JP2003015163A - Electrochromic device - Google Patents

Abstract

(57) Abstract: Provided is an electrochromic element which does not necessarily require disposition of a spacer material such as beads in a cell in order to produce a cell having a uniform electrode spacing. An electrochromic device in which an ion conductive layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer, and the ion conductive layer is a polyfluorinated layer. The vinylidene polymer matrix contains at least one ion-conductive substance selected from (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) a room temperature molten salt and a solvent. An electrochromic device comprising an ion conductive sheet.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrochromic device having a novel structure.

[0002]

2. Description of the Related Art Heretofore, various electrochromic elements have been proposed as applied to various light control elements and display elements. For example, transparent conductive substrate (transparent substrate with transparent conductive film), oxidative coloring type (or reduction coloring type)
Typical examples include an element having a structure in which an electrochromic film, an electrolyte, and a counter electrode substrate are sequentially provided, a transparent conductive substrate, an electrolyte containing an electrochromic compound, and an element in which a counter electrode substrate is sequentially provided. When an electrochromic device is manufactured, it is disclosed in JP-A-63-
It can be produced by a known method disclosed in Japanese Patent Application Laid-Open No. 139321 or Japanese Patent Application Laid-Open No. 2-155173. That is, a process of manufacturing a cell in which two electrodes are held at a uniform interval and injecting and curing an electrolytic solution is used. However, this method requires that a spacer material such as beads be placed in the cell in order to produce a cell having a uniform electrode spacing, and this spacer material has a problem that it reduces visual comfort. It was

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and it is not always necessary to dispose a spacer material such as beads in a cell in order to manufacture a cell having a uniform electrode spacing. An object is to provide an electrochromic device that is not essential.

[0004]

As a result of intensive studies conducted by the present inventors to solve the above conventional problems, an electrochromic device using a specific ion conductive sheet solves the above problems. They have found that they can do so and have completed the present invention. That is, the present invention is an electrochromic device in which an ion conductive layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer, and the ion conductive layer comprises:
In a polyvinylidene fluoride-based polymer matrix,
An ion conductive sheet comprising at least one ion conductive substance selected from (a) supporting electrolyte and solvent, (b) room temperature molten salt, and (c) room temperature molten salt and solvent. The present invention relates to a characteristic electrochromic device. Furthermore, the above-mentioned electrochromic element is characterized in that a member obtained by binding conductive fine particles with a binder is arranged on the conductive surface of one conductive substrate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The electrochromic element of the present invention is an electrochromic element in which an ion conductive layer is sandwiched between two transparent conductive substrates, the electrochromic layer having an electrochromic layer on at least one of the conductive substrates. In a polyvinylidene fluoride-based polymer matrix, (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt,
And (c) an ion conductive sheet containing at least one kind of ion conductive substance selected from a room temperature molten salt and a solvent.

First, the ion conductive sheet of the present invention will be described. The ion conductive sheet of the present invention comprises (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) in a polymer matrix made of a specific polymer compound.
It is characterized by containing at least one kind of ion conductive substance selected from a room temperature molten salt and a solvent. In the ion conductive sheet of the present invention, at least one or more ion conductive substances selected from (a) supporting electrolyte and solvent, (b) room temperature molten salt, (c) room temperature molten salt and solvent, or further desired. Other components added by the method are retained in a polymer matrix made of a polyvinylidene fluoride-based polymer compound to form a solid state or gel state.

As the polyvinylidene fluoride-based polymer compound used as the polymer matrix in the present invention, a vinylidene fluoride homopolymer or vinylidene fluoride and another polymerizable monomer, preferably a radically polymerizable monomer, is used. A copolymer can be mentioned. Other polymerizable monomers to be copolymerized with vinylidene fluoride (hereinafter,
It is called a copolymerizable monomer. Specific examples of) include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, methyl acrylate, ethyl acrylate, methyl methacrylate and styrene.

These copolymerizable monomers are contained in an amount of 1 to 50 mol%, preferably 1 to 25 mol% based on the total amount of the monomers.
It can be used in the range of 1%. Hexafluoropropylene is preferably used as the copolymerizable monomer. In the present invention, a vinylidene fluoride-hexafluoropropylene copolymer obtained by copolymerizing vinylidene fluoride with 1 to 25 mol% of hexafluoropropylene can be preferably used as an ion conductive film having a polymer matrix. Further, two or more kinds of vinylidene fluoride-hexafluoropropylene copolymers having different copolymerization ratios may be mixed and used.

