JPH11142892A - Electrochromic mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain an electrochromic mirror at a low cost by forming a specified electrochromic layer between a reflection conductive substrate and a transparent conductive substrate. SOLUTION: An electrochromic layer containing a polymer comprising a repeating unit expressed by formula I and a polymer comprising a repeating unit expressed by formula II, or containing a copolymer comprising a repeating unit expressed by formula I and a repeating unit expressed by formula II is formed between a reflection conductive substrate and a transparent conductive substrate. In the formula I, X<-> , Y<-> are each counter anions selected from halogen anions, ClO4 or the like, R<1> is hydrogen or 1 to 5C alkyl group, R<2> is 1 to 10C hydrocarbon residue, R<3> is 1 to 20C alkyl group, aryl group or the like. In the formula II, R<4> is hydrogen or 1 to 5C alkyl group, R<5> to R<9> are each hydrogen or 1 to 20C hydrocarbon groups, Ar<1> is a bivalent aromatic hydrocarbon residue, (c) is an integer of >=0, and (d) is an integer of >=1.

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 Conventional electrochromic anti-glare mirrors include, for example,
It is known that an inorganic oxide such as tungsten oxide (WO ₃ ) is formed on a transparent conductive substrate by a vacuum evaporation method or a sputtering method, and this is used as a color former (electrochromic substance) (Japanese Patent Application Laid-Open No. 63-18336). However, a vacuum pump is indispensable for performing the vacuum deposition method or the sputtering method, so that there is a disadvantage that the formation of a film serving as a color developing agent increases costs. Therefore, development of an electrochromic mirror that can be manufactured more easily and at lower cost is desired.

[0003]

SUMMARY OF THE INVENTION The present invention provides an electrochromic mirror which can be manufactured in a simple process at low cost by using a specific conductive polymer compound as an electrochromic substance. That is, one of the electrochromic mirrors according to the present invention includes (A) the following general formula (1) between a reflective conductive substrate and a transparent conductive substrate.
Or an electrochromic layer containing a polymer consisting of a repeating unit represented by the following general formula (2) or a polymer represented by the following general formula (1): An electrochromic layer containing a copolymer comprising a unit and a repeating unit represented by the following general formula (2) is provided.

Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BE _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from the R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is from 1 to 10 carbon atoms
R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. )

Embedded image (Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen or carbon 1
Represents up to 20 hydrocarbon groups or hydrocarbon residues, which may be the same or different. Ar ¹ represents a divalent aromatic hydrocarbon residue. c represents an integer of 0 or more, and d represents an integer of 1 or more. Further, another one of the electrochromic mirrors according to the present invention is characterized in that the electrochromic layer also serves as an ion conductive material layer.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a reflective conductive substrate and a transparent conductive substrate 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 made 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, the substrate itself needs to have a smooth surface at room temperature, but the surface is flat and may be a curved surface. It may be deformed. 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. 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%. On the other hand, as the form of the reflective conductive substrate, (1) a laminate in which a reflective electrode layer is laminated on a transparent or opaque substrate having no conductivity, and (2) one of a transparent substrate having no conductivity A laminate in which a transparent electrode layer is laminated on one surface and 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 reflection plate is used as a substrate and a transparent electrode layer is laminated on the substrate, and (5) a plate-like body in which the substrate itself has both functions of a light reflection layer and an electrode layer. There is no particular limitation on the material of the transparent substrate.For example, colorless or colored glass, tempered glass, etc. can be used, and a colorless or colored transparent resin, for example, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, poly Ether sulfone,
Polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene and the like can be used. The transparent electrode layer of the present invention is literally transparent, which means a thin film that functions as an electrode.
Metal such as gold, silver, chromium, copper, tungsten or ITO
(In ₂ O ₃ —SnO ₂ ), a conductive thin film made of a metal oxide such as tin oxide, silver oxide, zinc oxide, and vanadium oxide. The thickness of this film is usually 100 to 5,
000 angstrom, preferably 500-3,000
Surface resistance (resistivity) in the range of 0 angstrom
Is usually 0.5 to 500 Ω / cm ² , preferably 1 to 5
It is in the range of 0 Ω / cm ² . An arbitrary method can be adopted as a method for forming the conductive thin film, and an appropriate method can be selected depending on the type of metal or metal oxide constituting the thin film. 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 thin film. The conductive thin film may be provided with a partially opaque electrode active material for the purpose of providing oxidation-reduction ability, improving conductivity, and providing an electric double layer capacity, but the amount of the applied material may be less than the entire thin film. It is selected within a range where transparency is not impaired. Examples of the opaque electrode active material include metals such as copper, silver, gold, platinum, iron, tungsten, titanium, and lithium; organic substances having a redox ability such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; activated carbon and graphite. Carbon material, V ₂ O ₅ ,
Examples include metal oxides such as MnO ₂ , NiO, and Ir ₂ O ₃ or mixtures thereof. Then, in order to bind the electrode active substance to the conductive thin film, an arbitrary resin binder can be used. As an example of applying an opaque electrode active material or the like on a conductive thin film, a coating film of a composition composed of activated carbon fiber, graphite, acrylic resin, etc. is formed on an ITO thin film by forming a fine pattern such as a stripe or a dot. As another example, there is a gold (Au) thin film provided with a coating film of a composition composed of V ₂ O ₅ , acetylene black, butyl rubber, or the like in a mesh shape. The reflective electrode layer of the present invention refers to 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. ,osmium,
Metal films such as iridium, silver, nickel, palladium,
An alloy film of platinum-palladium, platinum-rhodium, stainless steel, or the like can be given. 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 also has a reflective layer and an electrode function include those having self-supporting properties among those exemplified as the reflective electrode layer.

