JP2021120691A - Manufacturing method of dimming element - Google Patents

Abstract

To provide a method for manufacturing a dimming element in which a yield in a manufacturing process is improved.SOLUTION: A method for manufacturing a dimming element laminates electrodes in which at least one of the two electrodes has a mesh-like metal thin wire pattern and a conductive non-metal layer on the mesh-like metal thin wire pattern forms electrochromic layers on each of the two electrodes, and then laminates the electrodes via a viscous electrolyte layer such that the electrochromic layers oppose each other.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a dimming element having an improved yield in the manufacturing process.

Dimming elements that change haze or color when energized are known. A dimming element whose haze changes when energized is being studied for line-of-sight shielding applications such as partitions in offices and the like. On the other hand, a dimming element whose color changes when energized is being studied for sunlight shading applications for windows of houses, automobiles, trains, airplanes, and the like.

A dimming element that changes color when energized is generally an electrochromic material (a material that changes color due to a redox reaction or the transfer of ions) and an electrolyte (electrons and ions to an electrochromic material) between two opposing electrodes. (Responsible for giving and receiving). As its configuration, as shown in JP-A-2019-168683 (Patent Document 1) and JP-A-2018-72490 (Patent Document 2), an electrochromic material is provided between two opposing electrodes. It has an electrochromic layer containing an electrochromic material between two opposing electrodes, as shown in Japanese Patent Application Laid-Open No. 2018-185424 (Patent Document 3). , Those having an electrolyte layer containing an electrolyte between the electrochromic layers are known. The latter configuration is attracting particular attention because it is excellent in response speed and also in color maintenance (so-called memory property) after the energization is terminated.

As described above, since it is necessary to transfer electrons to change the color of the dimming element, the better the conductivity of the electrode, the faster the color changing speed of the dimming element. Therefore, for the purpose of improving the color change rate of the dimming element, a conductive non-metal layer made of a conductive non-metal material such as a conductive metal oxide represented by ITO or graphene is laminated on a mesh-like fine metal wire pattern. Attempts have been made to use the resulting material as an electrode. For example, Japanese Patent Application Laid-Open No. 2017-194536 (Patent Document 4) aims to assist the electrical conduction of a transparent conductive layer containing ITO or the like as a main component of an electrode of a dimming element provided with an electrochromic layer. It is described that a metal conductive layer in which a metal thin film is patterned in a fine line shape is provided between the base material and the transparent conductive layer.

In Patent Document 4 described above, an electrochromic layer is formed on an electrode having a base material, a metal conductive layer, and a transparent conductive layer, and then an electrolyte layer is directly coated on the electrochromic layer. However, since the metal conductive layer in which the metal thin film is patterned in a fine line shape has irregularities, if the metal conductive layer is formed by directly coating the electrolyte layer, the metal conductive layer, the transparent conductive layer, and the electrochromic layer may be damaged. be. As a result, since the color change does not occur at the relevant portion, there is a problem that the yield at the time of manufacturing the dimming element is lowered, and a solution has been sought.

On the other hand, Japanese Patent Application Laid-Open No. 2012-73365 (Patent Document 5) discloses an ionic conductive sheet (electrolyte layer) containing a binder resin, a supporting electrolyte salt which is a cationic organic compound, and a solvent. Since the sheet has excellent adhesion to the conductive film and the electrochromic layer on the glass plate, the laminated glass using the ion conductive sheet as an interlayer film exhibits high penetration resistance and is intermediate with the glass plate during use. There is a description that the film does not peel off and has high safety.

Japanese Unexamined Patent Publication No. 2019-168683 JP-A-2018-72490 JP-A-2018-185424 JP-A-2017-194536 Japanese Unexamined Patent Publication No. 2012-73365

An object of the present invention is to provide a method for manufacturing a dimming element having an improved yield in the manufacturing process.

The above object of the present invention is achieved by the following invention.
An electrode having two electrodes, at least one of which has a mesh metal wire pattern on a support and a conductive non-metal layer on the mesh metal wire pattern, on the two electrodes. A method for manufacturing a dimming element in which the above-mentioned electrodes are bonded to each other via an adhesive electrolyte layer so that the electrochromic layers face each other after forming the electrochromic layers.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for manufacturing a dimming element in which the yield in the manufacturing process is improved.

Schematic cross-sectional view showing an example of the method for manufacturing the dimming element of the present invention.

Hereinafter, the present invention will be described in detail.

FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a dimming element of the present invention. In the dimming element 1 illustrated in FIG. 1, an electrochromic layer 41 and an electrochromic layer 42 are formed on the electrodes 2 and 3, respectively, and then the electrochromic layer 41 and the electrochromic layer 42 face each other. It is obtained by laminating the electrodes 2 and 3 described above via the adhesive layer 51 having adhesiveness. The electrode 2 has a mesh-like metal fine wire pattern 21 composed of metal fine wires 21a to 21d on the support 11, and a conductive non-metal layer 31 on the mesh-like metal fine wire pattern 21. As described above, in the prior art, since the electrolyte layer is provided by coating, scratches may occur due to the unevenness of the patterned metal conductive layer, but in the present invention, the dimming element 1 is manufactured by the above-mentioned manufacturing method. By obtaining the light, the problem that the mesh-like fine metal wire pattern 21, the conductive non-metal layer 31, and the electrochromic layer 41 of the electrode 2 are less likely to be scratched and the color change of the light control element 1 does not occur is improved. Therefore, the yield in the manufacturing process of the dimming element 1 is improved.

Note that FIG. 1 is a schematic view, and the relationship between the thickness and width of each layer in the figure does not have to be as shown in the figure.

In the present invention, as the support 11 included in the electrode 2, an insulating support such as resin, glass, or ceramics is preferably used. Among them, a resin film having excellent flexibility and transparency is preferably used because it has excellent handleability. Specific examples of the resin forming such a resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, diacetates resins, and birds. Examples thereof include triacetate resins such as acetyl cellulose, polyarylate resins, polyvinyl chlorides, polysulphon resins, polyether sulfone resins, polyimide resins, polyamide resins, polyolefin resins, cyclic polyolefin resins, and polyvinyl acetal resins. The total light transmittance of the support 11 is preferably 70% or more, more preferably 80% or more. The haze of the support 11 is preferably 0 to 7%, more preferably 0 to 4%.