Further, it is possible to copolymerize with vinylidene fluoride by using two or more kinds of these copolymerizable monomers. For example, use a copolymer obtained by copolymerizing vinylidene fluoride + hexafluoropropylene + tetrafluoroethylene, vinylidene fluoride + tetrafluoroethylene + ethylene, vinylidene fluoride + tetrafluoroethylene + propylene, etc. You can also

Further, in the present invention, a polyvinylidene fluoride polymer compound as a polymer matrix and a polymer compound selected from polyacrylate polymer compounds, polyacrylonitrile polymer compounds and polyether polymer compounds are used. It is also possible to mix and use more than one kind. The mixing ratio at this time is usually 200 parts by mass or less with respect to 100 parts by mass of the polyvinylidene fluoride-based polymer compound.

The number average molecular weight of the polyvinylidene fluoride polymer compound used in the present invention is usually 10,0.
0 to 2,000,000, preferably 100,
Those in the range of 000 to 1,000,000 can be preferably used.

Next, the ion conductive substance will be described. As the ion conductive substance of the present invention, at least one or more ion conductive substances selected from (a) supporting electrolyte and solvent, (b) room temperature molten salt, and (c) room temperature molten salt and solvent are used. . As the supporting electrolyte used in the present invention, salts, acids and alkalis usually used in the field of electrochemistry or the field of batteries can be used.

The salt is not particularly limited, and for example,
Inorganic ions such as alkali metal salts and alkaline earth metal salts
Salt; Quaternary ammonium salt; Cyclic quaternary ammonium salt; 4
-Grade phosphonium salt can be used, and Li salt is particularly preferable.
Yes. Specific examples of salts include halogen ions and SC
N^-, ClO_Four ^-, BF_Four ^-, CF₃SO₃ ^-, (CF₃SO₂)
₂N^-, (C₂F_FiveSO₂)₂N^-, PF₆ ^-, AsF₆ ^-, CH₃
COO^-, CH₃(C₆H_Four) SO₃ ^-, And (C₂F_FiveSO
₂)₃C^-Li salt having a counter anion selected from
Examples thereof include salt and K salt. Also halogen ions,
SCN^-, ClO_Four ^-, BF_Four ^-, CF₃SO₃ ^-, (CF₃S
O₂)₂N^-, (C₂F_FiveSO₂)₂N^-, PF₆ ^-, AsF₆ ^-,
CH₃COO^-, CH₃(C₆H_Four) SO₃ ^-, And (C₂F
_FiveSO₂)₃C^-Quaternary anion having a counter anion selected from
Monium salt, specifically (CH₃)_FourNBF_Four, (C₂H
_Five)_FourNBF_Four, (N-C_FourH₉)_FourNBF_Four, (C₂H_Five)_FourN
Br, (C₂H_Five)_FourNClO_Four, (N-C_FourH₉)_FourNCl
O_Four, CH₃(C₂H_Five)₃NBF_Four, (CH₃)₂(C₂H_Five)
₂NBF _Four, (CH₃)_FourNSO₃CF₃, (C₂H_Five)_FourNS
O₃CF₃, (N-C_FourH₉)_FourNSO₃CF₃,Moreover,

[0014]

[Chemical 1]

And the like. In addition, halogen ion, S
CN^-, ClO_Four ^-, BF_Four ^-, CF₃SO ₃ ^-, (CF₃S
O₂)₂N^-, (C₂F_FiveSO₂)₂N^-, PF₆ ^-, AsF₆ ^-,
CH₃COO^-, CH₃(C₆H_Four) SO₃ ^-, And (C₂F
_FiveSO₂)₃C^-Having a counter anion selected from
Um salts, specifically, (CH₃)_FourPBF_Four, (C₂H_Five)_Four
PBF_Four, (C₃H₇)_FourPBF_Four, (C_FourH₉)_FourPBF_Fouretc
Is mentioned. Also, it is preferable to use a mixture of these.
You can

The acids are not particularly limited, and inorganic acids, organic acids and the like can be used, and specifically sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like can be used. The alkalis are also not particularly limited, and sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can all be used.

Although the amount of the supporting electrolyte used is arbitrary, it is generally desirable that the supporting electrolyte is present in the solvent at an upper limit of 20 M or less, preferably 10 M or less, more preferably 5 M or less, and the lower limit. Is usually 0.0
It is desirable that 1M or more, preferably 0.05M or more, and more preferably 0.1M or more is present. Further, it is preferable that the upper limit value is 20% by mass or less, preferably 10% by mass or less, and the lower limit value is 0.01% by mass or more, preferably 0.1% by mass or more, in the ion conductive sheet.

Next, the solvent used in the present invention will be described. In the present invention, as the solvent in the components (a) and (c), any solvent generally used in electrochemical cells and batteries can be used. Specifically, acetic anhydride, methanol, ethanol,
Tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphoamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethoxyethane, propionnitrile, glutaronitrile, adiponitrile, methoxy. Acetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, ethyl dimethyl phosphate,
Tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, tris (trifluorofluoromethyl) phosphate, tris (pentafluoroethyl) phosphate, phosphate Triphenyl polyethylene glycol, polyethylene glycol and the like can be used. In particular,
Propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane,
Dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile,
Dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethyl phosphate and triethyl phosphate are preferred. As the solvent, one type thereof may be used alone, or two or more types may be mixed and used.

