JP6794621B2 - Gel electrolyte and electrochromic devices - Google Patents

Description

The present invention relates to gel electrolytes and electrochromic devices.

Electrochromism is a phenomenon in which a redox reaction occurs reversibly by applying a voltage and the color changes reversibly.

The electrochromic material exhibiting electrochromism is generally formed between two opposing electrodes, and undergoes a redox reaction in a configuration in which an ionic conductive electrolyte layer is filled between the electrodes.
In an electrochromic element using the electrochromic material, a device having a structure in which a transparent display device is obtained, or a device having three layers of cyan (C), magenta (M), and yellow (Y) are laminated. When constructing, it is important that it is composed of a material that has a colorless and transparent state.

Further, it is known that the electrochromic element has a significantly deteriorated color development response, particularly in a low temperature environment. It is important to reduce the impedance of the entire electrochromic element in order to promptly cause a change in color, and it is effective to improve the ionic conductivity of the electrolyte in order to reduce the impedance.
As the electrolyte, a gel electrolyte using an ionic liquid is known. The ionic liquid has features such as high ionic conductivity, low vapor pressure, high heat resistance, high withstand voltage, and low viscosity, and is suitably used as an electrolyte material for electrodevices.
However, due to its characteristic solubility, the ionic liquid causes phase separation to impair transparency when a gel having a high ionic liquid concentration is produced, or the ionic liquid bleeds out and causes liquid dripping. There are problems such as the occurrence and the inability to form a gel without curing even if a gelling agent is used.

Therefore, a photosensitive dye gel electrolyte containing an ionic liquid electrolyte, a gelation additive, and a highly soluble solvent has been proposed (see, for example, Patent Document 1).

The present invention can achieve a high ionic liquid concentration without impairing the low volatility and low viscosity that are the characteristics of ionic liquids, has good gelation, and can reduce impedance when used in electrochromic devices. An object of the present invention is to provide a gel electrolyte having excellent color development responsiveness.

The gel electrolyte of the present invention as a means for solving the above-mentioned problems has a composition containing an ionic liquid, a monomer represented by the following general formula (1), and a monomer represented by the following general formula (2). Contains a cured product of the material.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)

According to the present invention, a high ionic liquid concentration can be achieved without impairing the low volatility and low viscosity characteristic of the ionic liquid, gelation is good, and impedance is reduced when used in an electrochromic element. It is possible to provide a gel electrolyte having excellent color responsiveness.

FIG. 1 is a schematic view showing an example of the electrochromic device of the present invention. FIG. 2 is a graph showing a waveform obtained by measuring impedance at a measurement temperature of 25 ° C. in Example 101.

The gel electrolyte of the present invention contains a cured product of a composition containing an ionic liquid, a monomer represented by the following general formula (1), and a monomer represented by the following general formula (2), and is further required. It contains a polymerization initiator and other components according to the above.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
The gel electrolyte of the present invention is produced because the ordinary solvent having a small average molecular weight used in the conventional photosensitive dye gel electrolyte has a high vapor pressure and high volatility, so that the advantage of the ionic liquid having a low vapor pressure is lost. It is based on the finding that handling during the process can be difficult and that the solvent has a greater effect on heat resistance and withstand voltage, losing the benefits of ionic liquids.

(Gel electrolyte)
The gel electrolyte of the present invention contains a cured product of a composition containing an ionic liquid, a monomer represented by the following general formula (1), and a monomer represented by the following general formula (2).
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)

<Monomer represented by the general formula (1)>
The monomer represented by the general formula (1) is not particularly limited as long as it is represented by the following general formula (1), and can be appropriately selected depending on the intended purpose.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)

N in the general formula (1) is an integer of 7 or more and 12 or less. When n is 7 or more, low volatility can be obtained, and when n is 12 or less, low viscosity can be obtained.

<Monomer represented by the general formula (2)>
The monomer represented by the general formula (2) is not particularly limited as long as it is represented by the following general formula (2), and can be appropriately selected depending on the intended purpose.
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)

The R in the general formula (2) may be a methacrylic group or an acrylic group, and may be the same group or a different group, but the same group is preferable.

N in the general formula (2) is an integer of 7 or more and 12 or less. When n is 7 or more, low volatility can be obtained, and when n is 12 or less, low viscosity can be obtained.

[Mass ratio (A / B)]
-When R in the general formula (1) and R in the general formula (2) are methacrylic groups-
When R in the general formula (1) and R in the general formula (2) are methacrylic groups, the content A (mass%) of the monomer represented by the general formula (1) and the general formula. The mass ratio (A / B) with the content B (mass%) of the monomer represented by the formula (2) is preferably 18/82 or more and 53/47 or less, and 20/80 or more and 30/70 or less. preferable. When the mass ratio (A / B) is 18/82 or more and 53/47 or less, phase separation does not occur even if the content of the ionic liquid in the gel electrolyte is 80% by mass, and the transparency is impaired. It is possible to obtain a transparent and highly ionic conductivity gel electrolyte without causing liquid dripping or curing failure.

-When R in the general formula (1) and R in the general formula (2) are acrylic groups-
When R in the general formula (1) and R in the general formula (2) are acrylic groups, the content A (mass%) of the monomer represented by the general formula (1) and the general formula. The mass ratio (A / B) with the content B (mass%) of the monomer represented by the formula (2) is preferably 26/74 or more and 92/8 or less, and 28/72 or more and 63/37 or less. preferable. When the mass ratio (A / B) is 26/74 or more and 92/8 or less, even if the content of the ionic liquid in the gel electrolyte is 80% by mass, the mass ratio (A / B) is still high. When it is 28/72 or more and 63/37 or less, even if the content of the ionic liquid in the gel electrolyte is 90% by mass, phase separation is not performed, transparency is not impaired, and liquid dripping or curing is not impaired. A transparent, high-ionic conductivity gel electrolyte can be obtained without causing defects.

<Ionic liquid>
The ionic liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those in a liquid state near the operating temperature. The ionic liquid means a liquid in which a salt is dissolved and shows a liquid state at room temperature.

The ionic liquid includes cations and anions.

