JP2021099433A - Light control element - Google Patents

Abstract

To provide a light control element which can be manufactured with improved yield.SOLUTION: A light control element provided herein comprises an electrochromic layer provided on each of two opposing electrodes, and an electrolytic layer provided between the electrochromic layers, where at least one of the electrodes has a fine mesh-like metallic line pattern on a substrate and a conductive nonmetallic layer provided on the fine mesh-like metallic line pattern. The electrolytic layer contains a tetrazole compound and/or benzotriazole compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to 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 a layer in which and an electrolyte are mixed, and as shown in Japanese Patent Application Laid-Open No. 2018-185424 (Patent Document 3), it has an electrochromic layer containing an electrochromic material between two opposing electrodes. , 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 typified 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.

However, since the conductive non-metal layer represented by ITO has low bending resistance, the conductive non-metal layer may be cracked due to slight bending of the electrode in the manufacturing process of the dimming element. When a crack occurs in the conductive non-metal layer, the components of the electrolyte layer permeate from the crack to the reticulated metal fine line pattern through the electrochromic layer. If the power is applied in that state and the color change is repeated, the color change does not occur at the corresponding portion, so that there is a problem that the yield at the time of manufacturing the dimming element decreases, and a solution has been sought.

On the other hand, Japanese Patent Application Laid-Open No. 2016-11010 (Patent Document 5) describes the adjustment on the light transmissive electrode for the purpose of improving the decrease in the haze reduction rate when the light control film whose haze changes when energized is continuously operated. A dimming film in which the optical layer is a polymer liquid crystal body containing a liquid crystal compound, a binder resin, and a nitrogen-containing heterocyclic compound is disclosed, and a benzotriazole compound or a tetrazole compound is described as an example of the nitrogen-containing heterocyclic compound. Has been done. Further, Japanese Patent Application Laid-Open No. 2009-175718 (Patent Document 6) describes a dimming device having a layer of an electrolytic solution in which silver halide, which is an electrochromic material, and a supporting electrolyte containing halogen are mixed, between transparent electrodes. Benzotriazoles are described as an example of the additives (azoles) that can be contained in the electrolytic solution.

On the other hand, Japanese Patent Application Laid-Open No. 2017-87564 (Patent Document 7) contains a conductive metal wire and a tetrazole compound on the support for the purpose of suppressing ion migration and resistance value fluctuation of the conductive metal wire. A conductive material laminate obtained by laminating a pressure-sensitive adhesive layer and a functional material is disclosed, and Japanese Patent Application Laid-Open No. 2017-194731 (Patent Document 8) aims to suppress a change in resistance value due to chloride ions. A light-transmitting electrode laminate in which a light-transmitting electrode, a pressure-sensitive adhesive layer containing a benzotriazole compound, and a functional material are laminated on a support is disclosed.

Japanese Unexamined Patent Publication No. 2019-168683 JP-A-2018-72490 JP-A-2018-185424 JP-A-2017-194536 Japanese Unexamined Patent Publication No. 2016-11010 JP-A-2009-175718 Japanese Unexamined Patent Publication No. 2017-87564 Japanese Unexamined Patent Publication No. 2017-194731

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

The above object of the present invention is achieved by the following invention.
Each of the two opposing electrodes has an electrochromic layer, and an electrolyte layer is provided between the electrochromic layers, and at least one of the electrodes has a mesh metal fine wire pattern on the support and a mesh metal fine wire pattern on the mesh metal fine wire pattern. A dimming device having a conductive non-metal layer, wherein the electrolyte layer contains a tetrazole compound and / or a benzotriazole compound.

