JPH0726094B2 - 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> Various studies have been made on organic electrochromic display materials because of their excellent properties such as vivid colors, memory functions, and no viewing angle dependence, as compared with liquid crystal display materials. Among these, those using viologens, which are typical electrochromic compounds, have excellent durability and can select various hues, and therefore, solution systems in which low-molecular viologens are dissolved, or for example viologens on the display electrode are used. Practical application is being investigated in the form of a so-called modified electrode coated with a thin film of the polymer. Since these viologens develop color by one-electron reduction, an ECD that uses this as a display electrode develops color when the display electrode serves as a cathode, and erases when this serves as an anode. A conventional ECD element has a structure in which the transparent display electrode and the transparent counter electrode as described above are arranged via an electrolyte medium.

<Object of the Invention> Therefore, as a result of diligent studies by the present inventor about a method of obtaining a clearer and higher-contrast display with the same electric power as that of ECD using a conventional viologen, a resin containing a specific structure as its constituent component. Develops color by one-electron oxidation,
Similarly, the inventors have found that the above object can be achieved by decoloring by reduction, and by using a display electrode modified with a transparent electrode and the above viologen display electrode in combination, the present invention has been achieved.

<Structure of the Invention> That is, the present invention relates to an electrochromic display device comprising a pair of display electrodes arranged via an electrolyte medium, wherein one of the coloring layers of the display electrode has the following structural unit (I). [Here, R is a hydrogen atom or a hydrocarbon group. X and Y are the same or different and each is a halogen atom or a hydrocarbon group. m and n are the same or different and each is an integer of 0-4. R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is a hydrogen atom, a monovalent aliphatic group, an alicyclic group or an aromatic group, and at least one is a hydrogen atom or an epoxy group-containing fat. Group, alicyclic and aromatic groups. ] As a part of the constitutional component, and the above structural unit (I)
An electrochromic display device characterized in that at least a part of the amino group of the above is made of an epoxy resin obtained by quaternization treatment, and the other is made of a quaternized product of 4,4'-dipyridyl or a resin containing the same. Is.

The present invention will be described in detail below.

In the above structural unit (I), 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. An alkyl group as the hydrocarbon 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 epoxy resin containing the constituent component represented by the general formula (I) is synthesized, for example, as follows.

(A) using an epoxy compound having a structure of general formula (I) and reacting it with a conventionally known curing agent; (b) using an amino compound having a structure of general formula (I), which is a conventionally known epoxy compound To react with. These may be used alone, or may be appropriately combined to form 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 [ Four
-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- (2,3-epoxypropyl) -N
-Phenylaminophenyl] methane and the like are exemplified,
In particular, bis [4-N, N-di (2,3-epoxypropyl) aminophenyl] methane, bis [3-chloro-4-N, N-di (2,3-epoxypropyl) aminophenyl] methane,
Examples thereof include bis [2-methyl-4-N, N-di (2,3-epoxypropyl) aminophenyl] methane, and among these, particularly 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-aminophenyl) ethane, 1,1-bis (4-N-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-ethyl) Aminophenyl)-
Phenylmethane, bis (2-methyl-4-aminophenyl) methane, bis (3-methyl-4-aminophenyl)
Methane, bis (2-methyl-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-)
Examples thereof include (aminoethyl) aminophenyl) methane, and 4,4′-diaminodiphenylmethane is particularly preferable.

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

Examples of the curing agent used in the above (a) include aromatic polyamines, aliphatic polyamines, polyamideimides, polyphenols such as phenol novolac and polyhydroxystyrene, cyclic carboxylic acid anhydrides, compounds such as cation catalysts such as BF _{3, and the} like. Known ones are used.

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

1) Glycidyl ether compound: 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 an aromatic hydroxy compound such as dihydroxybenzene, naphthol, dihydroxynaphthalene and the like and an aldehyde such as glyoxal, glutaraldehyde, p-hydroxybenzaldehyde, benzaldehyde under an acidic catalyst, for example: butanediol , Glycidyl ethers of polyols such as polyhydric alcohols such as polypropylene glycol, polyethylene glycol, glycerol, etc. and their precursor polymers.

