JP2002202530A - Ion conductive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ion conductive substance which can be manufactured by a simple method and is suitable for forming an ion conductive layer of an electrochromic device having a variable color tone. SOLUTION: A polyether-based polymer compound and a bipyridinium ion pair structure represented by the general formula (1) in the molecule: ^{(X -,} Y -: a halogen _{^{ion, ClO 4 -, BF 4 -}} , PF
_{^{6 -, CH 3 COO -,}} CH 3 (C 6 H 4) SO 3 -, imide anion, main side anionic) and the general formula (2) or (3) represented by ferrocene structure: 2] (R ²¹ , R ²² , R ³¹ , R ³² : alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms; m ₂₁ , n ₂₁ , m ₃₁ , n ₃₂ : an integer of 0 to 4), and an organic compound having at least one structure selected from the group consisting of:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel ion-conductive substance. More specifically, the present invention relates to a transmissive element such as light control glass, an anti-glare mirror for automobiles and the like, a reflective element such as a decorative mirror, an ion conductive material useful for manufacturing an electrochromic element such as a display element, and the like. The present invention relates to an electrochromic device using the same.

[0002]

2. Description of the Related Art As a conventional electrochromic element used for a light control glass or the like, for example, an inorganic oxide such as tungsten oxide (WO ₃ ) is vacuum-coated on a transparent conductive film. A film formed by a vapor deposition method or the like and using this as a color former is known (Japanese Patent Application Laid-Open No. 63-18336). However, in this method, the film formation process must be performed in a vacuum, so that the cost is high, and a large-sized vacuum device is required to obtain a large-area electrochromic element. Further, when tungsten oxide is used, there is a problem that only blue color can be obtained. On the other hand, it is known to use an organic solvent such as propylene carbonate to form an ion conductive layer of an electrochromic device,
There has been a problem that liquid is scattered due to breakage of the element during use, and liquid leakage may occur during use.
The present invention has been made in view of such a situation, and an object thereof is to provide an ion conductive layer which can be manufactured by a simple method and is suitable for forming an ion conductive layer of an electrochromic device having a variable color tone. To provide sexual substances.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned conventional problems, and as a result, have found that a polyether polymer compound and a bipyridinium ion pair structure and / or Alternatively, they have found that an intended electrochromic device can be obtained by using an ion-conductive substance containing an organic compound having a ferrocene structure, and have completed the present invention.

The present invention relates to a polyether polymer compound and a bipyridinium ion pair structure represented by the general formula (1) in the molecule:

[0005]

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(In the general formula (1), X ⁻ and Y ⁻ are
Halogen ion, ClO ₄ ⁻ , BF ₄ ⁻ , P
A counter anion selected from F ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , imide anion, and meside anion is shown. ) And a ferrocene structure represented by the general formula (2) or (3):

[0007]

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(In the general formula (2) or (3),
R ²¹ , R ²² , R ³¹ and R ³² each independently represent a group selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms; When R ²¹ , R ²² , R ³¹ or R ³² is an aryl group, the parent ring may be bonded to a cyclopentadienyl ring to form a ring, and m ₂₁ , n ₂₁ , m ₃₁ and n ₃₁ are Each independently represents an integer of 0 to 4. ) And an organic compound having at least one structure selected from the group consisting of:

[0009] The present invention also resides in an electrochromic device, characterized in that an ion conductive layer containing the ion conductive substance is sandwiched between two conductive substrates at least one of which is transparent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The ion-conductive substance of the present invention comprises a bipyridinium ion-pair structure represented by the general formula (1) and a ferrocene structure represented by the general formula (2) or (3) in the molecule. It is characterized by containing an organic compound (A) having at least one selected structure and a polyether polymer compound (B).

First, the organic compound (A) will be described. The organic compound (A) having a bipyridinium ion pair structure and / or a ferrocene structure usually functions as an electrochromic substance. The organic compound preferably has a bipyridinium ion pair structure represented by the general formula (1) and a ferrocene structure represented by the general formula (2) or (3) in the molecule. The bipyridinium ion pair structure is represented by the following general formula (1).

