JPH1138453A - Electrochromic mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrochromic mirror with an inexpensive color developing agent in a simple process by incorporating a specified compd. into an electrochromic color developing layer. SOLUTION: This mirror consists of a reflective conductive substrate, a transparent conductive substrate, an ionic conductive material layer formed between the substrates, and an electrochormic color developing layer formed at least either between the tonic conductive material layer and the reflective conductive substrate or between the ionic conductive material layer and the transparent conductive layer. The electrochromic color developing layer contains a compd. expressed by the formula. In the formula, R<1> to R<5> are independently hydrogen or 1 to 20C hydrocarbon residues and may be the same or different, Ar<1> , Ar<2> are bivalent aromatic hydrocarbon residues, 1 is an integer 0 to 3, m is 1 or 2, and n is an integer >=2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic mirror useful as an anti-glare mirror for automobiles or the like or as a decorative mirror used indoors.

[0002]

2. Description of the Related Art As a conventional electrochromic anti-glare mirror, for example,
It is known that an inorganic oxide such as tungsten oxide (WO ₃ ) formed on a transparent conductive film by vacuum evaporation or sputtering is used as a coloring agent (Japanese Patent Application Laid-Open No. 63-18336). However, the formation of these films requires the use of a vacuum process, which raises the problem of increased costs. Therefore, there has been a demand for a method of manufacturing an electrochromic mirror that can be manufactured by an inexpensive color former and simple steps.

[0003]

The present invention has solved the above-mentioned problems by using a specific conductive polymer compound as a color-forming layer. That is, the electrochromic mirror according to the present invention comprises a reflective conductive substrate, a transparent conductive substrate, an ion conductive material layer provided between the two substrates, and the ion conductive material layer and the reflective conductive substrate. And an electrochromic coloring layer provided on at least one of the ion conductive material layer and the transparent conductive substrate, wherein the electrochromic coloring layer is a compound represented by the following general formula (1). It is characterized by containing.

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, which may be the same or different, and Ar ¹ and Ar ² are each Represents a divalent aromatic hydrocarbon residue, and 1 is 0 to 3
And m represents an integer of 1 or 2, and n represents an integer of 2 or more. )

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the conductive substrate used as the reflective conductive substrate and the transparent conductive substrate may be any substrate having a function as an electrode. The conductive substrate of the present invention may be constituted by a substrate having no conductivity and electrodes provided on the substrate. At least one of the conductive substrates used in the present invention is a transparent conductive substrate, and the other is a reflective conductive substrate capable of reflecting light. Both the transparent conductive substrate and the reflective conductive substrate may have a flat or curved surface, or may be deformed by stress. Examples of the form of the transparent conductive substrate include a laminate composed of a transparent substrate and a transparent electrode layer formed on the substrate. Further, the form of the reflective conductive substrate includes (1) a laminate in which a reflective electrode layer is provided on a transparent or opaque substrate, (2) a transparent electrode layer on one surface of the transparent substrate, and A laminate provided with a reflective layer, (3) a laminate provided with a reflective layer on a transparent substrate substrate, and a transparent electrode layer provided on the reflective layer, and (4) a substrate having conductivity and an electrode function with the reflective layer. And a plate-like body that also serves as a combination. The transparent substrate is not particularly limited. For example, colorless or colored glass, tempered glass, or the like may be used, and a colorless or colored transparent resin may be used. Specifically, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone,
Examples thereof include polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, and polystyrene. The transparency in the present invention is 10 to 10
The substrate has a transmittance of 0%, and the substrate in the present invention has a smooth surface at room temperature. The transparent electrode layer is not particularly limited as long as it achieves the object of the present invention, for example, gold, silver, chromium, copper,
Examples include a metal thin film such as tungsten and a conductive film made of a metal oxide. Examples of the metal oxide include:
Examples thereof include ITO (In ₂ O ₃ —SnO ₂ ), tin oxide, silver oxide, zinc oxide, and vanadium oxide. The thickness of the electrode layer is usually 100 to 5,000 angstroms, preferably 500 to 3,000 angstroms.
The surface resistance (resistivity) is usually 0.5 to 500 Ω /
cm ² , preferably 1 to 50 Ω / cm ² . The method for forming the electrode layer 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, it can be formed by a vacuum deposition method, an ion plating method, a sputtering method, a sol-gel method, or the like. At this time, the thickness of the electrode layer is selected within a range that does not impair the transparency of the electrode layer. The transparent electrode layer may be provided with a partially opaque electrode active material for the purpose of imparting oxidation-reduction ability, imparting conductivity, and imparting an electric double layer capacity. It is selected within a range that does not impair the transparency of the entire electrode layer.
Opaque electrode active materials include, for example, copper, silver, gold,
Metals such as platinum, iron, tungsten, titanium and lithium;
Organic substances having redox ability, such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; carbon materials such as activated carbon and graphite; V ₂ O ₅ , MnO ₂ , and Ni
Metal oxides such as O and Ir ₂ O ₃ or mixtures thereof can be used. Further, in order to bind them to the electrode layer, various resins may be further used. In order to apply the opaque electrode active material or the like to the electrode, for example, I
A composition comprising activated carbon fiber, graphite, acrylic resin, or the like is formed in a fine pattern such as a stripe or a dot on the TO transparent electrode, or V ₂ O ₅ , acetylene black is formed on a gold (Au) thin film. Or a composition comprising butyl rubber or the like can be formed into a mesh. The reflective electrode layer is not particularly limited as long as it is electrochemically stable and can obtain a mirror surface. Examples thereof include metal films and alloy films of platinum-palladium, platinum-rhodium, stainless steel, and the like. At this time, the reflective electrode layer needs to be provided on a substrate or a transparent substrate within a range satisfying the reflectivity and specularity of the electrode layer. The method for forming the reflective electrode layer is not particularly limited, and a known method can be appropriately used. For example, a vacuum evaporation method, an ion plating method, a sputtering method, or the like can be employed. The substrate on which the reflective electrode layer is provided is not particularly limited, and this substrate may be transparent or opaque. Specifically, in addition to those exemplified as the transparent substrate, various plastics, resins, glass, wood, stones, and the like can be mentioned. The material of the reflector or the reflector is not particularly limited as long as a mirror surface can be obtained, and examples thereof include silver, chromium, aluminum, and stainless steel. Examples of the plate-like body in which the substrate itself also has a reflective layer and an electrode function include those having self-supporting properties among those exemplified as the reflective electrode layer.

