JP6582607B2 - Electrochromic device, method for manufacturing the same, and electrochromic light control glasses - Google Patents

Description

  The present invention relates to an electrochromic device, a manufacturing method thereof, and electrochromic light control glasses.

  A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. A device using this electrochromism is an electrochromic device. Many studies have been conducted on electrochromic devices to date that applications derived from the characteristics of electrochromism can be realized.

  Electrochromic materials used in electrochromic devices include organic materials and inorganic materials. An organic material is promising as a color display device because it can generate various colors depending on its molecular structure. On the other hand, inorganic materials have problems in color control. However, practical application to light control glass and ND filters is being studied as an application that uses this feature and has an advantage of low color saturation.

  In general, these electrochromic devices are manufactured by forming an electrochromic material between two opposing electrodes and then bonding them together via an ion conductive electrolyte layer. Therefore, although it is easy to make a planar shape, there is a problem that it cannot be easily applied to applications such as 3D (three-dimensional) surfaces and curved surfaces. For example, if it can be applied to a 3D shape such as a lens, the applicable range is widened as an optical application. However, optical defects are likely to occur due to the curved surface accuracy and positional accuracy of the two substrates to be bonded. Furthermore, in the case of eyeglass lenses, it is necessary to adjust the frequency according to the user, and preparing a large number of substrates with different curved surfaces becomes a problem for mass production.

  In order to solve such a problem, an electrochromic device that can be manufactured without a bonding process has been proposed (see, for example, Patent Document 1). According to this proposal, it is possible to realize a 3D-shaped electrochromic device.

  However, the above-described electrochromic device capable of realizing the 3D shape has a problem that the peel strength is not sufficient and the end portion and the like are easily peeled off by thermoforming.

  This invention is made | formed in view of said point, and makes it a subject to provide the electrochromic apparatus which improved the peeling strength rather than before.

The electrochromic device is formed on a support, a first electrode layer formed on the support, an electrochromic layer formed on the first electrode layer, and the electrochromic layer. A peeling prevention layer that is a porous film; an electrolyte layer formed on the peeling prevention layer; and the first electrode layer facing the first electrode layer through the electrochromic layer, the peeling prevention layer, and the electrolyte layer. A second electrode layer, and the material of the peel prevention layer is a polymer mixed particle film or polyurethane resin, and the thickness of the peel prevention layer is 20 nm or more and 2000 nm or less, and one of the peeling prevention layers The surface is in contact with the electrolyte layer, and the other surface is in contact with the electrochromic layer.

  According to the disclosed technology, it is possible to provide an electrochromic device with improved peel strength compared to the conventional art.

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

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

<First Embodiment>
FIG. 1 is a cross-sectional view illustrating an electrochromic device according to the first embodiment. Referring to FIG. 1, the electrochromic device 1 includes a first support 11, a first electrode layer 12, an electrochromic layer 13, an electrolyte layer 14, a second electrode layer 15, and a second electrode layer 12. The support 16, the protective layer 17, and the peeling prevention layer 19 are provided.

  In the electrochromic device 1, the first electrode layer 12 is provided on the first support 11, the electrochromic layer 13 is provided on the first electrode layer 12, and the peeling prevention layer 19 is provided on the electrochromic layer 13. Is provided. And the 2nd electrode layer 15 provided on the 2nd support body 16 is arrange | positioned on the peeling prevention layer 19 on both sides of the electrolyte layer 14 with the 2nd support body 16 facing outside. And the outer peripheral part of each layer containing the 1st support body 11 and the 2nd support body 16 is sealed with the protective layer 17. FIG. One surface of the peeling prevention layer 19 is in contact with the electrolyte layer 14, and the other surface is in contact with the electrochromic layer 13.

  The first electrode layer 12 and the second electrode layer 15 are provided at positions facing each other. For convenience, in each of the first electrode layer 12 and the second electrode layer 15, a surface facing each other is referred to as an inner surface, and a surface opposite to each inner surface is referred to as an outer surface. In the present embodiment, the inner surface of the first electrode layer 12 is in contact with the electrochromic layer 13, and the outer surface of the first electrode layer 12 is in contact with the first support 11. The inner surface of the second electrode layer 15 is in contact with the electrolyte layer 14, and the outer surface of the second electrode layer 15 is in contact with the second support 16.

  In the method for manufacturing the electrochromic device 1 according to the first embodiment, the first electrode layer 12, the electrochromic layer 13, and the peeling prevention layer 19 are sequentially stacked on the first support 11. The process of producing this member is included. In addition, the method includes a step of stacking the second electrode layer 15 on the second support 16 to produce a second member. Further, the first member and the second member are bonded to each other via the electrolyte layer 14 with the first support body 11 and the second support body 16 facing outside, and a laminate is manufactured. It has the process of sealing the outer peripheral part of a body with the protective layer 17, and may have another process as needed.

  In the electrochromic device 1, when a voltage is applied between the first electrode layer 12 and the second electrode layer 15, the electrochromic layer 13 undergoes an oxidation-reduction reaction due to the transfer of charges, thereby causing the color to be turned off. Since the electrochromic device 1 has the peeling prevention layer 19, the peeling strength of the electrochromic device 1 as a whole is improved as compared with the conventional case. Hereinafter, each component of the electrochromic device 1 will be described in detail.

(First support, second support)
The first support body 11 and the second support body 16 have a function of supporting the first electrode layer 12, the electrochromic layer 13, the peeling prevention layer 19, the electrolyte layer 14, and the second electrode layer 15. As the first support body 11 and the second support body 16, a known thermoformable resin material can be used as it is as long as these layers can be supported.

  As the first support body 11 and the second support body 16, for example, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, polyimide resin or the like is used. Can be used.

  The surfaces of the first support 11 and the second support 16 may be coated with a transparent insulating layer, an antireflection layer, or the like in order to improve water vapor barrier properties, gas barrier properties, and visibility. The thicknesses of the first support body 11 and the second support body 16 are preferably set in a range where thermoforming is easy, and can be, for example, about 0.2 mm to 1.0 mm.

