JP2000305116A - Electrochromic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a device which is colored in a good state at about 1 V and which has excellent responding property, durability against repeated driving and durability by incorporating an org. compd. having both of a structure having both of cathodic electrochromic characteristics and a structure having an anodic electrochromic characteristics into an ionic conductive layer. SOLUTION: This device has a structure of an ionic conductive layer 3 having dispersion of a compd. interposed between a transparent conductive substrate consisting of a transparent substrate 1 and a transparent electrode layer 2 laminated on the substrate surface, and a conductive substrate consisting of a transparent or opaque substrate 5 and a transparent, opaque or reflective electrode layer 4 formed on the substrate 5 surface. That is, this electrochromic device has the ionic conductive layer 3 disposed between two conductive substrates at least one of which is transparent, and the ionic conductive layer 3 contains an org. compd. having both of a structure having cathodic electrochromic characteristics and a structure having an anodic electrochromic characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic device useful as a transmissive device such as light control glass, a reflective device such as an anti-glare mirror for automobiles and a decorative mirror, and a display device.

[0002]

2. Description of the Related Art A conventional electrochromic device (hereinafter abbreviated as an EC device) used for a light control glass is an electrochromic device such as tungsten oxide (WO ₃ ). It is known that an active substance is formed on a transparent conductive film by a vacuum deposition method or the like and this is used as a color former (Japanese Patent Laid-Open No.
No. 3-18336). However, in this EC device, since the film formation of the electrochromic active material must be performed under vacuum, the manufacturing cost increases, and a large-sized vacuum device is required to obtain a large-area EC device. Further, when tungsten oxide is used, there is another problem that only blue color can be obtained. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an EC element which can be manufactured by a simple method using an inexpensive color former and has a variable color tone. It is in.

[0003]

The present inventors have conducted intensive studies on means for solving the problems of the prior art as described above, and as a result, an electrochromic device having the following structure has solved these problems. They have found that they can be solved, and have completed the present invention. That is, an EC element according to the present invention is an electrochromic element in which an ion conductive layer is provided between two conductive substrates at least one of which is transparent, wherein the ion conductive layer has a cathodic electrochromic property. And an organic compound having a structure having anodic electrochromic properties. More specifically,
In the EC device according to the present invention, the ion conductive layer has (a) a bipyridinium ion pair structure represented by the following general formula (1), and (b) a bipyridinium ion pair structure represented by the following general formula (2) or (3). Characterized by containing an organic compound having at least one selected from metallocene structures.

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

Embedded image (Wherein R ¹ and R ² may be the same or different,
A hydrocarbon group selected from an alkyl group, an alkenyl group and an aryl group having 1 to 10 carbon atoms, and when R ¹ or R ² is an aryl group, the parent ring is bonded to a cyclopentadienyl ring to form a ring; M may represent an integer in the range of 0 ≦ m ≦ 4; n may represent an integer in the range of 0 ≦ n ≦ 4;
Is CR, CO, Fe, Mg, Ni, OS, Ru, V, X
-Hf-Y, X-MO-Y, X-Nb-Y, X-Ti-
Y, X-V-Y or X-ZR-Y is shown. In addition, X and Y mentioned here are hydrogen, halogen or C1-C1.
Represents two alkyl groups, which may be the same or different. )

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Two conductive substrates are used in an EC device of the present invention. Here, the conductive substrate means a substrate that functions as an electrode. Therefore, the conductive substrate referred to in the present invention includes a substrate in which the substrate itself is made of a conductive material, and a laminate in which an electrode layer is laminated on one or both surfaces 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 transparent, opaque, or a reflective conductive substrate that can reflect light. Good. In general, an element in which both conductive substrates are transparent is suitable for a display element or a light control glass, and an element in which one is a transparent conductive substrate and the other is an opaque conductive substrate is suitable for a display element. One having a transparent conductive substrate and the other having a reflective conductive substrate is suitable for an electrochromic mirror.

[0005] A 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, and may be, for example, colorless or colored glass, tempered glass, or the like, and may be colorless or colored transparent resin.
Specific examples of the transparent resin referred to herein include polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide,
Examples include polycarbonate, polyimide, polymethyl methacrylate, 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.
As the metal oxide, for example, ITO (In ₂ O ₃ −
SnO ₂ ), tin oxide, silver oxide, zinc oxide, vanadium oxide and the like. The thickness of the electrode layer is not particularly limited, but is usually 10 to 500 nm, preferably 50 to 500 nm.
Surface resistance (resistivity) is not particularly limited, but is usually 0.5 to 500 Ω / c.
m ² , preferably in the range of 1 to 50 Ω / cm ² . 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 electrode. Usually, a vacuum deposition method, an ion plating method, a sputtering method, a sol-gel method, or the like is employed. Addition of redox ability to transparent electrode layer, improvement of conductivity,
A partially opaque electrode active material layer can be provided on the surface of the transparent electrode layer for the purpose of providing an electric double layer capacitance or the like. As the electrode active material, for example, copper, silver,
Metals such as gold, platinum, iron, tungsten, titanium, and lithium; organic substances having redox ability such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; carbon materials such as activated carbon and graphite; V ₂ O ₅ , MnO ₂ , and N
Metal oxides such as iO, IR ₂ O ₃ or mixtures thereof can be used. When providing a layer of an electrode active material on a transparent electrode layer, care must be taken that the transparency of the transparent electrode layer is not excessively impaired. Therefore, for example, a method of applying a composition comprising activated carbon fiber, graphite, acrylic resin, etc. on a transparent ITO layer in the form of fine stripes or dots, or a method of applying V
A method of applying a composition composed of ₂ O ₅ , acetylene black, butyl rubber, or the like in a mesh shape is employed. The conductive substrate that does not need to be transparent is the same as the transparent conductive substrate by replacing the transparent substrate used for the transparent conductive substrate described above with a substrate made of a non-transparent plastic, glass, wood, stone, or other material. It can be manufactured by a simple method.

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 referred to in the present invention means a thin film having a mirror surface and exhibiting an electrochemically stable function as an electrode. Examples of such a thin film include gold, platinum, tungsten, tantalum, rhenium, osmium,
Metal films such as iridium, silver, nickel, palladium,
An alloy film of platinum-palladium, platinum-rhodium, stainless steel, or the like can be given. An arbitrary method can be used for forming such a thin film having a mirror surface. For example, a vacuum evaporation method, an ion plating method, a sputtering method, or the like can be appropriately used. The substrate on which the reflective electrode layer is provided may be transparent or opaque. Therefore, as the substrate on which the reflective electrode layer is provided, various non-transparent plastics, glass, wood, stone, and the like can be used in addition to the transparent substrate exemplified above. The reflection plate or the reflection layer referred to in the present invention means a substrate or a thin film having a mirror surface, and includes, for example, a plate-like body such as silver, chromium, aluminum, stainless steel, nickel-chromium, or a thin film thereof. . Note that the use of the substrate can be omitted if the above-described reflective electrode layer itself has rigidity.

