit laminated on the lens, and further includes other members as necessary.
The thin film dimming function unit includes: a first electrode layer stacked on the lens; a first electroactive layer stacked on the first electrode layer; and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and And an electrolyte layer provided in contact with the second electroactive layer.
One of the first electroactive layer and the second electroactive layer is an electrochromic layer that develops color by an oxidation reaction, and the other is an degradation prevention layer or an electrochromic layer that develops color by a reduction reaction.
The electrolyte layer contains an oxidizing agent.
The electrochromic light control lens of the present invention has excellent display characteristics that hardly cause deterioration coloring due to repeated driving and hardly causes a decrease in color density due to light deterioration.

Here, FIG. 4 is a sectional view showing an example of the electrochromic light control lens of the present invention. Referring to FIG. 4, the electrochromic light control lens 110 includes a lens 120 and a thin film light control function unit 130 stacked on the lens 120. The planar shape of the electrochromic light control lens 110 can be, for example, a round shape.
The thin-film light control function unit 130 has a structure in which a first electrode layer 131, an electrochromic layer 132, an insulating porous layer 133, a second electrode layer 134, a deterioration preventing layer 135, and a protective layer 136 are sequentially stacked. It is a part which performs electrochromic layer 132 light emission / discoloration (light control). Note that the protective layer 136 may be formed on the upper surface (the surface opposite to the lens 120) of the deterioration preventing layer 135, and is not necessarily limited to the first electrode layer 131, the electrochromic layer 132, and the insulating porous layer. 133, the second electrode layer 134, and the deterioration prevention layer 135 may not be formed on the respective side surfaces.

In the electrochromic dimming lens 110, a first electrode layer 131 is provided on the lens 120, and an electrochromic layer 132 is provided in contact with the first electrode layer 131. Further, a second electrode layer 134 is provided on the electrochromic layer 132 so as to face the first electrode layer 131 with the insulating porous layer 133 interposed therebetween.
The insulating porous layer 133 is provided to insulate the first electrode layer 131 and the second electrode layer 134, and the insulating porous layer 133 contains insulating metal oxide fine particles. . The insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134 is filled with an electrolyte (not shown).
The second electrode layer 134 is a porous electrode layer in which a large number of through holes penetrating in the thickness direction are formed. A deterioration preventing layer 135 is provided outside the second electrode layer 134. The deterioration preventing layer 135 is also porous in which a large number of through holes penetrating in the thickness direction are formed, and is filled with an electrolyte (not shown).
In the electrochromic dimming lens 110, by applying a voltage between the first electrode layer 131 and the second electrode layer 134, the electrochromic layer 132 undergoes an oxidation-reduction reaction due to the transfer of electric charges, and the color changes. .

<Method of manufacturing electrochromic light control lens>
The method of manufacturing the electrochromic light control lens used in the present invention includes a step of sequentially laminating the first electrode layer 131 and the electrochromic layer 132 on the lens 120, and an insulating porous layer 133 on the electrochromic layer 132. A step of laminating a second electrode layer 134, which is a porous electrode layer having a through hole formed so as to face the first electrode layer 131, and a through hole is formed on the second electrode layer 134. A step of laminating the porous porous deterioration preventing layer 135, and the insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134, and the deterioration preventing layer 135 and the second electrode layer. And a step of filling the electrolyte from the through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 via 134, and a step of forming the protective layer 136 on the deterioration preventing layer 135. Including the other steps in accordance to.

Here, the respective through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 are injected when the insulating porous layer 133 or the like is filled with an electrolyte in the manufacturing process of the electrochromic light control lens 110. It is a hole.
Thus, in the electrochromic light control lens 110 of the present invention, the deterioration preventing layer 135 and the second electrode are formed on the insulating porous layer 133 and the like sandwiched between the first electrode layer 131 and the second electrode layer 134. It is possible to fill the electrolyte from through holes formed in the layer 134.
Therefore, it is possible to form the low-resistance second electrode layer 134 before filling the electrolyte, and the performance of the electrochromic light control lens 110 can be improved.
Moreover, since the deterioration preventing layer 135 is provided on the second electrode layer 134, an electrochromic light control lens that operates repeatedly and stably can be realized.

Note that since the through hole is formed in the second electrode layer 134, the deterioration preventing layer 135 is in contact with the second electrode layer 134 outside the second electrode layer 134 (outside the two opposing electrode layers). Can be formed. This is because ions can move between the front and back of the second electrode layer through the through-hole formed in the second electrode layer 134. As a result, since it is not necessary to form the deterioration preventing layer 135 below the second electrode layer 134, the deterioration preventing layer 135 is prevented from being damaged by sputtering or the like when forming the second electrode layer 134. it can.
In addition, when the deterioration preventing layer 135 is formed, a process that can form either a homogeneous deterioration preventing layer 135 is formed on the permeable insulating porous layer 133 and the second electrode layer 134. You can choose as appropriate. Alternatively, the deterioration preventing layer 135 may be formed both above and below the second electrode layer 134 as necessary.
In FIG. 4, the electrochromic layer 132 is formed in contact with the first electrode layer 131, and the deterioration preventing layer 135 is formed in contact with the second electrode layer 134. Have a reductive reaction, and when one carries out a reductive reaction, the other carries out an oxidation reaction. Therefore, the position to be formed may be reversed. That is, the deterioration preventing layer 135 may be in contact with the first electrode layer 131 and the electrochromic layer 132 may be formed in contact with the second electrode layer 134.