Next, the electrochromic layer of the present invention will be described. The feature of the electrochromic layer of the present invention is that a polymer comprising a repeating unit represented by the following general formula (1) (polymer (I)) and a repeating unit represented by the following general formula (2) Or a copolymer having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) (polymer (II)) (III)).

Embedded image In the general formula (1), X ⁻ and Y ⁻ may be the same or different and each is independently a halogen anion, Cl
O ₄ ⁻ , BE ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH _{3
(C 6 H 4) SO 3} - represents a counter anion selected from,
The halogen ^{anion, F -, Cl -, Br} -, I
^-, and the like. R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group includes a methyl group,
Examples include an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group, and an n-pentyl group.
It is particularly preferred that R ¹ is hydrogen or a methyl group. R
² represents a hydrocarbon residue having 1 to 10 carbon atoms, specifically, And the like. R ³ represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 8 carbon atoms, an aryl group or an aralkyl group. As the alkyl group, a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n- Butyl group,
t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like,
Examples of the aralkyl group include a benzyl group. The polymer (I) has two or more repeating units represented by the general formula (1), and usually has 2 to 500, preferably 2 to 100.
And more preferably 2 to 50, and is a substantially linear polymer.

Embedded image In the general formula (2), R ⁴ is hydrogen or C 1-5
And the alkyl group includes methyl, ethyl, i-propyl, n-propyl, n-
Butyl, t-butyl, n-pentyl and the like. R ⁴ is particularly preferably hydrogen or a methyl group. R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are a hydrogen atom,
A hydrocarbon group or a hydrocarbon residue having 1 to 20, preferably 1 to 10 carbon atoms, which may be the same or different. The hydrocarbon group includes a methyl group, an ethyl group, n
Alkyl groups such as -propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, heptyl group and octyl group; alkylphenyl groups such as tolyl group and ethylphenyl group; Examples include an aryl group such as a group and an aralkyl group, and examples of the hydrocarbon residue include an alkoxyphenyl group such as a methoxyphenyl group and an ethoxyphenyl group. Ar ¹ represents a divalent aromatic hydrocarbon residue, specifically, a phenylene group (o-, m-, p-), a substituted phenylene group (as a substituent,
Examples thereof include the same as those described for R ⁶ , but typically include an alkyl-substituted phenylene group and the like, and a biphenylene group. c is an integer of 0 or more, and is usually 0 to 20, preferably 0 to 10, and more preferably 0 to 5. d is 1 or more, and is usually 1 to 20, preferably 1 to 5. The polymer (II) has two or more repeating units of the general formula (2), usually has 2 to 500, preferably 2 to 100, and is a substantially linear polymer. The electrochromic substance contained in the electrochromic layer is a polymer (I)
And a mixture of the polymer (II), the polymer (I)
: The mixing ratio of polymer (II) (viologen structure: phenyleneamine structure [molar composition ratio]) can be arbitrarily selected, but is usually 1: 500 to 100: 1, preferably 1: 1:
It is in the range of 50 to 10: 1. Further, when the electrochromic substance is composed of the copolymer (III), the ratio of the repeating unit of the general formula (1) to the repeating unit of the general formula (2) in the copolymer (III) (viologen structure: phenylene) The amine structure [molar composition ratio]) can be arbitrarily selected, but is usually in the range of 1: 500 to 100: 1, preferably 1:50 to 10: 1. Then, the copolymer (I
II) has at least two recurring units, usually from 2 to 500, and preferably from 2 to 100. The copolymer (III) may be any of a block copolymer, a random copolymer, and an alternating copolymer.

The polymer (I), the polymer (II) and the copolymer (I
II) can be easily produced by using a known method, and an example thereof is as follows. Polymer
(I) First, bipyridyl and R ³ Y are substantially 1: 1.
To obtain a monosubstituted bipyridyl represented by the following general formula (21), and then reacted with a compound having a reactive group represented by the following general formula (22) to obtain a polymer (I )), The following compound (23), which is a precursor monomer, is produced, and then the precursor monomer is subjected to radical polymerization in an organic solvent using benzoyl peroxide as an initiator.

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Embedded image (Wherein X ⁻ , Y ⁻ , R ¹ , R ² and R ³ are the same as defined in the general formula (1).) The polymer (II) is first represented by the general formula (24) The amine compound is reacted with a compound represented by the general formula (25) having a reactive group to produce a compound (26) which is a precursor monomer of the polymer (II). It can be easily produced by a method of radical polymerization in a solvent using benzoyl peroxide as an initiator.

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Embedded image (Wherein, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Ar
¹ is the same as defined in the general formula (2), and z
Represents a halogen such as fluorine, chlorine, bromine and iodine. In addition, the copolymer (III) is prepared from azobisisobutyronitrile in an organic solvent capable of uniformly dissolving the compound represented by the general formula (23) and the compound represented by the general formula (26). Can be easily produced by a method of radical polymerization using as an initiator.

