JPH11183939A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrochromic element having a variable color tone from a low-cost color producing reagent and through easy steps by disposing an electrochromic layer contg. a specified compd. between a specified ion conductive material layer and at least one of electrically conductive substrates. SOLUTION: An ion conductive material layer contg. a compd. having a viologen structure represented by formula II is disposed between two electrically conductive substrates including at least one transparent substrate and an electrochromic layer contg. a compd. represented by formula I is disposed between the ion conductive material layer and at least one of the electrically conductive substrates. In the formula I, each of R<1> -R<5> is H or a 1-20C hydrocarbon residue, each of Ar<1> and Ar<2> is a divalent arom. hydrocarbon residue, (1) is an integer of 0-3, (m) is an integer of 1 or 2 and (n) is an integer of >=2. In the formula II, each of X and Y is a counter anion such as a halogen anion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dimming window for vehicles such as buildings, automobiles and passenger vehicles, or as a dimming glass used for decoration and partitioning indoors, and as a display element. Also, the present invention relates to an electrochromic element that can be used as an anti-glare mirror for vehicles such as automobiles.

[0002]

2. Description of the Related Art A conventional electrochromic device used for a light control glass is, for example, a method in which an inorganic oxide such as tungsten oxide (WO ₃ ) is vacuum-deposited on a transparent conductive film. Alternatively, a film formed by a sputtering method and using this as a color former is known (Japanese Patent Application Laid-Open No. 63-18336). However, since these film forming means must be performed in a vacuum, the implementation is costly and requires a large area EC.
In order to obtain the element, a large vacuum device is required. In addition, since the substrate temperature is high in the sputtering method, when using a substrate other than glass, for example, a substrate made of synthetic resin, certain conditions must be selected, and it is difficult to reduce the weight of the electrochromic element. . Further, when tungsten oxide is used, there is a problem that only a blue color is obtained. Therefore, the present invention has been made in view of such a situation, its purpose is to be able to be manufactured by an inexpensive color former and simple steps, and
An object of the present invention is to provide an electrochromic device having a variable color tone.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above problems by using a specific conductive polymer compound as a color-forming layer and causing an electrochromic compound to be present in an ion-conductive substance layer to form a color. It is a solution.
That is, in the electrochromic device of the present invention, an ion conductive material layer containing a compound having a viologen structure represented by the following general formula (2) is provided between two conductive substrates at least one of which is transparent. An electrochromic layer containing a compound represented by the following general formula (1) is provided on at least one of the ion conductive material layer and the conductive substrate.

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, and may be the same or different; Ar ¹ and Ar ² Each independently represents a divalent aromatic hydrocarbon residue;
M is an integer of 1 to 2, and n is an integer of 2 or more. )

Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anions, ClO ₄ ⁻ , BF ₄ ⁻ ,
A counter anion selected from PF ₆ ⁻ , CH ₃ COO ⁻ , and CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ is shown. )

[0004]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. In the present invention, at least one transparent substrate is used, and two conductive substrates are used. Here, the conductive substrate means a substrate that functions as an electrode. Therefore,
The conductive substrate referred to in the present invention includes a substrate in which the substrate itself is formed of a conductive material, and a laminate in which an electrode layer is laminated on at least one surface of a substrate having no conductivity. Regardless of whether or not it has conductivity, it is necessary that the substrate itself has a smooth surface at room temperature, but the surface may be flat or curved. May be deformed. At least one of the conductive substrates used in the present invention may be a transparent conductive substrate, and the other may be transparent, opaque, or a reflective conductive substrate capable of reflecting light. The two conductive substrates each having a transparent conductive substrate are suitable for a display element or light control glass, and the one having a transparent conductive substrate and the other having an opaque conductive substrate is a display element. It is suitable, and one having a transparent conductive substrate and another being a reflective conductive substrate is suitable for an electrochromic mirror. The transparent conductive substrate usually has a form in which a transparent electrode layer is laminated on a transparent substrate. Here, "transparent" means having a light transmittance of 10 to 100% in a visible light region. Further, as the opaque conductive substrate, (1) a metal plate, (2) an opaque substrate having no conductivity (a variety of non-transparent plastics, glass, wood, stone, etc. can be used)
And a laminated body in which an electrode layer is laminated on one surface. Examples of the reflective conductive substrate include (1) a laminate in which a reflective electrode layer is laminated on a transparent or opaque substrate having no conductivity; and (2) a transparent electrode on one surface of the transparent substrate having no conductivity. Layer, a laminate in which a reflective layer is laminated on the other surface,
(3) a laminate in which a reflective layer is laminated on a transparent substrate having no conductivity, and a transparent electrode layer is laminated on the reflective layer; and (4) a laminate in which a reflective plate is used as a substrate and a transparent electrode layer is laminated thereon. And (5) a plate-like body in which the substrate itself has both functions of a light reflection layer and an electrode layer. The transparent substrate is not particularly limited. For example, a colorless or colored glass, a tempered glass, or the like, or a colorless or colored transparent resin is used. Specifically, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide,
Examples include polycarbonate, polyimide, polymethyl methacrylate, and polystyrene. The substrate in the present invention has a smooth surface at room temperature.
The transparent electrode layer is not particularly limited as long as the object of the present invention is achieved, and examples thereof include a metal thin film such as gold, silver, chromium, copper, and tungsten, and a conductive film made of a metal oxide. As the metal oxide,
For example, ITO (In ₂ O ₃ —SnO ₂ ), tin oxide, silver oxide, zinc oxide, vanadium oxide, and the like can be given. The thickness of the electrode is usually in the range of 100 to 5,000 angstroms, preferably 500 to 3,000 angstroms. The surface resistance (resistivity) is usually 0.5 to
500Ω / cm ^2, preferably is preferably in the range of 1~50Ω / cm ^2. The method for forming the electrode is not particularly limited, and a known method can be appropriately selected depending on the types of the metal, metal oxide, and the like constituting the electrode. Usually, a vacuum evaporation method, an ion plating method, a sputtering method, a sol-gel method, or the like is employed. At this time, the film thickness is, of course, selected within a range that does not impair the transparency of the electrode surface. In addition, a partially opaque electrode active material can be applied to the transparent electrode for the purpose of imparting oxidation-reduction ability, imparting conductivity, and imparting electric double layer capacitance. At this time, the applied amount is, of course, selected within a range that does not impair the transparency of the entire electrode surface. As the opaque electrode active material, for example, metals such as copper, silver, gold, platinum, iron, tungsten, titanium, lithium, polyaniline, polythiophene, polypyrrole, organic substances having a redox ability such as phthalocyanine, activated carbon, graphite, etc. Carbon materials, metal oxides such as V ₂ O ₅ , MnO ₂ , NiO, and Ir ₂ O ₃ or mixtures thereof can be used. Further, in order to bind them to the electrodes, various resins may be used. In order to apply the opaque electrode active material or the like to the electrode, for example, a composition comprising activated carbon fiber, graphite, acrylic resin, or the like is formed on the ITO transparent electrode in a fine pattern such as a stripe or a dot. A composition comprising V ₂ O ₅ , acetylene black, butyl rubber, or the like can be formed in a mesh shape on a thin film of gold (Au). The reflective electrode layer of the present invention means a thin film having a mirror surface and exhibiting an electrochemically stable function as an electrode. Examples of such a thin film include gold, platinum, tungsten, tantalum, and rhenium. And metal films of osmium, iridium, silver, nickel, palladium and the like, and alloy films of platinum-palladium, platinum-rhodium and stainless steel. An arbitrary method can be used for forming such a thin film having a mirror surface. For example, a vacuum evaporation method, an ion plating method, a sputtering method, or the like can be appropriately used. The substrate on which the reflective electrode layer is provided may be transparent or opaque. Therefore, as the substrate on which the reflective electrode layer is provided, various non-transparent plastics, glass, wood, stone, and the like can be used in addition to the transparent substrate exemplified above. The reflection plate or the reflection layer referred to in the present invention means a substrate or a thin film having a mirror surface, for example, a plate-like body of silver, chromium, aluminum, stainless steel or the like, or a thin film thereof. Examples of the plate-like body in which the substrate itself has both the reflective layer and the electrode function include those having self-supporting properties among those exemplified as the reflective electrode layers.

