JPH11183941A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrochromic element at a low cost through an easy step by disposing an electrochromic layer contg. a polymer or copolymer comprising specified repeating units between electrically conductive substrates. SOLUTION: An electrochromic layer contg. a polymer or copolymer comprising repeating units represented by formula I or II is disposed between electrically conductive substrates. In the formula I, each of X and Y is a counter anion such as a halogen anion, R<1> is H or 1-5C alkyl, R<2> is a 1-10C hydrocarbon residue, R<3> is 1-20C alkyl, aryl or aralkyl and Ar<1> is a divanent arom. hydrocarbon residue. In the formula II, R<4> is H or 1-5C alkyl, each of R<5> and R<7> -R<9> is H, 1-20C hydrocarbon or its residue, each of Ar<2> and Ar<3> is a divalent arom. hydrocarbon residue, (c) is an integer of >=0 and (d) is an integer of >=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As a conventional electrochromic device, for example, an inorganic oxide such as tungsten oxide (WO ₃ ) is formed on a transparent conductive substrate by a vacuum evaporation method or a sputtering method. However, there is known a color developing agent (electrochromic substance) (JP-A-63-18336). However, a vacuum pump is indispensable for performing the vacuum deposition method or the sputtering method, so that there is a disadvantage that the formation of a film serving as a color developing agent increases costs. Therefore, development of an electrochromic mirror that can be manufactured more easily and at lower cost is desired. Therefore, the present invention has been made in view of such a situation, and an object of the present invention is to provide an electrochromic device that can be manufactured in a simple process at low cost.

[0003]

In order to achieve the above object, an electrochromic device of the present invention comprises (A) the following general formula (A) between two conductive substrates, at least one of which is transparent. An electrochromic layer containing a polymer comprising a repeating unit represented by the following formula (1) and a polymer comprising a repeating unit represented by the following formula (2) or (B) represented by the following formula (1) And an electrochromic layer containing a copolymer comprising a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (2).

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

Embedded image (Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁵ , R ⁷ , R ⁸ and R ⁹ are hydrogen or C 1-20
Which may be the same or different. Ar ² and Ar ³ represent a divalent aromatic hydrocarbon residue. c represents an integer of 0 or more, and d represents an integer of 1 or more. Further, the electrochromic device of the present invention is characterized in that (A) a polymer comprising a repeating unit represented by the following general formula (3) is provided between two conductive substrates, at least one of which is transparent; Or an electrochromic layer containing a polymer comprising a repeating unit represented by the following general formula (2) or (B) a repeating unit represented by the following general formula (3) and a repeating unit represented by the above general formula (2) And an electrochromic layer containing a copolymer comprising a repeating unit represented by the above general formula (1), if desired.

Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BF _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from, R ^10, R ¹² is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ^11, R ¹³ is a hydrocarbon residue having 1 to 10 carbon atoms, Ar ^4, Ar ⁵ represents a divalent aromatic hydrocarbon residue. It is preferable that the electrochromic layer also serves as an ion conductive material layer.

[0004]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. In the present invention, at least one transparent substrate is used, and two conductive substrates are used. Here, the conductive substrate means a substrate that functions as an electrode. Therefore,
The conductive substrate referred to in the present invention includes a substrate in which the substrate itself is made of a conductive material, a laminated plate in which an electrode layer is laminated on at least one surface of a non-conductive substrate, and the like. Regardless of whether it has conductivity, the substrate itself needs to have a smooth surface at room temperature,
The surface can be flat or curved,
It may be deformed by stress. At least one of the conductive substrates used in the present invention may be a transparent conductive substrate, and the other may be transparent, opaque, or a reflective conductive substrate capable of reflecting light. Both of the two conductive substrates made of a transparent conductive substrate are used for a display element or a light control glass, one made of a transparent conductive substrate and the other made of an opaque conductive substrate is used for a display element, and one is used as a display element. A substrate having a transparent conductive substrate and another substrate having a reflective conductive substrate is suitable for an electrochromic mirror. The transparent conductive substrate is
Usually, it has a form in which a transparent electrode layer is laminated on a transparent substrate. Here, “transparent” means 10 to 100% in the visible light region.
It has a light transmittance of. Examples of the non-transparent conductive substrate include (1) a metal plate, and (2) an opaque substrate having no conductivity (various non-transparent plastics, glass,
(A wood, a stone, etc. can be used). On the other hand, as the form of the reflective conductive substrate, (1) a laminate in which a reflective electrode layer is laminated on a transparent or opaque substrate having no conductivity, and (2) one of a transparent substrate having no conductivity A laminate in which a transparent electrode layer is laminated on one surface and a reflective layer is laminated on the other surface; (3) a laminate in which a reflective layer is laminated on a transparent substrate having no conductivity and a transparent electrode layer is laminated on the reflective layer And (4) a laminate in which a reflection plate is used as a substrate and a transparent electrode layer is laminated on the substrate, and (5) a plate-like body in which the substrate itself has both functions of a light reflection layer and an electrode layer. There is no particular limitation on the material of the transparent substrate, for example, colorless or colored glass, tempered glass, etc. can be used, and a colorless or colored transparent resin, for example, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysulfone, poly Ether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene and the like can be used. The transparent electrode layer of the present invention literally means a thin film that is transparent and functions as an electrode. Examples of such a thin film include metals such as gold, silver, chromium, copper, and tungsten or ITO (In ₂ O _3). —SnO ₂ ), a conductive thin film made of a metal oxide such as tin oxide, silver oxide, zinc oxide, and vanadium oxide. The thickness of this film is usually 1
100 to 5,000 angstroms, preferably 500
The surface resistance (resistivity) is usually in the range of 0.5 to 500 Ω / cm ² , preferably 1 to 50 Ω / cm ² . An arbitrary method can be adopted as a method for forming the conductive thin film, and an appropriate method can be selected depending on the type of metal or metal oxide constituting the thin film. Usually, a vacuum evaporation method, an ion plating method, a sputtering method, a sol-gel method or the like is employed. At this time, the film thickness is, of course, selected within a range that does not impair the transparency of the thin film. The conductive thin film may be provided with a partially opaque electrode active material for the purpose of providing oxidation-reduction ability, improving conductivity, and providing an electric double layer capacity, but the amount of the applied material may be less than the entire thin film. It is selected within a range where transparency is not impaired. Examples of the opaque electrode active material include metals such as copper, silver, gold, platinum, iron, tungsten, titanium, and lithium; organic substances having a redox ability such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; activated carbon and graphite. Carbon material, V
Examples thereof include metal oxides such as ₂ O ₅ , MnO ₂ , NiO, and Ir ₂ O ₃ or mixtures thereof. Then, in order to bind the electrode active substance to the conductive thin film, an arbitrary resin binder can be used. An example in which an opaque electrode active material or the like is provided on a conductive thin film is ITO.
On a thin film, a coating film of a composition composed of activated carbon fiber, graphite, acrylic resin or the like is provided in a fine pattern such as a stripe shape or a dot shape. As another example, a thin film is formed on a gold (Au) thin film. , V ₂ O ₅ , acetylene black, butyl rubber and the like. The reflective electrode layer of the present invention has a mirror surface, and means a thin film that exhibits an electrochemically stable function as an electrode, such a thin film, for example,
Examples include a metal film such as gold, platinum, tungsten, tantalum, rhenium, osmium, iridium, silver, nickel, and palladium, and an alloy film such as platinum-palladium, platinum-rhodium, and stainless steel. Any method can be used to form a thin film having such a mirror surface, for example,
A vacuum evaporation method, an ion plating method, a sputtering method, or the like can be appropriately employed. The substrate on which the reflective electrode layer is provided may be transparent or opaque.
Therefore, as the substrate on which the reflective electrode layer is provided, various non-transparent plastics, glass, wood, stone, and the like can be used in addition to the transparent substrate exemplified above. The reflection plate or the reflection layer referred to in the present invention means a substrate or a thin film having a mirror surface, for example, a plate-like body of silver, chromium, aluminum, stainless steel or the like, or a thin film thereof. Examples of the plate-like body in which the substrate itself has both the reflective layer and the electrode function include those having self-supporting properties among those exemplified as the reflective electrode layers.