Generally, an electrochromic mirror is
Between the reflective conductive group and the transparent conductive substrate, a layer of an electrochromic material is arranged, and further, a layer of an ion conductive material, that is, an electrolyte layer is usually provided. In that case, it is preferable that the layer containing the electrochromic substance also functions as the electrolyte layer, in other words, the electrochromic layer and the electrolyte layer are substantially the same single layer. The electrochromic coloring layer of this preferred embodiment is easily redoxed and colorless by application of a voltage. The thickness of the electrochromic coloring layer is usually in the range of 1 μm to 3 mm, preferably 10 μm to 1 mm. In the present invention,
The ion conductive substance refers to a substance capable of causing coloring, decoloration, color change, and the like in the electrochromic layer, and the ion conductive substance is usually 1 × 10 ⁻⁷ at room temperature.
It preferably has an ionic conductivity of S / cm or more. The ion conductive material that can be used in the present invention is broadly classified into a liquid ion conductive material, a gelled liquid ion conductive material, and a solid ion conductive material.

[0008] The liquid ion-conductive substance can be prepared by dissolving a supporting electrolyte such as salts, acids, and alkalis in a solvent. The solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but a polar solvent is particularly preferable. Specifically, water can be used, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, Propionnitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide,
Organic polar solvents such as methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate and polyethylene glycol can be used, among them, propylene carbonate, ethylene carbonate,
Dimethylsulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol and the like Organic polar solvents are preferred. Each solvent may be used alone or in combination. The salt as the supporting electrolyte is not particularly limited, and various inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, and the like can be used. Specifically, LiC
_{lO 4, LiSCN, LiBF 4,} LiAsF 6, Li
CF ₃ SO ₃ , LiPF ₆ , LiI, NaI, NaSC
N, NaClO ₄ , NaBF ₄ , NaAsF ₆ , KSC
Alkali metal salts of Li, Na and K such as N and KCl: (C
_{H 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, can be mentioned _{(n-C 4 H 9)} 4 4 quaternary ammonium salts and cyclic quaternary ammonium salts, and various salts of NClO _4, and the like. Acids as a supporting electrolyte are not particularly limited, and inorganic acids, organic acids, and the like can be used. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like. The alkalis as the supporting electrolyte are also not particularly limited, and sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. In order to inject the liquid ion conductive material into a desired location between the reflective conductive substrate substrate and the transparent conductive substrate, a vacuum injection method or an air injection method can be adopted. It is possible to adopt a method in which the peripheral edge portion is sealed by opposing each other, and the liquid is injected into the gap between the substrates by a meniscus method.

The gelled liquid ion-conductive substance can be prepared by adding a polymer or a gelling agent to the liquid ion-conductive substance. As the polymer in this case, for example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, Nafion and the like can be used.
As the gelling agent, for example, oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used. In order to inject the gelled liquid-based ion-conductive substance into a desired location between the reflective conductive substrate and the transparent conductive substrate, a vacuum injection method or an air injection method can be adopted. It is possible to adopt a method in which the substrates are opposed to each other, the periphery thereof is sealed, and the substrate is injected into the gap between the substrates by a meniscus method.

As the solid ion conductive substance, a substance which is solid at room temperature and has ionic conductivity can be used. For example, polyethylene oxide, oxyethylene methacrylate polymer, Nafion, polystyrene sulfonic acid, Li ₃ N, Na-β-Al ₂ O ₃ , Sn (HPO
₄ ) ₂・ H ₂ O can be used. Particularly, a polymer compound obtained by polymerizing an oxyalkylene methacrylate-based compound, an oxyalkylene acrylate-based compound or a urethane acrylate-based compound (hereinafter, referred to as a polymer compound)
This is referred to as a polymer solid electrolyte) is preferable as the solid ion conductive material.

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

Embedded image (Wherein, R ¹⁰ and R ¹¹ are the same or different groups and represent a group selected from the following general formulas (4) to (6), and R ¹² and R ¹³ are the same or different groups; Y represents a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms, Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof, and e represents 1 to 100, preferably 1 And an integer in the range of 1 to 20, more preferably 1 to 20.)

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Embedded image In the general formulas (4) to (6), R ^{14 to} R ¹⁶ are the same or different groups, each representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁷ is a group having 1 to 20 carbon atoms. And preferably 2 to 8 divalent to tetravalent organic residues. 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 (7).

Embedded image In the general formula (7), R ¹⁸ represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and f represents an integer of 0 to 6. f is 2
In the above case, R ¹⁸ may be the same or different. The hydrocarbon residue such as an alkylene group represented by the general formula (7) has a part of hydrogen atoms 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. It may be substituted with an oxygen-containing hydrocarbon group. To summarize specific examples of R ^{17 in} the general formulas (4) to (6), And the like. R ^{12 of the} general formula (3)
And the divalent hydrocarbon residue represented by R ¹³ include a chain divalent hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and the like. And an alkylene group represented by the above general formula (7).
Examples of the aromatic hydrocarbon group and the alicyclic hydrocarbon group include hydrocarbon groups represented by the following general formulas (8) to (10).

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Embedded image In the general formulas (8) to (10), R ¹⁹ and R ²⁰ 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 ^{21 to} R ²⁴ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. G represents an integer of 1 to 5. Specific examples of R ¹² and R ^{13 in} the general formula (3) can be exemplified by the following general formulas (11) to (17).

