JPH0782175B2 - Electrochromic display element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an electrochromic display (ECD) device, and more particularly to a novel ECD device having low power consumption, large OD, vivid colors, and excellent durability. It is about.

<Prior art> ECD devices that utilize coloring / decoloring due to electrode reaction of substances fixed on electrodes are superior to liquid crystal display devices in that colors are vivid and have a memory function and no viewing angle dependence. Due to the characteristics, various studies have been made.

Among these, those using a transition metal oxide represented by a tungsten oxide thin film have already reached a stage of practical use because they have relatively good repetition resistance. However, such an ECD element is composed of a pair of electrodes. For example, when the electrode on which the tungsten oxide film is formed is in a reduced state, it develops color, and when it is in an oxidized state, it erases color.
At this time, the third substance contained in the electrolyte is in an oxidized or reduced state on the counter electrode, and the reversible property of the redox reaction of this third substance governs the repetitive property of such a device. It includes a problem that deteriorates the characteristics.

<Object of the invention> Therefore, in the ECD element using the conventional tungsten oxide thin film, etc., the present inventor diligently studied a method of obtaining a material having excellent reversible characteristics of electrolysis / redox reaction on the counter electrode, and as a result, a specific A resin containing a structure as its constituent develops color by one-electron oxidation, and also disappears by reduction.
Further, they have found that the above object can be achieved by using a display electrode modified with a transparent electrode and the above-mentioned tungsten oxide display electrode in combination, and arrived at the present invention.

<Structure of the Invention> That is, the present invention relates to an electrochromic display element in which a pair of display electrodes are arranged via an electrolyte medium, and one of the coloring layers of the display electrodes has one of the following structural units (I ) Is a polymer containing as a part of the constituent component, and has a resin in which at least a part of the amino group of the structural unit (I) in the polymer is quaternized, and the other is on a conductive transparent substrate. The present invention relates to an electrochromic display device characterized by having an oxide of a transition metal therein.

Hereinafter, the present invention will be described in detail.

In the above structural unit (I), a, b, c and d represent a bond and are the same or different and are respectively bonded to a hydrogen atom or a carbon atom constituting an aliphatic group, an alicyclic group or an aromatic group, and at least One is attached to a carbon atom.

Here, a, b, c, d may be bonded to an aliphatic group, an alicyclic group, or an aromatic group, which is a part of the component constituting the main chain or side chain of the polymer in the present invention, and examples thereof include an arylene group. , Alkylene groups, cycloalkylene groups and the like. It is preferably an alkylene group having 1 to 10 carbon atoms.

R is a hydrogen atom or a hydrocarbon group. Here, examples of the hydrocarbon group include an alkyl group, an aralkyl group, a cycloalkyl group, and an aryl group. R is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

X and Y are the same or different and each is a halogen atom or a hydrocarbon group. Here, the halogen atom is fluorine, chlorine,
Examples thereof include bromine. As a hydrocarbon group, an alkyl group,
Examples thereof include a cycloalkyl group and an aryl group. Preferred among the hydrocarbon groups are lower alkyl groups such as methyl and ethyl.

m and n may be the same or different and are an integer of 0-4. It is preferably 0 or 1, and particularly preferably 0.

The polymer having such a structural unit may have any structure such as polyamide, polyurethane, polyurea, polyester, polyether, polysulfone, polyimide, epoxy, polyolefin, polyamine and copolymers thereof.

Such a polymer preferably has the following structure (II) Can be synthesized by using the compound represented by as a part of the polymer-forming component. Here, as the polymer-forming functional group, an amino group, a hydroxyl group, an epoxy group, an unsaturated group and the like are exemplified as preferable ones.

The polymer containing the constituent component represented by the general formula (I) is synthesized, for example, as follows, using the compound represented by the general formula (II) as a part of the reaction component.