Alternatively, the electrochromic layer 132 may be formed in contact with the first electrode layer 131, and the deterioration preventing layer may be formed on both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Good. Further, the deterioration preventing layer 135 is formed in contact with the first electrode layer 131, and the electrochromic layer 132 is formed in both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Also good.
In the present invention, the deterioration preventing layer and the electrochromic layer may be referred to as an electroactive layer. That is, in the electrochromic light control lens 110 according to the present embodiment, the thin film light control function unit 130 includes the first electrode layer 131 stacked on the lens 120 and the first electrode layer 131 stacked on the first electrode layer 131. 1 electroactive layer, an insulating porous layer 133 laminated on the first electroactive layer, a porous second electrode layer 134 laminated on the insulating porous layer 133, A porous second electroactive layer formed on one or both of the upper side and the lower side of the second electrode layer 134 in contact with the second electrode layer 134, and the first electroactive layer One of the second electroactive layers is the electrochromic layer 132 and the other is the deterioration preventing layer 135.
In the electrochromic dimming lens 110 of the present invention, since the protective layer 136 is formed in the coating process after the electrolyte is injected, the thickness can be reduced with respect to the configuration in which the two lenses are bonded, and the weight is also reduced. Can be done at low cost.
The average thickness of the thin-film light control function unit 130 is preferably 2 μm or more and 200 μm or less. When the thickness of the thin-film light control function unit 130 is 200 μm or less, the round lens can be easily processed and the optical characteristics of the lens are not affected. Moreover, when the thickness of the thin film light control function unit 130 is 2 μm or more, a light control function is obtained.

Here, FIG. 5 is a perspective view showing an example of eyeglasses using the electrochromic light control lens of the present invention. Referring to FIG. 5, the electrochromic dimming glasses 150 include an electrochromic dimming lens 151, a spectacle frame 152, a switch 153, and a power source 154. The electrochromic light control lens 151 is obtained by processing the electrochromic light control lens 110 into a desired shape.
The two electrochromic dimming lenses 151 are incorporated in the spectacle frame 152. The eyeglass frame 152 is provided with a switch 153 and a power source 154. The power source 154 is electrically connected to the first electrode layer 131 and the second electrode layer 134 through a switch 153 and a wiring (not shown). By switching the switch 153, for example, one of a state in which a positive voltage is applied between the first electrode layer 131 and the second electrode layer 134, a state in which a negative voltage is applied, and a state in which no voltage is applied are selected. The state can be selected.

As the switch 153, for example, an arbitrary switch such as a slide switch or a push switch can be used. However, at least the three states are switchable. As the power source 154, for example, an arbitrary DC power source such as a button battery or a solar battery can be used. The power source 154 can apply a voltage of about plus or minus several volts between the first electrode layer 131 and the second electrode layer 134.
For example, by applying a positive voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are colored in a predetermined color. Further, by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are decolored and become transparent.
However, depending on the characteristics of the material used for the electrochromic layer 132, color is developed by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, and the color is erased by applying a positive voltage. However, it may be transparent. Note that once the color is developed, the color continues even if no voltage is applied between the first electrode layer 131 and the second electrode layer 134.
Hereinafter, materials of each component constituting the electrochromic light control lens 110 of the present invention, a film forming method, and the like will be described in detail.

<Lens>
The material of the lens 120 is not particularly limited as long as it functions as a lens for spectacles, and can be appropriately selected according to the purpose. Moreover, the one where expansion | swelling by a heat history is as small as possible is preferable, and a material with a high glass transition point (Tg) and a material with a small linear expansion coefficient are preferable.
Specifically, in addition to glass, any of those described in the technical summary document on high refractive index eyeglass lenses of the JPO can be used. Episulfide resin, thiourethane resin, methacrylate resin, polycarbonate Resin, urethane resin, etc., and mixtures thereof can be used. Moreover, you may form the primer for improving a hard coat and adhesiveness as needed.
In the present invention, the lens includes a lens whose power (refractive index) is not adjusted (simple glass plate or the like).

<First electrode layer, second electrode layer>
The material of the first electrode layer 131 and the second electrode layer 134 is not particularly limited as long as it is a conductive material, but when used as a light control glass, light transmittance is ensured. Since it is necessary, a transparent conductive material that is transparent and excellent in conductivity is used. Thereby, the transparency of the glass can be obtained and 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, one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) and zinc oxide (hereinafter referred to as Zn oxide) formed by vacuum film formation. It is preferable to use an inorganic material including one.
The In oxide, the Sn oxide, and the Zn oxide are materials that can be easily formed by a sputtering method, and that are excellent in transparency and electrical conductivity. Among these, particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO. Furthermore, transparent network electrodes such as silver, gold, carbon nanotube, and metal oxide, and composite layers thereof are also useful. The network electrode is an electrode in which carbon nanotubes or other highly conductive non-permeable materials are formed in a fine network shape to provide transmittance.

The thicknesses of the first electrode layer 131 and the second electrode layer 134 are adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 132 is obtained. When ITO is used as the material of the first electrode layer 131 and the second electrode layer 134, the thickness of each of the first electrode layer 131 and the second electrode layer 134 is preferably 50 nm or more and 500 nm or less. .
As a manufacturing method of each of the first electrode layer 131 and the second electrode layer 134, a vacuum evaporation method, a sputtering method, an ion plating method, or the like can be used. As long as each material of the first electrode layer 131 and the second electrode layer 134 can be formed by coating, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, Roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet Various printing methods such as a printing method can be used.

The second electrode layer 134 has a large number of fine through-holes penetrating in the thickness direction. For example, a fine through hole can be provided in the second electrode layer 134 by the following method. That is, before forming the second electrode layer 134, it is possible to use a method in which a layer having unevenness is formed in advance as a base layer, and the second electrode layer 134 having unevenness is used as it is.
Alternatively, a method may be used in which a convex structure such as a micro pillar is formed before the second electrode layer 134 is formed, and the convex structure is removed after the second electrode layer 134 is formed. Further, before forming the second electrode layer 134, a foaming polymer or the like is sprayed, and after the second electrode layer 134 is formed, a process such as heating or degassing is performed to foam. May be. Alternatively, a method may be used in which various radiations are directly emitted to the second electrode layer 134 to form pores.
Further, as a method for forming a fine through hole in the second electrode layer 134, a colloidal lithography method may be used. The colloidal lithography method is as follows. That is, the conductive film that becomes the second electrode layer 134 is formed on the surface on which the fine particles are dispersed using the dispersed fine particles as a mask by a vacuum film-forming method or the like on the lower layer on which the second electrode layer 134 is laminated. Form. Thereafter, patterning is performed by partially removing the conductive film together with the fine particles.