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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).

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Embedded image In the general formulas (a) to (d), R ^{25 to} R ³⁰ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Represents a divalent hydrocarbon residue of 12, h is an integer of 2 to 300, preferably 10 to 200, i is an integer of 1 to 300, preferably 2 to 200, j is 1 to 200, preferably An integer of 2 to 100, k is 1 to 200, preferably 2
1 to 300, preferably 10 to
Each represents an integer of 200. R ^{25 to} R ³⁰ are preferably a linear or branched alkylene group, and more preferably, R ²⁷ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group. Any of R ²⁵ to
R ²⁶ and R ^{28 to} R ³⁰ are preferably either an ethylene group or a propylene group. In addition, general formulas (a) to
In (d), each unit may be the same so-called homopolymerization, a copolymer of different units, or any of them.
The molecular weight of the urethane acrylate represented by the general formula (3) is usually from 2,500 to 30,000 in terms of weight average molecular weight.
0, preferably in the range of 3,000 to 20,000. The number of polymerizable functional groups in one urethane acrylate molecule is preferably 2 to 6, more preferably 2 to 4. 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) used in preparing the composition A is usually 100 to 1200 parts by weight, preferably 200 to 900 parts by weight, based on 100 parts by weight of the urethane acrylate. If the amount of the organic non-aqueous solvent is too small, the ionic conductivity is not reduced, and if the amount of the organic non-aqueous solvent is too large, the mechanical strength after the composition A is solidified is selected. May decrease. As the supporting electrolyte, those exemplified above can be used, and the amount thereof is selected in the range of 0.1 to 30% by weight, preferably 1 to 20% by weight based on the organic nonaqueous solvent. The composition A is basically obtained by solidifying a basic component consisting of urethane acrylate, an organic non-aqueous solvent (organic polar solvent) and a supporting electrolyte, but this composition does not impair the object of the present invention. Optional components can be added as needed within the range. Examples of such optional components include a crosslinking agent and a polymerization initiator (light or heat). In order to inject the composition A into a desired portion between the reflective conductive substrate substrate and the transparent conductive substrate, a vacuum injection method or an air injection method can be adopted, and the reflective conductive substrate substrate and the transparent conductive substrate are opposed to each other. A method of sealing the peripheral portion and injecting the composition A into the gap between the substrates by the meniscus method can be adopted.
Then, by solidifying the composition A injected between the substrates by an appropriate method, a polymer solid electrolyte layer can be formed. It means that a polymerizable component or a cross-linkable component is cured by polymerization (polycondensation) or a cross-linking reaction, so that the whole composition does not substantially flow at room temperature. In this case, it has a network-like basic structure.

A second example of the polymer solid electrolyte is a composition containing acryloyl-modified polyalkylene oxide, the above-mentioned organic polar solvent and a supporting electrolyte (hereinafter abbreviated as composition B).
Is a polymer compound obtained by solidifying One example of the acryloyl-modified polyalkylene oxide,
It is a monofunctional acryloyl-modified polyalkylene oxide represented by the general formula (18).

Embedded image In the general formula (18), R ³¹ , R ³² , R ³³ and R ³⁴
Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group includes a methyl group, an ethyl group,
i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, etc., and particularly, each of R ^{31 to} R ³³ may be hydrogen or a methyl group, and R ³⁴ may be hydrogen. , A methyl group or an ethyl group. The general formula (1
M in 8) represents an integer of 1 or more, usually 1 ≦ m ≦ 100, preferably 2 ≦ m ≦ 50, more preferably 2 ≦ m ≦ 30. Specific examples of the compound represented by the general formula (18) include an oxyalkylene unit of 1 to 10
0, preferably 2 to 50, more preferably 1 to 2
Methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate having a range of 0 or a mixture thereof Can be mentioned. When m in the general formula (18) is 2 or more, the oxyalkylene units may have different so-called copolymerized oxyalkylene units, and specific examples thereof include, for example, 1 to 50 oxyethylene units, preferably Methoxy poly (ethylene propylene) glycol methacrylate, having from 1 to 20, and having from 1 to 50, preferably from 1 to 20, oxypropylene units;
Examples include ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate, or a mixture thereof.

Other examples of the acryloyl-modified polyalkylene oxide that can be used in the present invention include a bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (19) and a trifunctional acryloyl-modified polyalkylene oxide represented by the general formula (20). The above polyfunctional acryloyl-modified polyalkylene oxides and the like are mentioned.