The ion-conductive substance used in the electrochromic device of the present invention contains a compound having the structure represented by the general formula (2) as described above, and contains a conductive substrate (hereinafter referred to as a counter conductive substrate). It is provided between. The formation method is not particularly limited, and a method of injecting into a gap provided between conductive substrates sealed by a vacuum injection method, an air injection method, a meniscus method, or the like, a sputtering method, an evaporation method, a sol-gel method, or the like is used. After a layer of an ion conductive substance is formed on an electrode, a method of combining an opposing conductive substrate, a method of glass-forming using a film-shaped ion conductive substance, or the like can be used. The ion-conductive substance is not particularly limited as long as it can color, decolor, and change the color of an electrochromic layer described later, but is usually 1 × 10 ⁻⁷ S / cm at room temperature.
A substance that exhibits the above-described ionic conductivity is preferable.
The ion conductive substance is not particularly limited, and a liquid ion conductive substance, a gelled liquid ion conductive substance, a solid ion conductive substance, or the like can be used. In the present invention, a solid ion conductive material is particularly desirable, whereby the electrochromic device of the present invention can be made into an all-solid-state electrochromic device having various practical performances. As the liquid-based ion conductive substance, a substance obtained by dissolving a supporting electrolyte such as a salt, an acid, or an alkali in a solvent can be used. The solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but a polar solvent is particularly preferable. Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propionnitrile, gluon Talonitrile,
Organic polar solvents such as adiponitrile, methoxyacetonitrile, dimethylacetamide, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol, and the like, preferably, propylene carbonate, ethylene carbonate, dimethylsulfoxide, dimethoxyethane, acetonitrile, Organic polar solvents such as γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, and polyethylene glycol are preferred. These can be used alone or as a mixture when used. The salt as the supporting electrolyte is not particularly limited, and examples thereof include inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts. Specifically, LiClO ₄ , LiSCN, LiBF
_{4, LiAsF 6, LiCF 3 SO} 3, LiPF 6, L
iI, NaI, NaSCN, NaClO ₄ , NaBF
₄ , Li, Na such as NaAsF ₆ , KSCN, KCl,
Alkali metal salt of K, (CH ₃ ) ₄ NBF ₄ , (C
_{2 H 5) 4 NBF 4,} (n-C 4 H 9) 4 NBF 4,
(C ₂ H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ ,
Suitable examples include quaternary ammonium salts such as (nC ₄ H ₉ ) ₄ NClO ₄ and cyclic quaternary ammonium salts, and mixtures thereof. The acids as the supporting electrolyte are not particularly limited, and include inorganic acids and organic acids. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids. Alkali as a supporting electrolyte is not particularly limited, sodium hydroxide,
Potassium hydroxide, lithium hydroxide and the like can be mentioned. As the gelled liquid-based ion-conductive substance, it is possible to use a viscous or gel-like substance obtained by adding a polymer or a gelling agent to the liquid-based ion-conductive substance. it can. The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, and Nafion. The gelling agent is not particularly limited and includes oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, agar, and the like. The solid ion-conductive substance is not particularly limited as long as it is solid at room temperature and has ionic conductivity, and polyethylene oxide, a polymer of oxyethylene methacrylate,
Nafion, polystyrene sulfonic acid, Li ₃ N, Na
-β-Al ₂ O ₃ , Sn (HPO ₄ ) ₂ .H ₂ O, and the like. A polymer solid electrolyte using a molecular compound or the like is preferable.

As a first example of the polymer solid electrolyte, a composite material containing a urethane acrylate represented by the following general formula (3), the organic polar solvent, and the supporting electrolyte (hereinafter abbreviated as composition A) ) Is obtained by solidifying the polymer solid electrolyte.

Embedded image (Wherein, R ⁶ and R ⁷ are the same or different groups and represent a group selected from general formulas (4) to (6). R ⁸
And R ⁹ are the same or different groups and have 1 to 1 carbon atoms.
20, preferably 2 to 12 divalent hydrocarbon residues.
Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof. N is 1
-100, preferably 1-50, more preferably 1
Shows an integer in the range of 20. )

Embedded image

Embedded image

Embedded image In the general formulas (4) to (6), R ^{10 to} R ¹² are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹³ represents a divalent to tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. As such organic residues, specifically, an alkyltolyl group,
And hydrocarbon residues such as an alkyltetralyl group and an alkylene group represented by the following general formula (7).

Embedded image In the general formula (7), R ¹⁴ represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and p represents an integer of 0 to 6. p is 2
In the above case, R ¹⁴ may be the same or different. In the above-mentioned hydrocarbon residue, a part of hydrogen atoms is substituted by an oxygen-containing hydrocarbon group such as an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms. Group. R ^{13 in the} general formulas (4) to (6)
Specifically, And the like. R ^{8 of the} general formula (3)
And the divalent hydrocarbon residue represented by R ⁹ includes a chain 2
Examples thereof include a divalent hydrocarbon group, an aromatic hydrocarbon residue, and an alicyclic hydrocarbon residue, and examples of the linear divalent hydrocarbon include an alkylene group represented by the general formula (7). Can be. In addition, examples of the aromatic hydrocarbon group and the alicyclic hydrocarbon group include hydrocarbon groups represented by the following general formulas (8) to (10).

Embedded image

Embedded image

Embedded image In the general formulas (8) to (10), R ¹⁵ and R ¹⁶ are the same or different groups, and include a phenylene group, a substituted phenylene group (such as an alkyl-substituted phenylene group), a cycloalkylene group, and a substituted cycloalkylene group ( Alkyl-substituted cycloalkylene group). R ^{17 to} R ²⁰ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q represents an integer of 1 to 5. Specific examples of R ⁸ and R ^{9 in} the general formula (3) can be exemplified by the following general formulas (11) to (17).

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image In the general formula (3), Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof, and the polyether unit, the polyester unit, the polycarbonate unit and the mixed unit thereof are represented by the following general formulas, respectively. Examples include units represented by formulas (a) to (d).

Embedded image

Embedded image

Embedded image

Embedded image In the general formulas (a) to (d), R ^{21 to} R ²⁶ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Shows 12 divalent hydrocarbon residues. In particular, R ²⁴ has 2 carbon atoms.
About 6 is preferable. As the above R ^{21 to} R ²⁶ , a linear or branched alkylene group or the like is preferable, and specifically,
R ²³ is preferably a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, or the like. Also, R ^{21 to} R ²²
And R ^{24 to} R ²⁶ are preferably an ethylene group, a propylene group or the like. Also, m is 2 to 300, preferably 10
Shows an integer of ~ 200. Further, r is an integer of 1 to 300, preferably 2 to 200, and s is 1 to 200, preferably 2
An integer of -100, t is 1-200, preferably 2-10
U represents an integer of 0 to 300, preferably 10 to 200. In the general formulas (a) to (d), each unit may be the same or a copolymer of different units. That is,
When a plurality of R ^{21 to} R ²⁶ are present, R ²¹ , R ²² , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ may be the same or different. Particularly preferred examples of the copolymer include copolymer units of ethylene oxide and propylene oxide. The above general formula (3)
The molecular weight of the urethane acrylate represented by
0 to 30,000, preferably 3,000 to 20,000
0 is desirable. The number of polymerization functional groups in one molecule of the urethane acrylate is preferably 2 to 6, more preferably 2
~ 4 is desirable. The urethane acrylate represented by the general formula (3) can be easily produced by a known method, and the production method is not particularly limited.

