JPH10239715A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrochromic(EC) element interposing an EC material which does not give such problems as liquid leakage and the adhesiveness of the EC material and electrodes, by interposing a specific conductive high- molecular composite between a pair of the electrodes. SOLUTION: The high-molecular gel composite composed of a self-doping type conductive high molecules having a Brϕnsted acid group having a dopant ability in the molecule and an N-vinyl carboxylic acid amide polymer is interposed between a pair of the electrodes at least one of which are transparent. The example of the self-doping type conductive high molecule includes a compd. contg. the chemical structure expressed by, for example, the formula as at least one repeating unit. In the formula, R<1> to R<5> respectively independently denote H, or a 1 to 10C hydrocarbon group, etc. L denotes the number of the condensed rings existing between a 5-membered ring having X<1> as a constituting member and an arom. ring having (B<1> )a -SO3 <-> M<1> . X<1> denotes a heteroatom. B<1> is a 1 to 10C hydrocarbon group and (a) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a self-organized compound having a Brönsted acid group having a dopant function (in the present invention, a functional group of Bronsted acid and a salt thereof). The present invention relates to an electrochromic device using a gel or solid composite of a doped conductive polymer compound.

[0002]

2. Description of the Related Art In recent years, an electrochromic (hereinafter abbreviated as EC) display element utilizing so-called electrochromism, in which light absorption characteristics are changed by application of voltage or current, has been developed. E used for EC display device
As the C material, an oxide of a transition metal typified by tungsten oxide as an inorganic material, a viologen derivative and a phthalocyanine complex of an organic material have been known. However, these EC materials have problems in response life, response speed, performance such as multicolor display, and the development of new EC materials has been desired. Therefore, recently, in addition to these materials, research using a π-electron conjugated conductive polymer as an EC material has been actively conducted.

[0003] Many conductive polymers are mainly made of a thin film on an electrode, taking advantage of the fact that they are hardly soluble in a solvent.
Problems such as a short response life due to poor adhesion between the C material and the electrode have been pointed out. A method of providing an intermediate layer in order to improve the adhesiveness is proposed (Japanese Patent Laid-Open No. 7-1343).
No. 17) is not sufficient. Also, when a conductive polymer soluble in organic solvents is used as a coating, it is effective in increasing the area that can be uniformly applied to a large electrode, but the adhesion between the EC material and the electrode is still improved. There was room for

On the other hand, as an example in which a self-doping type conductive polymer is used as an EC display material, focusing on the fact that the self-doping type conductive polymer itself is a polymer electrolyte, a self-doping type conductive polymer is placed between a pair of electrodes. EC with only aqueous solution
A display element is disclosed in JP-A-2-6588, and has attracted attention as an EC material having a function as a dye and also having a function as an electrolyte. When using the self-doped conductive polymer as an EC display material,
Since the same molecule contains a dopant, not only can the response life be maintained long, but also the response speed is faster than that in which anion is introduced and removed from the outside.

[0005] However, the above-mentioned EC display element uses a conductive polymer solution as it is as an electrolytic solution.
It has been pointed out that when broken by corrosion, movement, impact, or the like, liquid leakage to the outside of the EC display element is apt to occur, which causes a problem in long-term reliability of the element. In order to solve this liquid leakage, a method using a polymer gel electrolyte (Electro
chimica Acta, Vol. 40, pp. 227-232)
Has been proposed by Koyama et al., But there remains a problem with the adhesion between the EC material thin film and the electrode, and there is no problem with the self-doping type conductive polymer having no problem in the adhesion between the electrode, the EC display material, and the polymer electrolyte. The demand for an all-solid-state EC device or a non-solution type device using GaN is becoming stronger.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a self-doping type conductive polymer gel or EC as an EC material which does not cause the problem of liquid leakage and the problem of adhesion between an EC material and an electrode as described in the prior art. EC with solid electrolyte interposed
It is intended to provide an element.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a self-doping type conductive polymer having a Bronsted acid group having a dopant function in a molecule or a salt thereof and a hydrophilic polymer, In particular, an N-vinylcarboxylic acid amide-based polymer (in the present invention, refers to a polymer of N-vinylcarboxylic acid amide or a copolymer of N-vinylcarboxylic acid amide and acrylic acid or a metal salt thereof)
It has been found that a gel composite can be formed into a gel-like solid electrolyte by interposing a gel complex between a pair of electrodes at least one of which is transparent.

That is, the present invention provides (1) a self-doping type conductive polymer having a Bronsted acid group in a molecule and a N-type conductive polymer between at least one pair of transparent electrodes.
An electrochromic device in which a conductive polymer composite containing a vinyl carboxylic acid amide polymer is interposed, (2)
The self-doping type conductive polymer is poly (isothianaphthenesulfonic acid), poly (thiophenalkanesulfonic acid), poly (pyrrolealkanesulfonic acid), poly (anilinesulfonic acid), poly (carbazole-N-alkanesulfonic acid) ), Poly (phenylene-oxyalkanesulfonic acid), poly (thiophenealkanecarboxylic acid),
Or (3) the electrochromic device according to (1), which contains various salt structures and substituted derivatives thereof, and (3) the self-doping type conductive polymer is poly (isothianaphthene-5).
-Sulfonic acid-co-isothianaphthene), poly (thiophen-3-alkanesulfonic acid-co-thiophene), poly (pyrrole-3-alkanesulfonic acid-co
-Pyrrole), poly (anilinesulfonic acid-co-aniline), poly (carbazole-N-alkanesulfonic acid-co-carbazole), poly (phenylene-oxyalkanesulfonic acid-co-phenylene), poly (thiophen-3- Alkanecarboxylic acid-co-thiophene),
Or the electrochromic device according to (1), which is a salt structure or a substituted derivative thereof; and (4)
The electrochromic device according to any one of (1) to (3), wherein the self-doping conductive polymer is a polymer having a microgel structure, (5) a Bronsted acid in which the self-doping conductive polymer has a dopant function. (1) or (3) a copolymer comprising a monomer unit having a group and a monomer unit having no group, wherein the mole fraction of the monomer unit having no group is 0.01 to 0.5.
(6) The N-vinylcarboxylic acid amide-based polymer is a polymer of N-vinylcarboxylic acid amide or a copolymer of N-vinylcarboxylic acid amide and acrylic acid or an alkali metal salt thereof. The above problem has been solved by developing the electrochromic device according to any one of (1) to (5).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specifically, the present invention relates to a self-doping type conductive polymer having a Bronsted acid group having a dopant function in a molecule between a pair of electrodes at least one of which is transparent, and an N-vinyl carboxylic acid. EC characterized by interposing a polymer gel complex with an amide polymer
Providing an element.

Preferable specific examples of the self-doping type conductive polymer having a Bronsted acid group having a dopant function in a molecule or a salt thereof have a chemical structure represented by the following general formulas (1) to (10). A compound containing at least one of the above as a repeating unit.

[0011]

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(Wherein, R ^{1 to} R ⁵ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, Jo or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom or SO _3, ^- represents M ¹ group, M ¹ is, H ^+, .R ¹ representing an alkali metal ion or a quaternary ammonium ion, When R ⁵ is a hydrocarbon group, the hydrocarbon chains are bonded to each other at any position to form at least one or more saturated or unsaturated 3-7
A divalent chain forming a membered hydrocarbon cyclic structure may be formed. L is a 5-membered ring having X ¹ as a member, and (B ¹ ) _a
-SO ₃ ^- represents the number of condensed rings present between the aromatic ring with M ^1, is an integer value of 0 to 3. X ¹ represents a hetero atom and is S, O, Se, Te or NR ⁶ . R
⁶ represents H, a hydroxyl group, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms. B ¹ has ¹ carbon atom
To 10 linear or branched saturated or unsaturated divalent hydrocarbon groups, and an ether bond at an arbitrary position;
It may contain a carbonyl bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonamide bond, a thioether bond, or a sulfone bond. a is 0 or 1, when a is 0, it indicates that there is no B ^1. )

[0013]

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[0014]

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[0015]

