JP2014021452A - Electrochromic device and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic device that can be fabricated without a bonding process, and to provide a manufacturing method of the electrochromic device.SOLUTION: The present electrochromic device includes: a first electrode layer; a second electrode layer that is provided to face the first electrode layer; an electrochromic layer that is provided between the first electrode layer and the second electrode layer; and an electrolyte that is filled in a given area between the first electrode layer and the second electrode layer. At least one layer of the first electrode layer or the second electrode layer has a through-hole formed, and a supporting body is provided only on either one of outer sides of the first electrode layer and the second electrode layer.

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.

  As the electrochromic material used in the electrochromic device, an organic material or an inorganic material is used. An organic material is promising as a color display device because it can generate various colors depending on its molecular structure, but has a problem in durability because it is an organic material. On the other hand, inorganic materials have problems in color control, but are particularly durable when using a solid electrolytic layer. Utilizing this feature, practical application to light control glass and ND filters is being studied as an application that has an advantage of low color saturation. However, there is a problem that the response speed is slow in an apparatus using a solid electrolytic layer.

  In these electrochromic devices, an electrochromic material is generally formed between two electrodes facing each other, and an oxidation-reduction reaction is performed in a configuration in which an ion conductive electrolyte layer is filled between the electrodes. The electrochromic device has a drawback in that the response speed of color development / decoloration is slow because of the principle of performing color development / decoloration utilizing an oxidation-reduction reaction.

  Furthermore, since electrochromic is an electrochemical phenomenon, the performance of the electrolyte layer (ionic conductivity, etc.) affects the response speed and the memory effect of color development. When the electrolyte layer is in the form of a liquid in which the electrolyte is dissolved in a solvent, it is easy to obtain fast responsiveness. However, improvements in solidification and gelation have been studied in terms of device strength and reliability.

  That is, conventionally, since batteries and electrochromic devices as electrochemical elements have used an electrolytic solution, not only is there leakage of the electrolytic solution and drying of the battery due to volatilization of the solvent, but also in the battery container. Due to the bias of the electrolyte, the diaphragm was partially dried, which caused an increase in internal impedance and an internal short circuit.

  Especially when an electrochromic device is used for dimming glass or display applications, it is necessary to seal at least one direction with a transparent material such as glass or plastic. It is difficult, and leakage and volatilization of the electrolyte become a larger problem.

  As a method for solving the above-described drawbacks, it has been proposed to use a polymer solid electrolyte. Specific examples include a solid solution of a matrix polymer containing an oxyethylene chain or an oxypropylene chain and an inorganic salt, but these are completely solid and excellent in processability, but their conductivity is a normal non-aqueous electrolysis. It has a practical problem of being several orders of magnitude lower than the liquid.

  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 (for example, see Patent Document 1), or a liquid monomer to which an electrolyte is added A method for producing a crosslinked polymer containing an electrolyte by polymerization reaction has been proposed, but has not yet reached a practical level.

  By the way, these electrochromic devices are generally manufactured by forming an electrochromic material between two electrodes facing each other and then bonding them together via an ion conductive electrolyte layer. If an electrochromic device can be manufactured without this bonding process, it will be possible to form the device on various parts such as curved surfaces, so the range of application will be widened, and the support on one side will be unnecessary, so it will be produced at low cost. it can.

However, in the prior art, it has been difficult to form an electrochromic device on a support by a thin film process. That is, when an electrode is formed on an electrolyte layer in order to omit the bonding process, there is a problem that the response speed is slow as described above when an all-solid electrolyte layer is used. Furthermore, when an organic material layer is used as the all-solid 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 performed normally. In particular, oxide layers such as ITO, SnO ₂ and AZO formed by vacuum film formation, which are generally adopted as transparent electrodes, have both transparency and electrical conductivity when formed on the organic film surface. Hateful.

  On the other hand, when an inorganic material layer is used as the all-solid electrolyte layer, it is limited to an inorganic electrochromic 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 is disclosed in which a transparent intermediate layer composed mainly of a composite of a material and a metal is disposed (see, for example, Patent Document 2).