As a method of forming fine through holes in the second electrode layer 134, a general lift-off method using a photoresist, a dry film, or the like may be used in addition to the colloidal lithography method. Specifically, first, a desired photoresist pattern is formed, then a second electrode layer 134 is formed, and then the photoresist pattern is removed to remove unnecessary portions on the photoresist pattern. In this method, fine through holes are formed in the electrode layer 134.
When a fine through hole is formed in the second electrode layer 134 by a general lift-off method, it is used so that the light irradiation area to the object may be small in order to avoid damage to the lower layer due to light irradiation. It is preferable to use a negative type photoresist.
Negative photoresists include, for example, polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, polyhydroxystyrene / Mention may be made of melamine / photoacid generators, methylated melamine resins, methylated urea resins and the like.

Furthermore, it is possible to form fine through holes in the second electrode layer 134 by a processing apparatus using laser light.
The diameter of the fine through hole provided in the second electrode layer 134 is preferably 10 nm or more and 100 μm or less. When the diameter of the through hole is smaller than 10 nm (0.01 μm), there arises a problem that the permeation of electrolyte ions is deteriorated. Further, when the diameter of the fine through-hole is larger than 100 μm, the level is visually observable (the size of one pixel electrode (one counter electrode) in a normal display), and the display performance just above the fine through-hole is defective. It will be.
The ratio (hole density) of the hole area to the surface area of the second electrode layer 134 of the fine through holes provided in the second electrode layer 134 can be set as appropriate, and is, for example, 0.01% or more and 40% It can be as follows. If the hole density is too high, the surface resistance of the second electrode layer 134 is increased, which causes a problem that chromic defects are generated due to an increase in the area of the area where the second electrode layer 134 is absent. Further, if the hole density is too low, the permeability of the electrolyte ions is deteriorated.

<Electrochromic layer (electrochromic layer that develops color by oxidation reaction)>
The electrochromic layer 132 is an electrochromic layer that develops color by an oxidation reaction. The electrochromic layer of the electrochromic display element of the first embodiment or the first electrochromic display element of the second embodiment. The same mode as the chromic layer can be adopted.

<Insulating porous layer>
The insulating porous layer 133 has a function of isolating the first electrode layer 131 and the second electrode layer 134 so as to be electrically insulated and holding an electrolyte. The material of the insulating porous layer 133 is not particularly limited as long as the material is porous. However, organic materials and inorganic materials having high insulating properties and durability and excellent film forming properties, and composites thereof. It is preferable to use a body.

As a method of forming the insulating porous layer 133, for example, a sintering method (using fine holes or inorganic particles partially fused by adding a binder or the like to use holes generated between the particles) is used. be able to. As a method for forming the insulating porous layer 133, for example, an extraction method (after forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved in a solvent to To obtain holes) or the like.
As a method of forming the insulating porous layer 133, a foaming method in which a high molecular polymer or the like is foamed by heating or degassing, etc., or a phase change in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. Alternatively, a forming method such as a radiation irradiation method in which pores are formed by radiating various types of radiation may be used. Specific examples include a polymer mixed particle film containing metal oxide fine particles (SiO ₂ particles, Al ₂ O ₃ particles, etc.) and a polymer binder, a surface of a porous organic film (polyurethane resin, polyethylene resin, etc.) electrode layer 134. The resistance is greatly lost, causing display defects.
The thickness of the insulating porous layer 133 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 μm or more and 2 μm or less.

The insulating porous layer 133 is preferably used in combination with an inorganic film. This is because when the second electrode layer 134 formed on the surface of the insulating porous layer 133 is formed by sputtering, damage to the organic material of the insulating porous layer 133 or the electrochromic layer 132 as a lower layer is prevented. This is to reduce.
As the inorganic film, it is preferable to use a material containing ZnS in addition to SiO ₂ . ZnS can be deposited at high speed by sputtering without damaging the electrochromic layer 132 or the like. Furthermore, examples of the material containing ZnS as a main component include ZnS—SiO ₂ , ZnS—SiC, ZnS—Si, and ZnS—Ge.
Here, the ZnS content is preferably 50 mol% or more and 90 mol% or less in order to maintain good crystallinity when the insulating layer is formed. Among these, particularly preferable materials are ZnS—SiO ₂ (8/2 (mass ratio)), ZnS—SiO ₂ (7/3 (mass ratio)), ZnS, ZnS—ZnO—In ₂ O ₃ —Ga _2. O ₃ (60/23/10/7 (mass ratio)). By using the material as described above as the insulating porous layer 133, a good insulating effect can be obtained with a thin film, and a decrease in film strength and film peeling can be prevented.

<Deterioration prevention layer>
The role of the deterioration preventing layer 135 is to perform a chemical reaction opposite to that of the electrochromic layer 132, and to balance the charge, the first electrode layer 131 and the second electrode layer 134 are corroded or deteriorated by an irreversible redox reaction. Is to suppress it. As a result, the repeated stability of the electrochromic dimming lens 110 is improved. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.
The material of the deterioration preventing layer 135 is not particularly limited as long as it is a material that plays a role of preventing corrosion of the first electrode layer 131 and the second electrode layer 134 due to an irreversible oxidation-reduction reaction. As the material of the deterioration preventing layer 135, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used. Furthermore, when the coloring of the deterioration preventing layer does not matter, the same material as the electrochromic material can be used.
The deterioration preventing layer 135 can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive 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, phenol, etc. By fixing to the 2nd electrode layer 134 with this binder, the suitable porous thin film which satisfy | fills the permeability | transmittance of electrolyte and the function as a deterioration prevention layer can be obtained.
As the material of the deterioration preventing layer 135, a material that maintains a transparent state with charge exchange may be used. For example, a conductive polymer such as polypyrrole, polythiophene, polyaniline, or derivatives thereof, metal Examples include a hybrid polymer of a complex and an organic ligand, and a radical polymer. When these are used, it is necessary to adjust the film density so as not to inhibit the injection of the electrolyte, or to form through holes by laser processing or the like.
These materials may be used as the electrochromic layer 132, and the organic electrochromic compound supported on the conductive or semiconductive fine particles described above may be used as the deterioration preventing layer 135.
As the deterioration prevention layer 135, it is preferable to use highly transparent n-type semiconductor oxide fine particles (n-type semiconductor metal oxide). As a specific example, titanium oxide, tin oxide, zinc oxide, or compound particles containing a plurality of them, or a mixture of particles having a primary particle size of 100 nm or less can be used.
Furthermore, when these deterioration preventing layers 135 are used, the electrochromic layer 132 is preferably a material that changes from colored to transparent by an oxidation reaction. This is because the n-type semiconductor metal oxide is easily reduced (electron injection) at the same time as the electrochromic layer 132 undergoes an oxidation reaction, and the driving voltage can be reduced.