Examples of the cation include N, N-dimethylimidazole salt, N, N-methylethyl imidazole salt, N, N-methylpropyl imidazole salt, N, N-methylbutyl imidazole salt, N, N-allyl butyl imidazole salt. Imidazole derivatives such as N, N-dimethylpyridinium salt, pyridinium derivatives such as N, N-methylpropylpyridinium salt; N, N-dimethylpyrrolidinium salt, N-ethyl-N-methylpyrrolidinium salt, N- Pyrrolidinium derivatives such as methyl-N-propylpyrrolidinium salt, N-butyl-N-methylpyrrolidinium salt, N-methyl-N-pentylpyrrolidinium salt, N-hexyl-N-methylpyrrolidinium salt; Examples thereof include cations derived from aliphatic quaternary ammonium salts such as trimethylpropylammonium salt, trimethylhexylammonium salt and triethylhexylammonium salt. These may be used alone or in combination of two or more.

Examples of the anion, such as chlorine anion, bromine anion, iodine _{^{anion, BF 4 -, BF 3 CF}} 3 -, BF 3 C 2 F 5 -, PF 6 -, NO 3 -, CF 3 CO 2 -, CF 3 SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (FSO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) (FSO ₂ ) N ⁻ , (CN) ₂ N ⁻ , (CN) ₃ C ⁻ , ( _{^{CN) 4 B -, (CF}} 3 SO 2) 3 C -, (C 2 F 5 SO 2) 2 N -, (C 2 F 5) 3 PF 3 -, AlCl 4 -, Al 2 Cl 7 - , etc. Can be mentioned. These may be used alone or in combination of two or more.

Examples of the ionic liquid include ethylmethylimidazolium tetracyanoborate (EMIMTCB, manufactured by Merck), ethylmethylimidazolium bistrifluoromethanesulfonimide (EMIMTFSI, manufactured by Kanto Chemical Co., Ltd.), and ethylmethylimidazolium tripentafluholo. Ethyltrifluoroolophosphate (EMIMFAP, manufactured by Merck), allylbutylimidazolium tetrafluoroborate (ABIMBF4, manufactured by Kanto Chemical Co., Ltd.), methylpropylpyrrolidinium bisfluorosulfonimide (P13FSI, manufactured by Kanto Chemical Co., Ltd.), etc. Examples include dissolved liquids. These may be used alone or in combination of two or more.

The content of the ionic liquid is preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the gel electrolyte. When the content is 60% by mass or more, the ionic conductivity can be improved.

<Polymer initiator>
The polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a radical polymerization initiator.
Examples of the radical polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. These may be used alone or in combination of two or more.

Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, and 2,2'-azobis (2,4-dimethylvaleronitrile). , 2,2'-Azobis [2- (2-imidazolin-2-yl) propane] and other azo compounds; 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, di (4- Examples thereof include organic peroxides such as tert-butylcyclohexyl) peroxydicarbonate. These may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include a ketal-based photopolymerization initiator such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexylphenylketone, 2,2-diethoxyacetophenone, and the like. Acetophenone-based photopolymerization initiators such as 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, 4- (t-butyl) dichloroacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether. , Benzoin ether-based photopolymerization initiators such as benzoin isobutyl ether and the like. These may be used alone or in combination of two or more.

The content of the polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of all the monomer components. It is more preferably 0.01 part by mass or more and 2 parts by mass or less, and particularly preferably 0.01 part by mass or more and 1 part by mass or less.

[Manufacturing method of gel electrolyte]
The gel electrolyte of the present invention can be produced by first preparing a composition solution and then polymerizing the prepared composition solution by sandwiching it between a mold or a film by a polymerization reaction using a cast polymerization method or the like.
In the composition solution, the ionic liquid, the monomer represented by the general formula (1), and the monomer represented by the general formula (2) are mixed at a desired ratio, and if necessary, the polymerization is initiated. Agents and other ingredients can be mixed.
Examples of the mold include glass, a container made of resin, and a film with a mold release agent. It is also possible to fill the composition solution using an empty cell of the electrochemical device as a mold and polymerize directly in the device.

As the polymerization reaction, a radical polymerization reaction is preferable, and a thermal radical polymerization reaction and a photoradical polymerization reaction are more preferable. Further, it is preferable to deoxidize the composition solution in advance when performing radical polymerization.

(Electrochromic element)
The electrochromic device of the present invention has a first electrode, a second electrode, and a gel electrolyte between the first electrode and the second electrode, and if necessary, other components. Has a member.
At least one of the first electrode and the second electrode is transparent, and has an electrochromic layer containing an electrochromic compound on the surface of the first electrode.
As the gel electrolyte, the gel electrolyte of the present invention is used.

FIG. 1 is a schematic view showing an example of the electrochromic device of the present invention.
As shown in FIG. 1, a gel electrolyte 6 is provided between the first electrode 3, the second electrode 2, and the first electrode 3 and the second electrode 2, and the first electrode is provided. The electrode 3 and the second electrode 2 are sandwiched by the support 1, have an electrochromic layer 5 on the surface of the first electrode 3, and have an electrochromic layer 7 on the surface of the second electrode 2. It is preferable to have the electrochromic compound 4 in the electrochromic layers 5 and 7.

<Electrochromic layer>
The electrochromic layer is a functional layer containing an electrochromic compound and exhibiting electrochromism. The electrochromic layer has a form in which an electrochromic compound is bonded to a conductive or semiconductor nanostructure to form a layer, or the electrochromic compound is a radically polymerizable compound, and the layer is composed of a polymerized film thereof. Examples include the forms that have been polymerized. Among these, the electrochromic layer has a copolymerization weight consisting of a radically polymerizable electrochromic compound and at least one of the monomer represented by the general formula (1) and the monomer represented by the general formula (2). It is preferable to include coalescence. When the electrochromic layer contains a copolymer composed of the electrochromic compound and the monomer, the color development responsiveness can be improved when the gel electrolyte of the present invention is used.

The average thickness of the electrochromic layer is preferably 0.2 μm or more and 5.0 μm or less. When the average thickness is 0.2 μm or more, the color development density can be improved, and when it is 5.0 μm or less, the manufacturing cost can be lowered and the visibility due to coloring can be improved.