The thickness of the support 11 is not particularly limited, but it is preferably 25 to 500 μm because the dimming element can be made thinner. The support 11 may contain known additives such as an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a colorant, a flame retardant, and an antistatic agent. Although not shown in FIG. 1, the support 11 may have known layers such as an easy-adhesion layer, a hard coat layer, an antireflection layer, an antiglare layer, an adhesive layer, and an antistatic layer. Often, the support 11 may be subjected to known surface modification treatments such as corona treatment, plasma treatment, primer treatment, and saponification treatment.

In the present invention, the mesh-like fine metal wire pattern 21 is composed of the fine metal wires 21a to 21d. The metal type contained in the fine metal wire is not limited, and examples thereof include known metals such as gold, silver, copper, aluminum, and nickel, and alloys made of known metals, but the metal must be silver or copper from the viewpoint of conductivity. Is preferable. The ratio of the metal contained in the fine metal wire is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total solid content mass of the fine metal wire.

The thickness of the metal fine wires 21a to 21d constituting the mesh metal fine wire pattern 21 is not particularly limited, but if it is too thick, the metal fine wires may be easily visible, and if it is too thin, the conductivity of the mesh metal fine wire pattern 21 is insufficient. May be done. Therefore, the thickness of the thin metal wire is preferably 0.05 to 15 μm, more preferably 0.07 to 12 μm, and particularly preferably 0.1 to 10 μm.

In the present invention, the pattern shape of the mesh-like thin metal wire pattern 21 is described as visibility (difficult visibility of the pattern, hereinafter simply referred to as visibility) that the pattern shape is a geometric shape in which a plurality of unit lattices are arranged in a mesh pattern. ) Is preferable because an excellent dimming element can be obtained. The shape of the unit cell includes, for example, regular triangles, isosceles triangles, right-angled triangles and other triangles, squares, rectangles, rhombuses, parallelograms, trapezoids and other quadrangles, hexagons, octagons, dodecagons, icosagons, etc. Examples of shapes include a combination of n-sided triangles, star shapes, and the like, and examples thereof include a single repetition of these shapes or a combination of two or more types of a plurality of shapes. Of these, the shape of the unit cell is preferably square or rhombus. An irregular geometric shape represented by a Voronoi figure, a Delaunay figure, a Penrose tile figure, or the like is also one of the preferable pattern shapes.

The line width of the thin metal wires 21a to 21d constituting the mesh-like fine metal wire pattern 21 is preferably 30 μm or less, more preferably 1 to 20 μm from the viewpoint of pattern visibility. Further, the repetition interval of the unit cell is preferably 50 to 800 μm because it is excellent in visibility, and more preferably 100 to 500 μm. The aperture ratio of the mesh-like metal fine wire pattern 21 is preferably 60% or more because an electrode having excellent light transmission can be obtained, and more preferably 70% or more. In the present invention, the aperture ratio is the ratio of the area occupied by the portion excluding the area occupied by the mesh-like metal fine wire pattern 21 to the area occupied by the support 11.

The method for forming the mesh-like fine metal wire pattern 21 on the support 11 is not particularly limited, and for example, according to the method disclosed in JP-A-2015-69877, a conductive metal ink or a conductive paste containing a metal and a binder. The silver halide emulsion layer is provided on the support according to a method of forming a mesh metal fine line pattern on the support by a method such as printing or a method disclosed in Japanese Patent Application Laid-Open No. 2007-59270. On the support according to a method of forming a mesh-like metal fine line pattern using a silver salt photosensitive material and a curing and developing method, and a method disclosed in JP-A-2004-221564, JP-A-2007-12314 and the like. A method for forming a mesh metal fine line pattern by a direct development method using a silver salt photosensitive material having a silver halide emulsion layer, JP-A-2003-77350, JP-A-2005-250169, JP-A-2007- Soluble silver salt is formed by using a silver salt photosensitive material having a physically developed nuclear layer and a silver halide emulsion layer on a support in at least this order according to the methods disclosed in Japanese Patent Application Laid-Open No. 188655 and JP-A-2004-207001. A method of forming a network metal fine line pattern using a so-called silver salt diffusion transfer method in which an agent and a reducing agent are allowed to act in an alkaline solution, a method disclosed in Japanese Patent Application Laid-Open No. 2014-197531. Using a photosensitive resist material in which a ground layer and a photosensitive resist layer are laminated, the photosensitive resist layer is exposed to an arbitrary pattern, developed, formed into a resist image, and then electroless plated to cover the resist image. A metal film is formed on a support according to a method of localizing a metal on a non-existing base layer and then removing a resist image to form a mesh metal fine line pattern, which is disclosed in Japanese Patent Application Laid-Open No. 2015-82178. , A method in which a resist film is provided, the resist film is exposed and developed to form an opening, and the metal film of the opening is etched and removed to form a mesh metal fine line pattern, and the like can be exemplified.

Among the methods for forming a mesh-like metal fine wire pattern on the support described above, a silver salt photosensitive material is used because a mesh-like metal fine wire pattern composed of silver-containing metal fine wires having excellent conductivity can be easily formed. A method of forming a mesh-like metal fine wire pattern is preferable, and a method of forming a mesh-like metal fine wire pattern by using a silver salt diffusion transfer method is particularly preferable because the pattern can be easily miniaturized.

For the purpose of further improving the conductivity of the mesh metal fine wire pattern, it is also preferable to perform electrolytic plating or electroless plating after forming the mesh metal fine wire pattern on the support by the above method. This is one of the aspects. The method of electrolytic plating or electroless plating is not particularly limited, and using known plating baths such as electrolytic copper plating, electroless copper plating, electrolytic nickel plating, electroless nickel plating, and electrolytic gold plating, under known plating conditions. Can be plated.