(A) Example using epoxy compound having structure of general formula (II) (i) React with conventionally known curing agent (epoxy resin) (ii) React with carboxylic acid (polyester) (b) General formula (II) (I) React with a conventionally known epoxy compound (epoxy resin) (ii) React with isocyanate (polyurea) (iii) React with carboxylic acid (polyamide) (iv) React with maleimide React (maleimide resin) (v) React with cyclic iminoether (polyamine amide) (c) Example using hydroxy compound having structure of general formula (II) (i) React with isocyanate (polyurethane) (ii) With carboxylic acid Reacting (polyester) (d) Example using unsaturated compound having structure of general formula (II) (i) Radical Reacting with medium is (polyolefin) or the like. These may be used alone, or may be appropriately combined into a copolymer or a mixture.

Examples of the epoxy compound used in (a) above include bis [4
-N, N-di (2,3-epoxypropyl) aminophenyl]
Methane, bis [4-N, N-di (3,4-epoxybutyl) aminophenyl] methane, bis [4-N, N-di (4,5-epoxypentyl) aminophenyl] methane, bis [4- N,
N-di (5,6-epoxyhexyl) aminophenyl] methane, bis [4-N- (2,3-epoxypropyl) aminophenyl] methane, bis [4-N- (3,4-epoxybutyl) amino Phenyl] methane, bis [4-N- (4,5
-Epoxypentyl) aminophenyl] methane, bis [4-N- (5,6-epoxyhexyl) aminophenyl] methane, 1,1-bis [4-N, N-di (2,3-epoxypropyl) amino Phenyl] ethane, 1,1-bis [4-N, N
-Di (3,4-epoxybutyl) aminophenyl] ethane,
1,1-bis [4-N, N-di (4,5-epoxypentyl) aminophenyl] ethane, 1,1-bis [4-N, N-di (5,6-
Epoxyhexyl) aminophenyl] ethane, 1,1-bis [4-N, N-di (2,3-epoxypropyl) aminophenyl] propane, 1,1-bis [4-N, N-di (3, 4-epoxybutyl) aminophenyl] propane, 1,1-bis [4-N,
N-di (4,5-epoxypentyl) aminophenyl] propane, 1,1-bis [4-N, N-di (5,6-epoxyhexyl) aminophenyl] propane, bis [4-N- (2 , 3
-Epoxypropyl) -N-methylaminophenyl] methane, bis [4-N- (2,3-epoxypropyl) -N
-Ethylaminophenyl] methane, bis [4-N- (2,
3-epoxypropyl) -N-propylaminophenyl] methane, bis [4-N- (2,3-epoxypropyl) -N-butylaminophenyl] methane, bis [4-
N- (2,3-epoxypropyl) -N-pentylaminophenyl] methane, bis [4-N- (2,3-epoxypropyl) -N-benzylaminophenyl] methane, bis [4-N- (2 Examples include 3,3-epoxypropyl-N-phenylaminophenyl] methane, but especially bis [4
-N, N-di (2,3-epoxypropyl) aminophenyl]
Methane, bis [3-chloro-4-N, N-di (2,3-epoxypropyl) aminophenyl] methane, bis [2-methyl-4-N, N-di (2,3-epoxypropyl) amino Examples include phenyl] methane, and among these, bis [4
-N, N-di (2,3-epoxypropyl) aminophenyl]
Methane is preferred.