In such a form, a particularly preferred electrochromic material is an organic polymer material. The film can be easily formed by a coating process or the like, and the color can be adjusted and controlled by the molecular structure. Examples of these organic polymer materials include poly (3,4-ethylenedioxythiophene) -based materials, bis (terpyridine) s and iron ion complex-forming polymers, and the like.
As a method for forming the deterioration preventing layer 135, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used.
If the material of the deterioration prevention layer 135 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, Various printing methods such as a slit coating method, a capillary coating method, a spray coating method, 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 can be used.

<Electrochromic layer (electrochromic layer that develops color by reduction reaction)>
When the electrochromic layer 135 is formed by a reduction reaction without forming the deterioration preventing layer, the same mode as that of the second electrochromic layer in the electrochromic display element of the second embodiment can be adopted.

<Electrolyte layer>
The electrolyte layer (not shown) can have the same mode as the electrolyte layer of the electrochromic display element of the first embodiment.

<Protective layer>
The role of the protective layer 136 is unnecessary for protecting the device from external stress and chemicals in the cleaning process, preventing leakage of electrolyte, and stable operation of the electrochromic display device such as moisture and oxygen in the atmosphere. For example, to prevent the entry of things. At the same time, transparency, surface smoothness, refractive index, heat resistance, and light resistance are required so as not to impair the function as a lens.
The thickness of the protective layer 136 is preferably 1 μm or more and 200 μm or less.
As a material of the protective layer 136, an ultraviolet curable resin or a thermosetting resin can be used. Specifically, an acrylic resin, a urethane resin, an epoxy resin, or the like is preferably used.
There is no restriction | limiting in particular as a formation method of the protective layer 136, According to the objective, it can select suitably, For example, various film-forming methods, such as a spin coat method, a dip coat method, a spray coat method, a casting method, etc. are mentioned. It is done.
In addition to the protective layer 136, the electrochromic light control lens 110 preferably includes a hard coat layer for preventing scratches and an antireflection layer for suppressing reflection as necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

Example 1
<Production of electrochromic display element>
The electrochromic display element of the first embodiment as shown in FIG. 1 was produced as follows.

<Preparation of electrolyte composition>
An electrolyte composition having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan Ltd.): 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 In addition, 0.5 parts by mass of tris (4-bromophenyl) aminium hexachloroantimonate as an oxidant is added, and a resin bead spacer having a volume average particle size of 30 μm (manufactured by Sekisui Chemical Co., Ltd., for the purpose of controlling the electrolyte layer thickness, 0.2 parts by mass of Micropearl GS-230) was added and dispersed. Thus, an electrolyte composition was prepared.

<Formation of display electrode>
An ITO film having an average thickness of 100 nm was formed by sputtering on the entire surface of a glass substrate (40 mm × 40 mm) as a display substrate, and the display electrode 3 was produced. The surface resistance of the display electrode 3 was about 200Ω.

<Formation of electrochromic layer that develops color by oxidation reaction>
In order to form an electrochromic layer that develops color by an oxidation reaction on the display electrode, an electrochromic composition having the following composition was prepared.
Triarylamine compound having a monofunctional acrylate (Exemplary Compound 1 represented by the following structural formula): 50 parts by mass

[Exemplary Compound 1]
IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass Methyl ethyl ketone: 900 parts by mass The obtained electrochromic composition was used as the display electrode. The coating film obtained above was applied by spin coating, and the obtained coating film was irradiated for 60 seconds at 10 mW / cm ² with a UV irradiation apparatus (USHIO Corporation, SPOT CURE) under a nitrogen atmosphere and annealed at 60 ° C. for 10 minutes. Was performed to form a crosslinked electrochromic layer having an average thickness of 1.3 μm.

<Formation of white reflective layer>
On the electrochromic layer, titanium oxide particles (volume average particle size: 300 nm) and a TFP dispersion of an aqueous polyurethane resin were spin-coated, and a white reflective layer was formed by annealing at 120 ° C. for 10 minutes.

<Formation of counter electrode>
An ITO film having an average thickness of 100 nm was formed on the entire surface of a glass substrate (40 mm × 40 mm) as a counter substrate by sputtering to produce a display electrode. The surface resistance of this display electrode was about 200Ω.

<Formation of deterioration prevention layer>
On the counter electrode, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., volume average particle size: about 20 nm) is applied as a deterioration preventing layer by spin coating, and annealed at 120 ° C. for 15 minutes. As a result, a nanostructured semiconductor material composed of a titanium oxide particle film having an average thickness of 1.0 μm was formed.

<Lamination>
The following steps were performed in an argon-substituted glove box.
50 μL of the prepared electrolyte composition is supplied onto the deterioration preventing layer thus formed, and a display substrate is bonded so that the white reflective layer formed on the electrolyte composition is opposed thereto, and a UV (wavelength 250 nm) irradiation device (US The electrolyte composition was cured by irradiation with 10 mW / cm ² for 60 seconds using SPOT CURE manufactured by Denki Co., Ltd. Thus, an electrochromic display element was produced.

  Next, the produced electrochromic display element was evaluated for “deterioration coloring by repeated driving” and “light resistance” as follows.

