JP6589412B2 - Method for manufacturing electrochromic device - Google Patents

Description

  The present invention relates to a method for manufacturing an electrochromic device.

  A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. Electrochromism is generally formed between two electrodes facing each other, and undergoes a redox reaction in a configuration in which an electrolyte layer capable of ion conduction is filled between the electrodes. When a reduction reaction occurs in the vicinity of one of the two electrodes facing each other, an oxidation reaction that is a reverse reaction occurs in the vicinity of the other electrode.

  An electrochemical device using the coloring / decoloring of an electrochromic compound that causes the phenomenon of electrochromism is called an electrochromic element. This electrochromic element has a memory effect, can adjust the color density by the applied voltage intensity, and can be driven at a low voltage, so it is expected to be applied to various applications such as dimming lenses, dimming glass, and electronic paper. R & D has been conducted extensively from material development to device design and process development.

  In general, an electrochromic element is formed by forming an electrochromic material between two electrodes facing each other, and then bonding them together via an ion conductive electrolyte layer and sealing the outer periphery with a sealing material. At this time, there is a tendency to use a material that crosslinks by heat or light energy as the electrolyte layer or the sealing material.

  In such an electrochromic device, an electrolyte solution that becomes an electrolyte layer or a resin that becomes a sealing material is applied using a dispenser, and after the bonding step, the electrolyte solution and the resin are crosslinked by UV irradiation or the like. It is ideal to be made with. Further, at this time, since the electrolyte solution and the resin are in contact with each other in a liquid-liquid state, there is a concern that the resin may be eluted into the electrolyte solution.

  However, if the electrolyte solution and the resin are cross-linked at the same time immediately after bonding, excellent response characteristics cannot be obtained. In addition, when pattern coating of the electrolyte solution is performed, the coating marks are displayed as color unevenness at the time of color development, which causes a significant deterioration in display quality (uniform color development). This is because, when the electrolyte layer is formed by solidifying the electrolyte solution, resistance to ion migration at the interface between the electrode material and the solidified electrolyte layer increases.

  In order to solve such problems, a method of polymerizing a liquid monomer to which an electrolyte solution is added in order to improve the conductivity of the solid electrolyte to form a crosslinked polymer containing the electrolyte solution (for example, see Patent Document 1) Etc. have been proposed. However, at present, sufficient electrical conductivity has not been obtained.

  In addition, as another means for improving electrical conductivity, for example, a method using a solid electrolyte having a chemical cross-linking portion is also disclosed (see, for example, Patent Document 2). Is not fully obtained.

  The present invention has been made in view of the above points, and even when a material that crosslinks by heat or light energy is used as a material for the electrolyte layer and the sealing material, it is possible to ensure response characteristics and uniform color development. It is an object of the present invention to provide a method for manufacturing an electrochromic device.

The method of manufacturing the electrochromic device includes a first electrode and a second electrode facing each other, an electrochromic layer provided between the first electrode and the second electrode, and the first electrode An electrochromic element manufacturing method comprising: an electrolyte layer provided between an electrode and the second electrode, in contact with the electrochromic layer; and a sealing material provided along the periphery of the electrolyte layer. A step of forming the electrochromic layer on the first electrode, a step of applying an electrolyte solution to be the electrolyte layer on the electrochromic layer, and a periphery of the electrolyte solution on the electrochromic layer. along, after the step of crosslinking the step of applying a resin, and forming the sealing material by crosslinking the resin by heat or light energy, the resin, before Electrolytic electrolyte solution to form a step of applying heat energy to the electrolyte solution at a temperature range that does not initiate the crosslinking, after the step of applying the thermal energy, the electrolyte layer by crosslinking the electrolyte solution by the heat or light energy And having a process.

  According to the disclosed technology, there is provided an electrochromic device manufacturing method capable of ensuring response characteristics and uniform color development even when a material that crosslinks by heat or light energy is used as a material of an electrolyte layer and a sealing material. it can.

It is sectional drawing which illustrates the electrochromic element which concerns on 1st Embodiment. FIG. 6 is a diagram (part 1) illustrating a manufacturing process of the electrochromic device according to the first embodiment; FIG. 6 is a second diagram illustrating a manufacturing process of the electrochromic device according to the first embodiment; FIG. 6 is a diagram (No. 3) illustrating the manufacturing process of the electrochromic device according to the first embodiment; It is sectional drawing which illustrates the electrochromic element which concerns on 2nd Embodiment. It is a figure which illustrates the manufacturing process of the electrochromic element which concerns on 2nd Embodiment.