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(Wherein, R ^{7 to} R ²⁰ each independently represent H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, Represents a branched or branched saturated or unsaturated alkoxy group, hydroxyl group, halogen atom, nitro group or amino group, and M ^{2 to} M ¹¹ represent H ⁺ , an alkali metal ion or a quaternary ammonium ion. X ² is a heteroatom and is S, O, Se, Te or NR ^21. R ²¹ is H, a hydroxyl group, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. 6 to 1
0 represents a substituted or unsubstituted aromatic hydrocarbon group. B
^{2 to} B ¹¹ each represent a linear or branched saturated or unsaturated divalent hydrocarbon group having 1 to 10 carbon atoms, and an ether bond, a carbonyl bond, an ester bond, a sulfonic acid ester at any position. It may contain a bond, an amide bond, a sulfonamide bond, a thioether bond, or a sulfone bond. b, c, d, e, f, g, h, i, j, k
Is 0 or 1, and b, c, d, e, f, g, h,
When i, j, and k are 0, B ² , B ³ , B ⁴ , B ⁵ ,
B ⁶ , B ⁷ , B ⁸ , B ⁹ , B ¹⁰ and B ¹¹ are absent. )

Preferred specific examples of R ^{1 to} R ⁵ in the general formula (1) include H (hydrogen), methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy and the like. The cation M ¹ is H ⁺ , L
It is an alkali metal ion such as i ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ or a substituted quaternary ammonium ion. Preferred substituted ammonium ions include NH (CH ₃ ) ₃ ⁺ , N
(CH ₃ ) ₄ ⁺ , NH (C ₂ H ₅ ) ₃ ⁺ , N (C ₂ H
₅ ) ₄ ⁺ , N (C ₆ H ₅ ) ₄ ^{+ and the} like. Useful specific examples of X ¹ are S (sulfur), O (oxygen), NH, N—CH ₃
It is.

Preferred examples of B ¹ include methylene,
Ethylene, propylene, butylene, 1,1-dimethylethylene, pentylene, hexylene, heptylene, octylene, nonylene, _{decylene, -O (CH 2) 2 -} , - O
_{(CH 2) 2 O (CH} 2) 2 -, - O (CH 2) 2 O
_{(CH 2) 2 O (CH} 2) 2 -, - S (CH 2) 2 -,
_{-S (CH 2) 2 S (} CH 2) 2 -, - S (CH 2) 2
_{S (CH 2) 2 S (} CH 2) 2 -, - C (= O) CH 2
-, - C (= O) CH 2 CH 2 -, - C (= O) (C
_{H 2) 3 -, - C} (= O) (CH 2) 4 -, - C (=
_{O) (CH 2) 5 -} , - NHC (= O) CH 2 -, - N
_{HC (= O) (CH 2} ) 2 -, - NHC (= O) (C
_{H 2) 3 -, - NHC} (= O) (CH 2) 4 -, - NH
_{C (= O) (CH 2} ) 5 -, - OC (= O) CH 2 -,
—OC (＝ O) (CH ₂ ) ₂ —, —OC (＝ O) (CH
_{2) 3 -, - OC (} = O) (CH 2) 4 -, - OC (=
_{O) (CH 2) 5 -} , - (CH 2) 2 -OC (= O)
(CH ₂ ) _2- and the like.

In the general formulas (2) to (10), preferred examples of R ^{7 to} R ²⁰ include H (hydrogen), methyl, ethyl, propyl, butyl, hexyl,
Methoxy, ethoxy and the like can be mentioned. The cations M ^{2 to} M ¹¹ are alkali metal ions such as H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ or substituted quaternary ammonium ions. Preferred substituted ammonium ions are NH (CH ₃ ) ₃ ⁺ , N (CH ₃ ) ₄ ⁺ , NH (C _{2
^{H 5) 3 +, + N}} (C 2 H 5) 4, N (C 6 H 5) 4 + , and the like. Preferred specific examples of X ² are S (sulfur), O
(Oxygen), NH and NCH ₃ .

Preferred specific examples of B ^{2 to} B ⁴ and B ^{8 to} B ¹¹ include methylene, ethylene, propylene, butylene, 1,1-dimethylethylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and-.
_{O (CH 2) 2 -,} - O (CH 2) 2 O (CH 2) 2
_{-, - O (CH 2)} 2 O (CH 2) 2 O (CH 2) 2
_{-, - S (CH 2)} 2 -, - S (CH 2) 2 S (CH
_{2) 2 -, - S (} CH 2) 2 S (CH 2) 2 S (CH
_{2) 2 -, - C (} = O) CH 2 -, - C (= O) CH 2
CH ₂ —, —C (＝ O) (CH ₂ ) ₃ —, —C (=
_{O) (CH 2) 4 -} , - C (= O) (CH 2) 5 -, -
_{NHC (= O) CH 2 -} , - NHC (= O) (CH 2) 2
-, - NHC (= O) (CH 2) 3 -, - NHC
_{(= O) (CH 2)} 4 -, - NHC (= O) (CH 2)
_{5 -, - OC (= O} ) CH 2 -, - OC (= O) (CH
_{2) 2 -, - OC (} = O) (CH 2) 3 -, - OC (=
_{O) (CH 2) 4 -} , - OC (= O) (CH 2) 5 -,
— (CH ₂ ) ₂ —OC (＝ O) (CH ₂ ) ₂ — and the like.

Preferred examples of B ^{5 to} B ⁷ include methylene, ethylene, propylene, butylene, 1,1-dimethylethylene, pentylene, hexylene, heptylene,
Octylene, nonylene, decylene, -C (= O) CH ₂
-, - C (= O) CH 2 CH 2 -, - C (= O) (CH
_{2) 3 -, - C (} = O) (CH 2) 4 -, - C (= O)
_{(CH 2) 5 -, -} (CH 2) 2 -OC (= O) (CH
₂ ) _2- and the like.

Preferred specific examples of the chemical structure represented by the general formula (1) include 5-sulfoisothianaphthene-1,
3-diyl, 5-sulfomethylisothianaphthene-1,
3-diyl, 5- (2'-sulfoethyl) isothianaphthene-1,3-diyl, 5- (3'-sulfopropyl)
Isothianaphthene-1,3-diyl, 5- (4′-sulfobutyl) isothianaphthene-1,3-diyl, 5-
(5′-sulfopentyl) isothianaphthene-1,3-
Diyl, 5- (6'-sulfohexyl) isothianaphthene-1,3-diyl, 5- (7'-sulfoheptyl) isothianaphthene-1,3-diyl, 5- (8'-sulfooctyl) iso Tianaphthene-1,3-diyl, 5-
(9′-sulfononyl) isothianaphthene-1,3-diyl, 5- (10′-sulfodecyl) isothianaphthene-1,3-diyl, 5-sulfoisobenzofuran-1,
3-diyl, 5-sulfomethylisobenzofuran-1,
3-diyl, 5- (2'-sulfoethyl) isobenzofuran-1,3-diyl, 5- (3'-sulfopropyl)
Isobenzofuran-1,3-diyl, 5- (4′-sulfobutyl) isobenzofuran-1,3-diyl, 5-
(5′-sulfopentyl) isobenzofuran-1,3-
Diyl, 5- (6'-sulfohexyl) isobenzofuran-1,3-diyl, 5- (7'-sulfoheptyl) isobenzofuran-1,3-diyl, 5- (8'-sulfooctyl) isobenzofuran- 1,3-diyl, 5-
(9′-sulfononyl) isobenzofuran-1,3-diyl, 5- (10′-sulfodecyl) isobenzofuran-1,3-diyl,

5-sulfoisoindole-1,3-diyl, 5-sulfomethylisoindole-1,3-diyl, 5- (2'-sulfoethyl) isoindole-1,
3-diyl, 5- (3'-sulfopropyl) isoindole-1,3-diyl, 5- (4'-sulfobutyl) isoindole-1,3-diyl, 5- (5'-sulfopentyl) isoindole -1,3-diyl, 5- (6 ′
-Sulfohexyl) isoindole-1,3-diyl,
5- (7'-sulfoheptyl) isoindole-1,3
-Diyl, 5- (8'-sulfooctyl) isoindole-1,3-diyl, 5- (9'-sulfononyl) isoindole-1,3-diyl, 5- (10'-sulfodecyl) isoindole-1 , 3-Diyl, 6-sulfonaphtho [2,3-c] thiophene-1,3-diyl, 6-
Sulfomethylnaphtho [2,3-c] thiophene-1,3
-Diyl, 6- (2'-sulfoethyl) naphtho [2,3
-C] thiophen-1,3-diyl, 6- (3'-sulfopropyl) naphtho [2,3-c] thiophen-1,3
-Diyl, 6- (4'-sulfobutyl) naphtho [2,3
-C] thiophen-1,3-diyl, 6- (5'-sulfopentyl) naphtho [2,3-c] thiophen-1,3
-Diyl, 6- (6'-sulfohexyl) naphtho [2,
3-c] thiophen-1,3-diyl, 6- (7'-sulfoheptyl) naphtho [2,3-c] thiophen-1,
3-diyl, 6- (8'-sulfooctyl) naphtho [2,3-c] thiophen-1,3-diyl, 6-
(9′-sulfononyl) naphtho [2,3-c] thiophen-1,3-diyl, 6- (10′-sulfodecyl) naphtho [2,3-c] thiophen-1,3-diyl, and the like, and the like. Lithium salt, sodium salt, ammonium salt, methyl ammonium salt, ethyl ammonium salt,
Dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, triethyl ammonium salt,
Tetramethylammonium salt, tetraethylammonium salt and the like can be mentioned.