Next, the electrochromic layer of the present invention will be described. The feature of the electrochromic layer of the present invention is that a polymer comprising a repeating unit represented by the following general formula (1) (polymer (I)) and a repeating unit represented by the following general formula (2) Or a copolymer having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) (polymer (II)) (III)) or a polymer (polymer (IV)) comprising a repeating unit represented by the following general formula (3) and a polymer represented by the following general formula (2) Or a repeating unit represented by the general formula (2) or a repeating unit represented by the general formula (3), It contains a copolymer (copolymer (V)) having a repeating unit represented by the general formula (1). To the point it is there.

Embedded image In the general formula (1), X ⁻ and Y ⁻ may be the same or different and each is independently a halogen anion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH _{3
(C 6 H 4) SO 3} - represents a counter anion selected from,
The halogen ^{anion, F -, Cl -, Br} -, I
^-, and the like. R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group includes a methyl group,
Examples include an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group, and an n-pentyl group.
It is particularly preferred that R ¹ is hydrogen or a methyl group. R
² represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and is, for example, a hydrocarbon group such as a divalent alkylene group or an aralkylene group; And the like. Among them, —CH ₂ — is particularly preferred. R ³ represents an alkyl group having 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms, an aryl group or an aralkyl group, and as the alkyl group, a methyl group, an ethyl group, an i-
Propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, etc., and aralkyl groups such as benzyl group Etc. can be exemplified. Ar ¹ is 2
A phenylene group (o-, m-, p-), a substituted phenylene group ( As the substituent, various ones can be mentioned, and typically, an alkyl-substituted phenylene group), a biphenylene group, a naphthylene group and the like are mentioned. Among them, a phenylene group at the m- or p-position is particularly preferred. The polymer (I) has two or more repeating units represented by the general formula (1), and usually has a number of 2 to 500.
, Preferably 2 to 100, more preferably 5 to 5
It has 0 and is a substantially linear polymer.

Embedded image In the general formula (2), R ⁴ is hydrogen or C 1-5
And the alkyl group includes methyl, ethyl, i-propyl, n-propyl, n-
Butyl, t-butyl, n-pentyl and the like. R ⁴ is particularly preferably hydrogen or a methyl group. R ⁵ , R ⁷ , R ⁸ and R ^{9 each} represent a hydrogen atom, a hydrocarbon group or a hydrocarbon residue having 1 to 20, preferably 1 to 10 carbon atoms, which may be the same or different. Examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, heptyl group, and octyl group. , An alkylphenyl group such as an ethylphenyl group, an aryl group such as a phenyl group, an aralkyl group, and the like, and examples of the hydrocarbon residue include an alkoxyphenyl group such as a methoxyphenyl group and an ethoxyphenyl group. Can be Ar ² and Ar ³ may be the same or different, and represent a divalent aromatic hydrocarbon residue, and include those having 6 to 20, preferably 6 to 12 carbon atoms. Specifically, a phenylene group ( o-, m-, p-), as the substituted phenylene group (the substituent, can be mentioned those similar to R ^5, and typically such as an alkyl-substituted phenylene group), a biphenylene group, and naphthylene group . c is an integer of 0 or more, and is usually 0 to 20, preferably 0 to 10, and more preferably 0 to 5. d is 1 or more, and is usually 1 to 20, preferably 1 to 5. The polymer (II) has two or more repeating units of the general formula (2), usually has 2 to 500, preferably 5 to 100, and is a substantially linear polymer.

