JP2016133610A - Electrochromic device, lighting control lens and manufacturing method of electrochromic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a crack from occurring in an electrode layer at processing a curved surface.SOLUTION: An electrochromic device includes: a first electrode layer formed on a surface of a first board; a second electrode layer formed on a surface of a second board and arranged to face the first electrode layer; an electrochromic layer arranged between the first electrode layer and the second electrode layer; and an electrolyte layer formed between the first electrode layer and the second electrode layer. Fine irregularity is formed on the surface of the first board and the surface of the second board.SELECTED DRAWING: Figure 3

Description

  The present invention relates to an electrochromic element, a light control lens, and a method for manufacturing an electrochromic element.

  2. Description of the Related Art Conventionally, an electrochromic element utilizing a phenomenon (electrochromism) in which a redox reaction occurs reversibly by applying a voltage and a color changes reversibly is known. In general, an electrochromic element is manufactured by forming an electrochromic material between two opposing electrode layers and then bonding them together via an ion conductive electrolyte layer.

  As an electrochromic element, a structure in which a reduction coloring layer formed by a vacuum deposition method and an oxidation coloring layer formed by a vacuum deposition method are opposed to each other with a solid electrolyte layer interposed therebetween is disclosed (for example, (See Patent Document 1).

  However, in the above technique, the thermal influence of the film forming process is unavoidable, and the substrate is likely to be limited to a heat-resistant material such as glass. Therefore, it is difficult to mold the electrochromic element into a curved shape such as a 3D surface. Further, even when a substrate that can be molded into a curved shape is used, cracks may occur in the electrode layer. As a result, there arise problems that the appearance of the lens is deteriorated, the electric resistance value of the electrode layer is increased, and the driving voltage for color development / erasing is increased.

  Therefore, an object of the present invention is to suppress the generation of cracks in the electrode layer during curved surface processing.

  In one proposal, the first electrode layer formed on the surface of the first substrate and the second electrode formed on the surface of the second substrate and provided to face the first electrode layer. An electrochromic layer provided between the first electrode layer and the second electrode layer, and an electrolyte layer formed between the first electrode layer and the second electrode layer There is provided an electrochromic element in which fine irregularities are formed on the surface of the first substrate and the surface of the second substrate.

  According to one aspect, the generation of cracks in the electrode layer during curved surface processing can be suppressed.

The figure for demonstrating the electrochromic element which concerns on 1st Embodiment of this invention. The figure for demonstrating the electrochromic element which concerns on 1st Embodiment of this invention. 1 is a schematic cross-sectional view of an electrochromic device according to a first embodiment of the present invention. 1 is a schematic cross-sectional view illustrating an electrochromic element molded into a curved surface shape. 1 is a schematic cross-sectional view of a light control lens using an electrochromic element according to a first embodiment of the present invention. The flowchart which shows the manufacturing method of the electrochromic element which concerns on 1st Embodiment of this invention. The schematic sectional drawing of the electrochromic element which concerns on 2nd Embodiment of this invention. 1 is a schematic cross-sectional view illustrating an electrochromic element molded into a curved surface shape. The schematic sectional drawing of the light control lens using the electrochromic element which concerns on 2nd Embodiment of this invention. The flowchart which shows the manufacturing method of the electrochromic element which concerns on 2nd Embodiment of this invention. The figure for demonstrating the fine unevenness | corrugation formed in the surface of the 1st board | substrate. The figure for demonstrating the fine unevenness | corrugation formed in the surface of the 1st electrode layer.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has substantially the same function structure, the duplicate description is abbreviate | omitted by attaching | subjecting the same code | symbol.

[First Embodiment]
First, the electrochromic element 10 according to the first embodiment of the present invention will be described. 1 and 2 are diagrams for explaining an electrochromic device 10 according to a first embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of the electrochromic device 10 according to the first embodiment of the present invention. FIG. 4 is a schematic cross-sectional view illustrating the electrochromic element 10 molded into a curved shape.

  As shown in FIG. 1, the electrochromic element 10 includes a first electrode layer 12, an electrochromic layer 13, and an insulating layer 14 formed in this order on a first substrate 11, and as shown in FIG. The second electrode layer 16 is formed on the substrate 15, and as shown in FIG. 3, the first electrode layer 12 and the second electrode layer 16 form the electrochromic layer 13, the insulating layer 14, and the electrolyte layer 17. It has the structure bonded together so that it may oppose.