  Hereinafter, embodiments 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>
[Structure of electrochromic device]
FIG. 1 is a cross-sectional view illustrating an electrochromic element according to the first embodiment. Referring to FIG. 1, an electrochromic element 1 includes a first support 10, a second support 11, a first electrode 12, a second electrode 13, an electrochromic layer 14, and an electrolyte. The layer 16, the porous insulating layer 17, and the sealing material 18 are included.

  In the present embodiment, for the sake of convenience, the first support 10 side of the electrochromic element 1 is defined as the upper side or one side, and the second support 11 side is defined as the lower side or the other side. Further, the surface on the first support 10 side of each part is defined as one surface or upper surface, and the surface on the second support 11 side is defined as the other surface or lower surface. However, the electrochromic element 1 can be used upside down, or can be arranged at an arbitrary angle. The planar view refers to viewing the object from the normal direction of one surface of the first support 10, and the planar shape refers to the normal of the one surface of the first support 10. It shall refer to the shape viewed from the direction.

  In the electrochromic element 1, a first electrode 12 that is a display electrode is provided on the lower surface of the first support 10. An electrochromic layer 14 is provided on the lower surface of the first electrode 12.

  A second electrode 13 that is a counter electrode is provided on the upper surface of the second support 11. The first electrode 12 and the second electrode 13 are arranged to face each other at a predetermined interval in the thickness direction of the electrochromic element 1, and between the first electrode 12 and the second electrode 13. In this case, an electrolyte layer 16 in contact with the electrochromic layer 14 is disposed.

  In the electrochromic element 1, the first electrode 12 and the second electrode 13 are bonded to each other with the porous insulating layer 17 interposed therebetween with the electrolyte layer 16 provided between the electrodes, thereby forming a cell. ing. Each component of the electrochromic element 1 provided between the first electrode 12 and the second electrode 13 is sealed with a sealing material 18 provided on the outer periphery of each component. Hereinafter, each component of the electrochromic device 1 will be described in detail.

(First support, second support)
As the 1st support body 10 and the 2nd support body 11, if it is a transparent material which can support each layer, a well-known organic material and an inorganic material can be used as it is. As the 1st support body 10 and the 2nd support body 11, glass substrates, such as an alkali free glass, borosilicate glass, float glass, soda lime glass, can be used, for example. Also, as the first support 10 and the second support 11, resin substrates such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, polyimide resin, and the like are used. It may be used.

(First electrode)
The first electrode 12 is an electrode for controlling the potential with respect to the second electrode 13 and causing the electrochromic layer 14 to develop color. The material of the first electrode 12 is not particularly limited as long as it is a conductive material, but a transparent electrode made of a transparent material is used because it is necessary to ensure light transmission. The material for the transparent electrode is not particularly limited, but tin-doped indium oxide (hereinafter sometimes abbreviated as “ITO”), fluorine-doped tin oxide (hereinafter abbreviated as “FTO”). In some cases, tin oxide doped with antimony (hereinafter sometimes abbreviated as “ATO”) or the like is preferably used.

(Electrochromic layer)
The electrochromic layer 14 is a layer containing an electrochromic material. As the electrochromic material, an inorganic electrochromic compound, an organic electrochromic compound, a conductive polymer exhibiting electrochromism, or the like can be used. Specifically, for example, a known electrochromic compound such as a dye system, a polymer system, a metal complex system, or a metal oxide system can be used.

  Examples of the dye-based and polymer-based electrochromic compounds include, for example, azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, dipyridine-based, styryl-based, styrylspiropyran-based, spirooxazine-based, spirothiopyran-based, thioindigo-based, tetrathiafulvalene. , Terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluoran, fulgide, benzopyran Further, low molecular organic electrochromic compounds such as metallocenes, and conductive polymer compounds such as polyaniline and polythiophene can be used.

  In particular, it is preferable to contain a viologen compound or a dipyridine compound. These materials have a low color developing / erasing potential and exhibit good color values. A well-known thing can be used about a viologen type compound or a dipyridine type compound, for example, about a viologen type | system | group, about the compound currently described in patent 3955641, Unexamined-Japanese-Patent No. 2007-171781, etc., about a dipyridine type | system | group. Examples thereof include compounds described in JP-A-2007-171781, JP-A-2008-116718, and the like.

  Examples of the metal complex compound include an iron cyano complex, a ruthenium cyano complex, an osmium cyano complex, a tungsten oxalate complex, and a rare earth diphthalocyanine complex. Examples of the metal oxide compound include tungsten oxide, molybdenum oxide, iridium oxide, indium oxide, titanium oxide, nickel oxide, and vanadium oxide.