[0005] The ion conductive material used in the electrochromic mirror of the present invention is inserted between a reflective conductive substrate and a transparent conductive substrate (hereinafter referred to as a counter conductive substrate). The method of insertion is not particularly limited, and a method of injecting into a gap provided between conductive substrates whose peripheral portions are sealed by a vacuum injection method, an air injection method, a meniscus method, or the like, a sputtering method, or a vapor deposition method After forming a layer of an ion conductive material on an electrode of a conductive substrate by a method, a sol-gel method, or the like, a method of combining an opposing conductive substrate or a method of forming a glass by using a film-like ion conductive material may be used. it can. This ion conductive material is
Refers to an electrochromic layer described below that can cause coloring, decoloring, color change, and the like.
It is preferably a substance exhibiting an ionic conductivity of × 10 ⁻⁷ S / cm or more. 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 mirror of the present invention can be made an all-solid-state mirror excellent in various practical performances.

[0006] As the liquid-based ionic conductive material, a material obtained by dissolving a supporting electrolyte such as salts, acids and alkalis 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, adiponitrile, methoxyacetonitrile, dimethylacetamide,
Methyl pyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, organic polar solvents such as polyethylene glycol, and the like, preferably, propylene carbonate, ethylene carbonate,
Dimethylsulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol, etc. Organic polar solvents 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.
_{iClO 4, LiSCN, LiBF 4,} LiAsF 6,
LiCF ₃ SO ₃ , LiPF ₆ , LiI, NaI, Na
SCN, NaClO ₄ , NaBF ₄ , NaAsF ₆ , K
Alkali metal salts of Li, Na and K such as SCN and KCl, (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 , (n-C ₄ H ₉ ) ₄ NCl
Suitable examples include quaternary ammonium salts such as O ₄ and cyclic quaternary ammonium salts, and the like, and mixtures thereof. Acids as a supporting electrolyte are not particularly limited, and include inorganic acids, organic acids, and the like. Specifically, sulfuric acid,
Hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like. The alkali as a supporting electrolyte is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

As the gelled liquid ion-conductive substance, a viscous or gel-like substance obtained by further adding a polymer or a gelling agent to the liquid ion-conductive substance is used. Can be used. The polymer is not particularly limited, for example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride,
Examples include 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 material is a solid at room temperature,
There is no particular limitation as long as it has ionic conductivity, and polyethylene oxide, oxyethylene methacrylate polymer, Nafion, polystyrene sulfonic acid, Li ₃ N, Na-β-Al ₂ O ₃ , Sn (HP
O ₄ ) ₂ .H ₂ O, etc., and particularly, a polymer solid electrolyte using a polymer compound obtained by polymerizing an oxyalkylene methacrylate compound, an oxyalkylene acrylate compound or a urethane acrylate compound. Is preferred.

