JPH11142893A - Electrochromic mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic mirror which may be produced by an inexpensive color developing agent and simple stage. SOLUTION: This electrochromic mirror is constituted by disposing an electrochromic high-polymer solid electrolyte layer having a copolymer component composed of the precursor component of a high-polymer solid electrolyte and a biologen compd. having the acrylate based reactive group expressed by general formula (1) between a reflective conductive substrate and a transparent conductive substrate. In the formula, X<-> , Y<-> may be the same or different and respectively discretely denote a paired anion selected from halogen anion, ClO4 <-> , BF4 <-> , PF6 <-> , CH3 COO<-> , CH3 (C6 H4 )SO3 ; R1 denotes hydrogen or 1-5C alkyl group; R<2> denotes 1-10C hydrocarbon residue and R<3> denotes 1-20C hydrocarbon.

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 ) is formed on a transparent conductive film by a vacuum evaporation or sputtering method and this is used as a coloring agent (Japanese Patent Application Laid-Open No. 63-18336). . However, these film forming means require the use of a vacuum technique, which causes a problem of high cost. The present invention has been made in view of such circumstances, and has as its object to provide an inexpensive color former and an electrochromic mirror that can be manufactured by simple steps.

[0003]

In order to achieve the above object, an electrochromic mirror according to the present invention comprises a precursor component of a solid polymer electrolyte between a reflective conductive substrate and a transparent conductive substrate. This is provided with an electrochromic polymer solid electrolyte layer having a copolymer with a viologen compound having an acrylate-based reactive group represented by the formula (1).

Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , B
F ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃
^- represents a counter anion selected from, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is a hydrocarbon residue having 1 to 10 carbon atoms, R ³ is 1 to 20 carbon atoms Shows a hydrocarbon group. It is preferable that the electrochromic polymer solid electrolyte layer also functions as a coloring / decoloring layer.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a reflective conductive substrate and a transparent conductive substrate are used, and any conductive substrate may be used as long as it has a function as an electrode. Specifically, there are a substrate formed of a conductive material as a whole, and a substrate formed of a non-conductive substrate 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. The term “transparent” in the present invention refers to having a transmittance of 10 to 100%, and the substrate in the present invention has a smooth surface at room temperature. 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. Examples of the form of the reflective conductive substrate include (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 reflective layer on the other surface. (3) a laminate in which a reflective layer is provided on a transparent substrate substrate and a transparent electrode layer is provided on the reflective layer, and (4) a plate in which the substrate itself has both conductivity and an electrode function with the reflective layer. And the like.
The material of the transparent substrate is not particularly limited. For example, a colorless or colored glass, a 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,
Examples thereof include polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, and polystyrene.

[0005] The transparent electrode layer is not particularly limited as long as the object of the present invention is achieved.
Examples include a metal thin film of silver, chromium, copper, tungsten, or the like, and a conductive film made of a metal oxide. Examples of the metal oxide include ITO (In ₂ O ₃ —SnO ₂ ), tin oxide, silver oxide, zinc oxide, and vanadium oxide. The thickness of the transparent 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 .
cm ² is desirable. The method for forming the transparent electrode layer is not particularly limited, and a known method can be appropriately selected depending on the type of the metal and the metal oxide constituting the electrode. Usually, a vacuum deposition method, an ion plating method, a sputtering method, Alternatively, a sol-gel method or the like can be adopted. On this occasion,
The thickness of the electrode layer is appropriately selected within a range where the transparency of the electrode layer is not impaired. 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, platinum, iron, tungsten, titanium,
Metals such as 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 , metal oxides such as MnO ₂ , NiO, 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, a composition comprising activated carbon fiber, graphite, acrylic resin, or the like is formed on the ITO transparent electrode in a fine pattern such as a stripe or a dot. , Gold (Au) thin film, V ₂ O ₅ , acetylene black,
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 a mirror surface can be obtained. For example, gold, platinum, tungsten, tantalum, rhenium,
Examples include a metal film such as osmium, iridium, silver, nickel, and palladium, and an alloy film such as platinum-palladium, platinum-rhodium, and stainless steel. 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 deposition 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, stone materials And the like. The reflector or the reflective layer 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.

