JP2002311460A - Method for driving electrochromic mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for realizing an EC element system capable of stably maintaining reflectance in the case of coloration against change of temperature at a low cost by setting voltage to hold a coloration state as an optimal value and driving the coloration with the voltage in an electrochromic mirror. SOLUTION: In the method to drive the electrochromic mirror formed by providing an ion conductive layer including electrochromic compound between two conductive substrates at least one of which is transparent, if reflectance of light with wavelength of 633 nm when the voltage E is impressed on the mirror is expressed as TE, and the reflectance of the light with the wavelength of 633 nm when 0 V is impressed on the mirror as voltage to drive coloration is expressed as T0 , and the value of -log10 (TE/T0 ) when a differential coefficient becomes the first minimum value after the differential coefficient is first changed to reduction in a curved line of which a horizontal axis is defined as an absolute value |E| of the impressed voltage and a vertical axis is defined as -log10 (TE/T0 ), obtained by impressing optional voltage on the mirror, is expressed as ODflat , voltage corresponding to the one at which a value of -log10 (TE/T0 ) becomes within a range of 0.9×ODflat to 1.1×ODflat is impressed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for driving an electrochromic mirror which is useful as an anti-glare mirror, decoration, display or the like for automobiles.

[0002]

2. Description of the Related Art Several types of electrochromic devices (hereinafter abbreviated as EC devices) have been proposed. For example, tungsten oxide (WO ₃ )
Such an electrochromic active material as described above is formed on a conductive substrate by a vacuum evaporation method or the like, and this is used as a color former (Japanese Patent Application Laid-Open No. 63-18336). However, in this EC device, the film formation of the electrochromic active material must be performed in a vacuum, so that the manufacturing cost increases, and a large-sized vacuum device is required to obtain a large-area EC device. On the other hand, as a control method of the EC element, a method using an optical sensor to control the transmittance or the reflectance is known (JP-A-6-28).
No. 1967), which has the disadvantage of high cost.
In particular, for electrochromic mirrors, low cost is required for automotive applications, and reliability and stability are exhibited, such as exhibiting stable performance even under severe operating conditions such as wide operating temperature range and vibration. It has been desired to control the color erasing and discoloring by a method having high performance.

[0003]

SUMMARY OF THE INVENTION According to the present invention, in an electrochromic mirror, a voltage for maintaining a colored state is set to an optimum value, and coloring is driven by the voltage, so that the reflectance at the time of coloring changes with temperature. And stable EC
It is intended to provide a method for realizing an element system at low cost.

[0004]

That is, the present invention is a method for driving an electrochromic mirror provided with an ion conductive layer containing an electrochromic compound between two conductive substrates at least one of which is transparent. As the voltage for driving for coloring, the reflectance of light having a wavelength of 633 nm when the voltage E is applied to the mirror is T _E , the reflectance of light having a wavelength of 633 nm when 0 V is applied is T _0, and the reflectance of the mirror is arbitrary. And the horizontal axis represents the absolute value of the applied voltage | E
|, The value of -log ₁₀ (T _E / T ₀ ) at the time when the first minimum value is reached after the derivative first decreases in a curve with the vertical axis being −log ₁₀ (T _E / T ₀ ) If the set to OD _flat, the value is 0.9 × OD _flat ~ the _{-log 10 (T E / T 0} )
The present invention relates to a method for driving an electrochromic mirror, which applies a voltage corresponding to a voltage _falling within a range of 1.1 × OD _flat .

[0005] The present invention also relates to a driving method of the electrochromic mirror, wherein the electrochromic compound comprises at least an anodic electrochromic compound and a cathodic electrochromic compound. The present invention also relates to the method of driving an electrochromic mirror, wherein the electrochromic compound is a compound having both an anodic electrochromic structure and a cathodic electrochromic structure.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, an electrochromic mirror (hereinafter abbreviated as EC mirror) used in the present invention will be described. Two conductive substrates are used in the EC mirror of the present invention. Here, the conductive substrate means a substrate that functions as an electrode. Therefore, the conductive substrate according to the present invention includes
The substrate includes a substrate manufactured from a conductive material, and a laminate in which an electrode layer is laminated on one or both sides of a non-conductive substrate. Regardless of whether or not it has conductivity, the substrate itself preferably has a smooth surface at room temperature, but the surface may be flat or curved, and may be deformed by stress. It does not matter if it does.

One of the two 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 is usually manufactured by laminating a transparent electrode layer on a transparent substrate. Here, "transparent" means having a light transmittance of 10 to 100% in a visible light region. The material of the transparent substrate is not particularly limited,
For example, it may be a colorless or colored glass, a tempered glass, or the like, and may be a colorless or colored transparent resin. Specific examples of the transparent resin referred to here include polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide, polycarbonate, polyimide, polymethylmethacrylate, and polystyrene.

As the transparent electrode layer, for example, a metal thin film of gold, silver, chromium, copper, tungsten or the like, a conductive film made of a metal oxide, or the like can be used. Examples of the metal oxide include ITO (In ₂ O ₃ —SnO ₂ ), tin oxide,
Examples thereof include silver oxide, zinc oxide, and vanadium oxide. In particular, ITO is preferably used. The thickness of the transparent electrode layer is
Although not particularly limited, usually 10 to 1000 n
m, preferably in the range of 50 to 300 nm, and the surface resistance (resistivity) is not particularly limited, but is usually 0.5 to 500 Ω / sq. , Preferably 1 to 100Ω /
sq. , More preferably 3 to 30 Ω / sq. Is desirably within the range. For the formation of the transparent electrode layer, known means can be arbitrarily adopted, but it is preferable to select the means to be adopted depending on the kind of metal and / or metal oxide constituting the transparent electrode. Usually, a vacuum deposition method, an ion plating method, a sputtering method, a sol-gel method, or the like is employed.

The reflective conductive substrate usable in the present invention includes (1) a laminate in which a reflective electrode layer is laminated on a transparent or opaque substrate having no conductivity, and (2) a non-conductive material. A laminate in which a transparent electrode layer is laminated on one surface of a transparent substrate and a reflective layer is laminated on the other surface, (3) a reflective layer is formed on a transparent substrate having no conductivity, and a transparent electrode layer is formed on the reflective layer. A stacked body, (4) a stacked body in which a reflective plate is used as a substrate and a transparent electrode layer is stacked thereon, and (5) a plate body in which the substrate itself has both functions of a light reflecting layer and an electrode layer. And the like.