  When the electrochromic device 1 is a reflective display device that is visible from the second electrode layer 15 side, the transparency of either the first support 11 or the second support 16 is not necessary. .

(First electrode layer, second electrode layer)
As a material for the first electrode layer 12 and the second electrode layer 15, a transparent conductive oxide material can be used. Examples of the transparent conductive oxide material include indium oxide doped with tin (hereinafter sometimes referred to as “ITO”), tin oxide doped with fluorine (hereinafter sometimes referred to as “FTO”), and antimony. Inorganic materials such as tin oxide doped with (hereinafter sometimes referred to as “ATO”).

  Among these, indium oxide formed by vacuum film formation (hereinafter may be referred to as “In oxide”), tin oxide (hereinafter also referred to as “Sn oxide”), and zinc oxide An inorganic material containing any one of the materials (hereinafter sometimes referred to as “Zn oxide”) is preferable.

In oxides, Sn oxides, and Zn oxides are materials that can be easily formed by a sputtering method, and that can provide good transparency and electrical conductivity. Among these, InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO, and InZnO are particularly preferable.

  Furthermore, it is preferable that the first electrode layer 12 and the second electrode layer 15 have lower crystallinity. This is because if the crystallinity is high, the first electrode layer 12 and the second electrode layer 15 are easily divided by thermoforming. From this point, IZO and AZO which show high conductivity with an amorphous film are preferable.

  Further, a conductive metal thin film containing silver, gold, copper, and aluminum having transparency, a carbon film such as carbon nanotube and graphene, and a network electrode such as conductive metal, conductive carbon, and conductive oxide, or These composite layers are also useful. The network electrode is an electrode in which carbon nanotubes or other highly conductive non-permeable materials are formed in a fine network shape to provide transmittance. The network electrode is preferable in that it is difficult to be divided during thermoforming.

  Furthermore, it is more preferable that the first electrode layer 12 and the second electrode layer 15 have a laminated structure of a network electrode and a conductive oxide or a laminated structure of a conductive metal thin film and a conductive oxide. By adopting such a laminated structure, the electrochromic layer 13 can be colored and decolored without unevenness. The conductive oxide layer can also be formed by coating as nanoparticle ink. Specifically, the laminated structure of the conductive metal thin film and the conductive oxide is an electrode that achieves both conductivity and transparency in a thin film laminated structure such as ITO / Ag / ITO.

  The thickness of each of the first electrode layer 12 and the second electrode layer 15 can be adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 13 can be obtained. When ITO vacuum film formation is used as the material of the first electrode layer 12 and the second electrode layer 15, the thickness of each of the first electrode layer 12 and the second electrode layer 15 is preferably 20 nm to 500 nm, 50 nm to 200 nm is more preferable. The thickness when the conductive oxide layer is applied and formed as nanoparticle ink is preferably 0.2 μm to 5 μm. In the case of a network electrode, 0.2 μm to 5 μm is preferable.

  Further, when used as a dimming mirror, either the first electrode layer 12 or the second electrode layer 15 may have a reflecting function. In that case, a metal material can be included as a material of the first electrode layer 12 and the second electrode layer 15. Examples of the metal material include Pt, Ag, Au, Cr, rhodium, alloys thereof, or a laminated structure thereof.

  Examples of methods for producing each of the first electrode layer 12 and the second electrode layer 15 include a vacuum deposition method, a sputtering method, and an ion plating method. Moreover, as long as each material of the first electrode layer 12 and the second electrode layer 15 can be formed by coating, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, Roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet Various printing methods such as a printing method can be used.

(Electrochromic layer)
The electrochromic layer 13 is a layer containing an electrochromic material. The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound. Moreover, you may use the conductive polymer known by showing electrochromism. Examples of the inorganic electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide. Examples of the organic electrochromic compound include viologen, rare earth phthalocyanine, styryl and the like.

  Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, or derivatives thereof. As the electrochromic layer 13, it is preferable to use a structure in which an organic electrochromic compound is supported on conductive or semiconductive fine particles. Specifically, it has a structure in which fine particles having a particle size of about 5 nm to 50 nm are bound to the electrode surface, and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, silanol group or the like is adsorbed on the surface of the fine particle.

  In this structure, since electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, a high-speed response is possible as compared with a conventional electrochromic device. Furthermore, since a transparent film can be formed as the display layer by using fine particles, it is possible to obtain a high color density of the electrochromic dye. A plurality of types of organic electrochromic compounds can also be supported on conductive or semiconductive fine particles. Further, the conductive particles can also serve as the electrode layer.

  Specifically, polymer-based and dye-based electrochromic compounds include, for example, azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styrylspiropyran, spirooxazine, spirothiopyran, thioindigo. , Tetrathiafulvalene, terephthalic acid, triphenylmethane, benzidine, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, Examples thereof include low molecular organic electrochromic compounds such as fluoran, fulgide, benzopyran, and metallocene, and conductive polymer compounds such as polyaniline and polythiophene. These may be used individually by 1 type and may use 2 or more types together. Among these, a viologen compound and a dipyridine compound are preferable from the viewpoint of a low color development potential and a good color value. For example, a dipyridine compound represented by the following general formula (1) is more preferable.

一般式（１）において、Ｒ１及びＲ２は、それぞれ独立に置換基を有していてもよい炭素数１〜８のアルキル基、及びアリール基の何れかを表す。Ｒ１及びＲ２の少なくとも一方は、ＣＯＯＨ、ＰＯ（ＯＨ）_２、及びＳｉ（ＯＣ_ｋＨ_２ｋ＋１）_３（ただし、ｋは、１〜２０を表す）から選択される置換基を有する。

In General formula (1), R1 and R2 represent either the C1-C8 alkyl group which may have a substituent each independently, and an aryl group. At least one of R1 and R2 is COOH, PO _{(OH) 2,} and _{Si (OC k H 2k + 1} ) 3 ( however, k represents 1 to 20) having a substituent selected from.