Further, for the purpose of improving the visibility of the mesh-like metal fine line pattern, blackening treatment can be performed after forming the mesh-like metal fine line pattern on the support by the above method. Examples of such blackening treatment include a laminating method and a replacement method. As the laminating method, a known black plating method such as black nickel plating, black chrome plating, black tin-nickel alloy plating, or a metal material such as nickel copper, nickel copper titanium, nickel copper molybdenum is used as a target material, and oxygen is used. A method of plating under the supply of a reactive gas such as nickel or nitrogen, a method of printing black ink, and the like can be exemplified. Examples of the replacement method include a method of sulfurizing or oxidizing the surface of the fine metal wire, a method of replacing the surface of the fine metal wire with a more noble metal, and the like. Examples of the method of sulfurizing the surface of the fine metal wire include an aqueous solution of potassium sulfide, barium sulfide, and ammonium sulfide, and a method of applying a mixed aqueous solution of sulfur and sodium sulfide to the surface of the fine metal wire. As a method for oxidizing the surface of the fine metal wire, a mixed aqueous solution of hypochlorite and sodium hydroxide, a mixed aqueous solution of chlorite and sodium hydroxide, a mixed aqueous solution of peroxodisulfuric acid and sodium hydroxide, etc. are used on the surface of the fine metal wire. The method of giving to can be exemplified. As a method of replacing the surface of the fine metal wire with a more noble metal, an example of a method of applying an aqueous solution containing palladium chloride, palladium sulfate, or palladium nitrate to the surface of the fine metal wire can be exemplified.

In the present invention, the fine metal wire constituting the mesh-like fine metal wire pattern may be subjected to a known metal surface treatment other than the above-mentioned blackening treatment. For example, a reducing substance, a water-soluble phosphoric acid compound, or a water-soluble halogen compound as described in JP-A-2008-34366 may be allowed to act, as described in JP-A-2013-196779. Triazine having two or more mercapto groups in the molecule or a derivative thereof may be allowed to act. When forming a mesh-like metal fine wire pattern using a silver salt photosensitive material, the metal fine wire is treated with a treatment solution containing an enzyme such as a proteolytic enzyme as described in JP-A-2007-12404. , Residual gelatin and the like may be reduced.

In the present invention, the electrode 2 may have a solid pattern (filled pattern) on the support 11 in addition to the above-mentioned mesh-like fine metal wire pattern 21. For example, a terminal for connecting a wiring member responsible for electrical connection with the outside such as a flexible printed wiring board, and a peripheral wiring for electrically connecting a mesh-like thin metal wire pattern and a terminal can be provided by a solid pattern. .. The line width of the terminals and peripheral wiring is not particularly limited. As a method for forming the solid pattern, the same method as the method for forming the mesh-like fine metal wire pattern 21 described above can be exemplified.

The material constituting the conductive non-metal layer 31 is not particularly limited, and transparent conductive metal oxides such as indium oxide, zinc oxide, and tin oxide, and known conductive non-metal materials such as graphene can be used. It can be exemplified. Among the above, it is preferable to use a conductive metal oxide, and it is particularly preferable to use indium oxide because it is excellent in transparency and conductivity. When indium oxide is used as a material constituting the conductive non-metal layer, it is preferable to perform so-called doping in which tin oxide, titanium oxide, zinc oxide and the like are added for the purpose of improving conductivity. Above all, it is particularly preferable to use indium tin oxide (ITO) obtained by doping indium oxide with tin oxide as a material for forming the conductive non-metal layer.

The thickness of the conductive non-metal layer 31 is not particularly limited, but if it is too thick, the color of the conductive non-metal material may become apparent, so 5 to 500 nm is preferable, and 10 to 300 nm is particularly preferable.

The method for forming the conductive non-metal layer 31 is not particularly limited, and is conductive from known forming methods such as a dry process such as a vacuum deposition method, a sputtering method, and an ion plating method, and a wet process such as coating and printing. A method suitable for the material constituting the non-metal layer may be selected.

In the present invention, the configuration of the electrode 3 is not particularly limited as long as it has conductivity for functioning as an electrode. For example, similarly to the electrode 2, it may be an electrode having a mesh-like metal fine wire pattern on the support and a conductive non-metal layer on the mesh-like metal fine wire pattern, or a mesh-like metal fine wire on the support. The electrode may be an electrode having only a conductive non-metal layer on the support without providing a pattern. Among them, an electrode having a mesh-like metal fine wire pattern on the support and a conductive non-metal layer on the mesh-like metal fine wire pattern is particularly preferable as the electrode 3 because the color change rate of the light control element is excellent. However, in this case, since both the electrode 2 and the electrode 3 have a mesh metal fine wire pattern on the support and a conductive non-metal layer on the mesh metal fine wire pattern, it was described above that the electrolyte layer is provided by coating. Scratches are more likely to occur, and the yield during manufacturing is likely to decrease. Therefore, the present invention works particularly effectively in the manufacture of a dimming device having such a configuration.

As each element (material, thickness, etc.) of the support, the mesh-like fine metal wire pattern, and the conductive non-metal layer that the electrode 3 may have, the same contents as those of the electrode 2 can be exemplified. Each element of the electrode 2 and the electrode 3 may be the same or different.

In the present invention, the electrochromic layer 41 and the electrochromic layer 42 contain at least an electrochromic material. The electrochromic material is not particularly limited, and materials known as organic or inorganic electrochromic materials are exemplified.

Examples of organic electrochromic materials include biologen compounds, viologen salt compounds, ferrocene compounds, polypyrrole compounds, polythiophene compounds, polyparaphenylene vinylene compounds, polyaniline compounds, polyacetylene compounds, polyethylenedioxythiophene compounds, metallic phthalocyanine compounds, and dimethyl terephthalate. Compounds and the like are exemplified.

Inorganic electrochromic materials include tungsten oxide, nickel hydroxide, nickel oxide, niobium oxide, molybdenum oxide, iridium oxide, manganese oxide, cobalt oxide, vanadium oxide, vanadium hexaoxide, renium oxide, tantalum oxide, and rhodium oxide. Chromium oxide, tantalum oxide, copper oxide, paratheodium oxide, strontium-doped titanium acid, tungsten sulfite, indium nitride-tin nitride, Prussian blue, Prussian blue analog (part of the iron element of Prussian blue is replaced with other metal elements) ) Etc. are exemplified.

Since the color of the above-mentioned electrochromic material changes due to the redox reaction and the transfer of ions, for example, an electrochromic material that develops color in the electrochromic layer 41 by the oxidation reaction and decolorizes by the reduction reaction is used, and the electrochromic layer is used. When an electrochromic material that develops color by reduction reaction and decolorizes by oxidation reaction is used for 42, the entire dimming element 1 can be switched between a transparent state and a color development state by energization, and the color development density in the color development state can be improved. It is particularly preferable because it can be used. Such electrochromic material combinations include polyacetylene / polyaniline, polypyrrole / polyaniline, tungsten oxide / nickel oxide, tungsten oxide / tantalum oxide, tungsten oxide / Prussian blue, Prussian blue / Prussian blue analogs, polythiophene compounds / Prussian blue. , Tungsten oxide / polyaniline compound, etc. can be exemplified.