The reflective electrode layer in the present invention means a thin film having a mirror surface and exhibiting an electrochemically stable function as an electrode. As such a thin film, for example,
Examples include a metal film such as gold, platinum, tungsten, tantalum, rhenium, osmium, iridium, silver, nickel, and palladium, and an alloy film such as platinum-palladium, platinum-rhodium, and stainless steel. Any method can be used to form a thin film having such a mirror surface, for example,
A vacuum evaporation method, an ion plating method, a sputtering method, or the like can be appropriately employed.

[0011] 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, and includes, for example, a plate-like body such as silver, chromium, aluminum, stainless steel, nickel-chromium, or a thin film thereof. . In addition,
If the reflective electrode layer itself has rigidity, the use of the substrate can be omitted. Further, in the present invention, an electrode layer made of a conductive material having a lower resistance than the surface resistance of the conductive layer can be provided on the surface of the conductive layer around the conductive substrate. The electrode layer may be provided over the entire periphery of the conductive substrate or may be partially cut.

The electrode layer is not particularly limited as long as it has higher conductivity than the conductive substrate. For example, a conductive film made of a metal such as gold, silver, chromium, copper, tungsten, or the like, A conductive film formed from a conductive paste in which is dispersed in a resin can be used. The width, thickness and surface resistance (resistivity) of the electrode layer are not particularly limited as long as they are lower than the surface resistance of the conductive layer of the conductive substrate to be used. -10
0 mm, preferably 0.1-20 mm, more preferably 0.5-2 mm, and the film thickness is 0.2-500.
μm, preferably 0.5 to 100 μm, more preferably 1 to 20 μm, and the surface resistance (resistivity) is usually 1/5 of the surface resistance of the conductive layer of the conductive substrate used.
Or less, preferably 1/10 or less.

For forming the electrode layer, known means can be arbitrarily used, but it is preferable to select the means to be used depending on the material constituting the electrode. As long as the conductive film is made of a metal, a vacuum evaporation method, an ion plating method, a sputtering method, a sol-gel method, or the like is usually employed.
When a conductive film is formed from a conductive paste in which a metal is dispersed in a resin, screen printing, a dispenser method, or the like is employed.

The ion conductive layer of the EC mirror according to the present invention is usually at least 1 × 10 ⁻⁷ S / cm at room temperature, preferably at least 1 × 10 ⁻⁶ S / cm, more preferably 1 × 10 ⁻⁵ S / cm.
It is desirable to exhibit an ionic conductivity of S / cm or more. The thickness of the ion conductive layer is usually 1 μm or more, preferably 10 μm or more, and 3 mm or less, preferably 1 m or more.
m or less. In the present invention, the ion conductive layer may contain a spacer.

The ion conductive layer of the present invention contains an electrochromic compound. The electrochromic compound is not particularly limited as long as the object of the present invention is achieved, but usually has an anodic electrochromic compound, a cathodic electrochromic compound, and both an anodic electrochromic structure and a cathodic electrochromic structure. And the like.

The cathodic electrochromic compound is not particularly limited as long as it increases the absorption spectrum by an electrochemical reduction reaction. The cathodic electrochromic compound exhibits a reversible oxidation-reduction reaction, and is a styryl compound derivative, a viologen compound derivative, an anthraquinone compound. System compound derivatives and the like. The anodic electrochromic compound is not particularly limited as long as the absorption spectrum is increased by an electrochemical oxidation reaction. The anodic electrochromic compound exhibits a reversible oxidation-reduction reaction, and exhibits pyrazoline-based compound derivatives, metallocene compound derivatives, and phenylenediamine. Compound derivatives, phenazine compound derivatives, phenoxazine compound derivatives,
A phenothiazine compound derivative, a tetrathiafulvalene derivative, and the like are given.

An organic compound (hereinafter, referred to as compound (A)) having both the structure having the cathodic electrochromic property and the structure having the anodic electrochromic property can be used. In such a compound, the number of the cathodic electrochromic structure and the number of the anodic electrochromic structure contained in the compound are preferably two or less per molecule. In other words, the compound (A) is an organic compound containing one cathodic electrochromic structure and one anodic electrochromic structure in one molecule, and one cathodic electrochromic structure in one molecule. An organic compound containing two anodic electrochromic structures, two cathodic electrochromic structures in one molecule, an organic compound containing one anodic electrochromic structure in one molecule, and two organic compounds in one molecule.
It is desirable that one or two or more selected from the group consisting of two organic compounds containing a cathodic electrochromic structure and two anodic electrochromic structures.

The term "cathodic electrochromic structure" as used herein means any of a viologen compound derivative structure and an anthraquinone compound derivative structure, and the anodic electrochromic structure means a pyrazoline compound derivative structure and a metallocene compound derivative structure. , Phenylenediamine compound derivative structure, benzidine compound derivative structure, phenazine compound derivative structure, phenoxazine compound derivative structure, phenothiazine compound derivative structure,
It means any of tetrathiafulvalene derivative structures and the like.

In the present invention, the compound (A) which functions as an electrochromic active substance preferably has a bipyridinium ion pair structure represented by the following general formula (1) and the following general formula (2) or (3) ) Is contained.

[0020]

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[0021] In the general formula (1), A ^- and B ^- it may be the same or different, each independently halogen _{^{anion, ClO 4 -, BF 4 -}} , PF 6 -, CH 3 COO -, and CH _{3 (C 6 H 4) SO 3} - represents a counter anion selected from. The halogen anion here, F ^-, C
l ^-, Br ^-, I ^-, and the like.

In the general formulas (2) and (3), R ¹
And R ² represent a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group, and n
-Pentyl group, n-hexyl group, cyclohexyl group and the like are exemplified, and as the aryl group, a phenyl group is exemplified. Among these, a methyl group, an ethyl group, and a propyl group are particularly preferable. Note that R ¹ or R ² may be bonded to a cyclopentadienyl ring to form a ring, or may form a group that bridges different cyclopentadienyl rings.

M represents an integer in the range of 0 ≦ m ≦ 4, and n represents an integer in the range of 0 ≦ n ≦ 4. m and n are preferably 0 or 1, and particularly preferably 0. Me is Cr, Co, Fe, Mg, Ni, Os, R
u, V, X-Hf-Y, X-Mo-Y, X-Nb-Y,
X-Ti-Y, X-V-Y or X-Zr-Y,
Preferably, it is Fe. Here, X and Y represent hydrogen, halogen or an alkyl group having 1 to 12 carbon atoms, and may be the same or different from each other.

Preferred organic compounds as the compound (A) include compounds represented by the following general formulas (4) to (7).

[0025]

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In the general formulas (4) to (7), R ¹ ,
R ² , m, n, Me, A ⁻ and B ⁻ are the same as defined in the general formulas (1) to (3). R ³ and R ⁴ may be the same or different, and have 1 to 20 carbon atoms;
It preferably represents 1 to 10 divalent hydrocarbon residues. Preferable specific examples of the hydrocarbon residue include hydrocarbon groups such as alkylene, and esters, ethers, amides, thioethers, amines, urethanes, and silyls.