Preferred specific examples of the chemical structure represented by the general formula (2) include 3-sulfothiophene-2,5-diyl, 4-methyl-3-sulfothiophene-2,5-diyl and 4-ethyl -3-Sulfothiophene-2,5-diyl, 3-propyl-4-sulfothiophene-2,5-
Diyl, 4-butyl-3-sulfothiophene-2,5-
Diyl, 4-pentyl-3-sulfothiophene-2,5
-Diyl, 4-hexyl-3-sulfothiophene-2,
5-diyl, 4-methoxy-3-sulfothiophene-
2,5-diyl, 4-ethoxy-3-sulfothiophene-2,5-diyl, 3-sulfomethylthiophene-2,
5-diyl, 3- (2'-sulfoethyl) thiophene-
2,5-diyl, 3- (3'-sulfopropyl) thiophene-2,5-diyl, 3- (4'-sulfobutyl) thiophene-2,5-diyl, 3- (5'-sulfopentyl) thiophene- 2,5-diyl, 3- (6′-sulfohexyl) thiophene-2,5-diyl, 3- (7′-
Sulfoheptyl) thiophene-2,5-diyl, 3-
(8'-sulfooctyl) thiophen-2,5-diyl, 3- (9'-sulfononyl) thiophen-2,5-
Diyl, 3- (10'-sulfodecyl) thiophene-
2,5-diyl, 3-sulfofuran-2,5-diyl,
4-methyl-3-sulfofuran-2,5-diyl, 4-
Ethyl-3-sulfofuran-2,5-diyl, 4-propyl-3-sulfofuran-2,5-diyl, 4-butyl-3-sulfofuran-2,5-diyl, 4-pentyl-
3-sulfofuran-2,5-diyl, 4-hexyl-3
-Sulfofuran-2,5-diyl, 4-methoxy-3-
Sulfofuran-2,5-diyl, 4-ethoxy-3-sulfofuran-2,5-diyl, 3-sulfomethylfuran-2,5-diyl, 3- (2'-sulfoethyl) furan-2,5-diyl, 3- (3'-sulfopropyl) furan-2,5-diyl, 3- (4'-sulfobutyl) furan-2,5-diyl, 3- (5'-sulfopentyl) furan-2,5-diyl, 3- (6'-sulfohexyl)
Furan-2,5-diyl, 3- (7'-sulfoheptyl) furan-2,5-diyl, 3- (8'-sulfooctyl) furan-2,5-diyl, 3- (9'-sulfononyl) Furan-2,5-diyl, 3- (10'-sulfodecyl) furan-2,5-diyl,

3-sulfopyrrole-2,5-diyl, 1
-Methyl-3-sulfopyrrole-2,5-diyl, 4-
Methyl-3-sulfopyrrol-2,5-diyl, 4-ethyl-3-sulfopyrrol-2,5-diyl, 4-propyl-3-sulfopyrrol-2,5-diyl, 4-butyl-3-sulfo Pyrrole-2,5-diyl, 4-pentyl-3-sulfopyrrole-2,5-diyl, 4-hexyl-3-sulfopyrrole-2,5-diyl, 4-methoxy-3-sulfopyrrole-2,5 -Diyl, 4-ethoxy-3-sulfopyrrol-2,5-diyl, 3-sulfomethylpyrrole-2,5-diyl, 3- (2'-sulfoethyl) pyrrole-2,5-diyl, 3- (3 '-Sulfopropyl) pyrrole-2,5-diyl, 3- (4'-
Sulfobutyl) pyrrole-2,5-diyl, 3- (5 ′
-Sulfopentyl) pyrrole-2,5-diyl, 3-
(6′-sulfohexyl) pyrrole-2,5-diyl,
3- (7'-sulfoheptyl) pyrrole-2,5-diyl, 3- (8'-sulfooctyl) pyrrole-2,5-
Diyl, 3- (9'-sulfononyl) pyrrole-2,5
-Diyl, 3- (10'-sulfodecyl) pyrrole-
2,5-diyl or the like, or its lithium salt, sodium salt, ammonium salt, methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, triethyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt And the like.

Preferred specific examples of the chemical structure represented by the general formula (3) include 2-sulfo-1,4-phenylenevinylene, 2-sulfomethyl-1,4-phenylenevinylene, and 2- (2'-sulfoethyl). ) -1,4-phenylenevinylene, 2- (3′-sulfopropyl) -1,4-phenylenevinylene, 2- (4′-sulfobutyl) -1,
4-phenylenevinylene, 2- (5'-sulfopentyl) -1,4-phenylenevinylene, 2- (6'-sulfohexyl) -1,4-phenylenevinylene, 2-
(7'-sulfoheptyl) -1,4-phenylenevinylene, 2- (8'-sulfooctyl) -1,4-phenylenevinylene, 2- (9'-sulfononyl) -1,4-phenylenevinylene, 2- (10'-sulfodecyl)-
1,4-phenylenevinylene, 2-sulfomethoxy-
1,4-phenylenevinylene, 2- (2′-sulfoethoxy) -1,4-phenylenevinylene, 2- (3′-sulfopropyloxy) -1,4-phenylenevinylene,
2- (4'-sulfobutoxy) -1,4-phenylenevinylene, 2- (5'-sulfopentyloxy) -1,4
-Phenylenevinylene, 2- (6′-sulfohexyloxy) -1,4-phenylenevinylene, 2- (7′-sulfoheptyloxy) -1,4-phenylenevinylene,
2- (8'-sulfooctyloxy) -1,4-phenylenevinylene, 2- (9'-sulfononyloxy)-
1,4-phenylenevinylene, 2- (10′-sulfodecyloxy) -1,4-phenylenevinylene, 5-methyl-2-sulfo-1,4-phenylenevinylene, 6-methyl-2-sulfo-1, 4-phenylenevinylene, 5-
Ethyl-2-sulfo-1,4-phenylenevinylene, 5
-Hexyl-2-sulfo-1,4-phenylenevinylene, 5-methoxy-2-sulfo-1,4-phenylenevinylene, 5-ethoxy-2-sulfo-1,4-phenylenevinylene, 2-methyl-5 (2'-sulfoethyl)
-1,4-phenylenevinylene, 2-methoxy-5
(2′-sulfoethyl) -1,4-phenylenevinylene, 2-methyl-5- (3′-sulfopropyl) -1,
4-phenylenevinylene, 2-methoxy-5- (3'-
Sulfopropyl) -1,4-phenylenevinylene, 2-
Methyl-5- (2'-sulfoethoxy) -1,4-phenylenevinylene, 2-methoxy-5- (2'-sulfoethoxy) -1,4-phenylenevinylene, 2-methyl-
5- (3′-sulfopropyloxy) -1,4-phenylenevinylene, 2-methoxy-5- (3′-sulfopropyloxy) -1,4-phenylenevinylene, or the like, or a lithium salt, a sodium salt, or ammonium thereof Salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt, tetraethylammonium salt and the like can be mentioned.