The amount of the solvent used is not particularly limited, but usually,
20 mass% or more, preferably 5 in the ion conductive sheet
0 mass% or more, more preferably 70 mass% or more and 98 mass% or less, preferably 95 mass% or less,
More preferably, it can be contained in an amount of 90% by mass or less.

The room temperature molten salt used in the present invention will be described. In the present invention, the room temperature molten salt in the component (b) and the component (c) is melted (that is, liquid) at room temperature composed of only ion pairs containing no solvent component.
A salt consisting of an ion pair, which usually has a melting point of 20 ° C. or lower and is in a liquid state at a temperature exceeding 20 ° C., is shown. As the room temperature molten salt, one kind thereof may be used alone, or two or more kinds thereof may be mixed and used. Examples of the room temperature molten salt include the followings.

[0021]

[Chemical 2]

(Where R is a carbon number of 2 to 20, preferably
Represents an alkyl group of 2 to 10. X^-Is halogenio
SCN^-, ClO_Four ^-, BF_Four ^-, (CF₃SO₂)
₂N^-, (C₂F _FiveSO₂)₂N^-, PF₆ ^-, AsF₆ ^-, CH₃
COO^-, CH₃(C₆H_Four) SO₃ ^-, And (C₂F_FiveSO
₂)₃C^-Represents a counter anion selected from )

[0023]

[Chemical 3]

(Here, each of R1 and R2 has 1 carbon atom.
It represents an alkyl group having 10 to 10 (preferably a methyl group or an ethyl group) or an aralkyl group having 7 to 20, preferably 7 to 13 carbon atoms, which may be the same or different from each other. X ⁻ represents a counter anion, specifically, a halogen ion, SCN ⁻ , ClO _{4
^{-, BF 4 -, (CF}} 3 SO 2) 2 N -, (C 2 F 5 SO 2)
₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H
₄ ) SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , F (HF) _2.3 ^{− and the} like are shown. )

[0025]

[Chemical 4]

(Here, R1, R2, R3, and R4 are each an alkyl group having 1 or more carbon atoms, preferably 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms (phenyl group, etc.),
Alternatively, they represent a methoxymethyl group or the like, which may be the same or different. X ⁻ represents a counter anion, and specifically, a halogen ion, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ ,
(CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ ,
_{^{AsF 6 -, CH 3 COO -}} , CH 3 (C 6 H 4) SO 3 -,
(C ₂ F ₅ SO ₂ ) ₃ C ⁻ , F (HF) _2.3 ^−, etc. are shown. )

The amount of the room temperature molten salt used is not particularly limited,
Usually, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass in the ion conductive sheet. It can be contained in the following amounts.

The ion conductive sheet of the present invention may further contain other components. As another component that can be contained, an ultraviolet absorber can be mentioned. The ultraviolet absorber that can be used is not particularly limited, but representative examples thereof include organic ultraviolet absorbers such as compounds having a benzotriazole skeleton and compounds having a benzophenone skeleton.

Preferred examples of the compound having a benzotriazole skeleton include compounds represented by the following general formula (1).

[0030]

[Chemical 5]

In the general formula (1), R ⁸¹ is a hydrogen atom, a halogen atom or a carbon number of 1 to 10, preferably 1
The alkyl groups of ~ 6 are shown. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group and a cyclohexyl group. The substitution position of R ⁸¹ is the 4-position or 5-position of the benzotriazole skeleton, but the halogen atom and the alkyl group are usually located at the 4-position. R ⁸² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group and a cyclohexyl group. R ⁸³ represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, or an alkylidene group.
Examples of the alkylene group include a methylene group, ethylene group, trimethylene group, propylene group, and the like, and examples of the alkylidene group include an ethylidene group, propylidene group, and the like.

Specific examples of the compound represented by the general formula (1) include 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-.
Hydroxy-benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzeneethanoic acid, 3- (2
H-benzotriazol-2-yl) -4-hydroxybenzeneethanoic acid, 3- (5-methyl-2H-benzotriazol-2-yl) -5- (1-methylethyl)-
4-hydroxybenzenepropanoic acid, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-bis (α, α-
Dimethylbenzyl) phenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole , 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester and the like.

Suitable examples of the compound having a benzophenone skeleton include compounds represented by the following general formulas (2) to (4).