<Evaluation method of deterioration coloring by repeated driving>
The L ^* value at the time of color erasing was measured before and after 10,000 times of color erasing repeated driving, and the difference between them was used as an indicator of the degree of deterioration coloring.
The L ^* value is a characteristic value representing the brightness in the CIELAB color system, and is used here as an indicator of the brightness when the electrochromic display element is decolored and the color density during color development. The L ^* value was measured using a self-made device.
* Repetitive driving conditions: (coloring: constant current application: -0.3 mA / cm ² , application time: 1 second), (decoloring: constant current application: 0.3 mA / cm ² , application time: 1 second) alternately And repeatedly applied.
* Reflective measurements were made on transmissive electrochromic display elements with the elements placed in close contact on a standard white plate. The reflection type electrochromic display element was directly measured for reflection.

<Evaluation method of light resistance (reduction in color density due to light degradation)>
The L ^* value during color development was measured before and after the xenon lamp light irradiation (100 hours at 50,000 Lx) to the electrochromic display element, and the difference between the two was used as an indicator of the degree of light degradation. The L ^* value was measured using a self-made device.

-Deterioration coloring due to repeated driving-
A current was applied to the obtained electrochromic display element under the above-described driving conditions, and 10,000 times of color development / erasing was repeated. The L ^* value at the time of erasing immediately after the start is 80.9, the L ^* value at the time of erasing at the end of 10,000 times is 80.5, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .4, which was very small, almost no deterioration coloring was observed even by actual visual observation.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as in Example 1 ^. The value was 19.4. The hue at the time of coloring was greenish black. The display element was irradiated with xenon lamp light at 50,000 Lx for 100 hours, and then applied again (constant current application: -0.3 mA / cm ² , application time: 1 second) to develop an L ^* value. Was 20.5, and the difference between them (an indicator of the degree of photodegradation) was as small as 1.1. Even when actually observed visually, no difference in color density was felt.
From the above results, it was confirmed that the electrochromic display element of Example 1 hardly caused deterioration coloring due to repeated driving, and hardly caused a decrease in color density due to light deterioration.

(Example 2)
<Production of electrochromic display element>
In Example 1, an electrochromic display element was produced in the same manner as in Example 1 except that a transmissive display element was formed without forming a white reflective layer on the electrochromic layer that developed color by an oxidation reaction.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The L ^* value at the time of erasing immediately after the start is 80.5, the L ^* value at the time of erasing at the end of 10,000 times is 79.9, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as in Example 2 ^. The value was 19.8. The hue at the time of coloring was greenish black. The display element was irradiated with xenon lamp light at 50,000 Lx for 100 hours, and then applied again (constant current application: -0.3 mA / cm ² , application time: 1 second) to develop an L ^* value. Was 21.0, and the difference between them (an indicator of the degree of photodegradation) was as small as 1.2. Even when actually observed visually, no difference in color density was felt.
From the above results, it was confirmed that the electrochromic display element of Example 2 hardly caused deterioration coloring due to repeated driving, and hardly caused a decrease in color density due to light deterioration.

(Example 3)
<Production of electrochromic display element>
In Example 2, an electro display element was produced in the same manner as in Example 2 except that the deterioration preventing layer was not formed on the counter electrode and an electrochromic layer that developed color by a reduction reaction was formed as follows. did.

-Formation of electrochromic layer-
By applying SP210 (manufactured by Showa Titanium Co., Ltd.) as a titanium oxide nanoparticle dispersion liquid on the counter electrode by a spin coating method and performing an annealing treatment at 120 ° C. for 15 minutes, a titanium oxide particle film (average thickness 1.1 μm) ) Was formed. 2,2 containing 2% by mass of “4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide”, which is an electrochromic compound, on the titanium oxide particle film , 3,3-tetrafluoropropanol (hereinafter referred to as “TFP”) solution was spin-coated, and an electrochromic layer that developed color by a reduction reaction was formed by annealing at 120 ° C. for 10 minutes.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The L ^* value at the time of erasing immediately after the start is 80.4, the L ^* value at the time of erasing at the end of 10,000 times is 79.9, and the difference between them (an indicator of the degree of deterioration coloring) is 0. It was very small as .5, and almost no deterioration coloring was observed even in actual visual observation.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as in Example 3 ^. The value was 19.3. The hue at the time of color development was good black. The display element was irradiated with xenon lamp light at 50000 Lx for 100 hours and then reapplied (constant current application: −0.3 mA / cm ² , application time: 1 second) to develop color and the L ^* value was 20 The difference between the two (an index of the degree of photodegradation) was as small as 1.1, and no difference in color density was felt even when actually observed visually.
From the above results, it was confirmed that the electrochromic display element of Example 3 hardly caused deterioration coloring due to repeated driving, and hardly caused a decrease in color density due to light deterioration.

Example 4
<Production of electrochromic display element>
In Example 3, except that the oxidizing agent added to the electrolyte layer composition was 0.5 parts by mass of tris (2,2′-bipyridine) cobalt (III) tri (trifluoromethanesulfonimide). In the same manner, an electrochromic display element was produced.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and repeated driving of erasing / erasing 10,000 times. The L ^* value at the time of erasing immediately after the start is 80.3, the L ^* value at the time of erasing at the end of 10,000 times is 79.7, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as in Example 4 ^. The value was 20.1. The hue at the time of color development was good black. The display element was irradiated with xenon lamp light at 50,000 Lx for 100 hours, and then applied again (constant current application: -0.3 mA / cm ² , application time: 1 second) to develop an L ^* value. Was 21.5, and the difference between them (an index of the degree of photodegradation) was as small as 1.4. Even when actually observed visually, no difference in color density was felt.
From the above results, it was confirmed that the electrochromic display element of Example 4 hardly caused deterioration coloring due to repeated driving, and hardly caused a decrease in color density due to light deterioration.

