JP2018132718A - Electrochromic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic device that has good optical characteristics and electrical characteristics.SOLUTION: An electrochromic device comprises: a first conductive substrate 1; a first electrochromic layer 3 that is formed in contact with the first conductive substrate 1; a second conductive substrate 2 that is opposed to the first conductive substrate 1; a second electrochromic layer 4 that is formed in contact with the second conductive substrate 2; and an electrolyte layer 5 that has a spacer 6. The first electrochromic layer 3 is opposed to the second electrochromic layer 4 with the electrolyte layer 5 therebetween, and the spacer 6 contains an electrolyte and resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic device.

  When voltage is applied, the phenomenon of reversible oxidation and reduction, and reversibly coloring and decoloring is called electrochromism. Previous attempts have been made to use electrochromic elements for light control elements (for example, dimming glass or dimming lenses) by making electrochromic elements that can be colored and decolored by voltage operation and using a transparent substrate. It is made from.

As a method for producing an electrochromic device, a method is known in which an electrolytic layer containing an electrolyte is sandwiched between a display electrode and a counter electrode on which an oxide layer and a reduction layer are formed. In this case, in the conventional manufacturing process, a spacer is used in order to prevent a short circuit between the electrodes at the time of bonding.
However, conventionally, spherical beads or the like are used as spacers, and the beads are made of resin or glass. However, if the difference in refractive index from the electrolytic layer is large, haze deteriorates or uneven coloring occurs. There has been a problem with optical characteristics such as

Patent Document 1 discloses an electrochromic mirror in which a difference in refractive index between a bead used for a spacer and an electrolytic layer is ± 0.03 or less for the purpose of ensuring optical characteristics while maintaining a cell gap. .
Patent Documents 2 and 3 disclose a method in which an electrolyte layer containing a polymer binder and a spacer is formed on an electrode, and another electrode is bonded to the electrolyte layer. The thickness of the electrolyte layer is made substantially equal. As a result, attempts are made to eliminate uneven coloring.

  However, even if optical properties can be ensured in the past, since the spacer does not contribute to the redox reaction, the spacer portion affects the color decoloration reaction, and a good color decoloration reaction is obtained with respect to electrical characteristics. There wasn't. Therefore, an electrochromic element having good optical characteristics and electrical characteristics has been demanded.

  An object of this invention is to provide the electrochromic element which has a favorable optical characteristic and an electrical property.

  In order to solve the above problems, an electrochromic device of the present invention includes a first conductive substrate, a first electrochromic layer formed in contact with the first conductive substrate, and the first conductive substrate. And a second electrochromic layer formed in contact with the second conductive substrate, an electrolyte layer having a spacer, and the first electrochromic layer and the first electrochromic layer. The two electrochromic layers are opposed to each other through the electrolyte layer, and the spacer includes an electrolyte and a resin.

  ADVANTAGE OF THE INVENTION According to this invention, the electrochromic element which has a favorable optical characteristic and an electrical property can be provided.

It is a schematic sectional drawing along the thickness direction which shows an example of the electrochromic element of this invention. It is a schematic sectional drawing along the surface direction which shows an example of the electrochromic element of this invention.

  Hereinafter, an electrochromic device according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

  An embodiment of an electrochromic device will be described in the present invention. The electrochromic device of this embodiment is shown in FIGS. FIG. 1 is a schematic cross-sectional view along the thickness direction of the electrochromic device of this embodiment. FIG. 2 is a schematic cross-sectional view along the surface direction of the electrochromic element of the present embodiment, and is a cross-sectional view taken along line AA in FIG.

  The electrochromic element according to the present embodiment includes a first conductive substrate 1, a first electrochromic layer 3 formed in contact with the first conductive substrate 1, and a second electrode facing the first conductive substrate 1. It has a conductive substrate 2, a second electrochromic layer 4 formed in contact with the second conductive substrate 2, and an electrolyte layer 5 having a spacer 6. And the 1st electrochromic layer 3 and the 2nd electrochromic layer 4 oppose through the electrolyte layer 5, and the spacer 6 contains electrolyte and resin.

  Although details will be described later, the first conductive substrate 1 and the second conductive substrate 2 are preferably transparent, and when the electrochromic element is decolored, the first electrochromic layer 3 and the second electrochromic layer 4 are used. The electrolyte layer 5 is preferably transparent.