Preferred specific examples of the chemical structure represented by the general formula (4) include 2-sulfo-1,4-iminophenylene, 2-sulfomethyl-1,4-iminophenylene,
2- (2'-sulfoethyl) -1,4-iminophenylene, 2- (3'-sulfopropyl) -1,4-iminophenylene, 2- (4'-sulfobutyl) -1,4-iminophenylene, 2 -(5'-sulfopentyl) -1,4
-Iminophenylene, 2- (6'-sulfohexyl)-
1,4-iminophenylene, 2- (7'-sulfoheptyl) -1,4-iminophenylene, 2- (8'-sulfooctyl) -1,4-iminophenylene, 2- (9'-
Sulfononyl) -1,4-iminophenylene, 2- (1
0′-sulfodecyl) -1,4-iminophenylene, 3
-Methyl-2-sulfo-1,4-iminophenylene, 5
-Methyl-2-sulfo-1,4-iminophenylene, 6
-Methyl-2-sulfo-1,4-iminophenylene, 5
-Ethyl-2-sulfo-1,4-iminophenylene, 5
-Hexyl-2-sulfo-1,4-iminophenylene,
5-methoxy-2-sulfo-1,4-iminophenylene, 5-ethoxy-2-sulfo-1,4-iminophenylene, 2-sulfo-N-methyl-1,4-iminophenylene, 2-sulfo-N -Ethyl-1,4-iminophenylene or the like, or a lithium salt, sodium salt, ammonium salt, methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, triethyl ammonium salt, tetramethyl ammonium salt thereof And tetraethylammonium salts.

Preferred specific examples of the chemical structure represented by the general formula (5) include N-sulfomethyl-1,4-iminophenylene, N- (2'-sulfoethyl) -1,4-iminophenylene, and N-sulfomethyl-1,4-iminophenylene. (3′-sulfopropyl) -1,
4-iminophenylene, N- (4'-sulfobutyl)-
1,4-iminophenylene, N- (5'-sulfopentyl) -1,4-iminophenylene, N- (6'-sulfohexyl) -1,4-iminophenylene, N- (7'-
Sulfoheptyl) -1,4-iminophenylene, N-
(8'-sulfooctyl) -1,4-iminophenylene, N- (9'-sulfononyl) -1,4-iminophenylene, N- (10'-sulfodecyl) -1,4-iminophenylene, 2-methyl -N-sulfomethyl-1,4
-Iminophenylene, 3-methyl-N-sulfomethyl-
1,4-iminophenylene, 2,3-dimethyl-N-sulfomethyl-1,4-iminophenylene, 2,5-dimethyl-N-sulfomethyl-1,4-iminophenylene,
2,6-dimethyl-N-sulfomethyl-1,4-iminophenylene, 2-methoxy-N-sulfomethyl-1,4
-Iminophenylene, 2,5-dimethoxy-N-sulfomethyl-1,4-iminophenylene or the like, or a lithium salt, sodium salt, ammonium salt, methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl Examples thereof include ammonium salts, triethylammonium salts, tetramethylammonium salts, tetraethylammonium salts and the like.

Preferred specific examples of the chemical structure represented by the general formula (6) include 1-sulfomethylpyrrole-2,5
-Diyl, 1- (2'-sulfoethyl) pyrrole-2,
5-diyl, 1- (3'-sulfopropyl) pyrrole-
2,5-diyl, 1- (4′-sulfobutyl) pyrrole-2,5-diyl, 1- (5′-sulfopentyl) pyrrole-2,5-diyl, 1- (6′-sulfohexyl)
Pyrrole-2,5-diyl, 1- (7'-sulfoheptyl) pyrrole-2,5-diyl, 1- (8'-sulfooctyl) pyrrole-2,5-diyl, 1- (9'-sulfononyl) Pyrrole-2,5-diyl, 1- (10'-
Sulfodecyl) pyrrole-2,5-diyl or the like, or a lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt And tetraethylammonium salts.

A preferred specific example of the chemical structure represented by the general formula (7) is 9-sulfomethylcarbazole-
2,7-diyl, 9- (2'-sulfoethyl) carbazole-2,7-diyl, 9- (3'-sulfopropyl)
Carbazole-2,7-diyl, 9- (4'-sulfobutyl) carbazole-2,7-diyl, 9- (5'-sulfopentyl) carbazole-2,7-diyl, 9-
(6′-sulfohexyl) carbazole-2,7-diyl, 9- (7′-sulfoheptyl) carbazole-2,
7-diyl, 9- (8'-sulfooctyl) carbazole-2,7-diyl, 9- (9'-sulfononyl) carbazole-2,7-diyl, 9- (10'-sulfodecyl) carbazole-2,7 -Diyl and the like, or a lithium salt, a sodium salt, an ammonium salt, a methyl ammonium salt, an ethyl ammonium salt, a dimethyl ammonium salt, a diethyl ammonium salt, a trimethyl ammonium salt, a triethyl ammonium salt, a tetramethyl ammonium salt, a tetraethyl ammonium salt, and the like. be able to.

Preferred specific examples of the chemical structure represented by the general formula (8) include 3-carboxythiophene-2,5
-Diyl, 3-carboxy-4-methylthiophene-
2,5-diyl, 3-carboxy-4-ethylthiophen-2,5-diyl, 3-carboxy-4-propylthiophen-2,5-diyl, 4-butyl-3-carboxythiophen-2,5-diyl, 3-carboxy-4-
Pentylthiophene-2,5-diyl, 3-carboxy-4-hexylthiophene-2,5-diyl, 3-carboxy-4-methoxythiophene-2,5-diyl,
-Carboxy-4-ethoxythiophene-2,5-diyl, 3-thiopheneacetic acid-2,5-diyl, 3-thiophenepropionic acid-2,5-diyl, 3-thiophenebutanoic acid-2,5-diyl, 3 -Thiophenpentanoic acid-
2,5-diyl, 3-thiophenehexanoic acid-2,5-
Diyl, 3-thiophenheptanoic acid-2,5-diyl, 3
-2,5-diyl-thiophenoctanoate, 2,5-diyl 3-thiophenonanoate, 2,5-diyl 3-thiophenedecanoate, 3-carboxyfuran-2,5-
Diyl, 3-carboxy-4-methylfuran-2,5-
Diyl, 3-carboxy-4-ethylfuran-2,5-
Diyl, 3-carboxy-4-propylfuran-2,5
-Diyl, 4-butyl-3-carboxyfuran-2,5
-Diyl, 3-carboxy-4-pentylfuran-2,
5-diyl, 3-carboxy-4-hexylfuran-
2,5-diyl, 3-carboxy-4-methoxyfuran-2,5-diyl, 3-carboxy-4-ethoxyfuran-2,5-diyl,

3-furanacetic acid-2,5-diyl, 3-furanpropionic acid-2,5-diyl, 3-furanbutanoic acid-2,5-diyl, 3-furanpentanoic acid-2,5-
Diyl, 3-furanohexanoic acid-2,5-diyl, 3-
2,5-diyl furan heptanoate, 2,5-diyl 3-furan octanoate, 2,5-diyl 3-furanonanoate, 2,5-diyl 3-furandecanoate, 3-carboxypyrrole-2, 5-diyl, 1-methyl-3-carboxypyrrole-2,5-diyl, 3-carboxy-
4-methylpyrrole-2,5-diyl, 3-carboxy-4-ethylpyrrole-2,5-diyl, 3-carboxy-4-propylpyrrole-2,5-diyl, 4-butyl-3-carboxypyrrole- 2,5-diyl, 3-carboxy-4-pentylpyrrole-2,5-diyl, 3
-Carboxy-4-hexylpyrrole-2,5-diyl, 3-carboxy-4-methoxypyrrole-2,5-
Diyl, 3-carboxy-4-ethoxypyrrole-2,
5-diyl, 3-pyrroleacetic acid-2,5-diyl, 3-
2,5-diyl pyrrolepropionate, 2,5-diyl 3-pyrrolebutanoate, 3-pyrrolepentanoic acid-
2,5-diyl, 3-pyrrolehexanoic acid-2,5-diyl, 3-pyrroleheptanoic acid-2,5-diyl, 3-pyrroleoctanoic acid-2,5-diyl, 3-pyrrolenonanoic acid-2, 5-diyl, 3-pyrroledecanoic acid-2,5
-Diyl or the like, or a lithium salt or a sodium salt thereof,
Examples thereof include ammonium salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethyl ammonium salts, triethyl ammonium salts, tetramethyl ammonium salts, tetraethyl ammonium salts and the like.

