JP2015096879A - Electrochromic device and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic device excellent in durability and capable of operating stably.SOLUTION: An electrochromic device 10 comprises: a first electrode layer 12; a first electroactive layer in contact with the frist electrode layer; a second electrode layer 15 opposite to the first electrode layer and having a through hole formed therein; a second porous electroactive layer in contact with the second electrode layer; and electrolyte embedded between the first electrode layer and the second electrode layer, and in contact with the first electroactive layer and the second electroactive layer. At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer 13, and the other is either one of the electrochromic layer or a deterioration prevention layer. The first electrode layer and the second electrode layer respectively have inner surfaces facing each other and outer surfaces opposite the inner surfaces. The first electrode layer has a support on the outer surface, and the second electrode layer has at least an inorganic protective layer made of an inorganic material on the outer surface.

Description

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

A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. A device using this electrochromism is an electrochromic device. Many studies have been conducted on electrochromic devices to date that applications derived from the characteristics of electrochromism can be realized.
Electrochromic materials used in electrochromic devices include organic materials and inorganic materials. Organic materials are promising as a color display device because they can produce various colors depending on their molecular structures, but they have problems in durability because they are organic materials.
On the other hand, although inorganic materials are achromatic, the stability of the materials is superior to that of organic materials, and practical application to light control glass and ND filters is being studied. However, since protons are involved in the electrochromic reaction mechanism, it is necessary to seal moisture.
These electrochromic materials are generally formed between two opposing electrodes, and undergo an oxidation-reduction reaction in a configuration in which an electrolyte layer capable of ion conduction is filled between the electrodes. For this reason, an electrochromic device is usually produced by forming an electrochromic material between two opposing electrodes and then laminating them through an ion conductive electrolyte layer.

  However, if an electrochromic device can be manufactured without a bonding process, the device can be easily formed on various parts such as curved surfaces, so the application range is widened and a support on one side becomes unnecessary. Although it can be produced at low cost, it has been difficult to form an electrochromic device on a support by a thin film process in the prior art.

That is, when an electrode or the like is formed on the electrolyte layer in order to omit the bonding process, it cannot be laminated on the liquid electrolyte, so that the electrolyte needs to be solidified. As an attempt to solidify the electrolyte, it has been proposed to use a polymer solid electrolyte. Specific examples thereof include a solid solution of a matrix polymer containing an oxyethylene chain or an oxypropylene chain and an inorganic salt. Although these are completely solid and excellent in workability, they have a practical problem that their ionic conductivity is several orders of magnitude lower than that of a normal non-aqueous electrolyte.
Further, in order to improve the electrical conductivity of the polymer solid electrolyte, a method of dissolving an organic electrolyte in a polymer to make it semi-solid (see Patent Document 1), or a liquid monomer added with an electrolyte is polymerized. However, a method for producing a crosslinked polymer containing an electrolyte has been proposed, but it has not reached a practical level.

In addition to the problem of ionic conductivity, when an organic material layer is used as the electrolyte layer, there is a problem that the electric resistance of the electrode layer formed on the electrolyte layer tends to be high, and the redox drive cannot be normally performed. In particular, when an oxide layer such as ITO, SnO ₂ , or AZO formed by vacuum film formation, which is generally employed as a transparent electrode, is formed on the surface of the organic film by a technique such as sputtering, It is difficult to achieve both conductivity.

On the other hand, when an inorganic material layer is used as the all-solid electrolyte layer, the process temperature is high and the organic material cannot withstand, so the electrochromic material is limited to an inorganic compound. For example, in an inorganic electrochromic compound, in an electrochromic device having a structure in which a reduced color layer and an oxidized color layer are disposed opposite to each other with a solid electrolyte layer interposed therebetween, the reduced color layer is composed of a material containing tungsten oxide and titanium oxide. The oxidation coloring layer is made of a material containing nickel oxide, and a metal oxide or metal other than nickel oxide or a metal oxidation other than nickel oxide is formed between the oxidation coloring layer and the solid electrolyte layer. An electrochromic device has been proposed in which a transparent intermediate layer composed mainly of a composite of an object and a metal is disposed (see Patent Document 2).
According to this proposal, it is described that repeating characteristics and responsiveness are improved by forming an intermediate layer, and it is possible to perform color-decoloring driving within a few seconds.
However, the structure is complicated and it is difficult to increase the size of the inorganic electrochromic compound layer by vacuum film formation, which causes a cost increase. In addition, inorganic electrochromic materials have a problem in color control. In addition, since the temperature of the manufacturing process is high, it is necessary to use glass or the like as a support, and there is a problem that the application range of applications is limited.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides an electrochromic device that can be manufactured without a process in which an electrochromic material is formed between two opposing electrodes and then bonded via an electrolyte layer, and has excellent durability and stable operation. The task is to do.

The electrochromic device of the present invention as a means for solving the above problems includes a first electrode layer,
A first electroactive layer in contact with the first electrode layer;
A second electrode layer facing the first electrode layer and having a through hole formed thereon;
A second electroactive layer that is porous in contact with the second electrode layer;
An electrolyte filled between the first electrode layer and the second electrode layer and in contact with the first electroactive layer and the second electroactive layer;
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer;
Each of the first electrode layer and the second electrode layer has an inner surface that is a surface facing each other, and an outer surface that is a surface opposite to the inner surface,
An electrochromic device having a support on the outer surface of the first electrode layer,
At least an inorganic protective layer made of an inorganic material is provided on the outer surface of the second electrode layer.

  According to the present invention, the above-mentioned problems can be solved and the object can be achieved, and the electrochromic material is formed between two opposing electrodes and can be manufactured without a process of bonding via an electrolyte layer. Therefore, it is possible to provide an electrochromic device having excellent durability and stable operation.

FIG. 1 is a schematic cross-sectional view showing an example of the electrochromic device according to the first embodiment. FIG. 2 is a schematic cross-sectional view showing an example of the electrochromic device according to the second embodiment. FIG. 3 is a schematic cross-sectional view showing an example of the electrochromic device according to the third embodiment. FIG. 4 is a schematic cross-sectional view showing an example of the electrochromic device according to the fourth embodiment. FIG. 5 is a schematic cross-sectional view showing an example of an electrochromic device according to a fifth embodiment. FIG. 6 is a schematic cross-sectional view showing an example of an electrochromic device according to a sixth embodiment. FIG. 7 is a schematic cross-sectional view showing an example of an electrochromic device according to a seventh embodiment. FIG. 8 is a schematic cross-sectional view showing an example of an electrochromic device according to an eighth embodiment. FIG. 9 is a schematic cross-sectional view showing the electrochromic device of Comparative Example 1. FIG. 10 is a schematic cross-sectional view showing an electrochromic device of Comparative Example 2. FIG. 11 is a schematic cross-sectional view showing an electrochromic device of Comparative Example 3. FIG. 12 is a schematic cross-sectional view showing an electrochromic device of Comparative Example 5.

(Electrochromic device and method of manufacturing electrochromic device)
The electrochromic device of the present invention includes a first electrode layer,
A first electroactive layer in contact with the first electrode layer;
A second electrode layer facing the first electrode layer and having a through hole formed thereon;
A second electroactive layer that is porous in contact with the second electrode layer;
An electrolyte filled between the first electrode layer and the second electrode layer and in contact with the first electroactive layer and the second electroactive layer;
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer;
Each of the first electrode layer and the second electrode layer includes an inner surface that is a surface facing each other, and an outer surface that is a surface opposite to the inner surface,
A support is provided on the outer surface of the first electrode layer, and other members are provided as required.
The electrochromic device has at least an inorganic protective layer made of an inorganic material on the outer surface of the second electrode layer.
The outer surface of the second electrode layer includes at least the outer surface of the second electrode layer, and includes a support, a first electrode layer, a first electroactive layer, a second electrode layer, and a second electroactive layer. It is the meaning including the outer peripheral surface of the laminated body containing these.

The method for producing an electrochromic device of the present invention includes a step of sequentially laminating a first electrode layer and a first electroactive layer on a support;
Laminating a second electrode layer in which a through hole is formed on the first electroactive layer so as to face the first electrode layer via an insulating porous layer;
Laminating a second electroactive layer in contact with the second electrode layer;
Filling a predetermined region between the first electrode layer and the second electrode layer with an electrolyte from the through hole;
Semi-solidifying the electrolyte;
A step of laminating an inorganic protective layer made of an inorganic material on the surface of the second electrode layer not facing the first electrode layer, and further including other steps as necessary.
In the method for manufacturing an electrochromic device, at least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer. .