Specific examples of the amino compound used in (b) above include 4,
4'-diaminodiphenylmethane, N, N'-dimethyl-4,
4'-diaminodiphenylmethane, N, N'-diethyl-4,
4'-diaminodiphenylmethane, N, N'-dipropyl-
4,4'-diaminodiphenylmethane, N, N'-dibenzyl-4,4'-diaminodiphenylmethane, 1,1-bis (4-
Aminophenyl) ethane, 1,1-bis (4-N-methylaminophenyl) ethane, 1,1-bis (4-ethylaminophenyl) ethane, 1,1-bis (4-N-propylaminophenyl) ethane , 1,1-bis (4-N-benzylaminophenyl) ethane, 1,1-bis (4-aminophenyl) propane, 1,1-bis (4-aminophenyl) butane, 1,1-
Bis (4-N-methylaminophenyl) propane, 1,1-
Bis (4-N-ethylaminophenyl) propane, 1,1-
Bis (4-N-propylaminophenyl) propane, 1,1
-Bis (4-N-benzylaminophenyl) propane,
Bis (4-aminophenyl) -phenylmethane, bis (4-N-methylaminophenyl) -phenylmethane,
Bis (4-N-ethylaminophenyl) -phenylmethane, bis (2-methyl-4-aminophenyl) methane,
Bis (3-methyl-4-aminophenyl) methane, bis (2-ethyl-4-aminophenyl) methane, bis (3
-Ethyl-4-aminophenyl) methane, bis (2-chloro-4-aminophenyl) methane, bis (3-chloro-4-aminophenyl) methane, bis (2-bromo-4)
-Aminophenyl) methane, bis (3-bromo-4-aminophenyl) methane, bis (4-N- (aminoethyl) aminophenyl) methane and the like are exemplified, but especially 4,
4'-Diaminodiphenylmethane is preferred.

Examples of the hydroxy compound used in (c) above include bis [4-N- (hydroxyethyl) aminophenyl] methane and bis [4-N, N-bis (hydroxyethyl) aminophenyl] methane.

The unsaturated compound used in (d) above includes bis (4-
N-allylaminophenyl) methane, bis (4-N, N-
Examples include diallylaminophenyl) methane and the like.

Examples of the compound (reactant) to be reacted with the compound represented by the general formula (II) are as follows.

Examples of the curing agent used in the above (a)-(i) include aromatic polyamines, aliphatic polyamines, polyamideimides, polyphenols such as phenol novolac and polyhydroxystyrene, cyclic carboxylic acid anhydrides, and cation catalysts such as BF _3. Conventionally known compounds such as the above compounds are used.

(A)-(ii), (b)-(iii), (c)-(i
Examples of the carboxylic acid used in i) include aliphatic, alicyclic or aromatic polycarboxylic acids or their esters and acid anhydrides, and aliphatic polycarboxylic acids or their derivatives are particularly preferable.

The epoxy compound used in the above (b)-(i) may be a polyepoxy compound having two or more epoxy groups in the molecule, and specifically the following compounds are exemplified.

1) Glycidyl ether compounds: 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, resorcinol, phenol novolac, cresol novolac, resorcinol Aromatic polyols such as novolac, naphthol novolac, dihydroxynaphthalene, dihydroxynaphthalene novolac: phenol,
Polyols obtained by dehydration reaction of aromatic hydroxy compounds such as dihydroxybenzene, naphthol, dihydroxynaphthalene and the like and aldehydes such as glyoxal, glutaraldehyde, p-hydroxybenzaldehyde, benzaldehyde and the like under, for example, an acidic catalyst:
Glycidyl ethers of polyols such as polyhydric alcohols such as butanediol, polypropylene glycol, polyethylene glycol, glycerol and the like, and precursor polymers thereof.

2) Glycidyl ester-based compounds: Glycidyl esters of dicarboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, naphthalenedicarboxylic acid and precursor polymers thereof.

3) N-glycidyl compound: A compound in which active hydrogen bonded to the nitrogen atom of a nitrogen-containing compound such as aniline, isocyanuric acid and methylenedianiline is substituted with a glycidyl group.

4) Glycidyl ether ester compounds: Glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid and hydroxynaphthoic acid.

5) Others: Epoxy resins obtained from alicyclic compounds such as cyclopentadiene and dicyclopentadiene, triglycidyl compounds of p-aminophenol, vinylcyclohexenedioxide and the like.