<First conductive substrate and second conductive substrate>
A conductive substrate refers to a substrate having a function as an electrode. In the present embodiment, the first conductive substrate 1 may be formed by forming the first electrode 1b on the first substrate 1a. Alternatively, the second electrode 2b may be formed on the second substrate 2a to form the second conductive substrate 2.
Examples of the substrate (first substrate 1a, second substrate 2a) include glass and plastic base materials. As the plastic substrate, a known material such as PET (polyethylene terephthalate) resin or PC (polycarbonate) resin can be used. It is preferable to use a transparent support as the substrate.

  The first electrode 1b and the second electrode 2b are preferably made of a transparent conductive material. Indium tin oxide (indium oxide doped with tin) (hereinafter referred to as “ITO”), fluorine-doped tin oxide ( Hereinafter, inorganic materials such as tin oxide doped with antimony (hereinafter referred to as “ATO”), zinc oxide, and the like may be used. In addition, carbon nanotubes with transparency and other highly conductive non-permeable materials such as Au, Ag, Pt, and Cu are formed in a fine network to improve conductivity while maintaining transparency. An electrode may be used. Among these, ITO is suitable as an electrode included in the electrochromic device of the present invention because high adhesion can be obtained when ITO is used.

  As a manufacturing method of the first electrode 1b and the second electrode 2b, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used. In the case where the material of the first electrode 1b or the second electrode 2b can be applied and formed, for example, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire Various methods such as bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing Printing methods can be used.

  The film thicknesses of the first electrode 1b and the second electrode 2b are not particularly limited and can be appropriately changed. For example, when ITO is used, the film thickness is preferably about 50 nm to 500 nm.

  As the first conductive substrate 1 and the second conductive substrate 2, transparent substrates are used for the first substrate 1a and the second substrate 2a, and transparent electrodes are used for the first electrode 1b and the second electrode 2b. And transparent.

<First Electrochromic Layer and Second Electrochromic Layer>
Next, the first electrochromic layer 3 and the second electrochromic layer 4 in the present embodiment will be described.
Hereinafter, when the term “electrochromic layer” is used, the first electrochromic layer 3 and the second electrochromic layer 4 are not distinguished from each other, and both are described.
In addition, the first electrochromic layer may be referred to as a display electrode, and the second electrochromic layer may be referred to as a counter electrode. In the present embodiment, the first electrochromic layer is described as an oxide layer using an oxidized electrochromic compound, and the second electrochromic layer is described as a reduced layer using a reduced electrochromic compound. It is not something that can be done.

  As a material for forming the electrochromic layer, for example, an electrochromic compound is prepared by mixing with a binder, a solvent, an additive, and the like.

In the present embodiment, an oxidized electrochromic compound is used for the first electrochromic layer 3. The first electrochromic layer 3 includes a first electrochromic layer including a radical polymerizable compound having a triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. A cross-linked product obtained by cross-linking the layer forming material is preferable. In this case, it is preferable in terms of solubility and durability of the polymer.
In addition, by having a radically polymerizable compound having a triarylamine structure, a better color decoloring reaction can be exhibited.

The binder is not particularly limited, and a known polymer resin can be used. For example, other radical polymerizable compounds different from the above-described radical polymerizable compound having a triarylamine structure may be used.
Unlike the radical polymerizable compound having a triarylamine structure, the other radical polymerizable compound is a compound having at least one radical polymerizable functional group.
Examples of the other radical polymerizable compound include a monofunctional radical polymerizable compound, a bifunctional radical polymerizable compound, a trifunctional or higher functional radical polymerizable compound, a functional monomer, and a radical polymerizable oligomer. Among these, a bifunctional or higher radical polymerizable compound is particularly preferable.

The material for forming the first electrochromic layer 3 includes a crosslinking reaction between the radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. In order to advance efficiently, it is preferable to contain a polymerization initiator as needed.
Although it can change suitably as said polymerization initiator, For example, a thermal polymerization initiator, a photoinitiator, etc. are mentioned. A photopolymerization initiator is preferred from the viewpoint of polymerization efficiency.

  The method of forming the electrochromic layer is not particularly limited and can be changed as appropriate. Examples include inkjet, screen printing, gravure printing, die coating, spray coating, flexographic printing, and the like.

  In the present embodiment, a reduced electrochromic compound is used for the second electrochromic layer 4. Examples of reduced electrochromic compounds include azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styryl spiropyran, spirooxazine, spirothiopyran, thioindigo, tetrathiafulvalene, terephthalic acid , Triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorane, fulgide, benzopyran, metallocene, etc. And low molecular organic electrochromic compounds. These may be used individually by 1 type and may use 2 or more types together.