  As the electrochromic layer 14, it is particularly desirable to use a structure in which an organic electrochromic compound is supported on conductive or semiconductive fine particles. Specifically, ultrafine particles (conducting or semiconducting) having a particle size of about 5 nm to 50 nm are sintered on the electrode surface, and polar groups such as phosphonic acid, carboxyl group, and silanol group are formed on the surface of the ultrafine particles. The organic electrochromic compound is adsorbed.

  With such a structure, electrons are efficiently injected into the organic electrochromic compound using the large surface area effect of the ultrafine particles, so that the color density is large and the speed of color development and decoloration is high. Furthermore, since a transparent film can be formed as a display layer by using ultrafine particles, a high white reflectance can be obtained. Also, a plurality of types of organic electrochromic compounds can be supported on conductive or semiconductive fine particles.

  A preferable film thickness range of the electrochromic layer 14 is 0.1 to 10 μm. When the film thickness is thinner than 0.1 μm, it is difficult to obtain the color density. On the other hand, when the film thickness is thicker than 10 μm, the manufacturing cost increases, and the visibility tends to decrease due to coloring.

  Although it does not specifically limit as electroconductive or semiconductive fine particle, A metal oxide is desirable. Materials include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, oxygen boron, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide, ferrite, oxide A metal oxide mainly composed of hafnium, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, or the like is used. Moreover, these metal oxides may be used independently and 2 or more types may be mixed and used.

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

  Further, the shape of the conductive or semiconductive fine particles is not particularly limited, but in order to efficiently carry the electrochromic compound, the surface area per unit volume (hereinafter referred to as “specific surface area”) may be used. ) 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 supported more efficiently, and a display excellent in display contrast ratio of color development and decoloration is possible.

(Porous insulation layer)
The porous insulating layer 17 has a function of holding the electrolyte layer 16 while isolating the first electrode 12 and the second electrode 13 so as to be electrically insulated. The material of the porous insulating layer 17 is not particularly limited as long as it is porous, and it is preferable to use an organic material or an inorganic material having high insulating properties and durability and excellent film forming properties, and a composite thereof.

  Examples of the forming method include a sintering method, an extraction method, a foaming method, a phase change method, and a radiation irradiation method. The sintering method is a method in which polymer fine particles and inorganic particles are partially fused by adding a binder or the like and holes formed between the particles are used. The extraction method is a method 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. The foaming method is a method using foaming. The phase conversion method is a method in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. The radiation irradiation method is a method of forming pores by radiating various types of radiation.

(Second electrode)
The second electrode 13 is an electrode for controlling the potential of the paired first electrode 12 and causing the electrochromic layer 14 to develop color. The material of the second electrode 13 is not particularly limited as long as it is a conductive material, but a transparent electrode such as ITO, FTO, or zinc oxide is used because it is necessary to ensure light transmission. It is done. The method for forming the second electrode 13 is not particularly limited as long as it does not hinder the movement of the electrolyte. For example, the second electrode 13 may be formed directly on the porous insulating layer 17 or a plurality of perforations. You may form in the film etc. which have.

(Electrolyte layer)
The electrolyte layer 16 is for causing charge to move by moving ions between the first electrode 12 and the second electrode 13, thereby causing a coloring / decoloring reaction of the electrochromic layer 14. As the material of the electrolyte layer 16, 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.

  An ionic liquid can also be used. In particular, organic ionic liquids include compounds having a molecular structure that show a liquid state in a wide temperature range including room temperature. Examples of the molecular structure showing such a liquid state include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N- Aliphatic 4 such as dimethylpyridinium salt, pyridinium derivatives such as N, N-methylpropylpyridinium salt, aromatic salts, or tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, triethylhexylammonium salt, etc. Examples include quaternary ammonium salts.

On the other hand, the anion component is preferably a compound containing fluorine in terms of stability in the atmosphere, and examples thereof include BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{− and the} like. An ionic liquid formulated by a combination of these cationic components and anionic components can be used. These electrolyte materials can be used in the electrolyte layer 16 by being dissolved in a solvent and used as an electrolyte solution.

  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. In addition, an electrolyte solution that can be formed into a gel or a solid is used. This is also preferable from the viewpoints of improving element strength, improving reliability, and preventing color diffusion.

  As a solidification method, it is preferable to hold an electrolyte and a solvent in a resin (polymer). This is because solid strength can be obtained while maintaining high ionic conductivity. Furthermore, as the resin (polymer), a photocurable resin (photocurable resin) is preferable. Compared to the method of forming a thin electrolyte layer containing a resin and an electrolyte material by evaporating the solvent or by evaporating the solvent, there is an advantage that a device can be manufactured at a low temperature and in a short time when using a photocurable resin. is there. However, a thermosetting resin may be used.