As a first example of the polymer solid electrolyte, a composition containing a urethane acrylate represented by the following general formula (2), the organic polar solvent, and the supporting electrolyte (hereinafter abbreviated as composition A) is used. And a solid polymer electrolyte obtained by solidification.

Embedded image (Wherein R ⁶ and R ⁷ are the same or different groups,
It represents a group selected from general formulas (3) to (5). R ⁸ and R ⁹ are the same or different groups and have 1 to 2 carbon atoms.
0, 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 to
100, preferably 1 to 50, more preferably 1 to 2
Indicates an integer in the range of 0. )

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Embedded image In the general formulas (3) to (5), 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. Specific examples of the organic residue include a hydrocarbon residue such as an alkyltolyl group, an alkyltetralyl group, and an alkylene group represented by the following general formula (6).

Embedded image In the general formula (6), 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, preferably 1 to 3 carbon atoms or an aryloxy group having 6 to 12 carbon atoms. Group. As R ^{13 in the} general formulas (3) to (5), specifically, And the like. R ^{8 of the} general formula (2)
And the divalent hydrocarbon residue represented by R ⁹ includes a chain 2
Examples thereof include a monovalent hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. Examples of the chain divalent hydrocarbon group include an alkylene group represented by the above general formula (6). it can. Further, examples of the aromatic hydrocarbon group and the alicyclic hydrocarbon group include hydrocarbon groups represented by the following general formulas (7) to (9).

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Embedded image In the general formulas (7) to (9), 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. General formula (2)
Specific examples of R ⁸ and R ⁹ in the following general formula (1)
0) to (16).

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Embedded image In the general formula (2), 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).

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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 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 ²³ , R ²⁴ , R ^25, and R ²⁶ may be the same or different. Particularly preferred examples of the copolymer include a copolymerized unit of ethylene oxide and propylene oxide. The general formula (2)
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 polymerizable 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 (2) 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 to 1200 parts by weight, preferably 200 to 900 parts by weight, based on 100 parts by weight of urethane acrylate.
If the added amount of the organic non-aqueous solvent is too small, the ionic conductivity is not sufficient, and if the added 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 those exemplified above are preferred. The addition amount is 0.1 to 30% by weight, preferably 1 to 20% by weight based on the organic non-aqueous solvent.
It is. The composition A is basically obtained by solidifying the basic components consisting of the urethane acrylate, the organic non-aqueous solvent (organic polar solvent), and the supporting electrolyte. Optional components can be added as needed as long as the components are not impaired. Examples of such optional components include a crosslinking agent and a polymerization initiator (light or heat). The polymer solid electrolyte of the first example can be interposed between opposing conductive substrates by solidifying after injecting the composition A into a desired location by a known method as appropriate. 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 (17), the organic polar solvent, and the support A polymer solid electrolyte obtained by solidifying a composition containing an electrolyte (hereinafter, abbreviated as composition B) is exemplified.

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
In the general formula (17), 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. Particularly, R ²⁷ is hydrogen, methyl group, R ²⁸ is hydrogen, methyl group, R ²⁹ is hydrogen, methyl group, R ³⁰ is hydrogen, methyl group And an ethyl group. The general formula (1
N in 7) represents an integer of 1 or more, usually 1 ≦ n ≦ 100, preferably 2 ≦ n ≦ 50, and more preferably 2 ≦ n ≦ 30. Specific examples of the compound represented by the general formula (17) include an oxyalkylene unit of 1 to 10
Methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol methacrylate, ethoxypolyethylene glycol methacrylate having a range of 0, preferably 2 to 50, and more preferably 1 to 20;
Examples include ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate, and mixtures thereof. When n in the general formula (17) is 2 or more, the oxyalkylene unit may have a so-called copolymerized oxyalkylene unit different from each other, and specific examples thereof include, for example, 1 to 50, preferably 1 to 50 oxyethylene units. Oxypropylene unit in the range of 1 to 50, preferably 1 to
Methoxy poly (ethylene / propylene) glycol methacrylate, ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene)
Glycol acrylate, or a mixture thereof, and the like.