Of these, diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), from the viewpoint of easy availability and heat resistance of the resin to be formed,
Obtained by dehydration reaction of diglycidyl ether of 4,4'-dihydroxydiphenylmethane, polyglycidyl ether of phenol novolac, polyglycidyl ether of naphthol novolak, phenol and glycyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde under acidic catalyst Polyglycidyl ether of polyols, diglycidyl ether of polypropylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of butanediol, diglycidyl ether of glycerol, triglycidyl ether of glycerol, diglycidyl ether ester of p-hydroxybenzoic acid Diglycidyl ether ester of 2,2-hydroxy-6-naphthoic acid, of p-aminophenol Liglycidyl compounds and vinylcyclohexene dioxyside are preferred, and particularly bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, α-naphthol novolac polyglycidyl ether, phenol and glyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde. Diglycidyl ether of polyol, polyethylene glycol diglycidyl ether, butanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and p-aminophenol triglyceride Glycidyl compounds and vinylcyclohexenedioxide are preferred. These may be used alone or in combination of two or more.

As the isocyanate used in (b)-(ii) and (c)-(i), aromatic, aliphatic or alicyclic compounds having at least two isocyanate groups in the molecule and modified products thereof are preferably used. As the aromatic polyisocyanate, for example, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate and the like, and alicyclic polyisocyanates include, for example, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate).
And the like, examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, and examples of the modified product include dimer, trimer, prepolymer modified product, carbodiimide modified product, urea modified product of the above polyisocyanate. can do.

The maleimide used in (b)-(iv) is an aliphatic, alicyclic or aromatic compound having two maleimide structures in the molecule, and specifically, 4,4′-bismaleimidediphenylmethane, 3,3′-Bismaleimidophenylmethane, 4,4′-Bismaleimide diphenyl ether, 3,4 ′
-Bismaleimide diphenyl ether, 4,4'-bismaleimide diphenyl sulfone, 3,3'-bismaleimide diphenyl sulfone, N, N'-hexamethylene bismaleimide, N, N'-neopenpentylene bismaleimide, N, N ' -Dodecamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-tolylene bismaleimide, N, N'-p
-Xylylene bismaleimide, N, N'-m-xylylene bismaleimide and the like can be mentioned.

The cyclic iminoethers used in (b)-(v) are exemplified by polyoxazoline and polyoxazine compounds, specifically, 2,2'-bis (2-oxazoline), 2,2 '.
-Ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline) , 2,2'-1,4-Cyclohexylene bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (5-methyl-2-
Oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-
Oxazoline), 2,2'-m-phenylenebis (5-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (5-methyl-2-oxazoline), 1,3,5-tris (2-oxazolinyl-2) benzene, 2,2'-bis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,
2'-tetramethylene bis (5,6-dihydro-4H-1,3-
Oxazine), 2,2'-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-octamethylenebis (5,6-dihydro-4H-1,3-oxazine) , 2,2′−
1,4-cyclohexylene bis (5,6-dihydro-4H-1,3
-Oxazine), 2,2'-bis (4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (5-methyl-5,6-dihydro-4H-1) , 3-Oxazine), 2,2'-bis (6-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H
-1,3-oxazine), 2,2'-p-phenylene bis (5,6
-Dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5-methyl-
5,6-Dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (6-methyl-5,6-dihydro-4H-1,3-
Oxazine), 2,2'-p-phenylenebis (4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-p-
Phenylene bis (5-methyl-5,6-dihydro-4H-1,3
-Oxazine), 2,2'-p-phenylenebis (6-methyl-5,6-dihydro-4H-1,3-oxazine) and the like.

Of these, 2,2'-bis (2-oxazoline), 2,2 '
-Tetramethylene bis (2-oxazoline), 2,2'-m
-Phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-bis (5,6
-Dihydro-4H-1,3-oxazine), 2,2'-tetramethylenebis (5,6-dihydro-4H-1,3-oxazine),
2,2'-m-phenylene bis (5,6-dihydro-4H-1,3
-Oxazine), 7-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine) is preferred.

In the present invention, a system in which a polymer is produced by an addition curing reaction, that is, (a)-(i), (ii), (b)-
(I), (ii), (iv), (v), (c)-(i),
The system of (d)-(i) is preferable, and particularly (a)-(i),
Epoxy resin using (b)-(i), (b)-(v)
The amine amide resin using is preferred.