The amount of the organic polar solvent (organic non-aqueous solvent) is usually 100 parts by weight based on 100 parts by weight of urethane acrylate.
To 1200 parts by weight, preferably 200 to 900 parts by weight
Is the ratio of If the amount of the organic non-aqueous solvent is too small,
If the ionic conductivity is not sufficient and the amount of the organic non-aqueous solvent is too large, the mechanical strength may be reduced.
The supporting electrolyte is not particularly limited as long as the object of the present invention is not impaired, but preferred examples include those exemplified above. The amount of addition is 0.1 to the organic non-aqueous solvent.
It is 1 to 30% by weight, preferably 1 to 20% by weight. The composition A basically consists of the basic components consisting of the urethane acrylate, the organic non-aqueous solvent (organic polar solvent), and the supporting electrolyte, but does not impair the object of the present invention as an optional component of the composition. Other components can be added as needed, and such optional components include, for example, a crosslinking agent and a polymerization initiator (light or heat). The polymer solid electrolyte of the first example opposes by injecting the composition A containing the compound having the structure represented by the general formula (2) into a desired place by a known method as appropriate, and then solidifying. It can be sandwiched between conductive substrates.
The term “solidification” as used herein means that a polymerizable or crosslinkable component or the like hardens as polymerization (polycondensation) or crosslinking progresses, and the composition as a whole does not substantially flow at room temperature. In this case, it has a network-like basic structure.

As a second example of the polymer solid electrolyte, monofunctional acryloyl-modified polyalkylene oxide, polyfunctional acryloyl-modified polyalkylene oxide represented by the following general formula (18), the organic polar solvent, A composite material containing the above supporting electrolyte (hereinafter abbreviated as composition B)
Solid polymer electrolyte obtained by solidifying the polymer.

Embedded image Wherein R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is 1
Represents the above integer. In the general formula (18), R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰
Is hydrogen or an alkyl group having 1 to 5 carbon atoms, each of which is a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group. , N-pentyl group and the like, which may be the same or different, and in particular, R ²² is hydrogen, methyl group, R ²³ is hydrogen, methyl group, R ²⁴ is hydrogen, methyl group, R ²⁵ is hydrogen, methyl group And an ethyl group. Further, n in the general formula (18) is an integer of 1 or more, usually 1 ≦ n ≦ 100,
Preferably 2 ≦ n ≦ 50, more preferably 2 ≦ n ≦ 3
Indicates an integer in the range of 0. As the compound represented by the general formula (18), specifically, an oxyalkylene unit has 1 to 100, preferably 2 to 50, and more preferably 1 to 100.
Methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate having a range of
Examples thereof include methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate, and mixtures thereof. When n in the general formula (18) is 2 or more, oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other.
Methoxypoly (ethylene propylene) glycol methacrylate, ethoxy poly (ethylene propylene) glycol methacrylate having 0, preferably in the range of 1 to 20 and having oxypropylene units in the range of 1 to 50, preferably 1 to 20 , Methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate, or a mixture thereof. The polyfunctional acryloyl-modified polyalkylene oxide usable in the present invention includes a so-called bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (19) and a so-called trifunctional or higher polyfunctional alkylene oxide represented by the general formula (20). And functional acryloyl-modified polyalkylene oxide.

Embedded image (In the formula, R ³¹ , R ³² , R ³³ and R ³⁴ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 or more.)

Embedded image (Wherein R ³⁵ , R ³⁶ and R ³⁷ are each hydrogen or 1
An alkyl group having 5 to 5 carbon atoms, p represents an integer of 1 or more, q represents an integer of 2 to 4, and L represents a q-valent linking group. In the above general formula (19), R ³¹ , R ³² and R ³³ in the formula
And R ³⁴ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, Examples thereof include a t-butyl group and an n-pentyl group. In particular, R ³¹ is hydrogen, methyl, R ³² is hydrogen, methyl, R ³³
Is preferably a hydrogen or methyl group, and R ³⁴ is preferably a hydrogen or methyl group. Further, m in the general formula (19) represents an integer of 1 or more, usually 1 ≦ m ≦ 100, preferably 2 ≦ m ≦ 50, more preferably an integer in the range of 2 ≦ m ≦ 30. Is an oxyalkylene unit of 1 to 100, preferably 2 to 50, more preferably 1
Polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate having a range of ~ 20,
Examples thereof include polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. When m is 2 or more, the oxyalkylene unit may have a so-called copolymerized oxyalkylene unit different from each other. For example, 1 to 50, preferably 1
Having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20,
Examples thereof include poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, and a mixture thereof. R ³⁵ , R ³⁶ and R ³⁷ in the general formula (20) are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group and an i-
Propyl group, n-propyl group, n-butyl group, t-butyl group,
and an n-pentyl group. In particular, R ³⁰ , R ³¹ and R
³² is preferably hydrogen or a methyl group. Also, p in the formula is 1
Integer or more, usually 1 ≦ p ≦ 100, preferably 2 ≦ p ≦
50, more preferably an integer in the range of 2 ≦ p ≦ 30. q is the number of linkages of the linking group L, and 2 ≦ q ≦ 4
Indicates an integer. The linking group L usually has 1 to 3 carbon atoms.
0, preferably 1-20 divalent, trivalent or tetravalent hydrocarbon groups. Examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an arylalkylene group, an alkylarylene group, and a hydrocarbon group having these as a basic skeleton.Specifically, And the like. Further, as a trivalent hydrocarbon group,
Examples thereof include an alkyltolyl group, an aryltolyl group, an arylalkyltolyl group, an alkylaryltolyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Further, as a tetravalent hydrocarbon group,
Examples thereof include an alkyltetralyl group, an aryltetralyl group, an arylalkyltetralyl group, an alkylaryltetralyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Specific examples of such a compound include an oxyalkylene unit of 1 to 100, preferably 2 to 100.
Trimethylolpropane tri (polyethylene glycol methacrylate), trimethylol propane tri (polyethylene glycol methacrylate), trimethylol propane tri (polypropylene glycol acrylate), trimethylol propane tri (polypropylene glycol methacrylate) having a range of 50, more preferably 1 to 20 ), Tetramethylol methane tetra (polyethylene glycol acrylate), tetramethylol methane tetra (polyethylene glycol methacrylate), tetramethylol methane tetra (polypropylene glycol acrylate), tetramethylol methane tetra (polypropylene glycol methacrylate),
2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, 2,2-bis [4
-(Acryloxypolyisopropoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyisopropoxy) phenyl] propane, and mixtures thereof. When p is 2 or more, the oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other. For example, 1 to 50, preferably 1
Having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20,
Trimethylolpropane tri (poly (ethylene / propylene) glycol acrylate), trimethylolpropane tri (poly (ethylene / propylene) glycol methacrylate), tetramethylolmethanetetra (poly (ethylene / propylene) glycol acrylate),
Tetramethylolmethanetetra (poly (ethylene propylene) glycol methacrylate), or a mixture thereof, and the like. Of course, the general formula (1)
The bifunctional acryloyl-modified polyalkylene oxide represented by 9) may be used in combination with the trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (20). When the compound represented by the general formula (19) and the compound represented by the general formula (20) are used in combination, the weight ratio is usually 0.01 / 99.9 to 99.9 / 0.01, preferably 1/99. ~ 99/1, more preferably 20/8
The range of 0 to 80/20 is desirable. The weight ratio of the compound represented by the general formula (1) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / 0.00.
It is in the range of 1-1 / 1, preferably 1 / 0.05-1 / 0.5.