Commercially available products can be used as Prussian blue and Prussian blue analogs. For example, a wFeHCF nanoparticle dispersion (Prussian blue dispersion) or a wNiHCF nanoparticle dispersion (nickel-substituted Prusian blue analog dispersion) commercially available from Kanto Chemical Co., Ltd. can be obtained and used.

The content of the electrochromic material in the electrochromic layer 41 and the electrochromic layer 42 is not particularly limited, but if it is too small, the color density of the dimming element 1 may decrease, and if it is too large, the color change rate of the dimming element 1 may decrease. May decrease. Thus, the content is preferably ^{0.01~5.0g / m 2, 0.05~3.0g / m} 2 is particularly preferred.

In addition to the above-mentioned electrochromic materials, the electrochromic layer 41 and the electrochromic layer 42 further include surfactants, ultraviolet absorbers, infrared absorbers, colorants (pigments, dyes, etc.), antioxidants, silane coupling agents, etc. It may contain a known additive of.

The method for forming the electrochromic layer 41 and the electrochromic layer 42 is not particularly limited, and among known forming methods such as a dry process such as a vacuum deposition method, a sputtering method, and an ion plating method, and a wet process such as coating and printing. It may be appropriately selected and formed on the electrode 2 and the electrode 3. For example, when forming an electrochromic layer using the wFeHCF nanoparticle dispersion or wNiHCF nanoparticle dispersion commercially available from Kanto Chemical Co., Ltd., the bar coating method, dip coating method, spin coating method, die coating method, etc. Known coating methods such as blade coating method, gravure coating method, curtain coating method, spray coating method, kiss coating method, gravure printing, flexo printing, inkjet printing, screen printing, offset printing, gravure offset printing, dispenser printing, pad printing. An example is a method in which the nanoparticle dispersion liquid is applied onto the electrodes 2 and 3 using a known printing method such as the above and dried. Examples of the drying method include known drying methods such as natural drying, vacuum drying, hot air drying, low humidity air drying, infrared drying, and hot roll drying.

In the present invention, the electrolyte layer 51 is adhesive, and it is preferable that the electrolyte layer contains at least an electrolyte, a solvent, and a resin. When the electrolyte layer 51 contains a solvent, the color change rate of the dimming element becomes excellent, and when the electrolyte layer 51 contains a resin, it becomes easy to impart adhesive strength to the electrolyte layer 51. ..

The electrolyte contained in the electrolyte layer 51 is not particularly limited, and salts such as alkali metal salts and alkaline earth metal salts can be exemplified. Specifically, potassium hexafluorophosphate, potassium tetrafluoroborate, potassium chloride, bis (trifluoromethanesulfonyl) imide potassium, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, trifluoromethane Examples thereof include lithium sulfonate, lithium trifluoroacetate, sodium chlorate, and magnesium perchlorate. The electrolyte may be used alone or in combination of two or more.

The content of the electrolyte in the electrolyte layer 51 is not particularly limited, but is preferably 1.0% by mass or more, preferably 1.5% by mass, based on the total mass of the electrolyte layer 51, because the color change rate of the dimming element is excellent. The above is more preferable, and 2.0% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 10% by mass or less.

The solvent contained in the electrolyte layer 51 is not particularly limited, and a known solvent capable of dissolving the electrolyte contained in the electrolyte layer 51 can be used. Specifically, chain carbonate esters such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, cyclic carbonate esters such as ethylene carbonate, propylene carbonate and butylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and butyric acid. Aliphatic carboxylic acid esters such as methyl, methyl isobutyrate, methyl trimethylacetate, aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate, lactones such as γ-butyrolactone and γ-valerolactone, ε-caprolactam, N- Lactam such as methylpyrrolidone, cyclic ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, chain ethers such as 1,2-diethoxyethane and ethoxymethoxyethane, ethylmethylsulfone, sulfolane, 3 -Sulfones such as methyl sulfolane and 2,4-dimethyl sulfolane, nitriles such as acetonitrile, propionitrile and methoxypropionitrile, phosphate esters such as trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate and triethyl phosphate. , Ethanol, alcohols such as 2-propanol, glycols such as ethylene glycol, propylene glycol and polyethylene glycol, water and the like can be exemplified. The solvent may be used alone or in combination of two or more.

The content of the solvent in the electrolyte layer 51 is not particularly limited, but 5% by mass or more is preferable with respect to the total mass of the electrolyte layer 51, and 10% by mass, because the color change rate of the dimming element 1 is excellent. % Or more is more preferable, and 15% by mass or more is particularly preferable. Although the upper limit is not particularly limited, it is preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less because the adhesive strength of the electrolyte layer 51 can be made excellent.

The resin contained in the electrolyte layer 51 is not particularly limited, and includes acrylic resin, urethane resin, silicone resin, epoxy resin, vinyl chloride resin, ethylene resin, melamine resin, phenol resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyethylene oxide resin and the like. A known resin of the above can be exemplified. The above resin is obtained by polymerizing a resin precursor with a polymerization initiator.

The resin precursor is not particularly limited, and monomers and oligomers of various resins can be used. Among them, the (meth) acrylic monomer and the (meth) acrylic oligomer are particularly preferable because the resin obtained by polymerization has excellent transparency and it is easy to control the polymerization to impart adhesiveness to the resin. .. Therefore, in the present invention, it is particularly preferable that the electrolyte layer 51 contains an acrylic resin. A single (meth) acrylic monomer and / or (meth) acrylic oligomer may be used as the resin precursor, and two or more kinds of (meth) acrylic monomer and / or (meth) acrylic oligomer may be used in combination. You may. In addition, "(meth) acrylic" represents "acrylic" or "methacryl", and the same applies to others.

In the present invention, since the polypoly resin obtained by polymerization has excellent compatibility with the above-mentioned electrolyte and solvent, at least a (meth) acrylic oligomer and / or a (meth) acrylic monomer having an ethylene oxide structure is used. It is particularly preferable to use at least a (meth) acrylic oligomer because the adhesive strength of the acrylic resin obtained by polymerization is excellent.

Examples of the (meth) acrylic oligomer include (meth) acrylic oligomers such as urethane acrylate, epoxy acrylate, polyester acrylate, isoprene acrylate, and butadiene acrylate. The (meth) acrylic oligomer in the present invention means an oligomer having at least one (meth) acrylic group.