Preferred specific examples of the chemical structure represented by the general formula (9) include 2-carboxy-1,4-iminophenylene, 2-acetic acid-1,4-iminophenylene,
Propionic acid-1,4-iminophenylene, 2-butanoic acid-1,4-iminophenylene, 2-pentanoic acid-1,
4-iminophenylene, 2-hexanoic acid-1,4-iminophenylene, 2-heptanoic acid-1,4-iminophenylene, 2-octylic acid-1,4-iminophenylene, 2-
Nonylic acid-1,4-iminophenylene, 2-decanoic acid
1,4-iminophenylene, 2-carboxy-3-methyl-1,4-iminophenylene, 2-carboxy-5
Methyl-1,4-iminophenylene, 2-carboxy-
6-methyl-1,4-iminophenylene, 2-carboxy-5-ethyl-1,4-iminophenylene, 2-carboxy-5-hexyl-1,4-iminophenylene, 2
-Carboxy-5-methoxy-1,4-iminophenylene, 2-carboxy-5-ethoxy-1,4-iminophenylene, 2-carboxy-N-methyl-1,4-iminophenylene, 2-carboxy-N- Ethyl-1,4-
Iminophenylene or the like, or a lithium salt, a sodium salt, an ammonium salt, a methyl ammonium salt, an ethyl ammonium salt, a dimethyl ammonium salt, a diethyl ammonium salt, a trimethyl ammonium salt, a triethyl ammonium salt, a tetramethyl ammonium salt, a tetraethyl ammonium salt, or the like. be able to.

Preferred specific examples of the chemical structure represented by the general formula (10) include 2,5-dicarboxy-1,4-
Iminophenylene, 2,5-bisacetic acid-1,4-iminophenylene, 2,5-bispropionic acid-1,4-iminophenylene, 2,5-bisbutanoic acid-1,4-iminophenylene, 2,5- Bispentanoic acid-1,4-iminophenylene, 2,5-bishexanoic acid-1,4-iminophenylene, 2,5-bisheptanoic acid-1,4-iminophenylene, 2,5-bisoctylic acid-1,4-imino Phenylene, 2,5-bisnonylic acid-1,4-iminophenylene, 2,5-bisdecanoic acid-1,4-iminophenylene, 2,5-dicarboxy-3-methyl-1,4-iminophenylene, 2, 5-dicarboxy-3-ethyl-
1,4-iminophenylene, 2,5-dicarboxy-3
-Methoxy-1,4-iminophenylene, 2,5-dicarboxy-3-ethoxy-1,4-iminophenylene,
2,5-dicarboxy-N-methyl-1,4-iminophenylene, 2,5-dicarboxy-N-ethyl-1,4
-Iminophenylene or the like, or lithium salt, sodium salt, ammonium salt, methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, triethyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, etc. Can be mentioned.

The conductive polymer composite of the electrochromic device of the present invention comprises a self-doping conductive polymer having a Bronsted acid group having a dopant function in the molecule, more preferably a compound represented by the general formula (1) A dispersion containing a microgel of a self-doping type conductive polymer having a chemical structure represented by the formula (10) can be given. The chemical structures represented by the general formulas (1) to (10) are usually 100 mol% to 5 mol%, preferably 100 mol% to 30 mol%, of all the repeating units of the self-doping conductive polymer. Preferably 100
It may be in the range of mol% to 50 mol%, and may be a copolymer containing at least two kinds of these chemical structures.
Further, the copolymer may be a copolymer containing a repeating unit having another π-conjugated chemical structure, or may be a copolymer composition containing two to five kinds of repeating units. Specific examples of the π-conjugated chemical structure other than the self-doping type conductive polymer having the Bronsted acid group in the molecule include:
Any chemical structure may be used as long as it can have a π-conjugated structure in the polymer main chain. But not limited thereto. In the present invention, the “copolymer containing a repeating unit” is not necessarily limited to a copolymer containing the unit continuously, and may be π
As long as the desired conductivity based on the conjugated main chain is exhibited, a polymer containing irregular and discontinuous repeating units in the π-conjugated main chain, such as a random copolymer, may be used.

The molecular weight of the self-doping type conductive polymer used in the present invention cannot be specified unconditionally because it differs depending on the chemical structure of the constituent repeating unit, but may be any one which meets the purpose of the present invention. There is no particular limitation.
Usually, when represented by the number of repeating units (degree of polymerization) constituting the main chain, those having a degree of polymerization in the range of usually about 5 to about 2,000, preferably about 10 to about 1,000 can be mentioned. The self-doping type conductive polymer microgel of the present invention is
It means an aggregate of a polymer of 0.5 micron or less. That is, the present aggregate particles are a particle component that can pass through a filter having a pore size of 0.5 μm but cannot be filtered with a pore size smaller than 0.5 μm. Further, in the present invention, the microgel dispersion of the self-doping conductive polymer means a mixture of the microgel and a self-doping conductive polymer component uniformly dissolved in a solvent. Microgels are more stable than solution types, and are less likely to degrade in solution or gel because the polymer has a three-dimensional structure in the gel,
It has preferable properties when used as an EC element.

Particularly preferred specific examples of the self-doping type conductive polymer having a Bronsted acid group in a molecule used in the present invention include: i) 5-, which is an example of a chemical structure represented by the general formula (1):
A polymer of sulfoisothianaphthene-1,3-diyl or a lithium salt, a sodium salt, an ammonium salt, a triethylammonium salt thereof, ii) an example of a chemical structure represented by the general formula (1):
80 mol% of sulfoisothianaphthene-1,3-diyl
Random copolymer, poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-1,3-diyl) or a lithium salt, a sodium salt, an ammonium salt, a triethylammonium salt thereof, iii)) 3 which is an example of the chemical structure represented by the general formula (2)
-(3'-sulfopropyl) thiophen-2,5-diyl polymer or its lithium salt, sodium salt, ammonium salt, triethylammonium salt, iv) an example of the chemical structure represented by the general formula (4) 2-
A random copolymer containing 50 mol% or more of sulfo-1,4-iminophenylene, poly (2-sulfo-1,4
-Iminophenylene-co-1,4-iminophenylene) or its lithium salt, sodium salt, ammonium salt and triethylammonium salt.

The N-vinylcarboxylic acid amide-based polymer, which is another constituent of the conductive polymer composite of the present invention, has the general formula (11)

Embedded image (Wherein, R ²² and R ²³ independently represent hydrogen, methyl, ethyl, propyl and isopropyl), and is a nonionic polymer mainly composed of N-vinylcarboxylic acid amide. More specifically, the N-vinylcarboxylic acid amide includes N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, and the like. Preferred is N-vinylacetamide. Further, the N-vinylcarboxylic acid amide-based polymer may be a copolymer containing 1 to 50 mol% of an acrylic acid unit or a copolymer containing an alkali metal salt thereof. Although the molecular weight of the N-vinylcarboxylic acid amide-based polymer according to the present invention differs depending on the shape of the intended conductive polymer composite, it cannot be specified unconditionally.
Preferably from 000 to about 5,000,000, more preferably from about 10,000 to about 4,000,000 polymers.

The N-vinylcarboxylic acid amide-based polymer is obtained by polymerizing in the presence of a cross-linking agent with an N-vinylcarboxylic acid amide-based polymer having a crosslinked structure or an N-vinylcarboxylic acid amide having a crosslinked structure. It may be a copolymer with acrylic acid. When the N-vinyl carboxylic acid amide-based polymer is used as a uniform solution or emulsion in the production of the conductive polymer gel composite of the present invention, a soluble N-vinyl having no or little cross-linked structure is used. Carboxamide polymers are preferred. On the other hand, when higher mechanical strength is required, it is desirable to use an insoluble N-vinylcarboxylic acid amide polymer having a high crosslinking density. Further, in the N-vinyl carboxylic acid amide-based polymer, two or more different types of N-vinyl carboxylic amide-based polymers can be used in combination.