2) Glycidyl ester 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, methylenedianiline, etc. 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, heat resistance of the resin to be formed,
Obtained by dehydration reaction of 4,4'-dihydroxydiphenylmethane diglycidyl ether, phenol novolac polyglycidyl ether, naphthol novolac polyglycidyl ether, phenol and glycyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde under an 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 , 2-
Diglycidyl ether ester of hydroxy-6-naphthoic acid, triglycidyl compound of p-aminophenol and vinylcyclohexenedioxide are preferable,
In particular, diglycidyl ether of bisphenol A, polyglycidyl ether of phenol novolac, polyglycidyl ether of α-naphthol novolac, and polyol obtained by dehydration reaction of phenol and glyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde under an acidic catalyst. Diglycidyl ether, polyethylene glycol diglycidyl ether, butanediol diglycidyl ether,
Diglycidyl ether of glycerol, triglycidyl ether of glycerol, triglycidyl compound of p-aminophenol, vinylcyclohexanedioxide and the like are preferable. These may be used alone or in combination of two or more.

Further, in the present invention, the proportion of the structural unit (I) in the epoxy resin may include at least a part of the structural unit of (I), but the structural unit of (I) is preferably 5% by weight or more, Preferably, the structural unit of (I) is 10% by weight
As described above, most preferably the structural unit of (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), the epoxy compound of the general formula (I) is reacted with the curing agent, or in some cases, the general formula (I It is also possible to replace a part of the epoxy compound of) with another epoxy compound [epoxy compound used in (b)]. The same can be done for other systems.

Further, for example, when the epoxy resin containing the structural unit of the general formula (I) is synthesized by the method of (a), the epoxy compound of the general formula (I) is reacted with a curing agent, but in some cases, as an epoxy compound ( It is also possible to use the epoxy compound used in a) and use a curing agent containing the structural unit of the general formula (I).

The epoxy resin forming the color-developing layer of one of the display electrodes of the present invention is, for example, a preferred addition-curing type epoxy resin in which the above-mentioned compound and a reaction agent which is another type of epoxy resin constituent are reacted by heating. Is obtained by In this case, the ratio of the reaction components varies depending on the system, but the ratio is conventionally known, 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 conductive transparent substrate with an epoxy 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 for coating the resin thin film on the substrate is not particularly limited, but for example, solids and / or liquids of the above components are mixed,
A method in which a solution obtained by heating and dissolving this is directly applied onto the conductive transparent substrate (melting method), a solution in which the above-mentioned components are dissolved in an organic solvent is applied onto the conductive transparent substrate, and then this is heated, etc. Then, a method of removing the solvent (solution method) and the like can be mentioned. 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, modifies them, and does not react, but 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, chloroform, trichlene, dichloroethane,
Halogen solvents such as tetrachloroethane, esters such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, nitrile solvents such as acetonitrile, nitro solvents such as nitromethane, hydrocarbon solvents such as toluene and xylene. Etc. can be mentioned. In the solution method, it is also possible to partially react the epoxy 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 ratio 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 inert gas atmosphere of nitrogen, argon or the like 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 can be obtained by quaternizing at least a part of, for example, 1 equivalent% or more of the amino groups of the structural unit (I) such as the epoxy resin.

In the present invention, the above structural unit (I) in the epoxy resin
Examples of the method for quaternizing at least a part of the amino groups of the above include an acid treatment method, a salt treatment method, an alkyl halide treatment method, and an acid ester treatment method. is not. Acids used here include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphorous acid, phosphoric acid,
Examples thereof include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid.

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

As the alkyl halide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide,
Benzyl bromide and the like can be mentioned.

Examples of the acid ester include methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, dimethyl sulfate, trimethyl phosphate, triphenyl phosphate and the like.