The above (meth) acrylic oligomers are commercially available, and any of them can be preferably used. As urethane acrylate, Toagosei Co., Ltd. Aronix (registered trademark) M-1100, Aronix M-1200, Shin Nakamura Chemical Industry Co., Ltd. UA-1100H, UA-160TM, Daicel Ornex Co., Ltd. EBECRYL (registered) Examples thereof include 210, EBECRYL230, EBECRYL270, Beam Set (registered trademark) 505A-6 manufactured by Arakawa Chemical Industry Co., Ltd., Beam Set 550B, Beam Set 575, UV-3640PE80 manufactured by Mitsubishi Chemical Co., Ltd., UV-3630ID80, and the like. .. Examples of the epoxy acrylate include Unidic (registered trademark) V-5500 and Unidic V-5502 manufactured by DIC Corporation, epoxy ester 80MFA manufactured by Kyoeisha Chemical Co., Ltd., and epoxy ester 3000MK. Examples of the polyester acrylate include Aronix M-7100 and Aronix M-8100 manufactured by Toagosei Co., Ltd., EBECRYL436, EBECRYL450 and EBECRYL810 manufactured by Daicel Ornex Co., Ltd. Examples of the isoprene acrylate include UC-102 and UC-203 manufactured by Kuraray Co., Ltd. Examples of the butadiene acrylate include NISSO (registered trademark) -PB TE-2000 manufactured by Nippon Soda Corporation.

Examples of the (meth) acrylic monomer having an ethylene oxide structure include methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxypolyethylene glycol # 600 (meth) acrylate, and ethoxydiethylene glycol (meth) acrylate. Phenoxyethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) ) Acrylate, polyethylene glycol # 1000 di (meth) acrylate and the like can be exemplified.

Examples of (meth) acrylic monomers other than the above monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , S-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meta) Acrylate, Isooctyl (Meta) Acrylate, Nonyl (Meta) Acrylate, Isononyl (Meta) Acrylate, Decyl (Meta) Acrylate, Isodecyl (Meta) Acrylate, Dodecyl (Meta) Acrylate, Tridecyl (Meta) Acrylate, Tetradecyl (Meta) ) Acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, nonadecil (meth) acrylate, eicocil (meth) acrylate, etc. (Meta) acrylic acid alkyl ester having a group, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) (Meta) acrylic acid alkoxyalkyl esters such as acrylates, 3-ethoxypropyl (meth) acrylates, 4-methoxybutyl (meth) acrylates, 4-ethoxybutyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N -Amid group-containing monomers such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, aminoethyl (meth) acrylate, dimethylamino Amino group-containing monomers such as ethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate, glycidyl (meth) a. Glycidyl group-containing monomers such as clearate and methylglycidyl (meth) acrylate, cyano group-containing monomers such as acrylonitrile and methacrylonitrile, hexanediol di (meth) acrylate, butanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, trimethylpropantri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate and other polyfunctional monomers can be exemplified, but are not limited thereto.

The content of the resin in the electrolyte layer 51, that is, the content of the resin precursor is not particularly limited, but since the adhesive strength of the electrolyte layer 51 can be made excellent, it is 45% by mass or more with respect to the total mass of the electrolyte layer 51. Is preferable, 50% by mass or more is more preferable, and 55% by mass or more is particularly preferable.

The polymerization initiator used for the polymerization of the resin precursor is not particularly limited, and known polymerization initiators can be exemplified. Here, the polymerization initiator means a compound that initiates the polymerization reaction of the resin precursor by heat or ionizing radiation. Examples of the polymerization initiator that initiates the polymerization reaction by heat include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, (2-ethylhexanoyl) (tert-butyl) peroxide, and tert-butyl. Organic peroxides such as benzoyl peroxide and lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylbuty An azo compound such as ronitrile can be exemplified, and examples of the polymerization initiator that initiates the polymerization reaction by ionizing radiation include 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2, , 2-Dimethoxy-2-phenylacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1) -Acetphenone compounds such as -methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, benzoyl , Benzoyl compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ′, 4,4 ′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ) Ethyl] Benzenmethanamineium bromide, benzophenone compounds such as (4-benzoylbenzyl) trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone, 2- (3-dimethylamino-2-) Examples thereof include thioxanthone compounds such as hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride. The ionizing radiation means electromagnetic waves or charged particles having energy capable of initiating the polymerization reaction of the resin precursor, and examples thereof include ultraviolet rays, visible rays, gamma rays, X-rays, and electron beams, and among them, ultraviolet rays are used. Is preferable from the viewpoint of productivity.

The above-mentioned polymerization initiators are commercially available, and any of them can be preferably used. Specifically, IGM RESINS's Omnirad (registered trademark) 127, Omnirad 184, Omnirad 369, Omnirad 500, Omnirad 651, Omnirad 754, Omnirad 819, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 819, Omnirad 907, Omnirad 907, Omnirad 907, Omnirad 907, Otsuka Chemical Co., Ltd.

The content of the polymerization initiator in the electrolyte layer 51 is not particularly limited, but from the viewpoint of the polymerization rate, it is preferably 0.05 to 5% by mass, preferably 0.1 to 3% by mass, based on the total mass of the electrolyte layer 51. Especially preferable.

Examples of the polymerization method of the resin precursor include known polymerization methods such as a solution polymerization method, an emulsion polymerization method, a massive polymerization method, and an ionization radiation irradiation polymerization method. When a polymerization initiator that initiates the polymerization reaction by heat is used, When a polymerization initiator that initiates the polymerization reaction by ionizing radiation is used as the solution polymerization method, the ionization radiation irradiation polymerization method may be selected according to the characteristics of the polymerization initiator to be used.

In the present invention, the electrolyte layer 51 further includes a cross-linking agent (for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, etc.) and a silane coupling agent (for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane). Phenol coupling agents having an epoxy group such as 3-mercaptopropyltrimethoxysilane, silane coupling agents having a mercapto group such as 3-acryloxypropyltrimethoxysilane, silane coupling agents having an acrylic group such as 3-acryloxypropyltrimethoxysilane), etc. Adhesive-imparting agents (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), antioxidants (hindered phenol compounds, phosphite ester compounds, thioether compounds, etc.), ultraviolet absorbers (triazine compounds, etc.) Addition of known resins such as benzophenone compounds), light stabilizers (hindered amine compounds, etc.), fillers, colorants (pigments, dyes, etc.), chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may contain an agent.