[0034]

[Chemical 6]

In the above general formulas (2) to (4),
R⁹², R⁹³, R⁹⁵, R⁹⁶, R⁹⁸, And R ⁹⁹Are the same as each other
One or different groups, hydroxyl group, carbon number
1-10, preferably 1-6 alkyl or alkone
A xy group is shown. As the alkyl group, for example, methyl
Group, ethyl group, propyl group, i-propyl group, butyl
Group, t-butyl group, and cyclohexyl group
You can Further, as the alkoxy group, for example, methoxy group
Si group, ethoxy group, propoxy group, i-propoxy group,
And a butoxy group can be mentioned. R⁹¹, R⁹⁴, And
And R⁹⁷Is an alkyl having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
A len group or an alkylidene group is shown. As an alkylene group
For example, methylene group, ethylene group, trimethylene
And a propylene group. Archi
Examples of the den group include an ethylidene group and propyl group.
Examples thereof include a den group. p1, p2, p3, q1, q2,
And q3 each independently represent an integer of 0 to 3.

Preferred examples of the compounds having a benzophenone skeleton represented by the above general formulas (2) to (4) include:
2-hydroxy-4-methoxybenzophenone-5-carboxylic acid, 2,2'-dihydroxy-4-methoxybenzophenone-5-carboxylic acid, 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 2
-Hydroxy-4-methoxy-2'-carboxybenzophenone and the like can be mentioned. Of course, two or more of these may be used in combination.

The use of the ultraviolet absorber is optional, and the amount used is not particularly limited, but
When used, it is 0.1% by mass or more, preferably 1% by mass or more and 20% by mass or less in the ion conductive sheet,
Preferably, it is desirable to contain it in an amount in the range of 10% by mass or less.

Next, a method for producing the ion conductive sheet of the present invention will be described. The ion-conductive sheet of the present invention is formed into a sheet by a known method by mixing the above-mentioned ion-conductive substance and, if desired, an optional component such as an ultraviolet absorber in a polymer matrix component. It can be obtained. The molding method in this case is not particularly limited, and examples thereof include a method of obtaining in a film state by extrusion molding or a casting method. The extrusion molding can be carried out by a conventional method, and a polymer matrix and an electrolytic solution are mixed, melted by heating, and then film-molded. Regarding the casting method, it is possible to form a film by mixing a polymer matrix and an electrolytic solution, adjusting the viscosity with an appropriate diluent, coating with a usual coater used in the casting method, and drying. . As the coater, a doctor coater, a blade coater, a rod coater, a knife coater, a reverse roll coater, a gravure coater, a spray coater, or a curtain coater can be used, and the coater can be selected depending on the viscosity and the film thickness.

The ion conductive sheet of the present invention is
On-conductivity is usually 1 x 10 at room temperature ^-7Greater than S / cm
1x10 is better^-6S / cm or more, more preferably 1
× 10^-FiveIndicates S / cm or more. Ionic conductivity is complex
Can be obtained by a general method such as the impedance method.
It The thickness of the ion conductive sheet depends on the electrochromic
It is appropriately selected according to the application of the device and is not particularly limited
However, the lower limit is usually 1 μm or more, preferably 10 μm.
m or more, and the upper limit is usually 3 mm or less, preferably
Is 1 mm or less.

Further, the ion conductive sheet of the present invention preferably has self-supporting property. In that case, usually 2
Its tensile modulus at 5 ° C. is 5 × 10 ⁴ N / m ² or more,
Preferably 1 × 10 ⁵ N / m ² or more, most preferably 5 ×
It is desirable to have a characteristic of 10 ⁵ N / m ² or more.
In addition, this tensile elastic modulus is a value when measured with a normally used tensile tester using a rectangular sample of 2 cm × 5 cm.

Next, the transparent conductive substrate will be described.
A transparent conductive substrate is usually manufactured by laminating a transparent electrode layer on a transparent substrate. The transparent substrate is not particularly limited, and the material, thickness, size, shape and the like can be appropriately selected according to the purpose, and for example, colorless or colored glass, reticulated glass, glass block, etc. are used, and colorless. Alternatively, a colored transparent resin may be used. In particular,
Polyester such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide,
Examples include polycarbonate, polyimide, polymethylmethacrylate, polystyrene, cellulose triacetate, and polymethylpentene. The term "transparent" in the present invention means to have a transmittance of 10 to 100%, and the substrate in the present invention has a smooth surface at room temperature, and the surface is a flat surface or a curved surface. Alternatively, it may be deformed by stress.

The transparent conductive film forming the conductive layer of the electrode is not particularly limited as long as it achieves the object of the present invention. For example, a metal thin film of gold, silver, chromium, copper, tungsten, etc., a metal oxide. Examples thereof include a conductive film made of a material. Examples of metal oxides include tin oxide, zinc oxide, zinc oxide, and Indi
um Tin Oxide (ITO (In ₂ O ₃ : Sn)), Fluorine
doped Tin Oxide (FTO (SnO ₂ : F)), Aluminu
M doped Zinc Oxide (AZO (ZnO: Al)) or the like is preferably used. The film thickness is usually 100-5
The thickness is 000 μm, preferably 500 to 3000 μm.
The surface resistance (resistivity) is appropriately selected depending on the application of the substrate of the present invention, but is usually 0.5 to 50.
It is 0 Ω / sq, preferably 2 to 50 Ω / sq.