In order to solve the above problems, the present inventors have already provided a first electrode, a second electrode formed so as to face the first electrode, and a contact with the first electrode. An electrochromic layer, a deterioration preventing layer provided in contact with the second electrode, and a space between the first electrode and the second electrode, and in contact with the electrochromic layer and the deterioration preventing layer. And a through hole is formed in at least one of the first electrode layer and the second electrode layer, and an electrode provided in the electrode in which the through hole is formed. The chromic layer or the deterioration preventing layer is formed on the outer side between the pair of opposed electrodes, and is supported only on either the outer side of the first electrode layer or the outer side of the second electrode layer. Electro with the body It has been proposed for Mick device (Japanese Patent Application No. 2013-85526 specification).
According to this proposed electrochromic device, it can be manufactured without a bonding process, can be manufactured at a low cost, and can be easily formed on various parts such as curved surfaces, so that the application range is widened and one side can be formed. This support can be produced at low cost.
However, an electrochromic device manufactured without a bonding process has problems in terms of repeated durability and storage stability against oxygen and humidity in order to ensure practical reliability. That is, since the support is used only on one side, there arises a problem due to intrusion of oxygen or moisture from the opposite surface of the support. Conventionally, in an electrochromic device manufactured by a bonding method, a sealing method for preventing leakage of an electrolyte solution at an end portion of a bonded substrate has been studied, but has not been solved.
Therefore, as a result of further diligent investigations by the present inventors, the first electrode layer, the first electroactive layer in contact with the first electrode layer, the first electrode layer opposed to the first electrode layer, and Between the 2nd electrode layer in which the through-hole was formed, the 2nd electroactive layer which touches the 2nd electrode layer, and the 1st electrode layer and the 2nd electrode layer An electrolyte that is filled and is in contact with the first electroactive layer and the second electroactive layer, wherein at least one of the first electroactive layer and the second electroactive layer is An inner surface that is an electrochromic layer, the other is either an electrochromic layer or a deterioration preventing layer, and each of the first electrode layer and the second electrode layer faces each other; And an outer surface that is the opposite surface,
An electrochromic material is formed between two opposing electrodes by having a support on the outer surface of the first electrode layer and at least an inorganic protective layer made of an inorganic material on the outer surface of the second electrode layer. After that, it has been found that it can be produced without a process of bonding through an electrolyte layer, has excellent durability, can operate stably, and can improve storage stability against oxygen and humidity.

  Hereinafter, embodiments will be described with reference to the drawings. In addition, in each drawing, the same code | symbol is attached | subjected to the same component and the overlapping description may be abbreviate | omitted.

<First Embodiment>
FIG. 1 is a cross-sectional view illustrating an electrochromic device according to the first embodiment. Referring to FIG. 1, an electrochromic device 10 includes a support 11, a first electrode layer 12, an electrochromic layer 13, an insulating porous layer 14, and a second electrode that are sequentially stacked on the support 11. It has the layer 15, the deterioration prevention layer 16, the organic protective layer 171, the inorganic protective layer 172, and electrolyte (not shown).

  In the electrochromic device 10, a first electrode layer 12 is provided on a support 11, and an electrochromic layer 13 is provided in contact with the first electrode layer 12. Furthermore, a second electrode layer 15 is provided on the electrochromic layer 13 so as to face the first electrode layer 12 with an insulating porous layer 14 interposed therebetween. In addition, when the inner surface of the opposing surface of the first electrode and the second electrode is the inner surface and the opposite side is the outer surface, the support 11 is provided on the outer surface of the first electrode layer 12. No support is provided on the outer surface of the electrode layer 15.

  The insulating porous layer 14 is provided to insulate the first electrode layer 12 and the second electrode layer 15, and the insulating porous layer 14 contains insulating metal oxide fine particles. The insulating porous layer 14 sandwiched between the first electrode layer 12 and the second electrode layer 15 is filled with an electrolyte. The second electrode layer 15 has a large number of through holes penetrating in the thickness direction. A deterioration preventing layer 16 is provided outside the second electrode layer 15, and the deterioration preventing layer 16 contains semiconductive metal oxide fine particles. An organic protective layer 171 and an inorganic protective layer 172 are provided on the deterioration preventing layer 16.

  The manufacturing process of the electrochromic device 10 includes a step of sequentially laminating the first electrode layer 12 and the electrochromic layer 13 on the support 11, and a first step through the insulating porous layer 14 on the electrochromic layer 13. A step of laminating the second electrode layer 15 having through holes formed so as to face the electrode layer 12, a step of laminating the deterioration preventing layer 16 on the second electrode layer 15, and the first electrode layer 12 And filling the insulating porous layer 14 sandwiched between the second electrode layer 15 with an electrolyte from the through-hole formed in the second electrode layer 15 via the deterioration preventing layer 16, and making it semi-solid And a step of forming the organic protective layer 171 and a step of forming the inorganic protective layer 172.

  That is, the through hole formed in the second electrode layer 15 is an injection hole when the insulating porous layer 14 is filled with the electrolyte in the manufacturing process of the electrochromic device 10. As described above, when the second electrode layer is formed on the electrolyte layer in order to omit the bonding process, various problems arise, but through holes are formed on the insulating porous layer 14. The second electrode layer 15 is laminated first, and after the step of laminating the deterioration preventing layer 16, an electrolyte is applied to the insulating porous layer 14 through the through holes formed in the deterioration preventing layer 16 and the second electrode layer 15. By injecting, these problems can be avoided.

In the electrochromic device 10, when a voltage is applied between the first electrode layer 12 and the second electrode layer 15, the electrochromic layer 13 undergoes an oxidation-reduction reaction due to transfer of electric charges, thereby causing a color change.
Thus, in the electrochromic device according to the first embodiment, the through hole formed in the second electrode layer in the insulating porous layer sandwiched between the first electrode layer and the second electrode layer. It is possible to fill the electrolyte. Therefore, it is possible to form the second electrode layer having a low resistance before filling the electrolyte, and the performance of the electrochromic device can be improved.

In addition, since an electrochromic device can be manufactured without a bonding process, an electrochromic device can be formed at various sites, and the application range of the electrochromic device can be expanded.
Furthermore, since a support is not provided outside the second electrode layer (since a support on one side is unnecessary), an electrochromic device excellent in productivity (enlargement) can be provided. Further, it is not necessary to use an all-solid electrolyte layer, and it is possible to realize an electrochromic device having excellent responsiveness and excellent color characteristics by using an organic electrochromic material.

In addition, since the deterioration preventing layer is provided on the second electrode layer, an electrochromic device that operates repeatedly and stably can be realized. Conventionally, the deterioration preventing layer had to be formed between the opposing electrodes, but in the present invention, since the deterioration preventing layer is formed in contact with the electrode in which the through hole is formed, The effect can be obtained even if a deterioration preventing layer is formed outside the second electrode layer. This is because ions can move between the front and back of the electrode through the through hole.
Furthermore, since the organic protective layer and the inorganic protective layer are provided in this order on the outermost layer, the durability of the electroclock device is improved and stable operation can be obtained.

  Hereinafter, each component which comprises the electrochromic apparatus 10 which concerns on 1st Embodiment is demonstrated in detail.

<< Support >>
The support 11 has a function of supporting the first electrode layer 12, the electrochromic layer 13, the insulating porous layer 14, and the second electrode layer 15. If it can support each of these layers, there will be no restriction | limiting in particular, As the said support body 11, an organic material or an inorganic material can be used.

  As the support 11, for example, a glass substrate such as alkali-free glass, borosilicate glass, float glass, or soda lime glass can be used. Moreover, as the support body 11, you may use resin substrates, such as a polycarbonate resin, an acrylic resin, polyethylene, polyvinyl chloride, polyester, an epoxy resin, a melamine resin, a phenol resin, a polyurethane resin, a polyimide resin, for example. Furthermore, a metal substrate such as aluminum, stainless steel, or titanium may be used as the support 11.

  Note that when the electrochromic device 10 is a reflective display device that is visible from the second electrode layer 15 side, the transparency of the support 11 is not necessary. Further, when a conductive metal material is used as the support 11, the support 11 can also serve as the first electrode layer 12. Further, the surface of the support 11 may be coated with a transparent insulating layer, an antireflection layer or the like in order to improve the water vapor barrier property, gas barrier property, and visibility.