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

Schematic cross-sectional view showing an example of 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 the dimming element of the present invention. The dimming element 1 illustrated in FIG. 1 has an electrochromic layer 41 and an electrochromic layer 42 on the opposing electrodes 2 and 3, respectively, and has an electrolyte layer 51 between the electrochromic layers. 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. The electrolyte layer 51 contains a tetrazole compound and / or a benzotriazole compound. In the present invention, by adopting the dimming element 1 as described above, even if the electrode is slightly bent in the manufacturing process and the conductive non-metal layer is cracked, the color of the dimming element 1 is changed. The problem of disappearing 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, polysulfone 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 of the mesh-like thin metal wire pattern 21 has a geometric shape in which a plurality of unit lattices are arranged in a mesh pattern (difficult visibility of the pattern, hereinafter simply referred to as visibility). It 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, parallel quadrilaterals, trapezoids and other quadrangles, hexagons, octagons, dodecagons, and hexagons. Examples of shapes include a combination of n-sided triangles, star-shaped 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 diagram, a Delaunay diagram, a Penrose tile diagram, or the like is also one of the preferred shapes of the mesh-like metal fine line pattern 21.

The line width of the fine 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, a conductive metal ink or a conductive paste containing a metal and a binder is used according to the method disclosed in Japanese Patent Application Laid-Open No. 2015-69877. Is applied onto the support by a method such as printing to form a mesh metal fine line pattern, or a silver halide emulsion layer is provided on the support according to the method disclosed in Japanese Patent Application Laid-Open No. 2007-59270. On the support according to a method for 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 method disclosed in Japanese Patent Application Laid-Open No. 188655 and JP-A-2004-207001. A method of forming a network-like metal fine line pattern by 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, and a resist image is formed, and then electrolytic-free plating is applied to cover the resist image. A metal film is formed on a support according to a method of localizing a metal on a non-existent 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 of providing a resist film, exposing and developing the resist film to form an opening, and etching and removing the metal film of the opening 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 in the present invention 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 is illustrated. 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.

The dimming element 1 of the present invention may have a solid pattern (filled pattern) on the support 11 in addition to the mesh-like fine metal wire pattern 21 described above. 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 method for forming the above-mentioned mesh-like fine metal wire pattern 21 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.

The configuration of the electrode 3 included in the dimming element 1 of the present invention is not particularly limited, and may have conductivity for functioning as an electrode. For example, similarly to the electrode 2, the electrode may have a mesh-like metal fine wire pattern on the support and an electrode having a conductive non-metal layer on the mesh-like metal fine wire pattern, and the mesh-like metal fine wire pattern on the support. It may be an electrode having only a conductive non-metal layer on the support without providing. 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.

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.

The electrochromic layer 41 and the electrochromic layer 42 included in the dimming element 1 of the present invention contain at least an electrochromic material. The electrochromic material is not particularly limited, and known materials 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 contains at least a tetrazole compound and / or a benzotriazole compound and an electrolyte.

The tetrazole compound contained in the electrolyte layer 51 is not particularly limited, and a compound represented by the following general formula 1 can be exemplified.

_{R 1} and R ₂ in the general formula 1 independently represent a hydrogen atom, an alkyl group, an aralkyl group, and an aryl group, respectively.

In the general formula 1, the _{alkyl groups of R 1} and R ₂ include methyl group, ethyl group, propyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, nonyl group, 2-ethylhexyl group, isopropyl group and t-. A butyl group and the like can be exemplified, a benzyl group, a phenethyl group and the like can be exemplified as the aralkyl group, and a phenyl group, a naphthyl group and the like can be exemplified as the aryl group. The above-mentioned R ₁ and R ₂ may further have a substituent. Examples of the substituent include a hydroxy group, a hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, etc.), a cyano group, a sulfo group, a carboxyl group, an amino group, and an aminomethyl group, in addition to the substituents exemplified as _{R 1} and R _2. Examples thereof include a group, an alkoxy group, an aryloxy group, an amide group, a sulfonamide group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a phosphate amide group, a nitro group and an alkyloxycarbonyl group. ..

_{Among the tetrazole compounds represented by the general formula 1, a compound having at least one of R 1} and R ₂ having an aralkyl group or an aryl group is preferable because it is excellent in the effect of improving the yield in the manufacturing process of the light control element. Specific examples of the compound represented by the general formula 1 will be described below, but the present invention is not limited thereto.

The benzotriazole compound contained in the electrolyte layer 51 is not particularly limited, and a compound represented by the following general formula 2 can be exemplified.