<< Electrochromic compound >>
The electrochromic compound is a material that changes color by an oxidation reaction or a reduction reaction, and examples thereof include radical polymerizable compounds and polymer compounds. Among these, a radically polymerizable compound is preferable, and a radically polymerizable compound having a triarylamine is more preferable.
The electrochromic compound is not particularly limited, and a known electrochromic compound can be appropriately selected depending on the intended purpose. Examples thereof include dye-based compounds, metal complex-based compounds, and metal oxide-based compounds.
Examples of the dye-based compound include azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, styryl-based, styrylspiryrane-based, spiroxazine-based, spirothiopyran-based, thioindigo-based, tetrathiafluvalene-based, terephthalic acid-based, and triphenyl Low molecular weight compounds such as methane, triphenylamine, naphthopyrane, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorene, flugide, benzopyran, metallocene, etc. Organic electrochromic compounds; examples include conductive polymer compounds such as polyaniline and polythiophene.
Examples of the metal complex-based compound and the metal oxide-based compound include inorganic electrochromic compounds such as titanium oxide, vanadium oxide, tungsten oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue.
Among these, a dye-based compound is preferable, and a radically polymerizable compound of the dye-based compound is more preferable.
Examples of the radically polymerizable functional group in the radically polymerizable compound include a vinyl group, a methacryl group, an acrylic group, a styryl group, an allyl group and the like.

Specific examples of the electrochromic compound are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an exemplary compound (1), an exemplary compound (2), and an exemplary compound (3).

-Example compound (1)-

-Example compound (2)-

-Example compound (3)-

The radically polymerizable monomer other than the monomer represented by the general formula (1) and the monomer represented by the general formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. Methoxyethylene glycol acrylate, methoxyethoxyethylene glycol acrylate, methoxytriethylene glycol acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polypropylene glycol acrylate, trimethylpropane polyethylene oxide triacrylate, pentaerythritol pentaacrylate, N , N'-methylenediacrylamide and the like. These may be used alone or in combination of two or more.

<< Conductive or semiconductor nanostructures >>
The conductive or semiconducting nanostructures mean nanostructures having nanoscale irregularities such as nanoparticles or nanoporous structures.
When the electrochromic compound has a phosphonic acid group, a phosphoric acid group or a carboxyl group as a bond or adsorption structure, the electrochromic compound is easily compounded with the nanostructures and has excellent color image retention. It becomes a chromic composition, and an electrochromic layer can be formed from the electrochromic composition.

Further, when the electrochromic compound has a silyl group or a silanol group, it is bonded to the nanostructure via a siloxane bond to strengthen the bond, and a stable electrochromic composition can also be obtained. .. The siloxane bond means a chemical bond via a silicon atom and an oxygen atom. Further, the electrochromic composition is not particularly limited, and a known bonding method and form can be appropriately selected depending on the intended purpose, but the electrochromic compound and the nanostructure are bonded via a siloxane bond. It is preferable to have a structure like this.

The material constituting the conductive or semiconductor nanostructure is not particularly limited and may be appropriately selected depending on the intended purpose, but a metal oxide is preferable from the viewpoint of transparency and conductivity. Examples of the metal oxide 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, and oxidation. Calcium, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, indium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide are considered from the viewpoint of electrical properties such as electrical conductivity, physical properties such as optical properties, and response speed of decolorization. , Indium oxide and tungsten oxide are preferable, and titanium oxide is more preferable because the response speed of color development and decolorization is more excellent.

As the shape of the metal oxide, metal oxide particles having a number average primary particle diameter of 30 nm or less are preferable. When the average primary particle diameter is 30 nm or less, the transmittance of light with respect to the metal oxide is improved, and a shape having a large surface area per unit volume (hereinafter, also referred to as “specific surface area”) is used. By having a large specific surface area, the electrochromic compound is supported more efficiently, and multicolor display with an excellent display contrast ratio of color emission and extinction is possible.
The specific surface area of the metal oxide is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 100 m ² / g or more is preferable.

<1st electrode and 2nd electrode>
The first electrode and the second electrode are not particularly limited as long as at least one of the first electrode and the second electrode is transparent, and a known conductor is appropriately selected depending on the intended purpose. can do.

The transparent electrode is not particularly limited as long as it is a transparent material having conductivity, and can be appropriately selected depending on the intended purpose. For example, tin-doped indium oxide (hereinafter, also referred to as “ITO”). ), Fluorine-doped tin oxide (hereinafter, also referred to as “FTO”), antimonated tin oxide (hereinafter, also referred to as “ATO”); ITO, InSnO, GaZnO, SnO, Examples thereof include inorganic materials such as In ₂ O ₃ and zinc oxide (ZnO).

In addition, transparent carbon nanotubes 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. Electrodes may be used.

The average thickness of the first electrode and the second electrode is not particularly limited and can be appropriately selected depending on the intended purpose, and the electric resistance value required for the redox reaction of the electrochromic layer can be obtained. It is preferable to adjust so as to.
When ITO is used as the material for the first electrode and the second electrode, the average thickness of the first electrode and the second electrode is preferably 50 nm or more and 500 nm or less.

Examples of the method for producing the first electrode and the second electrode include a vacuum deposition method, a sputtering method, and an ion plating method.
Specific examples of the method for producing the first electrode and the second electrode are not particularly limited as long as they can be applied and formed, and can be appropriately selected depending on the intended purpose. For example, a spin coating method or casting. Method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing Various printing methods such as a method, a flexo printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be mentioned.

<Gel electrolyte>
As the gel electrolyte, the gel electrolyte of the present invention is used.
The average thickness of the electrolyte layer made of the gel electrolyte is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 nm or more and 1,000 μm or less.

<Other parts>
The other members are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a support, a sealing material, an insulating porous layer, a deterioration prevention layer and a protective layer.

<< Support >>
As the support, a well-known organic material or inorganic material can be used as it is as long as it is a transparent material that can support each layer.

Examples of the support include glass substrates such as non-alkali glass, borosilicate glass, float glass, and soda lime glass; polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, and phenol resin. Examples thereof include resin substrates such as polyurethane resin and polyimide resin.