The ester is represented by the general formula -R-COO-R
-Or -R-OCO-R- (R independently represents 1 to 8 carbon atoms.
Represents an alkylene. ) Those represented by at can be mentioned, specifically, _{-C 4 H 8 -COO-C 2} H 4 -, - C 4 H 8 -OC
_{O-C 2 H 4 -,} - C 4 H 8 -COO-C 4 H 8 -, - C 4 H 8
—OCO—C ₄ H ₈ —. General The ether type -R-O-R- (R is. To individually an alkylene having 1 to 10 carbon atoms) include those represented by, in particular -C ₄ H ₈ -O-C _{2 H 4 -, - C 4} H 8 -O-C 4 H 8 - and the like.

The amide is represented by the general formula -R-CONH-R
-Or -R-NHCO-R- (R independently represents 1 to
And 8 represents an alkylene. ),
Specifically _{-C 4 H 8 -CONH-C 2} H 4 -, - C 4 H 8 -
_{NHCO-C 2 H 4 -,} - C 4 H 8 -CONH-C 4 H 8 -,
—C ₄ H ₈ —NHCO—C ₄ H ₈ —. The thioether formula -R-S-R- (R is. To individually an alkylene having 1 to 10 carbon atoms) include those represented by, in particular -C ₄ H ₈ -S-C _{2 H 4 -, - C 4} H 8 -
S-C ₄ H ₈ - and the like.

The amine is represented by the general formula -R-NH-R-
(R independently represents alkylene having 1 to 10 carbon atoms), a general formula -R-NH-A- group (R represents alkylene having 1 to 10 carbon atoms, A represents 6 carbon atoms) . showing respectively 12 arylene groups or substituted arylene group) can be mentioned, specifically, _{-C 4 H 8 -NH-C 2} H 4 -, - C 4 H 8 -
NH-C ₄ H ₈ - and the like. As the urethane, a compound represented by the general formula -R-OCONH-R- or -R-NHCOO-R-
(R is. To individually an alkylene having 1 to 8 carbon atoms) include those represented by, specifically, -C ₄ H ₈ -OCON
_{H-C 2 H 4 -,} - C 4 H 8 -NHCOO-C 2 H 4 -, - C
_{4 H 8 -OCONH-C 4 H} 8 -, - C 4 H 8 -NHCOO-
C ₄ H ₈ - and the like.

As the silyl, a compound represented by the general formula -R-Si (R ')
_Two-R- (R is independently alkylene having 1 to 8 carbons, R '
Represents a methyl group or an ethyl group. )
And specifically, -C_FourH₈-Si (CH_Three)_Two-C_Two
H_Four-, -C_FourH₈-Si (CH _Three)_Two-C_FourH₈-, -C_FourH
₈-Si (C_TwoH_Five)_Two-C_TwoH_Four-, -C_FourH₈-Si (C_Two
H_Five)_Two-C_FourH₈-.

R ⁵ has 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
0 hydrocarbon groups exemplified by an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group and an aralkyl group;
A heterocyclic aromatic group having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, a substituted hydrocarbon residue or a substituted heterocyclic aromatic group in which a part of hydrogen of the hydrocarbon group or the heterocyclic aromatic group is substituted by a substituent; Group substituent, 4-20 carbon atoms, preferably 4-1
And 0 represents a heterocyclic aromatic group.

As the alkyl group, a methyl group, an ethyl group,
i-propyl group, n-propyl group, n-butyl group, t-
A butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group are exemplified, a cycloalkyl group is exemplified by a cyclohexyl group, and an aryl group is a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a naphthyl group. And the like. Examples of the alkenyl group include a vinyl group and an allyl group.Examples of the aralkyl group include a benzyl group and
Examples include a phenylpropyl group, and examples of the heterocyclic aromatic group include a 2-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, and an isoquinoline group.

Examples of the substituent in the substituted hydrocarbon residue or the substituted heterocyclic aromatic group include an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxycarbonyl group, an acyl group, a halogen, a cyano group and a hydroxy group. , A nitro group, an amino group, and the like.Examples of the alkoxy group include a methoxy group and an ethoxy group.The alkoxycarbonyl group is a methoxycarbonyl group, the acyl group is an acetyl group, and the halogen is Cl. F and the like, and examples of the substituted hydrocarbon residue include a methoxyphenyl group, a chlorophenyl group, a fluorophenyl group, a methoxychlorophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, and a methoxynaphthyl group. Can be

Specific examples of the compounds represented by formulas (4) to (7) are as follows.

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The concentration of these electrochromic compounds in the ion conductive layer is not particularly limited, but is usually 1 mM or more, preferably 5 mM or more, more preferably 10 mM or more, and 300 mM or more in the ion conductive layer.
Or less, preferably 200 mM or less, more preferably 1 mM or less.
It is less than 00 mM.

The ion conductive layer in the present invention can be formed using any of a liquid ion conductive substance, a gelled liquid ion conductive substance and a solid ion conductive substance. It is desirable to use a system-based ion conductive material, whereby the EC mirror of the present invention can be made into various solid-state EC mirrors having high practicality.

Liquid-based ion-conductive substance The liquid-based ion-conductive substance is prepared by dissolving a supporting electrolyte such as salts, acids and alkalis in a solvent. These supporting electrolytes need not be used if the electrochromic active is ionic. As the solvent, any solvent commonly used in electrochemical cells and batteries can be used. Specifically, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethoxy Ethane, propionitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol and the like can be used, especially propylene carbonate, ethylene carbonate, dimethyl Sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulf Orchids, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, polyethylene glycol, and the like are preferable. One of the solvents can be used alone,
Also, a mixture of two or more types can be used.

The amount of the solvent used is not particularly limited.
The solvent is at least 20% by weight of the ion conductive layer, preferably at least 50%.
Account for at least 70% by weight, more preferably at least 70% by weight,
And at most 98% by weight, preferably at most 95% by weight, more preferably at most 90% by weight.

As the supporting electrolyte, salts, acids and alkalis usually used in the field of electrochemistry or the field of batteries can be used. The salts are not particularly limited, for example,
Inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts; cyclic quaternary ammonium salts and the like. Specific examples of salts include LiClO ₄ , L
iSCN, LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ ,
LiPF ₆ , LiI, NaI, NaSCN, NaCl
Alkali metal salts of Li, Na, K such as O ₄ , NaBF ₄ , NaAsF ₆ , KSCN, KCl; (CH ₃ ) ₄ NB
_{F 4, (C 2 H 5} ) 4 NBF 4, (n-C 4 H 9) 4 NBF 4,
(C ₂ H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (n-C ₄
Quaternary ammonium salts such as H ₉ ) ₄ NClO ₄ and mixtures thereof are preferred.