  As described above, the electrolytes can be used alone or in combination. In addition, the film thickness of the electrolyte layer 16 is preferably in the range of 0.5 to 100 μm, more preferably 1 to 50 μm. This is because if the thickness of the electrolyte layer 16 is thicker than 50 μm, the charges are easily diffused, and if the thickness is thinner than 1 μm, it is difficult to maintain the function as an electrolyte.

(Encapsulant)
The sealing material 18 has a function of sealing the side surface of the electrochromic element 1 and preventing intrusion of unnecessary things such as moisture and oxygen in the atmosphere in order to stably operate the electrochromic element 1. The sealing material 18 is not particularly limited, and for example, an ultraviolet curable resin or a thermosetting resin can be used, and specific examples include acrylic, urethane, and epoxy resins.

[Method of manufacturing electrochromic element]
Next, features of the method for manufacturing the electrochromic element 1 will be described. 2 to 4 are diagrams illustrating the manufacturing process of the electrochromic device according to the first embodiment. FIGS. 2B and 3A are plan views, and the others correspond to FIG. It is sectional drawing.

  First, in the step shown in FIG. 2A, the electrochromic layer 14 is formed adjacent to the first electrode 12 of the first support 10 (for example, ITO glass substrate) on which the first electrode 12 is formed. To do. The electrochromic layer 14 is obtained by, for example, applying an electrochromic composition adjusted to a predetermined composition on the first electrode 12 formed on the first support 10 by a spin coating method or the like. The film can be formed by crosslinking with heat or light energy.

  Next, in the step shown in FIG. 2B, an electrolyte solution 16 </ b> L that becomes the electrolyte layer 16 when coated is applied onto the electrochromic layer 14. As the electrolyte solution 16L, a material that crosslinks by heat or light energy is used. It is preferable that the electrolyte solution 16L is uniformly applied on an application target using a jet dispenser or the like with a predetermined pattern shape such as a dot shape pattern or a line shape pattern on a macro scale. Thereby, uniform application on a macro scale corresponding to an application object of all kinds of sizes and a minute application amount control are possible.

  Next, in the step shown in FIG. 3A, a resin 18L that becomes a sealing material 18 when applied is applied along the periphery of the electrolyte solution 16L on the electrochromic layer 14 using a dispenser or the like. As the resin 18L, a material that crosslinks by heat or light energy is used.

  Next, in the step shown in FIG. 3B, the porous insulating layer 17 is adjacent to the second electrode 13 of the second support 11 (for example, ITO glass substrate) on which the second electrode 13 is formed. Form. The porous insulating layer 17 is obtained by, for example, applying a fine particle dispersion adjusted to a predetermined composition on the second electrode 13 formed on the second support 11 by a spin coating method or the like. The film can be formed by heat firing. The porous insulating layer 17 may be a layer in which a plurality of insulating materials are stacked.

  Next, in the step shown in FIG. 4A, the structure shown in FIG. 3A in which the electrolyte solution 16L and the resin 18L are applied on the electrochromic layer 14, and the porous insulation on the second electrode 13. The structure shown in FIG. 3B on which the layer 17 is formed is bonded with the first support 10 and the second support 11 facing outside. At this time, since the electrolyte solution 16L permeates between the first electrode 12 and the porous insulating layer 17, a thin layer of the electrolyte solution 16L is formed between the first electrode 12 and the porous insulating layer 17. The Thereafter, the sealing material 18 is formed by crosslinking the resin 18L with heat or light energy. At this time, the electrolyte solution 16L is not crosslinked.

  Next, in the step shown in FIG. 4B, first, thermal energy is applied to the electrochromic element 1 in a temperature range in which the electrolyte solution 16L does not start crosslinking. Thereafter, the electrolyte layer 16L is formed by crosslinking the electrolyte solution 16L with heat or light energy.

  As described above, in the method for manufacturing the electrochromic device 1 according to the first embodiment, the step of crosslinking the electrolyte solution 16L and the step of crosslinking the resin 18L are not performed simultaneously but sequentially. That is, the step of crosslinking the electrolyte solution 16L is performed after the step of crosslinking the resin 18L. Then, between the step of crosslinking the resin 18L and the step of crosslinking the electrolyte solution 16L, a step of applying thermal energy to the electrochromic element 1 is performed in a temperature range in which the electrolyte solution 16L does not start crosslinking.

  Therefore, when the resin 18L is cured and the sealing material 18 is formed, the electrolyte solution 16L is uncured and can penetrate into each layer in the electrochromic element 1. The electrolyte solution 16L whose hardening has been delayed can penetrate into each layer in the electrochromic element 1 with sufficient time.