The surface of the support may be coated with a transparent insulating layer, a UV cut layer, an antireflection layer, or the like in order to enhance water vapor barrier property, gas barrier property, ultraviolet ray resistance, and visibility.

The shape of the support is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a rectangle and a round shape.

A plurality of the supports may be superposed. For example, the water vapor barrier property and the gas barrier property can be improved by forming a structure in which the electrochromic element is sandwiched between two glass substrates.

<< Sealing material >>
The encapsulant seals the side surface of the bonded electrochromic element, prevents leakage of the gel electrolyte, and invades unnecessary substances such as moisture and oxygen in the atmosphere for stable operation of the electrochromic element. It has functions such as prevention.
The sealing material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ultraviolet curable type and thermosetting type resins, and specific examples thereof include acrylic resin and urethane type. Examples include resins and epoxy resins.

<< Insulating Porous Layer >>
The insulating porous layer has a function of separating the first electrode and the second electrode so as to be electrically insulated and holding an electrolyte.
The material of the insulating porous layer is not particularly limited as long as it is porous, and an organic material or an inorganic material having high insulation and durability and excellent film forming property, and a composite thereof may be used. preferable.

Examples of the method for forming the insulating porous layer include a sintering method (polymer fine particles and inorganic particles are partially fused by adding a binder or the like to utilize pores formed between the particles), and extraction. Method (after forming a constituent layer with a solvent-soluble organic or inorganic substance and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved with a solvent to obtain pores), foaming method for foaming, good solvent and poor Examples include a phase conversion method in which a solvent is manipulated to phase-separate a mixture such as a polymer compound, and a radiation irradiation method in which various types of radiation are radiated to form pores.

<< Protective layer >>
The protective layer is unnecessary for protecting the electrochromic element from external stress and chemicals in the cleaning process, preventing leakage of gel electrolyte, and for stable operation of the electrochromic element such as moisture and oxygen in the atmosphere. It has functions such as preventing the intrusion of things.

The average thickness of the protective layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm or more and 200 μm or less.
Examples of the material of the protective layer include an ultraviolet curable type resin and a thermosetting type resin, and specific examples thereof include an acrylic resin, a urethane resin, and an epoxy resin.

<Use>
The gel electrolyte of the present invention is not limited to electrochromic elements, and can be suitably used for various electrochemical devices such as lithium batteries, solar cells, fuel cells, and ion-conducting actuators.
Since the electrochromic element of the present invention has high transparency and excellent color responsiveness, for example, an electrochromic display, a large display board such as a stock price display board, a dimming element such as an antiglare mirror, a dimming glass, etc. It can be suitably used for low voltage drive elements such as touch panel type key switches, optical switches, optical memories, electronic papers, electronic albums, and the like.

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

(Example 1)
<Example of preparation of gel electrolyte>
First, the mass ratio (monomer / polymerization initiator) to methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400, manufactured by Nichiyu Co., Ltd., n = 9) as the monomer represented by the following general formula (1). Irgacure184 (manufactured by BASF) was dissolved as a polymerization initiator so that the ratio was 95/5 to obtain a monomer solution A1. Subsequently, as the monomer represented by the following general formula (2), the mass ratio (monomer / polymerization initiator) to polyethylene glycol dimethacrylate (trade name: Blemmer PDE-400, manufactured by Nichiyu Co., Ltd., n = 9) ) Was dissolved as a polymerization initiator in irgacure184 (manufactured by BASF) so as to have a ratio of 95/5 to obtain a monomer solution B1.
Next, the obtained monomer solutions A1 and B1 were mixed at 1/9, and ethylmethylimidazolium bisfluorosulfonimide (EMIMFSI, manufactured by Kanto Chemical Co., Inc.) was mixed and dissolved therein as a salt of an ionic liquid to compose the composition. A product solution was prepared. The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is It is 10/90.
Next, 50 μL of the obtained composition solution was dropped onto a glass plate, allowed to stand under N ₂ flow (100 mL / min) for 5 minutes, and then kept under N ₂ flow for a UV (wavelength 250 nm) irradiation device (Ushio). An electrolyte was obtained by irradiating with 10 mW for 60 seconds by SPOT CURE, manufactured by Denki Co., Ltd.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)

<Ionic liquid concentration>
Next, the "ionic liquid concentration" was evaluated using the electrolyte. Specifically, in the preparation of the electrolyte, when the electrolyte gelled, the content of the ionic liquid in the monomer solution was increased to prepare the electrolyte again, and the presence or absence of gelation was confirmed according to the following criteria. This was repeated until the electrolyte did not gel, and the maximum "ionic liquid concentration" at which the electrolyte could gel was evaluated. The composition ratio of the monomers and the maximum ionic liquid concentration at which the electrolyte can gel are shown in Table 1 below.
[Criteria]
Gelled: Electrolyte is cured and has no fluidity, and is transparent without dripping. Non-gelled: Electrolyte is cloudy, dripping, or is not cured and is fluid.

(Examples 2-27 and Comparative Example 1)
Electrolytes of Examples 2 to 27 and Comparative Example 1 were obtained in the same manner as in Example 1 except that the mass ratio (A / B) in Table 1 below was changed in Example 1. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

From the results in Table 1, as the monomer represented by the general formula (1) and the monomer represented by the general formula (2), methoxypolyethylene glycol methacrylate (PME-400, trade name: Blemmer PME-400), respectively, And when polyethylene glycol dimethacrylate (PDE-400, trade name: Blemmer PDE-400) is used and the mass ratio (PME-400 / PDE-400) is 18/82 or more and 53/47 or less, the gel electrolyte The ionic liquid concentration in the mixture was 80% by mass or more.