[0007] In the electrochromic mirror of the present invention, as described above, the specific function of both the electrolyte layer and the coloring / decoloring layer between the reflective conductive substrate and the transparent conductive substrate (hereinafter referred to as the opposing conductive substrate). The electrochromic polymer solid electrolyte layer is provided. In such a specific electrochromic polymer solid electrolyte layer, a structure derived from a viologen compound having an acrylate-based reactive group represented by the general formula (1) is usually bonded to the polymer solid electrolyte. The electrochromic polymer solid electrolyte layer is obtained by copolymerizing a polymerizable precursor component of the polymer solid electrolyte and a viologen compound having an acrylate-based reactive group represented by the following general formula (1). It is. As a specific production method, for example, a method in which a viologen compound having an acrylate-based reactive group represented by the general formula (1) is dissolved in a solvent together with a precursor of a polymer solid electrolyte and polymerized, and the like are preferable methods. No.

First, a viologen compound having an acrylate-based reactive group represented by the general formula (1) will be described.

Embedded image 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 COO ⁻ , CH ₃ (C ₆ H ₄ )
SO ₃ ^- represents a counter anion selected from. Examples of the halogen anion include F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ . R ¹ 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 and the like, and particularly preferably hydrogen or methyl group. R ² has 1 to 10 carbon atoms
Represents a hydrocarbon residue. In particular And the like. R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms, and examples of the hydrocarbon group include an alkyl group, an allyl group, and an aralkyl group. , I-propyl group,
Examples thereof include n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and benzyl groups. As a viologen compound having an acrylate-based reactive group represented by the general formula (1),

Embedded image

Embedded image And the like. Of course, two or more of these can be used in combination.

Next, the polymer solid electrolyte will be described.
As a polymer solid electrolyte, 1 × 10 ⁻⁷ S /
It is desirable to exhibit an ionic conductivity of not less than 1 cm.sup.2, preferably not less than 1.times.10.sup.- ⁶ S / cm. The polymer solid electrolyte is not particularly limited as long as it is solid at room temperature and has the ionic conductivity, and examples thereof include polyethylene oxide and oxyethylene methacrylate polymers, and particularly oxyalkylene methacrylate-based compounds. Those obtained by polymerizing an oxyalkylene acrylate compound or a urethane acrylate compound are preferred.

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

Embedded image (Wherein, R ⁴ and R ⁵ are the same or different groups and represent groups selected from the groups represented by formulas (3) to (5). R ⁶ and R ⁷ are the same or different groups. And represents a divalent hydrocarbon residue having 1 to 20 carbon atoms, preferably 2 to 12. Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof, and b represents 1 to 100, It is preferably an integer in the range of 1 to 50, more preferably 1 to 20.)

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Embedded image In the general formulas (3) to (5), R ^{8 to} R ¹⁰ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ 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 ¹² represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and c is an integer of 0 to 6. c is 2
In the above case, R ¹² may be the same or different. Also,
In the above-mentioned hydrocarbon residue, a part of the hydrogen atoms has 1 to 1 carbon atoms.
6, preferably 1 to 3 alkoxy groups, 6 to 12 carbon atoms
May be a group substituted by an oxygen-containing hydrocarbon group such as an aryloxy group. As R ¹¹ in the general formulas (3) to (5), specifically, And the like.

2 represented by R ⁶ and R ⁷ in the general formula (2)
Examples of the divalent hydrocarbon residue include a chain divalent hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. The chain divalent hydrocarbon group is represented by the general formula (6) And the like. 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 ¹³ and R ¹⁴ 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 group). A cycloalkylene group). R ^{15 to} R ¹⁸ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. D is an integer of 1 to 5. General formula (2)
Specific examples of R ⁶ and R ⁷ include groups represented by the following general formulas (10) to (16).

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In the general formula (2), Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof.
As the polyester unit, the polycarbonate unit, and the mixed unit thereof, the following general formulas (a) to
The unit shown by (d) can be mentioned.