The solvent for producing the conductive polymer gel composite of the present invention may be a solvent that dissolves a self-doping type conductive polymer and a copolymer with an N-vinylcarboxylic acid amide polymer. It is not particularly limited. Further, a mixed solvent of a solvent for dissolving the self-doping type conductive polymer and another solvent for dissolving the N-vinylcarboxylic acid amide-based polymer may be used. More specifically, water,
Monohydric alcohols such as methanol, ethanol, propyl alcohol, isopropanol, isoamyl alcohol, isobutyl alcohol, benzyl alcohol, and phenol, ethylene glycol, trimethylene glycol,
Dihydric alcohols such as 1,3-butylene glycol and propylene glycol, trihydric alcohols such as glycerin, chlorinated hydrocarbons such as chloroform and methylene chloride, ketones such as acetone and methyl ethyl ketone, 1,4-dioxane and tetrahydrofuran Ethers, nitriles such as acetonitrile, formamide, amides such as N-methylacetamide, organic acids such as acetic acid, dimethyl sulfoxide, propylene carbonate, carbonates such as ethylene carbonate, N-methyl-2-pyrrolidone,
Sulfolane and the like are mentioned, and more preferably, water or a mixed solvent of the above organic solvent and water is preferable.

Hereinafter, a method for producing the conductive polymer gel composite of the present invention will be described. The N-vinylcarboxylic acid amide-based polymer includes an N-vinylcarboxylic acid amide polymer having a linear structure that is soluble in water or the like and an N-vinylcarboxylic acid amide polymer having a crosslinked structure that is insoluble in water or the like. Copolymers of soluble and insoluble N-vinylcarboxylic acid amides and acrylic acid are known.

It is known that a soluble N-vinyl carboxylic acid amide-based polymer has a thickening effect on a solvent or a solution. Since the viscosity increase of the vinyl carboxylic acid amide polymer is enhanced, the polymer composite comprising the N-vinyl carboxylic acid amide polymer and the self-doping type conductive polymer can easily be in a polymer gel state or semi-solid state. State. For example, 30 cps
The concentration of the aqueous solution showing the viscosity of the polyvinyl alcohol (PVA-217C manufactured by Kuraray Co., Ltd.) is 4% by weight, whereas the N-vinylcarboxylic acid amide-based polymer (GE-191 manufactured by Showa Denko KK) is used. Then 0.4wt% of 1
A concentration of 1/0 is sufficient. Furthermore, when 0.1 wt% is added to an aqueous solution of sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl), the viscosity of polyvinyl alcohol solution increases to about 100 cps, whereas N In the case of a vinyl carboxylic acid amide-based polymer, there is a remarkable thickening effect such as an increase in solution viscosity up to 10,000 cps or more. Due to the feature that this thickening is enhanced, the mechanical strength of the N-vinylcarboxylic acid amide polymer can be effectively imparted to the self-doping type conductive polymer simply by adding a small amount of the N-vinylcarboxylic acid amide polymer. it can. The viscosity of the aqueous solution of the N-vinylcarboxylic acid amide-based polymer is affected by the pH, but its viscosity is not affected by the pH by forming a conductive polymer composite with a self-doping type conductive polymer. . These synergistic effects can significantly reduce the amount of N-vinyl carboxylic acid amide-based polymer conventionally required for expecting a viscosity increase. The amount required is small, and the dilution of the self-doping type conductive polymer is also small, so that its performance can be fully exhibited and used as a conductive gel composite that can be processed into various shapes. it can. An insoluble N-vinylcarboxylic acid amide-based polymer having a crosslinked structure and forming a microgel structure in a solvent can also be used as a uniform dispersion or a conductive gel composite.

On the other hand, in the case of an N-vinyl carboxylic acid amide-based polymer having a high crosslinking density and no longer being insoluble in various solvents, it is made into a powder or a molded body, and a solution of a self-doping type conductive polymer is added thereto. The conductive gel composite having an arbitrary shape can be produced by absorbing the liquid.
That is, a mold having a desired shape is prepared in advance, and N
-Filled with vinyl carboxylic acid amide polymer powder,
A solution of the self-doping type conductive polymer is added thereto, and the solution is absorbed and swelled, whereby a conductive polymer gel composite having a shape accurately reproducing the shape of the container can be produced.

The conductive polymer gel composite is prepared by slowly adding a solution in which a soluble N-vinylcarboxylic acid amide-based polymer is dissolved in a solution in which a self-doped conductive polymer is dissolved in the solvent. Manufactured by Furthermore, the polymer gel composite can be produced even if the order of addition of the solution in which the self-doped conductive polymer is dissolved and the solution in which the soluble N-vinylcarboxylic acid amide-based polymer is dissolved in the solvent are interchanged. Is soluble N-
When the concentration of the solution in which the vinyl carboxylic acid amide polymer is dissolved in the solvent is high, a method of adding a solution of the soluble N-vinyl carboxylic acid amide polymer to the solution in which the self-doping type conductive polymer is dissolved is adopted. Is preferred.
In this case, the amount of the N-vinylcarboxylic acid amide-based polymer to be added to the self-doping type conductive polymer cannot be specified unconditionally because it differs depending on the desired color depth of the conductive gel composite and the ionic conductivity. Generally, the N-vinylcarboxylic acid amide-based polymer is used in an amount of 0.01 to 100 parts by weight, preferably 0.1 to 100 parts by weight, based on 1 part by weight of the self-doping type conductive polymer.
It is desirable to add 1 to 100 parts by weight.

The conductive polymer composite is coated on at least one of the electrode substrates by a method such as roll coating to form a thin film, and then sandwiched by the other electrode via a spacer to form an electrochromic composite. An element can be manufactured. Alternatively, an electrochromic device can be produced by injecting a polymer gel composite between electrodes of an N-vinylcarboxylic acid amide-based polymer that has been produced in advance.

The concentration of the self-doping type conductive polymer contained in the polymer gel composite of the present invention cannot be specified unconditionally because it varies depending on its molecular weight.
It is preferably 0 g / liter, particularly preferably 0.01 to 10 g / liter. When the concentration of the self-doping type conductive polymer is lower than 0.001 g / liter, the ionic conductivity of the solution becomes low, and no color change occurs. Therefore, the ionic conductivity of the polymer gel composite is at least 1
It is desirable to set the concentration of the self-doping type conductive polymer so as to be × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S / cm or more.

The self-doping type conductive polymer contained in the conductive polymer gel composite of the present invention functions as an EC display material and as a polymer electrolyte. The function as an EC material utilizes the fact that the self-doping type conductive polymer changes its color tone because the π-electron conjugated system of the main chain is in a self-doping state when an external electric field is applied. The self-doping type conductive polymer in the self-doping state returns from the doping state to the undoped state by canceling the application of the external electric field, so that the color tone returns to the state before the application of the electric field. Further, the self-doping type conductive polymer functions as a polymer electrolyte due to the presence of a Bronsted acid group substituted on the π-electron conjugated main chain. Therefore, EC
Since the material itself is a polymer electrolyte, there is no need to add a separate electrolyte. However, when the ionic conductivity of the conductive polymer gel composite is low, the ionic conductivity of the polymer gel composite may be improved by adding another electrolyte to the polymer gel composite.

As the transparent electrode used in the electrochromic device of the present invention, a transparent conductive substrate obtained by depositing indium oxide-tin oxide (ITO), a noble metal or the like on a transparent insulator such as glass or polyester is used. Used. If one of the electrodes is transparent, the other electrode does not need to be transparent, and may be an opaque conductive substrate such as carbon or a noble metal. Further, an electrode processed into a predetermined pattern having a portion having conductivity and a portion having no conductivity by etching may be used.

The distance between the pair of electrodes of the electrochromic device of the present invention is not particularly limited, but is preferably 0.1 μm to 5 mm, more preferably 1 μm to obtain a uniform response.
μm to 1 mm is desirable. As described above, the electrochromic device obtained by the present invention can solve a problem such as liquid leakage to the outside of the EC display device and provide a semi-solid electrochromic device having long-term reliability.

[0050]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but these are merely examples for explanation, and the present invention is not limited to these.

(Synthesis example) Sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl), poly (5-sulfoisothianaphthene-1,3-diyl-co-isothia) which is a copolymer The sodium salt of (naphthene-1,3-diyl) (80 mol%: 20 mol%) is disclosed in JP-A-7-48.
It was synthesized according to the method disclosed in JP-A-436.