  Fine irregularities 11 a are formed on the surface of the first substrate 11, and fine irregularities 15 a are formed on the surface of the second substrate 15. The fine irregularities 11a and 15a cause flexibility in the first electrode layer 12 and the second electrode layer 16, and when the curved surface processing is performed by a method such as thermoforming, the first electrode layer 12 and Generation of cracks in the second electrode layer 16 can be suppressed.

  The electrochromic element 10 includes the first substrate 11, the first electrode layer 12, the electrochromic layer 13, the insulating layer 14, the electrolyte layer 17, the second electrode layer 16, the side surfaces of the second substrate 15, and / or the first substrate 11. The protective layer 18 formed so as to cover the surface of one substrate 11 may be provided.

  Next, the light control lens 100 using the electrochromic element 10 which concerns on 1st Embodiment of this invention is demonstrated. FIG. 4 is a schematic cross-sectional view illustrating the electrochromic element 10 molded into a curved shape. FIG. 5 is a schematic cross-sectional view of a light control lens 100 using the electrochromic element 10 according to the first embodiment of the present invention.

  4, after the electrochromic element 10 is processed into a curved shape by thermoforming or the like, as shown in FIG. 4, a resin material portion 19 is formed on the concave side of the curved shape as shown in FIG. Have a configuration. As a result, the second substrate 15 and the resin material part 19 constitute a thickened support that supports the electrochromic element 10. In addition, since a desired curved surface can be formed by machining the thickened support, lens processing (for example, power processing) that matches the user's specific conditions is possible, and adjustment with a desired curved surface shape is possible. The optical lens 100 is obtained.

  According to the light control lens 100, since it is not necessary to prepare a mold or a member for each shape of the light control lens 100, it is easy to produce a variety of products in small quantities.

  Hereinafter, each component which comprises the electrochromic element 10 which concerns on 1st Embodiment is demonstrated in detail.

(substrate)
The first substrate 11 and the second substrate 15 are members that support the first electrode layer 12, the electrochromic layer 13, the insulating layer 14, the second electrode layer 16, and the electrolyte layer 17.

  The material of the first substrate 11 and the material of the second substrate 15 are well known as long as they can support the first electrode layer 12, the electrochromic layer 13, the insulating layer 14, the second electrode layer 16, and the electrolyte layer 17. A resin material capable of thermoforming can be used. Specifically, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, or polyimide resin can be used.

  Fine irregularities 11 a and 15 a are formed on the surface of the first substrate 11 and the surface of the second substrate 15. The fine irregularities 11a and 15a are preferably formed with a period shorter than the wavelength of visible light from the viewpoint that they cannot be recognized by the human eye and the appearance is good. Further, when the electrochromic element 10 is used as the light control lens 100, the fine irregularities 11a and 15a may be formed in an irregular pattern from the viewpoint of suppressing the occurrence of moire on the lens surface. preferable.

  The surface of the first substrate 11 and the surface of the second substrate 15 may be coated with a transparent insulating layer, an antireflection layer, or the like from the viewpoint of improving water vapor barrier properties, gas barrier properties, and visibility. .

  As a method for forming fine irregularities 11a and 15a on the surface of the first substrate 11 and the surface of the second substrate 15, a dry etching method, a wet etching method, a nanoimprint method, or the like can be used. Among these methods, it is preferable to use the nanoimprint method from the viewpoint that the shape of the unevenness can be easily controlled.

  The thickness of the first substrate 11 and the thickness of the second substrate 15 are preferably in the range of 0.2 mm to 1.0 mm from the viewpoint of easy thermoforming.

(First electrode layer, second electrode layer)
The material of the first electrode layer 12 and the material of the second electrode layer 16 are not particularly limited as long as they are transparent and conductive, and can be appropriately selected according to the purpose. it can.

  As the transparent conductive material, indium oxide doped with tin (hereinafter referred to as “ITO”), tin oxide doped with fluorine (hereinafter referred to as “FTO”), and tin oxide doped with antimony (hereinafter referred to as “ATO”). ) And the like can be used. In particular, indium oxide (hereinafter referred to as “In oxide”), tin oxide (hereinafter referred to as “Sn oxide”), and zinc oxide (hereinafter referred to as “Zn oxide”) formed by vacuum film formation. It is preferable to use an inorganic material containing any one of the above.