<< first electrode layer and second electrode layer >>
The material of the first electrode layer 12 and the second electrode layer 15 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 inorganic materials such as tin-doped indium oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), and antimony-doped tin oxide (hereinafter referred to as ATO). In particular, indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) and zinc oxide (hereinafter referred to as Zn oxide) formed by vacuum film formation can be used. It is preferable to use an inorganic material containing any one of the above.
The In oxide, Sn oxide, and Zn oxide are materials that can be easily formed by a sputtering method, and can obtain good transparency and electrical conductivity. Particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO. Furthermore, the electrode is made of transparent silver, gold, carbon nanotubes, other highly conductive non-permeable materials, and the like formed into a fine network to have transmittance.

The thickness of each of the first electrode layer 12 and the second electrode layer 15 is adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 13 is obtained. When ITO is used as the material of the first electrode layer 12 and the second electrode layer 15, the thickness of each of the first electrode layer 12 and the second electrode layer 15 is, for example, about 50 nm to 500 nm. Can do.
When used as a dimming mirror, either the first electrode layer 12 or the second electrode layer 15 may have a reflective function. In that case, the first electrode layer 12 and the second electrode layer 15 A metal material can be included as the material of the second electrode layer 15. Examples of the metal material include Pt, Ag, Au, Cr, rhodium, alloys thereof, and laminates thereof.

As a manufacturing method of each of the first electrode layer 12 and the second electrode layer 15, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used.
There is no particular limitation as long as each material of the first electrode layer 12 and the second electrode layer 15 can be formed by coating. For example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar Coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing Various printing methods such as a printing method and an inkjet printing method can be used.

  In the present embodiment, the second electrode layer 15 has a large number of fine through holes penetrating in the thickness direction. For example, fine through holes can be provided in the second electrode layer 15 by the method described below. That is, it is possible to use a method in which a layer having projections and depressions is formed in advance as a base layer before forming the second electrode layer 15, and the second electrode layer 15 having projections and depressions is used as it is.

  A method of forming a convex structure such as a micro pillar before forming the second electrode layer 15 and removing the convex structure after forming the second electrode layer 15 may be used. Further, before forming the second electrode layer 15, a foaming polymer or the like is sprayed, and after the second electrode layer 15 is formed, a process such as heating or degassing is performed to foam. May be. Note that a method of directly irradiating various radiations to the second electrode layer 15 to form pores may be used.

  As a method of forming fine through holes in the second electrode layer 15, a colloidal lithography method is preferable. In the colloidal lithography method, fine particles are dispersed in the lower layer on which the second electrode layer 15 is laminated, and the second electrode layer 15 and the second electrode layer 15 are formed on the surface on which the fine particles are dispersed using the dispersed fine particles as a mask. In this method, patterning is performed by forming a conductive film and then removing the conductive film together with the fine particles.

A fine through hole can be easily formed in the second electrode layer 15 by the colloidal lithography method. In particular, by setting the diameter of the fine particles to be dispersed to be equal to or greater than the thickness of the second electrode layer 15, the through holes can be easily formed in the second electrode layer 15. Further, the density and area of the fine through holes can be easily adjusted by changing the concentration of the fine particle dispersion to be dispersed and the particle diameter of the fine particles.
Furthermore, since the in-plane uniformity of the colloidal mask can be easily increased by the dispersion method of the fine particle dispersion, it is possible to increase the in-plane uniformity of the color density of the electrochromic layer 13 and improve the display performance. It becomes. Hereinafter, specific contents of the colloidal lithography method will be described.

The material of the fine particles of colloidal mask used in colloidal lithography, but may be used what if it is possible to form fine through-holes in the second electrode layer 15, for example, SiO ₂ fine particles is Economic advantage. Further, the dispersion used at the time of the colloidal mask spraying is preferably good dispersibility, for example, in the case of using the SiO ₂ fine particles as fine particles comprising colloidal mask may be used a dispersion of water-based.
However, when there is a possibility of damaging the lower layer of the colloidal mask such as the electrochromic layer 13 or the insulating porous layer 14, the SiO ₂ fine particles that are surface-treated so as to be dispersed in a non-aqueous solvent as fine particles to be a colloidal mask are used. It is preferable to use it. In this case, a non-aqueous dispersion can be used as a dispersion used when colloidal mask is dispersed.

  The particle diameter (diameter) of the fine particles serving as the colloidal mask is preferably not less than the thickness of the second electrode layer 15 that forms fine through holes and not more than the thickness of the electrochromic layer 13. The colloidal mask can be removed by an ultrasonic irradiation method, a tape peeling method, or the like, but it is preferable to select a method with less damage to the lower layer. As another removal method of the colloidal mask, dry cleaning by spraying fine particles or the like is also possible.

  When removing a colloidal mask using a tape peeling method, the thickness of the adhesive layer in a general tape is 1 μm or more, and the colloidal mask is often buried. In this case, since the adhesive layer contacts the surface of the second electrode layer 15, it is preferable to use a tape with little adhesive residue. When removing a colloidal mask using an ultrasonic irradiation method, it is preferable to use a solvent with little damage to each functional layer already formed as the solvent to be immersed.

As a method of forming a fine through hole in the second electrode layer 15, 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, a desired photoresist pattern is first formed, then a second electrode layer 15 is formed, and then the photoresist pattern is removed to remove unnecessary portions on the photoresist pattern. This is a method of forming fine through holes in the electrode layer 15.
When a fine through hole is formed in the second electrode layer 15 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.
Examples of the negative photoresist include polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, and polyhydroxystyrene. / Melamine / photoacid generator, methylated melamine resin, methylated urea resin and the like.
Further, it is possible to form fine through holes in the second electrode layer 15 by a processing apparatus using laser light. In general, when laser processing is used, the diameter of fine through holes to be formed is 15 μm or more.

  The diameter of the fine through hole provided in the second electrode layer 15 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 may be a problem that the permeation of electrolyte ions is deteriorated. On the other hand, when the diameter of the fine through-hole is larger than 100 μm, it is at a level that can be visually observed (the size of one pixel electrode in a normal display), which causes a problem in display performance directly above the fine through-hole.

  Although the ratio (hole density) of the hole area with respect to the surface area of the 2nd electrode layer 15 of the fine through-hole provided in the said 2nd electrode layer 15 can be set suitably, for example, 0.01%-40 %. If the hole density is too high, the surface resistance of the second electrode layer 15 is increased, which causes a problem that a chromic defect is generated due to an increase in the area of the area where the second electrode layer 15 is not provided. On the other hand, when the hole density is too low, the permeability of the electrolyte ions is deteriorated, so that a problem that causes a problem in driving similarly occurs.

<< Electrochromic layer >>
The electrochromic layer 13 includes an electrochromic material, and further includes other components as necessary.
As the electrochromic material, either an inorganic electrochromic compound or an organic electrochromic compound may be used.
In addition, a conductive polymer known to exhibit electrochromism can also be used.

Examples of the inorganic electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide.
Examples of the organic electrochromic compound include viologen, rare earth phthalocyanine, and styryl.
Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, or derivatives thereof.

As the electrochromic layer 13, it is preferable to use a structure in which an organic electrochromic compound is supported on conductive or semiconductive fine particles.
Specifically, it is a structure in which fine particles having a particle size of about 5 nm to 50 nm are sintered on the electrode surface, and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, silanol group or the like is adsorbed on the surface of the fine particles. .
The structure utilizes a large surface effect of fine particles and efficiently injects electrons into the organic electrochromic compound. Therefore, the structure responds faster than a conventional electrochromic display element.
Furthermore, since a transparent film can be formed as a display layer by using fine particles, a high color density of the electrochromic dye can be obtained.
A plurality of types of organic electrochromic compounds can be supported on conductive or semiconductive fine particles.

Examples of the electrochromic material include polymer-based and dye-based electrochromic compounds such as azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styryl spiropyran, spirooxazine, spirothiopyran, Thioindigo, tetrathiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorane And low molecular organic electrochromic compounds such as fulgide, benzopyran, and metallocene, and conductive polymer compounds such as polyaniline and polythiophene. These may be used individually by 1 type and may use 2 or more types together.
Among these, a viologen compound or a dipyridine compound is preferable from the viewpoint of a low color developing / erasing potential and a good color value.

Examples of the viologen compound include compounds described in Japanese Patent No. 39555641 and Japanese Patent Application Laid-Open No. 2007-171781.
Examples of the dipyridine-based compound include compounds described in JP 2007-171781 A and JP 2008-116718 A.
Among these, a dipyridine compound represented by the following general formula 1 is preferable from the viewpoint of exhibiting a good color value.