The mixing ratio of the above polar organic solvent is usually 5 to the weight sum of the compound represented by the general formula (18) and the polyfunctional acryloyl-modified polyalkylene oxide.
A range of 0 to 800% by weight, preferably 100 to 500% by weight is desirable. The mixing ratio of the supporting electrolyte is
It is usually in the range of 1 to 30% by weight, preferably 3 to 20% by weight, based on the weight of the compound represented by the general formula (18), the polyfunctional acryloyl-modified polyalkylene oxide and the polar organic solvent. In addition to the above components, the composition B may further contain other optional components, if necessary, as long as the present invention is not impaired. Examples of the optional component include, but are not particularly limited to, a photopolymerization initiator for photopolymerization and a thermal polymerization initiator for thermal polymerization. The amount of the polymerization initiator used in the present invention is usually 0.005 to 5% by weight, preferably 0 to 5% by weight based on the weight of the compound represented by the general formula (18) and the polyfunctional acryloyl-modified polyalkylene oxide. .01-3
% By weight. The polymer solid electrolyte of the second example opposes by injecting the composition B containing the compound having the structure represented by the general formula (2) into a desired place by a known method as appropriate and then solidifying. It can be sandwiched between conductive substrates. The solidification here means that a polymerizable or crosslinkable component, such as a monofunctional or polyfunctional acryloyl-modified polyalkylene oxide, is cured as polymerization (polycondensation) or crosslinking proceeds, and the composition as a whole is substantially cured at room temperature. Means that the fluid does not flow. In this case, the monofunctional or polyfunctional acryloyl-modified polyalkylene oxide usually has a network-like basic structure. In the present invention, ion conductive substances other than those described above can of course be used.

In the present invention, as described above, the compound having a viologen structure represented by the general formula (2) is contained in the ion conductive material layer.

Embedded image In the structure represented by the general formula (2), X ⁻ and Y ⁻ represent counter anions, which may be the same or different, and may be a halogen anion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , C
An anion selected from H ₃ COO ⁻ and CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ is shown. Examples of the halogen anion include F ⁻ , C
l ^-, Br ^-, I ^-, and the like. The compound having a viologen structure is not particularly limited as long as it exhibits electrochromic properties.A compound having the viologen structural unit itself or a unit containing the structure as a repeating unit, or a compound having a high terminal at the end of the viologen structure is used. Any of so-called high molecular compounds such as those having a molecular weight substituent, those in which a part of the molecular chain of the high molecular compound is substituted by the group having the viologen structure, and low molecular compounds having the above viologen structure may be used. Among the high molecular compounds, as for the compound having a unit containing the viologen structure as a repeating unit, a main chain high molecular compound having a viologen structure in a main chain, even in a side chain high molecular compound having a viologen structure as a side chain Either may be good The repeating unit of the main chain portion in the side chain type polymer compound is not particularly limited, for example, a hydrocarbon unit, an oxygen-containing hydrocarbon unit, a nitrogen-containing hydrocarbon unit, a polysiloxane unit, or a copolymer unit thereof. And the like. Specific examples of the compound having the structure represented by the general formula (2) include N, N′-diheptylbipyridinium dibromide, N, N′-diheptylbipyridinium dichloride, and N, N′-diheptylbipyridinium dibromide. Perchlorate, N, N'-diheptylbipyridinium ditetrafluoroborate, N, N'-diheptylbipyridinium dihexafluorophosphate, N, N'-dihexylbipyridinium dibromide, N, N'-dihexylbipyridinium dichloride, N′-dihexylbipyridinium diperchlorate, N, N′-dihexylbipyridinium ditetrafluoroborate, N, N′-dihexylbipyridinium dihexafluorophosphate, N,
N'-dipropylbipyridinium dibromide, N,
N'-dipropylbipyridinium dichloride, N,
N′-dipropylbipyridinium diperchlorate,
N, N'-dipropylbipyridinium ditetrafluoroborate, N, N'-dipropylbipyridinium dihexafluorophosphate, N, N'-dibenzylbipyridinium dibromide, N, N'-dibenzylbipyridinium diperchlorate, N N, N'-dibenzylbipyridinium ditetrafluoroborate, N, N'-dibenzylbipyridinium dihexafluorophosphate, N, N'-
Dimethacryloylethyl bipyridinium dibromide,
N, N′-dimethacryloylethylbipyridinium dichloride, N, N′-dimethacryloylethylbipyridinium diperchlorate, N, N′-dimethacryloylethylbipyridinium ditetrafluoroborate,
N′-dimethacryloylethylbipyridinium dihexafluorophosphate, N, N′-diaacryloylethylbipyridinium dibromide, N, N′-diaacryloylethylbipyridinium dichloride, N, N′-diaacryloylethylbipyridinium diperchlorate,
N, N'-diaacryloylethylbipyridinium ditetrafluoroborate, N, N'-diaacryloylethylbipyridinium dihexafluorophosphate, N, N'-
Dimethacryloylmethylbipyridinium dibromide,
N, N′-dimethacryloylmethylbipyridinium dichloride, N, N′-dimethacryloylmethylbipyridinium diperchlorate, N, N′-dimethacryloylmethylbipyridinium ditetrafluoroborate,
N'-dimethacryloylmethylbipyridinium dihexafluorophosphate, N, N'-diaacryloylmethylbipyridinium dibromide, N, N'-diaacryloylmethylbipyridinium diperchlorate, N, N'-
Diacryloylmethylbipyridinium ditetrafluoroborate, N, N'-diaacryloylmethylbipyridinium dihexafluorophosphate, N-heptyl-N'-
Methacryloylethyl bipyridinium dibromide, N
-Heptyl-N'-methacryloylethylbipyridinium dichloride, N-heptyl-N'-methacryloylethylbipyridinium diperchlorate, N-heptyl-N'-methacryloylethylbipyridinium diditetrafluoroborate, N-heptyl-N'-methacryloylethyl bipyridinium Dihexafluorophosphate, N-heptyl-N'-methacryloylethyl bipyridinium dibromide, N-hexyl-N'-methacryloylethyl bipyridinium dichloride, N-hexyl-N'-methacryloylethyl bipyridinium diperchlorate, N-to Xyl-N'-methacryloylethylbipyridinium diditetrafluoroborate, N-
Hexyl-N'-methacryloylethylbipyridinium dihexafluorophosphate, N-benzyl-N'-methacryloylethylbipyridinium dibromide, N-
Benzyl-N'-methacryloylethylbipyridinium dichloride, N-benzyl-N'-methacryloylethylbipyridinium diperchlorate, N-benzyl-
N′-methacryloylethylbipyridinium diditetrafluoroborate, N-benzyl-N′-methacryloylethylbipyridinium dihexafluorophosphate,
N-butyl-N'-methacryloylethylbipyridinium dibromide, N-butyl-N'-methacryloylethylbipyridinium dichloride, N-butyl-N'-
Methacryloylethyl bipyridinium diperchlorate, N-butyl-N'-methacryloylethyl bipyridinium diditetrafluoroborate, N-butyl-N '
-Methacryloylethylbipyridinium dihexafluorophosphate, N-propyl-N'-methacryloylethylbipyridinium dibromide, N-propyl-N '
-Methacryloylethyl bipyridinium dichloride,
N-propyl-N'-methacryloylethyl bipyridinium diperchlorate, N-propyl-N'-methacryloylethyl bipyridinium diditetrafluoroborate, N-propyl-N'-methacryloylethyl bipyridinium dihexafluorophosphate, N-heptyl-N ' -Methacryloylmethylbipyridinium dibromide, N-heptyl-N'-methacryloylmethylbipyridinium dichloride, N-heptyl-N'-methacryloylmethylbipyridinium diperchlorate, N
-Heptyl-N'-methacryloylmethylbipyridinium diditetrafluoroborate, N-heptyl-N'-methacryloylmethylbipyridinium dihexafluorophosphate, N-heptyl-N'-methacryloylmethylbipyridinium dibromide, N-hexyl-N ' −
Methacryloylmethylbipyridinium dichloride, N
-Hexyl-N'-methacryloylmethylbipyridinium diperchlorate, N-hexyl-N'-methacryloylmethylbipyridinium diditetrafluoroborate,
N-hexyl-N'-methacryloylmethylbipyridinium dihexafluorophosphate, N-benzyl-
N′-methacryloylmethylbipyridinium dibromide, N-benzyl-N′-methacryloylmethylbipyridinium dichloride, N-benzyl-N′-methacryloylmethylbipyridinium diperchlorate, N-benzyl-N′-methacryloylmethylbipyridinium diditetrafluoroborate, N-benzyl-N'-methacryloylmethylbipyridinium dihexafluorophosphate, N-butyl-N'-methacryloylmethylbipyridinium dibromide, N-butyl-N'-methacryloylmethylbipyridinium dichloride, N-butyl-N'-methacryloylmethylbipyridinium Diperchlorate, N-butyl-N'-methacryloylmethylbipyridinium diditetrafluoroborate, N-butyl-N'-methacryloylmethylbipi Dinium dihexafluorophosphate, N-propyl-N'-methacryloylmethylbipyridinium dibromide, N-propyl-N'-methacryloylmethylbipyridinium dichloride, N-propyl-N'-methacryloylmethylbipyridinium diperchlorate, N-propyl- N'-methacryloylmethylbipyridinium diditetrafluoroborate, N-propyl-N'-methacryloylmethylbipyridinium dihexafluorophosphate, N-heptyl-N'-methacryloylphenylbipyridinium dibromide, N-heptyl-N'-methacryloylphenyl bipyridinium dichloride , N-heptyl-
N'-methacryloylphenylbipyridinium diperchlorate, N-heptyl-N'-methacryloylphenylbipyridinium diditetrafluoroborate, N-heptyl-N'-methacryloylphenylbipyridinium dihexafluorophosphate, N-heptyl-N'-
Methacryloylphenylbipyridinium dibromide,
N-hexyl-N'-methacryloylphenylbipyridinium dichloride, N-hexyl-N'-methacryloylphenylbipyridinium diperchlorate, N-hexyl-N'-methacryloylphenylbipyridinium diditetrafluoroborate, N-hexyl-N '-Methacryloylphenylbipyridinium dihexafluorophosphate, N-benzyl-N'-methacryloylphenylbipyridinium dibromide, N-benzyl-N'
-Methacryloylphenyl bipyridinium dichloride, N-benzyl-N'-methacryloylphenyl bipyridinium diperchlorate, N-benzyl-N'-methacryloylphenyl bipyridinium diditetrafluoroborate, N-benzyl-N'-methacryloylphenyl bipyridinium dihexafluorophosphate, N-
Butyl-N'-methacryloylphenylbipyridinium dibromide, N-butyl-N'-methacryloylphenylbipyridinium dichloride, N-butyl-N'-
Methacryloylphenylbipyridinium diperchlorate, N-butyl-N'-methacryloylphenylbipyridinium diditetrafluoroborate, N-butyl-
N′-methacryloylphenylbipyridinium dihexafluorophosphate, N-propyl-N′-methacryloylphenylbipyridinium dibromide, N-propyl-N′-methacryloylphenylbipyridinium dichloride, N-propyl-N′-methacryloylphenyl bipyridinium diperchlorate, N-propyl-
N'-methacryloylphenylbipyridinium diditetrafluoroborate; N-propyl-N'-methacryloylphenylbipyridinium dihexafluorophosphate;