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

  The film thickness of the first electrode layer 12 and the film thickness of the second electrode layer 16 are adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 13 is obtained. When ITO is used as the material of the first electrode layer 12 and the material of the second electrode layer 16, the film thickness of the first electrode layer 12 and the film thickness of the second electrode layer 16 are 50 nm or more and 500 nm or less. It is preferable that

  As a manufacturing method of the first electrode layer 12 and the second electrode layer 16, a vacuum film forming method such as a vacuum evaporation method, a sputtering method, an ion plating method, or the like can be used. In addition, as long as the material of the first electrode layer 12 and the material of the second electrode layer 16 can be formed by coating, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method. Method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method Various printing methods such as these can also be used.

(Electrochromic layer)
The electrochromic layer 13 is a layer containing an electrochromic material.

  As the electrochromic material, either an inorganic electrochromic compound or an organic electrochromic compound may be used. Moreover, you may use the conductive polymer known by showing electrochromism.

  As the inorganic electrochromic compound, tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, or the like can be used. As the organic electrochromic compound, viologen, rare earth phthalocyanine, styryl and the like can be used. As the conductive polymer, polypyrrole, polythiophene, polyaniline, or a derivative thereof can be used.

  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, a structure in which fine particles having a particle diameter of about 5 nm to 50 nm are sintered on the electrode surface and an organic electrochromic compound having a polar group such as a phosphonic acid, a carboxyl group, or a silanol group is adsorbed on the surface of the fine particles.

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

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

  Among these, it is preferable to include a viologen compound or a dipyridine compound that has a low color-decoloration potential and a good color value.

Note that in the formula [Chemical Formula 1] (general formula), R1 and R2 each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, and at least one of R1 and R2 _Has a substituent selected from COOH, PO (OH) ₂ , and Si (OC _k H _{2k + 1} ) ₃ (where k is 1 to 20). X represents a monovalent anion. For example, X is not particularly limited as long as it is stably paired with a cation moiety, but Br ion (Br ⁻ ), Cl ion (Cl ⁻ ), ClO ₄ ion ( ClO ₄ ⁻ ), PF ₆ ion (PF ₆ ⁻ ), BF ₄ ion (BF ₄ ⁻ ) and the like. n, m, and l represent 0, 1 or 2. A, B and C each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group or a heterocyclic group which may have a substituent.

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

  Although it does not specifically limit as electroconductive or semiconductive fine particle, It is preferable to use a metal oxide. Metal oxide materials include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide Use metal oxides mainly composed of ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. it can. Moreover, these metal compounds may be used independently and 2 or more types may be mixed and used for them.

  In view of physical properties such as electrical properties such as electrical conductivity and optical properties, one kind selected from titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, tungsten oxide, Or when these mixtures are used, the color display excellent in the response speed of color development / erasure is possible. In particular, when titanium oxide is used, it is possible to perform color display with a better response speed of color development and decoloration.

  The shape of the conductive or semiconductive fine particles is not particularly limited, but the surface area per unit volume (hereinafter referred to as “specific surface area”) is large in order to efficiently carry the electrochromic compound. Shape 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.

  The thickness of the electrochromic layer 13 is not particularly limited, but is preferably 0.2 μm or more and 5.0 μm or less. When the thickness of the electrochromic layer 13 is thinner than 0.2 μm, it is not preferable because the color density is difficult to obtain. Moreover, when the film thickness of the electrochromic layer 13 is thicker than 5.0 μm, it is not preferable because the manufacturing cost is increased and the visibility is easily lowered by coloring.

  The electrochromic layer 13 and the conductive or semiconductive fine particle layer can be formed by vacuum film formation, but from the viewpoint of productivity, it is preferably formed by coating as a particle-dispersed paste.