The acids are not particularly limited, and inorganic acids, organic acids and the like, specifically, sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like can be used. The alkalis are not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used.
The use amount of the supporting electrolyte is optional, but generally, the supporting electrolyte is present in the ion conductive layer in an amount of 0.01 M or more, preferably 0.1 M or more, more preferably 0.5 M or more,
Its upper limit is at a value of 20M, preferably 10M, more preferably 5M.

Gelled liquid-based ion-conductive substance The gelled liquid-based ion-conductive substance means a substance obtained by thickening or gelling the above-mentioned liquid-based ion-conductive substance. It is prepared by further blending a polymer or a gelling agent with the substance. The polymer used for this is not particularly limited, for example, polyacrylonitrile,
Carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate,
Polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, Nafion and the like can be used. The gelling agent is not particularly limited, and oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used.

[0042]Solid ion conductive material Solid ion conductive materials are solid at room temperature and
A substance that has on-conductivity, including polyethylene
Oxide, oxyethylene methacrylate polymer
ー, Nafion, polystyrene sulfonic acid, Li_ThreeN,
Na-β-Al_TwoO _Three, Sn (HPO_Four)_Two・ H_TwoUse O etc.
can do. In addition, oxyalkylene meth
Relate compounds, oxyalkylene acrylate compounds
Compound or urethane acrylate compound
The supporting electrolyte is dispersed in the polymer compound obtained by
The solid polymer electrolyte thus obtained can be used.

The first of the solid polymer electrolytes recommended by the present invention
Is a solid polymer electrolyte obtained by solidifying a composition containing a urethane acrylate represented by the following general formula (8) and the above-mentioned solvent and supporting electrolyte. The solidification in the context of the polymer solid electrolyte means that the polymerizable or crosslinkable component is cured by a polymerization (polycondensation) reaction or a cross-linking reaction, and the entire composition does not substantially flow at room temperature. By this solidification, the polymerizable or crosslinkable component forms a three-dimensional network structure (network).

[0044]

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(Wherein, R ⁶ and R ⁷ are the same or different groups and represent groups selected from the groups represented by formulas (9) to (11). R ⁸ and R ⁹ are the same or different. It is a different group 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 a represents 1 -100, preferably 1-50,
More preferably, it is an integer in the range of 1 to 20. )

[0046]

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In the general formulas (9) to (11), R ¹⁰ to
R ¹² is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹³ has 1 to 1 carbon atoms.
20, preferably a divalent to tetravalent organic residue having 2 to 8 carbon atoms. Specific examples of the organic residue include an alkyltriyl group, an alkyltetrayl group, and the following general formula (1)
And hydrocarbon residues such as the alkylene group represented by 2).

[0048]

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In the general formula (12), R ¹⁴ has 1 carbon atom
Represents an alkyl group of 3 to 3 or hydrogen, and b is an integer of 0 to 6. When b is 2 or more, R ¹⁴ may be the same or different. Part of the hydrogen atom in the general formula (12) is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and 6 carbon atoms.
To 12 aryloxy groups and the like. Specific examples of R ^{13 in} the general formulas (9) to (11) include a methylene group, a tetramethylene group, a 1-methyl-ethylene group, a 1,2,3-propanetriyl group, a neopentanetriyl group, and the like. Preferred examples are given.

Examples of the divalent hydrocarbon residue represented by R ⁸ and R ⁹ in the general formula (8) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alicyclic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkylene group represented by the general formula (12). Examples of the divalent aromatic hydrocarbon group and the divalent alicyclic hydrocarbon group include hydrocarbon groups represented by the following general formulas (13) to (15).

[0051]

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In the general formulas (13) to (15), R ¹⁵
And R ¹⁶ are the same or different groups and represent a phenylene group, a substituted phenylene group (such as an alkyl-substituted phenylene group), a cycloalkylene group, or a substituted cycloalkylene group (such as an alkyl-substituted cycloalkylene group). R ¹⁷ ~
R ²⁰ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. C is an integer of 1 to 5. Specific examples of R ⁸ and R ⁹ in the general formula (8) include the following divalent groups.

[0053]

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In the general formula (8), 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.

[0055]

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In the general formulas (a) to (d), R ^{21 to} R
²⁶ is the same or different and represents a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms. R ²¹ ~
R ²⁶ is preferably a linear or branched alkylene group. Specifically, R ²³ is preferably a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group or the like, and R ^{21 to} R ²² and R ^{24 to} R ²⁶ are preferably It is preferably an ethylene group, a propylene group or the like. c ′ is an integer of 2 to 300, preferably 10 to 200. d 'is 1 to 30
0, preferably an integer of 2 to 200, e ′ is 1 to 200,
Preferably, e is an integer of 2 to 100, e '' is an integer of 1 to 200, preferably 2 to 100, and f 'is an integer of 1 to 300, preferably 10 to 200.

In the general formulas (a) to (d), each unit may be the same or a copolymer of different units. That is, when a plurality of R ²¹ to R ²⁶ are present, R ²¹ comrades, R ²² comrades, R ²³
Comrades, R ²⁴ comrades, R ²⁵ comrades and R ²⁶ each other may be the same or different.

The urethane acrylate represented by the general formula (8) generally has a molecular weight of 2,500 to
30,000, preferably in the range of 3,000 to 20,000, and the number of polymerizable functional groups in one molecule is preferably 2
-6, more preferably 2-4. The urethane acrylate represented by the general formula (8) can be easily produced by a known method, and the production method is not particularly limited.

The polymer solid electrolyte containing the urethane acrylate represented by the general formula (8) is obtained by mixing the urethane acrylate with the solvent and the supporting electrolyte described in the liquid ion-conductive material. The composition is prepared by solidifying the composition, and the amount of the solvent is usually 1 to 100 parts by mass of urethane acrylate.
The amount is selected from the range of 00 to 1200 parts by mass, preferably 200 to 900 parts by mass. If the amount of the solvent is too small, the ionic conductivity of the polymer solid electrolyte finally obtained is insufficient, and if it is too large, the mechanical strength of the solid electrolyte may be reduced. The amount of the supporting electrolyte added is 0.1 to 3 times the amount of the solvent added.
0 mass%, preferably in the range of 1 to 20 mass%. A crosslinking agent or a polymerization initiator can be added to the polymer solid electrolyte containing urethane acrylate as needed.

The second preferred solid polymer electrolyte recommended by the present invention
Is an example of a polymer solid obtained by solidifying a composition containing an acryloyl-modified or methacryloyl-modified polyalkylene oxide (hereinafter, both are collectively referred to as a modified polyalkylene oxide), a solvent, and a supporting electrolyte. Electrolyte.