[0012]

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In the general formula (1), X^-And Y^-Is
Halogen ion, ClO individually_Four ^-, BF_Four ^-, P
F₆ ^-, CH_ThreeCOO^-, CH_Three(C₆H_Four) SO_Three ^-, Imide
Shows an anion or meside anion. Halogen
As ON, for example, F^-, Cl^-, Br^-, And I^-To
Can be mentioned. Examples of imide anions include
If (CF_ThreeSO_Two)_TwoN^-, (C_TwoF_FiveSO_Two)_TwoN^-, (C
F_ThreeSO_Two) (C_FourF₉SO_Two) N^-, And [(CF_Three)_TwoCH
SO_Two]_TwoN^-Can be mentioned. Meside anion and
For example, (CF_ThreeSO_Two)_ThreeC^-Can be
Wear. Among the above anions, X^-And Y^-Each
Individually Cl^-, Br^-, ClO_Four ^-, BF _Four ^-, (CF_ThreeS
O_Two)_TwoN^-Or (C_TwoF_FiveSO_Two)_TwoN^-Preferably
New

The ferrocene structure is represented by the general formula (2) or (3).

[0015]

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In the general formulas (2) and (3),
R ²¹ , R ²² , R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. These groups may have a substituent. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and And a cyclohexyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group and an allyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methoxyphenyl group, and a tolyl group. When R ²¹ , R ²² , R ³¹ or R ³² is an aryl group, the cyclopentadienyl ring may be bonded to an aromatic ring to form a condensed ring. R ²¹ , R ²² , R ³¹ or R
³² may form a group bridging two different cyclopentadienyl rings. m ₂₁ , n ₂₁ , m ₃₁ , and n ₃₁
Represents an integer of 0 to 4, m ₂₁ , n ₂₁ ,
m ₃₁ and n ₃₂ are each preferably 0.

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

[0018]

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[0019] In general formula (4), X ^- and Y ^- is X in the general formula (1) ^- and Y ^- represents the same meaning, R ⁴¹ and R ⁴² and R ⁴³ and R ^44, are each formula M has the same meaning as R ²¹ and R ^{22 in} (2), and m ₄₁ and n ₄₁ , and m ₄₂ and n ₄₂ represent m ₂₁ and n _{21 in the} general formula (2), respectively.
And R ⁴⁵ and R ⁴⁶ may be the same or different from each other, and represent a divalent linking group.

[0020]

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In the general formula (5), X ^- and Y ^- are
R ⁵¹ and R ⁵² have the same meanings as R ²¹ and R ^{22 in} the general formula (2), and m ₅₁ and n ₅₁ have the same meanings as X ⁻ and Y ^{− in} the general formula (1). represents the same meaning as m ₂₁ and n ₂₁ of (2), R ⁵³ represents a divalent linking group, R ⁵⁴ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon atoms 6 to 20 aryl groups and 7 to 2 carbon atoms
Represents a group selected from 0 aralkyl groups.

[0022]

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In the general formula (6), X^-And Y^-Is
X in general formula (1)^-And Y^-Has the same meaning as⁶¹Passing
And R⁶², And R⁶³And R⁶⁴Is the general formula (3)
R ³¹And R³²Has the same meaning as₆₁And n₆₁, Row
To m₆₂And n₆₂Is m in the general formula (3).₃₁And n
₃₁Has the same meaning as⁶⁵, R⁶⁶, R⁶⁷And R⁶⁸Is
Each may be the same or different,
Represents a linking group.

[0024]

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In the general formula (7), X ^- and Y ^- are
R ⁷¹ and R ⁷² have the same meanings as R ³¹ and R ^{32 in} the general formula (3), and m ₇₁ and n ₇₁ have the same meanings as X ⁻ and Y ^{− in} the general formula (1). (3) has the same meaning as m ₃₁ and n ₃₁ , R ⁷³ and R ⁷⁴ each independently represent a divalent linking group, and R ⁷⁵ and R ⁷⁶ each independently represent a carbon atom of 1
An alkyl group of 10 to 10, an alkenyl group having 2 to 10 carbon atoms,
Represents a group selected from an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms.

The general formulas (4), (5), (6) and (7) will be described in more detail. R ⁴⁵ , R ⁴⁶ , R ⁵³ , R ⁶⁵ ,
Examples of the divalent linking group represented by R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁷³ and R ⁷⁴ include an alkylene group having 1 to 20 carbon atoms,
Alkenylene group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms
Arylene group. These may have a substituent. It is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group.