In the general formula (1), X represents a monovalent anion. The monovalent anion is not particularly limited as long as it forms a stable pair with the cation moiety, and can be appropriately selected according to the purpose. Examples of the monovalent anion include Br ion (Br ⁻ ), Cl ion (Cl ⁻ ), ClO ₄ ion (ClO ₄ ⁻ ), PF ₆ ion (PF ₆ ⁻ ), BF ₄ ion (BF ₄ ⁻ ), and the like. Is mentioned.

  Moreover, in General formula (1), n, m, and 1 represent 0, 1, or 2 each independently. Moreover, in General formula (1), A, B, and C represent either the C1-C20 alkyl group, aryl group, and heterocyclic group which may have a substituent each independently.

  In addition, as the metal complex-based and metal oxide-based electrochromic compounds, for example, inorganic electrochromic compounds such as titanium oxide, vanadium oxide, tungsten oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue can be used. it can.

  The conductive or semiconductive fine particles supporting the electrochromic compound are not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable to use a metal oxide. Examples of the metal oxide material include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, Metal oxides mainly composed of calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Among these, from the viewpoint of physical properties such as electrical properties and optical properties such as electrical conductivity, from titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide. At least one selected from the above is preferable, and titanium oxide is particularly preferable from the viewpoint that a color display excellent in response speed of color development and decoloration is possible.

  The shape of the conductive or semiconductive fine particles is not particularly limited and can be appropriately selected according to the purpose. In order to efficiently carry the electrochromic compound, the surface area per unit volume (hereinafter referred to as specific surface area). ) Is used. For example, when the fine particle is an aggregate of nanoparticles, it has a large specific surface area, so that the electrochromic compound is more efficiently supported and the display contrast ratio of color development and decoloration is excellent.

  Although the electrochromic layer 13 and the conductive or semiconductive fine particle layer can be formed by vacuum film formation, it is preferably formed by coating as a particle-dispersed paste from the viewpoint of productivity. There is no restriction | limiting in particular in the thickness of the electrochromic layer 13, Although it can select suitably according to the objective, 0.2 micrometer-5.0 micrometers are preferable. If the thickness is less than 0.2 μm, it may be difficult to obtain the color density, and if it exceeds 5.0 μm, the manufacturing cost increases and the visibility may be easily lowered due to coloring.

(Peeling prevention layer)
The material of the peeling prevention layer 19 is not particularly limited as long as it is a porous film, but an organic material and an inorganic material excellent in durability and film formability can be used. As a method for forming the peeling preventing layer 19 made of a porous film, known forming methods can be used including various methods described below.

  For example, it is possible to use a sintering method in which polymer fine particles or inorganic particles are partially fused by adding a binder or the like and holes formed between the particles are used. In addition, an extraction method can be used in which pores are obtained by forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, and then dissolving the organic or inorganic substance with the solvent. Further, a foaming method in which foaming is performed by heating or degassing a polymer or the like can be used. Further, a phase change method in which a mixture of polymers is phase-separated by manipulating a good solvent and a poor solvent can be used. In addition, a radiation irradiation method in which pores are formed by radiating various types of radiation can be used.

As the porous film, a polymer mixed particle film made of inorganic nanostructure particles (SiO ₂ particles, Al ₂ O ₃ particles, etc.) and a polymer binder, a porous organic film (polyurethane resin, polyethylene resin), or the like can be used. .

Further, an inorganic insulating material film may be formed on the porous film described above. As the inorganic insulating material film, a material containing at least ZnS is preferable. ZnS has a feature that it can be deposited at high speed by sputtering without damaging the electrochromic layer 13 and the like. Furthermore, ZnO—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like can be used as a material containing ZnS as a main component.

Here, in order to keep the crystallinity of the formed peeling prevention layer 19 favorable, it is preferable that the content rate of ZnS shall be about 50-90 mol%. Therefore, as a particularly preferable material, ZnS—SiO ₂ (8/2), ZnS—SiO ₂ (7/3), ZnS, ZnS—ZnO—In ₂ O ₃ —Ga ₂ O ₃ (60/23/10/7) ) Can be used.

  By using such a material for the peeling prevention layer 19, it is possible to reduce the thickness necessary to ensure good insulation, so the film thickness becomes thicker when multilayered and the film strength decreases, The film can be prevented from peeling off.

  As described above, when ZnS or the like is formed by sputtering, a porous film such as ZnS can be formed by previously forming a porous particle film as an undercoat layer. In this case, the aforementioned nanostructured semiconductor material may be used as the porous particle film. However, in order to ensure the insulation of the peeling prevention layer 19, it is preferable to form a separate porous film containing silica, alumina or the like to form the peeling prevention layer 19 composed of two layers.

  By making the peeling prevention layer 19 into a porous film, the electrolyte layer 14 can penetrate into the peeling prevention layer 19 and further into the first electrode layer 12, so that the electrolyte layer accompanying the oxidation-reduction reaction The ionic charge in 14 can be easily moved, and the response speed of color development / decoloration can be improved.

  Moreover, it is preferable that the film thickness of the peeling prevention layer 19 exists in the range of 20-2000 nm. This is because it is difficult to ensure insulation when the film thickness is less than 20 nm. In addition, when the film thickness exceeds 2000 nm, the adhesiveness is lowered and peeling easily occurs, the manufacturing cost of the electrochromic device 1 is increased, and the optical characteristics of the electrochromic device 1 are likely to be lowered due to coloring. .

(Electrolyte layer)
The electrolyte layer 14 is preferably a solid electrolyte layer, and can be formed as a film holding the electrolyte in light or thermosetting resin. Furthermore, it is preferable to mix inorganic particles for controlling the layer thickness of the electrolyte layer 14. This is because leakage of the electrolyte layer 14 during molding can be prevented.