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Embedded image

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Embedded image In the general formulas (a) to (d), R ^{19 to} R ²⁴ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to ²⁴ carbon atoms.
Shows 12 divalent hydrocarbon residues. As R ^{19 to} R ²⁴ , a linear or branched alkylene group or the like is preferable. Specifically, R ²¹ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group. Groups and the like are preferred. Also, R
¹⁹ to R ²⁰ and R ²² to R Examples ²⁴ ethylene group, and propylene group are preferred. E is an integer of 2 to 300, preferably 10 to 200. F is 1 to 30
0, preferably an integer of 2 to 200, g is an integer of 1 to 200, preferably 2 to 100, h is an integer of 1 to 200, preferably 2 to 100, i is 1 to 300, preferably 10
It is an integer of ~ 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 ^{19 to} R ²⁴ are present, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ^23
24 Comrades may be the same or different. Particularly preferred examples of the copolymer include a copolymerized unit of ethylene oxide and propylene oxide.

The molecular weight of the urethane acrylate represented by the general formula (2) is usually from 2,500 to
30,000, preferably 3,000 to 20,000 is desirable. The number of the polymerizable functional groups in one molecule of the urethane acrylate is preferably 2 to 6, more preferably 2 to 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.

As the organic polar solvent (organic non-aqueous solvent),
Methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, γ-
Valerolactone, sulfolane, dimethylformamide,
Organic polar solvents such as dimethoxyethane, tetrahydrofuran, acetonitrile, propionnitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol and the like, preferably, Propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylol Faye , Organic polar solvents such as polyethylene glycol is desirable. These can be used alone or as a mixture when used. The amount of the organic polar solvent (organic non-aqueous solvent) added is usually 100 to 1200 parts by weight, preferably 2 to 100 parts by weight of urethane acrylate.
It is a ratio of 00 to 900 parts by weight. If the amount of the organic non-aqueous solvent is too small, the ionic conductivity is not sufficient, and if the amount of the organic non-aqueous solvent is too large, the mechanical strength may be reduced.

The supporting electrolyte is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include inorganic ionic salts such as various alkali metal salts and alkaline earth metal salts,
Quaternary ammonium salts and cyclic quaternary ammonium salts. Specific examples thereof include LiClO ₄ , LiSCN, and LiBF.
_{4, LiAsF 6, LiCF 3 SO} 3, LiPF 6, Li
I, NaI, NaSCN, NaClO ₄ , NaBF ₄ , N
aAsF ₆ , alkali metal salts of Na, K such as KSCN, KCl, etc .; (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ N
_{BF 4, (n-C 4} H 9) 4 NBF 4, (C 2 H 5) 4 NB
_{r, (C 2 H 5)} 4 NClO 4, (n-C 4 H 9) 4 NClO
Quaternary ammonium salts and cyclic quaternary ammonium salts such as _4, or mixtures thereof as preferred. Acids as a supporting electrolyte are not particularly limited,
Examples thereof include inorganic acids and organic acids, and specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids. The alkali as a supporting electrolyte is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The addition amount is 0.1 to 30% by weight, preferably 1 to 20% by weight based on the organic non-aqueous solvent.

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 within a range that does not impair the purpose of the above. Examples of such optional components include a crosslinking agent and a polymerization initiator (light or heat).

In a preferred embodiment of the present invention, a composition obtained by adding a viologen compound having an acrylate-based reactive group represented by the above-mentioned general formula (1) to these precursor compositions is provided. Is solidified to copolymerize the precursor of the polymer solid electrolyte with the viologen compound. This copolymerization can be carried out under the same conditions as when a polymer solid electrolyte is obtained without using the viologen compound alone. The ratio of using the precursor component and the viologen compound having an acrylate-based reactive group represented by the general formula (1) is not particularly limited,
The molar ratio of urethane acrylate to a viologen compound having an acrylate-based reactive group represented by the general formula (1) is usually 10,000 / 1 to 1/1, preferably 1,0.
About 00/1 to 10/1 is desirable. In the case of the polymer solid electrolyte of the first example, after the composition A containing the viologen compound having an acrylate-based reactive group represented by the general formula (1) is injected into a desired place by a known method as appropriate. , Can be interposed between the opposing conductive substrates by solidification. 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, referred to as “composition B”) is exemplified.