R ⁵⁴ , R ⁷⁵ and R ⁷⁶ each represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a C 7 to 20 carbon atom.
Represents a group selected from aralkyl groups. Carbon number 1-10
Examples of the alkyl group include a methyl group, an ethyl group, i
-Propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group and the like. Carbon number 2-10
Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a trityl group. The organic compound (A) is preferably a compound represented by the general formula (5).

The following are specific examples of the organic compound (A).

[0029]

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[0030]

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The amount of the organic compound (A) used is not particularly limited, but is usually contained in the ion conductive material at a concentration of 0.05 to 50% by mass, preferably 0.1 to 10% by mass.

Next, the polyether polymer compound (B) will be described. The polyether-based polymer compound functions as a matrix component of the ion conductive layer, and is a basic component for maintaining the ion conductive layer in a substantially solid state (that is, a solid polymer electrolyte). That is, the polymer forms a matrix (matrix) used to solidify the ion conductive layer, and the organic compound (A) and other optional components are retained in the polymer matrix. Thereby, a solid state or a gel state is formed.

The polyether polymer compound (B) used in the present invention is a polymer compound in which the main chain portion other than the molecular terminal has only an alkylene oxide structure. The polyether polymer compound can be obtained by ring-opening polymerization of a compound such as epoxide, oxetane, and tetrahydrofuran. Each of these compounds may have a substituent. Specifically, these compounds include polyethylene oxide, polytrimethylene oxide, polytetrahydrofuran and the like.
Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and those in which these groups have a group represented by RO- (R represents a hydrocarbon group) as a substituent. Can be. Examples of the alkyl group include C1-20, preferably C1
To 10 alkyl groups, and specifically,
Examples include a methyl group, an ethyl group, an n-butyl group, an s-butyl group, a heptyl group, an octyl group, and a dodecyl group.
Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and specific examples include a vinyl group and an allyl group. As the aryl group, for example, an aryl group having 6 to 30 carbon atoms, preferably 6 to 12 carbon atoms can be mentioned, and specifically, a phenyl group, a tolyl group, a p-ethylphenyl group, an o-ethylphenyl group Is mentioned. Examples of the aralkyl group include an aralkyl group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and specific examples include a benzyl group, a phenethyl group, and a trityl group. Examples of the substituent having a group represented by RO- (R represents a hydrocarbon group) include a methoxymethyl group, a 2-methoxyethoxymethyl group, and a 2-methoxyethoxymethyl group.
Methoxyethoxyethyl group, p-methoxyphenyl group,
Examples include a p-butoxyphenyl group, a p-methoxyphenylmethyl group, and a p-methoxystyryl group. RO-
The substituent having the group represented by the following formula as a substituent may be one having a higher molecular weight.
The substituent represented by (15) is mentioned.

[0034]

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In the above formulas (8) to (15), n is 1
To 1000, preferably 1 to 200, more preferably 3 to 100.

Specific examples of the polyether polymer having these substituents are described below.

[0037]

Embedded image In the above formula, l and n each represent an integer of 1 to 1000, preferably 1 to 200, more preferably 3 to 100, and m is 20 to 100,000, preferably 20 to 5
0000, more preferably 50 to 20,000.

The polyether polymer compound is not limited to a homopolymer containing the above repeating unit, but may be a copolymer. In that case, either a random copolymer or a block copolymer may be used. Examples of the polyether polymer compound composed of a copolymer are described below.
The composition ratio of the copolymer is not particularly limited, and can be arbitrarily selected.

[0039]

Embedded image In the above formula, n is 1 to 1000, preferably 1 to 2
00, more preferably an integer from 3 to 100, k,
m is 20 to 100,000, preferably 20 to 100, respectively.
50,000, more preferably 50 to 20,000.

The molecular terminal of the copolymer represented by the above formula is
Usually, it is a hydroxyl group, an alkyl group, or an aryl group. Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-butyl group, an n-pentyl group, and an n-octyl group. . In addition, examples of the aryl group include an aryl group having 6 to 20 carbon atoms, and specific examples include a phenyl group and a naphthyl group.

The molecular weight of the above polymer is not particularly limited, but it is necessary that the polymer is not in a liquid state at room temperature, and the molecular weight is usually 1,000 or more, preferably 5,000 or more. On the other hand, the upper limit of the molecular weight is not particularly limited, but preferably shows properties such as solubility or meltability, and is usually 1000
10,000 or less, preferably 5,000,000 or less. In addition, the molecular weight shown here is a number average molecular weight obtained by measurement by chromatography (size exclusion chromatography).