Further, in the present invention, the structural unit (I) in all polymers is
The proportion of the structural unit of (I) may be at least partially included, but the structural unit of (I) is preferably 5% by weight or more, more preferably the structural unit of (I) is 10% by weight or more,
Most preferably, the structural unit (I) is 30% by weight or more.

Therefore, for example, when the epoxy resin containing the structural unit of the general formula (I) is synthesized by the method of (a)-(i), the general formula (I
Use by reacting the epoxy compound of I) with a curing agent or, in some cases, replacing a part of the epoxy compound of general formula (II) with another epoxy compound [epoxy compound used in (b)-(i)]. You can also do it. The same can be done for other systems.

Further, for example, when synthesizing the epoxy resin containing the structural unit of the general formula (I) by the method of (a)-(i), the general formula (II)
The epoxy compound of (b)-(i) is used as the epoxy compound, and the curing agent containing the structural unit of the general formula (I) is used. May be.

The polymer forming the color-developing layer of one of the display electrodes of the present invention is, for example, a preferred addition-curing reaction type polymer, which is obtained by heating and reacting the above-mentioned compound with a reactant or the like serving as a polymer component of another type. To be In this case, the ratio of the reaction components varies depending on the system, but it is carried out at a conventionally known ratio which is generally carried out in each system. As a preferable ratio, for example, the ratio of the reaction components is close to the equivalent.

One display electrode of the present invention is obtained by coating a transparent conductive substrate with a resin obtained by heating and curing the above components. As the conductive transparent substrate used,
Conventionally known transparent conductive glass, transparent conductive film and the like can be appropriately used. The method of coating the resin thin film on the substrate is not particularly limited, but for example, a method of mixing solids and / or liquids of the above-mentioned respective components and directly heating and dissolving the solution to directly apply the solution to the conductive transparent substrate. (Melting method), a method in which a solution obtained by dissolving each of the above components in an organic solvent is applied onto a conductive transparent substrate, and then the solvent is removed by heating the solution (solution method) and the like. Of the above methods, the solution method is preferable because it can form a thinner film. The organic solvent used in the solution method is not particularly limited as long as it dissolves the above-mentioned resin components and does not modify or react them. For example, alcohols such as methanol, ethanol, propanol and isopropanol. , Acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, tetrahydrofuran, dioxane and other ethers, methylene chloride,
Halogen-based solvents such as chloroform, trichlene, dichloroethane, tetrachloroethane, esters such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, nitrile solvents such as acetonitrile,
Examples thereof include nitro solvents such as nitromethane and hydrocarbon solvents such as toluene and xylene. In the solution method, it is also possible to partially react the resin component by heating in the state of the solution.

The resin raw material applied by the above method is then heated and reacted. The reaction temperature at this time is preferably room temperature to 300 ° C., more preferably about 50 to 250 ° C., although it varies depending on the type of raw material used, the ratio of its use and the like. The reaction time may be a time sufficient for the resin to be sufficiently cured, and this time is preferably 1 minute to 3 hours, more preferably 3 minutes, although it varies depending on the type of raw materials used, the proportion used, the reaction temperature and the like. ~
2.5 hours, particularly preferably about 5 minutes to 2 hours.

This reaction can be carried out under normal pressure to increased pressure, but in this case, it is preferable to carry out under an atmosphere of an inert gas such as nitrogen or argon in order to prevent the influence of moisture in the atmosphere and the oxidative deterioration of the resin.

The resin forming the color-developing layer in the ECD element of the present invention is obtained by quaternizing at least a part of the amino groups in the polymer, for example, 1 equivalent% or more.

In the present invention, as a method of quaternizing at least a part of the amino groups of the structural unit (I) in the polymer, a method of treating with an acid, a method of treating with a salt, a method of treating with an alkyl halide, an acid ester However, the method is not limited to this.

Examples of the acid used here include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphorous acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid.

Examples of salts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium perchlorate, tetramethylammonium chloride, lithium bromide, lithium chloride and the like.

Alkyl halides include methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide,
Examples thereof include benzyl bromide.