  In addition, since the viscosity of the electrolyte solution 16L is temporarily reduced by heat in the step of applying thermal energy to the electrochromic device 1 in a temperature range where the electrolyte solution 16L does not start crosslinking, the electrolyte to each layer in the electrochromic device 1 The penetration of the liquid 16L can be promoted.

  As a result, the response characteristics and uniform color development of the electrochromic element 1 can be ensured, and the characteristic difference between elements can be minimized.

<Second Embodiment>
In the second embodiment, an example in which an electrochromic layer is provided also on the second electrode side will be described. In the second embodiment, description of the same components as those of the already described embodiments may be omitted.

  FIG. 5 is a cross-sectional view illustrating an electrochromic device according to the second embodiment. Referring to FIG. 5, the electrochromic element 2 is different from the electrochromic element 1 (see FIG. 1) in that an electrochromic layer 15 is provided on the upper surface of the second electrode 13. The material and film thickness of the electrochromic layer 15 can be the same as those of the electrochromic layer 14, for example.

  In order to manufacture the electrochromic element 2, the process shown in FIG. 6 may be performed instead of the process shown in FIG. 3B of the first embodiment. Other steps can be the same as those in the first embodiment.

  FIG. 6 is a diagram illustrating a manufacturing process of the electrochromic device according to the second embodiment, and is a cross-sectional view corresponding to FIG. 5. In the process shown in FIG. 6, the electrochromic layer 15 is formed adjacent to the second electrode 13 of the second support 11 (for example, ITO glass substrate) on which the second electrode 13 is formed. The electrochromic layer 15 is obtained by, for example, applying an electrochromic composition adjusted to a predetermined composition onto the second electrode 13 formed on the second support 11 by a spin coating method or the like. The film can be formed by crosslinking with heat or light energy.

  Subsequently, a porous insulating layer 17 is formed on the electrochromic layer 15. The porous insulating layer 17 can be formed, for example, by applying a fine particle dispersion adjusted to a predetermined composition on the electrochromic layer 15 by a spin coating method or the like, and thermally baking the obtained coating film. The porous insulating layer 17 may be a layer in which a plurality of insulating materials are stacked.

  Thus, an electrochromic layer may be provided on both the first electrode 12 and the second electrode 13. Also in this case, as in the first embodiment, the electrolyte solution delayed in curing penetrates into each layer in the electrochromic element 2 with sufficient time. As a result, it is possible to ensure the response characteristics and uniform color developability of the electrochromic element 2, and to minimize the characteristic difference between the elements. Moreover, the improvement of the coloring density by two electrochromic layers can be expected.

  In addition, the electrochromic layer 15 can be easily formed by selecting a layer in which a color that is complementary to the color due to the redox reaction of the electrochromic layer 14 is caused by the reverse reaction of the redox reaction. Black color can be developed.

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

<Example 1>
The electrochromic element 1 was produced by the following [1] to [7] based on the configuration shown in FIG.

[1] Formation of Electrochromic Layer 14 on First Electrode 12 In order to form the electrochromic layer 14 on the first electrode 12, an electrochromic composition having the following composition was prepared.
[composition]
-Triarylamine compound having a monofunctional acrylate 1: 50 parts by mass-IRGACURE 184 (manufactured by BASF Japan): 5 parts by mass-PEG400DA having a bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass-Methyl ethyl ketone: 900 parts by mass The obtained electrochromic composition is spin-coated on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as the first support 10 and the first electrode 12. It was applied by the method. The obtained coating film was irradiated with a UV irradiation device (USHIO Corporation, SPOT CURE) at 10 mW for 60 seconds, and annealed at 60 ° C. for 10 minutes, whereby a cross-linked electrochromic layer having an average thickness of 400 μm. 14 was formed.

[2] Formation of Porous Insulating Layer 17 on Second Electrode 13 In order to form the porous insulating layer 17 on the second electrode 13, a fine particle dispersion having the following composition was prepared.
[composition]
-Silica fine particle dispersion (silica solid content concentration 13 parts by weight, aqueous polyester urethane resin) (HW350, DIC Corporation): 2 parts by weight-2,2,2,3-tetrafluoropropanol: 85 parts by weight The fine particle dispersion is applied by spin coating onto an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as the second support 11 and the second electrode 13, and 120 ° C. Was fired for 10 minutes to obtain an insulating layer having an average film thickness of about 1 μm. Subsequently, an inorganic insulating layer of ZnS—SiO _{2 (} 8/2) was formed thereon with a thickness of 100 nm by a sputtering method. Thereby, the porous insulating layer 17 was formed.