In the present invention, the electrolyte layer 51 needs to have adhesiveness. If the electrolyte layer 51 does not have adhesiveness, floating will occur when the electrodes 2 and 3 are bonded via the electrolyte layer 51 or after bonding, and the color will not change even when energized at the relevant location. Therefore, the yield when manufacturing the dimming element is lowered. In the present invention, having adhesiveness means that the peeling adhesive strength measured in a 180 degree peeling test based on JIS Z0237: 2009 is 0.5 N / 25 mm or more.

The thickness of the electrolyte layer 51 is not particularly limited, but if it is too thick, the color change rate of the dimming element 1 may decrease, and if it is too thin, the electrodes 2 and 3 may be short-circuited and the color change may stop. Therefore, the thickness of the electrolyte layer 51 is preferably 0.5 to 500 μm, particularly preferably 1 to 300 μm.

The method for forming the electrolyte layer 51 is not particularly limited except for the method of forming the electrolyte layer 51 by directly coating it on the electrochromic layer 41 and the electrochromic layer 42, but for example, it is made of a resin film, glass, a metal plate or the like 2 A sheet of temporary support is prepared, and a coating liquid for forming an electrolyte layer in which the components contained in the electrolyte layer 51 are mixed and dissolved is applied onto one temporary support, or is applied by a known method such as printing, and further coated. A method of laminating the other temporary support on the liquid surface and then polymerizing the resin precursor contained in the coating liquid for forming the electrolyte layer to form the electrolyte layer 51 can be mentioned. The surface of the temporary support that comes into contact with the electrolyte layer forming coating liquid may be subjected to a known peeling process such as silicone-based or fluorine-based. Examples of the coating method and printing method for forming the electrolyte layer include the coating and printing methods of the wFeHCF nanoparticle dispersion liquid and the wNiHCF nanoparticle dispersion liquid described above. As a method for polymerizing the resin precursor, for example, a method using heating or ionizing radiation may be appropriately selected depending on the polymerization initiator contained in the coating solution for forming the electrolyte layer.

Since the electrolyte layer 51 sandwiched between the two temporary supports can be obtained by the above method, after peeling each temporary support from the electrolyte layer 51 to expose the electrolyte layer 51, the above-mentioned electrodes 2 and The dimming element 1 can be obtained by laminating the electrodes 3 so as to face each other via the electrolyte layer 51. Such a bonding method is not particularly limited, but a method using a laminator such as a roll laminator or a vacuum laminator can be exemplified.

In order to prevent the solvent from volatilizing and the liquid from leaking from the electrolyte layer 51, it is preferable to seal the side surface of the light control element 1. As a sealing method, an epoxy-based, acrylic-based, polyolefin-based, or silicone-based adhesive is applied to the side surface of the dimming element 1 and cured by heating, ionizing radiation irradiation, moisture, or the like, or a hot-melt adhesive is used. Examples thereof include a method of heating and melting and applying it to the side surface of the dimming element 1 and then cooling and curing it, and a method of adhering the side surface of the dimming element 1 with an acrylic adhesive tape or a silicone adhesive tape.

In the dimming element 1 obtained by the present invention, an adhesive layer is bonded to the surface of the electrode 2 opposite to the electrochromic layer 41 and the surface of the electrode 3 opposite to the electrochromic layer 42. Further, a functional material may be bonded on the pressure-sensitive adhesive layer. Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include known pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, acrylic-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives. Functional materials include chemically strengthened glass, soda glass, quartz glass, glass such as non-alkali glass, films made of various resins such as polyethylene terephthalate, and a hard coat layer on at least one surface of the above glass or film to prevent reflection. Examples of materials having known functional layers such as a layer, an antiglare layer, a polarizing layer, a conductive non-metal layer made of ITO and the like, a light-shielding layer, and a decorative layer.

The application of the dimming element of the present invention is not limited, and it can be suitably used for applications such as a dimming window, an antiglare mirror, and electronic paper.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Preparation of electrode A>
As a support, a polyethylene terephthalate film having a thickness of 100 μm was used. When the total light transmittance and the haze of the support were measured with a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd., the total light transmittance was 91.8% and the haze was 0.5%.

Next, a physically developed nuclear layer coating solution having the following composition was uniformly applied onto the support by a gravure coating and dried to provide a physically developed nuclear layer.

<Preparation of palladium sulfide sol>
Solution A Palladium chloride 5 g
Hydrochloric acid 40 mL
Distilled water 1000mL
Solution B Sodium sulfide 8.6 g
Distilled water 1000mL
Liquid A and liquid B were mixed with stirring, and after 30 minutes, they were passed through a column filled with an ion exchange resin to obtain a palladium sulfide sol.

<Physically developed nuclear lamina coating solution / per ^{1 m 2>}
Palladium sulfide sol (as solid content) 0.4 mg
2% by mass glyoxal aqueous solution 200 mg
Surfactant (S-1) 4 mg
Denacol® EX-830 25 mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10% by mass Epomin® SP-200 aqueous solution 500 mg
(Polyethyleneimine manufactured by Nippon Shokubai Co., Ltd .; average molecular weight 10,000)

Subsequently, the intermediate layer, the silver halide emulsion layer, and the protective layer having the following compositions are uniformly applied on the physically developed nuclear layer by slide coating in order from the one closest to the support, and dried to obtain the conductive material precursor. Obtained. The silver halide emulsion contained in the silver halide emulsion layer was produced by a controlled double jet method. The silver halide particles contained in this silver halide emulsion were prepared to have an average particle size of 0.15 μm with 95 mol% of silver chloride and 5 mol% of silver bromide. The silver halide particles thus obtained were sensitized with gold sulfur using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per 1 g of silver as a protective colloid (binder).