The modified polyalkylene oxide includes a monofunctional modified polyalkylene oxide, a bifunctional modified polyalkylene oxide, and a trifunctional or higher polyfunctional modified polyalkylene oxide. Each of these modified polyalkylene oxides may be used alone or in combination, and in particular,
It is essential to use a monofunctional modified polyalkylene oxide, and it is preferable to mix and use a bifunctional modified polyalkylene oxide and / or a polyfunctional modified polyalkylene oxide. In particular, it is preferable to use a mixture of a monofunctional modified polyalkylene oxide and a bifunctional modified polyalkylene oxide. The mixing ratio in the case of mixing and using can be arbitrarily selected, but the total amount of the bifunctional modified polyalkylene oxide and / or the polyfunctional modified polyalkylene oxide is 0 with respect to 100 parts by mass of the monofunctional modified polyalkylene oxide. 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass.
It is selected in the range of 5 to 10 parts by mass.

The monofunctional modified polyalkylene oxide is represented by the following general formula (16).

Embedded image (In the formula, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms, and g ′ is an integer of 1 or more.)

In the general formula (16), R ²⁷ , R ²⁸ , R
^Examples of the alkyl group of ²⁹ and R ³⁰ include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group,
t-butyl group, n-pentyl group and the like, which may be the same or different, and in particular, R ²⁷ is hydrogen or methyl group, R ²⁸ is hydrogen or methyl group, R ²⁹ is hydrogen or methyl group, R ³⁰ is It is preferably hydrogen, methyl or ethyl, respectively. In the general formula (16), g ′ is an integer of 1 or more, usually 1 ≦ g ′ ≦ 100, preferably 2 ≦ g ′.
It is an integer in the range of g ′ ≦ 50, more preferably 2 ≦ g ′ ≦ 30.

Specific examples of the compound represented by the general formula (16) include methoxypolyethylene glycol methacrylate having an oxyalkylene unit in the range of 1 to 100, preferably 2 to 50, more preferably 2 to 20;
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, or a mixture thereof, among others, Methoxy polyethylene glycol methacrylate and methoxy polyethylene glycol acrylate are preferably used.

When g 'in the general formula (16) is 2 or more, the oxyalkylene units may have so-called copolymerized oxyalkylene units which are different from each other, and the polymerization form thereof is alternating copolymerization, block copolymerization or random copolymerization. Either may be used. As a specific example, for example,
1-50, preferably 1-2 oxyethylene units
0 and the oxypropylene unit is 1 to
50, preferably an alternating copolymer having a range of 1 to 20,
Methoxy poly (ethylene / propylene) glycol methacrylate, ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate, which is a block copolymer or a random copolymer,
Or a mixture thereof.

The bifunctional modified polyalkylene oxide is represented by the following general formula (17), and the trifunctional or higher polyfunctional acryloyl modified polyalkylene oxide is represented by the following general formula (18).

[0067]

Embedded image (In the formula, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms, and h ′ is an integer of 1 or more.)

[0068]

Embedded image (Wherein R ³⁵ , R ³⁶ and R ³⁷ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
i 'is an integer of 1 or more, j' is an integer of 2 to 4, and L represents a j'-valent linking group. )

In the general formula (17), R ³¹ and R in the formula
³² , R ³³ and R ³⁴ each independently represent hydrogen or 1 to
An alkyl group having 5 carbon atoms is shown, such as a methyl group, an ethyl group, an i-propyl group,
Examples thereof include an n-propyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. In particular, each of R ³¹ , R ³² , R ³³ and R ³⁴ is preferably hydrogen or a methyl group.

H ′ in the general formula (17) is an integer of 1 or more, usually 1 ≦ h ′ ≦ 100, preferably 2 ≦ h ′ ≦
50, more preferably an integer in the range of 2 ≦ h ′ ≦ 30, but specific examples of such compounds have oxyalkylene units in the range of 1-100, preferably 2-50, more preferably 1-20. Examples thereof include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. When h ′ is 2 or more, the oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other, and the polymerization form may be any of alternating copolymerization, block copolymerization, or random copolymerization. For example,
For example, an alternating copolymer, a block copolymer or a random copolymer having oxyethylene units in the range of 1 to 50, preferably 1 to 20 and oxypropylene units in the range of 1 to 50, preferably 1 to 20. Examples of the polymer include poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, and a mixture thereof.

R ³⁵ , R ³⁶ and R ³⁷ in the general formula (18) are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.
Examples include 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-pentyl group. Particularly, each of R ³⁵ , R ³⁶ and R ³⁷ is preferably hydrogen or a methyl group.

Further, i ′ in the general formula (18) is an integer of 1 or more, usually 1 ≦ i ′ ≦ 100, preferably 2 ≦ i ′ ≦ 5.
0, more preferably an integer in the range of 2 ≦ i ′ ≦ 30. J ′ in the general formula (18) is the number of linked groups L, and is an integer in the range of 2 ≦ j ′ ≦ 4. Linking group L
Usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Is a divalent, trivalent or tetravalent hydrocarbon group. 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, a methylene group, an ethylene group,

[0073]

Embedded image And the like.

Examples of the trivalent hydrocarbon group include an alkyltriyl group, an aryltriyl group, an arylalkyltriyl group, an alkylaryltriyl group, and a hydrocarbon group having these as a basic skeleton. ,
In particular

Embedded image And the like.

Examples of the tetravalent hydrocarbon group include an alkyltetrayl group, an aryltetrayl group, an arylalkyltetrayl group, an alkylaryltetrayl group, and a hydrocarbon group having these as a basic skeleton. ,In particular

Embedded image And the like.

Specific examples of such compounds include oxyalkylene units of 1 to 100, preferably 2 to 5
0, more preferably in the range of 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 i ′ in the general formula (18) is 2 or more, oxyalkylene units having different so-called copolymerized oxyalkylene units may be used.
The polymerization form may be any of alternating copolymerization, block copolymerization, and random copolymerization. It has an oxyethylene unit in the range of 1 to 50, preferably 1 to 20, and an oxypropylene unit of 1 to 50, preferably 1
Trimethylolpropane tri (poly (ethylene propylene) glycol acrylate), trimethylol propane tri (poly (ethylene propylene) which is an alternating copolymer, block copolymer or random copolymer having a range of ) Glycol methacrylate), tetramethylol methane tetra (poly (ethylene propylene) glycol acrylate), tetramethylol methane tetra (poly (ethylene propylene) glycol methacrylate), or mixtures thereof.