[General Formula 1]

In the general formula 1, R1 and R2 each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, and at least one of R1 and R2 is COOH, PO ( OH) ₂ and Si (OC _k H _{2k + 1} ) ₃ (where k represents 1 to 20).
In the general formula 1, X represents a monovalent anion. The monovalent anion is not particularly limited as long as it forms a stable pair with the cation moiety, and can be appropriately selected according to the purpose. For example, Br ion (Br ⁻ ), Cl ion (Cl ⁻ ), ClO ₄ ions (ClO ₄ ⁻ ), PF ₆ ions (PF ₆ ⁻ ), BF ₄ ions (BF ₄ ⁻ ), and the like.
In the general formula 1, n, m, and l represent 0, 1, or 2. A, B, and C each independently represent a C 1-20 alkyl group, aryl group, or heterocyclic group that may have a substituent.

Examples of the metal complex-based and metal oxide-based electrochromic compounds include inorganic electrochromic compounds such as titanium oxide, vanadium oxide, tungsten oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue.
There is no restriction | limiting in particular as electroconductive or semiconductive fine particle, Although it can select suitably according to the objective, A metal oxide is preferable.
Examples of the metal oxide material include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, and calcium titanate. , Calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
In view of electrical properties such as electrical conductivity and physical properties such as optical properties, one selected from titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, tungsten oxide, or When these mixtures are used, it is possible to display colors with excellent response speed of color development and decoloration.
In particular, when titanium oxide is used, it is possible to display a color with an excellent response speed of color development and decoloration.
In addition, the shape of the conductive or semiconductive fine particles is not particularly limited, but a shape having a large surface area per unit volume (hereinafter referred to as a specific surface area) is used in order to efficiently carry the electrochromic compound. .
For example, when the fine particle is an aggregate of nanoparticles, it has a large specific surface area, so that the electrochromic compound is more efficiently supported and the display contrast ratio of color development and decoloration is excellent.

  In addition, a polymer-based coloring material can be used. Specifically, polypyrrole-based, polythiophene-based, polyaniline-based, or derivatives thereof such as a hybrid polymer of a metal complex and an organic ligand can be used. Since these materials can provide a high-speed chromic operation simply by being applied on the electrode, the number of members can be reduced by not using semiconductive fine particles. When these are used as the second electroactive layer, if necessary, the film density may be adjusted so as not to inhibit the injection of the electrolyte, or through holes may be formed by laser processing or the like.

There is no restriction | limiting in particular in the thickness of the said electrochromic layer, Although it can select suitably according to the objective, 0.05 micrometer-5.0 micrometers are preferable. When the thickness is less than 0.05 μm, it may be difficult to obtain a color density, and when it exceeds 5.0 μm, the manufacturing cost increases and the visibility may be easily lowered due to coloring.
The electrochromic layer 13 and the conductive or semiconductive fine particle layer can be formed by vacuum film formation, but it is preferably formed by coating as a particle dispersion paste from the viewpoint of productivity.

<< Insulating porous layer >>
The insulating porous layer 14 has a function of isolating the first electrode layer 12 and the second electrode layer 15 so as to be electrically insulated and holding an electrolyte.
The material of the insulating porous layer 14 is not particularly limited as long as it is porous, but it is an organic material, an inorganic material, or a composite thereof having high insulation and durability and excellent film-forming properties. It is preferable to use a body.

The insulating porous layer 14 may be formed by a sintering method (using fine pores or inorganic particles partially fused by adding a binder or the like, using pores formed between the particles) or extraction. The 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, and then dissolving the organic or inorganic substance with a solvent to obtain pores) can be used.
As the method for forming the insulating porous layer 14, a foaming method in which a polymer is foamed by heating or degassing, or a phase in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. You may use formation methods, such as a conversion method and the radiation irradiation method which irradiates various radiation and forms a pore. Specific examples include a polymer mixed particle film containing metal oxide fine particles (for example, SiO ₂ particles and Al ₂ O ₃ particles) and a polymer binder, a porous organic film (for example, polyurethane resin, polyethylene resin, etc.), Examples thereof include an inorganic insulating material film formed into a porous film.

The unevenness of the insulating porous layer 14 depends on the thickness of the second electrode layer 15. For example, when the thickness of the second electrode layer 15 is 100 nm, the surface roughness of the insulating porous layer 14 is as follows. Must satisfy the requirement of less than 100 nm in average roughness (Ra). When the average roughness exceeds 100 nm, the surface resistance of the second electrode layer 15 is greatly lost, causing display defects. The thickness of the insulating porous layer 14 can be, for example, about 0.5 μm to 3 μm.
The insulating porous layer 14 is preferably used in combination with an inorganic film. This is because when the second electrode layer 15 formed on the surface of the insulating porous layer 14 is formed by sputtering, damage to the organic material of the insulating porous layer 14 and the electrochromic layer 13 which are lower layers is prevented. This is to reduce.

The inorganic film is not particularly limited and may be appropriately selected depending on the purpose, for example, although the insulating transparent material such as SiO _2, Al ₂ O ₃ is preferred, that the further use of the material containing ZnS it can. ZnS has a feature that it can be deposited at high speed by sputtering without damaging the electrochromic layer 13 or the like. Furthermore, ZnS—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like may be used as a material containing ZnS as a main component.

Here, the ZnS content is preferably about 50 mol% to 90 mol% in order to maintain good crystallinity when the insulating layer is formed. Therefore, particularly preferable materials are ZnS—SiO ₂ (8/2), ZnS—SiO ₂ (7/3), ZnS, and ZnS—ZnO—In ₂ O 3 —Ga 2 O 3 (60/23/10/7). By using the material as described above as the insulating porous layer 14, 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 16 is to perform a chemical reaction opposite to that of the electrochromic layer 13, and to balance the charge, the first electrode layer 12 and the second electrode layer 15 are corroded by an irreversible oxidation-reduction reaction. It is to suppress deterioration. As a result, the repeated stability of the electrochromic device 10 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 16 is not particularly limited as long as it is a material that plays a role of preventing corrosion of the first electrode layer 12 and the second electrode layer 15 due to irreversible oxidation-reduction reaction. As the material of the deterioration preventing layer 16, 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 coloring of the deterioration preventing layer does not become a problem, the same material as the above-described electrochromic material can be used.

  The deterioration preventing layer 16 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., binders such as acrylic, alkyd, isocyanate, urethane, epoxy, phenol, etc. By fixing to the second electrode layer 15, a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer can be obtained.

  As the material of the deterioration preventing layer 16, a material that maintains a transparent state with charge exchange may be used. For example, conductive polymers such as polypyrrole, polythiophene, polyaniline, or derivatives thereof, hybrid polymers of metal complexes and organic ligands, radical polymers, and the like can be given. When these are used as the second electroactive layer, it is necessary to adjust the film density so as not to inhibit the injection of the electrolyte, or to form a through hole by laser processing or the like. Alternatively, these materials may be used as the electrochromic layer 13, and the organic electrochromic compound supported on the conductive or semiconductive fine particles described above may be used as the deterioration preventing layer 16.

  As the deterioration preventing layer 16, 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 a compound particle or a mixture containing a plurality of them can be used, which is composed of particles having a primary particle diameter of 100 nm or less.

  Furthermore, when using these degradation prevention layers 16, it is preferable that the electrochromic layer 13 is a material which changes from coloring 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 13 undergoes an oxidation reaction, and the drive 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, complex polymers of bis (terpyridine) s and iron ions, and the like.

  As a method for forming the deterioration preventing layer 16, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. The material for the deterioration preventing layer 16 is not particularly limited as long as it can be applied and formed. For example, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire Various methods such as bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing Printing methods can be used.

<< Electrolyte >>
In the present embodiment, the electrolyte (not shown) includes the first electrode layer 12 and the second electrode as an electrolytic solution from a minute through-hole formed in the second electrode layer 15 via the deterioration preventing layer 16. The insulating porous layer 14 disposed between the electrode layer 15 and the electrode layer 15 is filled. That is, the electrolyte (not shown) is filled between the first electrode layer 12 and the second electrode layer 15, is in contact with the electrochromic layer 13, and is formed in the second electrode layer 15. It is provided so as to be in contact with the deterioration preventing layer 16 through the hole.

As the electrolytic solution, a liquid electrolyte such as an ionic liquid or a solution obtained by dissolving a solid electrolyte in a solvent is used.
As an electrolyte material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and supporting salts of alkalis 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. These may be used individually by 1 type and may use 2 or more types together.