The method of forming the transparent electrode film is not particularly limited, and a known method is appropriately selected and used depending on the kind of the above-mentioned metal or metal oxide used as the conductive layer. Usually, a vacuum vapor deposition method, Ion plating method, C
The VD or sputtering method is used. In either case, it is desirable that the substrate temperature be formed within the range of 20 to 700 ° C.

In the electrochromic device of the present invention, at least one of the conductive substrates has an electrochromic layer. The material forming the electrochromic layer in the present invention may be any of an oxidation coloring type electrochromic compound and a reduction coloring type electrochromic compound, and examples thereof include inorganic compounds of metal oxides and various organic electrochromic compounds. However, it is not particularly limited. Specific examples thereof include transition metal oxides such as tungsten oxide, vanadium oxide, molybdenum oxide, iridium oxide, and titanium oxide, and oxide films containing these at an arbitrary ratio. As the film forming method, a wet method such as a sol-gel method or an electrochemical method, a vapor deposition method, a sputtering method, an ion plating method, or a vacuum film forming method such as pulse laser deposition can be used. As the organic electrochromic compound, polythiophene, oligothiophene, polypyrrole, polyphenylene vinylene, polyphenylene, polyaniline, viologen, metal phthalocyanine, pyrazoline, phenylenediamine, phenazine, phenoxazine, phenothiazine, tetrathiafulvalene and ferrocene, or these Polymers containing electrochromic compounds such as derivatives of Of course, two or more kinds of these compounds may be used in combination, and the film forming method may be a known method.

The thickness of the electrochromic layer in the present invention is appropriately selected depending on the kind of the electrochromic compound and other element structure, but is usually 0.2 μm to 2 μm, preferably 0.3 μm to 0.6.
About μm is desirable.

In the electrochromic device of the present invention, at least one of the transparent conductive substrates has an electrochromic layer. The conductive substrate facing the conductive substrate having the electrochromic layer is (a). In addition to a mode using a conductive substrate, (b) a mode using a conductive substrate having another electrochromic layer, (c) a member in which conductive fine particles are bound by a binder on the conductive surface of the conductive substrate is a counter electrode. As a whole substrate, there may be mentioned a form in which it is arranged to such an extent that the light transmissivity (or light reflectivity) required for the whole counter electrode is not impaired. Regarding the form (c) above, for example, Japanese Patent Laid-Open No.
-281970, JP-A-10-239716 and the like.

In the case where the electrochromic layers are arranged on both of the transparent conductive substrates, when one electrochromic layer is an oxidizing electrochromic layer, the other one is a reducing electrochromic layer and the other electrochromic layer is an electrochromic layer. When the chromic layer is a reducing electrochromic layer, it is preferable to use an oxidizing electrochromic layer on the other side.

In the electrochromic device of the present invention, it is preferable that a member in which conductive fine particles are bound with a binder is arranged on the conductive surface of the conductive substrate facing the conductive substrate having the electrochromic layer.

The conductive fine particles are usually 10 ⁻⁸ S · c.
It is desirable that the substance has a conductivity of m ⁻¹ or more, preferably 10 ⁻⁵ S · cm ⁻¹ or more, more preferably 10 ⁻² S · cm ⁻¹ or more. In addition, these conductive fine particles are usually 1 farad / g or more, preferably 5 farad / g.
It has an electric capacity of g or more, more preferably 10 farad / g or more, or can store a charge amount of 1 clone / g or more, preferably 5 coulomb / g or more, more preferably 10 clones / g or more. Things are desirable. As the material substance that constitutes such fine particles,
Specific examples include porous carbon, intercalation materials, conductive polymer compounds, and mixtures thereof.

The conductive fine particles having an electric capacity of 1 farad / g or more of the present invention have, for example, a surface area of 10 m.
² / g or more, preferably 50 to 5000 m ² / g, and particularly preferably 300 to 4000 m ² / g in the range of porous carbon and the like can be mentioned, and activated carbon and the like can be mentioned particularly, but not limited thereto. Not a thing. Such activated carbon can be obtained by, for example, a method of activating carbonization of coconut husk, petroleum pitch, phenol resin, rayon fiber, polyacrylonitrile fiber and the like.