Embedded image In the general formula (3), X ⁻ and Y ⁻ may be the same or different and each is independently a halogen anion, Cl −
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CH _{3
(C 6 H 4) SO 3} - represents a counter anion selected from,
The halogen ^{anion, F -, Cl -, Br} -, I
^-, and the like. R ¹⁰ and R ¹² may be the same or different and represent hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-propyl group. Butyl group, t-butyl group,
and an n-pentyl group. R ¹⁰ and R ¹² are particularly preferably hydrogen or a methyl group. R ¹¹ and R ¹³ may be the same or different and represent a hydrocarbon residue having 1 to 10 carbon atoms. And the like. Among them, —CH ₂ — is particularly preferred. Ar ⁴ and Ar ⁵ may be the same or different and represent a divalent aromatic hydrocarbon residue. Specifically, a phenylene group (o-, m-, p-), a substituted phenylene group (as a substituent) Are various, but typically include an alkyl-substituted phenylene group), a biphenylene group and the like. Among them, a phenylene group at the m- or p-position is particularly preferred. The polymer (IV) has at least two repeating units represented by the general formula (3),
Usually, it has 2 to 500, preferably 2 to 100, and more preferably 5 to 50, respectively, and is a substantially linear polymer. When the electrochromic substance contained in the electrochromic layer is composed of a mixture of the polymer (I) and the polymer (II), the mixing ratio of the polymer (I): polymer (II) (viologen structure: The phenyleneamine structure [molar composition ratio]) can be arbitrarily selected, but is usually 1: 500.
１００100: 1, preferably 1:50 to 10: 1. In the case of a mixture of the polymer (IV) and the polymer (II), a mixing ratio of the polymer (IV): the polymer (II) (viologen structure: phenyleneamine structure [molar composition ratio]) Can be arbitrarily selected, but is usually from 1: 500 to 10
It is in the range of 0: 1, preferably 1:50 to 10: 1.
When the electrochromic substance is composed of the copolymer (III), the ratio of the repeating unit of the general formula (1) to the repeating unit of the general formula (2) in the copolymer (III) (viologen structure: phenyleneamine structure) [Mole composition ratio]) can be arbitrarily selected, but is usually from 1: 500 to 100:
1, preferably in the range of 1:50 to 10: 1. The copolymer (III) has at least two repeating units, usually from 2 to 500, and preferably from 5 to 100. When the electrochromic substance is composed of the copolymer (V), the ratio of the repeating unit of the general formula (3) to the repeating unit of the general formula (2) in the copolymer (V) (viologen structure: phenyleneamine) The structure [molar composition ratio]) can be arbitrarily selected, but is usually 1:50.
It is in the range of 0-100: 1, preferably 1: 50-10: 1. The copolymer (V) has at least two repeating units each, usually 2 to 500, preferably 2 to 500.
There are ~ 100. In the copolymer (V),
When the copolymer also contains the structural unit represented by the general formula (1), the ratio [molar composition ratio] of the repeating unit of the general formula (1) to the repeating unit of the general formula (3) in the copolymer (V) is arbitrarily determined Although it can be selected, it is usually in the range of 99: 1 to 1:99, preferably 70:30 to 30:70. The copolymer (III) and the copolymer (V) may be any of a block copolymer, a random copolymer and an alternating copolymer, respectively.

Polymer (I), polymer (II), copolymer (III)
The polymer (IV) and the copolymer (V) can be easily produced by using a known method, and examples thereof are as follows. The polymer (I) is obtained by reacting bipyridyl and R ³ Y at a ratio of substantially 1: 1 to obtain a mono-substituted bipyridyl represented by the following general formula (4). Is reacted with a compound represented by the following general formula (5) having the following formula (5) to produce the following compound (6) which is a precursor monomer of the polymer (I), and then the precursor monomer is dissolved in an organic solvent, It can be easily produced by radical polymerization using a known initiator such as benzoyl peroxide.

Embedded image

Embedded image

Embedded image (Wherein X ⁻ , Y ⁻ , R ¹ , R ² and R ³ represent the same groups as X ⁻ , Y ⁻ , R ¹ , R ² and R ³ in the general formula (1)). II) is to react an amine compound represented by the following general formula (7) with a compound represented by the following general formula (8) having a reactive group to form a precursor of the polymer (II). The following compound (9), which is a base monomer, is produced, and then the precursor monomer can be easily produced by radical polymerization in an organic solvent using a known initiator such as benzoyl peroxide.

Embedded image

Embedded image

Embedded image (Wherein, R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , Ar ² and A
r ³ represents R ⁴ , R ⁵ , R ⁷ in the general formula (2),
It represents the same group as R ⁸ , R ⁹ , Ar ² and Ar ^3, and Z represents a halogen such as fluorine, chlorine, bromine or iodine. Specific examples of the compound represented by the general formula (8) include acrylic acid chloride and methacrylic acid chloride. Examples of the compound represented by the general formula (7) include phenylenediamine, N-methylphenylenediamine,
N, N'-dimethylphenylenediamine, N, N, N '
-Trimethylphenylenediamine, N-ethylphenylenediamine, N, N'-diethylphenylenediamine,
N, N, N'-triethylphenylenediamine, N-phenylphenylenediamine, N, N'-diphenylphenylenediamine, N, N, N'-triphenylphenylenediamine, N-tolylphenylenediamine, N, N '
-Tolylphenylenediamine, N, N, N'-tolylphenylenediamine, N- (4-aminophenyl)-
N'-phenylphenylenediamine, N- (4-aminophenyl) -N, N'-diphenylphenylenediamine, N- (4-aminophenyl) -N, N ', N'-triphenylphenylenediamine, N- ( 4-aminophenyl) -N ′, N′-diphenylphenylenediamine,
N- (4-aminophenyl) -N-tolylphenylenediamine, N- (4-aminophenyl) -N-phenyl-
N'-tolylphenylenediamine, N- (4-aminophenyl) -N-tolyl-N'-phenylphenylenediamine, N- (4-aminophenyl) -N, N'-ditolylphenylenediamine, N- (4 -Aminophenyl)-
N ', N'-ditolylphenylenediamine, N- (4-
Aminophenyl) -N-phenyl-N ′, N′-ditolylphenylenediamine, N- (4-aminophenyl)
-N, N'-diphenyl-N'-tolylphenylenediamine, N- (4-aminophenyl) -N, N ', N'-
Tolytolylphenylenediamine, N- (4-aminophenyl) -N-methylphenylenediamine, N- (4-aminophenyl) -N-phenyl-N′-methylphenylenediamine, N- (4-aminophenyl) -N -Methyl-N'-phenylphenylenediamine, N- (4-aminophenyl) -N, N'-dimethylphenylenediamine, N- (4-aminophenyl) -N ', N'-dimethylphenylenediamine, N- ( 4-aminophenyl)-
N-phenyl-N ', N'-dimethylphenylenediamine, N- (4-aminophenyl) -N, N'-diphenyl-N'-methylphenylenediamine, N- (4-aminophenyl) -N, N' , N'-trimethylphenylenediamine, benzidine, N-methylbenzidine, N,
N′-dimethylbenzidine, N, N, N′-trimethylbenzidine, N-ethylbenzidine, N, N′-diethylbenzidine, N, N, N′-triethylbenzidine,
N-phenylbenzidine, N, N'-diphenylbenzidine, N, N, N'-triphenylbenzidine, N-tolylbenzidine, N, N'-tolylbenzidine, N,
N, N'-tolyl benzidine, N- (4-aminophenyl) -N'-phenylbenzidine, N- (4-aminophenyl) -N, N'-diphenylbenzidine, N
-(4-aminophenyl) -N, N ', N'-triphenylbenzidine, N- (4-aminophenyl) -N',
N'-diphenylbenzidine, N- (4-aminophenyl) -N-tolylbenzidine, N- (4-aminophenyl) -N-phenyl-N'-tolylbenzidine, N-
(4-aminophenyl) -N-tolyl-N'-phenylbenzidine, N- (4-aminophenyl) -N, N'-
Ditolylbenzidine, N- (4-aminophenyl)-
N ', N'-ditolylbenzidine, N- (4-aminophenyl) -N-phenyl-N', N'-ditolylbenzidine, N- (4-aminophenyl) -N, N'-diphenyl-N '-Tolylbenzidine, N- (4-aminophenyl) -N, N', N'-tolylbenzidine, N
-(4-aminophenyl) -N-methylbenzidine, N
-(4-aminophenyl) -N-phenyl-N'-methylbenzidine, N- (4-aminophenyl) -N-methyl-N'-phenylbenzidine, N- (4-aminophenyl) -N, N ' -Dimethylbenzidine, N- (4-aminophenyl) -N ′, N′-dimethylbenzidine, N
-(4-aminophenyl) -N-phenyl-N ', N'
-Dimethylbenzidine, N- (4-aminophenyl)-
N, N'-diphenyl-N'-methylbenzidine, N-
(4-aminophenyl) -N, N ', N'-trimethylbenzidine and the like. The copolymer (III) is a known compound such as azobisisobutyronitrile in an organic solvent capable of uniformly dissolving the compound represented by the general formula (6) and the compound represented by the general formula (9). Can be easily produced by a method of radical polymerization using the above initiator. Polymer (IV)
Reacts bipyridyl with a compound represented by the general formula (10) at a ratio of substantially 1: 1 to obtain a compound represented by the following general formula (1)
After obtaining the mono-substituted bipyridyl represented by 1), the compound having a reactive group represented by the following general formula (12) and 1: 1
To produce the following compound (30), which is a precursor monomer of the polymer (IV), and then reacting the precursor monomer in an organic solvent using a known initiator such as benzoyl peroxide. It can be easily produced by radical polymerization.