[0007] Regardless of whether the conductive substrate is transparent or light-reflective, the 2
An electrode band can be provided on one or both of the conductive substrates at the peripheral portion as necessary.

In the present invention, a structure exhibiting cathodic electrochromic properties in the molecule (hereinafter abbreviated as “cathodic EC structure”) and a structure exhibiting anodic electrochromic properties (hereinafter referred to as “anodic EC structure”) ) (Hereinafter, referred to as “compound (A)”) is included in the ion conductive layer of the EC device as an electrochromic active substance. Therefore, when cyclic voltammetry is measured for a cell having an electrolyte containing the compound (A) (typically, an electrochemical measurement cell including an anode, a cathode, and a reference electrode), a reduction peak derived from the cathodic EC structure is obtained. And an oxidation peak, an oxidation peak and a reduction peak derived from the anodic EC structure,
An increase or decrease in the optical density in the visible light region is reversibly observed in the potential sweep region. The cyclic voltammetry mentioned here is performed by a usual method, that is, a triangular wave sweep by a potentiostat using a potentiostat, and the sweep range is within the range of the solvent used and the potential window of the electrode. The light source used for measuring the optical density is not particularly limited, but usually a tungsten lamp or the like is used.

The concentration of the compound (A) in the ion conductive layer is not particularly limited, but the lower limit is usually 1 mM.
Or more, preferably 5 mM or more, more preferably 10 m
M and the upper limit is 100 mM or less, preferably 5 mM or less.
The value is at most 0 mM, more preferably at most 40 mM. The number of the cathodic EC structure and the anodic EC structure contained in the compound (A) is preferably 2 or less per molecule. In other words, the compound (A)
Is an organic compound containing one cathodic EC structure and one anodic EC structure in one molecule, and one compound in one molecule.
Compound containing two cathodic EC structures and two anodic EC structures, two cathodic E molecules per molecule
One selected from the group consisting of a C structure, an organic compound containing one anodic EC structure, two cathodic EC structures in one molecule, and an organic compound containing two anodic EC structures in one molecule Alternatively, two or more kinds are desirable.
The term “cathodic EC structure” as used herein means any of a viologen compound derivative structure, an anthraquinone-based compound derivative structure, and the like, and the anodic EC structure is a pyrazoline-based compound derivative structure, a metallocene compound derivative structure,
It means any of a phenylenediamine compound derivative structure, a benzidine compound derivative structure, a phenazine compound derivative structure, a phenoxazine compound derivative structure, a phenothiazine compound derivative structure, a tetrathiafulvalene derivative structure, 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.

Embedded image

Embedded image In the general formula (1), A ^- and B ^- may be the same or different, and each is independently a halogen anion, Cl-
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C
₆ H ₄₎ SO ₃ ^- represents a counter anion selected from. The halogen anion ^{here, F -, Cl -, BR} -, I -
And the like. In the general formulas (2) and (3),
R ¹ and R ² each 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. Particularly, a methyl group, an ethyl group, and a propyl group are 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 is 0 ≦ n ≦
Represents an integer in the range of 4. m and n are preferably 0 or 1, and particularly preferably 0. M
e is CR, CO, Fe, Mg, Ni, OS, Ru, V,
X-Hf-Y, X-MO-Y, X-Nb-Y, X-Ti
-Y, XVY or X-ZR-Y, preferably Fe. Here, X and Y represent hydrogen, halogen, or an alkyl group having 1 to 12 carbon atoms, which may be the same or different.

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

Embedded imageIn the general formulas (4) to (7), R¹, R^Two, M, n, M
e, A^-And B^-In the general formulas (1) to (3)
The definition is the same. R^ThreeAnd R^FourAre the same but different
It may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Shows a hydride residue. As a preferred specific example of the hydrocarbon residue
Is a hydrocarbon group such as alkylene, ester, ether
, Amide, thioether, amine, urethane, silyl
And the like. The ester is represented by the general formula -RC
OO-R- or -R-OCO-R- (R is an alkyl group having 1 to 8 carbon atoms)
Alkylene), specifically, -C_Four
H₈-COO-C_TwoH_Four-, -C_FourH₈-OCO-C_TwoH_Four-, -C_FourH
₈-COO-C_FourH₈-, -C_FourH₈-OCO-C_FourH₈-
You. As the ether, a compound represented by the general formula -R-O-R- (where R is
To 10 alkylene), and specific
Typically -C_FourH₈-OC_TwoH_Four-, -C_FourH₈-OC_FourH₈-
Can be The amide has a general formula -R-CONH-R- or
-R-NHCO-R- (R is alkylene having 1 to 8 carbon atoms)
And specifically, -C_FourH₈-CONH
-C_TwoH_Four-, -C_FourH₈-NHCO-C_TwoH_Four-, -C_FourH₈-CON
HC_FourH₈-, -C_FourH₈-NHCO-C_FourH₈-
As the thioether, a compound represented by the general formula -RSR- (where R is
To 10 alkylene), and specific
Typically -C_FourH₈-S-C_TwoH_Four-, -C_FourH₈-S-C_FourH₈-
Can be As the amine, a compound represented by the general formula -R-NH-R- (R is a carbon
Represented by formulas (1) to (10), a general formula -R
-NH-Ph- group (R: alkylene having 1 to 10 carbon atoms,
Ph: an arylene group having 6 to 12 carbon atoms or a substituted arylene
Each represents a group), specifically, -C_FourH₈-NH-
C_TwoH_Four-, -C_FourH ₈-NH-C_FourH₈- Ureta
Is a compound of the general formula -R-OCONH-R- or -R-NHC
OO-R- (R is alkylene having 1 to 8 carbon atoms)
And specifically, -C_FourH₈-OCONH-C_TwoH
_Four-, -C_FourH₈-NHCOO-C_TwoH_Four-, -C_FourH₈-OCONH
-C_FourH₈-, -C_FourH₈-ONHCO-C_FourH₈-
Silyl is represented by the general formula -R-Si (R ')_Two-R- (R is carbon number
1-8 alkylene. R 'is a methyl group or ethyl
Base. )), Specifically, -C_FourH₈-
Si (CH_Three)_Two-C_TwoH_Four-, C_FourH₈-Si (CH_Three)_Two-C_FourH
₈-, -C_FourH₈-Si (C_TwoH_Five)_Two-C_TwoH_Four-, -C_FourH₈-Si
(C_TwoH_Five)_Two-C_FourH₈-And so on. R^FiveIs 1 carbon
-20, preferably 1-10 alkyl groups, cycloal
Kill, alkenyl, aryl and aralkyl groups
A hydrocarbon group, having 4 to 20 carbon atoms, preferably
4 to 10 heterocyclic aromatic groups, said hydrocarbon groups or heterocycles
A substituted carbon in which part of the hydrogen of an aromatic group has been replaced by a substituent
Hydrogen hydride residue or substituted heterocyclic aromatic substituent, having 4 to 4 carbon atoms
20, preferably 4 to 10 heterocyclic aromatic groups. A
As the alkyl group, a methyl group, an ethyl group, i-propyl
Group, n-propyl group, n-butyl group, t-butyl group, n
-A pentyl group, an n-hexyl group and an n-heptyl group are exemplified.
And a cycloalkyl group such as a cyclohexyl group
And aryl groups such as phenyl and naphthyl
Group, tolyl group, xylyl group, naphthyl group, etc.
Examples of the alkenyl group include a vinyl group and an allyl group.
Aralkyl groups include benzyl and phenyl
A ropyl group is exemplified. As the heterocyclic aromatic group, 2-py
Lysyl group, 4-pyridyl group, 2-pyrimidyl group,
A norin group is exemplified. Substituted hydrocarbon residue or compound
Substituents in the aromatic aromatic group may have 1 to 1 carbon atoms.
0, preferably 1 to 5 alkoxy groups, alkoxycal
Bonyl group, acyl group, halogen, cyano group (-CN
Group), a hydroxy group, a nitro group, an amino group and the like.
And the alkoxy group includes a methoxy group, an ethoxy group, etc.
And an alkoxycarbonyl group is methoxy
A carbonyl group is an acyl group such as an acetyl group,
Examples of the halogen include Cl, F and the like.
Residues include methoxyphenyl and chlorophenyl
Group, fluorophenyl group, methoxychlorophenyl group,
Cyanophenyl group, acetylphenyl group, methoxycal
Representative examples include a bonylphenyl group and a methoxynaphthyl group.
It is mentioned.