Examples of acid esters include methyl benzene sulfonate, ethyl benzene sulfonate, methyl p-toluene sulfonate, p
-Ethyl toluene sulfonate, dimethyl sulfate, trimethyl phosphate, triphenyl phosphate, etc. are exemplified.

The method of quaternization treatment is as follows: (a ') curing the polymer, and then impregnating and reacting the above-mentioned acid, salt, alkyl halide, acid ester, etc. (b') before curing the polymer, the reaction With agents, acids, salts, alkyl halides,
Examples include a method in which an acid ester or the like is added in advance and then heated to carry out curing and quaternization at the same time. It is also possible to use these methods together.

As the impregnation method in the above method, specifically, a polymer obtained by dissolving a quaternizing agent such as an acid, a salt, an alkyl halide, or an acid ester in water or an organic solvent such as acetone or methanol and curing the solution. Soak the quaternary agent in the resin by heating, if necessary,
A method of reacting with an amine residue in the resin can be mentioned.

It is desirable to use a salt as the quaternizing agent because the salt quaternizes the amine and also acts as an electrolyte.

By the above method, the electrode (display electrode A) having the polymer thin film used as one display electrode in the present invention can be manufactured. Although there are many unclear points about the detailed coloring mechanism of the display electrode A, the display electrode A has a characteristic that it is used as an anode to develop a color and when it is used as a cathode, a color is erased.

Next, the other display electrode B used in the present invention will be described.

These display electrodes B are obtained by providing a coloring layer made of a transition metal oxide on the above-mentioned conductive transparent substrate. Examples of the transition metal oxide include tungsten oxide, molybdenum oxide, vanadium oxide and the like.
Of these, tungsten oxide is preferable from the viewpoints of low-voltage color development characteristics and chemical stability. These color-developing layers use physical deposition methods such as vacuum deposition method and sputtering method,
It can be provided on a conductive transparent substrate. These thin films are usually 500 to 10,000 Å, preferably 1000 to 5000 Å, and since the ECD phenomenon of the thin films is observed in a crystalline state, it is necessary to form the film at 200 ° C. or lower. .

The display electrode B develops color when a voltage is applied to it as a cathode, and conversely disappears when a voltage is applied to it as an anode. The ECD element of the present invention comprises the above-mentioned two kinds of display electrodes A.
And B are arranged via an electrolyte medium. The electrolyte medium is not particularly limited, and liquid or solid media known in the art can be applied as they are. For example, as the liquid electrolyte medium, halogen, an inorganic electrolyte composed of an alkali metal salt of halogen peroxide and / or an organic electrolyte such as cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium perchlorate, water or acetonitrile, propylene carbonate,
A solution prepared by dissolving an organic solvent such as dimethylformamide, N-methyl-2-pyrrolidone, or dimethylsulfoxide, and a solid electrolyte medium such as polyethylene oxide, polyphosphazene, or polyethyleneimine containing an alkali metal salt, which has been publicly known. A polymer electrolyte can be preferably mentioned.

<Effects of the Invention> The ECD element according to the present invention exhibits excellent repetitive characteristics because a pair of electrodes whose electrode surfaces are modified with a substance having excellent reversible characteristics of electrolytic oxidation / reduction reaction are combined.

Further, in the ECD element of the present invention having the above structure, both electrodes serve as display electrodes as compared with the conventional element in which one electrode (counter electrode) does not directly contribute to color development. That is, the display electrode A
Both electrodes develop color when voltage is applied so that they become the anode and display electrode B becomes the cathode, and conversely, when voltage is applied so that display electrode A becomes the cathode and display electrode B becomes the anode, both electrodes disappear. To do. For this reason, although the power consumption is almost the same as that of the conventional element, the color development is extremely vivid, and the contrast between the color development and the color erasure is large. Furthermore, the resin used to modify the electrode on the opposite side of the tungsten oxide electrode has excellent solvent resistance and thermal stability, and the durability of the ECD element is also good, and its industrial significance as a new ECD is extremely large. .