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 (18) and a so-called trifunctional acryloyl-modified polyalkylene oxide represented by the general formula (19). The above polyfunctional acryloyl-modified polyalkylene oxides and the like are mentioned.

Embedded image Wherein R ³¹ , R ³² , R ³³ and R ³⁴ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and m is 1
The following integers are shown. )

Embedded image Wherein R ³⁵ , R ³⁶ and R ³⁷ are each hydrogen or 1 to
5 is an alkyl group having 5 carbon atoms, p is an integer of 1 or more, q is an integer of 2 to 4, and L is a q-valent linking group. R ³¹ , R ³² and R ^{33 of}
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, -Butyl group, n-pentyl group and the like. In particular, it is preferable that R ³¹ is hydrogen, methyl, R ³² is hydrogen, methyl, R ³³ is hydrogen, methyl, and R ³⁴ is hydrogen, methyl. Further, m in the general formula (18) represents an integer of 1 or more, usually 1 ≦ m ≦ 100, preferably 2 ≦ m ≦ 50, and 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 which is different from each other.
Poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) 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
Glycol diacrylate, or a mixture thereof, and the like. R ³⁵ , R ³⁶ and R ³⁷ in the general formula (19) are each hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group and an i-propyl group. Group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group and the like. Especially R
³⁵ , R ³⁶ and R ³⁷ are preferably hydrogen or methyl. Further, p in the formula represents an integer of 1 or more, usually 1 ≦ p ≦ 100, preferably 2 ≦ p ≦ 50, and more preferably 2 ≦ p ≦ 30. q is the number of links of the linking group L, and represents an integer of 2 ≦ q ≦ 4. The linking group L is usually a divalent, trivalent or tetravalent hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms. 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 is a specific example. Of course, the bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (18) may be used in combination with the trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (19). When the compound represented by the general formula (18) and the compound represented by the general formula (19) are used in combination, the weight ratio is usually 0.01 / 99.9 to 99.9 / 0.01,
Preferably 1/99 to 99/1, more preferably 20
The range of / 80 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.
001 to 1/1, preferably 1 / 0.05 to 1 / 0.5
Range. As the mixing ratio of the polar organic solvent,
The weight of the compound represented by the general formula (2) and the polyfunctional acryloyl-modified polyalkylene oxide is usually 5
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 (2), the polyfunctional acryloyl-modified polyalkylene oxide and the polar organic solvent. The composition B may further contain, if necessary, other components as necessary, in addition to the above components, 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 0.01 to 3% by weight, based on the weight of the compound represented by the general formula (1) and the polyfunctional acryloyl-modified polyalkylene oxide.
Range.

The solid polymer electrolyte of the second example can be interposed between the opposing conductive substrates by solidifying after injecting the composition B into a desired place by a known method as appropriate. 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.

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).

Embedded imageIn the general formula (1), R¹, R^Two, R^Three, R^FourAnd R
^FiveIs hydrogen or carbon number 1-20, preferably 1
１２12 hydrocarbon residues are shown. R¹, R^Two, R ^Three, R^Four
And R^FiveMay be the same or different. concrete
R¹, R^Two, R^ThreeEspecially as a methyl group, ethyl
Group, n-propyl group, i-propyl group, n-butyl group,
alkyl groups such as i-butyl group and n-hexyl group;
Alkoxyphenyl such as cyphenyl and ethoxyphenyl
Phenyl group; alkyl groups such as tolyl group and ethylphenyl group
Phenyl group; various aryl groups such as phenyl group, aral
A hydrocarbon residue exemplified by a kill group and a derivative thereof;
Is preferably H, and R^Four, R^FiveIn particular,
Methyl group, ethyl group, n-propyl group, i-propyl
Group, n-butyl group, i-butyl group, n-hexyl group, etc.
Alkyl group; methoxyphenyl group, ethoxyphenyl group
Alkoxyphenyl group such as; tolyl group, ethylphenyl
Alkylphenyl groups such as phenyl group; phenyl group, chlorophene
Various aryl groups such as a nitro group and a nitrophenyl group;
Alkyl group and its derivatives, furyl group, pyridyl group, etc.
Desirably, the hydrocarbon residue is exemplified or H.
No. In addition, Ar in the general formula (1)¹And Ar^TwoIs
Each represents a divalent aromatic hydrocarbon residue;¹And A
r^TwoMay be the same or different. Ar¹Examples of
Are represented by the general formulas (20), (21), and (22).
Functional groups.