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

Embedded image

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Generally, an ion conductive layer in an EC device has an ion conductivity of 1 × 10 ⁻⁷ S / cm or more at room temperature, and plays a role of coloring, decoloring, and discoloring the above-described electrochromic active material. Such an ion conductive layer can be formed using any one of a liquid ion conductive material, a gelled liquid ion conductive material, and a solid ion conductive material. Therefore, the EC device of the present invention can be made into various solid-state EC devices having high practicality. Liquid ion conductive substance The liquid ion conductive substance is prepared by dissolving a supporting electrolyte such as salts, acids and alkalis in a solvent. As the solvent, any solvent commonly used in electrochemical cells and batteries can be used. Specifically, water, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane , Dimethoxyethane, propionitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolan, sulfolane, trimethylphosphate, polyethylene glycol and the like can be used, especially propylene carbonate, ethylene carbonate , Dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, Ruhoran, 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, but usually, the solvent accounts for at least 20% by weight, preferably at least 50% by weight, more preferably at least 70% by weight of the ion conductive layer, and the upper limit is 98% by weight, preferably Is at a value of 95% by weight, more preferably 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.
Inorganic ions such as alkali metal salts and alkaline earth metal salts
Salt; quaternary ammonium salt; cyclic quaternary ammonium salt;
Grade phosphonium salts and the like can be used. Examples of salts
LiClO_Four, LiSCN, LiBF_Four, LiAs
F₆, LiCF_ThreeSO_Three, LiPF₆, LiI, NaI, N
aSCN, NaClO_Four, NaBF_Four, NaAsF₆, K
Alkali metal salts such as SCN and KCl; (CH_Three)_FourNBF
_Four, (C_TwoH_Five)_FourNBF_Four, (N-C_FourH₉)_FourNBF_Four,
(C_TwoH_Five)_FourNBr, (C _TwoH_Five)_FourNCLO_Four, (N-C_Four
H₉)_FourNCLO_Four, CH_Three(C_TwoH_Five)_ThreeNBF_Four, (C
H_Three)_Two(C_TwoH_Five)_TwoNBF_Four,Moreover

Embedded image Quaternary ammonium salts such as (CH ₃ ) ₄ PBF ₄ and (C ₂ H
₅ ) ₄ PBF ₄ , (C ₃ H ₇ ) ₄ PBF ₄ , (C ₄ H ₉ ) ₄ PBF
Phosphonium salts such as _4, or mixtures thereof, are mentioned as preferred. Acids are also not particularly limited, 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 also not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. The supporting electrolyte may be used in any amount including an unused case, but in general, the supporting electrolyte has an upper limit of 20 M or less, preferably 10 M or less, more preferably 5 M or less in the ion conductive layer. The following values, the lower limit is usually 0.01M or more, preferably 0.05M or more,
More preferably, it is desirable to be present at 0.1 M or more.

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 also not particularly limited, and oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used.

[0016]Solid ion conductive material Solid ion conductive materials are solid at room temperature and
A substance that has on-conductivity and includes 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 methac
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 present invention
The first example of the recommended solid polymer electrolyte is the following general formula
The urethane acrylate represented by (8)
Composition containing organic polar solvent and supporting electrolyte (optional component)
It is a polymer solid electrolyte obtained by solidifying a substance. What
In the context of solid polymer electrolyte, solidification refers to polymerizability.
Or the crosslinking component is caused by a polymerization (polycondensation) or crosslinking reaction.
And the whole composition does not substantially flow at room temperature.
To be in a state. This solidification causes polymerization or
Bridging components form a three-dimensional network structure (network)
You.

Embedded image (Wherein R ⁶ and R ⁷ are the same or different groups,
It represents a group selected from groups represented by formulas (11) to (13). R ⁸ and R ⁹ are the same or different groups,
It represents a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms. Y is a polyether unit, a polyester unit,
A polycarbonate unit or a mixed unit thereof is shown.
A is an integer in the range of 1 to 100, preferably 1 to 50, and more preferably 1 to 20. )

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

Embedded image In the general formula (12), R ¹⁴ represents an alkyl group having 1 to 3 carbon atoms 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. The hydrogen atom in the general formula (12) is partially substituted with an oxygen-containing hydrocarbon group such as an alkoxy group having 1 to 6, preferably 1 to 3 carbon atoms or an aryloxy group having 6 to 12 carbon atoms. Group. R ¹⁰ in the general formulas (9) to (11)
Specific examples of methylene group, tetramethylene group,
-Methyl-ethylene group, 1,2,3-propanetriyl group, neopentanetriyl group and the like can be preferably mentioned.

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).

Embedded image In the general formulas (13) to (15), R ¹⁵ and R ¹⁶ are the same or different groups and include a phenylene group, a substituted phenylene group (such as an alkyl-substituted phenylene group), a cycloalkylene group, and a substituted cycloalkylene group (alkyl-substituted group). A cycloalkylene group). R ^{17 to} R ²⁰ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 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.

Embedded image

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.