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Embedded image

Embedded image ^{(Wherein, X -, Y -, R} 10, R 11, R 12, R 13, Ar 4
And Ar ⁵ are the same as defined in the general formula (3). The copolymer (V) is prepared from an azobisisobutyronitrile or the like in an organic solvent capable of uniformly dissolving the compound represented by the general formula (13) and the compound represented by the general formula (9). It can be easily produced by a method of radical polymerization using a known initiator.

In general, in an electrochromic device, a layer of an electrochromic substance is disposed between two conductive substrates which are at least one transparent, and a layer of an ion conductive substance, that is, an electrolyte layer is provided. Usually, in the electrochromic device of the present invention, the layer containing the electrochromic substance also serves as the electrolyte layer, in other words, the electrochromic layer and the electrolyte layer are substantially the same single layer It is preferred that The electrochromic coloring layer of this preferred embodiment is easily redoxed and colorless by application of a voltage. The thickness of the electrochromic coloring layer is generally in the range of 1 μm to 3 mm, preferably 10 μm to 1 mm. In the present invention, the ion conductive substance refers to a substance capable of causing coloring, decoloring, color change, and the like in the electrochromic layer, and the ion conductive substance is usually 1 × 10 4 at room temperature.
It preferably has an ion conductivity of ^-7 S / cm or more.
The ion conductive material that can be used in the present invention is broadly classified into a liquid ion conductive material, a gelled liquid ion conductive material, and a solid ion conductive material.

[0008] The liquid ion-conductive substance can be prepared by dissolving a supporting electrolyte such as salts, acids, and alkalis in a solvent. The solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but a polar solvent is particularly preferable. Specifically, water can be used, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, Propionnitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide,
Organic polar solvents such as methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate and polyethylene glycol can be used, among them, propylene carbonate, ethylene carbonate,
Dimethylsulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, trimethylphosphate, polyethylene glycol and the like Organic polar solvents are preferred. Each solvent may be used alone or in combination. The salt as the supporting electrolyte is not particularly limited, and various inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, and the like can be used. Specifically, LiC
_{lO 4, LiSCN, LiBF 4,} LiAsF 6, Li
CF ₃ SO ₃ , LiPF ₆ , LiI, NaI, NaSC
N, NaClO ₄ , NaBF ₄ , NaAsF ₆ , KSC
Alkali metal salts of Li, Na and K such as N and KCl: (C
_{H 3) 4 NBF 4, (} C 2 H 5) 4 NBF 4, (n-C
_{4 H 9) 4 NBF 4,} (C 2 H 5) 4 NBr, (C 2 H
_{5) 4} NClO _4, can be mentioned _{(n-C 4 H 9)} 4 4 quaternary ammonium salts and cyclic quaternary ammonium salts, and various salts of NClO _4, and the like. Acids as a supporting electrolyte are not particularly limited, and inorganic acids, organic acids, and the like can be used. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like. The alkalis as the supporting electrolyte are also not particularly limited, and sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. In order to inject the liquid ion-conductive substance into a desired location between the two conductive substrates, a vacuum injection method or an air injection method can be adopted. In addition, the periphery of the conductive substrate is sealed by opposing the conductive substrate. A method of injecting into the gap by the meniscus method can be adopted.

The gelled liquid ion-conductive substance can be prepared by adding a polymer or a gelling agent to the above liquid ion-conductive substance. As the polymer in this case, for example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, Nafion and the like can be used.
As the gelling agent, for example, oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used. In order to inject the gelled liquid-based ion-conductive substance into a desired portion between the conductive substrates, a vacuum injection method or an air injection method can be adopted.In addition, the periphery of the conductive substrate is sealed by opposing the conductive substrate. A method of injecting into the gap by the meniscus method can be adopted.

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

A first example of the polymer solid electrolyte is a composition containing a urethane acrylate represented by the following general formula (14), the above-mentioned organic polar solvent and a supporting electrolyte (hereinafter abbreviated as composition A). Is a polymer compound obtained by solidifying

Embedded image (Wherein, R ¹⁴ and R ¹⁵ are the same or different groups and represent a group selected from the following general formulas (15) to (17), and R ¹⁶ and R ¹⁷ are the same or different groups;
Represents a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms, and Y represents a polyether unit, a polyester unit,
A polycarbonate unit or a mixed unit thereof is shown.
E represents an integer in the range of 1 to 100, preferably 1 to 50, and more preferably 1 to 20. )

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Embedded image In the general formulas (15) to (17), R ^{18 to} R ²⁰ are the same or different groups, and each represents a hydrogen atom or a group having 1 to 3 carbon atoms.
R ²¹ represents a divalent to tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. Examples of the organic residue include a hydrocarbon residue such as an alkyltolyl group, an alkyltetralyl group, and an alkylene group represented by the following general formula (18).