(Example 28)
In Example 1, methoxypolyethylene glycol methacrylate is used as the monomer represented by the general formula (1), polyethylene glycol dimethacrylate is used as the monomer represented by the general formula (2), and the monomer represented by the general formula (1) is used. As a methoxypolyethylene glycol acrylate (manufactured by Nichiyu Co., Ltd., trade name: Blemmer AME-400, n in the general formula (1) is 9), and as a monomer represented by the general formula (2), polyethylene glycol diacrylate (Japan). An electrolyte was obtained in the same manner as in Example 1 except that the product name: Blemmer ADE-400A, manufactured by Oil Co., Ltd., and n in the general formula (2) was changed to 9). The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

(Examples 29 to 59 and Comparative Examples 2 to 3)
In Example 28, the electrolytes of Examples 29 to 59 and Comparative Examples 2 and 3 were obtained in the same manner as in Example 28 except that the mass ratio (A / B) in Table 2 below was changed. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 28. The results are shown in Table 2 below.

From the results in Table 2, as the monomer represented by the general formula (1) and the monomer represented by the general formula (2), methoxypolyethylene glycol acrylate (AME-400, trade name: Blemmer AME-400), respectively. , And when polyethylene glycol diacrylate (ADE-400A, trade name: Blemmer ADE-400A) is used and the mass ratio (AME-400 / ADE-400A) is 26/74 or more and 92/8 or less, the gel is used. The ionic liquid concentration in the electrolyte was 80% by mass or more. Further, when the mass ratio (AME-400 / ADE-400A) was 28/72 or more and 63/37 or less, the ionic liquid concentration in the gel electrolyte was It was 90% by mass or more.

(Example 60)
In Example 1, the content A (mass%) of methoxypolyethylene glycol methacrylate and the monomer represented by the general formula (1) and the content B (mass%) of the monomer represented by the general formula (2). The mass ratio (A / B) with methoxypolyethylene glycol acrylate (manufactured by Nichiyu Co., Ltd., trade name: Blemmer AME-400, n in the general formula (1) is 9), and the mass ratio (A / B) The "ionic liquid concentration" was evaluated in the same manner as in Example 1 except that the value was changed to 30/70. The results are shown in Table 3 below.

(Examples 61-62)
In Example 60, the electrolytes of Examples 61 to 62 were obtained in the same manner as in Example 60, except that the mass ratio (A / B) in Table 3 below was changed. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 60. The results are shown in Table 3 below.

(Example 63)
In Example 1, the content A (mass%) of polyethylene glycol dimethacrylate and the monomer represented by the general formula (1) and the content B (mass%) of the monomer represented by the general formula (2). The mass ratio (A / B) with and was changed to polyethylene glycol diacrylate (ADE-400A, trade name: Blemmer ADE-400A), and the mass ratio (A / B) was changed to 30/70. Similarly, the "ionic liquid concentration" was evaluated. The results are shown in Table 4 below.

(Examples 64-65)
In Example 63, the electrolytes of Examples 64 to 65 were obtained in the same manner as in Example 63, except that the mass ratio (A / B) in Table 4 below was changed. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 63. The results are shown in Table 4 below.

(Example 66)
In Example 1, the electrolyte of Example 66 was obtained in the same manner as in Example 1 except that the salt of the ionic liquid shown in Table 5 below and the mass ratio (A / B) were changed to 30/70. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 1. The results are shown in Table 5 below.

(Examples 67 to 80 and Comparative Examples 4 to 8)
In Example 66, the electrolytes of Examples 67 to 80 and Comparative Examples 4 to 8 are the same as in Example 66, except that the salt of the ionic liquid shown in Table 5 below and the mass ratio (A / B) are changed. Got The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 66. The results are shown in Table 5 below.

In Table 5, the product names of the ingredients and the names of the manufacturing companies are as follows.
・ EMIMTCB: Ethylmethylimidazolium tetracyanobolate, manufactured by Merck ・ EMIMTFSI: Ethylmethylimidazolium bistrifluoromethanesulfonimide, manufactured by Kanto Chemical Co., Ltd. ・ EMIMFAP: Ethylmethylimidazolium tripentafluholoethyl trifluorophosphate, Merck ABIMBF4: Allylbutylimidazolium tetrafluoroborate, manufactured by Kanto Chemical Co., Ltd. ・ P13FSI: Methylpropylpyrrolidinium bisfluorosulfonimide, manufactured by Kanto Chemical Co., Ltd.

From the results in Table 5, methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400, manufactured by NOF CORPORATION, n = 9) and polyethylene glycol dimethacrylate (trade name) as a monomer represented by the following general formula (2). : When Blemmer PDE-400, manufactured by NOF CORPORATION, n = 9) is used and the mass ratio (A / B) is 30/70 or more and 50/50 or less, there is no fluidity and no liquid dripping. A clear, good gel electrolyte was obtained.

(Example 81)
In Example 66, as the monomer represented by the general formula (1), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400, manufactured by Nichiyu Co., Ltd., n = 9) is represented by the general formula (2). Polyethylene glycol dimethacrylate (trade name: Blemmer PDE-400, manufactured by Nichiyu Co., Ltd., n = 9) and methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400, Nichiyu Co., Ltd., n = 9). , And polyethylene glycol diacrylate (trade name: Blemmer ADE-400A, manufactured by Nichiyu Co., Ltd., n = 9), and the electrolyte of Example 81 was obtained in the same manner as in Example 66. The "ionic liquid concentration" of the obtained electrolyte was evaluated in the same manner as in Example 66. The results are shown in Table 6 below.

(Examples 82 to 100 and Comparative Examples 9 to 13)
In Example 81, the electrolytes of Examples 82 to 100 and Comparative Examples 9 to 13 were similarly changed to the salt of the ionic liquid shown in Table 6 below and the mass ratio (A / B). Got The "ionic liquid concentration" of the obtained electrolytes of Examples 82 to 100 and Comparative Examples 9 to 13 was evaluated in the same manner as in Example 81. The results are shown in Table 6.

In Table 6 above, the product names of the ingredients and the names of the manufacturing companies are as follows.
・ EMIMTCB: Ethylmethylimidazolium tetracyanoborate, manufactured by Merck ・ EMIMTFSI: Ethylmethylimidazolium bistrifluoromethanesulfonimide, manufactured by Kanto Kagaku Co., Ltd. ABIMBF4: Allylbutylimidazolium tetrafluoroborate, manufactured by Kanto Chemical Co., Ltd. ・ P13FSI: Methylpropylpyrrolidinium bisfluorosulfonimide, manufactured by Kanto Chemical Co., Ltd.