<Intermediate layer composition / per ^{1 m 2>}
Gelatin 0.5g
Surfactant (S-1) 5 mg
Dye 15 mg

<Silver halide emulsion layer composition / per ^{1 m 2>}
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3mg
Surfactant (S-1) 20 mg

<Protective layer composition / per ^{1 m 2>}
Gelatin 1g
Amorphous silica matting agent (average particle size 3.5 μm) 10 mg
Surfactant (S-1) 10 mg

The conductive material precursor thus obtained is brought into close contact with a positive transmission original having a mesh pattern having a square having a line width of 7.0 μm and a side length of 300 μm as a unit lattice, and a mercury lamp is used as a light source. It was exposed with a close contact printer through a resin filter that cuts light of 400 nm or less. Then, the exposed conductive material precursor is developed with a developer having the following composition (immersed in a developer at 20 ° C. for 90 seconds), and then the silver halide emulsion layer, the intermediate layer, and the protective layer are formed at 40 ° C. By washing and removing with warm water and drying, a mesh-like silver fine line pattern was formed on the polyethylene terephthalate film. When the silver fine wires constituting the mesh-like silver fine wire pattern were observed with a confocal microscope, the line width was 7.0 μm, the aperture ratio was 95%, and the thickness was 0.16 μm.

<Developer composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-Phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-Methylethanolamine 15g
Potassium bromide 1.2g
The total volume was adjusted to 1000 mL with water and pH = 12.2.

The above-mentioned mesh-like silver fine wire pattern was immersed in a degreasing solution (5% by mass diluted solution of Cleaner 160 manufactured by Meltex Inc.) at 60 ° C. for 1 minute, washed with water and degreased. Subsequently, electrolytic copper plating was performed using an electrolytic copper plating solution having the following composition under the conditions of ^{a temperature of 25 ° C. and a cathode current density of 3 A / dm 2.} When the fine wires constituting the mesh-like fine wire pattern after electrolytic copper plating were observed with a confocal microscope, the line width was 17 μm, the aperture ratio was 89%, and the thickness was 5.1 μm.

<Copper plating solution composition>
Copper sulfate pentahydrate 75g
Sulfuric acid 190g
Hydrochloric acid 50 mg
The total volume was adjusted to 1000 mL with water.

Then, a conductive non-metal layer made of ITO was provided on the mesh-like fine wire pattern by a sputtering method to obtain an electrode A. The thickness of the conductive non-metal layer measured using a stylus type film thickness meter was 23 nm.

<Preparation of electrode B>
As a support, a polyethylene terephthalate film having a thickness of 100 μm was used. When the total light transmittance and the haze of the support were measured with a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd., the total light transmittance was 91.8% and the haze was 0.5%.

An electrode B was obtained by providing a conductive non-metal layer made of ITO on the support by a sputtering method. The thickness of the conductive non-metal layer measured using a stylus type film thickness meter was 23 nm.

Next, the following electrolyte layers A to E were prepared.

<Preparation of electrolyte layer A>
Two silicone-based peeled PET films (temporary support A-1 and temporary support A-2, each having a thickness of 75 μm) were prepared as temporary supports. Next, a coating liquid A for forming an electrolyte layer having the following composition is applied onto the temporary support A-1 using a bar coater, and after further attaching the temporary support A-2 to the coated surface, a high-pressure mercury lamp 80W / an irradiation dose of 200 mJ / cm ² in cm (2 lamps), continuously polymerized until 5000 mJ / cm ² irradiation light quantity to obtain an electrolyte layer a. The thickness of the electrolyte layer A converted from the total thickness measured with a micrometer is 100 μm, and the peeling adhesive strength of the electrolyte layer A to the electrode A measured by a 180 degree peeling test based on JIS Z0237: 2009 is 4.3 N. It was / 25 mm.

<Coating liquid A composition for forming electrolyte layer>
UC-203 70g
(Isoprene acrylate manufactured by Kuraray Co., Ltd.)
Propylene carbonate 25g
Potassium hexafluorophosphate 4.5g
2-Hydroxy-2-methyl-1-phenyl-propane-1-one 0.5 g

<Preparation of electrolyte layer B>
An electrolyte layer B was obtained in the same manner as the electrolyte layer A except that the electrolyte layer forming coating solution B having the following composition was used instead of the electrolyte layer forming coating solution A. The thickness of the electrolyte layer B converted from the total thickness measured with a micrometer is 100 μm, and the peeling adhesive strength of the electrolyte layer B to the electrode A measured by a 180 degree peeling test based on JIS Z0237: 2009 is 6.6 N. It was / 25 mm.

<Coating liquid B composition for forming electrolyte layer>
Purple light UV-3640PE80 65g
(Urethane acrylate manufactured by Mitsubishi Chemical Corporation)
Polyethylene glycol # 1000 diacrylate 5g
Propylene carbonate 25g
Potassium hexafluorophosphate 4.5g
2-Hydroxy-2-methyl-1-phenyl-propane-1-one 0.5 g

<Preparation of electrolyte layer C>
An electrolyte layer C was obtained in the same manner as the electrolyte layer A except that the electrolyte layer forming coating solution C having the following composition was used instead of the electrolyte layer forming coating solution A. The thickness of the electrolyte layer C converted from the total thickness measured with a micrometer is 100 μm, and the peeling adhesive strength of the electrolyte layer C to the electrode A measured by a 180 degree peeling test based on JIS Z0237: 2009 is 3.1 N. It was / 25 mm.

<Coating liquid C composition for forming electrolyte layer>
NISSO-PB TE-2000 47g
(Butadiene acrylate manufactured by Nippon Soda Co., Ltd.)
Polyethylene glycol # 1000 diacrylate 5g
Dodecyl acrylate 15g
4-Hydroxybutyl acrylate 3g
Propylene carbonate 25g
Potassium hexafluorophosphate 4.5g
2-Hydroxy-2-methyl-1-phenyl-propane-1-one 0.5 g

<Preparation of electrolyte layer D>
An electrolyte layer D was obtained in the same manner as the electrolyte layer A except that the electrolyte layer forming coating solution D having the following composition was used instead of the electrolyte layer forming coating solution A. The thickness of the electrolyte layer D converted from the total thickness measured with a micrometer is 100 μm, and the peeling adhesive force of the electrolyte layer D with respect to the electrode A measured by a 180 degree peeling test based on JIS Z0237: 2009 is 1.6 N. It was / 25 mm.

<Coating liquid D composition for forming electrolyte layer>
Polyethylene glycol # 1000 diacrylate 60g
Polyethylene glycol # 200 diacrylate 10g
Propylene carbonate 25g
Potassium hexafluorophosphate 4.5g
2-Hydroxy-2-methyl-1-phenyl-propane-1-one 0.5 g

<Preparation of electrolyte layer E>
An electrolyte layer E was obtained in the same manner as the electrolyte layer A except that the electrolyte layer forming coating solution E having the following composition was used instead of the electrolyte layer forming coating solution A. The thickness of the electrolyte layer E converted from the total thickness measured with a micrometer was 100 μm. An attempt was made to measure the peeling adhesive strength of the electrolyte layer E in a 180-degree peeling test based on JIS Z0237: 2009, but the adhesive strength was too low to measure.