(Comparative Example 1)
<Production of electrochromic display element>
In Example 4, an electrochromic display element was produced in the same manner as in Example 4 except that no oxidizing agent was added to the electrolyte layer composition.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and 10,000 times of color development / erasing repeated driving was performed. The L ^* value at the time of erasing immediately after the start is 80.7, the L ^* value at the time of erasing at the end of 10,000 times is 51.8, and the difference between them (index of the degree of deterioration coloring) is 28. .9, which was very large, and even with actual visual observation, a remarkable yellowish brown color was observed.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as Comparative Example 1 ^. The value was 19.6. The hue at the time of color development was good black. When this display element was irradiated with xenon lamp light at 50,000 Lx for 100 hours and then reapplied (coloring voltage: -2 V, application time: 1 second) to develop color, the L ^* value was measured to be 21.0. The difference between them (index of the degree of photodegradation) was as small as 1.4, and even when actually visually observed, no difference in color density was felt.
From the above results, although the electrochromic display element of Comparative Example 1 has good light resistance reflecting that it was produced in an environment where air was shut off, significant deterioration and coloring could occur due to repeated color development and decoloration. Was confirmed.

(Comparative Example 2)
<Production of electrochromic display element>
In Comparative Example 1, an electrochromic display element was produced in the same manner as in Comparative Example 1 except that all production operations were performed in air without using an argon-substituted glove box.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and 10,000 times of color development / erasing repeated driving was performed. The L ^* value at the time of erasing immediately after the start is 81.1, the L ^* value at the time of erasing at the end of 10,000 times is 80.6, and the difference between them (an indicator of the degree of deterioration coloring) is 0. It was very small as .5, and almost no deterioration coloring was observed even in actual visual observation.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as Comparative Example 2 ^. The value was 20.5. When this display element is irradiated with xenon lamp light at 50,000 Lx for 100 hours and then colored again by applying (coloring voltage: -2 V, application time: 1 second), the L ^* value is 41.1. The difference between them (an indicator of the degree of light degradation) was as large as 20.6, and the color density after repeated driving was clearly small even when actually observed visually.
From the above results, it was confirmed that although the electrochromic display element of Comparative Example 2 was inferior in light resistance reflecting that it was produced in the air, deterioration coloring due to repeated color development and decoloration hardly occurred.

(Example 5)
<Production of electrochromic light control lens>
An electrochromic light control lens as shown in FIG. 4 was produced as follows.

<Formation of first electrode layer and electrochromic layer>
First, a lens having a diameter of 65 mm was prepared, and an ITO film was formed to a thickness of 100 nm by a sputtering method through a metal mask in a 25 mm × 45 mm region and a lead portion to form a first electrode layer 131.
Next, on the ITO film, an electrochromic layer that developed color by an oxidation reaction was formed in the same manner as in Example 1.

<Formation of Insulating Porous Layer, Second Electrode Layer with Fine Through Hole>
Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, water 74 mass%) having an average primary particle diameter of 20 nm is spin-coated on the electrochromic layer 132 to insulate. The porous layer 133 was formed. The film thickness of the formed insulating porous layer 133 was about 2 μm. Furthermore, a fine SiO ₂ fine particle dispersion (silica solid content concentration 1 mass%, 2-propanol 99 mass%) having an average primary particle diameter of 450 nm was spin coated to form a fine through-hole forming mask (colloidal mask).
Subsequently, an inorganic insulating layer of ZnS—SiO ₂ (8/2 (mass ratio)) was formed to a thickness of 40 nm on the fine through hole forming mask by a sputtering method. Further, an ITO film having a thickness of about 100 nm is formed on the inorganic insulating layer by a sputtering method in a region of 25 mm × 45 mm overlapping with the ITO film formed by the first electrode layer 131 and in a region different from the first electrode layer 131. A second electrode layer 134 was formed using a mask. Note that the ITO film formed in a region different from the first electrode layer 131 is a lead-out portion of the second electrode layer 134.
Thereafter, 2-in-propanol performs ultrasonic irradiation for 3 minutes, subjected to SiO ₂ removal treatment of the fine particles of 450nm is colloidal masks. It was confirmed by SEM observation that the second electrode layer 134 in which minute through holes of about 250 nm were formed was formed. The sheet resistance of the second electrode layer 134 was about 100Ω / □.

<Formation of deterioration prevention layer>
Subsequently, an antimony tin oxide particle dispersion was applied as a deterioration preventing layer 135 on the second electrode layer 134 by a spin coating method. Then, a nanostructured semiconductor material composed of an antimony tin oxide particle film having an average thickness of 1.0 μm was formed by performing an annealing treatment at 120 ° C. for 15 minutes.

<Electrolyte filling>
Tetrabutylammonium perchlorate as an electrolyte, dimethyl sulfoxide and polyethylene glycol (weight average molecular weight: 200) as a solvent were mixed at a mass ratio of 12:54:60, and 0.5% by mass as an oxidizing agent was mixed therewith. Tris (4-bromophenyl) aminium hexachloroantimonate was added to obtain an electrolytic solution. Then, the light control lens formed up to the deterioration preventing layer 135 was immersed for 1 minute, and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

<Formation of protective layer>
Furthermore, an ultraviolet curable adhesive (SD-17, manufactured by DIC Corporation) was spin-coated, and the protective layer 136 was formed to have an average thickness of about 3 μm by curing by ultraviolet light irradiation. Thereby, the electrochromic light control lens 110 shown in FIG. 4 was obtained.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1, and repeated driving of erasing and decoloring 10,000 times. The L ^* value at the time of erasing immediately after the start is 81.5, the L ^* value at the time of erasing at the end of 10,000 times is 80.3, and the difference between them (an indicator of the degree of deterioration coloring) is 1. .2 was very small, and almost no deterioration coloring was observed even in actual visual observation.

-Light resistance-
L when a color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic light control lens produced in the same manner as in Example 5. ^{* The} value was 26.9. This light control lens was irradiated with xenon lamp light at 50,000 Lx for 100 hours, and then applied again (constant current application: -0.3 mA / cm ² , application time: 1 second) to develop color L ^* The value was 28.1, and the difference between them (an indicator of the degree of photodegradation) was as small as 1.2, and even when visually observed, no difference in color density was felt.
From the above results, it was confirmed that the electrochromic light control lens of Example 5 hardly caused deterioration coloring due to repeated driving, and hardly caused a decrease in color density due to light deterioration.