  According to Patent Document 2, it is described that the repetition characteristics and responsiveness are improved by forming the intermediate layer, and the color development driving can be performed in a few seconds. However, the structure is complicated and it is difficult to increase the size of the inorganic chromic compound layer by vacuum film formation, which causes an increase in cost. In addition, inorganic electrochromic materials have a problem in color control.

  This invention is made | formed in view of said point, and makes it a subject to provide the electrochromic apparatus which can be produced without a bonding process, and its manufacturing method.

  The electrochromic device is provided between the first electrode layer, the second electrode layer provided to face the first electrode layer, and the first electrode layer and the second electrode layer. An electrochromic layer, and an electrolyte filled in a predetermined region between the first electrode layer and the second electrode layer, the first electrode layer or the second electrode layer There is a requirement that a through hole is formed in at least one of the layers, and that a support is provided only on either the outside of the first electrode layer or the outside of the second electrode layer. And

  According to the disclosed technology, it is possible to provide an electrochromic device that can be manufactured without a bonding process, and a manufacturing method thereof.

1 is a cross-sectional view illustrating an electrochromic device according to a first embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 2nd Embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 3rd Embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 4th Embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 5th Embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 6th Embodiment. It is sectional drawing which illustrates the electrochromic apparatus which concerns on 7th Embodiment.

  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 layer sequentially stacked on the support 11. And an electrode layer 15.

  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. The support 11 is provided outside the first electrode layer 12, but no support is provided outside the second 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.

  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 a second electrode layer 15 having a through-hole so as to face the electrode layer 12, and an insulating porous layer 14 sandwiched between the first electrode layer 12 and the second electrode layer 15; And a step of filling the electrolyte from the through-hole formed in the second electrode layer 15.

  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. These problems can be avoided by first laminating the second electrode layer 15 and then injecting the electrolyte into the insulating porous layer 14 through the through-hole formed in the second electrode layer 15.

  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.

  In addition, since no support is provided outside the second electrode layer (since the support on one side is not required), 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 also having excellent color characteristics by using an organic electrochromic material.

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

[Support 11]
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. As the support 11, a known organic material or inorganic material can be used as it is as long as these layers can be supported.

  As a specific example, a glass substrate such as alkali-free glass, borosilicate glass, float glass, or soda lime glass can be used as the support 11. Further, as the support 11, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, polyimide resin or the like may be used. 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 12, second electrode layer 15]
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 indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), tin oxide doped with antimony (hereinafter referred to as ATO), and the like. Inorganic materials can be used. In particular, indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) or zinc oxide (hereinafter referred to as In oxide) formed by vacuum film formation. It is preferable to use an inorganic material containing any one of Zn oxide.

In oxides, Sn oxides, and Zn oxides are materials that can be easily formed by a sputtering method, and that can provide good transparency and electrical conductivity. Particularly preferred materials are InSnO, GaZnO, SnO, In ₂ O ₃ , and ZnO. Furthermore, transparent network electrodes such as silver, gold, carbon nanotube, and metal oxide, and composite layers thereof are also useful.

  The 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 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 reflecting function. In that case, the first electrode layer 12 A metal material may be included as the material of the second electrode layer 15. As the metal material, for example, Pt, Ag, Au, Cr, rhodium, and alloys thereof, or a stacked structure thereof can be used.

  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. In addition, as long as each material of the first electrode layer 12 and the second electrode layer 15 can be formed by coating, a spin coat method, a casting method, a micro gravure coat method, a gravure coat method, a bar coat method, a roll coat Method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method Various printing methods such as these can be used.

  In 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.

  Alternatively, 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. Alternatively, a method in which various radiations are directly radiated 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 is formed by vacuum deposition or the like on the surface on which the fine particles are dispersed using the dispersed fine particles as a mask. In this method, the conductive film is formed, and then the conductive film is removed together with the fine particles to perform patterning.