The ionic liquid is not particularly limited and may be any substance that is generally studied and reported.
In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.
As the molecular structure, as a cation component, for example, imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt; N, N-dimethylpyridinium salt, Aromatic salts such as pyridinium derivatives such as N, N-methylpropylpyridinium salts; aliphatic quaternary ammonium compounds such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt and triethylhexylammonium salt Can be mentioned.
As the anionic 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, and polyethylene glycol. And alcohols. These may be used individually by 1 type and may use 2 or more types together.

The electrolytic solution does not need to be a low-viscosity liquid, and can take various forms such as a gel, a polymer cross-linking type, and a liquid crystal dispersion type.
The electrolytic solution is preferably formed in a gel or solid form from the viewpoints of improving element strength, improving reliability, and preventing color diffusion.
As a solidification method, it is preferable to hold the electrolyte and the solvent in the polymer resin. This is because high ionic conductivity and solid strength can be obtained.
Further, the polymer resin 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.

The electrolyte can be provided with a function of electrically insulating the first electrode layer and the second electrode layer by being combined and formed so as to fill the porous insulating film.
The material of the porous insulating film is not particularly limited as long as it is porous, but it is an organic material, an inorganic material, or those having high insulating properties, high durability, and excellent film forming properties. The complex of is preferable.
As a method for forming the porous film, a sintering method (using fine particles or inorganic particles that are partially fused by adding a binder or the like and utilizing pores formed between the particles), an extraction method (which can be used as a solvent). After forming a constituent layer with a soluble organic or inorganic substance and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved with a solvent to obtain pores), and the polymer is heated or degassed, etc. Use known forming methods such as foaming method, foaming method, phase change method in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent, and a radiation irradiation method in which various radiations are radiated to form pores. Can do.
Specific examples include a polymer mixed particle film composed of metal oxide fine particles (for example, SiO ₂ particles, Al ₂ O ₃ particles) and a polymer binder, a porous organic film (for example, polyurethane resin, polyethylene resin, etc.), Examples thereof include an inorganic insulating material film formed into a porous film.
There is no restriction | limiting in particular in the thickness of the said porous membrane, Although it can select suitably according to the objective, 100 nm-10 micrometers are preferable.

<< Organic protective layer, inorganic protective layer >>
The role of the organic protective layer and inorganic protective layer is to protect the device from external stress and chemicals in the cleaning process, to prevent leakage of electrolyte, and to operate electrochromic devices such as moisture and oxygen in the atmosphere stably. For example, it is necessary to prevent the entry of unnecessary objects. When moisture and oxygen in the atmosphere suppress intrusion, irreversible oxidative degradation reactions caused by the reaction of the electrochromic layer and degradation prevention layer with oxygen and electrochemical side reactions due to the ingress of moisture are suppressed. The durability against repeated use, deterioration resistance due to light absorption, storage stability, etc. are improved. Further, the organic protective layer and the inorganic protective layer are required to have transparency, surface smoothness, heat resistance, light resistance, and the like.
The organic protective layer and the inorganic protective layer may be alternately laminated twice or more.

By having the organic protective layer, effects such as prevention of electrolyte leakage, protection of functional materials from chemicals such as alcohol and alkali in the external stress and cleaning process, and suppression of intrusion of oxygen and moisture in the atmosphere can be obtained. .
Examples of the material of the organic protective layer include ultraviolet curable resins and thermosetting resins, and specific examples include acrylic resins, urethane resins, and epoxy resins.
As a method for forming the organic protective layer, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used as a dry process. In addition, if each material can be formed by coating, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method 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, an inkjet printing method, or the like can be used.
There is no restriction | limiting in particular in the thickness of the said organic protective layer, Although it can select suitably according to the objective, 0.5 micrometer-200 micrometers are preferable, and 1 micrometer-50 micrometers are more preferable.

The inorganic protective layer is provided mainly in the apparatus in order to more effectively suppress the entry of oxygen and moisture in the atmosphere.
The material for the inorganic protective layer is preferably a transparent material when used as a light control device. Examples of the material for the inorganic protective layer include SiO ₂ , SiN, SiON, Al ₂ O _{3 and the} like.
Examples of the method for forming the inorganic protective layer include a vacuum deposition method, a sputtering method, and an ion plating method.
There is no restriction | limiting in particular in the thickness of the said inorganic protective layer, Although it can select suitably according to the objective, 0.001 micrometer-1 micrometer are preferable and 0.01 micrometer-0.5 micrometer are more preferable.

<< Other layers >>
Examples of the other layers include a hard coat layer for preventing defects due to scratches and peeling, and an AR (Anti-Reflection) coat layer for suppressing reflection. The hard coat layer is formed by applying a solution, and is not particularly limited, such as a UV curable resin or a thermosetting resin, and a general hard coat material for an optical member can be used. Further, the layer may be formed with only the hard coat material and the AR coat material described above.

<Second Embodiment>
In the second embodiment, an electrochromic device having a layer structure different from that of the first embodiment is illustrated. In the second embodiment, description of the same components as those of the already described embodiments may be omitted.

FIG. 2 is a cross-sectional view illustrating an electrochromic device according to the second embodiment. Referring to FIG. 2, the electrochromic device 20 according to the second embodiment is characterized in that the electrochromic layer 13, the insulating porous layer 14, and the deterioration preventing layer 16 are replaced with the insulating porous layer 23. This is different from the electrochromic device 10 according to the first embodiment (see FIG. 1).
The insulating porous layer 23 is provided to insulate the first electrode layer 12 and the second electrode layer 15 from each other, and the insulating porous layer 23 contains insulating metal oxide fine particles. The insulating porous layer 23 sandwiched between the first electrode layer 12 and the second electrode layer 15 is filled with an electrolyte, an electrochromic material, and a deterioration preventing material. That is, in this embodiment, the insulating porous layer 23 functions as an electrochromic layer and a deterioration preventing layer. Therefore, the insulating porous layer 23 may be rephrased as an electrochromic layer.

  The manufacturing process of the electrochromic device 20 includes the steps of laminating the first electrode layer 12 on the support 11 and the first electrode layer 12 on the first electrode layer 12 via the insulating porous layer 23. A step of laminating the second electrode layer 15 having through holes formed so as to face each other, a step of laminating the deterioration preventing layer 16 on the second electrode layer 15, a first electrode layer 12 and a second electrode layer The step of filling the insulating porous layer 23 sandwiched between the electrode layers 15 from the through holes formed in the second electrode layer 15 with the electrolyte, the electrochromic material, and the deterioration preventing material, and the step of making them semi-solid And a step of forming an organic protective layer and a step of forming an inorganic protective layer.

That is, the through hole formed in the second electrode layer 15 is an injection hole when the insulating porous layer 23 is filled with the electrolyte, the electrochromic material, and the deterioration preventing material in the manufacturing process of the electrochromic device 20. . The electrolyte, the electrochromic material, and the deterioration preventing material need to be applied as a solution dissolved in a solvent or the like.
As described above, the electrochromic device according to the second embodiment has the following effects in addition to the effects of the first embodiment. That is, since the layer structure of the electrochromic device is simplified, productivity can be improved.

<Third Embodiment>
In the third embodiment, an electrochromic device having a layer structure different from that of the first embodiment is illustrated. In the third embodiment, the description of the same components as those of the already described embodiments may be omitted.

  FIG. 3 is a cross-sectional view illustrating an electrochromic device according to the third embodiment. Referring to FIG. 3, the electrochromic device 30 according to the third embodiment is different from the electrochromic device 30 according to the first embodiment in that the insulating porous layer 14 is replaced with the insulating porous layer 34. It is different from the chromic device 10 (see FIG. 1).

The insulating porous layer 34 is a layer in which white pigment particles are further contained in the insulating porous layer 14 and functions as a white reflective layer. Examples of the white pigment particles that can be used include titanium oxide, aluminum oxide, zinc oxide, silica, cesium oxide, yttrium oxide, and the like.
As described above, the electrochromic device according to the third embodiment has the following effects in addition to the effects of the first embodiment. That is, a reflective display element can be easily realized by adding white pigment particles to the insulating porous layer to function as a white reflective layer.

<Fourth embodiment>
In the fourth embodiment, an electrochromic device having a layer structure different from that of the first embodiment is illustrated. Note that in the fourth embodiment, the description of the same component as the already described embodiment may be omitted.

  FIG. 4 is a cross-sectional view illustrating an electrochromic device according to the fourth embodiment. Referring to FIG. 4, in the electrochromic device 40 according to the fourth embodiment, a deterioration preventing layer 461 is added between the insulating porous layer 14 and the second electrode layer 15, and the second electrode layer. 15 is different from the electrochromic device 10 (see FIG. 1) according to the first embodiment in that a deterioration preventing layer 462 is also formed on the layer 15.