  The electrolyte layer 14 is preferably a film cured with light or heat after being coated on the peeling prevention layer 19 as a mixed solution of inorganic fine particles, a curable resin, and an electrolyte. However, a porous inorganic fine particle layer may be formed in advance, and then coated as a mixed solution of a curable resin and an electrolyte so as to penetrate into the inorganic fine particle layer, and then a film cured by light or heat.

  Further, when the electrochromic layer 13 is a layer in which an electrochromic compound is supported on conductive or semiconducting nanoparticles, the electrochromic layer 13 is coated as a mixed solution of a curable resin and an electrolyte so as to penetrate into the electrochromic layer 13. . Then, it can also be set as the film | membrane hardened | cured with light or a heat | fever. As the electrolytic solution, a liquid electrolyte such as an ionic liquid or a solution obtained by dissolving a solid electrolyte in a solvent is used.

As the electrolyte material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts can be used. Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg ( BF ₄ ) _{2 and the} like. The ionic liquid is not particularly limited, and any substance that is generally studied and reported may be used.

  An organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature. This molecular structure consists of a cation component and an anion component.

  Examples of the cationic component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, and N, N-methylpropylimidazole salt; N, N-dimethylpyridinium salt, N, N-methyl Examples include aromatic salts such as pyridinium derivatives such as propylpyridinium salts; aliphatic quaternary ammonium compounds such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.

As the anion component, a compound containing fluorine is preferable in terms of stability in the atmosphere. For example, BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , B (CN ₄₎ ^-, and the like. An ionic liquid formulated by a combination of these cationic components and anionic components can be used.

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

  Examples of the curable resin include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, ethylene resins, melamine resins, photocuring resins such as phenolic resins, and general materials such as thermosetting resins. A material having high compatibility with the electrolyte is preferable. Such a material is preferably an ethylene glycol derivative such as polyethylene glycol or polypropylene glycol. Moreover, it is preferable to use a photocurable resin as the curable resin. This is because the device can be manufactured at a low temperature and in a short time compared to thermal polymerization or a method of thinning the film by evaporating the solvent.

  A particularly preferred combination is an electrolyte layer composed of a solid solution of a matrix polymer containing oxyethylene chains or oxypropylene chains and an ionic liquid. By using this configuration, it is easy to achieve both hardness and high ionic conductivity, and the uniform electrolyte layer 14 can be formed, and a good redox reaction can be obtained.

  The inorganic fine particle is not particularly limited as long as it is a material that can form a porous layer to hold the electrolyte and the cured resin. However, in terms of the stability and visibility of the electrochromic reaction, it is insulating and transparent. A material having high durability is preferable. Specific examples of the material include oxides or sulfides such as silicon, aluminum, titanium, zinc, and tin, or mixtures thereof. The size (average particle diameter) of the inorganic fine particles is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 nm to 10 μm, and more preferably 10 nm to 100 nm. The inorganic fine particles may be mixed in the electrochromic layer 13.

(Protective layer)
The protective layer 17 is formed so as to physically and chemically protect the side surface portion (outer peripheral portion) of the electrochromic device 1. The protective layer 17 can be formed, for example, by applying an ultraviolet curable or thermosetting insulating resin or the like so as to cover either one or both of the side surface and the upper surface, and then curing.

  More preferably, the protective layer 17 is a laminated protective layer of a cured resin and an inorganic material. By using a laminated structure with an inorganic material, barrier properties against oxygen and water are improved. As the inorganic material, a material having high insulation, transparency, and durability is preferable, and specific materials include oxides or sulfides such as silicon, aluminum, titanium, zinc, and tin, or a mixture thereof. It is done. These films can be easily formed by a vacuum film forming process such as sputtering or vapor deposition. There is no restriction | limiting in particular in the thickness of the protective layer 17, Although it can select suitably according to the objective, 0.5 micrometer-10 micrometers are preferable.

  As described above, in the electrochromic device 1 according to the first embodiment, the separation preventing layer 19 which is a porous film having a large specific surface area at the interface is provided between the electrochromic layer 13 and the electrolyte layer 14. . As a result, the contact area between the electrochromic layer 13 and the peeling prevention layer 19 and the contact area between the electrolyte layer 14 and the peeling prevention layer 19 are increased, so that the adhesion between the electrochromic layer 13 and the electrolyte layer 14 is caused by the anchor effect. (Peel strength) can be improved. As a result, it is possible to solve various problems in the coloring operation caused by peeling of the electrochromic device and provide a high-performance electrochromic device.

  In particular, the electrochromic device 1 is preferable in that peeling is unlikely to occur even when the electrochromic device 1 is processed into a curved shape by thermoforming.

  In addition, by making the peeling prevention layer 19 a porous film, the electrolyte of the electrolyte layer 14 can penetrate into the peeling prevention layer 19 and further penetrate into the first electrode layer 12. Therefore, the movement of ionic charges in the electrolyte layer 14 accompanying the oxidation-reduction reaction is facilitated, and the response speed of color development / decoloration can be improved.

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

  FIG. 2 is a cross-sectional view illustrating an electrochromic device according to the second embodiment. Referring to FIG. 2, in the electrochromic device 2 according to the second embodiment, the deterioration preventing layer 18 is formed in contact with (sandwiched) the electrolyte layer 14 and the second electrode layer 15. This is different from the electrochromic device 1 (see FIG. 1) according to the first embodiment. Hereinafter, the deterioration preventing layer 18 constituting the electrochromic device 2 will be described.

(Deterioration prevention layer)
The role of the deterioration preventing layer 18 is to perform an electrochemical reaction opposite to that of the electrochromic layer 13 and balance the electric charges to suppress corrosion and deterioration of the second electrode layer 15 due to an irreversible oxidation-reduction reaction. That is. As a result, the repeated stability of the electrochromic device 2 can be improved. The reverse reaction includes not only the case where the deterioration preventing layer 18 is oxidized and reduced, but also the functioning as a capacitor.