The polyether polymer compound used in the present invention may further have a double bond at the terminal of the main chain or the terminal of the branched chain of the above polymer. A cross-linking reaction can be performed by a double bond, and thus the heat resistance of the ion conductive layer can be improved by the cross-linking reaction. The introduction of a double bond can be performed using a known method for a functional group having a double bond. Specific examples of the functional group having a double bond include an acryl group, a methacryl group, an allyl group, a vinyl group, and a styryl group.

Examples of the polyether polymer compound having a double bond are shown below.

[0044]

Embedded image In the above formula, n is 1 to 1000, preferably 1 to 2
00, more preferably an integer from 3 to 100;
m is 20 to 100,000, preferably 20 to 50,
000, more preferably 50 to 20,000.

The crosslinking reaction can be carried out using a radical generator, and ordinary polymerization initiators such as a photopolymerization initiator and a thermal polymerization initiator can be used. The photopolymerization initiator is not particularly limited, but known photopolymerization initiators such as benzoin-based, acetophenone-based, benzylketal-based, and acylphosphine oxide-based can be used. These can be used alone or as a mixture when used. The thermal polymerization initiator is not particularly limited, but a known one such as a peroxide-based polymerization initiator or an azo-based polymerization initiator can be used. These can be used alone or as a mixture. The use of the polymerization initiator is optional, and the amount of the polymerization initiator used is not particularly limited. And 1
It is desirable to select an amount in the range of 0 parts by weight or less, preferably 5 parts by weight or less.

The light at the time of photocuring is not particularly limited, but examples include far ultraviolet light, ultraviolet light, and visible light. 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. Thermal curing can be usually performed using the above-mentioned thermal polymerization initiator. The reaction conditions for the thermosetting are selected depending on the polymerization initiator used, and are not particularly limited. The reaction temperature is usually 0 ° C. or higher, preferably 20 ° C. or higher, and 130 ° C. or lower.
Preferably it is 80 ° C. or lower. The curing time is usually 3
0 minutes or more, preferably 1 hour or more, and 100
Hours or less, preferably 40 hours or less.

The cross-linking reaction is carried out, for example, by applying the composition for forming an ion conductive layer to a desired portion by a known method as appropriate to form a film, or in a cell formed by using two conductive substrates. It is preferred to start after injecting the composition. The polymer takes a network-like (three-dimensional network structure) basic structure by a crosslinking reaction. When a crosslinking reaction is performed, the molecular weight of the precursor polymer having a double bond is not particularly limited, but needs to have low fluidity, and has a molecular weight of 100 or more, preferably 300 or more.

The amount of the polyether polymer compound used is
Although not particularly limited, 1 part by weight or more and 99.95 parts by weight or less based on 100 parts by weight of the ion conductive layer. When no solvent component described later is contained, 50 parts by weight or more and 99.95 parts by weight or less, preferably 70 parts by weight. To 99.9 parts by weight,
More preferably, the amount is 80 parts by weight or more and 99.5 parts by weight or less. When a solvent component is contained, an amount for gelling is required. The amount used varies depending on the type of the solvent, and is usually 1 part by weight or more and 95 parts by weight. Or less, preferably 2 to 80 parts by weight
It is not more than 3 parts by weight, more preferably not less than 3 parts by weight and not more than 70 parts by weight.

The ion conductive layer containing the ion conductive substance comprising the organic compound (A) and the polyether polymer compound (B) of the present invention may further contain other components. Other components that can be included include solvents. As the solvent, any solvent can be used as long as it is generally used for electrochemical cells and batteries. Specifically, water, acetic anhydride, methanol,
Ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphonamide, ethylene carbonate, dimethoxyethane, γ-
Butyrolactone, γ-valerolactone, sulfolane, dimethoxyethane, propionnitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, and polyethylene glycol can be used. . In particular, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolan, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone,
Dimethyl sulfoxide, dioxolan, sulfolane, trimethyl phosphate, polyethylene glycol and the like are preferred. One type of the solvent can be used alone, or two or more types can be used as a mixture.

The use of a solvent is optional, and the amount of the solvent used is not particularly limited.
0 parts by weight or more, preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and can be contained in an amount of 98 parts by weight or less, preferably 95 parts by weight or less, more preferably 90 parts by weight or less. .