  A fine through hole can be easily formed in the second electrode layer 15 by colloidal lithography. In particular, by setting the diameter of the fine particles to be dispersed to be equal to or larger than the thickness of the second electrode layer 15, it is possible to easily form a through hole in the second electrode layer 15. Further, the density and area of 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 when spraying the colloidal mask is preferably a dispersion having good dispersibility. For example, when SiO ₂ fine particles are used as the fine particles used as the colloidal mask, an aqueous dispersion can be used.

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 the colloidal mask is removed using the 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.

  Negative photoresists include, for example, polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, polyhydroxystyrene / Mention may be made of melamine / photoacid generators, methylated melamine resins, methylated urea resins and the like.

  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 arises a problem that the permeation of electrolyte ions is deteriorated. In addition, 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 immediately above the fine through hole.

  The ratio (hole density) of the hole area to the surface area of the second electrode layer 15 of the fine through holes provided in the second electrode layer 15 can be set as appropriate, for example, about 0.01 to 40% can do. 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 area where the second electrode layer 15 is not provided. Further, if the hole density is too low, the permeability of the electrolyte ions is deteriorated.

A deterioration preventing layer may be formed on the opposing surfaces of the first electrode layer 12 and the second electrode layer 15. The deterioration preventing layer 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. For example, Al ₂ O ₃ or SiO ₂ or an insulator material containing them can be used. Alternatively, zinc oxide, titanium oxide, or a semiconductor material containing them may be used. Further, an organic material such as polyimide may be used.

  As a method for forming the deterioration preventing layer, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. In addition, if the material for the deterioration preventing layer can be applied and formed, 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 Various printing methods such as a coating method, a capillary coating method, a spray coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

  In particular, it is useful to form a material that exhibits a reversible oxidation-reduction reaction in the second electrode layer 15 facing the electrochromic layer 13 by reacting with the electrochromic layer 13 in reverse. For example, conductive or semiconductive metal oxide fine particles such as antimony tin oxide and nickel oxide are formed on the second electrode layer 15 with a binder such as acrylic, alkyd, isocyanate, urethane, epoxy or phenol. Can be immobilized.

[Electrochromic layer 13]
The electrochromic layer 13 is a layer containing an electrochromic material, and any of an inorganic electrochromic compound and an organic electrochromic compound may be used as the electrochromic material. Moreover, you may use the conductive polymer known by showing electrochromism.

  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, styryl and the like. Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, or derivatives thereof.

  Further, as the electrochromic layer 13, it is particularly desirable 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 fine particle surface. .

  In this structure, since electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, a high-speed response is possible as compared with the 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 also be supported on conductive or semiconductive fine particles.

  Specifically, polymer-based and dye-based electrochromic compounds include azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styryl spiropyran, spirooxazine, spirothiopyran, thioindigo, tetra Thiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorane, fulgide, A low molecular organic electrochromic compound such as benzopyran or metallocene, or a conductive polymer compound such as polyaniline or polythiophene can be used.

  Among these, it is particularly preferable to include a viologen-based compound or a dipyridine-based compound having a low color development / discoloration potential and a good color value. For example, it is preferable to include a dipyridine compound represented by the formula [Chemical Formula 1] (general formula).

なお、式［化１］（一般式）中、Ｒ１及びＲ２は、それぞれ独立に置換基を有してもよい炭素数１から８のアルキル基、又はアリール基を表し、Ｒ１又はＲ２の少なくとも一方は、ＣＯＯＨ、ＰＯ（ＯＨ）_２、Ｓｉ（ＯＣ_ｋＨ_２ｋ＋１）_３から選ばれる置換基を有する。Ｘは１価のアニオンを表す。ｎ、ｍ、ｌは０、１、又は２を表す。Ａ、Ｂ、Ｃは各々独立に置換基を有してもよい炭素数１から２０のアルキル基、アリール基、複素環基を表す。

In the formula [Chemical Formula 1] (general formula), 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 _Has a substituent selected from COOH, PO (OH) ₂ , Si (OC _k H _{2k + 1} ) ₃ . X represents a monovalent anion. n, m, and l represent 0, 1, or 2. A, B and C each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group or a heterocyclic group which may have a substituent.

