JP2010014917A - Electrochromic element and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochromic element capable of preventing a switching speed from lowering as much as possible even when being made large in area. <P>SOLUTION: In the electrochromic element, a first transparent conductive film 4, an oxidation coloring layer 2, an electrolytic layer 1, a reduction coloring layer 3 and a second transparent conductive film 4 are sequentially or reverse-sequentially laminated and formed on a substrate 5, or in the electrochromic element, the electrolytic layer 1 in-between by the oxidation coloring layer 2 and the reduction coloring layer 3 is formed between the first substrate 5, on which the transparent conductive film 4 and the oxidation coloring layer 2 are sequentially laminated and formed on an internal surface side, and a second substrate 5, on which the transparent conductive film 4 and the reduction coloring layer 3 are sequentially laminated and formed on an internal surface. The electrochromic element has a metal grid electrode 6 in the at least one transparent conductive film 4. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an electrochromic device capable of changing the light transmittance by color development or decoloration by application of a voltage and a manufacturing method thereof, and more specifically, even for a large area of 10000 mm ² or more, The present invention relates to an electrochromic device capable of obtaining good responsiveness without causing a significant increase in switching time, and a method for manufacturing the same.

  In recent years, an electrochromic element that induces an electrochemical redox reaction by applying a voltage to cause coloring and decoloring is expected to be applied to a display, a light control window material, and the like.

  Usually, as shown in FIG. 3, an electrochromic element is formed by laminating an oxidation coloring layer 2 on one surface and an reducing coloring layer 3 on the other surface with an electrolytic layer 1 interposed therebetween, and these layers are formed into a transparent conductive film (electrode film). ) 4 and 4 are formed between the transparent substrates 5 and 5 formed thereon. When the voltage is applied between the transparent conductive films (electrode films) 4 and 4, the color developing layers 2 and 3 are colored and the light transmittance is reduced. The layer is decolored, the light transmittance is increased, and the light control performance can be exhibited. In some cases, a liquid electrolytic layer in which an electrolyte is sealed between the two coloring layers 2 and 3 is used as the electrolytic layer 1. In some cases, one transparent substrate 5 is omitted.

  Specific examples of such conventional electrochromic elements include the electrochromic elements described in the following Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-187993).

JP 2007-189933 A

However, in order to use such a conventional electrochromic device as dimming window material, when a larger area is also made to 10000 mm ² or more, the switching speed is too slow, coloring / decoloring response becomes worse It becomes a window material which is not easy to use, and this is a great drawback for application as a window material.

  The present invention has been made in view of the above circumstances, and even when the area is large, a reduction in switching speed can be prevented as much as possible, and a large-area light control window material having good responsiveness can be obtained. An object is to provide an electrochromic device.

  As a result of intensive studies to achieve the above object, the present inventor laminated a first transparent conductive film, an oxidation coloring layer, an electrolytic layer, a reducing coloring layer, and a second transparent conductive film on the substrate in order or in reverse order. When forming an electrochromic device by forming, a transparent conductive film and an oxidation coloring layer are sequentially laminated on the inner surface side of the first substrate, and a transparent conductive film and a reducing coloring layer are formed on the inner surface side of the second substrate. When an electrochromic device is manufactured by sequentially laminating and interposing an electrolytic layer between the oxidation coloring layer and the reduction coloring layer of the first substrate and the second substrate, a metal grid electrode is formed on the transparent conductive film. Therefore, even when the surface resistance of the transparent conductive film is reduced and the area is increased, a good switching speed is achieved without causing a decrease in switching speed due to an increase in the resistance value of the transparent conductive film. In addition, in this case, printing is performed on the transparent base material with ink containing catalyst particles, and a metal is deposited on the pattern by plating. By forming the above metal grid electrode, a fine grid with a narrow line width can be accurately and reliably formed, and a good transparency is maintained without greatly reducing the aperture ratio. The inventors have found that an electrochromic device having responsiveness can be obtained, and completed the present invention.