In the general formula 2, R _{3 to} R ₇ independently represent a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, an amino group, an aminomethyl group, and a nitro group, respectively. The alkyl groups mentioned above include methyl group, ethyl group, propyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, nonyl group and 2-ethylhexyl group. , Isopropyl group and the like can be exemplified. R _{3 to} R ₇ may further have a substituent. Examples of the substituent include _{the substituents exemplified as R 3 to} R ₇ , a mercapto group, a cyano group, a sulfo group, a hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, etc.), an aralkyl group (benzyl group, phenethyl group, etc.). ), Halkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, naphthoxy group, etc.), amide group, sulfonamide group, ureido group, urethane group, sulfamoyl group, carbamoyl group, aryl group (phenyl group, phenyl group, etc.) Examples thereof include a naphthyl group (such as a naphthyl group), an alkylthio group (methylthio group, a hexylthio group, etc.), an arylthio group (phenylthio group, a naphthylthio group, etc.), a phosphate amide group, an alkyloxycarbonyl group, and a group combining these.

_{Among the benzotriazole compounds represented by the general formula 2, R 7} is preferably an aminomethyl group having a hydrogen atom or a substituent because it is excellent in the effect of improving the yield in the manufacturing process of the dimming device. Specific examples of the compound represented by the general formula 2 will be described below, but the present invention is not limited thereto.

A commercially available product can be used as the benzotriazole compound represented by the general formula 2. For example, BT-120, CBT-1, 5M-BTA, BT-LX, TT-LX, TT-LYK, etc. marketed by Johoku Chemical Industry Co., Ltd., OA-386, etc. marketed by Yamato Kasei Co., Ltd. Can be obtained and used.

The electrolyte layer 51 may contain only one or more tetrazole compounds, one or more benzotriazole compounds, and one or more tetrazole compounds and one or more benzotriazole compounds at the same time. You may.

The content of the tetrazole compound and / or the benzotriazole compound in the electrolyte layer 51 is not particularly limited, but since it is excellent in the effect of improving the yield in the manufacturing process of the dimming element, it is 0. 1% by mass or more is preferable, 0.4% by mass or more is more preferable, and 0.8% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 5% by mass or less.

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.

When the electrolyte layer 51 contains the above-mentioned tetrazole compound and / or benzotriazole compound and a solvent capable of dissolving the electrolyte, the color change rate of the dimming device is excellent and the yield in the manufacturing process of the dimming device is improved. It is preferable because it has an excellent effect. Such a solvent is not particularly limited, and is a chain carbonate ester such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, a cyclic carbonate ester such as ethylene carbonate, propylene carbonate and butylene carbonate, methyl acetate, ethyl acetate, methyl propionate and propionic acid. Aliphatic carboxylic acid esters such as ethyl, methyl butyrate, 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. , Lactum such as N-methylpyrrolidone, cyclic ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, chain ethers such as 1,2-diethoxyethane, ethoxymethoxyethane, ethylmethylsulfone, Sulfones such as sulfolanes, 3-methylsulfolanes and 2,4-dimethylsulfolanes, nitriles such as acetonitrile, propionitrile and methoxypropionitrile, trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate and the like. Examples thereof include phosphoric acid esters, alcohols such as ethanol and 2-propanol, glycols such as ethylene glycol, propylene glycol and polyethylene glycol, and water. The solvent may be used alone or in combination of two 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 0.1 to 500 μm, particularly preferably 1 to 300 μm.

The electrolyte layer 51 may contain a resin for the purpose of improving the strength of the electrolyte layer 51 and stabilizing the thickness. Examples of such resins include known resins such as acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, ethylene resins, melamine resins, phenol resins, and polyethylene oxide resins.

The electrolyte layer 51 may contain inorganic particles as a spacer for stabilizing the thickness of the electrolyte layer 51. Examples of the material constituting the inorganic particles include silicon dioxide, aluminum oxide, zirconium oxide, and glass. The particle size of the inorganic particles is preferably the same as the thickness of the electrolyte layer 51.