  On the other hand, as the metal complex-based or metal oxide-based electrochromic compound, inorganic electrochromic compounds such as titanium oxide, vanadium oxide, tungsten oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue can be used.

  Although it does not specifically limit as electroconductive or semiconductive fine particle, It is preferable to use a metal oxide. Specific materials include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide, Metal oxides mainly composed of ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. can be used. .

  Moreover, these metal oxides may be used independently and 2 or more types may be mixed and used for them. In view of physical properties such as electrical properties such as electrical conductivity and optical properties, a kind 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.

  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 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.

  The film thickness of the electrochromic layer 13 can be set to, for example, about 0.2 to 5.0 μm. When the thickness of the electrochromic layer 13 is thinner than the above range, it is difficult to obtain the color density. Moreover, when the film thickness of the electrochromic layer 13 is thicker than the said range, while manufacturing cost will increase, visibility will fall easily by coloring. Although the electrochromic layer 13 and the conductive or semiconductive fine particle layer can be formed by vacuum film formation, it is preferably formed by coating as a particle-dispersed paste from the viewpoint of productivity.

[Electrolytes]
In the present embodiment, the electrolyte is an insulating solution disposed between the first electrode layer 12 and the second electrode layer 15 from a fine through-hole formed in the second electrode layer 15 as an electrolytic solution. The porous layer 14 is filled. As the electrolytic solution, a liquid electrolyte such as an ionic liquid or a solution obtained by dissolving a solid electrolyte in a solvent can be used.

As the electrolyte material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts can be used. Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg ( BF ₄ ) ₂ or the like can be used.

  An ionic liquid can also be used. The ionic liquid 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. Examples of molecular structures include cation components such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, Examples thereof include aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salts, and aliphatic quaternary ammonium systems such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.

As the anion component, a compound containing fluorine is preferable in terms of stability in the atmosphere, and examples thereof include BF ₄ , CF ₃ SO ₃ —, PF ₄ —, (CF ₃ SO ₂ ) _2N — and the like. An ionic liquid formulated by a combination of these cationic components and anionic components can be used.

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

  Further, the electrolytic solution need not be a low-viscosity liquid, and can take various forms such as a gel, a polymer cross-linked type, and a liquid crystal dispersed type. It is preferable to form the electrolyte in a gel or solid form from the viewpoint of improving element strength, improving reliability, and preventing color diffusion. As the solidification method, a method of holding the electrolyte and the solvent in the polymer resin is preferable. This is because high ionic conductivity and solid strength can be obtained. Further, it is preferable to use a photocurable resin as the polymer resin. This is because the device can be manufactured at a low temperature and in a short time compared to thermal polymerization or a method of thinning the film by evaporating the solvent.

[Insulating porous layer 14]
The insulating porous layer 14 functions to keep the electrolyte while isolating the first electrode layer 12 and the second electrode layer 15 so as to be electrically insulated. The material of the insulating porous layer 14 is not particularly limited as long as it is porous. However, organic materials and inorganic materials having high insulating properties and durability and excellent film forming properties, and composites thereof. Is preferably used.

  The insulating porous layer 14 can be formed by a sintering method (using fine pores or inorganic particles partially fused by adding a binder or the like to use pores generated between the particles), or an extraction method. (After forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, the organic substance or inorganic substance is dissolved with a solvent to obtain pores) and the like.

Further, as a method for forming the insulating porous layer 14, a foaming method in which a polymer or the like is foamed by heating or degassing, etc., and a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. Forming methods such as a phase inversion method and a radiation irradiation method in which various radiations are radiated to form pores may be used. Specific examples include polymer mixed particle films containing metal oxide fine particles (such as SiO ₂ particles and Al ₂ O ₃ particles) and a polymer binder, porous organic films (such as polyurethane resins and polyethylene resins), and porous film shapes. An inorganic insulating material film formed in the above.