From the results shown in Table 6, methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400, NOF CORPORATION, n = 9) and polyethylene glycol diacrylate (trade name: Blemmer ADE-400A, manufactured by NOF Corporation). When n = 9) was used, when the mass ratio (A / B) was 30/70 or more and 90/10 or less, a good gel electrolyte having no fluidity and no liquid dripping and being transparent was obtained.

<Evaluation of electrolyte volatility>
As the monomer represented by the general formula (1), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400, manufactured by Nichiyu Co., Ltd., n = 9) and polyethylene glycol as the monomer represented by the general formula (2). Dimethacrylate (trade name: Blemmer PDE-400, manufactured by Nichiyu Co., Ltd., n = 9) is mixed at a mass ratio of 50/50, and ethylmethylimidazolium bisfluorosulfonimide (EMIMFSI) is used as an ionic liquid salt therein. , Kanto Chemical Co., Ltd.) was mixed and dissolved so that the ionic liquid concentration was 83% by mass to prepare an electrolyte A.

In the preparation of the electrolyte A, methoxypolyethylene glycol methacrylate, polyethylene glycol dimethacrylate, and ionic liquid concentration were set to methoxypolyethylene glycol acrylate (manufactured by Nichiyu Co., Ltd., trade name: Blemmer AME-400, n in the general formula (1)). 9), polyethylene glycol diacrylate, and electrolyte B were prepared in the same manner as in the preparation of electrolyte A, except that the ionic liquid concentration was changed to 92% by mass.

After dropping one drop of ethylmethylimidazolium bisfluorosulfonimide (EMIMFSI, manufactured by Kanto Chemical Co., Inc.), which is an ionic liquid, onto a glass substrate (40 mm x 40 mm) in a glove box with an argon atmosphere and measuring its mass. It was left on a hot plate at 60 ° C. for 24 hours. As a result of measuring the mass of the sample after being left to stand, there was no change in mass.
Similarly, one drop of the electrolyte A and the electrolyte B was dropped on a glass substrate (40 mm × 40 mm), the mass thereof was measured, and then the mixture was left on a hot plate at 60 ° C. for 24 hours. As a result of measuring the mass of the sample after being left to stand, there was no change in mass in either case.
Therefore, it can be seen that the produced electrolyte has low volatility equivalent to that of an ionic liquid.

<Evaluation of electrolyte viscosity>
The liquid viscosities of the electrolyte A and the electrolyte B were measured. The measurement was carried out using a TV-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) at 23 ° C. and a rotation speed of 10 rpm. The viscosity of ethylmethylimidazolium bisfluorosulfonimide (EMIMFSI, manufactured by Kanto Chemical Co., Inc.), which is an ionic liquid, was 20 mPa · s. The results are shown in Table 7.

From the results in Table 7, it can be seen that the produced electrolyte has a viscosity equivalent to that of the ionic liquid.

(Example 101)
<Production example 1 of electrochromic element>
<< Formation of an electrochromic layer on the surface of the first electrode >>
Polyethylene glycol diacrylate (commodity) as a monomer represented by the general formula (2) on an ITO glass substrate (40 mm × 40 mm, average thickness: 0.7 mm, ITO film thickness: about 100 nm) as a first electrode. Name: PEG-400DA, manufactured by Nippon Kayaku Co., Ltd., irgacure184 (manufactured by BASF), and the compound represented by the following structural formula (2) (exemplified compound 2) and 2-butanone in a mass ratio (57/3). The solution mixed in (/ 140/800) was applied by a spin coating method, UV-cured in a nitrogen atmosphere, and the average thickness containing the compound represented by the structural formula (exemplified compound 2) on the first electrode was 1. A 1 μm electrochromic layer was formed.
Compound represented by structural formula (2) (exemplified compound (2))

<Formation of electrochromic layer on the second electrode>
Titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particles) on an ITO glass substrate (40 mm × 40 mm, average thickness: 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. (Diameter: about 20 nm) was applied by a spin coating method and annealed at 120 ° C. for 15 minutes to form a titanium oxide particle film. A 2% by mass 2,2,3,3-tetrafluoropropanol solution of the compound represented by the following structural formula (3) was applied to the titanium oxide particle film as a coating solution by a spin coating method, and annealed at 120 ° C. for 10 minutes. By performing the treatment, an electrochromic layer having an average thickness of 1.0 μm was formed by adsorbing the compound represented by the structural formula (3) on the surface of the titanium oxide particles on the second electrode.
Structural formula (3)

<< Preparation of empty cells >>
The first electrode and the second electrode on which the electrochromic layer is formed are bonded to each other with a 50 μm film sandwiched between them, and the two ends are bonded to each other with UV adhesive Photorec E (low moisture permeability type, Sekisui Chemical Co., Ltd.). After sealing with (manufactured by Sekisui Chemical Co., Ltd.), the film was removed to prepare an empty cell.

<< Filling with gel electrolyte >>
As the monomer represented by the general formula (1), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400, manufactured by Nichiyu Co., Ltd., n = 9) and polyethylene glycol as the monomer represented by the following general formula (2). Irgacure184 (trade name: Blemmer PDE-400, manufactured by Nichiyu Co., Ltd., n = 9) as a polymerization initiator so that the mass ratio (each monomer / polymerization initiator) is 95/5 with respect to dimethacrylate (trade name: Blemmer PDE-400, manufactured by Nichiyu Co., Ltd.). (Manufactured by BASF) was dissolved to obtain a monomer solution. The mass ratio (A / B) was 10/90. Next, a composition solution was prepared so that the content of ethylmethylimidazolium bisfluorosulfonimide (EMIMFSI, manufactured by Kanto Chemical Co., Inc.) as an ionic liquid was 50% by mass. The composition solution was carefully infiltrated to prevent air bubbles from entering the empty cell. Then, it was irradiated with a UV irradiation device at 10 mW for 60 seconds to cure the electrolyte. After that, the remaining two edges of the cell were sealed to fabricate the electrochromic device 1.