<Coating liquid E composition for forming electrolyte layer>
New Frontier® MF-001 70g
(Polyfunctional acrylic acid ester composition manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Propylene carbonate 25g
Potassium hexafluorophosphate 4.5g
2-Hydroxy-2-methyl-1-phenyl-propane-1-one 0.5 g

<Manufacturing of dimming element 1>
Prepare one electrode A and one electrode B cut into 6 cm x 5 cm, and put a Prussian blue dispersion (wFeHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) on the electrode A with a bar coater in a solid content of 0.30 g. After coating at / m ² , it was dried with hot air at 50 ° C. to form an electrochromic layer containing Prussian blue. Similarly, a nickel-substituted Prussian blue analog dispersion (wNiHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) is applied on the electrode B with a bar coater at a solid content of 0.30 g / m ² , and then dried with hot air at 50 ° C. An electrochromic layer containing a nickel-substituted Prussian blue analog was formed. Then, the electrodes A and B were bonded together with a vacuum laminator via the electrolyte layer A so that the electrochromic layer containing Prussian blue and the electrochromic layer containing the nickel-substituted Prussian blue analog faced each other. Finally, four sides were sealed with a silicone-based adhesive tape to obtain a dimming element 1. At this time, the electrodes A and B are exposed by 1 cm × 5 cm from the dimming element 1 by shifting them by 1 cm so that the 5 cm × 5 cm regions overlap each other, and electrically with the function generator described later. Enabled connection.

<Manufacturing of dimming elements 2 to 5>
Dimming elements 2 to 5 were obtained in the same manner as in the production of the dimming element 1 except that the electrolyte layers B to E were used instead of the electrolyte layer A. The dimming element 5 using the electrolyte layer E was found to be floating at the end when it was taken out from the vacuum laminator.

<Manufacturing of dimming element 6>
Prepare one electrode A and one electrode B cut into 6 cm x 5 cm, and put a Prussian blue dispersion (wFeHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) on the electrode A with a bar coater in a solid content of 0.30 g. After coating at / m ² , it was dried with hot air at 50 ° C. to form an electrochromic layer containing Prussian blue. Similarly, a nickel-substituted Prussian blue analog dispersion (wNiHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) is applied on the electrode B with a bar coater at a solid content of 0.30 g / m ² , and then dried with hot air at 50 ° C. An electrochromic layer containing a nickel-substituted Prussian blue analog was formed. Subsequently, the coating liquid A for forming an electrolyte layer having the above composition is coated on the electrochromic layer containing Prussian blue on the electrode A with a bar coater, and the coated surface further contains a nickel-substituted Prussian blue analog. The electrode B was attached so that the electrochromic layer was in contact with the coating liquid A for forming the electrolyte layer. Then, an irradiation dose of 200 mJ / cm ² by a high pressure mercury lamp 80W / cm (2 lamps), and an electrolyte layer F is polymerized continuously until 5000 mJ / cm ² irradiation light quantity. Finally, four sides were sealed with a silicone-based adhesive tape to obtain a dimming element 6. At this time, the electrodes A and B are exposed from the dimming element 6 by 1 cm × 5 cm by shifting them by 1 cm so that the regions of 5 cm × 5 cm overlap each other, and electrically with the function generator described later. Enabled connection. The thickness of the electrolyte layer F converted from the total thickness measured with a micrometer was 100 μm.

<Manufacturing of dimming elements 7 to 12>
Dimming elements 7 to 12 were obtained in the same manner as the dimming elements 1 to 6 except that two electrodes A were used instead of one electrode A and one electrode B. The dimming element 11 using the electrolyte layer E was found to be floating at the end when it was taken out from the vacuum laminator. With respect to the dimming element 12, the thickness of the electrolyte layer F converted from the total thickness measured with a micrometer was 100 μm.

<Evaluation of color change speed of dimming element>
Prepare a regulated DC power supply, and attach the negative electrode of the regulated DC power supply to the electrodes on the electrochromic layer side containing Prussian blue of the dimming elements 1 to 12, and the electrodes on the electrochromic layer side containing the nickel-substituted Prussian blue analog. After connecting the positive electrode of the regulated DC power supply to, a voltage of 1.0 V was applied, and the time during which the blue color of the dimming element disappeared and changed to yellow was measured. Subsequently, the positive electrode and the negative electrode were exchanged, a voltage of 1.0 V was applied, and the time for the dimming element to develop color and change to the original blue color was measured. The results are shown in Table 1.

From the results in Table 1, when a mesh metal fine wire pattern and an electrode having a conductive non-metal layer on the mesh metal fine wire pattern are used as both electrodes of the dimming element, the color change rate of the dimming element is excellent. It turns out.

<Yield evaluation of dimming element>
Twenty dimming elements 1 to 12 were produced. A function generator is prepared, and the negative electrode of the function generator is attached to the electrode on the electrochromic layer side containing Prussian blue for all the dimming elements, and the function generator is attached to the electrode on the electrochromic layer side containing the nickel-substituted Prussian blue analog. After connecting the positive electrodes of the above, 100 cycles of signals having + 1.0 V for 30 seconds and −1.0 V for 30 seconds as one cycle were applied. For each of the 20 dimming elements 1 to 12, a region of 5 cm × 5 cm was observed with a digital microscope at the 100th cycle, and there was no region where the color change of 1 mm × 1 mm or more did not occur. The number of (good products) was counted, and the yield of each of the dimming elements 1 to 12 was evaluated. The results are shown in Table 1.

From the results in Table 1, the effectiveness of the present invention can be seen.

1 Dimming element 2, 3 Electrode 11 Support 21 Reticulated metal wire pattern 21a, 21b, 21c, 21d Metal wire 31 Conductive non-metal layer 41, 42 Electrochromic layer 51 Electrolyte layer

Claims (1)

An electrode having two electrodes, at least one of which has a mesh metal wire pattern on a support and a conductive non-metal layer on the mesh metal wire pattern, on the two electrodes. A method for manufacturing a dimming element in which the above-mentioned electrodes are bonded to each other via an adhesive electrolyte layer so that the electrochromic layers face each other after forming the electrochromic layers.

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