Further, for example, a polymer or a copolymer represented by the following general formula (21) can be mentioned.

Embedded image In the general formula (21), m is an integer of 1 or more, preferably 1 to
An integer of 1000, n is an integer of 0 or more, preferably 0 to 1
Indicates an integer of 000. R ³⁸ is a divalent hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a simple covalent bond (that is, a form in which a viologen group is directly bonded to a polymer chain not via the above hydrocarbon residue). And the hydrocarbon residue includes a hydrocarbon group or an oxygen-containing hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; and an aromatic hydrocarbon group such as a phenylene group, a biphenylene group, and a benzylidene group. And oxygen-containing hydrocarbon groups such as —OCH ₂ —, —OCH ₂ CH ₂ —, and —OC.
An aliphatic alkoxylene group such as an H ₂ CH ₂ CH ₂ — group,
An aliphatic dialkoxylene group such as an OCH ₂ CH ₂ O— group or an —OCH ₂ CH ₂ CH ₂ O— group, —O (C ₆ H ₄ ) —
, An aromatic aryloxy group such as —OCH ₂ (C ₆ H ₄ ) —, —O (C ₆ H ₄ ) O—, and —OCH ₂ (C
And aromatic diaryloxy groups such as ₆ H ₄ ) O— groups. X ^-, Y ^- represents a monovalent anion in counter anion of the viologen, may be the same or different, for example ^{F -, Cl -, Br -} , I - a halogen anion or ClO the ₄ ^-, BF _{4 ^{-, PF 6 -, CH 3}} CO
_{^{O -, CH 3 (C 6}} H 4) SO 3 - and the like. R
^39, R ^40, R ⁴¹ having 1 to 20 carbon atoms, preferably 1 to 12
Represents a hydrocarbon group, a hetero atom-containing substituent group, or a halogen atom. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a hexyl group, a phenyl group, a tolyl group, a benzyl group, and the like. An aryl group such as a naphthyl group and the like are mentioned, and examples of the hetero atom-containing substituent include an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, an amide group, an amino group, a cyano group, and the like. Examples of the oxygen-containing hydrocarbon group include an alkoxyl group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and a troxy group, a carboxyl group, and a carboxylic acid ester group. When the compound represented by the general formula (21) is a copolymer, the copolymerization mode of the repeating unit may be any of block, random, and alternating. Other examples of the compound having a viologen structure include a compound represented by the following general formula (2)
The polymer or copolymer represented by 2) is mentioned.

Embedded image In the general formula (22), m, n and X ⁻ , Y
^{-Represents the same as} in the general formula (21), but it is more preferable that n = 0. R ⁴² and R ⁴⁴ are each represented by the general formula (2)
Represents the same as the R ³⁸ 1), it may be the same or different. R ⁴³ and R ⁴⁵ represent the same as R ^{39 in} formula (21), and may be the same or different. When the compound represented by the general formula (22) is a copolymer, the copolymerization mode of the repeating unit may be any of block, random, and alternating. Another example of the compound having a viologen structure includes a polymer or a copolymer represented by the following general formula (23).

Embedded image In the general formula (23), m and n and X ⁻ and Y ⁻ represent the same as in the general formula (21), but it is more preferable that n = 0. R ⁴⁶ represents the same as R ³⁸ in the general formula (21), and R ⁴⁷ , R ⁴⁸ , and R ⁴⁹ represent the same as R ^{39 in the} general formula (21), and may be the same or different. In addition,
When the compound represented by the general formula (23) is a copolymer, the repeating unit has a copolymerization mode of block, random,
Any of these may be alternated. Still another example is a polymer represented by the following general formula (24).

Embedded image In the general formula (24), p represents an integer of 0 or more, preferably 0 to 20, and q represents an integer of 1 to 1000. R ⁵¹ is the same as R ^{38 in} formula (21). Further, examples of the compound having a viologen structure include a polymer or a copolymer represented by the following general formula (25).

Embedded image In the general formula (25), r represents an integer of 1 or more, and preferably 1 to 1,000. R ⁴⁶ is the same as R ^{38 in} formula (21), and R ⁴⁷ is the same as R ^{41 in} formula (21).

Representative examples of the compound having a viologen structure used in the present invention are exemplified by the above-mentioned general formulas (21) to (25). Specific examples of the compounds usable in the above are as follows. In formulas representing specific examples, Pr represents a propyl group.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image The content of the compound having the structure represented by the general formula (2) in the ion conductive material layer is not particularly limited, but is usually usually 0.00001 to 50 wt%, preferably 0.0001 to 30%. , More preferably 0.
About 001 to 10% is desirable. If necessary, the compound having the structure represented by the general formula (2) can be further doped with a compound that promotes color development.