Embedded image In the general formula (18), R ²² represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and f represents an integer of 0 to 6. When f is 2 or more, R ²² may be the same or different. A hydrocarbon residue such as an alkylene group represented by the general formula (18)
Part of the hydrogen atoms may be 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. To summarize specific examples of R ^{21 in} the general formulas (15) to (17), And the like. R of the general formula (14)
^The divalent hydrocarbon residue represented by ¹⁶ and R ¹⁷ includes a chain divalent hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and the like. Is an alkylene group represented by the general formula (18), and the aromatic hydrocarbon group and the alicyclic hydrocarbon group are represented by the following general formulas (19) to (21). And a hydrocarbon group.

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Embedded image In the general formulas (19) to (21), R ²³ and R ²⁴ are the same or different groups, and include a phenylene group, a substituted phenylene group (such as an alkyl-substituted phenylene group), a cycloalkylene group, and a substituted cycloalkylene group ( Alkyl-substituted cycloalkylene group). R ^{25 to} R ²⁸ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. G represents an integer of 1 to 5. Specific examples of R ¹⁶ and R ^{17 in} the general formula (14) can be exemplified by the following general formulas (22) to (28).

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Embedded image In the general formula (14), Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof, and the polyether unit, the polyester unit, the polycarbonate unit, and the mixed unit thereof are represented by the following general formulas, respectively. Examples include units represented by formulas (a) to (d).

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Embedded image In the general formulas (a) to (d), R ^{29 to} R ³⁴ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Represents a divalent hydrocarbon residue of 12, h is an integer of 2 to 300, preferably 10 to 200, i is an integer of 1 to 300, preferably 2 to 200, j is 1 to 200, preferably An integer of 2 to 100, k is 1 to 200, preferably 2
1 to 300, preferably 10 to
Each represents an integer of 200. R ^{29 to} R ³⁴ are preferably a linear or branched alkylene group, and more preferably, R ³¹ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group. R ²⁹ or
R ³⁰ and R ^{32 to} R ³⁴ are preferably either an ethylene group or a propylene group. In addition, general formulas (a) to
In (d), each unit may be the same so-called homopolymerization, a copolymer of different units, or any of them.
The molecular weight of the urethane acrylate represented by the general formula (14) is usually 2,500 to 30,000 in terms of weight average molecular weight.
0, preferably in the range of 3,000 to 20,000. The number of polymerizable functional groups in one urethane acrylate molecule is preferably 2 to 6, more preferably 2 to 4. The urethane acrylate represented by the general formula (14) can be easily produced by a known method, and the production method is not particularly limited.

The amount of the organic polar solvent (organic non-aqueous solvent) used in preparing the composition A is usually 100 to 1200 parts by weight, preferably 200 to 900 parts by weight, based on 100 parts by weight of the urethane acrylate. If the amount of the organic non-aqueous solvent is too small, the ionic conductivity is not reduced, and if the amount of the organic non-aqueous solvent is too large, the mechanical strength after the composition A is solidified is selected. May decrease. As the supporting electrolyte, those exemplified above can be used, and the amount thereof is selected in the range of 0.1 to 30% by weight, preferably 1 to 20% by weight based on the organic nonaqueous solvent. The composition A is basically obtained by solidifying a basic component consisting of urethane acrylate, an organic non-aqueous solvent (organic polar solvent) and a supporting electrolyte, but this composition does not impair the object of the present invention. Optional components can be added as needed within the range. Examples of such optional components include a crosslinking agent and a polymerization initiator (light or heat). To inject composition A into a desired location between two conductive substrates,
In addition to a vacuum injection method and an air injection method, a method of injecting the composition A into a gap between the substrates by opposing a conductive substrate, sealing a peripheral portion thereof, and a meniscus method can be employed. Then, by solidifying the composition A injected between the substrates by an appropriate method, a polymer solid electrolyte layer can be formed. A polymerizable component or a cross-linkable component is cured by polymerization (polycondensation) or a cross-linking reaction,
It means that the entire composition becomes substantially non-flowable at normal temperature. In this case, it has a network-like basic structure.

A second example of the polymer solid electrolyte is a composition containing acryloyl-modified polyalkylene oxide, the above-mentioned organic polar solvent and a supporting electrolyte (hereinafter abbreviated as composition B).
Is a polymer compound obtained by solidifying One example of the acryloyl-modified polyalkylene oxide,
It is a monofunctional acryloyl-modified polyalkylene oxide represented by the general formula (29).

Embedded image In the general formula (29), R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸
Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group includes a methyl group, an ethyl group,
i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, etc., and particularly, each of R ^{35 to} R ³⁷ may be hydrogen or a methyl group, and R ³⁸ may be hydrogen. , A methyl group or an ethyl group. General formula (2
M in 9) represents an integer of 1 or more, usually 1 ≦ m ≦ 100, preferably 2 ≦ m ≦ 50, more preferably 2 ≦ m ≦ 30. Specific examples of the compound represented by the general formula (29) include an oxyalkylene unit of 1 to 10
0, preferably 2 to 50, more preferably 1 to 2
Methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate having a range of 0 or a mixture thereof Can be mentioned. When m in the general formula (29) is 2 or more, the oxyalkylene units may have different so-called copolymerized oxyalkylene units, and specific examples thereof include, for example, 1 to 50 oxyethylene units, preferably Methoxy poly (ethylene propylene) glycol methacrylate, having from 1 to 20, and having from 1 to 50, preferably from 1 to 20, oxypropylene units;
Examples include ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate, or a mixture thereof.

Other examples of the acryloyl-modified polyalkylene oxide that can be used in the present invention include a bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (30) and a trifunctional acryloyl-modified polyalkylene oxide represented by the general formula (31). The above polyfunctional acryloyl-modified polyalkylene oxides and the like are mentioned.