Examples of the conductive fine particles capable of storing a charge amount of 1 clone / g or more according to the present invention include intercalation materials and conductive polymer compounds. Particularly, the charge amount can be stored within an applied voltage of 3 V. Materials that can be obtained are preferred. Examples of the intercalation material include known disulfides such as TiS ₂ and MoS ₂ ; dioxides such as CoO ₂ and NiO ₂ ; oxides such as W ₁₈ O ₄₉ and W ₂₀ O _58. it can. On the other hand, as the conductive polymer compound,
Examples of the conductive polymer compound include polyalinine, polythiophene, polypyrrole, polyphenylene vinylene, polyacene, etc. as a main component, and are obtained by doping or the like.

The particle size of the fine particles is not particularly limited as long as the object of the present invention is not impaired, but is usually 500 μm.
The average particle size is preferably in the range of 0.1 μm, preferably 200 μm to 0.3 μm, and more preferably 50 μm to 0.5 μm.

As an example of the electrochromic element of the present invention, an electrochromic element having a cross section shown in FIG. 1 can be preferably mentioned. This device includes a substrate A having a transparent conductive film 32 on a transparent substrate 31 and an electrochromic layer 33 formed on the transparent conductive film 32, and a transparent conductive film 42 and a transparent conductive film 42 on a transparent substrate 41 as a counter electrode substrate. It has a substrate B having an electrochromic layer 43 formed on a transparent conductive film 42. The gap between the two is filled with the ion conductive sheet 51,
The periphery is sealed with the sealing material 61, and the transparent conductive film (32, 4
2) is connected to the power supply by a lead wire. The method for manufacturing the electrochromic device of the present invention is not particularly limited, but usually, it can be easily manufactured by stacking the substrate A, the ion conductive sheet, and the substrate B, and appropriately sealing the peripheral portion.

[0054]

The electrochromic device of the present invention is
It has excellent properties such as improved adhesion between the ion conductive sheet and the electrode and high ionic conductivity, mechanical strength, and stability over time. Further, the electrochromic element of the present invention does not necessarily need a spacer member such as beads in the ion conductive layer, and the ion conductive layer can be easily manufactured since it is in a sheet form. Excellent appearance characteristics. The electrochromic device of the present invention can be applied to various uses, and can be applied to, for example, a light control device such as a window, a partition, a lighting device, various display devices, and the like.

[0055]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 Polyvinylidene fluoride 2 g and 1
5 g of a propylene carbonate solution of mol / L LiClO ₄ was added, diluted with acetone and heated to obtain a uniform solution. This film was applied onto a tetrafluoroethylene substrate by the doctor blade method and dried by heating to obtain a uniform ion conductive sheet having a thickness of 50 μm. Sheet resistance value 10
Ω / sq 30 cm square ITO glass (I on the glass substrate
Two pieces of transparent conductive glass having a TO film formed thereon are used, and WO ₃ and Ir are sputtered onto the ITO film of each substrate.
O ₂ was deposited to form a WO ₃ substrate and an IrO ₂ substrate. The ion conductive sheet cut into a 25 cm square was sandwiched between a WO ₃ substrate and an IrO ₂ substrate, and pressure-bonded in an oven at 80 ° C. for 10 minutes. The lead wire was taken out from the opposing substrate, and the periphery of the cell was sealed by applying and curing an epoxy adhesive (trade name "Hi-Quick": Cemedine Co., Ltd.) at room temperature to produce an electrochromic device. Next, a voltage of 1.5 V was applied between the substrates so that the WO ₃ side was the negative electrode, and the coloration was prompt. On the other hand, when 1.5 V was applied so that the WO ₃ side became the positive electrode, the initial colorless and transparent state was restored, and electrochromic characteristics with good repeatability were exhibited. In the conventional method, the electrolytic solution is vacuum-injected into the cell in which the beads are arranged to hold the electrode substrate at uniform intervals, the injection port is sealed, and then the electrolytic solution is cured by light, heat, etc. Although the element was produced, in the method of the present invention, the ion conductive sheet is used, and since the element itself has a bead-like function, it is possible to prevent light refraction and the like caused by beads in the conventional method. There was no problem and it had a good appearance.

[Example 2] 2 mol of poly (vinylidene fluoride-hexafluoropropylene) was added with 1 mol / L of LiBF.
5 g of the propylene carbonate solution of ₄ was added, diluted with acetone and heated to obtain a uniform solution. This film was applied onto a tetrafluoroethylene substrate by the doctor blade method and dried by heating to obtain a uniform ion conductive sheet having a thickness of 50 μm. 30 cm square I with sheet resistance of 10 Ω / sq
Two pieces of TO glass were used, and WO ₃ and IrO ₂ were deposited on the ITO film of each glass substrate by a sputtering method to prepare a WO ₃ substrate and an IrO ₂ substrate. The ion conductive sheet cut into a 25 cm square was sandwiched between a WO ₃ substrate and an IrO ₂ substrate, and pressure-bonded in an oven at 80 ° C. for 10 minutes. A lead wire was taken out from the opposing substrate and the periphery of the cell was sealed in the same manner as in Example 1 to manufacture an electrochromic device. Next, a voltage of 1.5 V is applied to WO ₃
When it was applied between the substrates so that the side became the negative electrode, it rapidly colored. On the other hand, when 1.5 V was applied so that the WO ₃ side became the positive electrode, the initial colorless and transparent state was restored, and electrochromic characteristics with good repeatability were exhibited.