The bifunctional modified polyalkylene oxide represented by the general formula (17) may be used in combination with the trifunctional or higher polyfunctional modified polyalkylene oxide represented by the general formula (18). When used together, the mass ratio is usually 0.01 / 9.
9.9 to 99.9 / 0.01, preferably 1/99 to 9
9/1, more preferably in the range of 20/80 to 80/20.

The polymer solid electrolyte containing the modified polyalkylene oxide is obtained by mixing the modified polyalkylene oxide with the solvent and the supporting electrolyte described in the liquid ion-conductive substance as a precursor composition. It is prepared by solidifying the composition, but the amount of the solvent added is 50 to 800% by mass of the total amount of the modified polyalkylene oxide,
Preferably, it is selected in the range of 100 to 500% by mass. The amount of the supporting electrolyte added is 1 to 30% by mass, preferably 3 to 30% by mass of the total amount of the modified polyalkylene oxide and the solvent.
-20% by mass.

A crosslinking agent or a polymerization initiator can be added to the polymer solid electrolyte containing the modified polyalkylene oxide, if necessary. As a crosslinking agent that can be added to the polymer electrolyte, an acrylate-based crosslinking agent having two or more functional groups is preferable. Specific examples thereof include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate,
Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, and the like. These can be used alone or as a mixture.

The amount of the crosslinking agent used is 0.01 mol% with respect to 100 mol% of the polymerizable urethane acrylate or modified polyalkylene oxide contained in the solid polymer electrolyte.
Or more, preferably 0.1 mol% or more, and 10 mol%
Or less, preferably 5 mol% or less.

The polymerization initiator that can be added to the solid polymer electrolyte is roughly classified into a photopolymerization initiator and a thermal polymerization initiator. The type of the photopolymerization initiator is not particularly limited, and known photopolymerization initiators such as benzoin-based, acetophenone-based, benzylketal-based, and acylphosphine oxide-based can be used. Specifically, acetophenone, benzophenone, 4-methoxybenzophenone, benzoin methyl ether, 2,2
-Dimethoxy-2-phenyldimethoxy-2-phenylacetophenone, benzyl, benzoyl, 2-methylbenzoin, 2-hydroxy-2-methyl-1-phenyl-1-one, 1- (4-isopropylphenyl-2-hydroxy- 2-methylpropan-1-one, triphenylphosphine, 2-chlorothioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
1-hydroxycyclohexylphenyl ketone, 2,2
-Dimethoxy-2-phenylacetophenone, 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- 1-
On, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propane-1
-One, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzoin, 2,4,6-trimethylbenzoyldiphenylphosphine oxide or the like, alone or as a mixture. Can be used.

The type of the thermal polymerization initiator is not particularly limited. Known compounds such as a peroxide-based polymerization initiator or an azo-based polymerization initiator can be used. Specifically, the peroxide-based polymerization initiator includes, for example, benzoyl peroxide, methyl ethyl peroxide, t-butyl peroxypivalate, diisopropyl peroxycarbonate, and the like. 2'-azobis (2-isobutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-
Dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) and the like can be used alone or as a mixture.

The amount of the polymerization initiator used is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, based on 100 parts by mass of the polymerizable urethane acrylate or modified polyalkylene oxide contained in the solid polymer electrolyte. And 10 parts by mass or less, preferably 5 parts by mass or less.

The solidification of the polymer solid electrolyte is achieved by photo-curing or heat-curing the polymerizable urethane acrylate or modified polyalkylene oxide. The photocuring proceeds preferably by irradiating a solid polymer electrolyte containing a photopolymerization initiator with far ultraviolet light, ultraviolet light, visible light, or the like. As a light source, a high-pressure mercury lamp, a fluorescent lamp, a xenon lamp, or the like can be used. The light irradiation amount is not particularly limited, but is usually 100 mJ / cm ² or more,
It is preferably at least 1,000 mJ / cm ² , and the upper limit is 50,000 mJ / cm ² , preferably 20,000 mJ / cm ^2.
It is preferably J / cm ² .

The thermosetting is preferably carried out by subjecting the solid polymer electrolyte, which serves as a thermal polymerization initiator, to a temperature of usually 0 ° C. or higher, preferably 20 ° C.
It proceeds by heating as described above. Heating temperature is 13
It is desirably 0 ° C or lower, preferably 80 ° C or lower. The curing time is usually 30 minutes or more, preferably 1 hour or more, and desirably 100 hours or less, preferably 40 hours or less.

The EC mirror according to the present invention can be manufactured by any method. For example, when the ion conductive substance to be used is a liquid system or a gelling liquid system, two conductive substrates are opposed to each other at an appropriate interval via the spacer of the present invention, and a peripheral conductive portion is sealed. In the meantime, an ion-conductive substance in which an electrochromic compound is dispersed is injected by a vacuum injection method, an air injection method, a meniscus method, or the like, and thereafter, the E of the present invention is obtained by a method of closing the injection port.
A C mirror can be manufactured. Further, depending on the type of ion conductive material used, after forming an ion conductive layer containing an electrochromic compound on one conductive substrate by a sputtering method, an evaporation method, a sol-gel method, or the like, the spacer of the present invention is used. Alternatively, the EC mirror of the present invention can be manufactured by a method of bonding the other conductive substrate or by forming an ion-conductive substance containing an electrochromic compound into a film in advance and manufacturing a laminated glass sheet.

When the ion-conductive substance to be used is a solid type, particularly when a polymer solid electrolyte containing urethane acrylate, acryloyl or methacryloyl-modified alkylene oxide is used, an unsolidified state containing an electrochromic compound is contained. The solid polymer electrolyte precursor is placed at an appropriate interval between two conductive substrates via the spacer of the present invention, and a vacuum injection method and an air injection method are applied between the opposing conductive substrates whose peripheral edges are sealed. Injection is performed by a meniscus method or the like, the injection port is closed, and the solid polymer electrolyte is solidified by an appropriate means to obtain a solid electrolyte, whereby the EC mirror of the present invention can be obtained.

Next, a description will be given of a driving method relating to the color erasing and erasing of the EC mirror according to the present invention. In the present invention, EC
The reflectance of light at a wavelength of 633 nm when a voltage E is applied to the mirror is T _E , the reflectance of light at a wavelength of 633 nm when a voltage of 0 V is applied is T _0, and an arbitrary voltage is applied to the mirror, The axis is the absolute value of the applied voltage | E |, and the vertical axis is -log ₁₀
After the derivative starts decreasing for the first time on the curve (T _E / T ₀ ), −log ₁₀ (T
_When the value of _E / T ₀ is OD _flat , −log ₁₀ (T _E
/ T ₀ ) is applied with a voltage corresponding to a voltage in a range of 0.9 × OD _{flat to} 1.1 × OD _{flat to} the mirror to color the mirror.