  The second electrochromic layer 4 may have a structure in which an organic electrochromic compound is supported on conductive or semiconductive fine particles. Specifically, it has a structure in which fine particles having a particle diameter of, for example, about 5 nm to 50 nm are sintered on the electrode surface, and an organic electrochromic compound having a polar group such as phosphonic acid, a carboxyl group, or a silanol group is adsorbed on the surface of the fine particles. is there.

  In such a structure, electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, so that a high-speed response is possible as compared with a conventional electrochromic display element. Furthermore, since a transparent film can be formed 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.

  There is no restriction | limiting in particular in the average thickness of an electrochromic layer, Although it can select suitably according to the objective, 0.2 micrometer-5.0 micrometers are preferable. If the average thickness is less than 0.2 μm, it may be difficult to obtain the color density, and if it exceeds 5.0 μm, the manufacturing cost increases and the visibility may be easily lowered by coloring.

<Electrolyte layer>
The electrolyte layer 5 is a layer that can conduct ions for supplying ions to the electrochromic layer. In addition, the electrolyte layer 5 is preferably a transparent layer because of the properties as a display element of an electrochromic element. The electrolyte layer 5 includes a spacer 6 and an electrolyte, and further contains an electrolyte solvent and other components as necessary.

  The electrolyte layer 5 can be in the form of a liquid, a solid, a gel, a polymer crosslinked type, or the like. By forming the electrolyte layer 5 in a gel or solid state, advantages such as improved element strength and improved reliability can be obtained. In particular, it is preferable to form a gel that can maintain high ionic conductivity. As the gelation method, it is preferable to retain the electrolyte, the electrolyte solvent, and other components in the polymer resin. This provides high ionic conductivity and solid strength.

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

An ionic liquid can also be used as the electrolyte. Among these, an organic ionic liquid is preferable because it has a molecular structure showing a liquid in a wide temperature range including room temperature.
Examples of the ionic liquid include 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMTFSI, manufactured by Kanto Chemical Co., Inc.), ethylmethylimidazolium tetracyanoborate (EMIMTCB, manufactured by Merck), ethylmethyl, and the like. Imidazolium tripentafulholoethyl trifluorophosphate (EMIMFAP, manufactured by Merck & Co., Inc.), allylbutylimidazolium tetrafluoroborate (ABIMBF4, manufactured by Kanto Chemical Co., Inc.), methylpropylpyrrolidinium bisfluorosulfonimide (P13FSI, Kanto Chemical Co., Inc.) And the like in which the product is dissolved. These may be used individually by 1 type and may use 2 or more types together.

  The ionic liquid may be directly dissolved in any of photopolymerizable monomers, oligomers, and liquid crystal materials. If the solubility is poor, the solution may be dissolved in a small amount of solvent and mixed with any of photopolymerizable monomers, oligomers, and liquid crystal materials.

  There is no restriction | limiting in particular in the average thickness of the said electrolyte layer 5, Although it can select suitably according to the objective, 100 nm or more and 100 micrometers or less are preferable.

  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, and polyethylene glycol. , Alcohols, or a mixed solvent thereof.

  The polymer resin is preferably a photocurable resin. This is because an electrochromic 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 polymer resin is preferably a methacrylate polymer or an acrylate polymer. The polymer is preferably obtained by photocuring a compound having at least one radical polymerizable functional group. As the radical polymerizable compound, the same compounds as the examples given as the binder of the electrochromic layer can be used. For example, a monofunctional radical polymerizable compound, a bifunctional radical polymerizable compound, a trifunctional or higher functional radical polymerizable compound, a functional monomer, a radical polymerizable oligomer, and the like can be given. These can be used singly or in combination of plural kinds.

  A gelled electrolyte layer can be obtained by mixing the compound having a radical polymerizable functional group, the electrolyte, an electrolyte solvent, and other components described later and photocuring.

  The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents, plasticizers, polymerization initiators, leveling agents, sensitizers, dispersants, surfactants, and antioxidants. Agents, fillers and the like.

<< Spacer >>
Conventionally, spacers have been used in the electrolyte layer for the purpose of avoiding short-circuiting between electrodes when manufacturing an electrochromic element. The conventional spacer becomes an insulator that does not contribute to the oxidation-reduction reaction. However, since the spacer does not contribute to the oxidation-reduction reaction, the spacer portion has an influence on the color decoloration reaction, and a good color decoloration reaction with respect to electrical characteristics has not been obtained.