(Example 6)
<Production of electrochromic light control lens>
In Example 5, except that the oxidizing agent added to the electrolyte layer composition was tris (2,2′-bipyridine) cobalt (III) tri (trifluoromethanesulfonimide), An electrochromic light control lens was produced.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1, and repeated driving of erasing and decoloring 10,000 times. The L ^* value at the time of erasing immediately after the start is 82.3, the L ^* value at the time of erasing at the end of 10,000 times is 81.2, and the difference between them (an indicator of the degree of deterioration coloring) is 1. .1 and very little deterioration coloring was observed even in actual visual observation.

-Light resistance-
When another color was produced by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic light control lens produced in exactly the same manner as in Example 6. ^{* The} value was 26.7. This light control lens was irradiated with xenon lamp light at 50,000 Lx for 100 hours, and then applied again (constant current application: -0.3 mA / cm ² , application time: 1 second) to develop color L ^* The value was 28.0, and the difference between them (an indicator of the degree of photodegradation) was as small as 1.3. Even when actually observed visually, no difference in color density was felt.
From the above results, it was confirmed that the electrochromic light control lens of Example 6 hardly caused deterioration coloring due to repeated driving and hardly caused a decrease in color density due to light deterioration.

(Comparative Example 3)
<Production of electrochromic light control lens>
In Example 5, an electrochromic light control lens was produced in the same manner as in Example 5 except that no oxidizing agent was added to the electrolyte layer composition.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and 10,000 times of color development / erasing repeated driving was performed. The L ^* value at the time of erasing immediately after the start is 81.2, the L ^* value at the time of erasing at the end of 10,000 times is 53.4, and the difference between them (an indicator of the degree of deterioration coloring) is 27. .8, which was very large, and even with actual visual observation, a remarkable yellowish brown color was observed.

-Light resistance-
L ^* when color was developed by applying (constant current application: −0.3 mA / cm ² , application time: 1 second) to another electrochromic display device produced in exactly the same manner as in Comparative Example 3 ^. The value was 27.1. The hue at the time of color development was good black. When the L ^* value is measured when the dimming lens is irradiated with xenon lamp light at 50,000 Lx for 100 hours and then colored again by applying (coloring voltage: -2 V, application time: 1 second), 28. 2 and the difference between them (an indicator of the degree of photodegradation) was as small as 1.1, and even when actually observed visually, no difference in color density was felt.
From the above results, although the electrochromic light control lens of Comparative Example 3 has good light resistance reflecting that it was manufactured in an environment where air was blocked, remarkably deteriorated coloring occurs due to repeated color development and decoloration. It was confirmed.

Aspects of the present invention are as follows, for example.
<1> A display substrate, a display electrode provided on the display substrate, an electrochromic layer provided in contact with the display electrode, a counter substrate provided to face the display substrate, and the counter A counter electrode provided on the substrate, and an electrolyte layer provided between the display substrate and the counter substrate,
The electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction,
In the electrochromic display element, the electrolyte layer includes an oxidizing agent.
<2> The electrochromic display element according to <1>, further including a deterioration preventing layer provided in contact with the counter electrode, and having a white reflective layer between the electrochromic layer and the deterioration preventing layer. It is.
<3> The electrochromic display element according to any one of <1> to <2>, wherein the electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radically polymerizable compound having a triarylamine. is there.
<4> a display substrate, a display electrode provided on the display substrate, a first electrochromic layer provided so as to be in contact with the display electrode, and a counter substrate provided to face the display substrate A counter electrode provided on the counter substrate, a second electrochromic layer provided in contact with the counter electrode, and an electrolyte layer provided between the display substrate and the counter substrate. Have
The first electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction,
The second electrochromic layer includes an electrochromic compound that develops color by a reduction reaction,
In the electrochromic display element, the electrolyte layer includes an oxidizing agent.
<5> The electrochromic display element according to <4>, wherein the first electrochromic layer is made of a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine.
<6> The electrochromic according to any one of <3> and <5>, wherein the radical polymerizable functional group of the radical polymerizable compound having a triarylamine is at least one of an acryloyloxy group and a methacryloyloxy group. It is a display element.
<7> The radically polymerizable compound having a triarylamine is the electrochromic display element according to any one of the above <3>, <5>, and <6> 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, 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. .
<8> The <3>, <5>, wherein the electrochromic composition containing the radical polymerizable compound having a triarylamine contains another radical polymerizable compound different from the radical polymerizable compound having a triarylamine. <6> and the electrochromic display element according to any one of <7>.
<9> The electrochromic display element according to any one of <1> to <8>, wherein the oxidizing agent is any one of a bromophenylaminium compound and a cobalt complex compound.
<10> The electrochromic display element according to any one of <1> to <9>, wherein the content of the oxidizing agent is 0.1% by mass or more and 5% by mass or less.
<11> The electrochromic display element according to any one of <1> to <10>, a VRAM that stores display data, and a display controller that controls the electrochromic display element based on the display data. It is a display device characterized by comprising.
<12> An information device comprising: the display device according to <11>; and a control device that controls information displayed on the display device.
<13> a step of forming display electrodes on the display substrate;
Forming an electrochromic layer that develops color by an oxidation reaction on the display electrode;
Forming a counter electrode on the counter substrate;
Forming a deterioration preventing layer or an electrochromic layer that develops color by a reduction reaction on the counter electrode;
A method for manufacturing an electrochromic display element, comprising: a step of bonding the display substrate and the counter substrate through an electrolyte layer.
<14> forming a display electrode on the display substrate;
Forming an electrochromic layer that develops color by an oxidation reaction on the display electrode;
Forming a counter electrode on the counter substrate;
Forming a deterioration preventing layer on the counter electrode;
Forming a white reflective layer on the electrochromic layer that develops color by the oxidation reaction or on the deterioration preventing layer;
Bonding the display substrate and the counter substrate through an electrolyte layer;
It is the manufacturing method of the electrochromic display element characterized by including.
<15> a lens, and a thin film dimming function unit laminated on the lens,
The thin film dimming function unit includes a first electrode layer stacked on the lens, a first electroactive layer stacked on the first electrode layer, and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and An electrolyte layer provided in contact with the second electroactive layer,
One of the first electroactive layer and the second electroactive layer is an electrochromic layer containing an electrochromic compound that develops color by an oxidation reaction, and the other is an electrochromic layer that develops color by a degradation prevention layer or a reduction reaction Yes,
In the electrochromic light control lens, the electrolyte layer includes an oxidizing agent.
<16> The electrochromic light control lens according to <15>, wherein the electrochromic layer that develops color by the oxidation reaction is made of a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine. .
<17> The electrochromic light control lens according to any one of <16>, wherein the radical polymerizable functional group of the radical polymerizable compound having a triarylamine is at least one of an acryloyloxy group and a methacryloyloxy group. is there.
<18> The electrochromic light control lens according to any one of <16> and <17>, wherein the radical polymerizable compound having a 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, 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. .
<19> The electrochromic light control lens according to any one of <15> to <18>, wherein the oxidizing agent is any one of a bromophenylaminium compound and a cobalt complex compound.
<20> The electrochromic light control lens according to any one of <15> to <19>, wherein the content of the oxidizing agent is 0.1% by mass or more and 5% by mass or less.