  The material of the deterioration preventing layer 18 is not particularly limited as long as it is a material that plays a role of preventing corrosion of the first electrode layer 12 and the second electrode layer 15 due to an irreversible oxidation-reduction reaction. As the material of the deterioration preventing layer 18, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used. Furthermore, when coloring of the deterioration preventing layer 18 does not matter, the same electrochromic material as described above can be used.

  In particular, when the electrochromic device 2 is manufactured as an optical element such as a lens that requires transparency, it is preferable to use a highly transparent material for the deterioration preventing layer 18. As such a material, it is preferable to use n-type semiconducting oxide fine particles (n-type semiconducting metal oxide). As a specific example of the n-type semiconducting metal oxide, titanium oxide, tin oxide, zinc oxide, compound particles containing a plurality of them, or a mixture composed of primary particle diameter particles of 100 nm or less can be used.

  Furthermore, when these deterioration preventing layers 18 are used, it is preferable that the electrochromic layer 13 is a material that changes color by an oxidation reaction. As a result, the electrochromic layer 13 undergoes an oxidation reaction, and at the same time, the n-type semiconductor metal oxide is easily reduced (electron injection), and the drive voltage can be reduced.

  In such a form, a particularly preferred electrochromic material is an organic polymer material. The film can be easily formed by a coating process or the like, and the color can be adjusted and controlled by the molecular structure. Specific examples of these organic polymer materials include “Chemistry of Materials review 2011.23, 397-415 Navigating the Color Palette of Solution-Processable Electrochemical Polymers 29, Reynol76, Reyolde 30”. "Polymer journal, Vol. 41, No. 7, Electrochromic Organic Material Hybrid Polymers" and the like. Examples of these organic polymer materials include poly (3,4-ethylenedioxythiophene) -based materials, bis (terpyridine) s and iron ion complex-forming polymers, and the like.

  On the other hand, examples of the material of the highly transparent p-type semiconducting layer are organic materials having a nitroxyl radical (NO radical), and 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO). Or a polymer material of the derivative.

  In addition, without providing the deterioration preventing layer 18 in particular, the deterioration preventing layer material can be mixed with the electrolyte layer 14 to give the electrolyte layer 14 a deterioration preventing function. The layer structure in that case is the same as that of the electrochromic device 1 shown in FIG.

  Examples of the method for forming the deterioration preventing layer 18 include a vacuum deposition method, a sputtering method, and an ion rating method. Further, as long as the material of the deterioration preventing layer 18 can be formed by coating, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating. Use various printing methods such as printing method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Can do.

  Thus, in the electrochromic device 2 according to the second embodiment, the deterioration preventing layer 18 that performs an electrochemical reaction opposite to the oxidation-reduction reaction of the electrochromic layer 13 is provided. Thereby, in addition to the effect of 1st Embodiment, in addition to the effect of 1st Embodiment, there exist the following effects in the electrochromic apparatus 2 which concerns on 2nd Embodiment. That is, the driving voltage can be reduced, and the second electrode layer 15 can be prevented from being corroded or deteriorated by an irreversible oxidation-reduction reaction by balancing the charge, and the repetitive stability of the electrochromic device 2 can be reduced. It can be improved.

  In the example of FIG. 2, the peeling prevention layer 19 is provided between the electrochromic layer 13 and the electrolyte layer 14, but the peeling prevention layer 19 may be provided between the electrolyte layer 14 and the deterioration prevention layer 18. . That is, the peeling prevention layer 19 that is a porous film may be formed on one of the electrochromic layer 13 and the deterioration prevention layer 18. The peeling prevention layer 19 is in contact with one surface of the electrolyte layer 14, and the other surface of the electrolyte layer 14 is either the electrochromic layer 13 or the deterioration preventing layer 18 where the peeling prevention layer 19 is not formed. As long as it touches the surface of The same effect is obtained when the peeling prevention layer 19 is provided between the electrochromic layer 13 and the electrolyte layer 14 and when the peeling prevention layer 19 is provided between the electrolyte layer 14 and the deterioration prevention layer 18. .

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

  FIG. 3 is a cross-sectional view illustrating an electrochromic device according to the third embodiment. Referring to FIG. 3, the electrochromic device 3 according to the third embodiment is that the second peeling prevention layer 29 is formed between the electrolyte layer 14 and the deterioration prevention layer 18. This is different from the electrochromic device 2 (see FIG. 2) according to the second embodiment. One surface of the second peeling preventing layer 29 is in contact with the deterioration preventing layer 18 and the other surface is in contact with the electrolyte layer 14. The second peel prevention layer 29 is a porous film similar to the peel prevention layer 19.

  Thus, in the electrochromic device 3 according to the third embodiment, the second peeling prevention layer 29 that is a porous film having a large specific surface area at the interface between the deterioration preventing layer 18 and the electrolyte layer 14. Is provided. As a result, the contact area between the deterioration preventing layer 18 and the second peeling preventing layer 29 and the contact area between the electrolyte layer 14 and the second peeling preventing layer 29 are increased. The adhesion (peel strength) with the electrolyte layer 14 can be improved. As a result, the peel strength of the entire electrochromic device 3 can be further improved as compared with the electrochromic device 1 according to the first embodiment and the electrochromic device 2 according to the second embodiment.

  In particular, the electrochromic device 3 is preferable in that peeling is less likely to occur even when the electrochromic device 3 is processed into a curved shape by thermoforming.

<Fourth embodiment>
In the fourth embodiment, a curved electrochromic device is illustrated. Note that in the fourth embodiment, descriptions of the same components as those of the above-described embodiments may be omitted.

  FIG. 4 is a cross-sectional view illustrating an electrochromic device according to the fourth embodiment. Referring to FIG. 4, the electrochromic device 4 according to the fourth embodiment includes a curved surface shape, and the resin material portion 20 is formed on the concave surface side of the curved surface shape, according to the third embodiment. It differs from the electrochromic device 3 (see FIG. 3). The electrochromic device 4 can be used as a light control lens device, for example.