Embedded image (Wherein, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms, and j is an integer of 1 or more.) General formula (17) In the above, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸
Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, wherein the alkyl group is a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group; Butyl group, n-pentyl group and the like, and may be the same or different from each other. In particular, R ²⁵ is hydrogen, methyl group,
Preferably, R ²⁶ is hydrogen, methyl, R ²⁷ is hydrogen, methyl, and R ²⁸ is hydrogen, methyl, ethyl. J in the general formula (17) is an integer of 1 or more, usually 1 ≦ j
≦ 100, preferably 2 ≦ j ≦ 50, more preferably 2 ≦ j ≦ 30. Specific examples of the compound represented by the general formula (17) include methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol methacrylate having an oxyalkylene unit in the range of 1 to 100, preferably 2 to 50, more preferably 1 to 20; Examples include ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate, and mixtures thereof. The general formula (1
When j in 7) 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, preferably 1 to 20 oxyethylene units.
And the oxypropylene unit is 1 to 5
Methoxy poly (ethylene / propylene) glycol methacrylate, ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate having a range of 0, preferably 1 to 20; Or a mixture thereof.

The polyfunctional acryloyl-modified polyalkylene oxide usable in the present invention includes a so-called bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (18) and a so-called trifunctional acryloyl-modified polyalkylene oxide represented by the general formula (19). Examples thereof include polyfunctional acryloyl-modified polyalkylene oxides having functional or higher functionality.

Embedded image (In the formula, R ²⁹ , R ³⁰ , R ³¹ and R ³² each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms, and k is an integer of 1 or more.)

Embedded image (Wherein R ³³ , R ³⁴ and R ³⁵ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms;
Is an integer of 1 or more, m is an integer of 2 to 4, and L represents an m-valent linking group. ) In the general formula (18), R ²⁹ , R ³⁰ and R ³¹ in the formula
And R ³² each independently represent 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, and an n-butyl group. , T-butyl group, n-pentyl group and the like. In particular, it is preferable that R ²⁹ is hydrogen, methyl, R ³⁰ is hydrogen, methyl, R ³¹ is hydrogen, methyl, and R ³² is hydrogen, methyl. In addition, k in the general formula (18) is an integer of 1 or more, usually 1 ≦ k ≦ 100, preferably 2 ≦ k ≦ 50, and more preferably 2 ≦ k ≦ 30. Examples of the polyethylene glycol dimethacrylate having an oxyalkylene unit in the range of 1 to 100, preferably 2 to 50, more preferably 1 to 20, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, or These mixtures can be mentioned. When k is 2 or more, the oxyalkylene unit may have a so-called copolymerized oxyalkylene unit different from each other, and examples thereof include an oxyethylene unit of 1 to 50, preferably 1 to 20. Holding
And poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, or a mixture thereof having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20. R ³³ , R ³⁴ and R ³⁵ in the general formula (19) each independently represent hydrogen or 1
Alkyl groups having from 5 to 5 carbon atoms, such as methyl, ethyl, i-propyl,
Examples thereof include an n-propyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. Particularly, R ³³ , R ³⁴ and R ³⁵ are preferably hydrogen and methyl. In the formula, l represents an integer of 1 or more, usually 1 ≦ l ≦ 100, preferably 2 ≦ l ≦ 50, and more preferably 2 ≦ l ≦ 30. m
Is the number of linking groups L, and is an integer of 2 ≦ m ≦ 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. (Bz represents a benzene ring). Also,
Examples of the tetravalent hydrocarbon group include an alkyltetralyl group, an aryltetralyl group, an arylalkyltetralyl group,
Examples thereof include an alkylaryltetralyl group, and a hydrocarbon group having these as a basic skeleton. (Bz represents a benzene ring) and the like.