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Embedded image (Formula (20), in R ¹ to (21), defines the same in R ¹ in the general formula (1)) These functional groups, e.g., 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. In addition, as Ar ² , the above general formulas (20) to (2)
In addition to the various phenylene groups and derivatives thereof represented by 2), 1,5- or 2,7-naphthylene group, 1,4- or 1,5- or 2,6-anthraquinonylene group, 2,4- or 2,7-fluorenonylene group, bilenylene group, 2,7-phenanthraquinonylene group, 2,7- (9-dicyanomethylene) fluorenonylene group, dibenzotrobondiyl group, dicyanomethylenedibenzotrobondi group A divalent monocyclic or condensed polycyclic aromatic hydrocarbon residue exemplified by an yl group, a benzanthronylene group, etc., a 2-phenylbenzoxazolediyl group, a 2-phenylbenzimidazolediyl group, a carbazolediyl Group, 2-phenylbenzotriazolediyl group, dibenzothiophenediyl group, dibenzothiophenoxide diyl , 9 Akuridonjiiru group, xanthone-diyl group, divalent divalent heteroatom-containing fused heterocyclic aromatic hydrocarbon residues exemplified heterocyclic groups such as phenoxazinediyl yl group. 1 in the general formula (1) is an integer of 0 or more, and is usually 0 to 50, preferably 0 to 10, and more preferably 0 to 5. m is 1 or more, and is usually 1 to 50, preferably 1 to 30. n
Is 2 or more, usually 2 to 1000, preferably 5 to 200, and has a substantially linear structure. Although both ends of the general formula (1) are not particularly specified, they are usually nuclear-substituted hydrogen. 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 prepared by polycondensing a compound represented by the general formula (23) with a compound represented by the general formula (24) or a polymer thereof. However, the production method is not limited at all.

Embedded image R ⁴ COR ⁵ (24) (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Ar ¹ , Ar ² , l
And the definition of m is the same as that of the general formula (1). As the compound represented by the general formula (23), 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 (24) include various carbonyl compounds such as aldehydes, aldehyde polymers, and ketones. Representative aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde, nitrobenzaldehyde, chlorobenzaldehyde, furfural and the like. The aldehyde polymer refers to a polymer obtained by subjecting the aldehyde represented by the general formula (24) to a concentrated solution and self-condensing, or condensing in the presence of an acid catalyst. It represents a compound which easily hydrolyzes under the reaction conditions for synthesizing the electrochromic compound of the present invention to produce an aldehyde monomer. Representative examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, cyclohexyl acetone, and the like. The polycondensation of the compound represented by the general formula (23) and the compound represented by the general formula (24) is carried out in an organic solvent in which both are soluble, from 0 to
The reaction can be carried out at a temperature of 200 ° C. using an acid or alkali catalyst. Examples of acid catalysts are sulfuric acid, hydrochloric acid, phosphoric acid,
Examples include inorganic acids such as perchloric acid and diphosphorus pentoxide, and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more. Also,
Preferred examples of the organic solvent include ethers such as ethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene; nitro compounds such as nitrobenzene, acetonitrile, propion carbonate, dimethylformamide, N-methylpyrrolidone and the like. Is mentioned. The reaction time is 1 minute to 500 hours, preferably 5 minutes to 200 hours.
It can be appropriately selected within the time range.

The electrochromic coloring layer of the present invention comprises:
Although it 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 use the compound as an electrochromic color-forming layer, it can be usually obtained by forming the compound in a film or a layer on the conductive substrate.
The method of forming the film or layer is not particularly limited, but 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 solution is represented by the general formula (1). A method in which the compound is melted by heating, and the melt is cast on the conductive substrate and then cooled, and the former is particularly preferable. The solvent used in the former method is not particularly limited as long as it dissolves the compound and can be removed by volatilization after coating. 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. The coating method may be any of cast coating, spin coating, dip coating, spray coating, blade coating, and flow coating. The drying method can be appropriately performed by a conventional method. The electrochromic coloring layer thus obtained is easily oxidized and reduced by application of a voltage, so that the color is erased. The thickness of the electrochromic coloring layer is usually 0.01 μm to
50 μm, preferably 0.1 μm to 20 μm is desirable.