  In order to manufacture the electrochromic device 4 having a curved surface as shown in FIG. 4, first, the first electrode layer 12 is formed on the first support 11 having a planar shape made of a resin material, and further thereon. A first member in which the electrochromic layer 13 and the peeling prevention layer 19 are sequentially laminated is prepared. Also, a second member is produced in which the second electrode layer 15 and the deterioration preventing layer 18 are sequentially laminated on the planar second support 16 made of a resin material. Then, the first member and the second member are bonded to each other through the electrolyte layer 14 with the first support body 11 and the second support body 16 facing outside, and a stacked body is manufactured. The outer periphery is sealed with a protective layer 17. Then, a desired curved surface shape can be formed by thermoforming the laminate.

  The “desired curved surface shape” is a shape composed of a curved surface having a curvature, and examples thereof include a spherical shape, a cylindrical shape, a conical shape, and various three-dimensional (3D) shapes. The “desired curved surface shape” may be at least a part of the laminate and may be the whole.

  The resin material part 20 is formed outside the first support 11 after the laminated body is thermoformed. As a method for forming the resin material portion 20, a laminated body having a curved portion after thermoforming is set in a desired mold, and a resin material having the same refractive index as that of the first support body 11 or a low refractive index is used. Examples include injection molding and cast molding. Specific examples of the resin material include an episulfide resin, a thiourethane resin, a methacrylate resin, a polycarbonate resin, a urethane resin, and a mixture thereof. Moreover, you may form the primer for improving a hard coat and adhesiveness as needed.

  When the thickness of the first support 11 or the second support 16 is increased, thermoforming becomes difficult. On the other hand, when the thickness is decreased, the first support 11 or the second support 16 is added. Work becomes difficult. Therefore, the first support body 11 and the second support body 16 are formed relatively thin, and after the laminated body is thermoformed, the resin material portion 20 is formed outside the first support body 11 to form the first support body 11 and the second support body 16. 1 support 11 is made thicker.

  As a result, it is possible to avoid the difficulty in thermoforming and to facilitate additional machining. For example, a desired curved surface shape can be formed by forming the resin material portion 20 on the concave surface side of the curved surface (outside the first support 11) and cutting the thick resin material portion 20. Lens processing (power processing, etc.) that matches the specific conditions becomes possible. That is, it is not necessary to prepare a mold or a member for each product shape, and multi-product small-quantity production is facilitated. The resin material portion 20 may be provided outside the second support 16. Alternatively, it may be provided on both the outside of the first support 11 and the outside of the second support 16.

  In the present embodiment, the first member and the second member are bonded together via the electrolyte layer 14 to produce a laminate, and then the laminate is thermoformed to form a curved surface shape. The film forming productivity is excellent, and a large electrochromic device 4 can be provided. The thermoforming is preferably performed after all layers are formed, but the first member and the second member may be separately thermoformed. Also in this case, the effect of improving productivity can be obtained.

  Note that the configuration of the electrochromic device 4 is not limited to the configuration having the first support 11 and the second support 16, and may have only one of the supports.

  In the electrochromic device 4, it is preferable that the first electrode layer 12 and the second electrode layer 15 contain conductive particles or conductive carbon. Thereby, even if the 1st support body 11 and the 2nd support body 16 deform | transform at the time of thermoforming, the 1st electrode layer 12 and the 2nd electrode layer 15 become difficult to be divided. Furthermore, it is preferable that the auxiliary electrode has a stacked structure with a conductive oxide layer. Thereby, an in-plane uniform electrochromic reaction (color development and decoloration) is possible.

Further, in order to prevent the first electrode layer 12 and the second electrode layer 15 from being divided, the medium curved surface length after thermoforming is molded to be 120% or less with respect to the medium surface length before thermoforming. It is preferable to do. This is because if the first electrode layer 12 and the second electrode layer 15 expand more than 120%, they are likely to be divided. In particular, when a transparent conductive oxide formed by vacuum film formation is used for the first electrode layer 12 and the second electrode layer 15, the medium curved surface length after thermoforming is the medium surface length before thermoforming. It is preferable to mold to 103% or less. The transparent conductive oxide formed by vacuum film formation is, for example, ITO, IZO, SnO ₂ , AZO, GZO or the like.

  In such thermoforming, a member is heated by a convex mold and a concave mold having a desired 3D shape without fixing the ends of the first support body 11 and the second support body 16. Can be used. The heating temperature can be set near the softening temperature of the material constituting the first support 11 and the second support 16.

  For example, when polycarbonate is used as the first support 11 and the second support 16, the heating temperature is preferably between 130 ° C. and 190 ° C. Further, thermoforming and vacuum forming may be combined. In addition, when forming a transparent conductive oxide by vacuum film formation, it is so preferable that the crystallinity of the 1st electrode layer 12 and the 2nd electrode layer 15 is low. This is because if the crystallinity is high, the first electrode layer 12 and the second electrode layer 15 are easily divided. In this respect, it is preferable to use IZO and AZO which show high conductivity with an amorphous film.

<Fifth embodiment>
In the fifth embodiment, electrochromic light control glasses using the electrochromic device (light control lens device) according to the fourth embodiment will be exemplified. Note that in the fifth embodiment, description of the same components as those of the above-described embodiments may be omitted.

  FIG. 5 is a perspective view illustrating electrochromic dimming glasses according to the fifth embodiment. Referring to FIG. 5, the electrochromic dimming glasses 5 include two electrochromic devices 4, a spectacle frame 52, a switch 53, and a power source 54.

  The two electrochromic devices 4 are incorporated in the spectacle frame 52. The spectacle frame 52 is provided with a switch 53 and a power source 54. The power source 54 is electrically connected to the first electrode layer 12 and the second electrode layer 15 through a switch 53 by a predetermined wiring.

  By switching the switch 53, for example, one of a state in which a positive voltage is applied between the first electrode layer 12 and the second electrode layer 15, a state in which a negative voltage is applied, and a state in which no voltage is applied is selected. The state can be selected. As the switch 53, for example, any switch that can switch at least the above-described three states, such as a slide switch and a push switch, can be used.