  The unevenness of the insulating porous layer 14 also depends on the film thickness of the second electrode layer 15. For example, when the film thickness of the second electrode layer 15 is 100 nm, the surface roughness of the insulating porous layer 14 is 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 film thickness of the insulating porous layer 14 can be, for example, about 50 to 500 nm.

  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.

As the inorganic film, a material containing at least ZnS is preferably used. 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 to 90 mol% in order to maintain good crystallinity when the insulating layer is formed. Therefore, particularly preferred materials are ZnS—SiO ₂ (8/2), ZnS—SiO ₂ (7/3), ZnS, 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.

<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 different from the first embodiment in that the electrochromic layer 13 and the insulating porous layer 14 are replaced with the insulating porous layer 23. This is different from the electrochromic device 10 according to the 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 includes 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 and an electrochromic material. That is, in this embodiment, the insulating porous layer 23 functions as an electrochromic 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. The step of laminating the second electrode layer 15 having through-holes so as to face each other, and the insulating porous layer 23 sandwiched between the first electrode layer 12 and the second electrode layer 15, Filling the electrolyte and the electrochromic material from the through holes formed in the electrode layer 15.

  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 and the electrochromic material in the manufacturing process of the electrochromic device 20. The electrolyte and the electrochromic 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 configuration 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 10 according to the first embodiment (see FIG. 1) in that a protective layer 36 is added. To do.

  The protective layer 36 covers the side surface of the first electrode layer 12, the side surface of the electrochromic layer 13, the side surface of the insulating porous layer 14, and the side surface and upper surface of the second electrode layer 15 on the support 11. Is formed. The protective layer 36 is made of, for example, an ultraviolet curable or thermosetting insulating resin on the support 11, the side surface of the first electrode layer 12, the side surface of the electrochromic layer 13, and the insulating porous layer 14. It can form by apply | coating so that a side surface and the side surface and upper surface of the 2nd electrode layer 15 may be covered, and making it harden | cure after that. The film thickness of the protective layer 36 can be about 0.5-10 micrometers, for example.

  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, by forming the protective layer, the second electrode layer and the like can be protected from scratches and electrical failures. Further, by forming the protective layer, it is possible to prevent electrolyte leakage and improve durability. More preferably, the protective layer is provided with an ultraviolet cut function or an antistatic function.

<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, the electrochromic device 40 according to the fourth embodiment is different from the electrochromic device according to the first embodiment in that the insulating porous layer 14 is replaced with the insulating porous layer 44. It is different from the chromic device 10 (see FIG. 1).

  The insulating porous layer 44 is a layer in which white pigment particles are further contained in the insulating porous layer 14 and functions as a white reflective layer. As a material of the white pigment particles, for example, titanium oxide, aluminum oxide, zinc oxide, silica, cesium oxide, yttrium oxide, or the like can be used.

  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, a reflective display element can be easily realized by adding white pigment particles to the insulating porous layer and causing the insulating porous layer to function as a white reflective layer.

<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, the electrochromic device 50 according to the fifth embodiment includes a support body 11, a first electrode layer 12, and a second electrode layer 15, which are a support body 51 and a first electrode, respectively. The point that the layer 52 and the second electrode layer 55 are replaced is different from the electrochromic device 10 (see FIG. 1) according to the first embodiment.

  Similar to the second electrode layer 15 of the electrochromic device 10, fine through-holes are formed in the support 51 and the first electrode layer 52. That is, the support body 51 in which fine through holes are formed is provided outside the first electrode layer 52 in which fine through holes are formed. On the other hand, fine through holes are not formed in the second electrode layer 55 (similar to the first electrode layer 12 of the electrochromic device 10).

  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, the insulating porous layer is filled with the electrolyte from the support side through the electrochromic layer by forming fine through holes in both the support and the first electrode layer formed on the support. Is possible. As a result, an electrochromic device can be formed at various sites, and the application range of the electrochromic device can be further expanded. The electrolyte can be filled into the insulating porous layer from the gap between the electrochromic materials forming the electrochromic layer.