Using the produced electrochromic element 1, the "impedance" was measured as follows.

The impedance of the device was measured by the AC impedance method. The measuring device uses a modular electrochemical measurement system (device name: modulab, manufactured by Toyo Technica Co., Ltd.), applied AC voltage: 10 mV, measurement frequency range: 1 Hz to 1,000,000 Hz, measurement temperature of 25 ° C. , 15 ° C, 5 ° C, -5 ° C, and -15 ° C. As a result of the measurement, an impedance waveform having a shape as shown in FIG. 2 was obtained. The length of the arc chord at this time was measured as the impedance of the electrochromic element 1. The results are shown in Table 8.

(Examples 102 to 117 and Comparative Examples 14 to 15)
In Example 101, electrochromic devices of Examples 102 to 117 and Comparative Examples 14 to 15 were produced in the same manner as in Example 101 except that the composition and content were changed to those shown in Table 8 below. Impedance was measured using the produced electrochromic device in the same manner as in Example 101. The results are shown in Table 8 below.

In Table 8, the product names of the ingredients and the names of the manufacturing companies are as follows.
-PME-400: Methoxypolyethylene glycol methacrylate, manufactured by NOF CORPORATION, trade name: Blemmer PME-400, n in the general formula (1) is 9.
-AME-400: Methoxypolyethylene glycol acrylate, manufactured by NOF CORPORATION, trade name: Blemmer AME-400, n in the general formula (1) is 9.
-PDE-400: Polyethylene glycol dimethacrylate, manufactured by NOF CORPORATION, trade name: Blemmer PDE-400, n in the general formula (2) is 9.
-ADE-400A: Polyethylene glycol diacrylate, manufactured by NOF CORPORATION, trade name: Blemmer ADE-400A, n in the general formula (2) is 9
-EMIMTFSI: Ethylmethylimidazolium bistrifluoromethanesulfonimide, manufactured by Kanto Chemical Co., Inc.)

From the results in Table 8 above, the higher the ionic liquid concentration, the smaller the impedance. Therefore, since the gel electrolyte of the present invention can increase the ionic liquid concentration, the impedance of the electrochromic device can be reduced.

(Examples 118 to 146, and Comparative Examples 16 to 17)
<Manufacturing of electrochromic elements>
In Example 101, the electrochromic compound used as the electrochromic layer on the first electrode, the monomer represented by the general formula (1), and the monomer represented by the general formula (1) are shown in the table. Except for changing to the electrochromic compound shown in 9, the monomer represented by the general formula (1), the monomer represented by the general formula (2), the mass ratio (A / B), and the ionic liquid concentration. , And the electrochromic elements of Examples 118 to 146 and Comparative Examples 16 to 17 were produced in the same manner as in Example 101.

Using the produced electrochromic device, the "color development response" was evaluated as follows.

<Color responsiveness>
Using the prepared electrochromic devices of Examples 118 to 146 and Comparative Examples 16 to 17, a voltage of -2V was applied to the second electrode for 1 second with respect to the first electrode to develop the color of the electrochromic device. I let you. At that time, the transmittance at the center of the display region is measured with a multi-channel spectroscope (device name: USB4000, manufactured by Ocean Optics), and the average value of the transmittance of each wavelength in the visible region (wavelength 380 nm or more and 780 nm or less) is measured. did. The lower the transmittance, the better the color development response.

In Table 9, the product names of the ingredients and the names of the manufacturing companies are as follows.
-PME-400: Methoxypolyethylene glycol methacrylate, manufactured by NOF CORPORATION, trade name: Blemmer PME-400, n in the general formula (1) is 9.
-AME-400: Methoxypolyethylene glycol acrylate, manufactured by NOF CORPORATION, trade name: Blemmer AME-400, n in the general formula (1) is 9.
-PDE-400: Polyethylene glycol dimethacrylate, manufactured by NOF CORPORATION, trade name: Blemmer PDE-400, n in the general formula (2) is 9.
-ADE-400A: Polyethylene glycol diacrylate, manufactured by NOF CORPORATION, trade name: Blemmer ADE-400A, n in the general formula (2) is 9
・ EMIMFSI: Ethylmethylimidazolium bisfluorosulfonimide, manufactured by Kanto Chemical Co., Ltd. ・ EMIMTCB: Ethylmethylimidazolium tetracyanoborate, manufactured by Merck Co., Ltd. ・ EMIMFSI: Ethylmethylimidazolium bistrifluoromethanesulfonimide, manufactured by Kanto Chemical Co., Ltd. EMIMFAP: Ethylmethylimidazolium tripentafluholoethyltrifluoroophosphate, manufactured by Merck, ABIMBF4: Allylbutylimidazolium tetrafluoroborate, manufactured by Kanto Chemical Co., Ltd., P13FSI: Methylpropylpyrrolidinium bisfluorosulfonimide, Kanto Chemical Manufactured by Co., Ltd., Exemplified compound (1):
-Example compound (2):
-Exemplified compound (3):
-PEG-400DA: Polyethylene glycol diacrylate, trade name: PEG-400DA, manufactured by Nippon Kayaku Co., Ltd.

From the results in Table 9 above, it was found that the electrochromic devices of Examples 118 to 146 exhibited good color development responsiveness.