  As the power source 54, for example, an arbitrary DC power source such as a button battery or a solar battery can be used. The power source 54 can apply a voltage of about plus or minus several volts between the first electrode layer 12 and the second electrode layer 15.

  For example, by applying a positive voltage between the first electrode layer 12 and the second electrode layer 15, the two electrochromic devices 4 are colored in a predetermined color. Further, when a negative voltage is applied between the first electrode layer 12 and the second electrode layer 15, the two electrochromic devices 4 are decolored and become transparent.

  However, depending on the characteristics of the material used for the electrochromic layer 13 constituting the electrochromic device 4, a color is developed by applying a negative voltage between the first electrode layer 12 and the second electrode layer 15, and a positive voltage is applied. In some cases, the color disappears and becomes transparent. Note that once the color is developed, the color continues even if no voltage is applied between the first electrode layer 12 and the second electrode layer 15.

  Thus, by using the electrochromic device 4 (light control lens device) as the lens of the electrochromic light control glasses 5, it is possible to realize electrochromic light control glasses with excellent light resistance and high performance.

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

<Example 1>
Example 1 shows an example in which the electrochromic device 1 shown in FIG. 1 is manufactured and thermoformed similarly to the electrochromic device 4 shown in FIG. However, the resin material part 20 is not provided. The electrochromic device manufactured in Example 1 can be used as a light control lens device.

(Formation of the 1st electrode layer 12, the electrochromic layer 13, and the peeling prevention layer 19)
First, an elliptic polycarbonate substrate having a major axis of 80 mm, a minor axis of 55 mm, and a thickness of 0.5 mm was prepared as the first support 11. Then, an ITO film was formed to a thickness of about 100 nm by sputtering on the prepared elliptical polycarbonate substrate to form the first electrode layer 12.

Next, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle size: 20 nm) is applied to the surface of the ITO film by a spin coating method.
By performing an annealing process at 15 ° C. for 15 minutes, a nanostructured semiconductor material made of a titanium oxide particle film having a thickness of about 1.0 μm was formed.

  Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 1.5% by mass of a compound represented by the following structural formula A was applied as an electrochromic compound by a spin coating method. Then, by carrying out an annealing treatment at 120 ° C. for 10 minutes, the titanium oxide particle film was supported (adsorbed) to form the electrochromic layer 13.

続いて、エレクトロクロミック層１３上に、平均一次粒径２０ｎｍのＳｉＯ_２微粒子分散液（シリカ固形分濃度２４．８質量％、ポリビニルアルコール１．２質量％、及び水７４質量％）をスピンコートし、剥離防止層１９を形成した。形成した剥離防止層１９の厚みは約２μｍであった。

Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, and water 74 mass%) having an average primary particle diameter of 20 nm is spin-coated on the electrochromic layer 13. Then, a peeling prevention layer 19 was formed. The thickness of the formed peeling prevention layer 19 was about 2 μm.

(Formation of the second electrode layer 15 and the electrolyte layer 14)
An elliptic polycarbonate substrate having the same shape and thickness as the first support 11 was prepared as the second support 16. Then, an ITO film was formed to a thickness of about 100 nm by sputtering on the prepared elliptical polycarbonate substrate, thereby forming the second electrode layer 15.

  Subsequently, a polyethylene diacrylate, a photoinitiator (IRG184, manufactured by BASF), and an electrolyte (1-ethyl-3-methylimidazolium salt) are mixed in a mass ratio (100: 5: The solution mixed in 40) was applied. Then, it was bonded to the surface of the second support 16 on the second electrode layer 15 side and UV cured to form a solid electrolyte layer 14.

(Formation of protective layer 17)
Next, an ultraviolet curable adhesive (trade name: KARAYAD R604, manufactured by Nippon Kayaku Co., Ltd.) was dropped on the side surface of each layer from the first support 11 to the second support 16. And the protective layer 17 was formed in thickness of about 3 micrometers by making it harden | cure by ultraviolet light irradiation, and the electrochromic apparatus 2 was produced.

(Thermoforming)
The produced electrochromic device 2 was sandwiched between a convex mold having a curvature of about 90 mm and a concave mold while being heated at 135 ° C. to produce an electrochromic device having a 3D spherical surface. At this time, the length of the long axis of the convex spherical surface was 81 mm. Thus, the electrochromic device of Example 1 was completed.

<Example 2>
Example 2 shows an example in which the electrochromic device 2 shown in FIG. 2 is manufactured. However, the resin material part 20 is not provided. In addition, the electrochromic device produced in Example 2 can be used as a light control lens device.

  Here, an ATO particle dispersion (ATO average particle diameter: 20 nm / 2,2,3,3-tetrafluoropropanol in a 6 wt% solution of urethane binder HW140SF ( A dispersion liquid containing 6 wt% of DIC) was applied by spin coating and annealed at 120 ° C. for 15 minutes to form a deterioration preventing layer 18 made of an ATO particle film having a thickness of about 1.0 μm. . Other than this, an electrochromic device was formed in the same manner as in Example 1.

<Example 3>
Example 3 shows an example in which the electrochromic device 4 shown in FIG. 4 is manufactured. However, the resin material part 20 is not provided. The electrochromic device manufactured in Example 4 can be used as a light control lens device.

Here, the SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, and water 74 mass%) having an average primary particle diameter of 20 nm is also spin coated on the deterioration preventing layer 18. Then, the second peeling preventing layer 29 was formed. Other than this, an electrochromic device was formed in the same manner as in Example 2.

<Comparative example>
The electrochromic device according to the comparative example was manufactured by the same method as in Example 1 except that the peeling prevention layer 19 was not formed.

<< Color-decoloring drive >>
The color of each electrochromic device was confirmed. Specifically, the end portion of the first support 11 and a part of the end portion of the second support 16 are peeled off, and the contact portion of the first electrode layer 12 and the contact portion of the second electrode layer 15 are separated. Formed. Then, a voltage of −3.5 V was applied between the first electrode layer 12 and the second electrode layer 15 for 3 seconds so that the first electrode layer 12 became a negative electrode.