[3] Application of electrolyte solution 16L An electrolyte solution 16L having the composition shown below was prepared.
IRGACURE184 (manufactured by BASF Japan KK): 5 parts by mass PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (manufactured by Merck): 50 parts by mass The obtained electrolyte solution 16L · 43 mg was dropped in a dot-like pattern shown in FIG. 2B onto an ITO glass substrate (first support 10 and first electrode 12) having a cross-linked electrochromic layer 14. did. In addition, the jet dispenser (made by Musashi engineering) was used for dripping.

[4] Application of resin 18L As resin 18L to be the sealing material 18, 18 mg of Photorec (manufactured by Sekisui Chemical Co., Ltd.), which is a photosensitive resin, is used in a pattern shown in FIG. It was applied along the circumference of 16L.

[5] Bonding A structure in which each layer is formed on an ITO glass substrate (second support 11 and second electrode 13) and an ITO glass substrate (first support 10 and first electrode 12) The structure having each layer formed thereon was bonded to each other with each ITO glass substrate facing outward.

[6] Crosslinking of Resin 18L Immediately after the bonding, a photomask covering the coating portion of the electrolyte solution 16L was placed on the first support 10 and subjected to light shielding treatment. Thereafter, the element was irradiated at 10 mW for 60 seconds with a UV (wavelength 250 nm) irradiation device (USHIO Corporation, SPOT CURE), and only the resin 18L was crosslinked to form the sealing material 18.

[7] Penetration Acceleration Treatment and Crosslinking of Electrolyte Solution 16L For the device in which only resin 18L was crosslinked, the entire device was heated at 60 ° C. for 10 minutes. Thereafter, the device is irradiated with UV (wavelength 250 nm) irradiation device (USHIO Inc., SPOT CURE) at 10 mW for 60 seconds, the coating portion of the electrolyte solution 16L is crosslinked to form the electrolyte layer 16, and the electrochromic Element 1 was completed.

The electrochromic element 1 produced in Example 1 was subjected to the response speed test shown below.
<Test 1: Response speed test>
A voltage of 2.0 V was applied to the electrochromic device 1 produced in Example 1 for 3 seconds to cause color development, and the reflectance at a wavelength of 450 nm having an absorption peak at the time of color development was measured with USB4000 manufactured by Ocean Optics. The response speed was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: Reflectance less than 5% B: Reflectance 5% or more but less than 10% Δ: Reflectivity 10% or more Next, in the electrochromic device 1 of Example 1, the following uniform color test was performed.
<Test 2: Uniform color development test>
The electrochromic device 1 was colored by applying a constant voltage with a charge amount of 10.0 mC / cm ² for 10 seconds, and the state of uniform color development in the colored state was evaluated according to the following criteria.
[Evaluation criteria]
◎: There is no color unevenness and the entire surface is uniformly colored. ○: During the color development, only the portion where the electrolyte solution is dripped with a dot is darkly colored and color unevenness occurs. Only the part dripped in is darkly colored and color unevenness occurs.

<Comparative example 1>
In Example 1, the encapsulant 18 and the electrolyte layer 16 are formed by simultaneously crosslinking the application portion of the resin 18L and the application portion of the electrolyte solution 16L without using a photomask in the step [6], and the step [7] is performed. An electrochromic element was produced in the same manner as in Example 1 except that the above was not performed. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative example 2>
In Example 1, an electrochromic device was produced in the same manner as in Example 1 except that the heating was not performed in the step [7] and left at room temperature. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative Example 3>
An electrochromic device was produced in the same manner as in Example 1 except that the heating temperature was changed to 40 ° C. in the step [7] in Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative example 4>
An electrochromic device was produced in the same manner as in Example 1 except that the heating temperature was changed to 80 ° C. in the step [7] in Example 1. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Example 2>
The electrochromic element 2 was produced by the following [1] to [7] based on the configuration shown in FIG.

[1] Formation of the electrochromic layer 14 on the first electrode 12 In order to form the electrochromic layer 14 on the first electrode 12, a first electrochromic composition that develops yellow-green color with the following composition A product was prepared.
[composition]
-Triarylamine compound having a monofunctional acrylate 1: 50 parts by mass-IRGACURE 184 (manufactured by BASF Japan): 5 parts by mass-PEG400DA having a bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass-Methyl ethyl ketone: 900 parts by mass The obtained electrochromic composition is spin-coated on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as the first support 10 and the first electrode 12. It was applied by the method. The obtained coating film was irradiated with a UV irradiation device (USHIO Corporation, SPOT CURE) at 10 mW for 60 seconds, and annealed at 60 ° C. for 10 minutes, whereby a cross-linked electrochromic layer having an average thickness of 400 μm. 14 was formed.
[2] Formation of Electrochromic Layer 15 and Porous Insulating Layer 17 on Second Electrode 13 In order to form electrochromic layer 15 on second electrode 13, the first electro A second electrochromic composition that produces a purple color that is complementary to the color of the chromic composition was prepared.
[composition]
Viologen compound: 2 parts by mass2,2,2,3-tetrafluoropropanol: 98 parts by mass ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, second electrode 11 and second electrode 13) A titanium oxide fine particle dispersion (SP210 Showa Titanium) was spin-coated on an ITO film thickness (about 100 nm). Then, a titanium oxide particle film was formed by annealing at 120 ° C. for 15 minutes, the second electrochromic composition was spin-coated, and annealing was performed at 120 ° C. for 10 minutes.