<Examples> The present invention will be described in detail below with reference to examples, but the examples are for the purpose of explanation and the present invention is not limited thereto. In the examples, "part" means "part by weight".

Example 1 2,2'-m-phenylene bis (2-oxazoline) 31.2
Parts, 4,4'-diaminodiphenylmethane 20.0 parts, ethyl p-toluenesulfonate 14.0 parts and tetra-n-butyl-
Ammonium perchlorate 15.0 parts chloroform 1500
Dissolved in part. Then, a part of the solution was cast on NESA glass and heated to 100 ° C. to remove chloroform, then 150
When it was heated at 0 ° C for 3 minutes, it was cured. (This is referred to as display electrode A.) On the other hand, tungsten oxide was vacuum-deposited from the tungsten oxide pellets in the alumina-coated tungsten crucible on NESA glass so as to have a film thickness of 5000 Å to form display electrode B.

The display electrodes A and B were immersed in an electrolyte solution prepared by dissolving 100 parts of sodium perchlorate in 7900 parts of deoxygenated acetonitrile, and then a voltage of about 3 V was used with the display electrode A side as an anode and the B side as a cathode. Upon application, colorless or pale yellow was colored blue or green at the anode and colorless to blue at the cathode.

Further, when the polarity of voltage application was reversed, both electrodes were rapidly decolorized.

When the above coloring and decoloring operations were repeated, the color of the electrode was reversibly changed.

Example 2 2.5 parts of 3,3'-diaminodiphenyl sulfone and bis [4-
N, N-di (2,3-epoxypropyl) aminophenyl] methane 4.6 parts, ethyl paratoluenesulfonate 4 parts and tetrabutylammonium perchlorate 3 parts 1,1,2,2-
It was well dissolved in 50 parts of tetrachloroethane and cast on a glass substrate transparent electrode.

When this transparent electrode was heated at 180 ° C. for 1 hour in a nitrogen atmosphere, the coated resin was cured.

When voltage was applied by combining the electrodes in the same manner as in Example 1 except that this was used as the display electrode A, both electrodes were colored blue when the display electrode A was an anode and B was a cathode, and voltage was applied in the opposite direction. , Both electrodes were decolorized. The coloring and decoloring could be repeated with good reproducibility.

Example 3 1.0 part of 4,4'-diaminodiphenylmethane and epoxy equivalent
195g / eq bisphenol A type epoxy compound 3.4
Parts, tetrabutylammonium perchlorate 1.0 parts
It was dissolved in 40 parts of 1,1,2,2-tetrachloroethane. Next, this solution was cast on a transparent electrode of a glass substrate and heated at 180 ° C. for 1 hour in a nitrogen atmosphere to cure. Using this as the display electrode A, the display electrode B used in Example 1 was used as it is, and both electrodes were immersed in an electrolyte solution prepared by dissolving 30 parts of sodium perchlorate in 1000 parts of N, N-dimethylacetamide in advance. When a voltage of about 3 V was applied with the A side as the anode and the B side as the cathode, both display electrodes A and B were colorless and colored blue to purple, and when the polarity of the voltage application was reversed, both electrodes were rapidly decolorized. When the above coloring and decoloring operations were repeated, the color of the electrode changed reversibly.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C08L 77/00 KKR C09K 9/02 A (72) Inventor Hiroshi Okanaba 4-3 Asahigaoka, Hino-shi, Tokyo No. 2 Inside Teijin Ltd. Thin Film Materials Research Laboratory (56) Reference JP-A 63-260979 (JP, A) JP-A 2-110187 (JP, A) JP-A 2-16187 (JP, A)

Claims (1)

[Claims] 1. An electrochromic display element comprising a pair of display electrodes arranged via an electrolyte medium, wherein one of the coloring layers of the display electrode is on a conductive transparent substrate and the following structural unit (I) is provided. Is a polymer containing as a part of the constituent component, and has a resin in which at least a part of the amino group of the structural unit (I) in the polymer is quaternized, and the other is on a conductive transparent substrate. An electrochromic display device characterized by having a transition metal oxide therein.