(Electrolyte layer)
The electrolyte layer 17 is a solid electrolyte layer and is formed as a film in which an electrolyte is held in a photocurable resin or a thermosetting resin. The electrolyte layer 17 is preferably mixed with inorganic fine particles that control the film thickness. The electrolyte layer 17 is preferably a film cured with light or heat after coating the electrochromic layer 13 with a solution in which inorganic fine particles, a curable resin and an electrolyte are mixed. Further, as the electrolyte layer 17, a porous inorganic fine particle layer is formed in advance, a solution in which a curable resin and an electrolyte are mixed is coated so as to penetrate into the inorganic fine particle layer, and then a film cured by light or heat. You can also When the electrochromic layer 13 is a layer in which an electrochromic compound is supported on conductive or semiconducting nanoparticles, after coating a solution in which a curable resin and an electrolyte are mixed so as to penetrate the electrochromic layer 13, light or A film cured by heat can also be used.

  As a solution containing an electrolyte (hereinafter referred to as “electrolytic solution”), a liquid electrolyte such as an ionic liquid or a solution obtained by dissolving a solid electrolyte in a solvent can be used.

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

  The ionic liquid is not particularly limited as long as it is a substance that is generally studied and reported. In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.

  Examples of molecular structures include cation components such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, Examples thereof include aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salt, and aliphatic quaternary ammonium such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.

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

  Solvents include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, alcohols Or a mixed solvent thereof can be used.

  As the curable resin, a general material such as an acrylic resin, a urethane resin, an epoxy resin, a vinyl chloride resin, an ethylene resin, a melamine resin, a phenolic resin or the like, or a thermosetting resin can be used. A material having high compatibility with the electrolyte is preferable. Examples of the material having high compatibility with the electrolyte include ethylene glycol derivatives such as polyethylene glycol and polypropylene glycol. Further, as the curable resin, it is preferable to use a photocurable resin from the viewpoint that the device can be manufactured at a low temperature and in a short time as compared with a method of thinning by thermal polymerization or evaporation of a solvent. .

  The electrolyte layer 17 is particularly preferably composed of a solid solution of a matrix polymer containing an oxyethylene chain or an oxypropylene chain and an ionic liquid from the viewpoint that both hardness and high ionic conductivity are easily achieved.

  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 curable resin, but from the viewpoint of stability of the electrochromic reaction and visibility, it is insulated. It is preferable that the material has high properties, transparency and durability. As specific materials, oxides or sulfides of silicon, aluminum, titanium, zinc, tin, or the like, or a mixture thereof can be used.

  The size (average particle diameter) of the inorganic fine particles is not particularly limited, but is preferably 10 nm or more and 10 μm or less, and more preferably 10 nm or more and 100 nm or less.

(Protective layer)
The protective layer 18 includes a side surface of the first substrate 11, a side surface of the first electrode layer 12, a side surface of the electrochromic layer 13, a side surface of the insulating layer 14, a side surface of the electrolyte layer 17, a side surface of the second electrode layer 16, It is formed so as to cover the side surface of the second substrate 15. Further, the protective layer 18 may be formed so as to cover the surface of the first substrate 11.

  The protective layer 18 is made of, for example, an ultraviolet curable or thermosetting insulating resin, and the like. The side surface of the first substrate 11, the side surface of the first electrode layer 12, the side surface of the electrochromic layer 13, the side surface of the insulating layer 14, It can be formed by coating the side surface of the electrolyte layer 17, the side surface of the second electrode layer 16, the side surface of the second substrate 15 and / or the surface of the first substrate 11, and then curing.

  The protective layer 18 preferably has a structure in which a curable resin and an inorganic material are laminated from the viewpoint of improving barrier properties against oxygen, water, and the like.

  As the inorganic material, a material having high insulation, transparency, and durability is preferable. For example, an oxide or sulfide such as silicon, aluminum, titanium, zinc, or tin, or a mixture thereof can be used. These films can be easily formed by a vacuum film formation process such as sputtering or vapor deposition.

  The thickness of the protective layer 18 is not particularly limited, but is preferably 0.5 μm or more and 10 μm or less.

  Next, a method for manufacturing the electrochromic element 10 according to the first embodiment of the present invention will be described. FIG. 6 is a flowchart showing a method for manufacturing the electrochromic device 10 according to the first embodiment of the present invention.

  First, fine irregularities 11a are formed on the surface of the first substrate 11 (step S11). Then, the 1st electrode layer 12 is formed in the surface of the 1st board | substrate 11 with which the fine unevenness | corrugation 11a was formed (step S12). Subsequently, the electrochromic layer 13 is formed on the surface of the first electrode layer 12 (step S13). Subsequently, the insulating layer 14 is formed on the surface of the electrochromic layer 13 (step S14).