T _E refers to the value at the time when the value does not substantially change after the voltage E is applied. _TE is usually the reflectance value when a voltage is applied for 20 minutes, more preferably the reflectance value when a voltage is applied for 20 minutes or more, for example, 30 minutes.

The reflectivity of light having a wavelength of 633 nm may be, for example, a value measured by fixing the wavelength to 633 nm using a spectrophotometer, or substantially a light having a wavelength of 633 nm, such as He-Ne laser light. It may be measured using single-wavelength light as a light source.

The range of the voltage to be measured is usually 0 to 1.6 V. However, it must be within a range in which the electrochemical reaction of the electrochromic compound occurs in only one stage. For example, in the case of a cathodic electromic compound, the reaction that generates a one-electron reductant is the first-stage reaction,
The reaction in which the electron reductant is generated is the second stage reaction. The voltage range to be measured must be lower than the voltage generated by the two-electron reductant. The voltage at which the second-stage reaction occurs can be determined by a general electrochemical method. For example, chronopotentiometry is an effective technique. The measurement was carried out by the method described in "Tetsuya Osaka, Noboru Koyama, Takeo Osaka, Electrochemical Method Basic Measurement Manual, p. 133, Kodansha Scientific (1992)".

The voltage interval at the time of measurement is preferably 10 mV. However, measurement may be performed at 100 mV intervals in a voltage range where the change of -log ₁₀ (T _E / T ₀ ) is small.
The voltage applied to maintain the colored state is -log ₁₀
The value of (T _E / T ₀ ) is 0.9 × OD _{flat to} 1.1 × OD
_A voltage corresponding to a voltage _falling within the _flat range is preferable. More preferably, the value of -log ₁₀ (T _E / T ₀ ) is 0.95 ×
A voltage corresponding to a voltage within the range of OD _{flat to} 1.05 × OD _flat , and more preferably −log ₁₀ (T _E / T ₀ )
Is desirably a voltage corresponding to a voltage that makes the value of 0.99 × OD _{flat to} 1.01 × OD _flat .

[0094]

According to the driving method of the EC mirror of the present invention, it has been found that the reflectance can be stably maintained by driving in a specific voltage range in a practically used temperature range. Therefore, even if the optical sensor or the control circuit is not provided with a special temperature compensation function, it can be driven stably under practical use conditions. Further, the durability of the EC mirror can be improved by the driving method of the present invention.

[0095]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Example 1) << Manufacture of EC mirror >> An epoxy-based adhesive was linearly applied to the periphery of a transparent glass substrate one side of which was coated with ITO, except for the solution injection port, to obtain a 200 μm diameter. Beads were sprinkled on the substrate. On this, a reflective glass substrate having a reflective film (aluminum) formed on the opposite surface of the same ITO-coated transparent glass substrate is overlapped so that the ITO surfaces face each other, and the adhesive is cured while pressing, An empty cell with an inlet was made.

On the other hand, methoxypolyethylene glycol monomethacrylate (M4 manufactured by Shin-Nakamura Chemical Co., Ltd.)
OGN [oxyethylene unit number 4]) 1.0 g, polyethylene glycol dimethacrylate (9G [oxyethylene unit number 9] manufactured by Shin-Nakamura Chemical Co., Ltd.)
0.02 g, γ-butyrolactone 4.0 g, 1- (4-
0.02 g of isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2- (5-methyl-2-hydroxyphenyl) benzotriazole (C
To a mixed solution of 0.03 g of TINUVIN P) (IBA-GEIGY), 0.8 mol / L of lithium perchlorate, 3 mmol / L of ferrocene, and 3 mmol / L of a compound represented by the following formula (19): To obtain a uniform solution.

[0098]

Embedded image

After the solution was degassed, it was injected from the injection port of the cell prepared as described above. After sealing the injection port with an epoxy adhesive, the solution in the cell was cured by irradiating light from a fluorescent lamp to obtain an EC mirror having the configuration shown in FIG.

<< Driving of EC Mirror >> A voltage was applied to this EC mirror, and the reflectance at 633 nm was measured. Here, the reflectance is a value finally reached when a constant voltage is continuously applied. Specifically, the value when a constant voltage was continuously applied for 20 minutes was defined as the reflectance. The measurement of the reflectance was performed from 0 V to 1.6 V at intervals of 100 mV. The measurement was performed at intervals of 10 mV between 0.7 and 0.9 V where the change in reflectance with voltage was large. −log ₁₀ (T _E / T ₀ ) with respect to the voltage
Was plotted, and curve fitting was performed using the following equation.

Y = [c × Exp [F × (xb) / (2 × R × T)]] / [1 + a × E
xp [F × (xb) / (2 × R × T)]]

The meanings of the symbols in the above formula are as follows. x is voltage (V), y is -log ₁₀ (T _E / T ₀ ) F = 96500 C / mol (Faraday constant) R = 8.31 J / K · mol (gas constant) T is absolute temperature during measurement a, b and c are fitting parameters

As a result of obtaining fitting parameters by regression analysis, a = 1.848296 and b = 0.
8515265, c = 0.6579933. In FIG. 2, the horizontal axis represents the absolute value of the applied voltage | E |, and the vertical axis represents -log.
A curve with ₁₀ (T _E / T ₀ ) is shown. In the curve,
After the derivative starts to decrease for the first time, it becomes the first minimum value at 1.3 V. Therefore, -lo at 1.3V
0.356, which is the value of g ₁₀ (T _E / T ₀ ), was defined as OD _flat . Since the value of -log ₁₀ (T _E / T ₀ ) became 1.0 × OD _flat when 1.3 V was applied, 1.3 V was set to EC.
The drive voltage of the mirror was used. This EC mirror was not colored when assembled. The temperature change of the luminous reflectance when colored at a constant voltage of 1.3 V was measured.
The range of change in reflectance was small in the range of 0 ° C to 80 ° C.
The reflectance fell within 32 ± 1% over the measured temperature range.

(Example 2) << Manufacture of EC mirror >> An epoxy-based adhesive was linearly applied to the periphery of a transparent glass substrate one side of which was coated with ITO, except for the solution injection port, to obtain a 200 μm diameter. Beads were sprinkled on the substrate. A reflective glass substrate on which a reflective film (aluminum) is formed on the surface opposite to the conductive surface of the transparent glass substrate also covered with ITO is superimposed thereon so that the ITO surfaces face each other. Was cured to produce an empty cell with an inlet.