Embedded image In the general formulas (a) to (d), R ^{21 to} R ²⁶ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Shows 12 divalent hydrocarbon residues. R ^{21 to} R ²⁶ are preferably a linear or branched alkylene group. Specifically, R ²³ is a methylene group, an ethylene group, a trimethylene group,
R ^{21 to} R ²² are preferably a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, or the like.
And R ^{24 to} R ²⁶ are preferably an ethylene group, a propylene group or the like. c ′ is 2 to 300, preferably 10 to
It is an integer of 200. d 'is 1 to 300, preferably 2
E 'is an integer of 1 to 200, preferably 2 to 1
An integer of 00, e '' is 1 to 200, preferably 2 to 100
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 ²⁰
Comrades, R ²¹ comrades, R ²² comrades and R ²³ each other may be the same or different. The molecular weight of the urethane acrylate represented by the general formula (8) is usually 2,500 in weight average molecular weight.
~ 30,000, preferably 3,000 ~ 20,000
And the number of polymerizable functional groups in one molecule is preferably in the range of 2 to 6, more preferably 2 to 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 urethane acrylate represented by the general formula (8) is a precursor composition 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 such a composition. The amount of the solvent to be added is usually 100 to 1200 parts by weight, preferably 200 to 1200 parts by weight, per 100 parts by weight of urethane acrylate.
It is selected in the range of 900 parts by weight. If the added amount of the solvent is too small, the ionic conductivity of the finally obtained solid polymer electrolyte becomes insufficient, and if it is too large, the mechanical strength of the solid electrolyte may be reduced. The amount of the supporting electrolyte to be added is not particularly limited, even when it is not added, but the upper limit is usually 30% by weight or less, preferably 20% by weight or less of the amount of the solvent added, and the lower limit is 0.1% by weight. %, Preferably 1% by weight or more. 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 obtained by solidifying a composition containing an acryloyl-modified or methacryloyl-modified polyalkylene oxide (hereinafter, both of them are collectively referred to as a modified polyalkylene oxide), a solvent, and a supporting electrolyte (optional component). It is a polymer solid electrolyte. The modified polyalkylene oxide includes monofunctional modified polyalkylene oxide, bifunctional modified polyalkylene oxide, and trifunctional or higher polyfunctional modified polyalkylene oxide. Each of these modified polyalkylene oxides may be used alone or as a mixture. In particular, a monofunctional modified polyalkylene oxide is essential, and a bifunctional modified polyalkylene oxide and / or a polyfunctional modified polyalkylene oxide may be used. Are preferably used in combination. 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 to 100 parts by weight of the monofunctional modified polyalkylene oxide. .1 to 20 parts by weight,
Preferably it is selected in the range of 0.5 to 10 parts by weight.

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

Embedded image (Wherein, 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.) General formula (16) )), R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰
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 an n-pentyl group. R ²⁷ is hydrogen, a methyl group, R ²⁸ is hydrogen,
A methyl group, R ²⁹ is preferably hydrogen and a methyl group, and R ³⁰ is preferably hydrogen, a methyl group and an ethyl group. G ′ in the general formula (16) is an integer of 1 or more, usually 1 ≦ g ′ ≦ 10
0, preferably 2 ≦ g ′ ≦ 50, more preferably 2 ≦ g ′
It is an integer in the range of g ′ ≦ 30. Specific examples of the compound represented by the general formula (16) include methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol methacrylate having an oxyalkylene unit in the range of 1 to 100, preferably 2 to 50, more preferably 2 to 20; Ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polypropylene glycol acrylate,
Examples thereof include ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate, and a mixture thereof. Of these, methoxy polyethylene glycol methacrylate and methoxy polyethylene glycol acrylate are particularly preferably used. When g ′ in the general formula (16) 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. As a specific example, for example, 1 to 50, preferably 1
Methoxypoly (ethylene / propylene), which is an alternating copolymer, a block copolymer or a random copolymer having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20. Glycol methacrylate, ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate, or a mixture thereof, and the like.

The 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).

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.)

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 , R ³² , R ³³ and R ³⁴ in the formula each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms. Group, ethyl group, i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group and the like. In particular, it is preferable that R ³¹ is hydrogen, methyl, R ³² is hydrogen, methyl, R ³³ is hydrogen, methyl, and R ³⁴ is hydrogen, methyl. H ′ in the general formula (18) is an integer of 1 or more, usually 1 ≦ h ′ ≦ 10
0, preferably 2 ≦ h ′ ≦ 50, more preferably 2 ≦ h ′
Specific examples of such compounds include polyethylene glycol dimethacrylate and polypropylene glycol having an oxyalkylene unit in the range of 1 to 100, preferably 2 to 50, and more preferably 1 to 20. Examples thereof include 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. Examples thereof include oxyethylene units in the range of 1 to 50, preferably 1 to 20, and oxypropylene units of 1 to 50, preferably 1 to 50.
Poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, or a mixture thereof, which is an alternating copolymer, a block copolymer or a random copolymer having a range of from 20 to 20; Is mentioned. 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 of the alkyl group include a methyl group, an ethyl group and an i-propyl Group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group and the like. Particularly, R ³⁵ , R ³⁶ and R ³⁷ are preferably hydrogen or a methyl group. Further, i ′ in the formula represents an integer of 1 or more, usually 1 ≦ i ′ ≦ 100, preferably 2 ≦ i ′ ≦ 50, more preferably 2 ≦ i ′ ≦ 30. j ′ is the number of links of the linking group L, and is an integer of 2 ≦ j ′ ≦ 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, a methylene group, an ethylene group,

Embedded image And the like. Further, as a trivalent hydrocarbon group,
Examples thereof include an alkyltriyl group, an aryltriyl group, an arylalkyltriyl group, an alkylaryltriyl group, and a hydrocarbon group having these as a basic skeleton.

Embedded image And the like. Further, as a tetravalent hydrocarbon group,
Examples thereof include an alkyltetrayl group, an aryltetrayl group, an arylalkyltetrayl group, an alkylaryltetrayl group, and a hydrocarbon group having these as a basic skeleton.

Embedded image And the like.

Specific examples of such a compound include an oxyalkylene unit 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, the oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other, and the polymerization form may be alternating copolymerization, block copolymerization,
Any of random copolymerization may be used. 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 Where, trimethylolpropane tri (poly (ethylene propylene) glycol acrylate), trimethylol propane tri (poly (ethylene propylene) glycol methacrylate), tetramethylol methane tetra (poly (ethylene propylene) glycol acrylate), Tetramethylolmethanetetra (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 weight 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 described above is a precursor composition obtained by mixing the modified polyalkylene oxide with the solvent and the supporting electrolyte described in the liquid ion conductive material, It is prepared by solidification, and the amount of the solvent to be added is selected in the range of 50 to 800% by weight, preferably 100 to 500% by weight of the total amount of the modified polyalkylene oxide. The amount of the supporting electrolyte to be added is not particularly limited, even when the supporting electrolyte is not added, but the upper limit is 30% by weight or less, preferably 20% by weight or less of the total amount of the modified polyalkylene oxide and the solvent. The lower limit is usually 0.1.
1% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more. A crosslinking agent or a polymerization initiator can be added to the solid polymer electrolyte containing the modified polyalkylene oxide as needed.