  Further, fine irregularities 15a are formed on the surface of the second substrate 15 (step S15). Then, the 2nd electrode layer 16 is formed in the surface of the 2nd board | substrate 15 with which the fine unevenness | corrugation 15a was formed (step S16).

  Next, an electrolyte layer 17 is formed on the surface of the insulating layer 14 formed on the first substrate 11, and the insulating layer 14 and the second electrode layer 16 are opposed so that the first electrode layer 12 and the second electrode layer 16 face each other. The two electrode layers 16 are bonded together via the electrolyte layer 17 (step S17). Subsequently, the side surface of the first substrate 11, the side surface of the first electrode layer 12, the side surface of the electrochromic layer 13, the side surface of the insulating layer 14, the side surface of the electrolyte layer 17, the side surface of the second electrode layer 16, the second A protective layer 18 is formed so as to cover the side surface of the substrate 15 (step S18). Subsequently, by performing thermoforming (step S19), the electrochromic element 10 is processed into a curved shape as shown in FIG.

  Through the above steps, the electrochromic element 10 according to the first embodiment of the present invention can be manufactured.

  As described above, according to the electrochromic element 10 according to the first embodiment of the present invention, the fine irregularities 11 a and 15 a are formed on the surface of the first substrate 11 and the surface of the second substrate 15. Yes. For this reason, flexibility arises in the 1st electrode layer 12 and the 2nd electrode layer 16, and generation | occurrence | production of the crack when performing curved surface processing by methods, such as thermoforming, can be suppressed.

  In addition, when the electrochromic element 10 according to the first embodiment of the present invention is used for the light control lens 100, it is not necessary to prepare a mold or a member for each shape of the light control lens 100, so that it is easy to produce a large variety of products in small quantities. It becomes.

[Second Embodiment]
Next, the electrochromic element 20 according to the second embodiment of the present invention will be described. FIG. 7 is a schematic cross-sectional view of an electrochromic element 20 according to the second embodiment of the present invention.

  As shown in FIG. 7, in the electrochromic element 20 according to the second embodiment, fine irregularities 12 a are formed on the surface of the first electrode layer 12, and fine irregularities 16 a are formed on the surface of the second electrode layer 16. It differs from the electrochromic element 10 which concerns on 1st Embodiment by the point formed.

  Since other configurations are the same as those of the electrochromic element 10 according to the first embodiment, the description will focus on differences from the first embodiment.

(First electrode layer, second electrode layer)
On the surface of the first electrode layer 12, fine irregularities 12a are formed. On the surface of the second electrode layer 16, fine irregularities 16a are formed. The fine irregularities 12a and 16a are preferably formed with a period shorter than the wavelength of visible light from the viewpoint that the minute appearance cannot be recognized by human eyes and the appearance is good. Furthermore, when using the electrochromic element 20 as a light control lens, it is preferable that the fine unevenness | corrugations 12a and 16a are formed in the irregular pattern from a viewpoint that generation | occurrence | production of a moire can be suppressed on the lens surface.

  As a method of forming fine irregularities 12a and 16a on the surface of the first electrode layer 12 and the surface of the second electrode layer 16, a sand blast method, a dry etching method, a wet etching method, a laser ablation method, a colloidal lithography method, etc. Can be used. Among these, it is preferable to use a colloidal lithography method from the viewpoint that a simple method and a spin coater used when forming the electrochromic layer 13 and the insulating layer 14 can be used.

  Next, the light control lens 200 using the electrochromic element 20 which concerns on 2nd Embodiment of this invention is demonstrated. FIG. 8 is a schematic cross-sectional view illustrating the electrochromic element 20 molded into a curved shape. FIG. 9 is a schematic cross-sectional view of a light control lens 200 using the electrochromic element 20 according to the second embodiment of the present invention.

  As shown in FIG. 8, the photochromic lens 200 has a configuration in which the electrochromic element 20 is processed into a curved shape by thermoforming or the like, and a resin material portion 19 is formed on the concave side of the curved shape as shown in FIG. Have Thereby, the second substrate 15 and the resin material portion 19 constitute a thickened support body that supports the electrochromic element 20. In addition, since a desired curved surface can be formed by machining the thickened support, lens processing (for example, power processing) that matches the user's specific conditions is possible, and adjustment with a desired curved surface shape is possible. The optical lens 100 is obtained.