Another component that may be contained in the ion conductive layer is an ultraviolet absorber. Examples of the ultraviolet absorber that can be used include a compound having a benzotriazole skeleton or a benzophenone skeleton. As the compound having a benzotriazole skeleton, for example, a compound represented by the following general formula (16) is preferably mentioned.

[0052]

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In the general formula (16), R ⁸¹ is a hydrogen atom, a halogen atom or a carbon atom having 1 to 10, preferably 1
And 6 to 6 alkyl groups. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a cyclohexyl group, and the like. The substitution position of R ⁸¹ is at the 4- or 5-position of the benzotriazole skeleton, and the halogen atom and the alkyl group are usually located at the 4-position. R ⁸² represents a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a cyclohexyl group, and the like. R ⁸³ represents an alkylene group or an alkylidene group having 1 to 10, preferably 1 to 3 carbon atoms.
Examples of the alkylene 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.

Specific examples of the compound represented by the formula (16) are described below. 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, 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, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl) benzotriazole, 2- (2′-hydroxy -3 ', 5'-di-
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 3- (5-chloro-2H-benzotriazol-2-yl) -5-
(1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester and the like.

Preferred examples of the compound having a benzophenone skeleton include compounds represented by the following formulas (17) to (19).

[0056]

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In the above general formulas (17) to (19),
R ⁹² , R ⁹³ , R ⁹⁵ , R ⁹⁶ , R ⁹⁸ , and R ⁹⁹ are the same or different groups, and each represents a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms. Show. p1, p2, p3, q1, q2, and q
3 independently represents an integer of 0 to 3; Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group. R ⁹¹ , R ⁹⁴ and R ^{97 each} have 1 to 1 carbon atoms.
It represents 0, preferably 1 to 3 alkylene or alkylidene groups. Examples of the alkylene 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.

Preferred examples of the compounds having a benzophenone skeleton represented by the general formulas (17) to (19) are described below. 2-hydroxy-4-methoxybenzophenone-5-carboxylic acid, 2,2'-dihydroxy-4-
Methoxybenzophenone-5-carboxylic acid, 4- (2-
(Hydroxybenzoyl) -3-hydroxybenzenepropanoic acid, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2
-Hydroxy-4-n-octoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

The use of an ultraviolet absorber is optional, and the amount of use is not particularly limited.
When used, it is desirable that it be contained in the ion conductive layer in an amount of 0.1 part by weight or more, preferably 1 part by weight or more, and 20 parts by weight or less, preferably 10 parts by weight or less.

The method of forming the ion conductive layer is not particularly limited, and the composition for forming the ion conductive layer is injected into the cell by a method of obtaining a film state by extrusion molding, casting, vacuum injection, air injection, or the like. Then, if desired, a method of curing can be used. Note that a method for manufacturing a cell formed using two conductive substrates will be described later.

Although the properties of the ion conductive layer are not particularly limited, the ion conductivity is usually 1 × 10 ⁻⁷ S at room temperature.
/ Cm or more, preferably 1 × 10 ⁻⁶ S / cm or more, more preferably 1 × 10 ⁻⁵ S / cm or more. The thickness of the ion conductive layer is not particularly limited, but is usually 1 μm or more,
It is preferably at least 10 μm and at most 3 mm, preferably at most 1 mm.

The electrochromic device of the present invention is obtained by sandwiching an ion conductive layer containing the ion conductive substance of the present invention between two conductive substrates at least one of which is transparent. Two conductive substrates are used for the electrochromic device. Here, the conductive substrate means a substrate that functions as an electrode. Therefore, the conductive substrate includes a substrate in which the substrate itself is made of a conductive material, and a laminated plate in which an electrode layer is laminated on one or both sides of a non-conductive substrate to impart conductivity. 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. At least one of the two conductive substrates used in the present invention is a transparent conductive substrate, and the other may be transparent or opaque,
Further, a reflective conductive substrate that can reflect light may be used. In general, an element in which two conductive substrates are both transparent is suitable for a display element or light control glass, and one in which one is a transparent conductive substrate and the other is an opaque conductive substrate is a display element. It is suitable for, one sheet is a transparent conductive substrate,
One having another reflective conductive substrate is suitable for an electrochromic mirror.