Specific examples of such compounds include oxyalkylene units of 1 to 100, preferably 2 to 5
0, more preferably 1 to 20, trimethylolpropane tri (polyethylene glycol acrylate), trimethylol propane tri (polyethylene glycol methacrylate), trimethylol propane tri (polypropylene glycol acrylate), trimethylol propane tri (polypropylene glycol methacrylate) ), Tetramethylolmethanetetra (polyethylene glycol acrylate), tetramethylolmethanetetra (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,
Examples thereof include 2,2-bis [4- (methacryloxypolyisopropoxy) phenyl] propane, and a mixture thereof. When l is 2 or more, oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other. For example, oxyethylene units may have 1 to 50, preferably 1 to 20, and oxypropylene 1-5 units
0, preferably in the range of 1 to 20, trimethylolpropane tri (poly (ethylene propylene)
Glycol acrylate), trimethylolpropane tri (poly (ethylene / propylene) glycol methacrylate), tetramethylolmethanetetra (poly (ethylene / propylene) glycolacrylate), tetramethylolmethanetetra (poly (ethylene / propylene) glycol methacrylate), or Specific examples thereof include mixtures thereof. Of course, the general formula (1)
The bifunctional acryloyl-modified polyalkylene oxide represented by 7) and the trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (18) may be used in combination. When the compound represented by the general formula (17) and the compound represented by the general formula (18) 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 20/8
The range of 0 to 80/20 is desirable. The weight ratio of the compound represented by the general formula (1) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / 0.00.
It is in the range of 1-1 / 1, preferably 1 / 0.05-1 / 0.5.

The mixing ratio of the polar organic solvent is usually 5 to the weight of the compound represented by the general formula (17) and the polyfunctional acryloyl-modified polyalkylene oxide.
A range of 0 to 800% by weight, preferably 100 to 500% by weight is desirable. The mixing ratio of the supporting electrolyte is
It is usually in the range of 1 to 30% by weight, preferably 3 to 20% by weight, based on the weight of the compound represented by the general formula (17), 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 0.005 to 5% by weight based on the weight of the compound represented by the general formula (17) and the polyfunctional acryloyl-modified polyalkylene oxide. 0.01-3
% By weight.

In a preferred embodiment of the present invention, a composition obtained by adding a viologen compound having an acrylate-based reactive group represented by the general formula (1) to the composition B, By solidifying, the precursor of the solid polymer electrolyte and the viologen compound are copolymerized. The copolymerization can be carried out under the same conditions as when a polymer solid electrolyte is obtained without using the viologen compound alone. The ratio of using the precursor component and the viologen compound having an acrylate-based reactive group represented by the general formula (1) is not particularly limited, but the general formula (17)
In a molar ratio of the compound represented by the formula (1) to the viologen compound having an acrylate-based reactive group represented by the general formula (1), usually from 10,000 / 1 to 1/1, preferably from 1,000 /
About 1 to 10/1 is desirable. The polymer solid electrolyte of the second example is solidified by appropriately injecting a composition B containing a viologen compound having an acrylate-based reactive group represented by the general formula (1) into a desired place by a known method. Thus, the conductive substrate can be interposed between the opposing conductive substrates. The solidification here means a polymerizable or crosslinkable component,
For example, it means that a monofunctional or polyfunctional acryloyl-modified polyalkylene oxide or the like is cured with the progress of polymerization (polycondensation) or crosslinking, so that the composition as a whole does not substantially flow at room temperature. 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. Although the thickness of the electrochromic polymer solid electrolyte layer is not particularly limited, it is usually 1
μm to 3 mm, preferably 10 μm to 1 mm. The electrochromic polymer solid electrolyte layer thus obtained is easily redox-reduced and colored by application of a voltage. If necessary, a compound that promotes color development may be used in combination with the viologen compound having an acrylate-based reactive group represented by the general formula (1). Further, a compound that promotes color formation may be bonded to the compound having the viologen structure. The method of forming the electrochromic polymer solid electrolyte layer is not particularly limited, and is opposed by a vacuum injection method, an air injection method, a meniscus method, or the like.
In addition, a method of injecting into a gap provided between conductive substrates whose peripheral portions are sealed, a method of forming an electrolyte / color erasing layer on electrodes of the conductive substrate, and then a method of matching an opposing conductive substrate are used. it can.