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Embedded image In the general formula (19), R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸
Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group,
i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group and the like. Particularly, each of R ^{35 to} R ³⁸ is preferably hydrogen or a methyl group. N in the general formula (19) is an integer of 1 or more, usually 1 ≦ n ≦ 10
0, preferably 2 ≦ n ≦ 50, more preferably 2 ≦ n
Indicates an integer in the range of ≦ 30. A specific example of the bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (19) is a polyethylene glycol dialkylene having 1 to 100, preferably 2 to 50, and more preferably 1 to 20 oxyalkylene units. Examples thereof include methacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. When n is 2 or more, oxyalkylene units may have different so-called copolymerized oxyalkylene units, and examples thereof include, for example,
1 to 50 oxyethylene units, preferably 1 to
Poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, having in the range of 20 and having 1 to 50, preferably 1 to 20 oxypropylene units; Or a mixture thereof. In the general formula (20), R ³⁹ , R ⁴⁰ and R
⁴¹ individually represents hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, and a t-butyl group. , N-pentyl group and the like. R ^{39 to} R ⁴¹ are preferably hydrogen or a methyl group. P in the general formula (20) is an integer of 1 or more, usually 1 ≦ p ≦ 100, preferably 2
≦ p ≦ 50, more preferably an integer in the range of 2 ≦ p ≦ 30, q represents the number of linked groups 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,
Or a hydrocarbon group having these as a basic skeleton, and specifically, And the like. Examples of the trivalent hydrocarbon group 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. (Bz represents a benzene ring) and the like. Specific examples of the polyfunctional acryloyl-modified polyalkylene oxide include trimethylolpropane tri (polyethylene glycol acrylate) having 1 to 100 oxyalkylene units, preferably 2 to 50, and more preferably 1 to 20. Trimethylolpropane tri (polyethylene glycol methacrylate), trimethylol propane tri (polypropylene glycol acrylate), trimethylol propane tri (polypropylene glycol methacrylate), tetramethylol methane tetra (polyethylene glycol acrylate), tetramethylol methane tetra (polyethylene glycol methacrylate), Tetramethylolmethanetetra (polypropylene glycol acrylate), tetramethylolmethanete La (polypropylene glycol methacrylate), 2,2-bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane, 2,2
Examples thereof include bis [4- (acryloxypolyisopropoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyisopropoxy) phenyl] propane, and a mixture thereof. When p is 2 or more, oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other, for example, 1 to 50 oxyethylene units, preferably 1 to 20 oxyethylene units, and Trimethylolpropane tri (poly (ethylene propylene) glycol acrylate) having 1 to 50, preferably 1 to 20 oxypropylene units,
Trimethylolpropane tri (poly (ethylene propylene) glycol methacrylate), tetramethylol methane tetra (poly (ethylene propylene) glycol acrylate), tetramethylol methane tetra (poly (ethylene propylene) glycol methacrylate), or a mixture thereof Is a specific example.
The monofunctional acryloyl-modified polyalkylene oxide represented by the general formula (18) and the general formula (19) or the general formula (2)
The polyfunctional acryloyl-modified polyalkylene oxide represented by 0) can be used in combination. When used in combination, the weight ratio of monofunctional acryloyl-modified polyalkylene oxide / polyfunctional acryloyl-modified polyalkylene oxide is usually 0.01 / 99.9 to 99.9 / 0.01, preferably 1/99 to 99/1, More preferably, 20/80 to 8
It is in the range of 0/20. The amount of the polar organic solvent used for preparing the composition B is usually in the range of 50 to 800% by weight, preferably 100 to 500% by weight, based on the acryloyl-modified polyalkylene oxide. It is usually in the range of 1 to 30% by weight, preferably 3 to 20% by weight, based on the weight of the acryloyl-modified polyalkylene oxide and the polar organic solvent. A photopolymerization initiator or a thermal polymerization initiator can be added to the composition B if necessary, and the amount of the polymerization initiator is usually 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the acryloyl-modified polyalkylene oxide. It is in the range of 0.01 to 3% by weight.

In order to inject the composition B into a desired portion between the reflective conductive substrate substrate and the transparent conductive substrate, a vacuum injection method or an atmospheric injection method can be adopted. A method of injecting the composition A into the gap between the substrates by a meniscus method can be adopted by opposing and sealing the periphery thereof. Then, the composition A injected between the substrates
Is solidified by an appropriate method, whereby a solid polymer electrolyte layer can be formed. Polymerizable component (monofunctional or polyfunctional acryloyl-modified polyalkylene oxide)
Alternatively, it means that a crosslinkable component or the like is cured by polymerization (polycondensation) or a crosslinking reaction, and the composition as a whole does not substantially flow at room temperature. In this case, it has a network-like basic structure.

The liquid ion conductive material, the gel liquid ion conductive material, and the solid ion conductive material described above provide the electrolyte layer necessary for the electrochromic mirror of the present invention separately from the electrochromic layer. Although it can be used when providing, in the present invention, a mode in which the single layer sandwiched between the reflective conductive substrate and the transparent conductive substrate plays a role of both the electrochromic layer and the electrolyte layer is preferable . The following method can be adopted to realize this mode. Using a liquid or gelled liquid system for the ion conductive material,
The above-mentioned polymer (I) and polymer (II) or copolymer (III) are homogeneously dissolved or dispersed therein, or the polymer
(I) and the precursor monomer or copolymer of the polymer (II) (II
A method in which the precursor monomer of I) is dissolved in a liquid or gelled liquid ion-conductive substance and polymerized. Using a solid system as the ion conductive material, typically using the polymer solid electrolyte described above, the polymer (I) and the polymer (II) in the composition A or the composition B which is a precursor thereof. Or the copolymer (III) is homogeneously dissolved or dispersed to solidify the composition, or in the composition A or the composition B, a precursor monomer of the polymer (I) and the polymer (II) Or copolymer
A method of polymerizing the precursor monomer of (III).