The electrochromic mirror according to the present invention comprises:
As described above, the reflective conductive substrate, the transparent conductive substrate, the ion conductive material layer inserted between the two substrates, and the ion conductive material layer and the reflective conductive substrate or between the ion conductive material layer and the reflective conductive substrate. An electrochromic coloring layer inserted into at least one of the conductive material layer and the transparent conductive substrate, wherein the electrochromic coloring layer contains a compound represented by the following general formula (1). The basic configuration is described below. Representative configuration examples of the electrochromic mirror according to the present invention are shown in FIGS. The electrochromic mirror illustrated in FIG. 1 includes a first laminate in which an electrochromic coloring layer 3 is formed on a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, and a transparent or transparent layer. A second laminate composed of a reflective conductive substrate having a reflective electrode layer 6 formed on an opaque substrate 7 is opposed at appropriate intervals so that the electrochromic coloring layer 3 and the reflective electrode layer 6 face each other. Here, an ion conductive substance is sandwiched. An electrochromic mirror illustrated in FIG. 2 includes a first laminate in which an electrochromic coloring layer 3 is formed on a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, The transparent electrode layer 2 is formed on one surface of the transparent substrate 1 and the second laminate having the reflective layer 8 formed on the other surface is formed by combining the electrochromic coloring layer 3 of the first laminate with the second laminate. The transparent electrode layers 2 face each other at appropriate intervals so as to face each other, and an ion conductive substance is sandwiched between them. The electrochromic mirror illustrated in FIG. 3 includes a transparent conductive substrate (first laminate) having a transparent electrode layer 2 formed on one surface of a transparent substrate 1 and a reflective electrode on a transparent or opaque substrate 7. A second laminate in which the layer 6 is formed and the electrochromic coloring layer 3 is formed on the reflective electrode layer, and a transparent electrode layer of the first laminate and an electrochromic coloring layer of the second laminate. 3 are opposed to each other at an appropriate interval so as to face each other, and an ion conductive substance is sandwiched between them. The electrochromic mirror illustrated in FIG. 4 is a transparent conductive substrate (first laminate) having a transparent electrode layer 2 formed on one surface of a transparent substrate 1.
And a second laminate in which a transparent electrode layer 2 is formed on one surface of the transparent substrate 1, an electrochromic coloring layer 3 is further formed thereon, and a reflective layer 8 is formed on the other surface of the transparent substrate 1. The transparent electrode layer 2 of the first laminate and the electrochromic coloring layer 3 of the second laminate face each other at an appropriate interval so as to face each other, and an ion conductive substance is sandwiched between them. Of course, the electrochromic mirrors shown in FIGS. 1 to 4 can cause color development / decoloration due to the electrochromic phenomenon by applying a voltage between the respective electrodes. A known means can be used as the voltage applying means.