<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, the electrochromic device 60 according to the sixth embodiment is related to the first embodiment in that an insulating inorganic protective layer 67 is added on the second electrode layer 15. This is different from the electrochromic device 10 (see FIG. 1).

As a material of the insulating inorganic protective layer 67, for example, a metal oxide, a metal sulfide, a metal nitride, or the like, which is a general insulating material, can be used. Particularly preferable materials for the insulating inorganic protective layer 67 include SiO ₂ , SiN, Al ₂ O ₃ , ZnS, ZnS—SiO ₂ (8/2), ZnS—SiO ₂ (7/3), and the like. The film thickness of the insulating inorganic protective layer 67 can be, for example, about 0.05 to 1 μm.

  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, by forming the insulating inorganic protective layer on the second electrode layer, the electrical failure of the second electrode layer can be effectively protected with a thin film configuration. Further, it is possible to efficiently prevent the charge diffusion of the second electrode layer and improve the durability.

<Seventh embodiment>
In the seventh embodiment, an electrochromic device in which each layer is formed on a support different from the first to sixth embodiments will be exemplified. 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, the electrochromic device 70 according to the seventh embodiment is different from the electrochromic device 30 according to the third embodiment in that the support 11 is replaced with the support 71 (FIG. 3). Different from reference).

  The support body 71 is an optical lens. Since the support 71 has a curved surface on which each layer is formed, it is extremely difficult to form each layer with the conventional method of bonding two supports with an electrolyte interposed therebetween. 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 71 may be glasses or the like.

  Thus, the electrochromic device according to the seventh embodiment has the following effects in addition to the effects of the first embodiment. That is, since a support having a curved surface 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.

[Example 1]
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 and electrochromic 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 of about 100 nm is formed on the glass substrate 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 by forming a film to a thickness.

  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. A nanostructured semiconductor material made of a titanium oxide particle film of about 1.0 μm was formed.

  Subsequently, as an electrochromic compound, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 wt% of the compound represented by the structural formula [Chemical Formula 2] was applied by spin coating, and then 120 ° C. × 10 An electrochromic layer 13 was formed by carrying (annealing) the titanium oxide particle film by performing an annealing treatment for a minute.

（絶縁性多孔質層、微細な貫通孔が形成された第２の電極層の形成）
続いて、エレクトロクロミック層１３上に平均一次粒径２０ｎｍのＳｉＯ_２微粒子分散液（シリカ固形分濃度２４．８重量％、ポリビニルアルコール１．２重量％、水７４重量％）をスピンコートし、絶縁性多孔質層１４を形成した。形成した絶縁性多孔質層１４の膜厚は約２μｍであった。更に、平均一次粒径４５０ｎｍのＳｉＯ_２微粒子分散液（シリカ固形分濃度１重量％、２−プロパノール９９重量％）をスピンコートし、微細貫通孔形成用マスク（コロイダルマスク）を形成した。

(Formation of insulating porous layer, second electrode layer with fine through-holes formed)
Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8% by weight, polyvinyl alcohol 1.2% by weight, water 74% by weight) having an average primary particle diameter of 20 nm is spin-coated on the electrochromic layer 13 for insulation. The porous layer 14 was formed. The film thickness of the formed insulating porous layer 14 was about 2 μm. Further, a fine SiO ₂ fine particle dispersion (silica solid content concentration 1 wt%, 2-propanol 99 wt%) having an average primary particle diameter of 450 nm was spin-coated to form a fine through-hole forming mask (colloidal mask).

Subsequently, an inorganic insulating layer of ZnS—SiO ₂ (8/2) was formed to a thickness of 40 nm on the fine through hole forming mask by a sputtering method. Further, an ITO film having a thickness of about 100 nm is formed on the inorganic insulating layer by a sputtering method in a region of 20 mm × 20 mm 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 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, 2-in-propanol performs ultrasonic irradiation for 3 minutes, subjected to SiO ₂ removal treatment of the fine particles of 450nm is colloidal masks. It was confirmed by SEM observation that the second electrode layer 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 / □.