The electrochromic mirror according to the present invention comprises:
An electrochromic layer and an electrolyte layer (ion conductive material layer) may be separately sandwiched between a reflective conductive substrate and a transparent conductive substrate, but the same layer may be composed of an electrochromic layer and an electrolyte layer. A method of manufacturing an electrochromic mirror having the role of (1) will be described with reference to the drawings. The electrochromic mirror shown in FIG. 1 comprises a transparent substrate 1 comprising a transparent substrate 1 and a transparent electrode layer 2 laminated on the surface thereof, and a transparent or opaque substrate 5 and a reflective conductive substrate laminated on the surface. The electrochromic mirror has a structure in which an electrochromic layer / electrolyte layer 6 is sandwiched. The electrochromic mirror can be manufactured by the following method. First, a laminate A is formed by forming a transparent electrode layer 2 on a transparent substrate 1, and a laminate B is formed by forming a reflective electrode layer 4 on a substrate 5. Next, the laminate A and the laminate B are opposed to each other at an interval of about 1 to 1000 μm so that the transparent electrode layer and the reflective electrode layer face each other. Create an empty cell. Subsequently, the electrochromic substance of the present invention (polymer (I) and polymer
(II) or a copolymer (III)) and an ion-conductive substance (usually liquid) are injected from the above-mentioned injection port, and then sealed to produce the electrochromic mirror shown in FIG. can do. When the laminate A and the laminate B are opposed to each other, a spacer can be used to secure a constant interval between them. The spacer is not particularly limited, but beads or sheets made of glass, polymer, or the like can be used. The spacer may be provided directly on the surface of the laminate. When the solid ion-conductive substance of the present invention is used as the ion-conductive substance, the composition A or the composition B is cured after injection. Curing methods are available. Further, the electrochromic mirror of the present invention includes a laminate A ′ in which a transparent electrode layer 2 and an electrochromic layer / ion conductive material layer 3 are sequentially formed on a transparent substrate 1 in the stated order, and a reflective electrode on a substrate 5. After each of the laminates B ′ on which the layer 4 was formed, the electrochromic layer / ion conductive material layer 3 of the laminate A ′ and the reflective electrode layer 4 of the laminate B ′ were brought into close contact with each other. Can be manufactured by a method of sealing the periphery of the seal with the sealing material 6.
The electrochromic mirror shown in FIG.
A transparent conductive substrate having a transparent electrode layer 2 formed on one surface thereof;
The transparent electrode layer 2 is formed on one side of the transparent substrate 1 and the reflective conductive substrate having the reflective layer 4 formed on the other side is opposed at appropriate intervals so that the transparent electrode layers of both substrates face each other. In which an electrochromic layer and an ion conductive material layer 3 are sandwiched. The electrochromic mirror shown in FIG. 2 is the same as the electrochromic mirror shown in FIG. 1 except that the transparent electrode layer 2 is formed on one surface of the transparent substrate 1 and the reflection layer 8 is formed on the other surface. Can be manufactured by procedure. The electrochromic mirror of the present invention may be provided with an ultraviolet cut layer such as an ultraviolet reflection layer or an ultraviolet absorption layer, an overcoat layer for protecting the surface of the entire mirror or each film layer, and the like, if necessary. When an ultraviolet cut layer is provided, it is placed on the outside of the transparent substrate 1 or on the transparent electrode layer side. When an overcoat layer is placed, it is placed on the outside of the transparent substrate 1 or the outside of the reflective layer 8. Preferably, it is provided.

[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 and has a simple process, it can be manufactured relatively easily and inexpensively, and the specification of the compound can be changed. Has an excellent feature that the coloring density can be easily adjusted. It is easy to use a solid electrolyte for the ion conductive material layer, so that a large-sized and highly safe mirror can be manufactured without electrolyte solution scattering. Moreover, the electrochromic mirror of the present invention
By applying a voltage between the respective electrodes, color development / decoloration due to the electrochromic phenomenon can be caused, and a known voltage application means can be used. 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 it should not be construed that the invention is limited thereto. Example 1 (1) Synthesis of electrochromic compound 3.12 g (20 mmol) of bipyridyl was dissolved in 100 ml of acetonitrile in a flask, and 2-bromoethyl obtained by the reaction of 2-bromoethanol and methacrylic acid chloride was added thereto. 7.72 g of methacrylate (4
0 mmol) was added. After stirring at room temperature for 24 hours, the precipitated solid was separated by filtration and dried to obtain N, represented by the formula (27).
9.22 g (17 mmol) of N'-di-methacrylethylbipyridinium dibromide were obtained.

Embedded image (2) Synthesis of electron donor compound Diphenylamine was placed in a 500 ml three-necked flask.
4 g (150 mmol), cesium fluoride 22.8
g (150 mmol) was weighed, the atmosphere in the flask was replaced with nitrogen, 250 ml of dimethyl sulfoxide was added, and the mixture was stirred. 21.3 g of 1-fluoro-4-nitrobenzene (1
50 mmol) and heat to 120 ° C in an oil bath,
Stirring was continued for 24 hours. The reaction solution was poured into ice water to precipitate a solid, and the obtained solid was recrystallized from acetic acid to obtain a compound of the formula (2)
29.5 g (102 mmol) of the compound represented by 8) was obtained.