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Embedded image In the general formula (30), R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴²
Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group,
i-propyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group and the like. Particularly, R ^{39 to} R ⁴² are each preferably hydrogen or a methyl group. N in the general formula (30) is an integer of 1 or more, usually 1 ≦ n ≦ 10
0, preferably 2 ≦ n ≦ 50, more preferably 2 ≦ n
Indicates an integer in the range of ≦ 30. Specific examples of the bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (30) include a polyethylene glycol dialkylene having 1 to 100, preferably 2 to 50, and more preferably 1 to 20 oxyalkylene units. Examples thereof include methacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. When n is 2 or more, oxyalkylene units may have different so-called copolymerized oxyalkylene units, and examples thereof include, for example,
1 to 50 oxyethylene units, preferably 1 to
Poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, having in the range of 20 and having 1 to 50, preferably 1 to 20 oxypropylene units; Or a mixture thereof. In the general formula (31), R ⁴³ , R ⁴⁴ and R
⁴⁵ independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group and a t-butyl group. , N-pentyl group and the like. R ^{43 to} R ⁴⁵ are preferably hydrogen or a methyl group. 4 General formula (3
P in 1) represents an integer of 1 or more, usually 1 ≦ p ≦ 100, preferably 2 ≦ p ≦ 50, more preferably an integer in the range of 2 ≦ p ≦ 30, q represents the number of linked groups L, 2 ≦ q ≦
Indicates an integer of 4. The linking group L generally has 1 to 30 carbon atoms,
It is preferably a divalent, trivalent or tetravalent hydrocarbon group of 1 to 20. 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. And the like. Examples of the trivalent hydrocarbon group include an alkyltolyl group, an aryltolyl group, an arylalkyltolyl group, an alkylaryltolyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Further, as a tetravalent hydrocarbon group,
Examples thereof include an alkyltetralyl group, an aryltetralyl group, an arylalkyltetralyl group, an alkylaryltetralyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Specific examples of the polyfunctional acryloyl-modified polyalkylene oxide include trimethylolpropane tri (polyethylene glycol acrylate) having 1 to 100 oxyalkylene units, preferably 2 to 50, and more preferably 1 to 20. Trimethylolpropane tri (polyethylene glycol methacrylate), trimethylol propane tri (polypropylene glycol acrylate), trimethylol propane tri (polypropylene glycol methacrylate),
Tetramethylol methane tetra (polyethylene glycol acrylate), tetramethylol methane tetra (polyethylene glycol methacrylate), 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, 2,2-bis [4- (methacryloxypolyiso) Propoxy) phenyl] propane, and mixtures thereof. When p is 2 or more, oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other, for example, 1 to 50 oxyethylene units, preferably 1 to 20 oxyethylene units, and Trimethylolpropane tri (poly (ethylene propylene) glycol acrylate), trimethylol propane tri (poly (ethylene propylene) glycol methacrylate) having 1 to 50, preferably 1 to 20 oxypropylene units ), Tetramethylolmethanetetra (poly (ethylene / propylene) glycol acrylate), tetramethylolmethanetetra (poly (ethylene / propylene)
Glycol methacrylate), or mixtures thereof. The monofunctional acryloyl-modified polyalkylene oxide represented by the general formula (29) and the polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (30) or (31) can be used in combination. When used in combination, the weight ratio of monofunctional acryloyl-modified polyalkylene oxide / polyfunctional acryloyl-modified polyalkylene oxide is usually 0.01 / 99.9 to 99.9.
/0.01, preferably in the range of 1/99 to 99/1, more preferably 20/80 to 80/20. The amount of the polar organic solvent to be used for preparing the composition B is usually 50 parts based on the acryloyl-modified polyalkylene oxide.
The supporting electrolyte is used in an amount of usually 1 to 30% by weight, preferably 3 to 30% by weight based on the weight of the acryloyl-modified polyalkylene oxide and the polar organic solvent. It is in the range of 20% by weight. A photopolymerization initiator or a thermal polymerization initiator can be added to the composition B as necessary, and the amount of the polymerization initiator is usually 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the acryloyl-modified polyalkylene oxide. It is in the range of 0.01 to 3% by weight.

In order to inject the composition B into a desired location between at least one transparent conductive substrate, a vacuum injection method or an air injection method can be adopted, and the two conductive substrates are opposed to each other. A method of sealing the peripheral portion and injecting the composition A into the gap between the substrates by the meniscus method can be adopted.
Then, by solidifying the composition A injected between the substrates by an appropriate method, a polymer solid electrolyte layer can be formed. The polymerizable component (mono- or polyfunctional acryloyl-modified polyalkylene oxide) or the cross-linkable component is cured by polymerization (polycondensation) or cross-linking reaction, so that the entire composition does not substantially flow at room temperature. Say. In this case, it has a network-like basic structure.

The liquid ion conductive material, the gel liquid ion conductive material, and the solid ion conductive material described above provide the electrolyte layer necessary for the electrochromic device of the present invention separately from the electrochromic layer. Although it can be used when it is provided, in the present invention, a mode in which a single layer sandwiched between two conductive substrates plays a role of both the electrochromic layer and the electrolyte layer is preferable. The following method and the like can be adopted to realize this mode. Using a liquid or gelled liquid system for the ion conductive material,
The above polymer (I) and polymer (II), or copolymer (III), or polymer (IV) and polymer (II)
Or the copolymer (V) is homogeneously dissolved or dispersed, or the polymer (I) and the polymer (II) or the polymer (IV)
And precursor monomer or copolymer (III) of polymer (II)
Alternatively, a method in which a precursor monomer of the copolymer (V) is dissolved in a liquid or gelled liquid ion-conductive substance to polymerize the same. A solid system for the ion-conductive substance, typically using the polymer solid electrolyte described above, in the composition A or composition B which is a precursor thereof, the polymer (I) and the polymer (II) or The composition is solidified by homogeneously dissolving or dispersing the polymer (IV) and the polymer (II), or the copolymer (III) or the copolymer (V), or the composition A or the composition In B, the precursor monomer of the polymer (I) and the polymer (II) or the polymer (IV) and the polymer (II) or the precursor monomer of the copolymer (III) or the copolymer (V) , Polymerization method.