As a crosslinking agent that can be added to the polymer electrolyte, an acrylate 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 when used. The amount of the cross-linking agent used is 0.0 mol per 100 mol% of the polymerizable urethane acrylate or modified polyalkylene oxide contained in the solid polymer electrolyte.
1 mol% or more, preferably 0.01 mol% or more;
The upper limit is 10 mol%, preferably 5 mol%.

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, as the peroxide-based polymerization initiator, for example, benzoyl peroxide, methyl ethyl peroxide,
Examples include t-butyl peroxypivalate, diisopropyl peroxycarbonate, and the like, and examples of the azo type include 2,2′-azobis (2-isobutyronitrile) and
2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1 ′
-Azobis (cyclohexane-1-carbonitrile) or the like can be used alone or as a mixture.
The amount of the polymerization initiator used is at least 0.1 part by weight, preferably at least 0.5 part by weight, based on 100 parts by weight of the polymerizable urethane acrylate or modified polyalkylene oxide contained in the solid polymer electrolyte. The upper limit is 10 parts by weight, preferably 5 parts by weight 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 proceeds preferably by heating the solid polymer electrolyte which serves as a thermal polymerization initiator to a temperature of usually 0 ° C. or higher, preferably 20 ° C. or higher. The heating temperature is desirably 130 ° 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. As described above, the ion-conductive layer of the present invention comprises the compound (A)
However, the production method and form are not particularly limited. For example, in the case of a liquid-based ion-conductive substance, the compound (A) may be appropriately dispersed or dissolved in a conductive substance. A) can be exemplified by mixing A) and finally dispersing or dissolving the compound appropriately.
The solid ion conductive material layer has a form in which the compound (A) is mixed in advance at the stage of a solid electrolyte in an uncured state, and then solidified to appropriately disperse or dissolve the compound. And typically
In the case of the polymer solid electrolyte, the compound (A) is mixed with the solid electrolyte similarly in an uncured state, that is, the above-described polymer solid electrolyte precursor composition, and the compound is cured by curing the composition. Examples include dispersed or dissolved solid polymer electrolytes.

Regardless of whether the ion-conductive substance constituting the ion-conductive layer is liquid, gelled liquid, or solid, the ion-conductive layer of the present invention containing compound A can be used. Preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, a salicylate-based compound, a cyanoacrylate-based compound, and an oxalic anilide-based compound. It can be suitably used. As the benzotriazole-based compound, for example, a compound represented by the following general formula (19) is preferably exemplified.

Embedded image In the formula, R ³⁸ is a hydrogen atom, a halogen atom or a carbon atom
Represents 10 to 10, preferably 1 to 6, alkyl groups. As the halogen atom, fluorine, chlorine, bromine, iodine and the like, and as the alkyl group, a methyl group, an ethyl group, a propyl group, an i-
Examples thereof include a propyl group, a butyl group, a t-butyl group, and a cyclohexyl group, and a hydrogen atom and a chlorine atom are particularly preferable. The substitution position of R ³⁸ is the 4-position or 5-position of the benzotriazole skeleton, but in the case of a halogen atom and an alkyl group, it is usually located at the 5-position. R ³⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a t-butyl group.
Examples thereof include an amyl group, a cyclohexyl group, and a 1,1-dimethylbenzyl group, and particularly preferred are a t-butyl group, a t-amyl group, and a 1,1-dimethylbenzyl group. R
⁴⁰ represents an alkyl carboxylic acid group having 2 to 10, preferably 2 to 4 carbon atoms, or an alkylidene carboxylic acid group.
Examples of the alkyl group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group. Further, as other R ⁴⁰ , t-butyl group, t-amyl group, 1,
Alkyl groups such as 1,3,3, -tetramethylbutyl group,
Examples thereof include alkyl alkanoates such as octyl propanoate, and arylalkyl groups such as 1,1-dimethylbenzyl group. Examples of such a benzotriazole-based compound include 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid and 3- (2
H-benzotriazol-2-yl) -5- (1,1-
Dimethylethyl) -4-hydroxy-benzeneethanic acid, 3- (2H-benzotriazol-2-yl) -4
-Hydroxybenzene ethane acid, 3- (5-methyl-2
H-benzotriazol-2-yl) -5- (1-methylethyl) -4-hydroxybenzenepropanoic acid, iso-octyl-3- (3- (2H-benzotriazole-
2-yl) -5-tert-butyl-4-hydroxyphenylpropionate, methyl-3- [3-tert-butyl-5-
(2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 2- (5'-methyl-
2′-hydroxyphenyl) benzotriazole, 2-
[2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-
Butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3'-dodecyl-
5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t-amyl-phenyl) -2H-benzotriazole,
2- (2′-hydroxy-3 ′-(3 ″, 4 ″,
5 ″, 6 ″ -tetrahydrophthalimidomethyl)-
5-methylphenyl) benzotriazole, 2- (3 ′
-T-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ',
5'-di-t-butyl-2'-hydroxyphenyl)-
5-chlorobenzotriazole, 2- [2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl]
-2H-benzotriazole, 2- [2-hydroxy-
3-dimethylbenzyl-5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, 3- (5-chloro-2H-benzotriazole-2
-Yl) -5-tert-butyl-4-hydroxyphenylpropanoic acid octyl ester, 3- (5-chloro-2H-
Benzotriazol-2-yl) -5-t-butyl-4
-Hydroxyphenyl-n-propanol; among these, octyl 3- (5-chloro-2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenylpropanoate, 3- ( 5-
Chloro-2H-benzotriazol-2-yl) -5
t-Butyl-4-hydroxyphenyl-n-propanol is particularly preferably used.

As the benzophenone-based ultraviolet absorber,
For example, compounds represented by the following general formulas (20) to (23) can be mentioned.