Next, the compound used in the electrochromic coloring layer of the present invention will be described. This compound is represented by the following general formula (1) as described above.

Embedded image In the compound represented by the general formula (1), R ¹ , R ² ,
R ³ , R ⁴ and R ⁵ are each hydrogen or carbon number 1-2.
It represents 0, preferably 1 to 12 hydrocarbon residues. R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different. Specifically, as R ¹ , R ² , and R ³ , particularly, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and an n-hexyl group In addition, methoxyphenyl group, alkoxyphenyl group such as ethoxyphenyl group, alkylphenyl group such as tolyl group, ethylphenyl group, various aryl groups such as phenyl group, hydrocarbon residues exemplified in aralkyl group and derivatives thereof Or H, and R ⁴ and R ⁵ are particularly preferably a methyl group, an ethyl group, n-
Alkyl groups such as propyl group, i-propyl group, n-butyl group, i-butyl group, and n-hexyl group; and alkyl groups such as methoxyphenyl group, ethoxyphenyl group and other alkoxyphenyl groups, tolyl group and ethylphenyl group. It is preferably H or a hydrocarbon residue exemplified by various aryl groups such as phenyl group, phenyl group, chlorophenyl group and nitrophenyl group, aralkyl group and derivatives thereof, furyl group, pyridyl group and the like. Ar ¹ and Ar ² in the compound represented by the general formula (1) each represent a divalent aromatic hydrocarbon residue having 6 to 18 carbon atoms, and Ar ¹ and Ar ² may be the same or different. May be different. Specifically, Ar ¹ includes functional groups represented by general formulas (26) to (29).

Embedded image

Embedded image

Embedded image

Embedded image (R ^{1 in the} general formulas (26) to (28) is the same group as R ¹ in the general formula (1).) Examples of these functional groups include a p-phenylene group,
m-phenylene group, p-biphenylene group, methyl-p-
Phenylene group, ethyl-p-phenylene group, methoxy-
Various phenylene groups such as p-phenylene group, methyl-m-phenylene group, ethyl-m-phenylene group, and methoxy-m-phenylene group, and derivatives thereof are preferable. Further, as Ar ² , the above general formulas (26) to (2)
9) In addition to various phenylene groups and derivatives thereof represented by 9), 1,5- or 2,7-naphthylene group, 1,4-
Or a 1,5- or 2,6-anthraquinonylene group,
2,4- or 2,7-fluorenonylene group, birenylene group, 2,7-phenanthraquinonylene group, 2,7-
2 exemplified by (9-dicyanomethylene) fluorenonylene group, dibenzotrobondiyl group, dicyanomethylenedibenzotrobondiyl group, benzanthronylene group and the like.
Monovalent or condensed polycyclic aromatic hydrocarbon residue, 2-phenylbenzoxazolediyl group, 2-phenylbenzimidazolediyl group, carbazolediyl group, 2-phenylbenzotriazoldiyl group, dibenzothiophendiyl group Divalent heteroatom-containing fused heterocyclic aromatic hydrocarbon residues exemplified by divalent heterocyclic groups such as dibenzothiophenoxide diyl group, 9-acridone diyl group, xanthone diyl group, and phenoxazine diyl group Is mentioned. L in the general formula (1) is 0
Is an integer of at least 0, usually 0 to 50, preferably 0 to 10
More preferably, it is 0-5. m is 1 or more, and is usually 1 to 50, preferably 1 to 30. n is 2 or more,
It is usually from 2 to 1,000, preferably from 5 to 200, and has a substantially linear structure. Although both terminals of (1) are not particularly specified, they are usually nuclear-substituted hydrogen. Also,
If necessary, the compound represented by the general formula (1) can be doped with a compound that promotes color development. The compound represented by the general formula (1) is usually represented by the general formula (30)
And the compound represented by the general formula (31) or a polymer thereof is produced by polycondensation, but the production method is not limited at all.

Embedded image (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Ar ¹ , Ar ² , l and m
Is the same as R ¹ , R ² , R ³ , R ⁴ , R
⁵ , the same groups and integers as Ar ¹ , Ar ² , l and m. R ⁴ COR ⁵ (31) As the compound represented by the general formula (30), N, N′-
Diphenyl-p-phenylenediamine compound, N-phenyl-N '-(4-phenylamino) phenyl-p-
Examples thereof include phenylenediamine-based compounds. Representative of these N, N'-diphenyl-p-phenylenediamine-based compounds include N, N'-dimethyl-N, N'-diphenyl-p-phenylenediamine,
N, N'-diethyl-N, N'-diphenyl-p-phenylenediamine, N, N'-dipropyl-N, N'-diphenyl-p-phenylenediamine and the like can be mentioned. Examples of the compound represented by the general formula (31) include various carbonyl compounds such as aldehydes, aldehyde polymers, and ketones. Representative aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde, nitrobenzaldehyde, chloro111 lobenzaldehyde, furfural and the like. The aldehyde polymer is a polymer obtained by self-condensing the aldehyde represented by the general formula (31) in a concentrated solution or condensing it in the presence of an acid catalyst. It represents an aldehyde monomer which is easily hydrolyzed under the reaction conditions for synthesizing the copolymer of the present invention. Representative examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde. Examples of ketones include:
Acetone, methyl ethyl ketone, diethyl ketone, cyclohexyl acetone and the like can be mentioned. The polycondensation of the compound represented by the general formula (30) and the compound represented by the general formula (31) is carried out in an organic solvent in which both are soluble at a temperature of 0 to 200 ° C. using an acid or alkali catalyst. It can be carried out.
Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, and diphosphorus pentoxide, and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, and p-toluenesulfonic acid. it can. These acid catalysts may be used alone or in combination of two or more. Examples of preferred organic solvents include ethyl ether, tetrahydrofuran, ethers such as dioxane, chloroform, dichloromethane, halogenated hydrocarbons such as chlorobenzene,
Examples include nitro compounds such as nitrobenzene, acetonitrile, propion carbonate, dimethylformamide, N-methylpyrrolidone, and the like. The reaction time can be appropriately selected in the range of 1 minute to 500 hours, preferably 5 minutes to 200 hours. If necessary, the compound represented by the general formula (1) or the compound having the structure represented by the general formula (2) can be doped with a compound that promotes color development.

The electrochromic layer of the present invention essentially contains the compound represented by the general formula (1). Typically, substantially all of the color-forming layer is composed of only the compound. In order to make the compound into an electrochromic layer, it can be usually obtained by forming the compound in a film or layer on the conductive substrate. The method of forming the film or layer is not particularly limited,
A method of dissolving the compound represented by the general formula (1) in a solvent, applying the solution to the conductive substrate, and drying the same; heating the compound represented by the general formula (1) to melt;
A method in which the melt is cast on the above-mentioned conductive substrate and then cooled, etc. may be mentioned, and the former is particularly preferable. The solvent used in the former method is not particularly limited as long as it can dissolve the above compound and can be removed by volatilization after coating, and for example, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone , Γ-valerolactone, dimethoxyethane, acetonitrile, propionnitrile, tetrahydrofuran, dioxane, methanol, ethanol, propanol, chloroform, toluene, benzene, nitrobenzene, dioxolan and the like. In addition, as a coating method, any of cast, spin coating and dip coating may be used. The drying method can be appropriately performed by a conventional method. Thus, by applying a voltage, an electrochromic color-forming layer that is easily redox-reduced and color-decolored can be obtained.
The thickness of the electrochromic coloring layer is usually 0.0
1 μm to 50 μm, preferably 0.1 μm to 20 μm