The method of forming each film and layer constituting the electrochromic mirror of the present invention is not particularly limited, and a method of sequentially forming each film and layer according to the above-mentioned manufacturing method can be used. For example, in the case of an electrochromic mirror having the configuration shown in FIG. 1, a transparent electrode layer 2 is formed on a transparent substrate 1 by the above-described method, and then an electrochromic coloring layer 3 is formed by the above-described method to obtain a laminated plate ( Laminate A). Separately, the reflective electrode layer 6 is formed on the substrate 7 by the method described above to obtain a laminate (laminate B). Subsequently, the laminated board A and the laminated board B are 1 to 1000 μm
The cells are opposed to each other at a certain interval, and the periphery excluding the injection port is sealed with a sealing material 5 to create an empty cell with the injection port. The electrochromic mirror can be obtained by injecting the ion conductive substance 4 or its precursor (usually liquid) by the above-described method and forming the ion conductive substance layer 6. When the laminates A and B are opposed to each other, a spacer can be used to secure a constant interval. 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 ionic conductive material layer 4 can be formed by, for example, a method of injecting a precursor of the solid ionic conductive material or the like into a gap between the opposing conductive substrates and then curing the same. 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. Also,
As another method, a transparent electrode layer 2, an electrochromic coloring layer 3, and an ion conductive material layer 4 are sequentially formed on the transparent substrate 1 in the stated order to obtain a laminate (laminate A '). . Separately, the reflective electrode layer 6 is formed on the substrate 7 by the above-described method to obtain a laminate (laminate B ′). Then, both laminates are opposed to each other at an interval of about 1 to 1000 μm so that the ion conductive material layer of the laminate A ′ and the reflective electrode layer of the laminate B ′ are in close contact with each other. There is a sealing method. In the case of the electrochromic mirror having the configuration shown in FIG. 2, the transparent electrode layer 2 is provided on one surface of the transparent substrate 1 and the reflective layer 8 is provided on the other surface.
After that, an electrochromic mirror can be obtained by the same procedure as in the case of the configuration shown in FIG.
The electrochromic mirror shown in FIGS. 3 and 4 can be manufactured by the same procedure as that of the configuration shown in FIGS. The typical configuration examples of the electrochromic mirror of the present invention are as shown in FIGS. 1 to 4 described above, but the electrochromic mirror of the present invention is not limited to these configurations at all. , And other configuration requirements. Other constituent requirements include, for example, an ultraviolet cut layer such as an ultraviolet reflective layer and an ultraviolet absorbing layer, an overcoat layer for the purpose of protecting the entire mirror or the surface of each film layer, and the like. Transparent substrate 1
It is preferable that the outer side or the transparent electrode layer side and the overcoat layer be disposed on the outer side of the transparent substrate 1 or the outer side of the reflective layer 8.

[0018]

According to the electrochromic mirror of the present invention, the use of an electrochromic layer containing a specific compound has a high response speed and has sufficient durability and memory properties. Since the electrochromic mirror of the present invention uses an electrochromic layer containing a specific compound, it can be manufactured relatively easily and inexpensively, and the color density can be easily changed by changing the specification of the compound. It has the advantage of being adjustable. It is easy to use a solid electrolyte as the ion conductive material layer, so that a large-sized and highly safe mirror can be manufactured without the electrolyte solution scattering. From the above, the electrochromic mirror of the present invention can be suitably used for an anti-glare mirror represented by a vehicle such as an automobile, a decorative mirror, and the like.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the 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 as catalyst 0.05
g (0.4 mmol) was added dropwise. After 120 hours, the reaction solution was dropped into ethanol to precipitate a polymer, and the polymer having the following structure (average molecular weight: 3,50
0, n in the formula was about 10 (average value)).

Embedded image (2) Preparation of Electrochromic Mirror The electrochromic compound produced in the above (1) was dissolved in nitrobenzene to form a 10% by weight solution, which was used for IT.
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 (laminate A). On the other hand, a substrate provided with a platinum thin film was used as a highly reflective electrode layer, and this was used as a laminate B. An epoxy-based material was provided around the platinum thin film side of the laminate B except for the injection port for the electrolyte precursor solution. An adhesive was applied linearly, and a laminate A was superimposed thereon such that the electrochromic layer and the platinum 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]
0 g, polyethylene glycol dimethacrylate (9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) [Oxyethylene unit number 9] 0.02 g and γ-butyrolactone 4.0 g were added to a mixed solution of lithium perchlorate, and then homogeneously added. The solution was used. In a dark room, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name "Dicure-1116") as a photopolymerization initiator was added to the homogeneous solution. After the homogeneous solution obtained by adding 02 g was degassed, 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, light of a fluorescent lamp was applied from the transparent substrate side to cure the electrolyte precursor to obtain a solid electrolyte. Thus, an all-solid-state electrochromic mirror having the configuration shown in FIG. 1 was obtained. The mirror was not colored when assembled and had a reflectivity of about 80%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, it is colored when a voltage of 1.5 V is applied, and has a reflectance of about 1 for light having a wavelength of 633 nm.
It became 0%. Keep the colored state even after stopping the voltage application
Even after 00 hours, the reflectance was 10%. Example 2 (1) Synthesis of electrochromic compound N, N'-dimethyl- was added to a 100 ml three-necked flask.
1.50 g of N, N'-diphenylbenzidine (4.12
mmol), 0.42 g of methyl ethyl ketone (5.8
mmol) and 30 ml of nitrobenzene at 60 ° C.
While stirring with a magnetic stirrer. 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. As a result, a polymer having the following structure (average molecular weight: 4,000, n in the formula was about 10 (average value)) was obtained.