  On the other hand, when the spacer 6 of this embodiment contains an electrolyte, it contributes to the color decoloring reaction, and the electrical characteristics of the color decoloration can be improved. Moreover, since the refractive index of an electrolyte layer and a spacer can be closely approached when the spacer 6 contains an electrolyte, an internal haze can be reduced and an optical characteristic can be improved.

  The spacer 6 of this embodiment includes an electrolyte and a resin. Examples of the electrolyte contained in the spacer 6 include an electrolyte that can be used for the electrolyte layer 5 described above. Among these, the ionic liquid is preferable.

  The electrolyte contained in the spacer 6 may be the same as or different from the electrolyte contained in the electrolyte layer 5, but the electrolyte contained in the spacer 6 is the same as the electrolyte contained in the electrolyte layer 5. It is preferable to include a component. In this case, the difference in refractive index between the spacer and the electrolyte layer can be further reduced, and the optical characteristics are improved.

  The resin contained in the spacer 6 can be appropriately changed, and examples thereof include a resin that can be used for the electrolyte layer 5 described above.

  The content of the electrolyte contained in the spacer 6 can be changed as appropriate. For example, the content is preferably 1% by mass or more and 80% by mass or less with respect to the spacer. In this case, the spacer can contribute to the color decoloring reaction, the resin content can be adjusted appropriately, and the strength necessary to prevent short-circuiting of the electrodes can be imparted.

  The shape of the spacer 6 is not particularly limited and can be appropriately changed. For example, as shown in the cross-sectional view along the thickness direction of FIG. 1, the shape may be a taper, or other shapes such as a circle or a rectangle may be used. Further, as shown in the cross-sectional view along the surface direction of FIG. 2, the shape may be a circle, or other shapes such as a rectangle may be used.

  The height of the spacer is approximately the thickness of the electrolyte layer, but is not particularly limited and can be appropriately selected depending on the purpose. For example, the average height of the spacers is preferably 100 nm or more and 100 μm or less.

  It is not necessary for all spacers included in the electrolyte layer to be in contact with the first electrochromic layer and the second electrochromic layer, and there may be one that is in contact with either one or both. . Since the spacer is in contact with at least one of the first electrochromic layer and the second electrochromic layer, it is possible to more reliably prevent the electrode from being short-circuited.

  The ratio of the spacer contained in the electrolyte layer can be changed as appropriate so that the optical characteristics and the electrical characteristics are good. In this case, the spacer can contribute to the coloring and decoloring reaction, and can have the strength necessary to prevent short-circuiting of the electrodes.

  Further, the spacer and the electrolyte layer may be the same component, and the manufacturing process can be simplified. In this case, the spacer is preferably harder than the electrolyte layer. In the case of the same component and the same hardness, the coloring and decoloring reaction can be improved, but the function of the spacer to prevent the electrode from being short-circuited is lowered. The hardness can be examined using a nanoindenter.

Next, a method for manufacturing the spacer and the electrolyte layer in the present embodiment will be described.
First, a spacer forming material containing an electrolyte and a resin is provided on the first electrochromic layer or the second electrochromic layer formed on the conductive substrate. The spacer forming material can be applied by inkjet, screen printing, gravure printing, dispenser, or the like.
The spacer may be formed on either the first electrochromic layer or the second electrochromic layer, or may be formed on both.

  After applying the spacer forming material on the electrochromic layer, it is cured. Although it can change suitably as a method of hardening, For example, the method of hardening by UV exposure, the method of hardening with heat, etc. are mentioned.

  After forming the spacer, an electrolyte layer forming material is applied on the electrochromic layer on which the spacer is formed. The material for forming an electrolyte layer can be applied using, for example, a dispenser, screen printing, inkjet, or the like.

Next, a conductive substrate on which an electrochromic layer is separately formed is bonded to the conductive substrate on which the electrochromic layer and the spacer are formed. At this time, they may be bonded by pressing with a laminator or a vacuum bonding machine while releasing air.
Further, the adhesive strength may be improved by using an adhesive or the like at the time of bonding. In this case, the adhesive can function as a sealing material.

  Since the electrolyte layer functions even when it is liquid, an electrochromic element can be obtained by bonding the conductive substrates. However, after bonding, the electrolyte layer may be cured to be solid or gel. In the case of solid or gel, liquid leakage can be prevented and a more reliable element can be manufactured.