As described above, the electrochromic device of the present invention comprises two conductive substrates, at least one of which is transparent, an ion conductive material layer provided between the substrates, An electrochromic coloring layer provided between one or both of the substrates, wherein the electrochromic coloring layer contains a compound represented by the general formula (1); It contains a compound having a structure represented by the general formula (2), and its basic structure will be described below. FIG. 1 shows a typical configuration example of the electrochromic device according to the present invention. The electrochromic device illustrated in FIG. 1 includes a first substrate in which an electrochromic film is further formed on a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, and a transparent substrate 6.
A second substrate made of a transparent conductive substrate having a transparent electrode layer 7 formed on one surface thereof is opposed to the electrochromic film on the first substrate and the transparent electrode on the second substrate inside. Here, an ion conductive substance is sandwiched. Needless to say, in FIG. 1, by applying a voltage between the electrodes, it is possible to cause color development / decoloration due to the electrochromic phenomenon. A known means can be used as the voltage applying means. The method for forming each film and layer constituting the electrochromic device of the present invention is not particularly limited, and a method of sequentially forming each film and layer according to the above-described manufacturing method can be used. For example, in the case of the electrochromic device having the configuration shown in FIG. 1, the transparent electrode layer 2 is sequentially formed on the transparent substrate 1 by the above-described method, and the transparent conductive substrate 1 + 2 is obtained. Next, the electrochromic layer 3 is formed by the above-described method to obtain a substrate 1 + 2 + 3 (substrate A). Separately, the transparent electrode layer 6 is formed on the substrate 7 by the method described above to obtain the substrate 6 + 7 (substrate B). Subsequently, the substrate A and the substrate B are opposed to each other at an interval of about 1 to 1000 μm, and the periphery excluding the injection port is sealed with the sealing material 5 to form an empty cell with the injection port. Injecting the ion conductive substance or its precursor (usually liquid) and the compound having the structure represented by the general formula (2) by the above-described method to form the ion conductive substance layer 4 and obtain an electrochromic element Can be. When the substrates A and B are opposed to each other,
Spacers can be used to ensure a constant spacing. The spacer is not particularly limited, but beads or sheets made of glass, polymer, or the like can be used. The spacer can be provided by a method of inserting the spacer into a gap between the opposing conductive substrates, a method of forming a projection made of an insulating material such as a resin on an electrode of the conductive substrate, or the like. The method of forming the ion conductive material layer 4 is, for example, to inject a precursor of the solid ion conductive material and a compound having a structure represented by the general formula (2) into a gap between the opposing conductive substrates. , And then cured. The curing method is not particularly limited, and examples thereof include a method using light, a method using heat, a method in which a reaction liquid that cures with time is mixed immediately before injection, and then immediately injected and cured. Note that the injection port may be appropriately sealed. As another method, the transparent substrate 1
The transparent electrode layer 2 is sequentially formed thereon by the above-described method, and a transparent conductive substrate 1 + 2 is obtained. Next, an electrochromic layer is formed by the above-described method, and a substrate 1 + 2 + 3 is obtained. Subsequently, an ionic conductive material layer 4 containing a compound having a structure represented by the general formula (2) is formed on the substrate 1 + 2 + 3 to obtain a substrate 1 + 2 + 3 + 4 (substrate A). Separately, the transparent electrode layer 6 is formed on the substrate 7 by the method described above,
+7 (substrate B) is obtained. Then, the substrate A and the substrate B are
There is a method in which the ion conductive substance of the substrate A is opposed to the transparent electrode layer of the substrate B so as to be in close contact with the transparent electrode layer of the substrate B at intervals of about 1000 μm, and the periphery thereof is sealed with the sealing material 5. In addition, a typical configuration example of the electrochromic device of the present invention is as shown in FIG. 1 described above, but the electrochromic device of the present invention is not limited to these configurations. , And other configuration requirements. Other constituent requirements include, for example, an ultraviolet-cutting layer such as an ultraviolet-reflective layer or an ultraviolet-absorbing layer, an overcoat layer for the purpose of protecting the entire surface or the surface of each film layer, and a reflector for use as an anti-glare mirror. Examples of the ultraviolet cut layer include the outside of the transparent substrate 1 or the transparent electrode layer, the outside of the transparent substrate 7 or the transparent electrode layer, and the overcoat layer includes the outside of the transparent substrate 1 and the transparent substrate 7. As a preferred embodiment, it is preferable to install the transparent electrode 1 in place of the transparent electrode 2 or the transparent electrode 6 if the reflective plate is an external side of the transparent substrate 1, the external side of the transparent substrate 7, or a conductive reflective plate. . For example, an electrochromic mirror as shown in FIG.
The transparent electrode layer 2 on one side and the reflective layer 7 on the other side.
Is formed by the same procedure as in the case of the electrochromic device shown in FIG.

[0016]

The electrochromic device of the present invention has
By using an electrochromic layer containing a specific compound and adding a specific electrochromic compound to the ion conductive material layer, the response speed is high, and sufficient durability and memory properties are obtained. Since the electrochromic device of the present invention uses an electrochromic layer containing a specific compound, it can be manufactured relatively easily and inexpensively. It has an excellent feature that it can be easily adjusted. It is easy to use a solid electrolyte as the ion conductive material layer, so that an electrolyte solution does not scatter and a large and highly safe electrochromic device can be manufactured. From the above, the electrochromic device of the present invention is suitable for use as a dimming window represented by a vehicle such as a building or an automobile, for decoration, for partitioning, and for an anti-glare mirror for an automobile. Can be.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Example 1 (1) Synthesis of electrochromic compound N, N′-dimethyl- was added to a 100 ml three-necked flask.
N, N'-diphenyl-p-phenylenediamine
50 g (5.20 mmol), propionaldehyde
0.39 g (6.8 mmol), nitrobenzene 30
Then, the mixture was stirred with a magnetic stirrer while heating to 40 ° C. Trifluoroacetic acid 0.05g as catalyst
(0.4 mmol) was added dropwise. After 120 hours, the reaction solution was dropped into ethanol to precipitate a polymer. A polymer having a structure represented by the following formula (32) (weight average molecular weight: 3,500, where n is about 10 (average value)) I got

Embedded image (2) Synthesis of viologen compound 3.12 g (20 mmol) of bipyridyl was dissolved in 100 ml of acetonitrile in a flask, and 7.16 g (40 mmol) of n-heptyl bromide was added thereto.
The mixture was reacted for 12 hours at the distillation temperature of acetonitrile, and the precipitated solid was separated by filtration and dried to obtain 8.74 g (17 mmol) of N, N, -diheptylbipyridinium dibromide. (3) Preparation of electrochromic device The electrochromic compound prepared in the above (1) was dissolved in nitrobenzene to form a 10% by weight solution.
It was applied to the ITO side of a glass substrate coated with O. By heating on a hot plate to remove nitrobenzene, a thin film of the compound was obtained (thickness: about 5 μm), which was used as a transparent conductive substrate with an electrochromic layer (substrate A). As the other transparent electrode, an epoxy-based adhesive is linearly applied to the periphery of the ITO of the glass substrate (substrate B) also coated with ITO, except for the inlet of the electrolyte precursor solution,
Substrate A was overlaid on top of this so that the electrochromic layer and the ITO layer of substrate B faced each other, and the adhesive was cured while applying pressure to produce an empty cell with an inlet. On the other hand, methoxy polyethylene glycol monomethacrylate (MEO4 manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxyethylene unit number 4] 1.0 g, polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
9G) [9 oxyethylene units] 0.02 g, γ
-To a mixed solution of 4.0 g of butyrolactone, 0.4 g of lithium perchlorate and 0.1 g of heptyl viologen were added to form a homogeneous solution. In a dark room, 1- (4-isopropylphenyl) -2- photopolymerization initiator is added to the homogeneous solution.
After degassing the homogeneous solution obtained by adding 0.02 g of hydroxy-2-methylpropan-1-one (trade name “Dicure-1116” manufactured by Merck Ltd.), the empty cell prepared as described above was degassed. It was injected as an electrolyte precursor from the inlet. After sealing the injection port with an epoxy-based adhesive, the electrolyte precursor is cured by applying light from a fluorescent lamp from the transparent substrate B side,
A solid electrolyte was obtained. Thus, an all-solid-state electrochromic device having the configuration shown in FIG. 1 was obtained. The device was not colored at the time of assembly, and the transmittance was about 80%. In addition, when voltage was applied, the responsiveness was excellent, and good electrochromic characteristics were exhibited. That is, 1.5
When a voltage of V was applied, the layer was colored, and after 10 seconds, the transmittance of light having a wavelength of 633 nm was about 10%.