Examples of aspects of the present invention are as follows.
<1> With ionic liquids
The monomer represented by the following general formula (1) and
It is a gel electrolyte characterized by containing a cured product of a composition containing a monomer represented by the following general formula (2).
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
<2> R in the general formula (1) and R in the general formula (2) are methacrylic groups.
The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is , 18/82 or more and 53/47 or less, according to the above <1>.
<3> The gel electrolyte according to <2>, wherein the mass ratio (A / B) is 20/80 or more and 30/70 or less.
<4> R in the general formula (1) and R in the general formula (2) are acrylic groups.
The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is , 26/74 or more and 92/8 or less, according to the above <1>.
<5> The gel electrolyte according to <4>, wherein the mass ratio (A / B) is 28/72 or more and 63/37 or less.
<6> The gel electrolyte according to any one of <1> to <5>, wherein the content of the ionic liquid is 80% by mass or more.
<7> The gel electrolyte according to <6>, wherein the content of the ionic liquid is 90% by mass or more.
<8> The gel electrolyte according to any one of <1> to <7>, which further contains a polymerization initiator.
<9> The gel electrolyte according to <1>, wherein the monomer represented by the general formula (1) is either methoxypolyethylene glycol methacrylate or methoxypolyethylene glycol acrylate.
<10> The gel electrolyte according to <1>, wherein the monomer represented by the general formula (2) is either polyethylene glycol dimethacrylate or polyethylene glycol diacrylate.
<11> The salts of the ionic liquid are ethylmethylimidazolium tetracyanoborate, ethylmethylimidazolium bistrifluoromethanesulfonimide, ethylmethylimidazoliumtripentafluholoethyltrifluoroolophosphate, and methylpropylpyrrolidinium bisfluoro. The gel electrolyte according to any one of <1> to <10>, which is at least one selected from sulfonimide.
<12> The gel electrolyte according to any one of <7> to <11>, which is a radical polymerization initiator.
<13> The gel electrolyte according to <12>, wherein the radical polymerization initiator is a photopolymerization initiator.
<14> The gel electrolyte according to <13>, wherein the photopolymerization initiator is a ketal-based photopolymerization initiator.
<15> The gel electrolyte according to <14> above, wherein the ketal-based photopolymerization initiator is 1-hydroxycyclohexylphenyl ketone.
<16> The gel electrolyte according to any one of <7> to <15>, wherein the content of the polymerization initiator is 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of all the monomer components. is there.
<17> A gel electrolyte is provided between the first electrode, the second electrode, and the first electrode and the second electrode.
At least one of the first electrode and the second electrode is transparent.
An electrochromic device having an electrochromic layer containing an electrochromic compound on the surface of the first electrode.
The electrochromic device is characterized in that the gel electrolyte is the gel electrolyte according to any one of <1> to <16>.
<18> The electrochromic compound is a radically polymerizable compound.
The <17. The electrochromic layer contains a copolymer composed of the electrochromic compound and at least one of the monomer represented by the general formula (1) and the monomer represented by the general formula (2). > Is the electrochromic element.
<19> The electrochromic device according to any one of <17> to <18>, wherein the average thickness of the electrochromic layer is 0.2 μm or more and 5.0 μm or less.
<20> The electrochromic device according to any one of <17> to <19>, wherein the radically polymerizable compound is a compound represented by the following structural formula.

According to the gel electrolyte according to any one of <1> to <16> and the electrochromic element according to any one of <17> to <20>, the conventional problems are solved and the present invention is described. The purpose can be achieved.

Japanese Patent No. 5049322

1: Support 2: First electrode 3: Second electrode 4: Electrochromic compound 5, 7: Electrochromic layer 6: Gel electrolyte

Claims (8)

With ionic liquids
The monomer represented by the following general formula (1) and
A gel electrolyte containing a cured product of a composition containing a monomer represented by the following general formula (2).
R in the general formula (1) and R in the general formula (2) are methacrylic groups.
The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is , 18/82 or more and 53/47 or less,
The ionic liquid contains cations and anions and contains
The cation is at least one selected from the group consisting of N, N-methylethylimidazole cation, N, N-allylbutylimidazole cation, and N-methyl-N-propylpyrrolidinium cation.
The anion is selected from the group consisting of BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (FSO ₂ ) ₂ N ⁻ , (CN) ₄ B ⁻ , and (C ₂ F ₅ ) ₃ PF ₃ ^−. A gel electrolyte characterized by being at least one kind.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.) The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is The gel electrolyte according to claim 1, wherein the gel electrolyte is 20/80 or more and 30/70 or less . With ionic liquids
The monomer represented by the following general formula (1) and
A gel electrolyte containing a cured product of a composition containing a monomer represented by the following general formula (2).
R in the general formula (1) and R in the general formula (2) are acrylic groups.
The mass ratio (A / B) of the monomer content A (mass%) represented by the general formula (1) and the monomer content B (mass%) represented by the general formula (2) is state, and are 26/74 more than 92/8 or less,
The ionic liquid contains cations and anions and contains
The cation is at least one selected from the group consisting of N, N-methylethylimidazole cation, N, N-allylbutylimidazole cation, and N-methyl-N-propylpyrrolidinium cation.
The anion is selected from the group consisting of BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (FSO ₂ ) ₂ N ⁻ , (CN) ₄ B ⁻ , and (C ₂ F ₅ ) ₃ PF ₃ ^−. A gel electrolyte characterized by being at least one kind .
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.) The gel electrolyte according to claim 3, wherein the mass ratio (A / B) is 28/72 or more and 63/37 or less. The gel electrolyte according to any one of claims 1 to 4, wherein the content of the ionic liquid is 80% by mass or more. It has a first electrode, a second electrode, and a gel electrolyte between the first electrode and the second electrode.
At least one of the first electrode and the second electrode is transparent.
An electrochromic device having an electrochromic layer containing an electrochromic compound on the surface of the first electrode.
An electrochromic device, wherein the gel electrolyte is the gel electrolyte according to any one of claims 1 to 5. The electrochromic compound is a radically polymerizable compound and
6. Claim 6 in which the electrochromic layer comprises a copolymer composed of the electrochromic compound and at least one of the monomer represented by the general formula (1) and the monomer represented by the general formula (2). The electrochromic element described in. It has a first electrode, a second electrode, and a gel electrolyte between the first electrode and the second electrode.
At least one of the first electrode and the second electrode is transparent.
An electrochromic device having an electrochromic layer containing an electrochromic compound on the surface of the first electrode.
The gel electrolyte
With ionic liquids
The monomer represented by the following general formula (1) and
A gel electrolyte containing a cured product of a composition containing a monomer represented by the following general formula (2).
The electrochromic compound is a radically polymerizable compound and
The electrochromic layer is characterized by containing a copolymer composed of the electrochromic compound and at least one of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2). Electrochromic element.
(However, in the general formula (1), R represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)
(However, in the general formula (2), R independently represents a methacrylic group or an acrylic group, and n represents an integer of 7 or more and 12 or less.)