The electrochromic element of the present invention
Even when an electrochromic layer and an electrolyte layer (ion conductive material layer) are separately sandwiched between a single conductive substrate, the same layer serves as both the electrochromic layer and the electrolyte layer. Here, a method for manufacturing an electrochromic element in which the electrochromic layer and the electrolyte layer serve as the same layer will be described with reference to the drawings. The electrochromic device shown in FIG. 1 has 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. It has a structure in which the electrochromic layer / electrolyte layer 3 is sandwiched between the substrate 4 and the electrochromic element. This electrochromic element can be manufactured by the following method. First, a transparent electrode layer 2 is formed on a transparent substrate 1.
Is formed, and a transparent, opaque or reflective electrode layer 4 is formed on a substrate 5 to obtain a laminated plate B. Next, the laminated plate A and the laminated plate B are placed on each other by 1 to 100 so that the electrode layers face each other.
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 sealing material 6 to form an empty cell with the injection port.
Subsequently, the electrochromic substance of the present invention (polymer
(I) and polymer (II), or polymer (IV) and polymer (I
I) or copolymer (III) or copolymer (V)),
After injecting an ion-conductive substance (usually liquid) from the above-described injection port and sealing the same, the electrochromic mirror shown in FIG. 1 can be manufactured. Laminated plate A
When the and the laminate B are opposed to each other, a spacer can be used to secure a constant interval between them. The spacer is not particularly limited, but beads or sheets made of glass, polymer, or the like can be used. The spacer may be provided directly on the surface of the laminate. When the solid ion-conductive substance of the present invention is used as the ion-conductive substance, the composition A or the composition B is cured after injection. Curing methods are available. The electrochromic device of the present invention comprises a transparent electrode layer 2, an electrochromic layer and an ion conductive material layer 3 on a transparent substrate 1.
Are sequentially formed in the order described, and a laminate B ′ in which a transparent, opaque or reflective electrode layer 4 is formed on a substrate 5
Is formed, the electrochromic layer / ion conductive material layer 3 of the laminate A ′ and the electrode layer 4 of the laminate B ′ are brought into close contact with each other, and the periphery of both laminates is sealed with a sealing material 6. It can also be manufactured. FIG. 2 shows examples of a display element and electrochromic light control glass. A transparent conductive substrate 2 having a transparent electrode layer 2 formed on one surface of a transparent substrate 1
The sheets are opposed at appropriate intervals so that the transparent electrode layers of both substrates face each other, and the electrochromic layer and the ion conductive material layer 3 is sandwiched in the gap. The display element and the electrochromic light control glass shown in FIG. 2 can be manufactured by the same procedure as that of the electrochromic element shown in FIG. 1 except that two transparent electrode layers are used. FIG. 3 shows an example of an electrochromic mirror. A transparent conductive substrate having a transparent electrode layer formed on one surface of a transparent substrate; and a transparent electrode layer formed on one surface of the transparent substrate.
And a reflective conductive substrate having a reflective layer 7 formed on the other surface thereof at appropriate intervals so that the transparent electrode layers of both substrates face each other, and an electrochromic layer / ion conductive material layer 3 is provided in this gap. It has a structure that is pinched. The electrochromic mirror shown in FIG. 3 is the same as the electrochromic device shown in FIG. 1 except that a transparent electrode layer 2 is formed on one surface of one transparent substrate 1 and a reflective layer 7 is formed on the other surface. It can be manufactured by the same procedure as described above. The electrochromic device of the present invention may be provided with an ultraviolet cut layer such as an ultraviolet reflective layer or an ultraviolet absorbing layer, an overcoat layer for protecting the surface of the entire device or each film layer, and the like, if necessary. When an ultraviolet cut layer is provided, it is placed on the outside of the transparent substrate 1 or on the transparent electrode layer side. When an overcoat layer is placed, it is placed on the outside of the transparent substrate 1 or the outside of the reflective layer 7. Preferably, it is provided.

[0018]

The electrochromic device of the present invention has
By using an electrochromic layer containing a specific compound, the response speed is high, and sufficient durability and memory properties are obtained. The electrochromic device of the present invention uses an electrochromic layer containing a specific compound,
Since the process is simple, it can be produced relatively easily and inexpensively, and has an excellent feature that the coloring concentration can be easily adjusted by changing the specification of the compound. It is easy to use a solid electrolyte for the ion conductive material layer, so that an electrolyte solution does not scatter and a large and highly safe device can be manufactured. In addition, the electrochromic device of the present invention can cause color development / decoloration due to the electrochromic phenomenon by applying a voltage between the respective electrodes, and a known voltage application means can be used. From the above, the electrochromic element of the present invention can be suitably used for an electrochromic mirror such as a display element, a light control glass, an anti-glare mirror of an automobile or the like, or a decorative mirror used indoors. .

[0019]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Example 1 (1) Synthesis of Electrochromic Compound Bipyridyl and benzyl chloride were reacted in equimolar amounts in acetone to obtain a mono-substituted N-benzylbipyridinium chloride. 5.66 g (20 mmol) of this N-benzylbipyridinium chloride was dissolved in 150 ml of 2-propanol, and 3.05 g of 4-chloromethylstyrene (4-vinylbenzyl chloride) (2
0 mmol) and 50 mg of hydroquinone as a polymerization inhibitor
(0.45 mmol), and the mixture was stirred at room temperature for 24 hours to obtain N-benzyl-N'-vinylstyrylpyridinium dichloride represented by the formula (32).

Embedded image (2) Synthesis of electron donor compound Diphenylamine was placed in a 500 ml three-necked flask.
4 g (150 mmol), cesium fluoride 22.8
g (150 mmol) was weighed, the atmosphere in the flask was replaced with nitrogen, and 250 ml of dimethyl sulfoxide was added and stirred. 11.3 g of 1-fluoro-4-nitrobenzene
(150 mmol), and the mixture was heated to 120 ° C. in an oil bath, and the stirring was continued for 24 hours. The reaction solution was poured into ice water to precipitate a solid, and the obtained solid was recrystallized from acetic acid to give 29.5 g of a compound represented by the formula (33) (102 mmol).
1) was obtained.

Embedded image 14. of the compound (33) obtained as described above.
0 g (52 mmol) was transferred to a 500 ml three-necked flask, 200 ml of dimethylformamide and 1.5 g of 5% palladium / carbon were added, and hydrogen was supplied at normal pressure. After continuing stirring at room temperature for 12 hours, palladium carbon was removed by filtration, and the reaction solution was poured into ice water to precipitate a solid. The obtained white solid was dried under reduced pressure to obtain the compound of the formula (3)
12.5 g (48 mmol) of the compound represented by 4) was obtained.

Embedded image 12.5 g (48 mmol) of the compound (34) was 500 m
Then, 250 ml of benzene and 10 ml of triethylamine were added, and the mixture was stirred under ice cooling. A solution of 6.3 g (60 mmol) of methacrylic chloride / 20 ml of benzene was added dropwise. The reaction solution was washed twice with a 1N aqueous HCl solution, twice with water, twice with a 1N aqueous NaOH solution, and dried over sodium sulfate. The solvent was distilled off to obtain 13.4 g (41 mmol) of the compound (35).