Embedded image 14. Compound (27) obtained as described above.
0 g (52 mmol) was transferred to a 500 ml three-necked flask, 200 ml of dimethylformamide and 1.5 g of 5% palladium / carbon were added, and hydrogen was supplied at normal pressure. After stirring was continued at room temperature for 12 hours, the palladium carbon was removed by filtration, and the reaction solution was poured into ice water to precipitate a solid. The obtained white solid was dried under reduced pressure to obtain the compound of the formula (29)
12.5 g (48 mmol) of the compound represented by were obtained.

Embedded image 12.5 g (48 mmol) of the compound (29) was 500 m
Then, the mixture was transferred to a three-necked flask, and 250 ml of benzene and 10 ml of triethylamine were added thereto, followed by stirring under ice cooling. A solution of 6.3 g (60 mmol) of methacrylic chloride / 20 ml of benzene was added dropwise. The reaction solution was washed twice with a 1N aqueous HCl solution, twice with water, twice with a 1N aqueous NaOH solution, and dried over sodium sulfate. The solvent was distilled off to obtain 13.4 g (41 mmol) of the compound (30).

Embedded image (3) Electrochromic compound and electron donor compound
5.4 g (10 mmol) of the polymerized compound (27) and the compound (3
0) 6.6 g (20 mmol) was dissolved in 30 ml of γ-butyrolactone, 0.2 g of AIBN was added, and the mixture was heated to 80 ° C. in an oil bath to give compound (27) and compound (3).
0) was obtained. The average molecular weight of the polymer obtained by GPC analysis was about 12,000. (4) Preparation of Electrochromic Mirror A substrate provided with a platinum thin film was used as a highly reflective electrode, and this was used as a laminate B. A portion around the platinum thin film side of the laminate B was an injection port for an electrolyte precursor solution. Except for applying an epoxy-based adhesive in the form of a line, and overlying the transparent glass substrate A coated with ITO so that the ITO surface and the platinum electrode layer face each other, and curing the adhesive while applying pressure, An empty cell with an inlet was made. On the other hand, methoxy polyethylene 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. 02 g was added to obtain a homogeneous solution. Here, the compound (27) obtained in the above (3)
2 ml of a copolymer solution of the compound and the compound (30) was added to homogenize the mixture. After degassing, the mixture was injected as an electrolyte precursor from the injection port of the cell prepared as described above. After sealing the injection port with an epoxy-based adhesive, the electrolyte precursor was cured by applying light from a fluorescent lamp from the transparent substrate side to obtain a solid polymer electrolyte. Thus, an all-solid-state electrochromic mirror having the configuration shown in FIG. 1 was obtained. This mirror was not colored when assembled and had a reflectivity of about 85%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, when a voltage of 1.5 V was applied, the layer was colored, and the reflectance of light having a wavelength of 633 nm was about 10%. The colored state was maintained even after the voltage application was stopped, and the reflectance was 10% after 100 hours. Example 2 (1) Synthesis of Electrochromic 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, and the mixture was stirred at room temperature for 24 hours. Heptyl
N'-methacrylethyl bipyridinium dibromide was obtained.

Embedded image (2) Electrochromic compound and electron donor compound
10.6 g (20 mmol) of polymerized compound (31) and 6.6 g (20 mmol) of compound (30) were dissolved in 30 ml of γ-butyrolactone, 0.2 g of AIBN was added, and the mixture was heated to 80 ° C. in an oil bath to obtain a compound. A copolymer solution of (31) and compound (30) was obtained. The average molecular weight of the polymer obtained by GPC analysis was about 10,000. (3) Preparation of Electrochromic Mirror A substrate provided with a palladium thin film was used as a highly reflective electrode, this was used as a laminate D, and the portion of the electrolyte precursor solution injection port was placed around the palladium of the laminate D. except epoxy adhesive was streaked with a transparent glass substrate C that is SnO ₂ coated thereon, superposed so as to face and the SnO ₂ surface and the palladium layer, curing the adhesive under pressure, An empty cell with an inlet was made. On the other hand, (2)
5.0 g of a copolymer solution of the compound (31) and the compound (30) obtained in the above was added to methoxypolyethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
MEO4) [Number of oxyethylene units 4] 1.0
g, 9 g of polyethylene glycol dimethacrylate (9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) [9 oxyethylene units] and 0.4 g of lithium perchlorate were added to form a uniform 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. 02 g was added. After degassing this solution, it was injected as an electrolyte precursor from the injection port of the 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. 1 was obtained. This mirror was not colored when assembled and had a reflectivity of about 85%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, when a voltage of 1.5 V was applied, the layer was colored and the reflectance was about 15%. The colored state was maintained even after the voltage application was stopped, and the reflectance was 10% after 100 hours.

[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.

[Explanation of symbols]

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

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[Procedure amendment]

[Submission date] November 6, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

(Wherein X ⁻ and Y ⁻ may be the same or different and each independently represents a halogen anion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃
A counter anion selected from (C ₆ H ₄ ) SO ₃ ^— ,
R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is a hydrocarbon residue having 1 to 10 carbon atoms, and R ³ is 1 to 2 carbon atoms.
0 represents an alkyl group, an aryl group or an aralkyl group, respectively. )

Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁵ , R ⁶ , R ^7, R ⁸ and R ⁹ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group. Ar ¹ represents a divalent aromatic hydrocarbon residue, c represents an integer of 0 or more, and d represents an integer of 1 or more.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0003

[Correction method] Change

[Correction contents]

[0003]

SUMMARY OF THE INVENTION The present invention provides an electrochromic mirror which can be manufactured in a simple process at low cost by using a specific conductive polymer compound as an electrochromic substance. That is, one of the electrochromic mirrors according to the present invention includes (A) the following general formula (1) between a reflective conductive substrate and a transparent conductive substrate.
Or an electrochromic layer containing a polymer consisting of a repeating unit represented by the following general formula (2) or a polymer represented by the following general formula (1): An electrochromic layer containing a copolymer comprising a unit and a repeating unit represented by the following general formula (2) is provided.