Embedded image (2) Preparation of Electrochromic Mirror The electrochromic compound prepared in the above (1) was dissolved in nitrobenzene to prepare a 10% by weight solution, which was applied on the platinum electrode layer of the laminate B as used in Example 1. Then, the mixture was heated on a hot plate to remove nitrobenzene to obtain a thin film of the electrochromic compound (thickness: about 5 μm), which was used as a reflective conductive substrate with an electrochromic layer (laminate C). On the other hand, a glass substrate provided with palladium as a transparent electrode layer was used as a transparent conductive substrate, and this was used as a laminate D. Epoxy-based adhesive was applied to the periphery of the palladium except for the inlet for the electrolyte precursor solution. The adhesive is applied linearly, the two laminates are overlapped so that the electrochromic layer of the laminate C and the transparent electrode layer of the laminate D face each other, the adhesive is cured while applying pressure, and an empty cell with an inlet is formed. Produced. 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] 0.02 g, γ-butyrolactone
0.4 g of lithium perchlorate was added to 0 g of the mixed solution to obtain a homogeneous solution. In a dark room, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name "Dicure-1116") as a photopolymerization initiator was added to the homogeneous solution. After adding 02 g and degassing the obtained homogeneous solution, it was injected as an electrolyte precursor from the injection port of the empty cell prepared as described above. After sealing the injection port with an epoxy-based adhesive, light of a fluorescent lamp was applied from the transparent substrate side to cure the electrolyte precursor to obtain a solid electrolyte. Thus, an all-solid-state electrochromic mirror having the configuration shown in FIG. 3 was obtained. This mirror is uncolored when assembled and has a reflectivity of about 75
%Met. 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 color was obtained, and the reflectance became about 10%. The colored state is maintained even after the voltage application is stopped, and the reflectance is 1 after 100 hours.
It was 0%. 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 dropped into ethanol to precipitate a polymer. As a result, a polymer having the following structure (average molecular weight: 3,000, n in the formula was about 5 (average value)) was obtained.

Embedded image (2) Preparation of Electrochromic Mirror The electrochromic compound produced in the above (1) was dissolved in nitrobenzene to form a 10% by weight solution, and this was Sn.
It was applied on the SnO ₂ layer on an O ₂ -coated glass substrate. 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 (laminate E). On the other hand, a glass substrate provided with an aluminum thin film as a reflective layer material on one side and a SnO ₂ film as a transparent electrode on the other side was used as a laminate F. In the periphery of the SnO ₂ surface of the laminate F,
The epoxy-based adhesive was applied linearly except for the injection port of the electrolyte precursor solution. The two laminated plates are overlapped so that the electrochromic layer of the laminated plate E and the SnO ₂ surface of the laminated plate F face each other, and the adhesive is cured while pressing,
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 homogeneous 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 obtained homogeneous solution was degassed, and then injected into the cell prepared as described above as an electrolyte precursor. After sealing the injection port with an epoxy-based adhesive, light of a fluorescent lamp was applied from the transparent substrate side to cure the electrolyte precursor to obtain a solid electrolyte. Thus, an all-solid-state electrochromic mirror having the configuration shown in FIG. 2 was obtained. This mirror was not colored when assembled and had a reflectivity 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 color was obtained, and the reflectance became about 10%. The colored state is maintained even after the voltage application is stopped, and the reflectance is 10% even after 100 hours.
Met.

[Brief description of the drawings]

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

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

FIG. 3 is a sectional view showing another configuration of the electrochromic mirror of the present invention.

FIG. 4 is a cross-sectional view showing still another configuration of the electrochromic mirror of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Transparent electrode layer 3 Electrochromic coloring layer 4 Ion conductive material layer 5 Sealing material 6 Reflective electrode layer 7 Substrate 8 Reflective layer

Claims (1)

[Claims] 1. A reflective conductive substrate, a transparent conductive substrate, an ion conductive material layer provided between the two substrates, and a portion between the ion conductive material layer and the reflective conductive substrate or the ion conductive material. An electrochromic coloring layer provided on at least one of the material layer and the transparent conductive substrate, wherein the electrochromic coloring layer contains a compound represented by the following general formula (1). An electrochromic mirror characterized by the following. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, which may be the same or different, and Ar ¹ and Ar ² are each Represents a divalent aromatic hydrocarbon residue, and 1 is 0 to 3
And m represents an integer of 1 or 2, and n represents an integer of 2 or more. )