  In the case where the electrolyte layer is cured, when the spacer forming material and the electrolyte layer forming material are the same, it is preferable to cure both so that the spacer is harder than the electrolyte layer. In this case, it is preferable that the curing of the electrolyte layer is lower than the integrated light amount of the spacer.

<Encapsulant>
The sealing material 7 is not particularly limited and can be appropriately changed. For example, a resin such as an adhesive can be used. The sealing material 7 is used for the purpose of preventing the electrolyte layer 5 from sticking out or increasing the adhesion between the substrates. The shape of the sealing material 7 is not particularly limited, and can be a shape as illustrated in FIGS. 1 and 2, for example.
Moreover, as thickness of the sealing material 7 with respect to the surface direction of an element, it is preferable to set it as 100 micrometers-10 mm, for example.

<Method for manufacturing electrochromic element>
As described above, the method of manufacturing the electrochromic device according to the present embodiment includes the step of forming the first electrochromic layer on the first conductive substrate, and the second electrochromic layer on the second conductive substrate. Forming a spacer, applying a spacer forming material on the first electrochromic layer or the second electrochromic layer, and curing the material, forming the spacer, the first electrochromic layer, and the first electrochromic layer Bonding the first conductive substrate and the second conductive substrate so that two electrochromic layers face each other with the spacer interposed therebetween, and forming an electrolyte layer forming material with the first electrochromic layer and the Providing between the second electrochromic layers to form an electrolyte layer. The spacer forming material includes an electrolyte and a resin.

  Also, the spacer forming material and the electrolyte layer forming material can be produced with the same composition, and the spacer is preferably formed to be harder than the electrolyte layer. In this case, an electrochromic element can be manufactured more easily.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

Example 1
<Conductive substrate>
For the conductive substrate, ITO glass (40 mm × 40 mm, glass thickness 0.7 mm, ITO thickness 100 nm) on which ITO was formed was used. The size of the color erasing portion of the element was 30 mm × 30 mm.

<Formation of first electrochromic layer>
A first electrochromic layer forming material was prepared with the following composition.

[composition]
-15% by mass of an electrochromic compound represented by the following structural formula (1)
-Polyethylene glycol diacrylate (PEG400D manufactured by Nippon Kayaku Co., Ltd.) 14.25% by mass
Photoinitiator (Irgacure 184 manufactured by BASF) 0.75% by mass
・ Cyclohexanone 70% by mass

  The first electrochromic layer forming material was dissolved by ultrasonic waves for 10 minutes. Then, after applying to a conductive substrate to a required location using an inkjet apparatus, in order to dry the solvent, it was dried at 80 ° C. for 1 minute on a hot plate, and then exposed to UV to obtain a thickness of 1.3 μm. A first electrochromic layer was formed.

<Formation of second electrochromic layer>
Titanium oxide nanoparticle dispersion (SP210 manufactured by Showa Titanium Co., Ltd., average particle size 20 nm) is applied on a conductive substrate by a spin coat method, and annealed at 120 ° C. for 15 minutes to obtain a 1.0 μm titanium oxide particle film. A nanostructured semiconductor material consisting of Next, a second electrochromic layer forming material having the following composition was prepared.

[composition]
-2% by mass of an electrochromic compound represented by the following structural formula (2)
・ 98% by mass of 2,2,3,3-tetrafluoropropanol

  The second electrochromic layer forming material was applied to the semiconductor material obtained as described above by a spin coating method. Next, an annealing treatment was performed at 120 ° C. for 10 minutes to form a second electrochromic layer having a thickness of 1.0 μm made of a titanium oxide particle film and an electrochromic compound.

<Formation of electrolyte layer>
-Preparation of electrolyte layer forming material-
An electrolyte layer forming material was prepared with the following composition.

[composition]
1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide 60% by mass
・ Polyethylene glycol diacrylate (PEG400D manufactured by Nippon Kayaku Co., Ltd.) 20% by mass
・ Methoxypolyethylene glycol monoacrylate (Blenmer PME, manufactured by NOF Corporation) 18% by mass
Photoinitiator (Irgacure 184 manufactured by BASF) 2% by mass

-Preparation of spacer forming material-
A spacer forming material was prepared with the following composition.