Example 3 Preparation of Counter Electrode Substrate Activated carbon powder (trade name “YP17”, manufactured by Kuraray Co., Ltd., surface area 1500 m ² / g, average particle size 30 μm) 8 g, graphite ((trade name “USSP”, Japan Graphite Trading Company) 4
24 g of butyl cellosolve was added to 34.3 g of silicone resin (trade name "RZ7703", manufactured by Nippon Unicar Co., Ltd.) to prepare an activated carbon paste. Next, using a screen in which stripe members having a stripe width of 300 μm and a height of 120 μm are arranged at equal intervals so that 15% of the total area is used, the IT of ITO glass of 30 cm square of 10 Ω / sq is used.
The activated carbon paste was printed as a stripe member on the O film and then heat-cured at 180 ° C. for 90 minutes to prepare a counter electrode substrate. Film formation of ion conductive sheet Poly (vinylidene fluoride-hexafluoropropylene) 2
5 g of 1 mol / L propylene carbonate solution of LiBF ₄ was added to g, diluted with acetone and heated to obtain a uniform solution. This film was coated on a tetrafluoroethylene substrate by the doctor blade method, and dried by heating to 250
A uniform ion conductive sheet having a thickness of μm was obtained. The WO ₃ substrate prepared in the same manner as in Example 1 and the counter electrode substrate were sandwiched with the above ion-conductive sheet cut into a 25 cm square, and pressure-bonded in an oven at 150 ° C. for 30 minutes. A lead wire was taken out from the opposing substrate and the periphery of the cell was sealed in the same manner as in Example 1 to manufacture an electrochromic device. Next, a voltage of 1.5 V was applied between the substrates so that the WO ₃ side was the negative electrode, and the coloration was prompt. on the other hand,
When 1.5 V was applied so that the WO ₃ side became the positive electrode, the initial colorless and transparent state was restored, and electrochromic characteristics with good repeatability were exhibited.

Comparative Example 1 Preparation of Electrochromic Element Two pieces of 30 cm square ITO glass having a sheet resistance value of 10 Ω / sq were used, and WO ₃ and IrO ₂ were formed on the ITO film of the glass substrate by the sputtering method. , WO ₃ substrate and IrO ₂ substrate were prepared. The WO ₃ substrate and the IrO ₂ substrate were made to face each other using beads having a particle size of 0.3 mm so that the substrate spacing was uniform, and the periphery was made of epoxy resin (the same as in Example 1) except for the injection port. After sealing with a width of 5 mm and injecting a propylene carbonate solution of LiClO ₄ (1 M / liter) as an electrolytic solution, the injection port was sealed with an epoxy resin (the same as in Example 1). Then, a lead wire was attached to each of the substrates to manufacture an electrochromic device. When a voltage of 1.5 V was applied between the substrates so that the WO ₃ side became the negative electrode, the product was rapidly colored. Meanwhile, 1 as WO ₃ side is a positive electrode.
When 5 V was applied, it returned to the initial colorless and transparent state, and exhibited electrochromic characteristics with good repeatability. However, when a white light source was placed on the background of this device and the bleaching surface was observed especially in the decolored state, spot-like defects derived from beads were observed.

[Brief description of drawings]

FIG. 1 is an example showing a cross section of an electrochromic device.

[Explanation of symbols]

31,41 Transparent substrate 32, 42 transparent conductive film 33,43 Electrochromic layer 51 Ion conductive sheet 61 Seal material

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 28, 2001 (2001.6.2)
8)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Example 1 Polyvinylidene fluoride 2 g and 1
5 g of a propylene carbonate solution of mol / L LiClO ₄ was added, diluted with acetone and heated to obtain a uniform solution. The film was coated by a doctor blade method to polytetrafluoroethylene substrate was heated and dried, 50.mu.
A uniform m-thick ion conductive sheet was obtained. Two pieces of 30 cm square ITO glass (transparent conductive glass having an ITO film formed on a glass substrate) with a sheet resistance value of 10 Ω / sq were used.
WO ₃ and IrO ₂ were deposited on the ITO film of each substrate by a sputtering method to prepare a WO ₃ substrate and an IrO ₂ substrate. The ion conductive sheet cut into a 25 cm square was sandwiched between a WO ₃ substrate and an IrO ₂ substrate, and pressure-bonded in an oven at 80 ° C. for 10 minutes. The lead wire was taken out from the opposing substrate, and the periphery of the cell was sealed by applying and curing an epoxy adhesive (trade name "Hi-Quick": Cemedine Co., Ltd.) at room temperature to produce an electrochromic device. Next, a voltage of 1.5 V was applied between the substrates so that the WO ₃ side was the negative electrode, and the coloration was prompt. On the other hand, when 1.5 V was applied so that the WO ₃ side became the positive electrode, the initial colorless and transparent state was restored, and electrochromic characteristics with good repeatability were exhibited. In the conventional method, the electrolytic solution is vacuum-injected into the cell in which the beads are arranged to hold the electrode substrate at uniform intervals, the injection port is sealed, and then the electrolytic solution is cured by light, heat, etc. Although the element was produced, in the method of the present invention, the ion conductive sheet is used, and since the element itself has a bead-like function, it is possible to prevent light refraction and the like caused by beads in the conventional method. There was no problem and it had a good appearance.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