The electrochromic mirror of the present invention
As described above, a reflective conductive substrate, a transparent conductive substrate, and an electrochromic polymer solid electrolyte layer provided between these substrates are characterized in that the basic configuration is described below. . A typical configuration example of the electrochromic mirror according to the present invention is shown in FIGS. The electrochromic mirror illustrated in FIG.
A second laminate including a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1 and a reflective conductive substrate having a reflective electrode layer 4 formed on a transparent or opaque substrate 5; Are disposed at predetermined intervals so that the transparent electrode 2 and the reflective electrode 4 face each other, and the electrochromic polymer solid electrolyte layer 3 is interposed between the electrodes 2 and 4. The electrochromic mirror illustrated in FIG. 2 includes a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, a transparent electrode layer 2 on one surface of the transparent substrate 1, and a transparent electrode layer 2 on the other surface. The second laminate on which the reflective layer 7 is formed is opposed to the transparent electrode 2 of the first laminate and the transparent electrode layer 2 of the second laminate at predetermined intervals so as to face each other. The conductive polymer solid electrolyte layer is interposed. Needless to say, the electrochromic mirrors shown in FIGS. 1 and 2 can cause color development / decoloration by an 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 of the films and layers constituting the electrochromic mirror of the present invention is not particularly limited, and a method of sequentially forming each of the films and layers according to the above-described 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 (laminate A).
The reflective electrode layer 4 is formed on the substrate 5 by the method described above to obtain a laminate (laminate B). Subsequently, the laminated plate A and the laminated plate B are opposed to each other at an interval of about 1 to 1000 μm, and the periphery except for the injection port is sealed with the sealing material 6 to form an empty cell with the injection port. Then, after injecting a polymer solid electrolyte precursor (usually liquid) containing a viologen compound having an acrylate-based reactive group represented by the general formula (1) by the above-described method, an electrochromic polymer solid electrolyte layer is formed. By forming 3, an electrochromic mirror can be obtained. When the laminates A and B are opposed to each other,
For example, 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 method for curing the polymer solid electrolyte precursor containing the viologen compound having an acrylate-based reactive group represented by the general formula (1) is not particularly limited, but may be a method using light, a method using heat, or a method using time. There is a method in which a reaction liquid to be cured is mixed immediately before injection, and then immediately injected and cured. Note that the injection port may be appropriately sealed. As another method, the transparent electrode layer 2 and the electrochromic polymer solid electrolyte layer 3 are sequentially formed on the transparent substrate 1 by the above-described method in the stated order to obtain a laminate (laminate A ′). Separately, the reflective electrode layer 4 is formed on the substrate 5 by the above-described method to obtain a laminate (laminate B ′). Then, both laminates are opposed at an interval of about 1 to 1000 μm so that the electrochromic polymer solid electrolyte layer of the laminate A ′ and the reflective electrode layer of the laminate B ′ are in close contact with each other, and the periphery is sealed. A method of sealing with the material 6 can be used. In the case of the electrochromic mirror having the configuration shown in FIG. 2, the transparent electrode layer 2 is formed on one surface of the transparent substrate 1 and the reflection layer 7 is formed on the other surface. An electrochromic mirror can be obtained according to the procedure.

The typical constitutional examples of the electrochromic mirror of the present invention are as shown in FIGS. 1 and 2 described above, but the electrochromic mirror of the present invention is not limited to these constitutions. However, other components may be provided. 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. It is preferable that the outer side or the transparent electrode layer side of the transparent substrate 1 and the overcoat layer are provided on the outer side of the transparent substrate 1 or the outer side of the reflective layer 8.

As described above, the electrochromic mirror of the present invention has a high response speed and sufficient durability by bonding the electrochromic compound having a reactive group to the solid electrolyte. Since the electrochromic mirror of the present invention uses a specific electrochromic polymer solid electrolyte layer and is simple in process, it can be manufactured relatively easily and inexpensively, and since the electrochromic compound does not diffuse. In addition, the compound has an excellent feature that coloration and decoloration are fast, and an excellent feature that the coloring density can be easily adjusted by changing the specification of the compound. It is easy to use a solid electrolyte as the ion conductive material layer, so that a large and highly safe mirror can be manufactured without the electrolyte solution being scattered. 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.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention.