(Electrolyte filling)
Second electrode layer 15 in which fine through-holes are formed by using, as an electrolyte, a solution obtained by mixing tetrabutylammonium perchlorate as an electrolyte and dimethyl sulfoxide and polyethylene glycol (molecular weight: 200) as a solvent in a ratio of 12:54:60. The element thus formed was immersed for 1 minute, and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

(Formation of protective layer)
Further, a protective layer 36 was formed to a thickness of about 3 μm by spin coating an ultraviolet curable adhesive (trade name: manufactured by SD-17 DIC) and curing it by irradiation with ultraviolet light. Thereby, the electrochromic device 30 shown in FIG. 3 was obtained.

(Color-erasing drive)
The color generation / decoloration of the produced electrochromic device 30 was confirmed. Specifically, when a voltage of −5 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 represented by the structural formula [Chemical Formula 2] was confirmed in the overlapping portion of the electrode layer 15.

  Further, when a voltage of +5 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 15 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

[Example 2]
Example 2 shows an example in which the electrochromic device 40 shown in FIG. 4 is manufactured. Note that the electrochromic device manufactured in Example 2 can be used as a reflective display device.

(Production of electrochromic device)
White titanium oxide particles having an average particle diameter of 250 nm were added to and mixed with the SiO ₂ fine particle dispersion at 50 wt% with respect to the silica particles to form an insulating porous layer 44 (white reflective layer). Except this, it carried out similarly to Example 1, and obtained the electrochromic apparatus 40 shown in FIG.

(Color-erasing drive)
The color generation / decoloration of the produced electrochromic device 40 was confirmed. Specifically, when a voltage of −5 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 represented by the structural formula [Chemical Formula 2] was confirmed in the overlapping portion of the electrode layer 15.

  Further, when a voltage of +5 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 15 are applied. It was confirmed that the dye in the overlapped area was decolored and turned white.

[Example 3]
Example 3 shows another example of producing the electrochromic device 30 shown in FIG. In addition, the electrochromic device produced in Example 3 can be used as a light control glass device.

(Production of electrochromic device)
Lithium perchlorate as the electrolyte, polyethylene glycol (molecular weight: 200) and propylene carbonate as the solvent, and urethane adhesive (trade name: 3301 made by Henkel) as the UV curing material were mixed in a ratio of 1.4 to 6 to 8 to 10. The solution was used as an electrolytic solution, spin-coated on the surface of the second electrode layer 15 in which fine through holes were formed, and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

  Further, a protective layer 36 was formed to a thickness of about 3 μm by spin coating an ultraviolet curable adhesive (trade name: Nopco 134 manufactured by San Nopco Co., Ltd.) and curing it by irradiation with ultraviolet light. Except this, it carried out similarly to Example 1, and obtained the electrochromic apparatus 30 shown in FIG.

(Color-erasing drive)
The color generation / decoloration of the produced electrochromic device 30 was confirmed. Specifically, when a voltage of −5 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 represented by the structural formula [Chemical Formula 2] was confirmed in the overlapping portion of the electrode layer 15.

  Further, when a voltage of +5 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 15 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

[Example 4]
Example 4 shows an example in which the electrochromic device 50 shown in FIG. 5 is manufactured. In addition, the electrochromic device produced in Example 4 can be used as a light control film.

(Production of electrochromic device)
As the support 51, a polyethylene porous film (trade name: Sunmap LC, average pore diameter: 17 μm, porosity: 30%, manufactured by Nitto Denko Corporation) was used, and the second electrode layer 15 of Example 1 was formed on the support 51. Similarly, the 1st electrode layer 52 in which the through-hole was formed was formed. In addition, an inorganic insulating layer of ZnS—SiO ₂ (8/2) and a second electrode layer 55 of ITO were directly formed on the insulating porous layer 14 (no colloidal lithography is used, that is, no through hole is formed). . Except this, it carried out similarly to Example 1, and obtained the electrochromic apparatus 50 shown in FIG.