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 the 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 include polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, 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. Examples of the metal oxide include ITO (In ₂ O ₃ —SnO ₂ ), tin oxide,
Silver oxide, zinc oxide, vanadium oxide, and the like can be given. Although the thickness of the electrode layer is not particularly limited, it is usually 1
0 to 500 nm, preferably 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
50Ω / sq. In the range. To form the transparent electrode layer,
Known means can be arbitrarily used, but it is preferable to select the means to be used depending on the type 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.

A partially opaque electrode active material layer is provided on the surface of the transparent electrode layer for the purpose of imparting oxidation-reduction ability to the transparent electrode layer, improving conductivity, imparting electric double layer capacitance, and the like. Can be. As this electrode active substance, for example,
Metals such as copper, silver, gold, platinum, iron, tungsten, titanium and lithium; organic substances having a redox ability such as polyaniline, polythiophene, polypyrrole and phthalocyanine; carbon materials such as activated carbon and graphite;
Metal oxides such as ₂ O ₅ , MnO ₂ , NiO, and 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 V ₂ O ₅ , acetylene black on a thin gold film, And a method of applying a composition comprising butyl rubber and butyl rubber in a mesh form. The conductive substrate that does not need to be transparent is made by replacing the transparent substrate used for the transparent conductive substrate described above with a substrate made of various non-transparent plastics, glass, wood, stone, and the like. It can be manufactured in the same manner as the substrate.

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 laminate having a conductivity. 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. And (4) a laminate in which a reflective plate is used as a substrate and a transparent electrode layer is laminated thereon, and (5) a plate in which the substrate itself has both functions of a light reflective layer and an electrode layer. A body etc. can be illustrated.

The above-mentioned reflective electrode layer 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,
Examples include a metal film such as iridium, silver, nickel, chromium, rhodium, or palladium, and an alloy film such as platinum-palladium, platinum-rhodium, silver-palladium, silver-palladium-copper, or stainless steel. 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 above-mentioned reflecting plate or reflecting layer 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.

Next, the basic structure of the electrochromic device (EC device) of the present invention will be described. The EC device shown in FIG. 1 includes a transparent conductive substrate composed of a transparent substrate 1 and a transparent electrode layer 2 laminated on its surface, a transparent or opaque substrate 5 and a transparent, opaque or reflective conductive layer laminated on its surface. In this structure, the ion conductive layer 3 is sandwiched between the conductive substrate 4 and the conductive substrate 4. FIG. 2 shows a configuration example of a display element and light control glass. A structure in which 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, and an ion conductive layer 3 is sandwiched between them. It is. 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, and a reflective conductive substrate having a transparent electrode layer 2 formed on one surface of the transparent substrate 1 and a reflective layer 7 formed on the other surface. Are arranged at appropriate intervals so that the transparent electrode layers of both substrates face each other, and the ion conductive layer 3 is sandwiched between them.

The EC device shown in FIGS. 1 to 3 can be manufactured by any method. For example, E of the configuration shown in FIG.
In the case of the C element, the transparent electrode layer 2 is formed on the transparent substrate 1 by the above-described method, and the electrode band 8 is further provided on the periphery of one side thereof to prepare the laminate A. Separately, a transparent, opaque or reflective electrode layer 4 is formed on a substrate 5 by the above-described method, and an electrode band 8 is attached to a peripheral portion of one side thereof to obtain a laminate B. Next, the laminated board A and the laminated board B are
The cells are opposed to each other at an interval of about 0 μm, and the periphery excluding the injection port is sealed with a sealant 6 to form an empty cell with the injection port.
Then, the composition for forming an ion conductive layer is injected by the above-described method, or thereafter, if necessary, is cured to form the ion conductive layer 3, whereby an EC device can be obtained.

When the laminates A and B are opposed to each other, for example, a spacer can be used to secure a constant interval. The spacer is not particularly limited,
Beads or sheets made of glass, polymer, or the like can be used. The spacer can be provided by a method of inserting the spacer into the peripheral portion or the entire surface of the opposing conductive substrate, or a method of forming a projection made of an insulating material such as a resin on the electrode of the conductive substrate.

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 band 8 are formed on the substrate 5 by the above-mentioned method to obtain the laminate B ′.
Next, both the laminates were 1 to 1000 μm so that the ion conductive layer of the laminate A ′ and the reflective electrode layer of the laminate B ′ were in close contact with each other.
For example, a method of facing each other at intervals of about m and sealing the periphery with a sealant 6 may be used.