Example 2 (1) Synthesis of electrochromic compound N, N'-dimethyl- was added to a 100 ml three-necked flask.
N, N'-diphenylbenzidine 1.50 g (4.1
2 mmol), 0.42 g of methyl ethyl ketone (5.
8 mmol), 30 ml of nitrobenzene and 60
The mixture was stirred with a magnetic stirrer while being heated to ℃.
As a catalyst, 0.05 g (0.5 mmol) of sulfuric acid was added dropwise. After 140 hours, the reaction solution was dropped into ethanol to precipitate a polymer. A polymer having a structure represented by the following formula (33) (average molecular weight: 4,000, where n is about 10 (average value)) was obtained. Obtained.

Embedded image (2) Synthesis of viologen compound Biviridyl and heptyl chloride were reacted in an equimolar amount in methanol to obtain a mono-substituted N-heptylbipyridinium chloride. This N-heptylbipyridinium chloride (7.06 g, 21 mmol) was dissolved in methanol (150 ml), 2-bromoethyl methacrylate (11.39 g, 21 mmol) was added, the mixture was stirred at room temperature for 24 hours, and N-heptyl-N′-methacrylethyl was added. Bipyridinium dibromide was obtained. (2) Preparation of anti-glare mirror The electrochromic compound produced in the above (1) was dissolved in nitrobenzene to form a 10% by weight solution, which was provided with an aluminum reflecting plate on one side and a SnO ₂ transparent conductive film on the other side. The substrate was coated on SnO ₂ and heated on a hot plate to remove nitrobenzene to obtain a thin film of the electrochromic compound (thickness of about 5 μm).
m) This was used as a reflective conductive substrate with an electrochromic layer (substrate B ′). On the other hand, as a transparent conductive substrate,
A glass substrate coated with SnO ₂ was used as a transparent electrode layer. This was used as a substrate A, and an epoxy-based adhesive was linearly applied to the periphery of the SnO ₂ except for the inlet for the electrolyte precursor solution. Then, a substrate B ′ was superposed on this so that the electrochromic layer and the transparent electrode layer faced each other, and the adhesive was cured while applying pressure, thereby producing an empty cell with an inlet. On the other hand, methoxypolyethylene glycol monomethacrylate (MEO4 manufactured by Shin-Nakamura Chemical Co., Ltd.)
[Oxyethylene unit number 4] 1.0 g, polyethylene glycol dimethacrylate (9G manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxyethylene unit number 9] 0.0
0.4 g of lithium perchlorate was added to a mixed solution of 2 g and 4.0 g of γ-butyrolactone to obtain a homogeneous solution. In a dark room, the homogeneous solution was added to the photopolymerization initiator 1- (4-
0.02 g of (isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name “Dicure-1116”) and 0.1 g of N-heptyl-N′-methacrylethylbipyridinium dibromide are added. After degassing the obtained homogeneous solution, it was injected as an electrolyte precursor from the injection port of the empty cell created as described above. After sealing the injection port with an epoxy-based adhesive, the electrolyte precursor is cured by applying light from a fluorescent lamp from the transparent substrate B side,
A solid electrolyte was obtained. Thus, the all-solid-state electrochromic electrochromic device having the configuration shown in FIG. 2 was obtained. This electrochromic device was not colored at the time of assembly, and had a reflectance of about 75%. Further, when a voltage was applied, the responsiveness was excellent and good electrochromic characteristics were exhibited. When a voltage of 1.5 V was applied, the coloration was achieved, and the reflectance became about 10%.

Example 3 (1) Synthesis of electrochromic compound N, N'-dimethyl- was added to a 100 ml three-necked flask.
N, N'-di (N-methyl-N-phenyl-p-anilino) -phenyl-p-phenylenediamine 3.00 g
(6.02 mmol) and 0.83 g of benzaldehyde
(7.8 mmol) and 30 ml of nitrobenzene were added and stirred with a magnetic stirrer while heating to 60 ° C. Sulfuric acid 0.05g (0.5mmo) as catalyst
l) was added dropwise. After 150 hours, the reaction solution was added dropwise to ethanol to precipitate a polymer.
4) The polymer having the structure as described above (average molecular weight: 3,000,
N in the formula was about 5 (average value).

Embedded image (2) Preparation of Electrochromic Element The electrochromic compound prepared in the above (1) was dissolved in nitrobenzene to form a 10% by weight solution.
It was applied to the SnO ₂ side on a glass substrate coated with O ₂ . By heating on a hot plate to remove nitrobenzene, a thin film of the copolymer was obtained, which was used as a transparent conductive substrate with an electrochromic layer (substrate A). On the other hand, an epoxy-based adhesive was linearly applied to the periphery of the glass substrate B having a SnO ₂ film as a transparent electrode on one side, on the SnO ₂ side except for the injection port of the electrolyte precursor solution. Substrate A on this
Are stacked so that the electrochromic layer and the SnO ₂ surface face each other, and the adhesive is cured while applying pressure.
An empty cell with an inlet was made. On the other hand, 1.0 g of methoxypolyethylene glycol monomethacrylate (MEO9 manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxygen unit number 9], polyethylene glycol dimethacrylate (9G manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) [oxygen unit number 9] 0.02 g, γ-butyrolactone
0.4 g of lithium perchlorate was added to 4.0 g of the mixed solution to obtain a uniform solution. In a dark room, 1- (4-isopropylphenyl)-as a photopolymerization initiator is added to the homogeneous solution.
0.02 g of 2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name "Dicure-1116")
Was added, and the homogeneous solution obtained was degassed and injected into the cell prepared as described above as an electrolyte precursor. After sealing the injection port with an epoxy-based adhesive, light from a fluorescent lamp was applied from the transparent substrate B side to cure the electrolyte precursor to obtain a solid electrolyte. Thus, an all-solid-state electrochromic electrochromic device having the configuration shown in FIG. 1 was obtained. This electrochromic device was not colored at the time of assembly, and had a transmittance of about 70%. In addition, when a voltage was applied, the responsiveness was excellent and good electrochromic characteristics were exhibited. When a voltage of 1.5 V was applied, the film was colored and the transmittance was about 10%.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a configuration of an electrochromic device of the present invention.

FIG. 2 is a sectional view showing another example of the configuration of the electrochromic device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent substrate 2 transparent electrode layer 3 electrochromic layer 4 ion conductive material layer 5 sealing material 6 transparent electrode layer 7 transparent substrate 8 conductive aluminum plate

Claims (1)

[Claims] An ion conductive material layer containing a compound having a viologen structure represented by the following general formula (2) is provided between two conductive substrates at least one of which is transparent, An electrochromic device comprising an electrochromic layer containing a compound represented by the following general formula (1) provided on at least one of a material layer and a conductive substrate. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, and may be the same or different; Ar ¹ and Ar ² Each independently represents a divalent aromatic hydrocarbon residue;
M is an integer of 1 to 2, and n is an integer of 2 or more. ) (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anions, ClO ₄ ⁻ , BF ₄ ⁻ ,
A counter anion selected from PF ₆ ⁻ , CH ₃ COO ⁻ , and CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ is shown. )