[composition]
1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide 30% by mass
-Polyethylene glycol diacrylate (PEG400D manufactured by Nippon Kayaku Co., Ltd.) 66.5% by mass
Photoinitiator (Irgacure 184 manufactured by BASF) 3.5% by mass

A spacer forming material was patterned on the first electrochromic layer obtained as described above to form a 30 μm protrusion using an ink jet apparatus, and cured by UV exposure to form a spacer. The curing condition was irradiation with an integrated light amount of 0.6 J / cm ² at a wavelength of 240 to 275 nm.
Thereafter, the material for forming an electrolyte layer was filled on the first electrochromic layer using an air jet dispenser. After filling the electrolyte layer forming material, the conductive substrates were bonded together using an optical adhesive. After bonding, the electrolyte layer was cured by UV exposure to form a gel. The curing condition was irradiation with an integrated light amount of 0.3 J / cm ² at a wavelength of 240 to 275 nm.

  As described above, the electrochromic device of this example was manufactured. The obtained electrochromic device had the configuration shown in FIGS. In addition, the optical adhesive was formed as a sealing material, and was produced in the shape as illustrated.

(Example 2)
In Example 1, an electrochromic device was produced in the same manner as in Example 1 except that the same material as the electrolyte layer forming material was used as the spacer forming material. The curing conditions such as the integrated light amount were the same as in Example 1.

(Comparative Example 1)
In the preparation of the spacer forming material of Example 1, only polyethylene glycol diacrylate and Irgacure 184 were used without adding an electrolyte. Other than that was carried out similarly to Example 1, and produced the electrochromic element.

(Comparative Example 2)
In the preparation of the spacer forming material of Example 1, acrylic resin beads having a diameter of 30 μm (Micropearl manufactured by Sekisui Chemical Co., Ltd.) were added without adding an electrolyte. Other than that was carried out similarly to Example 1, and produced the electrochromic element.

(Comparative Example 3)
In Example 1, an electrochromic device was produced in the same manner as in Example 1 except that the spacer was not formed.

(Measurement)
The haze was measured based on JIS-K-7136.
For coloring unevenness, a voltage of −2.0 V was applied to the first electrochromic layer and the second electrochromic layer for 5 seconds at the time of coloring, and color unevenness by visual observation at that time was evaluated. Those in which the color unevenness could not be visually confirmed were rated as ◯, and those that could be confirmed were marked as x.
The memory property was evaluated as ◯ when the color did not change for 30 seconds or more after the application of voltage was stopped after being colored.

  The results are shown in Table 1.

In Comparative Example 1, since the electrolyte is not present in the spacer, a portion that does not react during coloring is formed, and uneven coloring occurs. In Comparative Example 2, since beads are used, it is difficult to control the haze, and similarly to Comparative Example 1, there is a portion that does not contribute to fading, so uneven coloring occurs. In Comparative Example 3, the first electrochromic layer and the second electrochromic layer are contacted and short-circuited at the center, and the memory property after coloring is deteriorated.
On the other hand, in Examples 1 and 2, haze, coloring unevenness, and memory property were good.
From the above, an electrochromic device having good optical characteristics and electrical characteristics can be obtained by the present invention.

DESCRIPTION OF SYMBOLS 1 1st conductive substrate 1a 1st substrate 1b 1st electrode 2 2nd conductive substrate 2a 2nd substrate 2b 2nd electrode 3 1st electrochromic layer 4 2nd electrochromic layer 5 Electrolyte layer 6 Spacer 7 Sealing material

Japanese Patent No. 4360663 JP 2008-139745 A JP 2008-145830 A

Claims (6)

A first conductive substrate;
A first electrochromic layer formed in contact with the first conductive substrate;
A second conductive substrate facing the first conductive substrate;
A second electrochromic layer formed in contact with the second conductive substrate;
An electrolyte layer having a spacer, and
The first electrochromic layer and the second electrochromic layer are opposed to each other through the electrolyte layer,
The electrochromic device, wherein the spacer includes an electrolyte and a resin.   The electrochromic device according to claim 1, wherein the electrolyte included in the spacer includes the same component as the electrolyte included in the electrolyte layer.   The electrochromic device according to claim 1, wherein the spacer is in contact with at least one of the first electrochromic layer and the second electrochromic layer.   The electrochromic device according to claim 1, wherein the electrolyte is an ionic liquid.   The electrochromic device according to any one of claims 1 to 4, wherein the first electrochromic layer or the second electrochromic layer has a radical polymerizable compound having a triarylamine structure. The first conductive substrate and the second conductive substrate are transparent,
6. The electrochromic according to claim 1, wherein when the electrochromic element is decolored, the first electrochromic layer, the second electrochromic layer, and the electrolyte layer are transparent. element.