  According to the light control lens 200, since it is not necessary to prepare a mold or a member for each shape of the light control lens 200, it is easy to produce a variety of products in small quantities.

  Next, a method for manufacturing the electrochromic element 20 according to the second embodiment of the present invention will be described. FIG. 10 is a flowchart showing a method for manufacturing the electrochromic device 20 according to the second embodiment of the present invention.

  First, the first electrode layer 12 is formed on the surface of the first substrate 11 (step S21). Subsequently, fine irregularities 12a are formed on the surface of the first electrode layer 12 (step S22). Subsequently, the electrochromic layer 13 is formed on the surface of the first electrode layer 12 on which the fine irregularities 12a are formed (step S23). Subsequently, the insulating layer 14 is formed on the surface of the electrochromic layer 13 (step S24).

  Further, the second electrode layer 16 is formed on the surface of the second substrate 15 (step S25). Subsequently, fine irregularities 16a are formed on the surface of the second electrode layer 16 (step S26).

  Next, an electrolyte layer 17 is formed on the surface of the insulating layer 14 formed on the first substrate 11, and the insulating layer 14 and the second electrode layer 16 are opposed so that the first electrode layer 12 and the second electrode layer 16 face each other. The two electrode layers 16 are bonded together via the electrolyte layer 17 (step S27). Subsequently, the protective layer 18 is formed (step S28). Subsequently, by performing thermoforming (step S29), the electrochromic element 20 is processed into a curved shape as shown in FIG.

  Through the above steps, the electrochromic element 20 according to the second embodiment of the present invention can be manufactured.

  As described above, according to the electrochromic element 20 according to the second embodiment of the present invention, fine irregularities 12 a and 16 a are formed on the surface of the first electrode layer 12 and the surface of the second electrode layer 16. Has been. For this reason, flexibility arises in the 1st electrode layer 12 and the 2nd electrode layer 16, and generation | occurrence | production of the crack when performing curved surface processing by methods, such as thermoforming, can be suppressed.

  In the second embodiment, since the fine irregularities 12a and 16a can be formed without using the nanoimprint method, it is not necessary to prepare a mold, and the fine irregularities can be formed by a simpler method. .

[Example 1]
In Example 1, the electrochromic element 10 shown in FIG. 4 was produced. This will be specifically described below. FIG. 11 is a diagram for explaining the fine irregularities 11 a formed on the surface of the first substrate 11.

(Formation of first electrode layer, electrochromic layer, insulating layer)
First, an elliptical 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 substrate 11. Subsequently, as shown in FIG. 11A, fine irregularities 11a having a period P of 350 nm and a depth D of 100 nm were formed on the surface of the polycarbonate substrate by nanoimprinting.

  Subsequently, an ITO film, which is a transparent conductive film having a film thickness of about 100 nm, is formed on the surface of the polycarbonate substrate on which the fine irregularities 11a are formed by sputtering as shown in FIG. 1 electrode layer 12 was formed.

  Subsequently, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle size: about 20 nm) was applied to the surface of the ITO film by spin coating, and annealed at 120 ° C. for 5 minutes. As a result, a nanostructured semiconductor material composed of a titanium oxide particle film of about 1.0 μm was formed.

  Subsequently, as an electrochromic compound, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 wt% of the compound represented by the structural formula [Chemical Formula 2] was applied by a spin coating method. After the application, an annealing treatment was performed at 120 ° C. for 10 minutes, thereby supporting (adsorbing) the titanium oxide particle film to form the electrochromic layer 13.

Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, water 74 mass%) having an average primary particle diameter of 20 nm is applied to the surface of the electrochromic layer 13 by spin coating. The insulating inorganic fine particle layer as the insulating layer 14 was formed. At this time, the film thickness of the insulating inorganic fine particle layer was about 2 μm.

(Formation of second electrode layer)
A polycarbonate substrate similar to the first substrate 11 was prepared as the second substrate 15, and fine irregularities 15a having a period P of 350 nm and a depth D of 100 nm were formed on the surface of the polycarbonate substrate by a nanoimprint method.