Accordingly, the present invention provides an electrochromic device in which a first transparent conductive film, an oxidation coloring layer, an electrolytic layer, a reduction coloring layer, and a second transparent conductive film are laminated on a substrate in order or in reverse order, or transparent on the inner surface side. Between the first substrate in which the conductive film and the oxidation coloring layer are sequentially laminated and the second substrate in which the transparent conductive film and the reduction coloring layer are sequentially laminated on the inner surface side, the oxidation coloring layer and the reduction coloring layer In an electrochromic element in which an electrolytic layer is formed in a state sandwiched between, an electrochromic element having a metal grid electrode in at least one transparent conductive film, and
When a transparent conductive film having a metal grid electrode is laminated on a transparent substrate, and further, a coloring layer and an electrolytic layer are laminated on the transparent conductive film to produce an electrochromic device, catalyst particles are placed on the transparent substrate. An electrode pattern is printed with the contained ink, a metal film is deposited on the pattern by a plating method to form the metal grid electrode, and a transparent conductive film is formed on the transparent substrate on which the metal grid electrode is formed. The present invention provides a method for producing an electrochromic device, which is characterized by forming a transparent conductive film with electrodes.

According to the electrochromic device of the present invention, even if it is formed in a large area of 10000 mm ² or more, the dimming operation can be performed with good responsiveness while exhibiting a good switching speed without significantly reducing the switching speed. The area of the light control window material can be increased.

Hereinafter, the present invention will be described in more detail.
In the electrochromic device of the present invention, for example, as shown in FIG. 1, an oxidation coloring layer 2 is laminated on one surface and an reducing coloring layer 3 is laminated on the other surface with an electrolytic layer 1 interposed therebetween. , 3 are laminated on the outer sides of the transparent conductive films 4, 4, respectively, and are laminated between a pair of transparent base materials (substrates) 5, 5. It is what you have.

  The electrolytic layer 1, the oxidation coloring layer 2, the reduction coloring layer 3, the transparent conductive film 4 and the transparent substrate 5 can be formed using a known material as a material of these portions of the electrochromic element. Specifically, as the transparent substrate 5, a plastic plate such as a glass plate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), acrylic resin, triacetyl cellulose (TAC), polyimide resin, or the like. Or a polymer film can be used. The thickness of the transparent substrate 5 is usually 0.05 to 5 mm, particularly about 0.1 to 3 mm, although it depends on the material. The two transparent substrates 5 and 5 may be the same material or different materials.

  Examples of the transparent conductive film 4 include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-added zinc oxide (AZO), gallium-added zinc oxide (GZO), aluminum / gallium-added zinc oxide (AGZO), and indium oxide. -Tungsten (IWO), antimony tin oxide (ATO), etc. are illustrated, These 1 type (s) or 2 or more types can be used. The thickness of the transparent conductive film 4 is not particularly limited, but is usually 0.05 to 2 μm, particularly 0.1 to 1 μm.

Examples of the oxidation coloring layer 2 include nickel oxide (NiO) and iridium oxide (IrO _x ), and examples of the reducing coloring layer 3 include tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), and vanadium oxide. (VO) and the like are exemplified. The thickness of the oxidation coloring layer 2 is not particularly limited, but is usually 0.1 to 2 μm, particularly 0.3 to 1 μm.

As the electrolyte layer 1, a _{Ta 2 O 5, ZrO 2,} SiO 2, Nb 2 O 5, Cr 2 O 3 · V 2 O 5, HfO 2 or the like of the metal oxide film and MgF ₂ metal fluoride film Examples thereof include a solid layer; a liquid layer in which a liquid obtained by dissolving LiClO ₄ in propylene carbonate or γ-butyllactone is encapsulated. The thickness of the electrolytic layer 1 is not particularly limited, but is usually 0.1 to 2 μm, particularly 0.3 to 1 μm for a solid electrolyte, and 5 to 500 μm, particularly 20 to 200 μm for a liquid electrolyte. can do.

  In the present invention, the metal grid electrode 6 is attached to the transparent conductive film 4, and the metal forming the metal grid electrode 6 includes Cu, Ni, Au, Ag, Al, Sn, Co, Zn, and the like. It can be set as the electrode which has these 1 type, or 2 or more types of metals as a main component.

  This metal grit electrode can be formed on the transparent substrate 5 by a plating method, and the transparent conductive film 4 having the metal grid electrode 6 can be formed by forming the transparent conductive film 4 thereon. . Specifically, as a method by the plating method, first, a grid electrode pattern is printed with an ink containing catalyst particles, and the metal is deposited on the pattern by an electroless plating method. Further, if necessary, further electroplating is performed. The metal grid electrode 6 can be formed by further growing the metal film.