Embedded imageWhere R⁴¹Is a covalent bond, a methylene group, an ethylene group,
Represents a pyrene group or the like; ⁴²And R⁴³Are the same or different
A hydroxyl group, having 1 to 10 carbon atoms,
And preferably represents 1 to 6 alkyl groups or alkoxy groups.
You. Also, -R⁴⁵There may be no -COOH group. g,
k represents an integer in the range of 0 ≦ g ≦ 3 and 0 ≦ k ≦ 3. Al
As the kill group, a methyl group, an ethyl group, a propyl group, i
-Propyl, butyl, t-butyl, cyclohexyl
A methoxy group, an ethoxy group, etc.
Si group, propoxy group, i-propoxy group, butoxy group, etc.
Is exemplified. R⁴¹Has 1 to 10 carbon atoms, preferably 1
And represents an alkylene group or an alkylidene group. Al
Examples of the kylene group include a methylene group, an ethylene group, and a trimethyl group.
Rene group, propylene group, etc., as alkylidene group,
Examples include an ethylidene group and a propylidene group. Benzo
Specific examples of the phenone ultraviolet absorber include 2-hydrogen
Xy-4-methoxybenzophenone-5-carboxylic acid,
2,2'-dihydroxy-4-methoxybenzophenone
-5-carboxylic acid, 4- (2-hydroxybenzoyl)
-3-Hydroxybenzenepropanoic acid, 2,4-dihydric
Roxybenzophenone, 2-hydroxy-4-methoxy
Benzophenone, 2-hydroxy-4-methoxybenzo
Phenone-5-sulfonic acid, 2-hydroxy-4-n-
Octoxybenzophenone, 2-hydroxy-4-dode
Siloxybenzophenone, 2,2'-dihydroxy-
4-methoxybenzophenone, 2,2'-dihydroxy
-4,4'-dimethoxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2-hydr
Roxy-4-methoxy-2'-carboxybenzopheno
2-hydroxy-4-methoxy-5-sulfobenzo
Phenone and the like are preferable, and among them, 2,2 ′,
4,4'-tetrahydroxybenzophenone is preferred
Used.

The triazine-based UV absorbers include 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-[(hexyl) oxy] -phenol, 2
-[4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and the like can be mentioned. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3 ^, diphenyl acrylate and ethyl-2-cyano-3,3 ^, -diphenyl acrylate. Examples of the oxalic acid anilide-based ultraviolet absorber include 2-ethoxy-2'-ethyl-oxalic acid bisanilide. When an ultraviolet absorber is contained in the ion conductive layer, the lower limit of the amount of the ultraviolet absorber present in the ion conductive layer is 0.1% by weight or more, preferably 1%, regardless of the type of the ultraviolet absorber used. % By weight or more, and its upper limit is 20% by weight, preferably 10% by weight.

The EC device 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, the two conductive substrates are opposed at an appropriate interval, and the compound (A) is placed between the opposed conductive substrates whose peripheral edges are sealed. Is injected by a vacuum injection method, an air injection method, a meniscus method, or the like, and then the EC element of the present invention can be manufactured by a method of closing the injection port. Further, depending on the type of the ion conductive substance used, an ion conductive layer containing the compound (A) is formed on one conductive substrate by a sputtering method, an evaporation method, a sol-gel method, or the like, and then the other conductive substrate is formed. Alternatively, the EC element of the present invention can be manufactured in the same manner as in the method of manufacturing a laminated glass sheet, or by forming an ion-conductive substance containing compound A into a film beforehand. When the ion conductive substance to be used is a solid system, particularly when a polymer solid electrolyte containing urethane acrylate or modified alkylene oxide is used, the polymer solid in the unsolidified state containing the compound (A) is used. The electrolyte precursor is injected between the opposing conductive substrates whose peripheral edge is sealed by a vacuum injection method, an air injection method, a meniscus method, etc., and after closing the injection port, the solid polymer electrolyte is solidified by an appropriate means. Thus, the EC element of the present invention can be obtained. The ion conductive layer of the EC device according to the present invention usually has a thickness of 1 at room temperature.
× 10 ⁻⁷ S / cm or more, preferably 1 × 10 ⁻⁶ S / cm
As described above, it is more desirable to exhibit an ion conductivity of 1 × 10 ⁻⁵ S / cm or more. The thickness of the ion conductive layer is usually at least 1 μm, preferably at least 10 μm, and more preferably at most 3 mm, preferably at most 1 mm.

The basic structure of the EC device according to the present invention will be described below with reference to the drawings. The EC device shown in FIG. 1 comprises a transparent conductive substrate comprising a transparent substrate 1 and a transparent electrode layer 2 laminated on the surface thereof, a transparent or opaque substrate 5 and a transparent, opaque or reflective electrode layer laminated on the surface. And an ion conductive layer 3 in which the compound (A) is dispersed. FIG. 2 shows a configuration example of the display element and the light control glass. Two transparent conductive substrates, each having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, are opposed at appropriate intervals so that the transparent electrode layers of both substrates face each other. It has a structure in which the conductive layer 3 is sandwiched. FIG. 3 shows a configuration example of an electrochromic mirror. A transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, a transparent electrode layer 2 formed on one surface of the transparent substrate 1, and a reflective conductive substrate having a reflective layer 7 formed on the other surface. In such a structure, the transparent electrode layers of both substrates face each other at an appropriate interval so as to sandwich the ion conductive layer 3 in which the compound (A) is dispersed. E shown in FIGS.
The C element can be manufactured by any method. For example, in the case of the EC device having the configuration shown in FIG. 1, the transparent electrode layer 2 is formed on the transparent substrate 1 by the above-described method, and the electrode band 8 is attached to the periphery of one side thereof to prepare the laminate A. I do. Separately, the transparent, opaque or reflective electrode layer 4 is formed on the substrate 5 by the above-described method, and further, the electrode band 8 is attached to the periphery of one side thereof to obtain the 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, the EC element can be obtained by injecting the composition of the ion conductive layer by the above-described method, or thereafter curing the composition as desired, thereby forming the ion conductive layer 3. 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 is
It can be inserted into the peripheral portion of the opposing conductive substrate or a gap on the entire surface, or can be provided by a method of forming a projection made of an insulator such as resin on the electrode of the conductive substrate. Further, as another method, the transparent electrode layer 2, the electrode strip 8, and the ion conductive layer 3 are sequentially formed on the transparent substrate 1 by the above-described method in the stated order to obtain a laminate A '. Separately, the transparent, opaque or reflective electrode layer 4 and the electrode strip 8 are formed on the substrate 5 by the above-mentioned method to obtain a laminate B ′. Then, the two laminates are opposed to each other at an interval of about 1 to 1000 μm so that the ion conductive 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 with the sealing material 6. Method. In the case of the electrochromic light control glass having the configuration shown in FIG.
Are prepared. In the case of the electrochromic mirror shown in FIG. 3, a transparent conductive substrate having a transparent electrode layer 2 and an electrode band 8 formed on one surface of a transparent substrate 1 is provided. A transparent electrode layer 2 and an electrode strip 8 are formed on one surface of the substrate 1.
Is prepared with a reflective conductive substrate having a reflective layer 7 formed on the other surface, and thereafter each element can be obtained in the same procedure as in the case of the element having the configuration shown in FIG. Although not shown, a lead wire for applying a voltage to the electrochromic element is connected to the electrode layer and the electrode band. The lead wire may be directly connected to the electrode layer or the electrode band, or may be a clip-shaped member (a highly conductive member such as a metal that holds a conductive substrate in contact with the electrode layer or the electrode band).
May be connected via a lead wire. The size of the clip-shaped member is not particularly limited, and the upper limit of the length of the clip portion is generally the length of an arbitrary side of the substrate.