[Example 2] 2 mol of poly (vinylidene fluoride-hexafluoropropylene) was added with 1 mol / L of LiBF.
5 g of the propylene carbonate solution of ₄ was added, diluted with acetone and heated to obtain a uniform solution. Po this film
It was applied on a lithofluoroethylene substrate by the doctor blade method and dried by heating to obtain a uniform ion conductive sheet having a thickness of 50 μm. Sheet resistance value 10Ω / sq 30cm
WO ₃ and IrO ₂ were deposited on the ITO film of each glass substrate by a sputtering method using two pieces of square ITO glass to prepare a WO ₃ substrate and an IrO ₂ substrate. The ion conductive sheet cut into a 25 cm square was sandwiched between a WO ₃ substrate and an IrO ₂ substrate, and pressure-bonded in an oven at 80 ° C. for 10 minutes. Take out the lead wires from the facing substrate,
The periphery of the cell was sealed in the same manner as in Example 1 to produce an electrochromic device. Next, apply a voltage of 1.5 V to WO
_{When the} voltage was applied between the substrates so that the negative electrode was on the ₃ side, it was rapidly colored. On the other hand, 1.5 V so that the WO ₃ side becomes the positive electrode
When applied, it returned to the initial colorless and transparent state, and exhibited electrochromic characteristics with good repeatability.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

Example 3 Preparation of Counter Electrode Substrate Activated carbon powder (trade name “YP17”, manufactured by Kuraray Co., Ltd., surface area 1500 m ² / g, average particle size 30 μm) 8 g, graphite ((trade name “USSP”, Japan Graphite Trading Company) 4
24 g of butyl cellosolve was added to 34.3 g of silicone resin (trade name "RZ7703", manufactured by Nippon Unicar Co., Ltd.) to prepare an activated carbon paste. Next, using a screen in which stripe members having a stripe width of 300 μm and a height of 120 μm are arranged at equal intervals so that 15% of the total area is used, the IT of ITO glass of 30 cm square of 10 Ω / sq is used.
The activated carbon paste was printed as a stripe member on the O film and then heat-cured at 180 ° C. for 90 minutes to prepare a counter electrode substrate. Film formation of ion conductive sheet Poly (vinylidene fluoride-hexafluoropropylene) 2
5 g of 1 mol / L propylene carbonate solution of LiBF ₄ was added to g, diluted with acetone and heated to obtain a uniform solution. The film was coated by a doctor blade method to polytetrafluoroethylene substrate was heated and dried, 2
A uniform ion conductive sheet having a thickness of 50 μm was obtained. The WO ₃ substrate prepared in the same manner as in Example 1 and the counter electrode substrate were sandwiched with the above ion-conductive sheet cut into a 25 cm square, and pressure-bonded in an oven at 150 ° C. for 30 minutes.
A lead wire was taken out from the opposing substrate and the periphery of the cell was sealed in the same manner as in Example 1 to manufacture an electrochromic device. Next, a voltage of 1.5 V was applied between the substrates so that the WO ₃ side was the negative electrode, and the coloration was prompt. On the other hand, when 1.5 V was applied so that the WO ₃ side became the positive electrode, the initial colorless and transparent state was restored, and electrochromic characteristics with good repeatability were exhibited.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor, Sadan Nishikiya             Mitsuru Hishi, 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa             Ryo Corporation Central Technology Research Institute F-term (reference) 2K001 AA01 AA06 BB30 CA08 CA37                       DA19

Claims (2)

[Claims] 1. An electrochromic device in which an ion conductive layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer, and the ion conductive layer is a polyfluoride layer. A vinylidene chloride-based polymer matrix containing at least one or more ion-conductive substances selected from (a) supporting electrolyte and solvent, (b) room temperature molten salt, and (c) room temperature molten salt and solvent. An electrochromic device, which is an ion conductive sheet. 2. The electrochromic device according to claim 1, wherein a member in which conductive fine particles are bound with a binder is arranged on the conductive surface of one conductive substrate.