Here, the catalyst particles may be any catalyst that can serve as a catalyst for electroless plating, and are selected according to the type of metal to be deposited by electroless plating and the plating solution used. For example, PdTiO ₃ .6H ₂ O (metal oxide) Hydrate) fine particles, fine particles in which Pd is supported on a metal oxide such as titanium oxide, and the like.

  The ink containing the catalyst particles can be prepared, for example, by mixing and dispersing the catalyst particles in an organic solvent in which a resin such as a polyester resin is dissolved. The printing method using this ink is not particularly limited, and an appropriate printing method may be adopted.For example, printing methods such as screen printing, gravure printing, flexographic printing, offset printing, and ink jet printing may be adopted. Usually, screen printing and gravure printing are preferably employed, and gravure printing is particularly preferably employed since finer and finer printing is possible.

  The electroless plating for depositing the metal film on the electrode pattern printed on the transparent substrate 5 and the electroplating for depositing and growing the metal film on the electrode pattern are performed by conventional methods and conditions conventionally known. Just do it.

  Here, the metal grid electrode 6 is not particularly limited, but has a thickness of 1 to 10 μm, particularly 1 to 7 μm, a width of 10 to 1000 μm, particularly 10 to 50 μm, and a grid pitch (width between electrodes) of 0. 0.1 to 20 μm, particularly 0.1 to 10 μm is preferable, whereby a sufficient aperture ratio can be maintained to ensure good transparency and good responsiveness can be obtained. The form of the grid can be various forms such as a stripe form such as a vertical lattice form, a horizontal lattice form, an oblique lattice form, a mesh form such as a cross lattice, and other lattice forms.

  Thus, by forming a pattern by printing such as screen printing or gravure printing as described above, and depositing a metal electrode on the pattern by plating, the line width is thin and fine as described above. The metal grit electrode 6 can be formed, whereby a good switching speed can be obtained without reducing the aperture ratio. In addition, the formation method of this metal grid electrode 6 is not limited to the said method, For example, it can also form by the following method. For example, (a) a predetermined pattern is printed with water-soluble ink on the transparent substrate (substrate) 5, a conductive film is formed thereon, and the water-soluble ink print pattern portion is removed by washing with water. Patterning the conductive film (reverse printing method), a method of depositing a metal film on the conductive film by electroplating, or (b) printing a pattern with conductive ink on the transparent substrate (substrate) 5, The metal grid electrode 6 can also be formed by a method of depositing a metal film on the pattern by electroplating. Further, in some cases, in the method (b), the metal film deposition operation by electroplating is omitted, and the conductive film patterned by the reverse printing method obtained after washing with water is used as the metal grit electrode 6 as it is. In the method (b), it is possible to omit the metal film deposition operation by electroplating and use the conductive ink printed with the pattern as the metal grit electrode 6. The conductive film patterned by the reversal printing method obtained by these methods and the pattern printed with the conductive ink may not be exactly the metal material, but these are also convenient for the present invention. It is called “metal grit electrode”.

  The method for forming the electrolytic layer 1 (in the case of a solid electrolyte), the oxidation coloring layer 2, the reduction coloring layer 3, and the transparent conductive film 4 is not particularly limited, and may be formed by a known method, and usually a sputtering method or a vapor deposition method. However, sputtering methods such as ordinary planar type magnetron sputtering method and gas flow sputtering method which has been attracting attention in recent years are preferably employed. Among them, gas flow sputtering method can be formed in a short time and at low cost. In particular, it is preferably used for forming the electrolytic layer 1 (in the case of a solid electrolyte), the oxidation coloring layer 2 and the reduction coloring layer 3.

That is, this gas flow sputtering method is a method in which sputtering is performed under a relatively high pressure, and sputtered particles are transported to a deposition target substrate by a forced flow of gas and deposited.
Since this gas flow sputtering method does not require high vacuum evacuation, it is possible to form a film by mechanical pump evacuation without using a large evacuation device like the conventional normal sputtering method. It can be implemented with inexpensive equipment. Moreover, the gas flow sputtering method can form a film 10 to 1000 times faster than the usual sputtering method. Therefore, the light control window material of the present invention can be manufactured at low cost by reducing the equipment cost and the film formation time by adopting this gas flow sputtering method. And if it is a gas flow sputtering method, the film | membrane with favorable adhesiveness with respect to a board | substrate can be formed, and the light control window material which consists of a high quality electrochromic element can be manufactured.