A typical configuration example of the EC device of the present invention is as shown in FIGS. 1 to 3. The EC device of the present invention may have an ultraviolet reflecting layer or an ultraviolet absorbing layer if necessary. An ultraviolet-cutting layer such as a layer, and in the case of a mirror, an overcoat layer for protecting the entire mirror layer or the surface of each film layer can be arbitrarily added. It is preferable that the ultraviolet cut layer is provided on the outer side or the transparent electrode layer side of the transparent substrate 1, and the overcoat layer is provided on the outer side of the transparent substrate 1 or the outer side of the reflective layer 7. The element of the present invention can be suitably used for a display element, a light control glass, an antiglare mirror for an automobile or the like, or an electrochromic mirror such as a decorative mirror used indoors. Further, the EC element of the present invention is excellent not only in basic characteristics but also particularly in color responsiveness. The EC element of the present invention has such features that it can be driven at a lower voltage than conventional ones. When the EC element of the present invention is used as a display element, it is used as an information display in a station, an airport, an underground shopping mall, an office building, a school, a hospital, a bank, and other public facilities, a monument, an information display in a store (sales counter information, Display of prices, ticket reservation status, etc.), display of other devices (large electronic book, game machine, electronic clock, electronic calendar), and the like. In this case, monochrome display can be performed by using single-color elements, and color display can be performed by arbitrarily arranging several types of color elements. Further, the present element can be provided between the color filter and the light source, and a color display can be obtained by using the color erasing function of the element as a shutter function.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto. Example 1 An epoxy-based adhesive was linearly applied to the periphery of an ITO-coated transparent glass substrate except for the solution injection port, and a transparent glass substrate of the same size also coated with ITO was placed thereon. The cells were superposed so that the ITO surfaces faced each other with a slight shift, and the adhesive was cured while applying pressure to produce an empty cell with an inlet. On the other hand, methoxypolyethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
M40GN) [Number of oxyethylene units 4] 1.0
g, polyethylene glycol dimethacrylate (9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxyethylene unit number 9] 0.02 g, γ-butyrolactone 4.0 g, 1
-(4-isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one 0.02 g, 3- (5-methyl-2H-benzotriazol-2-yl) -5-
Lithium perchlorate was added to 0.15 g of a mixed solution of (1-methylethyl) -4-hydroxybenzenepropanoic acid in 0.1 g.
8M, a compound represented by the following formula was added to a concentration of 30 mM to obtain a homogeneous solution.

Embedded image After the solution was degassed, it was injected from the inlet of the cell prepared as described above. After sealing the injection port with epoxy adhesive, the solution in the cell is cured by irradiating fluorescent light from both sides, and the electrode strip is soldered on the ITO of the shifted part of the board which is slightly shifted and overlapped. Then, an electrochromic device (light control glass) was obtained. Thus, an electrochromic light control glass having the configuration shown in FIG. 1 was obtained. This light control glass was not colored at the time of assembling, and had a transmittance 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 1.1 V is applied, the color is increased, and
The transmittance of light having a wavelength of nm was about 20%. Also 10
The color was repeatedly applied and erased every second, but no residual disappearance occurred after about 200 hours. Example 2 An epoxy-based adhesive was linearly applied to the periphery of the ITO-coated transparent glass substrate except for the solution injection port, and the ITO-coated transparent glass substrate was further coated with I.
The sheets were overlapped so that the TO surfaces faced each other, and the adhesive was cured while applying pressure, thereby producing an empty cell with an inlet. On the other hand, 1.0 g of methoxypolyethylene glycol monomethacrylate (M40GN manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxyethylene unit number: 4], polyethylene glycol dimethacrylate (4 manufactured by Shin-Nakamura Chemical Co., Ltd.)
G) [oxyethylene unit number 4] 0.02 g, propylene carbonate 4.0 g, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
To a mixed solution of 0.02 g of 1-one and 0.15 g of 2-hydroxy-4-methoxybenzophenone, 0.8 M of lithium perchlorate and a compound represented by the following formula were added to a concentration of 30 mM. A homogeneous solution was obtained.

Embedded image After the solution was degassed, it was injected from the inlet of the cell prepared as described above. After sealing the injection port with an epoxy-based adhesive, the solution in the cell was cured by applying light from a fluorescent lamp from both sides to obtain an electrochromic device (light control glass). Thus, an electrochromic light control glass having the configuration shown in FIG. 1 was obtained. This light control glass was not colored at the time of assembling, and had a transmittance of about 87%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, when a voltage of 1.1 V was applied, the film was colored, and the transmittance of light having a wavelength of 633 nm was about 25%. Further, the color was repeatedly applied and erased every 10 seconds, but after 200 hours, no disappearance was observed. Example 3 A laminate having a palladium thin film on a substrate was used as a highly reflective electrode, and an epoxy-based adhesive was linearly applied to the periphery of the palladium layer of the laminate except for the inlet of the electrolyte precursor solution. Then, a transparent glass substrate coated with SnO ₂ thereon is overlapped so that the SnO ₂ surface and the palladium layer of the substrate face each other, and the adhesive is cured while applying pressure,
An empty cell with an inlet was made. On the other hand, 1.0 g of methoxypolyethylene glycol monomethacrylate (M40GN manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxygen unit number 4], polyethylene glycol dimethacrylate (4G manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxygen unit number 4] 0.02 g, propylene carbonate 4.0 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.02 g, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4 -Hydroxy-benzene ethane acid 0.15 g
Was added to a mixed solution of 0.8M and a compound represented by the following formula at a concentration of 30 mM to obtain a homogeneous solution.

Embedded image After sealing the inlet with an epoxy-based adhesive, the solution in the cell was cured by irradiating light from a fluorescent lamp from the transparent substrate side to obtain an electrochromic device. Thus, an electrochromic mirror having the configuration shown in FIG. 3 was obtained. This mirror is uncolored when assembled and has a reflectivity of about 70
%Met. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is,
When a voltage of 1.1 V was applied, the layer was colored and the reflectance was about 10%. The color was repeatedly applied and erased every 10 seconds.
Even after the elapse of 0 hours, no disappearance or the like occurred. Example 4 A laminate having a palladium thin film on a substrate was used as a highly reflective electrode, and an epoxy-based adhesive was applied linearly to the periphery of the palladium layer of the laminate except for the inlet for the electrolyte precursor solution. Then, a transparent glass substrate coated with SnO2 is superimposed on the _two substrates so that the SnO2 surface and the palladium layer face each other with a slight shift, and the adhesive is cured while applying pressure, and an empty space with an inlet is provided. A cell was prepared. On the other hand,
1.0 g of methoxypolyethylene glycol monomethacrylate (M40GN manufactured by Shin-Nakamura Chemical Co., Ltd.) [oxyethylene unit number 4], polyethylene glycol dimethacrylate (9 manufactured by Shin-Nakamura Chemical Co., Ltd.)
G) [Oxyethylene unit number 9] 0.02 g, propylene carbonate 4.0 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.02 g,
To a mixed solution of 0.15 g of 2-hydroxy-4-methoxybenzophenone-5-carboxylic acid was added 0.8 M of lithium tetrafluoroborate and 3 parts of a compound represented by the following formula.
It was added to a concentration of 0 mM to obtain a homogeneous solution.