In the case of the electrochromic light control glass having the structure shown in FIG. 2, two transparent conductive substrates having a transparent electrode layer 2 formed on one surface of a transparent substrate 1 are prepared, and the electroconductive glass shown in FIG. In the case of a chromic mirror, a transparent conductive substrate having a transparent electrode layer 2 and an electrode band 8 formed on one surface of a transparent substrate 1, a transparent electrode layer 2 and an electrode band 8 on one surface of the transparent substrate 1, and the other Then, a reflective conductive substrate having the reflective layer 7 formed on the surface thereof is prepared, 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, the electrode layer and the electrode band include:
A lead wire for applying a voltage to the electrochromic element is connected. The lead wire may be directly connected to the electrode layer or the electrode band, or may be connected via a clip-shaped member (a highly conductive member such as a metal that sandwiches the conductive substrate so as to be in contact with the electrode layer or the electrode band). Wires may be connected. 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.

Typical examples of the configuration of the EC device of the present invention are shown in FIGS. 1 to 3, but the EC device of the present invention is not limited to these configurations at all, and further has other configurations. Requirements may be met. Other constituent elements include, for example, an ultraviolet cut layer such as an ultraviolet reflective layer and an ultraviolet absorbing layer, and in the case of a mirror, an overcoat layer for protecting the entire mirror layer or the surface of each film layer.
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 EC 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. When the EC element of the present invention is used as a display element, it can be used as an information display in a station, an airport, an underground shopping mall, an office building, a school, a hospital, a bank, other public facilities, a monument, an information display in a store (store) Guidance, price display, ticket reservation status, etc.) and other device displays (large electronic book, game machine, electronic clock, electronic calendar), and the like. In this case, monochrome display can be performed by using a single-color EC element, or color display can be performed by arbitrarily arranging EC elements of several types of colors. 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 present element as a shutter function.

[0075]

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 4 g of polyethylene oxide (molecular weight: 1,000,000) and 2 g of propylene carbonate were mixed, and 200 mg of a compound represented by the following formula was added thereto, diluted with acetone, and heated to obtain a homogeneous solution. Was.

[0077]

Embedded image

After the solution was degassed, it was cast on a transparent glass substrate coated with ITO and applied by a spin coater to obtain an ion conductive layer. Further, a transparent glass substrate coated with ITO was bonded to the counter electrode to obtain an electrochromic device (light control glass) having the configuration shown in FIG. Then, the adhesive was applied to the periphery and sealed. This light control glass is not colored at the time of assembly and the transmittance is about 87%
Met. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, 1.
It was colored when a voltage of 1 V was applied, and the transmittance of light having a wavelength of 633 nm was about 25%. The color was repeatedly applied and erased every 5 minutes, but no disappearance remained after about 1000 hours.

Example 2 1 g of polyethylene oxide (molecular weight: 500), polyethylene oxide (molecular weight: 2,000)
0) 2 g, and polyethylene oxide (molecular weight 10,000
1) was mixed, and 200 mg of a compound represented by the following formula was added thereto, and the mixture was diluted with methanol and heated to obtain a uniform solution.

[0080]

Embedded image

After the solution was degassed, it was cast on a transparent glass substrate coated with ITO and applied by a spin coater to obtain an ion conductive layer. Further, a transparent glass substrate coated with ITO was bonded to the counter electrode to obtain an electrochromic device (light control glass) having the configuration shown in FIG. Subsequently, an adhesive was applied to the periphery and sealed. This light control glass is not colored at the time of assembly and the transmittance is about 87%
Met. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, 1.
It was colored when a voltage of 1 V was applied, and the transmittance of light having a wavelength of 633 nm was about 25%. The color was repeatedly applied and erased every 20 minutes, but no disappearance remained after about 1000 hours.

Example 3 A copolymer of polyethylene oxide and polypropylene oxide having polyethylene oxide in the branched chain (product name: P (EO /
EM), 4 g of a molecular weight of 2,000,000) and 1 g of propylene carbonate, and a compound represented by the following formula was added to the mixture.
00 mg was added, diluted with acetone and heated to obtain a homogeneous solution.