  As a result, it was confirmed that the electrochromic devices according to Examples 1 and 2 developed a magenta color derived from the electrochromic compound of the structural formula A. At this time, the electrochromic device according to Example 1 was partially peeled off, and color development could not be confirmed in some areas.

  Furthermore, when a voltage of +3.5 V is applied for 2 seconds between the lead portions of the first electrode layer 12 and the second electrode layer 15, the electrochromic dye is decolored and the electrochromic device becomes transparent. It was confirmed that

  On the other hand, in the electrochromic device according to the comparative example, peeling occurred entirely by thermoforming, and a gap was generated inside the electrochromic device. For this reason, when the color development / erasure driving was performed in the same manner as the electrochromic devices according to Examples 1 and 2, the color development / erasure could not be confirmed.

<< Peel test >>
The adhesion of each electrochromic device was confirmed by a 90 degree peel test. A part of the end portion of the first support 11 was peeled off, and the end portion was pulled and peeled in a direction perpendicular to the surface of the electrochromic device (90 degree angle). When the peel strength at that time was measured, compared with the peel strength of the electrochromic device according to the comparative example, the electrochromic device according to Example 1 was doubled, and the electrochromic device according to Example 2 was doubled. It was confirmed that the electrochromic device according to Example 3 showed 10 times the peel strength.

  Thus, in Example 1, although partial peeling and partial coloring defect were confirmed, peeling strength compared with the case where a peeling prevention layer is not provided by providing a peeling prevention layer (comparative example). Has been confirmed to improve. In particular, it was confirmed that the peel strength was significantly improved in Example 3 in which the peel prevention layers were provided on both the upper and lower sides of the electrolyte layer.

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

1, 2, 3, 4 Electrochromic device 5 Electrochromic dimming glasses 11 First support 12 First electrode layer 13 Electrochromic layer 14 Electrolyte layer 15 Second electrode layer 16 Second support 17 Protective layer DESCRIPTION OF SYMBOLS 18 Deterioration prevention layer 19 Peeling prevention layer 20 Resin material part 29 2nd peeling prevention layer 52 Eyeglass frame 53 Switch 54 Power supply

Japanese Patent No. 4105537

Claims (8)

A support;
A first electrode layer formed on the support;
An electrochromic layer formed on the first electrode layer;
A peeling prevention layer that is a porous film formed on the electrochromic layer;
An electrolyte layer formed on the anti-peeling layer;
A second electrode layer facing the first electrode layer via the electrochromic layer, the peeling prevention layer, and the electrolyte layer;
Have
The material of the peeling prevention layer is a polymer mixed particle film or a polyurethane resin, and the thickness of the peeling prevention layer is 20 nm or more and 2000 nm or less,
An electrochromic device in which one surface of the peeling prevention layer is in contact with the electrolyte layer and the other surface is in contact with the electrochromic layer. A support;
A first electrode layer formed on the support;
An electrochromic layer formed on the first electrode layer;
A second electrode layer facing the first electrode layer;
A deterioration preventing layer that is in contact with the second electrode layer and has an electrochemical reaction opposite to the redox reaction of the electrochromic layer;
Have
The electrochromic in contact with either one of the layers of the electrochromic layer or the deterioration preventing layer, the peeling-preventing layer is formed is a porous membrane,
The material of the peeling prevention layer is a polymer mixed particle film or a polyurethane resin, and the thickness of the peeling prevention layer is 20 nm or more and 2000 nm or less,
The peeling prevention layer is in contact with one surface of the electrolyte layer, and the other surface of the electrolyte layer is either the electrochromic layer or the deterioration preventing layer on which the peeling prevention layer is not formed. Electrochromic device in contact. A support;
A first electrode layer formed on the support;
An electrochromic layer formed on the first electrode layer;
A second electrode layer facing the first electrode layer;
A deterioration preventing layer that is in contact with the second electrode layer and has an electrochemical reaction opposite to the redox reaction of the electrochromic layer;
Have
A peeling prevention layer that is a porous film is formed in contact with the electrochromic layer,
The peeling prevention layer is in contact with one surface of the electrolyte layer;
The material of the peeling prevention layer is a polymer mixed particle film or a polyurethane resin, and the thickness of the peeling prevention layer is 20 nm or more and 2000 nm or less,
Between the deterioration prevention layer and the electrolyte layer, a second peeling prevention layer that is a porous film is formed,
The one surface of the second release preventing layer in contact with the deterioration preventing layer, the other surface of the second release preventing layer the electrolyte layer second surface and contact have Rue recto potter's wheel electrochromic device. The laminate including the support, the first electrode layer, the electrochromic layer, the peeling prevention layer, the electrolyte layer, and the second electrode layer has a curved portion,
The electrochromic device according to any one of claims 1 to 3, wherein a resin material portion is formed on the concave side of the curved shape.   Electrochromic dimming glasses comprising the electrochromic device according to any one of claims 1 to 4. A step of sequentially laminating a first electrode layer, an electrochromic layer, and an anti-peeling layer that is a porous film on the first support, to produce a first member;
Laminating a second electrode layer on a second support to produce a second member;
Bonding the first member and the second member with the first support body and the second support body facing outside through an electrolyte layer to produce a laminate. And
The material of the said peeling prevention layer is a polymer mixed particle film or a polyurethane resin, The film thickness of the said peeling prevention layer is a manufacturing method of the electrochromic apparatus which is 20 nm or more and 2000 nm or less .   In the step of producing the second member, on the second support, a second electrode layer, a deterioration preventing layer that performs an electrochemical reaction opposite to the oxidation-reduction reaction of the electrochromic layer, and porous The method for manufacturing an electrochromic device according to claim 6, wherein a second peeling preventing layer that is a porous film is sequentially laminated.   The method for producing an electrochromic device according to claim 6, further comprising a step of thermoforming the laminate.

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