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 obtained by the reaction between 2-bromoethanol and methacrylic acid chloride. -Bromoethyl methacrylate 7.72 g
(40 mmol) was added. After stirring at room temperature for 24 hours, the precipitated solid was separated by filtration, dried and 9.22 g of N, N'-di-methacrylethylbipyridinium dibromide.
(17 mmol) was obtained. (2) Preparation of Electrochromic Mirror On the other hand, a substrate provided with a platinum thin film as a highly reflective electrode was used as a laminate B, and an electrolyte precursor solution injection port was provided around the platinum thin film side of the laminate B. Except for the part, apply an epoxy-based adhesive in a linear shape, and place the ITO-coated transparent glass substrate A on top of this so that the ITO surface and the platinum electrode layer face each other, and cure the adhesive while pressing. Then, an empty cell with an inlet was prepared. On the other hand, 1.0 g of methoxypolyethylene glycol monomethacrylate (MEO4 manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxygen unit number 4], polyethylene glycol dimethacrylate (9G manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) [oxygen unit number 9] 0.4 g of lithium perchlorate was added to a mixed solution of 0.02 g and 4.0 g of γ-butyrolactone to obtain a uniform solution. In a dark room, 1- (4-isopropylphenyl)-as a photopolymerization initiator is added to the homogeneous solution.
0.02 g of 2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name "Dicure-1116")
Was added to obtain a homogeneous solution. Here, 1.00 g (1.84 mmol) of N, N'-di-methacrylethylbipyridinium dibromide synthesized in the above (1) was added to homogenize the mixture, and after degassing, injection of the cell prepared as described above was performed. It was injected from the inlet 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 an electrochromic polymer 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 is applied, the color is increased to 633 nm.
Is 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 methanol in equimolar amounts to obtain a monosubstituted 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, and N-heptyl-N′-methacrylethyl was added. Bipyridinium dibromide was obtained. (2) Preparation of Electrochromic Mirror On the other hand, a substrate provided with a palladium thin film was used as a highly reflective electrode, and this was used as a laminated plate D. except for the portion coated with epoxy adhesive into a linear shape, curing the transparent glass substrate C that is SnO ₂ coated thereon, superposed so as to face and the SnO ₂ surface and the palladium layer, the adhesive under pressure Then, an empty cell with an inlet was prepared. 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 (9 manufactured by Shin-Nakamura Chemical Co., Ltd.)
G) [9 oxyethylene units] 0.02 g, γ-
To a mixed solution of 4.0 g of butyrolactone, 0.4 g of lithium perchlorate was added to obtain a uniform solution. In a dark room, the photopolymerization initiator 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one (trade name "DAICURE-111" manufactured by Merck & Co., Ltd.)
6 ") 0.02 g was added, and 2 g of N-heptyl-N'-methacrylethylbipyridinium dibromide obtained in (1) was added. The obtained homogeneous solution was degassed and prepared as described above. The electrolyte was injected as an electrolyte precursor from the injection port of the cell. 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 an electrochromic polymer solid electrolyte. Thus, an all-solid-state electrochromic mirror having the structure shown in FIG. 1 was obtained. This mirror was not colored when assembled and had a reflectivity of about 85%. Also,
When a voltage was applied, the responsiveness 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.

[0031]

In summary, according to the present invention, an inexpensive color former and an electrochromic mirror which can be manufactured by simple steps can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of an electrochromic mirror of the present invention.

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

[Explanation of symbols]

 Reference Signs List 1 transparent substrate 2 transparent electrode layer 3 electrochromic polymer solid electrolyte layer 4 reflective electrode 5 substrate 6 sealing material 7 reflective layer

Claims (2)

[Claims] A precursor component of a solid polymer electrolyte is disposed between a reflective conductive substrate and a transparent conductive substrate by the following general formula (1):
An electrochromic mirror comprising an electrochromic polymer solid electrolyte layer having a copolymer with a viologen compound having an acrylate-based reactive group represented by the formula: Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anions, ClO ₄ ⁻ , BF ₄ ⁻ ,
A counter anion selected from PF ₆ ⁻ , CH ₃ COO ⁻ , and CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , wherein R ¹ is hydrogen or a carbon atom
5 represents an alkyl group, R ² represents a hydrocarbon residue having 1 to 10 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 20 carbon atoms. ) 2. The electrochromic mirror according to claim 1, wherein the electrochromic polymer solid electrolyte layer also functions as a coloring / decoloring layer.