  Subsequently, an ITO film, which is a transparent conductive film having a film thickness of about 100 nm, was formed on the surface of the polycarbonate substrate on which the fine irregularities 15a were formed by sputtering, and the second electrode layer 16 was formed.

(Formation and bonding of electrolyte layers)
On the surface of the insulating inorganic fine particle layer, a mass ratio (100: 5: 40) of polyethylene diacrylate, photoinitiator (IRG184, manufactured by BASF) and electrolyte (1-ethyl-3-methylimidazolium salt) The electrolyte solution 17 was formed by applying the solution mixed in (1) and pasting the ITO film as the second electrode layer 16 and UV curing.

(Formation of protective layer)
After bonding the insulating inorganic fine particle layer and the ITO film, an ultraviolet curable adhesive (trade name: KARAYADR604 made by Nippon Kayaku Co., Ltd.) is dropped and cured by irradiating with ultraviolet light, so that the protective layer 18 of about 3 μm is formed. Formed.

(Thermoforming)
The produced electrochromic element 10 was sandwiched between a convex mold and a concave mold having a curvature of about 90 mm while being heated at 135 ° C. to obtain an electrochromic element having a 3D spherical surface shown in FIG. At this time, the length of the convex spherical major axis was 81 mm.

[Example 2]
In Example 2, the electrochromic element 20 shown in FIG. 8 was produced. This will be specifically described below. FIG. 12 is a view for explaining fine irregularities 12 a formed on the surface of the first electrode layer 12.

(Formation of first electrode layer, electrochromic layer, insulating layer)
First, the same polycarbonate substrate as in Example 1 was prepared as the first substrate 11.

Subsequently, as shown in FIG. 12A, an ITO film, which is a transparent conductive film having a film thickness of about 30 nm, was formed on the surface of the polycarbonate substrate by sputtering. Subsequently, as shown in FIG. 12B, SiO ₂ fine particles having a particle diameter of 400 nm dispersed in IPA were applied to the surface of the ITO film by a spin coating method to form a colloidal mask layer 21. Subsequently, as shown in FIG. 12C, an ITO film having a thickness of about 100 nm was formed by sputtering, and then immersed in IPA, and the colloidal mask layer 21 was removed by ultrasonic cleaning. As a result, as shown in FIG. 12D, the first electrode layer 12 having fine irregularities 12a in which crater-like depressions with a depth of about 100 nm are formed in an irregular pattern on the surface of the ITO film is formed. did.

  Subsequently, an insulating inorganic fine particle layer was formed as the electrochromic layer 13 and the insulating layer 14 on the surface of the ITO film on which the fine irregularities 12a were formed by the same method as in Example 1.

(Formation of second electrode layer)
A polycarbonate substrate similar to that in Example 1 was prepared as the second substrate 15.

  Subsequently, an ITO film as the second electrode layer 16 having fine irregularities 16a was formed by a method similar to the method of forming the first electrode layer 12.

(Formation of electrolyte layer, bonding, formation of protective layer, thermoforming)
Subsequently, by the same method as in Example 1, the electrolyte layer 17 was formed and bonded, and the protective layer 18 was formed.

(Thermoforming)
The produced electrochromic element 20 was thermoformed by the same method as in Example 1 to obtain an electrochromic element 20 having a 3D spherical surface shown in FIG.

  In Example 2, compared to Example 1, since the nano-imprint method is not used when forming the fine irregularities 12a and 16a, it is not necessary to prepare a mold, and the fine irregularities 12a are formed by a simpler method. 16a could be formed. Further, since the fine irregularities 12a and 16a are irregularly formed, it is considered that when the electrochromic element 20 is used as the light control lens 100, it is possible to suppress the occurrence of moire on the lens surface.

[Comparative example]
In the comparative example, an electrochromic element having a 3D spherical surface in the same manner as in Example 1 except that the fine irregularities 11a and 15a are not formed on the surface of the first substrate 11 and the surface of the second substrate 15. Was made.

  In the comparative example, cracks occurred in the first electrode layer 12 and the second electrode layer 16 during thermoforming, resulting in poor appearance.

(Color-erasing drive)
Next, the color development / decoloration of the electrochromic device having the 3D spherical surface prepared in Example 1, Example 2, and Comparative Example was confirmed.