The sodium salt of poly (3- (2′-sulfoethyl) thiophene-2,5-diyl) and poly (3
-(4'-Sulfobutyl) thiophene-2,5-diyl)) sodium salt is available from Synthetic Met.
The compound was synthesized according to the method described in als Magazine, Vol. 30, 1989, pp. 305-319. The sodium salt of poly (3- (3′-sulfopropyl) thiophene-2,5-diyl) is described in J. Am. Chem. Soc. Chem. Commu
n. Journal, 1990, pp. 1694-1695. The sodium salt of poly (3- (3′-sulfopropyl) pyrrole-2,5-diyl) and the sodium salt of poly (3- (4′-sulfobutyl) pyrrole-2,5-diyl) are available from Chemistry of
The synthesis was carried out with reference to the method described in Material 1, Vol. 650 to 659.

The sodium salt of poly (2-methoxy-3- (3'-sulfopropyl) -1,4-phenylenevinylene) was produced with reference to the method described in US Pat. No. 5,367,041.

The copolymer poly (2-sulfo-1,4
Sodium salt of -iminophenylene-co-l, 4-iminophenylene) (50 mol%: 50 mol%)
J. Am. Chem. Soc. Magazine, 112, 2800
The compound was synthesized with reference to the method described on page 2801 (1990).

Poly (N- (3'-sulfopropyl)-
The sodium salt of (1,4-iminophenylene) is described in J. Am. C
hem. Soc. Chem. Commun. Magazine, 19
1990, referring to the method described on pages 180-182.

The sodium salt of poly (N- (3'-sulfopropyl) pyrrole-2,5-diyl) is disclosed in
The compound was synthesized with reference to the method described in JP-A-117373.
Poly (9- (3'-sulfopropyl) carbazole-
2,7-diyl) sodium salt is described in J. Am. Electr
ochem. Soc. Magazine 1990, Vol. 137, 180-1
The compound was synthesized with reference to the method described on page 82.

Poly (3-carboxythiophene-2,5)
-Diyl) sodium salt is described in Macromol. Ch
em. Rapid Commun. The compound was synthesized by referring to the method described in Vol. 19, No. 13, pp. 461-465. The sodium salt of poly (thiophene-2,5-diyl 3-pentanoate) is available from Advanced Materials
The compound was synthesized with reference to the method described in Vol. 2, pp. 490-494, 1990.

The sodium salt of poly (2,5-dicarboxy-1,4-iminophenylene) is disclosed in JP-A-63-39.
The compound was synthesized with reference to the method described in JP-A-916.

The sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-1,3-diyl) (65 mol%: 35 mol%) described in Example 4 was used. A microgel dispersion having a chemical structure was produced as follows.

In a mixture of 1.4 g of sodium 1,3-dihydro-5-isothianaphthenesulfonate and 8.0 g of ferric chloride prepared according to the method disclosed in JP-A-8-3156. A mixture of 1.0 g of water, 2.0 g of 1,4-dioxane and 0.34 g of 1,3-dihydroisothianaphthene was added with vigorous shaking and stirred. 3
The black reaction mixture obtained after 0 minutes was mixed with 200 ml of water,
And wash well with 40 ml of acetone and dry 1.7 g
Was obtained as a black powder. Add 100 ml of this black powder to 0.1 ml
After dissolving the precipitate in N NaOH with good stirring, removing the precipitate, and performing ion exchange with an acid-type ion exchange resin, a microgel aqueous dispersion containing an acid-type self-doped conductive polymer microgel (pH = 1.9) was obtained. The aqueous solution of the microgel dispersion was evaporated to dryness, the obtained polymer solid was separated, and the molar fraction of the structural unit substituted with sulfonic acid of the copolymer was determined by neutralization titration. As a result, it was 0.65 (65 mol%). Further, as other physical properties, the weight average molecular weight is 7,700, and the electric conductivity is 2S.
/ Cm. 0.1μm microgel dispersion aqueous solution
By filtering through a membrane filter having a pore diameter of 0.2 μm and 0.2 μm, respectively, the existence ratio of microgels of 0.1 to 0.2 μm was determined, and the existence ratio was 73%. The target sodium salt type microgel dispersion is
This microgel aqueous dispersion was produced by ion exchange with a sodium-type ion exchange resin.

Chemistry of poly (5-sulfoisothianaphthene-1,3-diyl-co-5'-methoxyisothianaphthene-1,3-diyl) (79 mol%: 21 mol%) described in Example 5 A microgel dispersion of a self-doped conductive polymer having a structure was produced as follows.

1,3-dihydroisothianaphthene-5
9.0 g of sodium sulfonate and 40.0 g of ferric chloride
5.0 g of water, 1,4-dioxane 1
A mixture of 0.0 g and 0.70 g of 5-methoxy-1,3-dihydroisothianaphthene was added with vigorous shaking and stirred. The black reaction mixture obtained after 30 minutes is washed with water 1
Wash well with 000ml and remove insolubles with 500ml 0.1N
Dissolved in NaOH with good stirring. Subsequently, after removing the precipitate, ion-exchange was performed with an acid-type ion-exchange resin to obtain a water dispersion (pH = 1.9) containing a microgel of a self-doping type conductive polymer. The mole fraction of the sulfonic acid-substituted structural unit represented by the general formula (1) in the copolymer measured by the same method as in Example 1 was 0.79 (79 mol%). As other physical properties, the weight average molecular weight was 7,600, and the electric conductivity was 1.8 S / cm. When the abundance of microgels of 0.1 to 0.2 μm was determined in the same manner as in Example 1, the abundance was 48%.
The intended sodium salt type microgel dispersion was produced by ion-exchanging the microgel aqueous dispersion with a sodium type ion exchange resin.

The self-doping type conductive polymer having the chemical structure of poly (3- (3′-sulfopropyl) thiophen-2,5-diyl-co-thiophen-2,5-diyl) described in Example 6 The microgel dispersion was produced as follows.

In a mixture of 8.0 g of sodium thiophene-3-propanesulfonate and 40.0 g of ferric chloride, a mixture of 5.0 g of water, 10.0 g of 1,4-dioxane and 0.74 g of thiophene was vigorously added. The mixture was shaken and stirred. The black reaction mixture obtained after 30 minutes is washed with water 1
Wash well with 000ml and remove insolubles with 500ml 0.1N-
Dissolved in NaOH with good stirring. Subsequently, after removing the precipitate, ion-exchange was performed with an acid-type ion-exchange resin to obtain a water dispersion (pH = 1.9) containing a microgel of a self-doping type conductive polymer. The molar fraction of the sulfonic acid-substituted structural unit in the copolymer measured by the same method as in Example 1 was 0.75 (75 mol%). As other physical properties, the weight average molecular weight was 9,200, and the electric conductivity was 1.5 S / cm. When the abundance of microgels having a thickness of 0.1 to 0.2 μm was determined by the same method using membrane filtration and fractionation as in Example 1, the abundance was 32%. The intended sodium salt type microgel dispersion was produced by ion-exchanging the microgel aqueous dispersion with a sodium type ion exchange resin. The application of the voltage between the electrodes was performed using a potentiometer galvanostat HA-501.
(Manufactured by Hokuto Denko KK).

(Example 1) 0.9% of poly (N-vinylacetamide) (GE-191 manufactured by Showa Denko KK)
(W / w) of 5.0 g of an aqueous solution and 0.9 of sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl)
When 9.8 g of a 2% (w / w) aqueous solution was mixed with stirring, a viscous jelly-like polymer gel composite was obtained.
This polymer gel composite was pressed between a pair of transparent electrodes as shown in FIG. 1 to obtain an EC device. At this time, a test cell in which two glass substrates 1 having a surface resistance value of 10 Ω / □ and a transparent electrode made of ITO 2 are opposed to each other with a gap of 0.2 mm through the seal material 3 is used. Was. The polymer gel composite was sealed between the electrodes so that air bubbles did not enter, and the mixture was sealed. When a voltage of 2.0 V was applied between the electrodes, the color of the polymer gel composite instantaneously changed from vivid blue to colorless (slightly blueish). When the electrodes were short-circuited, the color returned from colorless to vivid blue. This discoloration and recoloring were repeatedly and reversibly observed.