On the other hand, methoxypolyethylene glycol monomethacrylate (M4 manufactured by Shin-Nakamura Chemical Co., Ltd.)
OGN [oxyethylene unit number 4]) 1.0 g, polyethylene glycol dimethacrylate (Shin-Nakamura Chemical Co., Ltd. 4G [oxyethylene unit number 4])
0.02 g, propylene carbonate 4.0 g, 2,
0.02 g of 4,6-trimethylbenzoyldiphenylphosphine oxide and 2- (5-methyl-2-hydroxyphenyl) benzotriazole (CIBA-GE
IGY TINUVIN P) 0.03g mixed solution,
0.5 mol / L of lithium perchlorate was obtained by the following formula (2)
Compounds represented by the formula (0) were added to give a concentration of 3 mmol / L to obtain a homogeneous solution.

[0106]

Embedded image

After the solution was degassed, it was injected from the injection port of the cell prepared as described above. After sealing the injection port with an epoxy adhesive, the solution in the cell was cured by irradiating light from a fluorescent lamp to obtain an EC mirror having the configuration shown in FIG.

<< Driving of EC Mirror >> As in the first embodiment,
Continue applying a constant voltage to this EC mirror for 20 minutes.
The reflectivity at 33 nm was measured. The measurement of the reflectance was performed from 0 V to 1.6 V at intervals of 100 mV. The measurement was performed at intervals of 10 mV between 0.7 and 0.9 V where the change in reflectance with voltage was large. −log ₁₀ (T _E / T ₀ ) with respect to the voltage
Was plotted, and curve fitting was performed in the same manner as in Example 1.

In FIG. 3, the horizontal axis represents the absolute value of the applied voltage | E |
A curve with the vertical axis being −log ₁₀ (T _E / T ₀ ) is shown. In the curve, after the derivative starts decreasing for the first time.
It is the first minimum value at 4V. Therefore, 1.4
0.342 which is the value of -log ₁₀ (T _E / T ₀ ) at the time of V
_{Was set} to OD _flat . -Log when 1.4V is applied
_Since the value of ₁₀ (T _E / T ₀ ) became 1.0 × OD _flat , 1.4 V was set as the driving voltage of the EC mirror. This EC
The mirror was uncolored when assembled. 1.
When the temperature change of the luminous reflectance when colored at a constant voltage of 3 V was measured, it was found that the change width of the reflectance was small in the range of 10 ° C. to 80 ° C. The reflectivity was within 33 ± 1% over the measured temperature range.

Example 3 << Manufacture of EC Mirror >> An epoxy-based adhesive was linearly applied to the periphery of a transparent glass substrate one side of which was coated with ITO, except for the solution injection port, to obtain a 200 μm diameter. Beads were sprinkled on the substrate. A reflective glass substrate on which a reflective film (aluminum) is formed on the opposite side of the conductive surface of the same ITO substrate is placed on top of this so that the ITO surfaces face each other, and the adhesive is cured while applying pressure. An empty cell with an inlet was made. On the other hand, 5.0 g of propylene carbonate
And 2- (5-methyl-2-hydroxyphenyl) benzotriazole (TINUVI manufactured by CIBA-GEIGY)
NP) To a mixed solution of 0.03 g, lithium perchlorate was added at a concentration of 0.5 mol / L and a compound represented by the following formula (21) at a concentration of 3 mmol / L, respectively.
A homogeneous solution was obtained.

[0111]

Embedded image After this solution was degassed, it was injected from the injection port of the cell prepared as described above, to obtain an EC mirror having the configuration shown in FIG.

<< Driving of EC Mirror >> As in the first embodiment,
Continue applying a constant voltage to this EC mirror for 20 minutes.
The reflectivity at 33 nm was measured. The measurement of the reflectance was performed from 0 V to 1.6 V at intervals of 100 mV. The measurement was performed at intervals of 10 mV between 0.7 and 0.9 V where the change in reflectance with voltage was large. −log ₁₀ (T _E / T ₀ ) with respect to the voltage
Was plotted, and curve fitting was performed in the same manner as in Example 1.

In FIG. 4, the horizontal axis represents the absolute value of the applied voltage | E |
A curve with the vertical axis being −log ₁₀ (T _E / T ₀ ) is shown. In the curve, after the derivative starts decreasing for the first time.
It is the first minimum value at 4V. Therefore, 1.4
0.434 which is the value of −log ₁₀ (T _E / T ₀ ) at the time of V
_{Was set} to OD _flat . -Log when 1.4V is applied
_Since the value of ₁₀ (T _E / T ₀ ) became 1.0 × OD _flat , 1.4 V was set as the driving voltage of the EC mirror. This EC
The mirror was uncolored when assembled. 1.
When the temperature change of the luminous reflectance when colored at a constant voltage of 3 V was measured, it was found that the change width of the reflectance was small in the range of 10 ° C. to 80 ° C. The reflectance fell within 29 ± 1% over the measured temperature range.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of an EC mirror used in Examples 1 to 3.

FIG. 2 is a curve showing a relationship between an absolute value | E | of an applied voltage and −log ₁₀ (T _E / T ₀ ) in the EC mirror of Example 1.

FIG. 3 is a curve showing a relationship between an absolute value | E | of an applied voltage and −log ₁₀ (T _E / T ₀ ) in the EC mirror of Example 2.

FIG. 4 is a curve showing a relationship between an absolute value | E | of an applied voltage and −log ₁₀ (T _E / T ₀ ) in the EC mirror of Example 3.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent substrate 2 transparent electrode layer 3 ion conductive layer 4 reflective electrode layer 5 transparent or opaque substrate 6 sealing material

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2K001 AA01 AA06 BA07 BB18 CA22 EA17

Claims (3)

[Claims] 1. A method for driving an electrochromic mirror provided with an ion conductive layer containing an electrochromic compound between two conductive substrates at least one of which is transparent, wherein a voltage for coloring driving is applied to the mirror. The reflectance of light having a wavelength of 633 nm when voltage E is applied is T _E , the reflectance of light having a wavelength of 633 nm when 0 V is applied is T ₀ , an arbitrary voltage is applied to the mirror, and the horizontal axis is applied. The absolute value of the voltage | E | and the vertical axis is -log ₁₀ (T _E /
After the derivative starts decreasing for the first time on the curve defined as T ₀ ), the logarithm becomes −log ₁₀ (T _E /
When the value of T ₀ ) is OD _flat , −log ₁₀ (T _E / T
₀ ) A method of driving an electrochromic mirror, characterized by applying a voltage corresponding to a voltage having a value of 0.9 × OD _{flat to} 1.1 × OD _flat . 2. The method according to claim 1, wherein the electrochromic compound comprises at least an anodic electrochromic compound and a cathodic electrochromic compound. 3. The method of driving an electrochromic mirror according to claim 1, wherein the electrochromic compound is a compound having both an anodic electrochromic structure and a cathodic electrochromic structure.