  As described above, the electrochromic device according to the fourth embodiment has the following effects in addition to the effects of the first embodiment. That is, by forming a deterioration preventing layer between the insulating porous layer and the second electrode layer, a display element with improved repeated stability can be realized.

<Fifth embodiment>
In the fifth embodiment, an electrochromic device having a layer configuration different from that of the first embodiment is illustrated. Note that in the fifth embodiment, description of the same components as those of the above-described embodiment may be omitted.

  FIG. 5 is a cross-sectional view illustrating an electrochromic device according to a fifth embodiment. Referring to FIG. 5, in the electrochromic device 50 according to the fifth embodiment, the first electrode layer 12 and the deterioration preventing layer 56 are sequentially formed on the substrate 11, and the insulating porous layer 14 is formed thereon. A second electrode layer 15 and an electrochromic layer are sequentially formed through the first and second electrodes. These points are different from the electrochromic device 10 according to the first embodiment (see FIG. 1).

  As described above, the electrochromic device according to the fifth embodiment has the following effects in addition to the effects of the first embodiment. That is, damage due to the electrochromic layer stacking process can be suppressed. Conventionally, the electrochromic layer had to be formed between the opposing electrodes.In the present invention, since the electrochromic layer is formed in contact with the electrode in which the through hole is formed, Even if an electrochromic layer is formed outside the second electrode layer, the effect can be obtained. This is because ions can move between the front and back of the electrode through the through hole.

<Sixth Embodiment>
In the sixth embodiment, an electrochromic device having a layer configuration different from that of the first embodiment is illustrated. Note that in the sixth embodiment, description of the same components as those of the above-described embodiment may be omitted.

  FIG. 6 is a cross-sectional view illustrating an electrochromic device according to a sixth embodiment. Referring to FIG. 6, in the electrochromic device 60 according to the sixth embodiment, the first electrode layer 12 and the deterioration preventing layer 56 are sequentially formed on the substrate 11, and the insulating porous layer 14 is formed thereon. Thus, an electrochromic layer 631, a second electrode layer 15, and an electrochromic layer 632 are sequentially formed. These points are different from the electrochromic device 10 according to the first embodiment (see FIG. 1).

  As described above, the electrochromic device according to the sixth embodiment has the following effects in addition to the effects of the first embodiment. That is, the coloring density of the electrochromic layer can be increased.

<Seventh embodiment>
In the seventh embodiment, an electrochromic device having a layer structure different from that of the first embodiment is illustrated. Note that in the seventh embodiment, description of the same components as those of the above-described embodiment may be omitted.

  FIG. 7 is a cross-sectional view illustrating an electrochromic device according to a seventh embodiment. Referring to FIG. 7, in an electrochromic device 70 according to the seventh embodiment, a first electrode layer 72 that reflects light is formed on a substrate 11. This is different from the electrochromic device 10 according to the first embodiment (see FIG. 1).

  Thus, the electrochromic device according to the seventh embodiment has the following effects in addition to the effects of the first embodiment. That is, it is possible to easily obtain a device that functions as a dimming mirror.

<Eighth Embodiment>
In the eighth embodiment, an electrochromic device in which each layer is formed on a support different from the first to seventh embodiments will be exemplified. Note that in the eighth embodiment, description of the same components as those of the above-described embodiment may be omitted.

  FIG. 8 is a cross-sectional view illustrating an electrochromic device according to an eighth embodiment. Referring to FIG. 8, the electrochromic device 80 according to the eighth embodiment is different from the electrochromic device 10 according to the first embodiment in that the support 11 is replaced with a support 81 (FIG. 1). Different from reference).

  The support body 81 is an optical lens. Since the support 81 has a curved surface on which each layer is formed, it is extremely difficult to form each layer by the conventional method of bonding two supports with an electrolyte interposed therebetween. Even if they can be bonded together, since two lenses are used, the thickness, weight, and cost increase. On the other hand, in the present embodiment, even when the layer forming surface of the support is a curved surface, the layers are formed in the same manner as in the case where the layer forming surface of the support is a flat surface by the manufacturing method that does not have the bonding process described above. Stacked formation is possible. The support 81 may be glasses or the like.

  Thus, the electrochromic device according to the eighth embodiment has the following effects in addition to the effects of the first embodiment. That is, since a support having curved surfaces can be used for forming each layer, an optical element having a curved surface such as an optical lens or glasses can be selected as the support. By using an optical element such as an optical lens or glasses, an electrochromic device (an optical device that can be electrically dimmed) that can be easily dimmed can be realized.

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

Example 1
<Production of electrochromic device>
Example 1 shows an example in which the electrochromic device 30 shown in FIG. 3 is manufactured. In addition, the electrochromic device produced in Example 1 can be used as a light control glass device.

<< Formation of First Electrode Layer >>
First, a glass substrate of 40 mm × 40 mm and a thickness of 0.7 mm is prepared as the support 11, and an ITO film is formed on the glass substrate with a thickness of about 100 nm by a sputtering method through a metal mask in a 20 mm × 20 mm region and a drawn portion. The first electrode layer 12 was formed.
Next, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle size: about 20 nm) is applied to the surface of the ITO film by a spin coating method, and annealed at 120 ° C. for 15 minutes. Thus, a nanostructured semiconductor material composed of a titanium oxide particle film having a thickness of about 1.0 μm was formed.

<< Formation of electrochromic layer >>
Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 1.5% by mass of a compound represented by the following structural formula A as an electrochromic compound was applied to the nanostructured semiconductor material by a spin coating method. Thereafter, the electrochromic compound was supported (adsorbed) on the titanium oxide particle film by performing an annealing process at 120 ° C. for 10 minutes, whereby the electrochromic layer 13 was formed.

<Structural formula A>

<< Formation of Insulating Porous Layer >>
Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, and water 74 mass%) having an average primary particle diameter of 20 nm is applied to the electrochromic layer 13 by spin coating. Then, the insulating porous layer 14 was formed. The thickness of the formed insulating porous layer 14 was about 2 μm.

<< Formation of Second Electrode Layer with Fine Through Holes >>
Next, an SiO ₂ fine particle dispersion liquid (silica solid content concentration 1 mass%, 2-propanol 99 mass%) having an average primary particle diameter of 450 nm is applied on the insulating porous layer by a spin coating method to form fine through-holes. A forming mask (colloidal mask) was formed.
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 sputtering in a 20 mm × 20 mm region overlapping with the ITO film formed by the first electrode layer 12 and in a region different from the first electrode layer 12. A second electrode layer 15 was formed by forming through a metal mask. The ITO film formed in a region different from the first electrode layer 12 is a lead-out portion of the second electrode layer 15.
Thereafter, ultrasonic irradiation was performed in 2-propanol for 3 minutes to remove 450 nm SiO ₂ fine particles as a colloidal mask. It was confirmed by SEM observation that the second electrode layer 15 in which fine through holes of about 250 nm were formed was formed. The sheet resistance of the second electrode layer 15 was about 100Ω / □.
Here, the sheet resistance was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, MCP-T610) by a four-terminal four-end needle method in a region different from the first electrode layer.

<< Formation of degradation preventing layer >>
Subsequently, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle diameter: about 20 nm) is applied as a deterioration preventing layer on the second electrode layer 15 by a spin coating method at 120 ° C. By performing an annealing process for 15 minutes, a nanostructured semiconductor material made of a titanium oxide particle film having a thickness of about 1.0 μm was formed, and the deterioration preventing layer 16 was obtained.

<< Electrolyte filling >>
Tetrabutylammonium perchlorate as the electrolyte, dimethyl sulfoxide and polyethylene glycol (molecular weight: 200) as the solvent, and tetrabutylammonium perchlorate: dimethyl sulfoxide: polyethylene glycol (mass ratio) become 12:54:60. The solution thus mixed was used as an electrolytic solution, and the element formed up to the deterioration preventing layer 16 was immersed for 1 minute, and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

<< Formation of organic protective layer >>
Next, the organic protective layer 171 is formed to a thickness of about 3 μm by applying an ultraviolet curable adhesive (trade name: SD-17, manufactured by DIC) to the element by spin coating and curing by ultraviolet light irradiation. did.