  Furthermore, when the electrolytic layer 1 (solid electrolyte) is formed, the film formation rate is very fast, so that voids can be easily formed during film formation, and an electrolytic layer excellent in ionic conductivity can be formed. it can. Further, since a magnet is not provided under the target, even when a ferromagnetic material such as Ni is used as a target, there is no restriction on the thickness thereof.

  There are no particular restrictions on the specific procedure for producing the electrochromic device of the present invention by laminating the transparent conductive film 4, the oxidation coloring layer 2, the electrolytic layer 1, and the reduction coloring layer 3 on the transparent substrate 5, but an example is given. For example, the layers may be laminated as follows. For example, first, the grid electrode pattern is printed on the transparent substrate 5 as described above, and the electroless plating and electroplating are sequentially performed to form the metal grid electrode 6. Next, the transparent conductive film 4 having the metal grid electrode 6 is formed by forming the first transparent conductive film 4 on the surface of the transparent substrate 5 on which the metal grid electrode 6 is formed by an ordinary DC sputtering method. To do. Further, the oxidation coloring layer 2, the electrolytic layer 1 and the reduction coloring layer 3 are sequentially formed on the transparent conductive film 4 by a gas flow sputtering method, and the second transparent conductive film 4 is formed thereon by a normal DC sputtering method. And finally a grit electrode. In this case, one transparent substrate 5 can be omitted, but when a transparent substrate is provided on both sides, a transparent substrate in which a transparent conductive film 4 having a metal grit electrode 6 is laminated in the same manner as described above. The material may be bonded onto the reduced coloring layer 3. When one transparent substrate is omitted, the first transparent conductive film 4, the oxidation coloring layer 2, the electrolytic layer 1, the reduction coloring layer 3, and the second transparent conductive film 4 are formed on the transparent substrate 5. It is also possible to form an electrochromic device in which the layers are stacked in the reverse order.

  When a liquid electrolyte is used as the electrolytic layer 1, a pair of transparent base materials in which a transparent conductive film 4 having a metal grid electrode 6 is formed in a stacked manner are prepared in the same manner as described above. The oxidation coloring layer 2 is formed by a gas flow sputtering method, the reducing coloring layer 3 is formed on the other transparent conductive film 4, and the liquid electrolyte is sealed between them using a sealing material. Thus, the electrolytic layer 1 may be formed.

  Note that the conditions for DC sputtering and gas flow sputtering may be appropriately set to normal conditions according to the type of target material, the area of film formation, the thickness, and the like. Further, the metal grid electrode 6 is not necessarily provided on both the first and second transparent conductive films 4, and the metal grid electrode 6 of one transparent conductive film 4 may be omitted depending on circumstances.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

[Example]
The light control window material of the structure shown by FIG. 1 was produced in the following procedures. In this case, two types of electrochromic elements having a normal area (50 mm × 50 mm) and a large area (500 mm × 500 mm) were produced by the same method.

First, 15% by mass of a polyester resin as a solid content is dissolved in cyclohexanone, and 60% by mass of PdTiO ₃ .6H ₂ O (metal oxide hydrate) fine particles are mixed and dispersed in the rheology agent. The ink was prepared by adjusting the viscosity. A stripe pattern was printed by screen printing on the transparent substrate 5 made of a glass plate having a thickness of 1 mm using this ink. The dimensions of this pattern are a line width of 25 μm, a line height of 1 μm, and a pitch of 0.5 mm.

The transparent substrate 5 is immersed in an electroless copper plating solution (Melplate CU-5100, manufactured by Meltex Co., Ltd.) heated to 50 ° C., and 10 μm thick metallic copper is placed on the printed pattern of the ink. To be deposited. Subsequently, an electroplating bath of pure water: copper sulfate: sulfuric acid: hydrochloric acid = 10: 1: 2: 0.002 (mass ratio) is constructed, and the plating base is heated and maintained at 30 ° C. to obtain the transparent substrate. 5 was immersed, and a current of ² A / dm ² was passed by a rectifier to deposit metal copper having a thickness of 4 μm on the pattern, thereby forming a striped grid electrode 6 made of copper.