(Color-erasing drive)
The color generation / decoloration of the produced electrochromic device 50 was confirmed. Specifically, when a voltage of −5 V is applied between the lead portion of the first electrode layer 52 and the lead portion of the second electrode layer 55 for 3 seconds, the first electrode layer 52 and the second electrode layer 52 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 55.

  Further, when a voltage of +5 V is applied for 3 seconds between the lead portion of the first electrode layer 52 and the lead portion of the second electrode layer 55, the first electrode layer 52 and the second electrode layer 55 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

[Example 5]
Example 5 shows another example of producing the electrochromic device 30 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)
An inorganic insulating layer of ZnS—SiO ₂ (8/2) and an ITO second electrode layer 15 were formed directly on the insulating porous layer 14 (without using colloidal lithography). Moreover, the electrolyte was changed to ethyl methyl imidazolium salt alone as an ionic liquid, dropped onto the second electrode layer 15, and then heated on a hot plate at 120 ° C. for 10 minutes to fill the electrolyte. Except this, it carried out similarly to Example 1, and obtained the electrochromic apparatus 30 shown in FIG.

(Color-erasing drive)
The color generation / decoloration of the produced electrochromic device 30 was confirmed. Specifically, when a voltage of −5 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 represented by the structural formula [Chemical Formula 2] was confirmed in the overlapping portion of the electrode layer 15.

  Further, when a voltage of +5 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 15 are applied. It was confirmed that the pigment in the overlapped area was decolored and became transparent.

  The preferred embodiments and examples have been described in detail above, but the present invention is not limited to the above-described embodiments and examples, and the above-described embodiments are not deviated from the scope described in the claims. Various modifications and substitutions can be made to the embodiments. For example, the above embodiments can be combined as appropriate.

10, 20, 30, 40, 50, 60, 70 Electrochromic device 11, 71 Support 12 First electrode layer 13 Electrochromic layer 14, 23, 44 Insulating porous layer 15, 55 Second electrode layer 36 Protective layer 67 Insulating inorganic protective layer

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

Claims (10)

A first electrode layer;
A second electrode layer provided to face the first electrode layer;
An electrochromic layer provided between the first electrode layer and the second electrode layer;
An electrolyte filled in a predetermined region between the first electrode layer and the second electrode layer,
A through hole is formed in at least one layer of the first electrode layer or the second electrode layer,
An electrochromic device in which a support is provided only on one of the outer side of the first electrode layer and the outer side of the second electrode layer.   The electrochromic device according to claim 1, wherein the through-hole is an injection hole for filling the electrolyte or the electrolyte and the electrochromic material. The support is provided on the outer side of the first electrode layer or the second electrode layer in which a through hole is formed,
The electrochromic device according to claim 1, wherein a through hole is formed in the support.   The electrochromic device according to any one of claims 1 to 3, wherein a diameter of the through hole is 10 nm or more and 100 µm or less. An insulating porous layer that insulates 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 claims 1 to 4, wherein the insulating porous layer includes insulating metal oxide fine particles.   The electrochromic device according to any one of claims 1 to 5, wherein the support is an optical element. A step of sequentially laminating a first electrode layer and an electrochromic layer on a support;
Laminating a second electrode layer having a through hole on the electrochromic layer so as to face the first electrode layer with an insulating porous layer interposed therebetween;
Filling a predetermined region between the first electrode layer and the second electrode layer with an electrolyte from the through-hole. Laminating a first electrode layer on a support;
Laminating a second electrode layer having a through-hole formed on the first electrode layer so as to face the first electrode layer with an insulating porous layer interposed therebetween;
Filling a predetermined region between the first electrode layer and the second electrode layer with an electrolyte and an electrochromic material from the through hole. The step of laminating the second electrode layer includes:
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 7, further 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 film thickness of the second electrode layer.

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