<< Formation of inorganic protective layer >>
Subsequently, an SiO ₂ film having a thickness of about 100 nm was formed as an inorganic protective layer on the organic protective layer by sputtering.
Thus, the electrochromic device 30 shown in FIG. 3 was produced.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 30 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 A blue coloration derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Note that the description of the drive voltage is the potential of the first electrode layer in all subsequent descriptions.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

<Repeat test>
The electrochromic device produced was repeated 500 times for -4V for 5 seconds and + 4V for 5 seconds, but no significant deterioration such as the inability to confirm the color erasing operation was confirmed and stable. It was confirmed that it works.

(Example 2)
Example 2 shows another example of producing the electrochromic device 10 shown in FIG. In addition, the electrochromic device produced in Example 2 can be used as a light control glass device.

<Production of electrochromic device>
<< Formation of inorganic protective layer >>
In Example 1, the electrochromic device shown in FIG. 1 was used in the same manner as in Example 1 except that aluminum oxide (Al ₂ O ₃ ) was formed by sputtering so as to have a thickness of about 100 nm as the inorganic protective layer. 10 was produced.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 10 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 A blue color derived from the electrochromic compound represented by the structural formula [Chemical Formula 2] was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the dye in the overlapped area was decolored and turned white.

<Repeat test>
The electrochromic device produced was repeated 500 times for -4V for 5 seconds and + 4V for 5 seconds, but no significant deterioration such as the inability to confirm the color erasing operation was confirmed and stable. It was confirmed that it works.

(Example 3)
Example 3 shows an example in which the electrochromic device 30 shown in FIG. 3 is manufactured. Note that the electrochromic device manufactured in Example 3 can be used as a reflective display device.

<Production of electrochromic device>
<< Formation of Insulating Porous Layer >>
In Example 1, white titanium oxide particles having an average particle diameter of 250 nm were added to and mixed with the SiO ₂ fine particle dispersion of the insulating porous layer at 50% by mass with respect to the silica particles, and the insulating porous layer 34 (white reflective layer) was mixed. 3 was produced in the same manner as in Example 1 except that (1) was formed.

<Color generation / erasing drive>
The color generation / decoloration of the produced electrochromic device 30 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 A blue coloration derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the dye in the overlapped area was decolored and turned white.

<Repeat test>
The electrochromic device produced was repeated 500 times for -4V for 5 seconds and + 4V for 5 seconds, but no significant deterioration such as the inability to confirm the color erasing operation was confirmed and stable. It was confirmed that it works.

Example 4
Example 4 shows an example in which the electrochromic device 70 shown in FIG. 7 is manufactured. In addition, the electrochromic device produced in Example 4 can be used as a light control mirror.

<Production of electrochromic device>
<< Formation of First Electrode Layer >>
In Example 1, except that Al was formed as a first electrode on the glass substrate so as to have a thickness of about 50 nm by vacuum deposition, and subsequently ITO was formed by sputtering to have a thickness of about 100 nm. In the same manner as in Example 1, the electrochromic device 70 shown in FIG.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 70 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 72 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 72 and the second electrode layer 72 The blue reflection color derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied between the lead portion of the first electrode layer 72 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 72 and the second electrode layer 15 are applied. It was confirmed that the dye in the overlapped area disappeared and returned to the mirror state.

<Repeat test>
The electrochromic device produced was repeated 500 times for -4V for 5 seconds and + 4V for 5 seconds, but no significant deterioration such as the inability to confirm the color erasing operation was confirmed and stable. It was confirmed that it works.

(Example 5)
Example 5 shows another example of producing the electrochromic device 10 shown in FIG. In addition, the electrochromic device produced in Example 5 can be used as a light control glass device.

<Production of electrochromic device>
<< Formation of electrochromic layer >>
As an electrochromic layer, a tetrahydrofuran solution containing 2.5% by mass of a compound represented by the following structural formula B (average molecular weight 10,000) was applied by spin coating. Then, the electrochromic layer 13 made of an organic polymer material was formed by performing an annealing process at 120 ° C. for 5 minutes. The electrochromic layer 13 showed a magenta color.

<Structural formula B>
In the structural formula B, n is about 30.

<< Electrolyte filling >>
Lithium perchlorate as the electrolyte, polyethylene glycol (molecular weight: 200) and propylene carbonate as the solvent, urethane adhesive (trade name: 3301, manufactured by Henkel) as the ultraviolet curable resin, lithium perchlorate: polyethylene glycol: The surface of the second electrode layer 15 in which fine through-holes are formed by mixing the propylene carbonate: urethane adhesive (mass ratio) to be 1.4: 6: 8: 10 and using the solution as an electrolyte. The solution was applied by spin coating and dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

<< Formation of organic protective layer >>
Further, an organic protective layer 37 was formed to a thickness of about 3 μm by applying an ultraviolet curable adhesive (trade name: Nopco 134, manufactured by San Nopco) by a spin coat method and curing by ultraviolet irradiation.

<< Formation of inorganic protective layer >>
Subsequently, on the organic protective layer, silicon oxide (SiO ₂ ) having a thickness of about 100 nm was formed as an inorganic protective layer by sputtering.
Except these, the electrochromic device 10 shown in FIG. 1 was produced in the same manner as in Example 1.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 10 was confirmed. Specifically, when a voltage of +3 V is applied for 3 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 12 It was confirmed that the dye in the overlapping portion of the electrode layer 15 was decolored and became transparent.
Furthermore, when a voltage of −2.5 V was applied for 3 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, it was derived from the electrochromic compound of the structural formula B It was confirmed that the magenta color developed and returned to the initial state.

<Repeat test>
For the produced electrochromic device, the color development / erasure drive was repeated 500 times for 3 seconds at + 3V and 3 seconds at -2.5V, but no significant deterioration such as the inability to confirm the color emission / erasure operation was confirmed. It was confirmed that it works stably.

(Example 6)
Example 6 shows an example in which the electrochromic device 50 shown in FIG. 5 is manufactured. In addition, the electrochromic device produced in Example 6 can be used as a light control glass device.

<Production of electrochromic device>
<< Formation of First Electrode Layer >>
An ITO film was formed on the support 11 through a metal mask so as to have a thickness of about 100 nm by a sputtering method to form a first electrode layer 12.

<< Formation of degradation preventing layer >>
Subsequently, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle size: about 20 nm) is applied as a deterioration preventing layer 56 on the first electrode layer 11 by a spin coat method. By performing an annealing process at 15 ° C. for 15 minutes, a nanostructured semiconductor material composed of a titanium oxide particle film having a thickness of about 1.0 μm was formed.
Subsequently, the insulating porous layer 14 and the second electrode layer 15 having fine through holes were formed in the same manner as in Example 1.
Subsequently, an electrochromic layer 53 was formed in the same manner as in Example 1.
Subsequently, the electrolyte was filled in the same manner as in Example 5.
Further, an organic protective layer and an inorganic protective layer were formed in the same manner as in Example 5.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 50 was confirmed. Specifically, when a voltage of +4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 3 seconds, the first electrode layer 12 and the second electrode layer 12 A blue color derived from the electrochromic compound of the structural formula B was confirmed in the overlapping portion of the electrode layer 15.
Furthermore, when a voltage of −4 V was applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 3 seconds, the first electrode layer 12 and the second electrode layer It was confirmed that the 15 overlapping portions of the dye disappeared and became transparent.

<Repeat test>
The electrochromic device produced was repeated 500 times for -4V for 5 seconds and + 4V for 5 seconds, but no significant deterioration such as the inability to confirm the color erasing operation was confirmed and stable. It was confirmed that it works.

(Comparative Example 1)
In Example 1, an electrochromic device 90 shown in FIG. 9 was produced in the same manner as in Example 1 except that the inorganic protective layer was not formed.

<Color generation / erasing drive>
The color generation / decoloration of the produced electrochromic device 90 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 A blue coloration derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

<Repeat test>
For the produced electrochromic device, erasing / decoloring driving at -4 V for 5 seconds and +4 V for 5 seconds was repeated 500 times, but the device resistance increased significantly, and sufficient color erasing / decoloring could not be obtained.

(Comparative Example 2)
In Example 3, the electrochromic device 100 shown in FIG. 10 was produced in the same manner as in Example 3 except that the inorganic protective layer was not formed.

<Color generation / erasing drive>
The color development / erasing of the produced electrochromic device 100 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 A blue coloration derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the dye in the overlapped area was decolored and turned white.

<Repeat test>
For the produced electrochromic device, erasing / decoloring driving at -4 V for 5 seconds and +4 V for 5 seconds was repeated 500 times, but the device resistance increased significantly, and sufficient color erasing / decoloring could not be obtained.

(Comparative Example 3)
In Example 4, the electrochromic device 110 shown in FIG. 11 was produced in the same manner as in Example 4 except that the inorganic protective layer was not formed.