Next, in order to form the porous insulating layer 17 on the second electrode 13, a fine particle dispersion having the following composition was prepared.
[composition]
-Silica fine particle dispersion (silica solid content concentration 13 parts by weight, aqueous polyester urethane resin) (HW350, DIC Corporation): 2 parts by weight-2,2,2,3-tetrafluoropropanol: 85 parts by weight The fine particle dispersion was applied onto the second electrode 13 having the electrochromic layer 15 by spin coating, and baked at 120 ° C. for 10 minutes to obtain an insulating layer having an average film thickness of about 1 μm. Subsequently, an inorganic insulating layer of ZnS—SiO ₂ (8/2) was formed thereon with a thickness of 100 nm by a sputtering method. Thereby, the porous insulating layer 17 was formed.
[3] Application of electrolyte solution 16L An electrolyte solution 16L having the composition shown below was prepared.

IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (manufactured by Merck): 50 parts by mass The obtained electrolyte solution 16L · 43 mg was dropped in a dot-like pattern shown in FIG. 2B onto an ITO glass substrate (first support 10 and first electrode 12) having a cross-linked electrochromic layer 14. did. In addition, the jet dispenser (made by Musashi engineering) was used for dripping.
[4] Application of resin 18L As resin 18L to be the sealing material 18, 18 mg of Photorec (manufactured by Sekisui Chemical Co., Ltd.), which is a photosensitive resin, is used in a pattern shown in FIG. It was applied along the circumference of 16L.
[5] Bonding A structure in which each layer is formed on an ITO glass substrate (second support 11 and second electrode 13) and an ITO glass substrate (first support 10 and first electrode 12) The structure having each layer formed thereon was bonded to each other with each ITO glass substrate facing outward.
[6] Crosslinking of Resin 18L Immediately after the bonding, a photomask covering the coating portion of the electrolyte solution 16L was placed on the first support 10 and subjected to light shielding treatment. Thereafter, the element was irradiated at 10 mW for 60 seconds with a UV (wavelength 250 nm) irradiation device (USHIO Corporation, SPOT CURE), and only the resin 18L was crosslinked to form the sealing material 18.
[7] Penetration Acceleration Treatment and Crosslinking of Electrolyte Solution 16L For the device in which only resin 18L was crosslinked, the entire device was heated at 60 ° C. for 10 minutes. Thereafter, the device is irradiated with UV (wavelength 250 nm) irradiation device (USHIO Inc., SPOT CURE) at 10 mW for 60 seconds, the coating portion of the electrolyte solution 16L is crosslinked to form the electrolyte layer 16, and the electrochromic Element 2 was completed.
<Color generation / erasing drive>
When the electrochromic element 2 manufactured in the item [7] is driven, each of the electrochromic layer 14 and the electrochromic layer 15 exhibits a corresponding color, and both are in a complementary color relationship. Confirmed black coloration.

  For the produced electrochromic element 2, tests 1 and 2 were performed in the same manner as in Example 1.

<Comparative Example 5>
In Example 2, the encapsulating material 18 and the electrolyte layer 16 were formed by simultaneously crosslinking the application portion of the resin 18L and the application portion of the electrolyte solution 16L without using a photomask in the step [6], and carrying out [7]. An electrochromic device was fabricated in the same manner as in Example 2 except that the above was not performed. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative Example 6>
In Example 2, an electrochromic device was produced in the same manner as in Example 2 except that the heating was not performed in the step [7] and left at room temperature. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative Example 7>
In Example 2, an electrochromic device was produced in the same manner as in Example 2 except that the heating temperature was changed to 40 ° C. in the step [7]. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Comparative Example 8>
In Example 2, an electrochromic device was produced in the same manner as in Example 2 except that the heating temperature was changed to 80 ° C. in the step [7]. About the produced electrochromic element, it carried out similarly to Example 1, and performed Test 1 and 2.

<Examination of Examples and Comparative Examples>
Table 1 shows the results of Tests 1 and 2 in Examples 1 and 2 and Comparative Examples 1 to 8.