(Wherein X ⁻ and Y ⁻ may be the same or different and each is independently a halogen anion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃
A counter anion selected from (C ₆ H ₄ ) SO ₃ ^— ,
R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is a hydrocarbon residue having 1 to 10 carbon atoms, and R ³ is 1 to 2 carbon atoms.
And 0 represents an alkyl group, an aryl group, or an aralkyl group, respectively. )

Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group. Ar ¹ represents a divalent aromatic hydrocarbon residue, c represents an integer of 0 or more, and d represents an integer of 1 or more.) Another one of the electrochromic mirrors according to the present invention is characterized in that the electrochromic layer also serves as an ion conductive material layer.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

Next, the electrochromic layer of the present invention will be described. The feature of the electrochromic layer of the present invention is that a polymer comprising a repeating unit represented by the following general formula (1) (polymer (I)) and a repeating unit represented by the following general formula (2) (Polymer (II))
Or a copolymer having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) (copolymer (III)). On the point.

In the general formula (1), X ⁻ and Y ⁻ may be the same or different, and each is independently a halogen anion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ CO _3.
O ⁻ represents a counter anion selected from CH ₃ (C ₆ H ₄ ) SO ₃ ^—, and examples of the halogen anion include F ⁻ and C ⁻ .
l ^{-, Br -,} I ^-, and the like. R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group, and an n- And a pentyl group. It is particularly preferred that R ¹ is hydrogen or a methyl group. R ² represents a hydrocarbon residue having 1 to 10 carbon atoms, and specifically, And the like. R ³ represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 8 carbon atoms, an aryl group or an aralkyl group. As the alkyl group, a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n- Butyl group,
t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like,
Examples of the aralkyl group include a benzyl group. The polymer (I) contains two repeating units represented by the general formula (1).
Or more, usually 2 to 500, preferably 2 to 10
It has 0, more preferably 2 to 50, and is a substantially linear polymer.

In the general formula (2), R ⁴ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, i-propyl, n-propyl, n-propyl. -Butyl group, t-butyl group, n-pentyl group and the like. It is particularly preferred that R ⁴ is hydrogen or a methyl group. R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are
A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms or a hydrocarbon residue, which may be the same or different. Examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, heptyl group, and octyl group. , An alkylphenyl group such as an ethylphenyl group, an aryl group such as a phenyl group, an aralkyl group, and the like, and examples of the hydrocarbon residue include an alkoxyphenyl group such as a methoxyphenyl group and an ethoxyphenyl group. Can be Ar ¹
To represents a divalent aromatic hydrocarbon residue, specifically, a phenylene group (o-, m-, p-), as the substituted phenylene group (the substituent, can be mentioned those similar to R ⁶ , Typically an alkyl-substituted phenylene group), a biphenylene group and the like. c is an integer of 0 or more, usually 0 to
20, preferably 0 to 10, more preferably 0 to 5. d is 1 or more, usually 1 to 20, preferably 1 to
5 The polymer (II) has two or more repeating units of the general formula (2), usually has 2 to 500, preferably 2 to 100, and is a substantially linear polymer. When the electrochromic substance contained in the electrochromic layer is composed of a mixture of the polymer (I) and the polymer (II), the mixing ratio of the polymer (I): polymer (II) (viologen structure: The phenyleneamine structure [molar composition ratio]) can be arbitrarily selected, but is usually 1: 500.
１００100: 1, preferably 1:50 to 10: 1. Further, the electrochromic substance is a copolymer (I
Also in the case of being constituted by II), the ratio of the repeating unit of the general formula (1) to the repeating unit of the general formula (2) (viologen structure: phenyleneamine structure [molar composition ratio]) in the copolymer (III) is arbitrary. But usually 1: 500 to 100: 1, preferably 1:50 to 10:
1 range. The copolymer (III) has at least two repeating units, and is usually from 2 to 500.
, Preferably 2 to 100. Copolymer (I
II) may be any of a block copolymer, a random copolymer, and an alternating copolymer.

Claims (2)

[Claims] 1. A polymer comprising a repeating unit represented by the following general formula (1) and a polymer represented by the following general formula (2) between a reflective conductive substrate and a transparent conductive substrate. An electrochromic layer containing a polymer comprising a repeating unit or (B) a copolymer comprising a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) An electrochromic mirror provided with an electrochromic layer. Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BE _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from the R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is from 1 to 10 carbon atoms
R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. ) (Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen or carbon 1
Represents up to 20 hydrocarbon groups or hydrocarbon residues, which may be the same or different. Ar ¹ represents a divalent aromatic hydrocarbon residue. c represents an integer of 0 or more, and d represents an integer of 1 or more. ) 2. The electrochromic mirror according to claim 1, wherein said electrochromic layer also serves as an ion conductive material layer.