The electrolyte layer 51 contains known additives such as thickeners, rheology modifiers, surfactants, UV absorbers, infrared absorbers, colorants (pigments, dyes, etc.), antioxidants, silane coupling agents, and the like. You may be doing it.

The method for forming the electrolyte layer 51 is not particularly limited, but after mixing and dissolving the components contained in the electrolyte layer 51, the electrolyte layer 51 is applied onto the electrochromic layer 41 on the electrode 2 by a known method such as coating or printing. After that, the electrode 3 is attached so that the electrochromic layer 42 is in contact with the electrolyte layer 51. As such a bonding method, a method using a laminator such as a roll laminator or a vacuum laminator can be exemplified.

When the electrolyte layer 51 contains a solvent, it is preferable to seal the side surface of the light control element 1 in order to prevent the solvent from volatilizing and liquid leakage from the electrolyte layer 51. 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, ultraviolet irradiation, moisture, or the like, or a hot-melt adhesive is heated. Examples include, but are not limited to, a method of melting and applying the light control element 1 to the side surface, cooling and curing, and a method of sticking the side surface of the light control element 1 with an acrylic adhesive tape or a silicone adhesive tape. The step of sealing the side surface of the light control element 1 may be before or after forming the electrolyte layer 51.

The light control element 1 of the present invention may have an adhesive layer bonded to the surface of the electrode 2 opposite to the electrochromic layer 41 or 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 light control element of the present invention is not limited, and it can be suitably used for applications such as a light control window, an antiglare mirror, electronic paper, and improvement of design.

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.

<Manufacturing of dimming element 1>
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 92.1% and the haze was 0.6%.

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

<Physical development nuclear lamina coating liquid / per ^{1m 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 conductive material 1 having a mesh-like silver fine wire pattern on the support was obtained. When the silver fine wires constituting the mesh-like silver fine wire pattern of the conductive material 1 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.

An electrode A was obtained by providing a conductive non-metal layer made of ITO by a sputtering method on a mesh-like silver fine wire pattern of the conductive material 1. The thickness of the conductive non-metal layer measured using a stylus type film thickness meter was 23 nm.

Two electrodes A (electrode A-1 and electrode A-2) cut into 6 cm × 5 cm were prepared. On the electrode A-1, a Prussian blue dispersion (wFeHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) was applied on a conductive non-metal layer with a bar coater at 0.30 g / m ^{2 in} solid content, and Prussian blue was applied. The containing electrochromic layer was formed. A nickel-substituted Prussian blue analog dispersion (wNiHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) was applied to electrode A-2 with a bar coater at a solid content of 0.30 g / m ^2, and a nickel-substituted Prussian blue analog was applied. An electrochromic layer containing the above was formed. Subsequently, an electrolyte layer 1 having the following composition is coated on the electrochromic layer containing Prussian blue on the electrode A-1 with a bar coater to form an electrochromic layer further containing a nickel-substituted Prussian blue analog. The electrode A-2 was bonded with a roll laminator so as to be in contact with the electrolyte layer. Finally, four sides were sealed with a silicone-based adhesive tape to obtain a dimming element 1. At this time, the electrodes A-1 and A-2 are exposed from the dimming element 1 by 1 cm × 5 cm by shifting them by 1 cm so that the regions of 5 cm × 5 cm overlap each other, and the function generator described later is used. Allowed electrical connection with. The thickness of the electrolyte layer 1 converted from the total thickness measured with a micrometer was 100 μm.

<Electrolyte layer 1 composition>
Potassium hexafluorophosphate 0.5 g
Polyethylene oxide resin 0.5g
(PEO-4 manufactured by Sumitomo Seika Chemical Co., Ltd., viscosity average molecular weight 1.1 million to 1.5 million)
Propylene carbonate 8.5g
Spherical glass beads (average particle size 100 μm) 0.5 g

<Manufacturing of dimming elements 2 to 15>
The compound shown in Table 1 was added to the composition of the electrolyte layer 1 so that the content of the electrolyte layer with respect to the total mass became the value shown in Table 1, and the dimming element 1 was provided except that the electrolyte layers 2 to 15 were used. Dimming elements 2 to 15 were obtained in the same manner as in the production. The thickness of the electrolyte layers 2 to 15 converted from the total thickness measured with a micrometer was 100 μm.