Next, this transparent base material 5 is set in a vacuum chamber, an ITO thin film having a thickness of 0.1 μm is formed using a magnetron sputtering apparatus, and the transparent conductive film 4 with the metal grid electrode 6 is formed on the transparent base material 5. Formed. The sputtering conditions are as follows.
(Sputtering conditions)
DC magnetron sputtering target: Ceramic ITO
Deposition pressure: 0.5Pa
Introduced gas: Ar = 200 sccm, O ₂ = 4 sccm
Input power: 4W / cm ²
Substrate temperature: Room temperature

Using the gas flow sputtering apparatus shown in FIG. 2, an oxidation coloring layer 2 (NiO, thickness 500 μm), an electrolytic layer 1 (Ta ₂ O ₅ , thickness 500 μm) and a transparent conductive film 4 of the transparent substrate 5 A reduction coloring layer 3 (WO ₃ , thickness of 500 μm) was sequentially formed. That is, the transparent base material 5 was set in a vacuum chamber, exhausted to 1 × 10 ⁻¹ Pa with a roughing pump (rotary pump + mechanical booster pump), and then the three-layer multilayer film was formed under the following conditions. . At this time, in order to obtain a desired film thickness, a multilayer film was produced by adjusting the substrate moving speed.

(Deposition conditions)
[Gas flow sputtering equipment]
・ Cathode shape: Parallel flat plate (disposed with two targets facing each other in parallel, distance 30 mm)
-Substrate temperature: Room temperature (no substrate heating)
・ Substrate moving speed: 0.1 to 10 M / min variable ・ Substrate position: Distance between cathode end and substrate 50 mm)
[Film formation conditions]
Argon gas: 3000sccm
Oxygen gas: 30 sccm
Deposition pressure: 40 Pa
Film thickness: 500nm
Target: oxidation coloring layer (Ni), electrolyte layer (Ta), reduction coloring layer (W)

  An ITO thin film (second transparent conductive film 4) and a grid electrode 6 having a thickness of 0.1 μm were formed in the same manner as described above on the reduced coloring layer to obtain an electrochromic device.

  When a voltage was applied between the electrodes of the obtained electrochromic device (a voltage of 1.5 V was applied between the electrodes with the reduction color layer side being negative and the oxidation color layer side being positive), both color layers were colored. The transmittance changed from 75% to 10%. On the other hand, when a voltage was applied in the opposite direction in the same manner, both the colored layers were decolored, and the transmittance was changed from 10% to 75%, confirming reversible light control performance. The response speed at that time was measured. The results are shown in Table 1.

[Comparative example]
An electrochromic device was fabricated in the same manner as in the example except that the copper grid electrode was not formed. At this time, similar to the above-described example, two kinds of light control window materials having a normal area (50 mm × 50 mm) and a large area (500 mm × 500 mm) were produced. When voltage was applied to the obtained electrochromic device in the same manner as in the above example, the transmittance was reversibly changed between 75% and 10%, and light control performance was obtained. The response speed at this time was measured. The results are also shown in Table 1.

  As shown in Table 1, the electrochromic device of the present invention has a small decrease in switching speed even when the area is increased, can maintain a good switching speed and can exhibit a good response speed, and has a large area dimming window. It was confirmed that it can be suitably used as a material.

It is a schematic sectional drawing which shows the electrochromic element concerning one Example of this invention. It is a schematic explanatory drawing which shows an example of the gas flow sputtering apparatus used for manufacture of this invention electrochromic element. It is a schematic sectional drawing which shows the conventional electrochromic element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolytic layer 2 Oxidation coloring layer 3 Reduction coloring layer 4 Transparent conductive film 5 Transparent base material 6 Metal grid electrode

Claims (19)