[Thickening Action] (Reference Example) Poly (N-vinylacetamide) exhibiting a viscosity of 30 cps at 0.4 (w / w)% (Showa Denko KK)
0.8- (w / w)% aqueous solution of GE-191)
0 g of a 0.2 (w / w)% aqueous solution of sodium salt of poly (5-sulfoisothianaphthene-1,3 diyl) in 1 g
When 0.0 g was added with stirring, 10,000 c
A gel-like conductive gel composite having a viscosity of not less than ps was obtained. An EC device was prepared in the same manner as in Example 1 except that this polymer gel composite was used as an EC material. 2.0V between electrodes
As a result, a change in color tone similar to that in Example 1 was observed. Even if this EC display element was divided into two at the center, no leakage of the EC display material from between the electrodes was observed.

(Reference Comparative Example) 30% at 4.0 (w / w)%
Poly (5-sulfoisothianaphthene-) was added to 10.0 g of an 8.0 (w / w)% aqueous solution of polyvinyl alcohol (PVA-217C, manufactured by Kuraray Co., Ltd.) having a viscosity of cps.
0.2 (w / w)% of the sodium salt of 1,3-diyl)
When 10.0 g of the aqueous solution was added with stirring, 10 g
A gel conductive gel of 0 cps was obtained. An EC device was prepared in the same manner as in Example 1 except that this polymer gel composite was used as an EC material. When a voltage of 2.0 V was applied between the electrodes, a change in color tone similar to that in Example 1 was observed.
However, when the EC element was divided into two parts at the center, it was found that the EC material leaked from between the electrodes, and the gelation of the electrolyte was insufficient.

Example 2 An EC cell similar to that of Example 1 was prepared, and 1 mg of insoluble poly (N-vinylacetamide), white powder (NA-010, manufactured by Showa Denko KK) was placed between the electrodes. In which 0.9% of the sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl) is added.
When 1.0 g of a 2% (w / w) aqueous solution was injected, the poly (N-vinylacetamide) absorbed the aqueous solution of the self-doping type conductive polymer to form a bright blue polymer gel composite. Thus, a displayable EC device was obtained.
Then, when a voltage of 2.0 V is applied between the electrodes, the color of the polymer gel composite instantaneously changes from vivid blue to colorless (slight blue color remains). The color returned from colorless to vivid blue. This discoloration and recoloring were repeatedly and reversibly observed.

Example 3 In Example 1, the poly (5
Poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-1,3-diyl) which is a copolymer instead of the sodium salt of -sulfoisothianaphthene-1,3-diyl) (80 mol%: 20 mol%) A polymer gel composite was obtained in the same manner as in Example 1 except that the sodium salt was used. Using this polymer gel composite as an EC material, an EC device similar to that of Example 1 was produced. When a voltage of 2.0 V was applied between the electrodes, a change in color tone similar to that in Example 1 was observed.

Example 4 0.4 (w) of poly (N-vinylacetamide) (GE-167 manufactured by Showa Denko KK)
/ W)% aqueous solution and 5.0 g of poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-
When 5.0 g of a microgel aqueous dispersion (0.2 (w / w)% aqueous solution) of a sodium salt of 1,3-diyl) (65 mol%: 35 mol%) was mixed with stirring, a jelly-like solution was obtained. A polymer gel composite was obtained. An EC device was prepared in the same manner as in Example 1, except that this polymer gel composite was used as an EC material. When a voltage of 2.0 V was applied between the electrodes, a change in color tone was observed as in Example 1.

(Example 5) In Example 1, the poly (5
Poly (5-sulfoisothianaphthene) instead of the sodium salt of sulfoisothianaphthene-1,3-diyl)
The same procedure as in Example 1 was carried out except that a microgel aqueous dispersion of sodium salt of 1,3-diyl-co-5′-methoxyisothianaphthene-1,3-diyl) (79 mol%: 21 mol%) was used. Thus, a polymer gel composite was obtained. Example 1 except that this polymer gel composite was used as an EC material
An EC device was prepared in the same manner as described above. When a voltage of 2.0 V was applied between the electrodes, a change in color tone similar to that in Example 1 was observed.

(Example 6) In Example 1, the poly (5
Poly (3- (3′-sulfopropyl) instead of the sodium salt of sulfoisothianaphthene-1,3-diyl)
Thiophene-2,5-diyl-co-thiophen-2,
A uniform polymer gel composite was obtained in the same manner as in Example 1, except that a microgel aqueous dispersion of sodium salt of 5-diyl) was used. An EC device was prepared in the same manner as in Example 1 except that this polymer gel composite was used as an EC material.
When a voltage of 2.0 V was applied between the electrodes, a change in color tone similar to that in Example 1 was observed.

(Examples 7 to 19) In Example 1, the self-doped conductive polymer shown in Table 1 was used instead of the sodium salt of poly (5-sulfoisothianaphthene-1,3-diyl). Except for using it, the polymer gel composites of Examples 7 to 19 were obtained in the same manner as in Example 1. An electrochromic display element was prepared in the same manner as in Example 1 except that each of the polymer gel composites was used as an EC display material, and a voltage shown in Table 1 was applied between the electrodes. Different electrochromic devices were obtained. Table 1 shows the color tone of each polymer gel composite.
The color changed instantaneously as described, and when the electrodes were short-circuited, the color was restored to the original color. This discoloration and recoloring were repeatedly and reversibly observed. The color tone at the time of discoloration in all the examples is EC
There is a slight variation due to the influence of the difference in element configuration.

[0074]

[Table 1]

[0075]

Industrial Applicability A self-doped conductive polymer having a Bronsted acid group having a dopant function in a molecule and a hydrophilic polymer, particularly a copolymer of an N-vinylcarboxylic acid amide polymer or a metal salt thereof. Was found to have the behavior of a gel-like polymer electrolyte and the characteristics of EC response, and it was possible to provide an EC device without liquid leakage. The conductive polymer composite comprising the self-doped conductive polymer of the present invention and a copolymer of an N-vinyl carboxylic acid amide-based polymer or an alkali metal salt thereof is a highly conductive conductive polymer composite. It is easy to make a thin film by devising a coating method as a body, and self-doping of a self-doping type conductive polymer contained by application of an electric field,
It is effective as an EC material utilizing the function of undoping. Further, by selecting the type of the self-doping type conductive polymer in the conductive polymer composite, it is possible to make the EC change multi-colored, so that it can be used as a display material for various display devices.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of an electrochromic device according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent glass substrate 2 ITO layer 3 Seal material 4 Conductive polymer composite (electrochromic layer) 5 Lead wire

Claims (6)

[Claims] 1. A conductive polymer composite comprising a self-doping conductive polymer having a Bronsted acid group in a molecule and an N-vinyl carboxylic acid amide polymer between a pair of electrodes at least one of which is transparent. An electrochromic device characterized by interposing. 2. The self-doping type conductive polymer includes poly (isothianaphthenesulfonic acid), poly (thiophenealkanesulfonic acid), poly (pyrrolealkanesulfonic acid), poly (anilinesulfonic acid), and poly (carbazole- 2. The electrochromic device according to claim 1, comprising N-alkanesulfonic acid), poly (phenylene-oxyalkanesulfonic acid), poly (thiophenalkanecarboxylic acid), or various salt structures and substituted derivatives thereof. 3. The self-doping type conductive polymer is poly (isothianaphthene-5-sulfonic acid-co-isothianaphthene), poly (thiophen-3-alkanesulfonic acid-).
co-thiophene), poly (pyrrole-3-alkanesulfonic acid-co-pyrrole), poly (anilinesulfonic acid-co-aniline), poly (carbazole-N-alkanesulfonic acid-co-carbazole), poly (phenylene- Oxyalkanesulfonic acid-co-phenylene), poly (thiophen-3-alkanecarboxylic acid-c)
The electrochromic device according to claim 1, which is o-thiophene), or various salt structures or substituted derivatives thereof. 4. The electrochromic device according to claim 1, wherein the self-doping conductive polymer is a polymer having a microgel structure. 5. The self-doping type conductive polymer is a copolymer composed of a monomer unit having a Bronsted acid group having a dopant function and a monomer unit having no such group, wherein the mole of the monomer unit having no group is used. 4. The electrochromic device according to claim 1, wherein the fraction is at most 50 mol% or less. 6. The N-vinylcarboxylic acid amide-based polymer is a polymer of N-vinylcarboxylic acid amide or a copolymer of N-vinylcarboxylic acid amide and acrylic acid or an alkali metal salt thereof. 6. The electrochromic device according to any one of 5.