<Manufacturing of dimming element 16>
The conductive material 1 was immersed in a degreasing solution (a 5% by mass diluted solution of a 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} , to obtain a conductive material 2. When the copper fine wires forming the mesh-like copper fine wire pattern of the conductive material 2 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>
Copper sulfate pentahydrate 75g
Sulfuric acid 190g
Hydrochloric acid 50 mg
The total volume was adjusted to 1000 mL with water.

An electrode B was obtained by providing a conductive non-metal layer made of ITO by a sputtering method on a mesh-like copper wire pattern of the conductive material 2. The thickness of the conductive non-metal layer measured using a stylus type film thickness meter was 23 nm.

Two electrodes B (electrode B-1, electrode B-2) cut into 6 cm × 5 cm were prepared. On the electrode B-1, a Prussian blue dispersion (wFeHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) was applied on a conductive non-metal layer with a bar coater at 0.30 g / m ^{2 in} solid content, and Prussian blue was applied. The containing electrochromic layer was formed. A nickel-substituted Prussian blue analog dispersion (wNiHCF nanoparticle dispersion manufactured by Kanto Chemical Co., Ltd.) was applied to the electrode B-2 with a bar coater at a solid content of 0.30 g / m ^2, and a nickel-substituted Prussian blue analog was applied. An electrochromic layer containing the above was formed. Subsequently, an electrolyte layer 16 having the following composition is coated on the electrochromic layer containing Prussian blue on the electrode B-1 with a bar coater to form an electrochromic layer further containing a nickel-substituted Prussian blue analog. The electrode B-2 was bonded with a roll laminator so as to be in contact with the electrolyte layer. Finally, four sides were sealed with a silicone-based adhesive tape to obtain a dimming element 16. At this time, the electrodes B-1 and B-2 are exposed from the dimming element 16 by 1 cm × 5 cm by shifting them by 1 cm so that the 5 cm × 5 cm regions overlap each other, and the function generator described later is used. Allowed electrical connection with. The thickness of the electrolyte layer 16 converted from the total thickness measured with a micrometer was 100 μm.

<Electrolyte layer 16 composition>
Potassium hexafluorophosphate 0.5 g
Polyethylene oxide resin 0.5g
(PEO-4 manufactured by Sumitomo Seika Chemical Co., Ltd., viscosity average molecular weight 1.1 million to 1.5 million)
Propylene carbonate 8.5g
Spherical glass beads (average particle size 100 μm) 0.5 g

<Manufacturing of dimming elements 17 and 18>
To the composition of the electrolyte layer 16, the compounds shown in Table 1 were added so that the content of the electrolyte layer with respect to the total mass was the value shown in Table 1, and the dimming element 16 was provided except that the electrolyte layers 17 and 18 were used. Dimming elements 17 and 18 were obtained in the same manner as in the production. The thicknesses of the electrolyte layers 17 and 18 converted from the total thickness measured with a micrometer were 100 μm.

<Yield evaluation of dimming element>
Twenty dimming elements 1 to 18 were produced. Next, using a function generator between the electrodes on the electrochromic layer side containing Prussian blue and the electrodes on the electrochromic layer side containing nickel-substituted Prussian blue analogs for all dimming elements- A signal having one cycle of 1.0 V for 30 seconds and + 1.0 V for 30 seconds was applied for 100 cycles. For each of the 20 dimming elements 1 to 18, 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 18 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)

Each of the two opposing electrodes has an electrochromic layer, and an electrolyte layer is provided between the electrochromic layers, and at least one of the electrodes has a mesh metal fine wire pattern on the support and a mesh metal fine wire pattern on the mesh metal fine wire pattern. A dimming device having a conductive non-metal layer, wherein the electrolyte layer contains a tetrazole compound and / or a benzotriazole compound.

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