Embedded image (3) Electrochromic compound and electron donor compound
8.7 g (20 mmol) of the polymerized compound (32) with the compound (3)
5) 6.6 g (20 mmol) was dissolved in 30 ml of γ-butyrolactone, 0.2 g of AIBN was added, and the mixture was heated to 80 ° C. in an oil bath to give compound (32) and compound (3).
5) was obtained. The average molecular weight of the polymer obtained by GPC analysis was about 10,000. (4) Preparation of Electrochromic Mirror A substrate provided with a palladium thin film was used as a highly reflective electrode, and this was used as a laminate D. A portion of the injection port of the electrolyte precursor solution was placed around the palladium of the laminate D. except epoxy adhesive was streaked with a transparent glass substrate C that is SnO ₂ coated thereon, superposed so as to face and the SnO ₂ surface and the palladium layer, curing the adhesive under pressure, An empty cell with an inlet was made. On the other hand, (3)
To 5.0 g of the copolymer solution of the compound (32) and the compound (35) obtained in the above was added methoxypolyethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.
MEO4) [Number of oxyethylene units 4] 1.0
g, 9 g of polyethylene glycol dimethacrylate (9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) [9 oxyethylene units] and 0.4 g of lithium perchlorate were added to form a uniform solution. In a dark room, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (manufactured by Merck, trade name "Dicure-1116") as a photopolymerization initiator was added to the homogeneous solution. 02 g was added. After degassing this solution, it was injected as an electrolyte precursor from the injection port of the cell prepared as described above. After sealing the injection port with an epoxy-based adhesive, light of a fluorescent lamp was applied from the transparent substrate side to cure the electrolyte precursor to obtain a solid electrolyte. Thus, an all-solid-state electrochromic mirror having the configuration shown in FIG. 1 was obtained. This mirror was not colored when assembled and had a reflectivity of about 85%. In addition, when a voltage was applied, the response was excellent, and good electrochromic characteristics were exhibited. That is, when a voltage of 1.5 V was applied, the layer was colored and the reflectance was about 15%. The colored state was maintained even after the voltage application was stopped, and the reflectance was 10% after 100 hours.

Example 2 (1) Synthesis of Electrochromic Compound 3.12 g (20 mmol) of bipyridyl was dissolved in 100 ml of acetonitrile in a flask, and 4-chloromethylstyrene (4-vinylbenzyl chloride) was added thereto.
6.10 g (40 mmol) and 50 mg (0.45 mmol) of hydroquinone as a polymerization inhibitor were added. After stirring at room temperature for 24 hours, the precipitated solid was separated by filtration, dried, and 7.84 g (17 mmol) of N, N'-di-vinylbenzylbipyridinium dichloride represented by the formula (36).
I got

Embedded image (2) Electrochromic compound and electron donor compound
4.6 g (10 mmol) of a polymerized compound (36) of compound (3) and compound (3)
5) 6.6 g (20 mmol) was dissolved in 30 ml of γ-butyrolactone, 0.2 g of AIBN was added, and the mixture was heated to 80 ° C. in an oil bath to give compound (36) and compound (3).
5) was obtained. The average molecular weight of the polymer obtained by GPC analysis was about 12,000. (3) Preparation of electrochromic dimming glass Two transparent conductive substrate electrodes were used as ITO transparent glass substrates A and B, and an electrolyte precursor solution was injected around the platinum thin film side of the transparent glass substrate B. An epoxy adhesive is applied linearly except for the entrance, and a transparent glass substrate A is superimposed on the epoxy adhesive so that the ITO surfaces face each other, and the adhesive is cured while applying pressure. Was prepared. On the other hand, methoxypolyethylene glycol monomethacrylate (MEO manufactured by Shin-Nakamura Chemical Co., Ltd.)
4) [Oxyethylene unit number 4] 1.0 g, polyethylene glycol dimethacrylate (9G manufactured by Shin-Nakamura Chemical Co., Ltd.) [Oxyethylene unit number 9]
0.4 g of lithium perchlorate was added to a mixed solution of 0.02 g and 4.0 g of γ-butyrolactone to obtain a uniform solution. In a dark room, the homogeneous solution was added to the photopolymerization initiator 1-
(4-Isopropylphenyl) -2-hydroxy-2-
0.02 g of methylpropan-1-one (trade name “Dicure-1116” manufactured by Merck) was added to obtain a uniform solution. 2 ml of a copolymer solution of the compound (36) and the compound (35) obtained in the above (2) was added thereto to homogenize the mixture. After degassing, the electrolyte precursor was injected through the inlet of the cell prepared as described above. Injected as body. After sealing the injection port with an epoxy-based adhesive, light from a fluorescent lamp was applied from both sides to cure the electrolyte precursor to obtain a solid polymer electrolyte. Thus, an all-solid-state electrochromic light control glass having the configuration shown in FIG. 2 was obtained. The light control glass was not colored at the time of assembling, and had a transmittance of about 90%. 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 1.5 V is applied, and has a transmittance of about 2 for light having a wavelength of 633 nm.
It became 0%. Keep the colored state even after stopping the voltage application
Even after 00 hours, the transmittance was 20%.

[Brief description of the drawings]

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

FIG. 2 is a cross-sectional view illustrating another configuration of the electrochromic light control glass of the present invention.

FIG. 3 is a sectional view showing another configuration of the electrochromic mirror of the present invention.

[Explanation of symbols]

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

Claims (3)

[Claims] 1. A polymer comprising a repeating unit represented by the following general formula (1) and a polymer represented by the following general formula (2) between at least one transparent substrate and two conductive substrates: Or (B) an electrochromic layer containing a polymer composed of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2): An electrochromic device comprising an electrochromic layer containing a polymer. Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BF _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from the R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is from 1 to 10 carbon atoms
R ³ represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, and Ar ¹ represents a divalent aromatic hydrocarbon residue. ) (Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁵ , R ⁷ , R ⁸ and R ⁹ are hydrogen or C 1-20
Which may be the same or different. Ar ² and Ar ³ represent a divalent aromatic hydrocarbon residue. c represents an integer of 0 or more, and d represents an integer of 1 or more. ) 2. A method comprising: (A) a polymer comprising a repeating unit represented by the following general formula (3) and a polymer represented by the following general formula (2) between at least one transparent substrate and two conductive substrates: Or (B) a repeating unit represented by the following general formula (3) and a repeating unit represented by the following general formula (2); The following general formula (1)
An electrochromic device comprising an electrochromic layer containing a copolymer comprising a repeating unit represented by the formula: Embedded image (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BF _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from, R ^10, R ¹² is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ^11, R ¹³ is a hydrocarbon residue having 1 to 10 carbon atoms, Ar ^4, Ar ⁵ represents a divalent aromatic hydrocarbon residue. ) (Wherein R ⁴ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁵ , R ⁷ , R ⁸ and R ⁹ are hydrogen or C 1-20
Which may be the same or different. Ar ² and Ar ³ represent a divalent aromatic hydrocarbon residue. c represents an integer of 0 or more, and d represents an integer of 1 or more. ) (Wherein X ⁻ and Y ⁻ may be the same or different,
Halogen anion, ClO ₄ ⁻ , BF _{4
^{-, PF 6 -, CH 3}} COO -, CH 3 (C 6 H 4) S
O ₃ ^- represents a counter anion selected from the R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² is from 1 to 10 carbon atoms
R ³ represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, and Ar ¹ represents a divalent aromatic hydrocarbon residue. ) 3. The electrochromic device according to claim 1, wherein the electrochromic layer also serves as an ion conductive material layer.