表１の結果から、実施例１は応答速度及び均一発色性に関して何れも良好な結果を示した。これに対して、比較例１では応答速度は遅く、色ムラも大きく目立つ結果となった。これは、電解質液の架橋のタイミングが早いために、エレクトロクロミック素子内の各層に電解質液が一様に浸透できず、ジェットディスペンサー塗布領域のみしか発色しなかったためと考えられる。

From the results of Table 1, Example 1 showed good results with respect to response speed and uniform color development. On the other hand, in Comparative Example 1, the response speed was slow and the color unevenness was greatly conspicuous. This is considered to be because the electrolyte solution cannot be uniformly penetrated into each layer in the electrochromic element because the timing of the crosslinking of the electrolyte solution is early, and only the jet dispenser application region is colored.

  In Comparative Examples 2 and 3, although the permeation time was provided, the viscosity of the electrolyte solution was not sufficiently lowered because the heating temperature was low, and as a result, the permeation was considered to be insufficient. Moreover, the result of the comparative example 4 has shown that the bridge | crosslinking of electrolyte solution will be accelerated | stimulated with a heat | fever and the penetration | infiltration will not fully advance when heating temperature is too high. This is true even if the configuration of the electrochromic element is changed, such as the results of Example 2 and Comparative Examples 5 to 8 in which electrochromic layers are provided on both electrodes.

  As described above, the electrolyte solution 16L is crosslinked by performing the heat treatment at 60 ° C. without crosslinking the electrolyte solution 16L serving as the electrolyte layer 16 at the timing of crosslinking of the resin 18L serving as the sealing material 18. Has been confirmed to sufficiently penetrate into each layer in the electrochromic device. That is, even when a jet dispenser was used for the cross-linked electrolyte solution or the coating method, an electrochromic element having no color unevenness and good response speed could be produced. In other words, this technique is extremely effective as a technique for producing a safe and scalable electrochromic element without significantly reducing the response characteristics and the uniform color development.

  In addition, although the Example which bridge | crosslinks the resin 18L and the electrolyte solution 16L by light energy was shown here, the same effect as the above is also obtained when either one or both of the resin 18L and the electrolyte solution 16L are crosslinked by thermal energy. Is obtained. In this case as well, the electrolyte solution 16L that has delayed the curing penetrates into each layer in the electrochromic element with sufficient time.

  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.

DESCRIPTION OF SYMBOLS 1, 2 Electrochromic element 10 1st support body 11 2nd support body 12 1st electrode 13 2nd electrode 14, 15 Electrochromic layer 16 Electrolyte layer 16L Electrolyte liquid 17 Porous insulating layer 18 Sealing material 18L resin

JP-A-63-94501 JP-A-11-288873

Claims (5)

A first electrode and a second electrode facing each other;
An electrochromic layer provided between the first electrode and the second electrode;
An electrolyte layer provided between the first electrode and the second electrode and in contact with the electrochromic layer;
A sealing material provided along the periphery of the electrolyte layer, and a method for producing an electrochromic device comprising:
Forming the electrochromic layer on the first electrode;
Applying an electrolyte solution to be the electrolyte layer on the electrochromic layer;
Applying a resin along the periphery of the electrolyte solution on the electrochromic layer;
A step of forming the sealing material by crosslinking the resin by heat or light energy,
After the step of crosslinking the resin, the step of pre-Symbol electrolytic electrolyte solution applies thermal energy to the electrolyte solution at a temperature range that does not initiate crosslinking,
And a step of forming the electrolyte layer by crosslinking the electrolyte solution with heat or light energy after the step of applying the thermal energy. Is pre-Symbol the electrochromic layer on the first electrode is formed, of the electrolyte solution and the resin is coated structure to the electrochromic layer, and a step of bonding the second electrode on the resin side Have
The electrochromic device manufacturing method according to claim 1, wherein the step of cross-linking the resin, the step of applying the thermal energy, and the step of cross-linking the electrolyte solution are sequentially performed after the bonding step. Method.   The method of manufacturing an electrochromic device according to claim 2, wherein the electrolyte solution is applied in a predetermined pattern shape.   4. The method of manufacturing an electrochromic device according to claim 1, further comprising a step of providing a porous insulating layer between the first electrode and the second electrode. 5. The electrochromic layer is selected so that the first electrochromic layer and the color development complementary to the color development due to the redox reaction of the first electrochromic layer are caused by the reverse reaction of the redox reaction. A second electrochromic layer,
Forming the first electrochromic layer adjacent to the first electrode; and forming the second electrochromic layer adjacent to the second electrode. The manufacturing method of the electrochromic element as described in any one of Claim 1 thru | or 4.

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