  Specifically, a part of the end portion of the first substrate 11 and a part of the end portion of the second substrate 15 are peeled off to expose the first electrode layer 12; A second contact portion exposing the second electrode layer 16 was formed. Subsequently, a voltage of −3.5 V was applied for 3 seconds between the first contact portion and the second contact portion so that the first contact portion became a negative pole, and the presence or absence of color development was confirmed. Furthermore, a voltage of +3.5 V was applied for 2 seconds between the first contact portion and the second contact portion, and the presence or absence of color development was confirmed.

  In Example 1 and Example 2, when a voltage of −3.5 V was applied between the first contact part and the second contact part for 3 seconds, it was derived from the electrochromic compound represented by the structural formula [Chemical Formula 2]. The magenta color was confirmed. Furthermore, when a voltage of +3.5 V was applied between the first contact portion and the second contact portion for 2 seconds, it was confirmed that the electrochromic dye disappeared and became transparent.

  On the other hand, in the comparative example, when a voltage of −3.5 V is applied for 3 seconds between the first contact portion and the second contact portion, the first electrode layer 12 and the second electrode layer The resistance values of the first electrode layer 12 and the second electrode layer 16 were increased due to the cracks generated in FIG. 16, and the color was not developed as in Example 1 and Example 2. Further, when a voltage of +3.5 V was applied between the first contact portion and the second contact portion for 2 seconds, the color was not sufficiently erased.

  As mentioned above, although the electrochromic element, the light control lens, and the manufacturing method of the electrochromic element have been described by the embodiments, the present invention is not limited to the above embodiments, and various modifications and improvements can be made within the scope of the present invention. Is possible.

DESCRIPTION OF SYMBOLS 10 Electrochromic element 11 1st board | substrate 12 1st electrode layer 13 Electrochromic layer 15 2nd board | substrate 16 2nd electrode layer 17 Electrolyte layer 19 Resin material part 100 Light control lens

Japanese Patent No. 4105537

Claims (8)

A first electrode layer formed on the surface of the first substrate;
A second electrode layer formed on the surface of the second substrate and provided to face the first electrode layer;
An electrochromic layer provided between the first electrode layer and the second electrode layer;
An electrolyte layer formed between the first electrode layer and the second electrode layer,
Fine irregularities are formed on the surface of the first substrate and the surface of the second substrate,
Electrochromic element. A first electrode layer formed on the surface of the first substrate;
A second electrode layer formed on the surface of the second substrate and provided to face the first electrode layer;
An electrochromic layer provided between the first electrode layer and the second electrode layer;
An electrolyte layer formed between the first electrode layer and the second electrode layer,
Fine irregularities are formed on the surface of the first electrode layer facing the second electrode layer and the surface of the second electrode layer facing the first electrode layer,
Electrochromic element. The fine irregularities are formed in an irregular pattern,
The electrochromic device according to claim 1 or 2. The fine irregularities are formed with a period shorter than the wavelength of visible light,
The electrochromic device according to any one of claims 1 to 3. The first electrode layer and the second electrode layer are made of an inorganic material containing any of indium oxide, tin oxide, and zinc oxide.
The electrochromic device according to any one of claims 1 to 4. A light control lens using the electrochromic device according to any one of claims 1 to 5,
The electrochromic element has a curved shape, and a resin material portion is formed on the concave side of the curved shape,
Photochromic lens. Forming fine irregularities on the surface of the first substrate and the surface of the second substrate;
Laminating a first electrode layer and an electrochromic layer in this order on the surface of the first substrate;
Forming a second electrode layer on the surface of the second substrate;
Forming an electrolyte layer between the first electrode layer and the second electrode layer, and bonding the first electrode layer and the second electrode layer;
Thermoforming the bonded substrates, and
Manufacturing method of electrochromic element. Forming a first electrode layer on the surface of the first substrate;
Forming fine irregularities on the surface of the first electrode layer;
Laminating an electrochromic layer in this order on the surface of the first electrode layer;
Forming a second electrode layer on the surface of the second substrate;
Forming fine irregularities on the surface of the second electrode layer;
Forming an electrolyte layer between the first electrode layer and the second electrode layer, and bonding the first electrode layer and the second electrode layer;
Thermoforming the bonded substrates, and
Manufacturing method of electrochromic element.

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