Embedded image After sealing the injection port with an epoxy-based adhesive, the solution in the cell was cured by applying light from a fluorescent lamp from the transparent substrate side. Sn
On the SnO2 surface of the slightly shifted portion of the O2 substrate,
An electrode band was provided by soldering to obtain an electrochromic device. Thus, an electrochromic mirror having the configuration shown in FIG. 3 was obtained. The mirror was not colored when assembled and had a reflectivity of about 70%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, when a voltage of 1.1 V was applied, the color was obtained, and the reflectance became about 10%. Further, the color was repeatedly applied and erased every 10 seconds, but after 200 hours, no disappearance was observed. Example 5 A laminate having a palladium thin film on a substrate was used as a highly reflective electrode, and an epoxy-based adhesive was applied linearly to the periphery of the palladium layer of the laminate except for the inlet for the electrolyte precursor solution. Then, a transparent glass substrate coated with SnO ₂ thereon is overlapped so that the SnO ₂ surface and the palladium layer of the substrate face each other, and the adhesive is cured while applying pressure,
An empty cell with an inlet was made. On the other hand, 1.0 g of methoxypolyethylene glycol monomethacrylate (M40GN 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] 0.02 g, 4.0 g of propylene carbonate, 0.02 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (5-methyl-
2-hydroxyphenyl) benzotriazole (CIB
0.03 g of TINUVIN P manufactured by A-GEIGY)
Was added to a mixed solution of 0.5M and a compound represented by the following formula so as to have a concentration of 30 mM to obtain a homogeneous solution.

Embedded image After sealing the inlet with an epoxy-based adhesive, the solution in the cell was cured by irradiating light from a fluorescent lamp from the transparent substrate side to obtain an electrochromic device. Thus, an electrochromic mirror having the configuration shown in FIG. 3 was obtained. The mirror was not colored when assembled and had a reflectivity of about 70%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, 1.1V
When the voltage was applied, the color was changed, and the reflectance became about 10%.
Further, the color was repeatedly applied and erased every 10 seconds, but after 200 hours, no disappearance was observed. Example 6 An epoxy-based adhesive was applied linearly to the periphery of an ITO-coated transparent glass substrate (4 cm × 4 cm) except for the solution injection port, and the ITO-coated transparent glass was further applied thereon. The substrates are slightly shifted and 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, 1.0 g of methoxypolyethylene glycol monomethacrylate (M40GN, 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] 0.02 g, γ-butyrolactone
4.0 g, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 0.02 g,
To a mixed solution of 0.15 g of 3- (5-methyl-2H-benzotriazol-2-yl) -5- (1-methylethyl) -4-hydroxybenzenepropanoic acid was added 0.5 M of lithium tetrafluoroborate. And a compound represented by the following formula:
It was added to a concentration of 00 mM to obtain a homogeneous solution.

Embedded image After the solution was degassed, it was injected from the inlet of the cell prepared as described above. After sealing the injection port with an epoxy-based adhesive, the solution in the cell was cured by irradiating fluorescent light from both sides, and an electrode layer was provided on the ITO of the shifted part of the substrate that was slightly shifted and overlapped, An electrochromic device was obtained. This light control glass was not colored at the time of assembling, and had a transmittance 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 1.3 V was applied, the film was colored, and the transmittance of light having a wavelength of 633 nm was about 5%.
Further, the color was repeatedly applied and erased every 10 seconds, but after 200 hours, no disappearance was observed. A total of 15 elements, 5 in length and 3 in width, were arranged and wired to a power supply so that each could be independently turned on and off. Thus, a display panel capable of displaying numbers was manufactured (FIGS. 4 and 5).

[0034]

The electrochromic device of the present invention has
It is well colored at a voltage of about 1 V, has excellent responsiveness, and has excellent repetitive driving resistance and durability.

[Brief description of the drawings]

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

FIG. 2 is a sectional view showing an example of the electrochromic light control glass according to the present invention.

FIG. 3 is a sectional view showing an example of an electrochromic mirror according to the present invention.

FIG. 4 is a plan view showing a non-display state of the electrochromic display panel according to the present invention.

FIG. 5 is a plan view showing a display state of the electrochromic display panel according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Transparent electrode layer 3 Ion conductive layer 4 Transparent, opaque or reflective electrode layer 5 Transparent or opaque substrate 6 Sealing material 7 Reflective layer 8 Electrode band

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaaki Kobayashi 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Central Research Laboratory, Nisseki Mitsubishi Co., Ltd. (72) Inventor Hiroshi Imafuku 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Address: Nishiishi Mitsubishi Co., Ltd.

Claims (2)

[Claims] 1. An electrochromic device having an ion conductive layer provided between two conductive substrates at least one of which is transparent, wherein the ion conductive layer has a cathode electrochromic property, An electrochromic device comprising an organic compound having a structure having chromic properties. 2. An electrochromic device in which an ion conductive layer is provided between two conductive substrates at least one of which is transparent, wherein the ion conductive layer is represented by (a) the following general formula (1). Bipyridinium ion pair structure;
(b) An electrochromic device comprising at least one metallocene structure represented by the following general formula (2) or (3). Embedded image (Wherein A ^- and B ^- may be the same or different,
Halogen anions, ClO ₄ ⁻ , BF ₄ ⁻ ,
A counter anion selected from PF ₆ ⁻ , CH ₃ COO ⁻ , and CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ is shown. ) (Wherein R ¹ and R ² may be the same or different,
A hydrocarbon group selected from an alkyl group, an alkenyl group and an aryl group having 1 to 10 carbon atoms, and when R ¹ or R ² is an aryl group, the parent ring is bonded to a cyclopentadienyl ring to form a ring; M may represent an integer in the range of 0 ≦ m ≦ 4; n may represent an integer in the range of 0 ≦ n ≦ 4;
Is CR, CO, Fe, Mg, Ni, OS, Ru, V, X
-Hf-Y, X-MO-Y, X-Nb-Y, X-Ti-
Y, X-V-Y or X-ZR-Y is shown. In addition, X and Y mentioned here are hydrogen, halogen or C1-C1.
Represents two alkyl groups, which may be the same or different. )