<Color generation / erasing drive>
The color development / erasing of the produced electrochromic device 100 was confirmed. Specifically, when a voltage of −4 V is applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer 12 The blue reflection color derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 15 are applied. It was confirmed that the dye in the overlapping area disappeared and became a mirror state.

<Repeat test>
For the produced electrochromic device, erasing / decoloring driving at -4 V for 5 seconds and +4 V for 5 seconds was repeated 500 times, but the device resistance increased significantly, and sufficient color erasing / decoloring could not be obtained.

(Comparative Example 4)
In Example 5, an electrochromic device 90 shown in FIG. 9 was produced in the same manner as in Example 5 except that the inorganic protective layer was not formed.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 90 was confirmed. Specifically, when a voltage of +3 V is applied for 3 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 12 It was confirmed that the dye in the overlapping portion of the electrode layer 15 was decolored and became transparent.
Furthermore, when a voltage of −2.5 V was applied for 3 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, it was derived from the electrochromic compound of the structural formula B It was confirmed that the magenta color developed and returned to the initial state.

<Repeat test>
For the produced electrochromic device, the erasing / erasing drive for 3 seconds at +3 V and 3 seconds at -2.5 V was repeated 500 times. However, the element resistance increased significantly, and sufficient erasing and decoloring could not be obtained. It was.

(Comparative Example 5)
In Example 6, an electrochromic device 120 shown in FIG. 12 was produced in the same manner as in Example 6 except that the inorganic protective layer was not formed.

<Coloring / erasing drive>
The color generation / decoloration of the produced electrochromic device 120 was confirmed. Specifically, when a voltage of +4 V is applied for 5 seconds between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15, the first electrode layer 12 and the second electrode layer 12 A blue color derived from the electrochromic compound of the structural formula A was confirmed in the overlapping portion of the electrode layer 15.
Further, when a voltage of −4 V was applied between the lead portion of the first electrode layer 12 and the lead portion of the second electrode layer 15 for 5 seconds, the first electrode layer 12 and the second electrode layer It was confirmed that the 15 overlapping portions of the dye disappeared and became transparent.

<Repeat test>
When the electrochromic drive of + 4V for 5 seconds and -4V for 5 seconds was repeated 500 times for the produced electrochromic device, the element resistance increased significantly, and sufficient color development / decoloration could not be obtained.

  Although the embodiments and examples have been described in detail above, the present invention is not limited to the above-described embodiments and examples, and is described above without departing from the scope described in the claims. Various modifications and substitutions can be made to the embodiments and examples. For example, the above embodiments can be combined as appropriate.

As an aspect of this invention, it is as follows, for example.
<1> a first electrode layer;
A first electroactive layer in contact with the first electrode layer;
A second electrode layer facing the first electrode layer and having a through hole formed thereon;
A second electroactive layer that is porous in contact with the second electrode layer;
An electrolyte filled between the first electrode layer and the second electrode layer and in contact with the first electroactive layer and the second electroactive layer;
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer;
Each of the first electrode layer and the second electrode layer has an inner surface that is a surface facing each other, and an outer surface that is a surface opposite to the inner surface,
An electrochromic device having a support on the outer surface of the first electrode layer,
An electrochromic device having at least an inorganic protective layer made of an inorganic material on an outer surface of the second electrode layer.
<2> The electrochromic device according to <1>, wherein an outer surface of the second electrode layer includes an organic protective layer containing a resin material and an inorganic protective layer.
<3> The electrochromic device according to any one of <1> to <2>, wherein the inorganic material in the inorganic protective layer is at least one selected from silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide. is there.
<4> The electrochromic device according to any one of <1> to <3>, wherein a diameter of a through hole of the second electrode layer is 10 nm to 100 μm.
<5> An insulating porous layer for electrically insulating the first electrode layer and the second electrode layer is provided between the first electrode layer and the second electrode layer. ,
The electrochromic device according to any one of <1> to <4>, wherein the insulating porous layer includes insulating metal oxide fine particles.
<6> The electrochromic device according to any one of <1> to <5>, wherein the deterioration preventing layer includes semiconductive metal oxide fine particles.
<7> The electrochromic device according to any one of <1> to <6>, wherein any one of the first electrode and the second electrode is an electrochromic dimming mirror that reflects light.
<8> The electrochromic device according to any one of <1> to <6>, wherein the insulating porous layer includes white particles and is an electrochromic reflective display element.
<9> The electrochromic device according to any one of <1> to <8>, wherein the support is an optical lens.
<10> A step of sequentially laminating a first electrode layer and a first electroactive layer on a support;
Laminating a second electrode layer in which a through hole is formed on the first electroactive layer so as to face the first electrode layer via an insulating porous layer;
Laminating a second electroactive layer in contact with the second electrode layer;
Filling a predetermined region between the first electrode layer and the second electrode layer with an electrolyte from the through hole;
Semi-solidifying the electrolyte;
Laminating an inorganic protective layer made of an inorganic material on the surface of the second electrode layer not facing the first electrode layer,
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer. Is the method.
<11> The step of laminating the second electrode layer comprises:
Spraying fine particles on the lower layer on which the second electrode layer is laminated;
Forming a conductive film on the surface on which the fine particles are dispersed by a vacuum film formation method;
The method for producing an electrochromic device according to <10>, further comprising: removing the conductive film together with the fine particles.
<12> The method for producing an electrochromic device according to <11>, wherein a diameter of the fine particle is equal to or greater than a thickness of the second electrode layer.

10, 20, 30, 40, 50, 60, 70, 90, 100, 110, 120 Electrochromic device 11 Support body 12, 72 First electrode layer 13, 53 Electrochromic layer 14, 34 Insulating porous layer 15 Second electrode layer 16, 56 Deterioration prevention layer 23 Insulating porous layer 80 Electrochromic light control lens 81 Lens 87, 171 Organic protection layer 172 Inorganic protection layer 461, 462 Deterioration prevention layer 631, 632 Electrochromic layer

Japanese Patent Publication No. 3-73081 Japanese Patent No. 4105537

Claims (10)

A first electrode layer;
A first electroactive layer in contact with the first electrode layer;
A second electrode layer facing the first electrode layer and having a through hole formed thereon;
A second electroactive layer that is porous in contact with the second electrode layer;
An electrolyte filled between the first electrode layer and the second electrode layer and in contact with the first electroactive layer and the second electroactive layer;
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer;
Each of the first electrode layer and the second electrode layer has an inner surface that is a surface facing each other, and an outer surface that is a surface opposite to the inner surface,
An electrochromic device having a support on the outer surface of the first electrode layer,
An electrochromic device comprising at least an inorganic protective layer made of an inorganic material on an outer surface of the second electrode layer.   The electrochromic device according to claim 1, further comprising an organic protective layer containing a resin material and an inorganic protective layer on an outer surface of the second electrode layer.   The electrochromic device according to claim 1, wherein the inorganic material in the inorganic protective layer is at least one selected from silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide.   The electrochromic device according to any one of claims 1 to 3, wherein a diameter of the through hole of the second electrode layer is 10 nm to 100 µm. An insulating porous layer for electrically insulating the first electrode layer and the second electrode layer between the first electrode layer and the second electrode layer;
The electrochromic device according to claim 1, wherein the insulating porous layer includes insulating metal oxide fine particles.   The electrochromic device according to claim 1, wherein the deterioration preventing layer includes semiconductive metal oxide fine particles.   The electrochromic device according to claim 1, wherein the support is an optical lens. Sequentially laminating a first electrode layer and a first electroactive layer on a support;
Laminating a second electrode layer in which a through hole is formed on the first electroactive layer so as to face the first electrode layer via an insulating porous layer;
Laminating a second electroactive layer in contact with the second electrode layer;
Filling a predetermined region between the first electrode layer and the second electrode layer with an electrolyte from the through hole;
Semi-solidifying the electrolyte;
Laminating an inorganic protective layer made of an inorganic material on the surface of the second electrode layer not facing the first electrode layer,
At least one of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is either an electrochromic layer or a deterioration preventing layer. Method. The step of laminating the second electrode layer comprises:
Spraying fine particles on the lower layer on which the second electrode layer is laminated;
Forming a conductive film on the surface on which the fine particles are dispersed by a vacuum film formation method;
The method for producing an electrochromic device according to claim 8, comprising: removing the conductive film together with the fine particles.   The method for manufacturing an electrochromic device according to claim 9, wherein a diameter of the fine particles is equal to or greater than a thickness of the second electrode layer.