An electrochromic element in which a first transparent conductive film, an oxidation coloring layer, an electrolytic layer, a reduction coloring layer, and a second transparent conductive film are sequentially or reversely stacked on a substrate, or a transparent conductive film and an oxidation coloring layer on the inner surface side. Is sandwiched between the oxidation coloring layer and the reduction coloring layer between the first substrate in which the transparent coloring layer and the reduction coloring layer are sequentially laminated on the inner surface side. In an electrochromic device in which an electrolytic layer is formed in
An electrochromic device comprising a metal grid electrode in at least one transparent conductive film.   2. The electrochromic device according to claim 1, wherein the metal grid electrode is formed by depositing metal by a plating method on a pattern printed on the substrate with an ink containing catalyst particles.   The metal grid electrode deposits a thin metal film of 0.3 to 1.5 μm on the pattern printed with the ink by an electroless plating method, and further a metal of 1 to 10 μm on the thin metal film by an electroplating method. The electrochromic device according to claim 2, which is formed by depositing a film. The catalyst particles, PdTiO ₃ · 6H ₂ O particles, or electrochromic device according to claim 2 or 3, wherein the metal oxide is a fine particles was supported Pd.   The electrochromic device according to claim 4, wherein the catalyst particles are fine particles in which Pd is supported on titanium oxide.   The metal grid electrode prints a predetermined pattern with water-soluble ink on the substrate, laminates a conductive film thereon, and patterns the conductive film by removing the water-soluble ink print pattern portion by washing with water. The electrochromic device according to claim 1, which is formed by a reversal printing method.   2. The electrochromic device according to claim 1, wherein the metal grid electrode is formed by printing a pattern with conductive ink on the substrate.   The metal grid electrode prints a predetermined pattern with water-soluble ink on the substrate, laminates a conductive film thereon, patterns the conductive film by removing the water-soluble ink print pattern portion by washing with water. 2. The electrochromic device according to claim 1, wherein a metal film is deposited on the conductive film by electroplating.   2. The electrochromic device according to claim 1, wherein the metal grid electrode is obtained by printing a pattern with conductive ink on the substrate and depositing a metal film on the pattern by electroplating.   10. The metal electrode according to claim 1, wherein the metal grid electrode is a metal electrode mainly composed of one or more metals selected from Cu, Ni, Au, Ag, Al, Sn, Co, and Zn. The electrochromic device according to item.   The electrochromic device according to any one of claims 1 to 10, wherein the reduction coloring layer is a metal oxide film selected from tungsten oxide, molybdenum oxide, and vanadium oxide.   The electrochromic device according to any one of claims 1 to 11, wherein the oxidation coloring layer is a metal oxide film selected from nickel oxide and iridium oxide. The electrolytic _{layer, Ta 2 O 5, ZrO 2} , SiO 2, Nb 2 O 5, Cr 2 O 3 · V 2 O 5, metal selected from HfO ₂ oxide film; or MgF ₂ metal fluoride film 13. The electrochromic device according to claim 1, wherein the electrochromic device is a solid layer comprising: a liquid layer in which a liquid obtained by dissolving LiClO ₄ in propylene carbonate or γ-butyllactone is encapsulated.   The transparent conductive film is indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-added zinc oxide (AZO), gallium-added zinc oxide (GZO), aluminum / gallium-added zinc oxide (AGZO), indium oxide-tungsten. The electrochromic device according to claim 1, which is a conductive film made of a material selected from (IWO) and antimony tin oxide (ATO).   The metal grid electrodes are arranged and formed in a vertical grid pattern, horizontal grid pattern, diagonal grid pattern, cross grid pattern, or other grid pattern with a thickness of 1 to 10 μm and a width of 10 to 1000 μm at a pitch of 0.1 to 20 mm. The electrochromic device according to claim 1, wherein the electrochromic device is one. The electrochromic device according to claim 1, which has a large area of 10,000 mm ² or more.   When a transparent conductive film having a metal grid electrode is laminated on a transparent substrate, and further, a coloring layer and an electrolytic layer are laminated on the transparent conductive film to produce an electrochromic device, catalyst particles are placed on the transparent substrate. An electrode pattern is printed with the contained ink, and a metal film is deposited on the pattern by a plating method to form the metal grid electrode. A transparent conductive film is formed on the transparent substrate on which the metal grid electrode is formed. A method for producing an electrochromic element, comprising forming a transparent conductive film with an electrode.   18. The electrochromic according to claim 17, wherein a metal grid electrode is formed by depositing and growing a metal film by an electroplating method after depositing and forming a metal film on a pattern printed with an ink having catalyst particles. Device manufacturing method.   The method for producing an electrochromic device according to claim 171 or 18, wherein the coloring layer and the electrolytic layer are formed by a gas flow sputtering method.

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