  Any one of the electrochromic display elements according to any one of <1> to <10>, the display device according to <11>, the information device according to <12>, and any one of <13> to <14>. According to the method for producing an electrochromic display element described in 1. and the electrochromic light control lens described in any one of <15> to <20>, the above-described problems are solved and the object of the present invention is achieved. can do.

DESCRIPTION OF SYMBOLS 1 Display substrate 2 Display electrode 3 Counter substrate 4 Counter electrode 5 Electrolytic layer 6 Electrochromic layer 7 Deterioration prevention layer 8 White reflective layer 9 Electrochromic layer 20 Electrochromic display element 21 Electrochromic display element 100 Information apparatus (electronic book reader)
101 Display (Discoloration: constant current application: 0.3 mA / cm ² , application time: 1 second)
102 Control device (main controller)
110, 151 Electrochromic light control lens 113 Display controller 114 VRAM
DESCRIPTION OF SYMBOLS 120 Lens 130 Thin film light control function part 131 1st electrode layer 132 Electrochromic layer 133 Insulating porous layer 134 2nd electrode layer 135 Deterioration prevention layer 136 Protective layer 150 Electrochromic light control glasses 152 Eyeglass frame 153 Switch 154 Power supply

JP 2003-121883 A JP 2006-106669 A JP 2010-33016 A JP 2012-137736 A JP 2015-14743 A

Claims (13)

A display substrate, a display electrode provided on the display substrate, an electrochromic layer provided in contact with the display electrode, a counter substrate provided to face the display substrate, and the counter substrate A counter electrode provided, and an electrolyte layer provided between the display substrate and the counter substrate,
The electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction,
The electrochromic display element, wherein the electrolyte layer contains an oxidizing agent.   The electrochromic display element according to claim 1, further comprising a deterioration preventing layer provided so as to be in contact with the counter electrode, and having a white reflective layer between the electrochromic layer and the deterioration preventing layer.   The electrochromic display element according to claim 1, wherein the electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radical polymerizable compound having a triarylamine. A display substrate; a display electrode provided on the display substrate; a first electrochromic layer provided in contact with the display electrode; a counter substrate provided to face the display substrate; A counter electrode provided on the substrate, a second electrochromic layer provided in contact with the counter electrode, and an electrolyte layer provided between the display substrate and the counter substrate,
The first electrochromic layer includes an electrochromic compound that develops color by an oxidation reaction,
The second electrochromic layer includes an electrochromic compound that develops color by a reduction reaction,
The electrochromic display element, wherein the electrolyte layer contains an oxidizing agent.   The electrochromic display element according to claim 4, wherein the first electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radical polymerizable compound having a triarylamine.   The electrochromic display element according to claim 1, wherein the oxidizing agent is any one of a bromophenylaminium compound and a cobalt complex compound.   The electrochromic display element according to claim 1, a VRAM that stores display data, and a display controller that controls the electrochromic display element based on the display data. Display device.   An information device comprising: the display device according to claim 7; and a control device that controls information displayed on the display device. Forming a display electrode on the display substrate;
Forming an electrochromic layer that develops color by an oxidation reaction on the display electrode;
Forming a counter electrode on the counter substrate;
Forming a deterioration preventing layer or an electrochromic layer that develops color by a reduction reaction on the counter electrode;
And a step of bonding the display substrate and the counter substrate through an electrolyte layer. A method for manufacturing an electrochromic display element. Forming a display electrode on the display substrate;
Forming an electrochromic layer that develops color by an oxidation reaction on the display electrode;
Forming a counter electrode on the counter substrate;
Forming a deterioration preventing layer on the counter electrode;
Forming a white reflective layer on the electrochromic layer that develops color by the oxidation reaction or on the deterioration preventing layer;
Bonding the display substrate and the counter substrate through an electrolyte layer;
The manufacturing method of the electrochromic display element characterized by including. A lens, and a thin-film light control function unit laminated on the lens,
The thin film dimming function unit includes a first electrode layer stacked on the lens, a first electroactive layer stacked on the first electrode layer, and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and An electrolyte layer provided in contact with the second electroactive layer,
One of the first electroactive layer and the second electroactive layer is an electrochromic layer containing an electrochromic compound that develops color by an oxidation reaction, and the other is an electrochromic layer that develops color by a degradation prevention layer or a reduction reaction Yes,
The electrochromic light control lens, wherein the electrolyte layer contains an oxidizing agent.   The electrochromic light control lens according to claim 11, wherein the electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radical polymerizable compound having triarylamine. The electrochromic light control lens according to claim 11, wherein the oxidizing agent is any one of a bromophenylaminium compound and a cobalt complex compound.