[0083]

Embedded image

After the solution was degassed, it was cast on a transparent glass substrate coated with ITO and applied with a spin coater to obtain an ion conductive layer. Further, a transparent glass substrate coated with ITO was bonded to the counter electrode to obtain an electrochromic device (light control glass) having the configuration shown in FIG. Subsequently, an adhesive was applied to the periphery and sealed. This light control glass is not colored at the time of assembly and the transmittance is about 87%
Met. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, 1.
It was colored when a voltage of 1 V was applied, and the transmittance of light having a wavelength of 633 nm was about 25%. The color was repeatedly applied and erased every 5 minutes, but no disappearance remained after about 1000 hours.

Example 4 Copolymer of allyl group-containing polyethylene oxide and polypropylene oxide having polyethylene oxide in the branched chain (manufactured by Daiso Co., Ltd., product name P (EO / EM / AGE), molecular weight 200,000) ) 0.3
g, 10 g of propylene carbonate, and 200 mg of a compound represented by the following formula were added, diluted with acetone, and heated to obtain a uniform solution.

[0086]

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After the solution was degassed, it was injected from the injection port of the cell prepared as described above, and the solution in the cell was cured by irradiating light from a fluorescent lamp. The injection port was sealed with an epoxy-based adhesive to obtain an electrochromic device (light control glass) having the configuration shown in FIG. 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, it is colored when a voltage of 1.1 V is applied, and the transmittance of light having a wavelength of 633 nm is about 2
It was 5%. The color was repeatedly applied and erased every 5 minutes, but no disappearance remained after about 1000 hours.

[Example 5] A copolymer of polyethylene oxide and polypropylene oxide having polyethylene oxide in the branched chain (product name: P (EO /
EM), 4 g of a molecular weight of 2,000,000) and 1 g of propylene carbonate, 200 mg of a compound represented by the following formula was added, diluted with acetone, and heated to obtain a uniform solution.

[0089]

Embedded image

After degassing this solution, the ITO-coated PE
It was cast on a T substrate and applied with a spin coater to obtain an ion conductive layer. Further, a transparent glass substrate coated with ITO was bonded to the counter electrode to obtain an electrochromic device (light control glass) having the configuration shown in FIG. Subsequently, an adhesive was applied to the periphery and sealed. 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 color was colored, and the transmittance of light having a wavelength of 633 nm was about 25%. The color was repeatedly applied and erased every 5 minutes, but no disappearance remained after about 1000 hours.

[0091]

According to the present invention, the ion conductive substance of the present invention is obtained by using a polyether-based polymer compound. It can be easily manufactured by a manufacturing method by bonding, and thereby, it has become possible to reduce the cost or manufacture an electrochromic device using a flexible substrate. The electrochromic device incorporating the ion conductive material of the present invention is well colored even at a voltage of about 1 V, exhibits excellent responsiveness, and has excellent repetitive driving resistance.

[Brief description of the drawings]

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

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

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

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

FIG. 5 is a plan view showing a display state of the electrochromic display panel of 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 agent 7 Reflective layer 8 Electrode band

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takaya Kubo 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Nippon Steel Research Institute Co., Ltd. (72) Inventor Yoshinori Nishitani Chidori, Naka-ku, Yokohama, Kanagawa No.8, Town Nishiishi Mitsui Co., Ltd. Central Research Laboratory F-term (reference) 2K001 AA08 AA10 BA07 BB26

Claims (2)

[Claims] 1. A polyether polymer compound and a bipyridinium ion pair structure represented by the general formula (1) in the molecule: (In the general formula (1), X ⁻ and Y ⁻ are each independently a halogen ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH
₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , imide anion,
And a counter anion selected from the group consisting of a medic anion and a medic anion. ) And a ferrocene structure represented by the general formula (2) or (3): (In the general formula (2) or (3), R ²¹ , R ²² , R ³¹
And R ³² each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and
0 represents an aryl group; R ²¹ , R ²² , R
^{When 31} or R ³² is an aryl group, the parent ring may be bonded to a cyclopentadienyl ring to form a ring, m ₂₁ , n
₂₁ , m ₃₁ and n ₃₁ each independently represent an integer of 0 to 4. And an organic compound having at least one structure selected from the group consisting of: 2. An electrochromic device comprising an ion conductive layer containing the ion conductive material according to claim 1 sandwiched between two conductive substrates at least one of which is transparent.