The method of quaternization treatment is as follows: (a ') after curing the epoxy resin, impregnating and reacting with the above acid, salt, alkyl halide, acid ester, etc. (b') before curing the epoxy resin Examples of the method include a method in which an acid, a salt, an alkyl halide, an acid ester and the like are added in advance together with the reaction agent, and then heating is performed to simultaneously perform curing and quaternization. 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, for the other display electrode B used in the present invention,
Explain. The electrode was used in the display electrode described above.
Quaternization of 4,4'-dipyridyl on the same transparent conductive substrate as
Obtained by coating a resin containing
It Here, the quaternized product of 4,4′-dipyridyl is, for example,
Formula (II) below[Here, D is a monovalent hydrocarbon group, Z is a C1-C3
Alkyl group, r is 0, 1 or 2, A Is inorganic or
It is a monovalent anion. ] Lower viologens represented by the following formula (III) or
Is (IV)[Wherein D'is a divalent hydrocarbon group, Z, l, r or
2A Is the same as in formula (II). ][Wherein D "is a trivalent hydrocarbon group, Z, l or r is
Same as formula (II). ] A so-called viologen having a repeating unit represented by
Mention may be made of polymers.

In the above formulas (II) (III) (IV), A Sometimes
Anions in polyanions such as polystyrene sulfonate
May be

The display electrode B of the present invention can be obtained by coating the above quaternary compound of 4,4'-dipyridyl alone or with another resin and coating it on a conductive transparent substrate.
As the display electrode B using these quaternized products of 4,4′-dipyridyl, those known in the art can be used as they are (for example, J. Phys. Chem. 85 , 8).
18 (1981), JP-A-59-217787, JP-A-59-217791.
No. JP-A-61-204224, etc.).

The resin containing the quaternized product of 4,4'-dipyridyl is not particularly limited, but among them, other than epoxy resin, cyclic iminoethers and polycarboxylic acid, polyhydroxy compound and 4,4'-diaminodiphenylmethane derivative A resin obtained by heating and reacting at least one compound selected from the group consisting of polyamine compounds described above in the presence of a catalyst with the quaternary compound of 4,4'-dipyridyl contained therein by blending, Or cyclic imino ethers, quaternary 4,4'-dipyridyl and optionally polycarboxylic acid compound, polyhydroxy compound, 4,
Preferable examples include resins obtained by reacting at least one compound selected from the group consisting of polyamine compounds other than 4'-diaminodiphenylmethane derivative in the presence of a catalyst with heating. Here, as the polyamine compounds other than the cyclic imino ethers, polycarboxylic acid compounds, polyhydroxy compounds, and 4,4-diaminodiphenylmethane derivatives, those described in detail for the display electrode A can be used as they are. In the case of the latter resin, a cyclic imino ether and a quaternized product of 4,4'-dipyridyl are reacted to form a viologen structure. 4,4 ′ in this case
The amount of the quaternized product of dipyridyl is preferably 0.01 to 70 mol% with respect to the cyclic imino ether, and more preferably
The amount is 0.05 to 60 mol%, particularly preferably about 0.1 to 50 mol%. When at least one compound selected from the group consisting of polycarboxylic acid compounds, polyhydroxy compounds and polyamine compounds other than 4,4'-diaminodiphenylmethane derivative is used in combination, a quaternary compound of 4,4'-dipyridyl is used. And the total amount of these other components are preferably 10 to 120 mol%, more preferably 20 to 110 mol%, and particularly preferably 30 to 100 mol% based on the cyclic imino ether. As the reaction conditions, the above-mentioned various conditions can be used as they are.

The display electrode B modified with a resin containing a quaternized product of 4,4'-dipyridyl as described above 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 is constructed by arranging the above-mentioned two kinds of display electrodes A and B 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, the liquid electrolyte medium may be an inorganic electrolyte such as LiCl, LiClO ₄ , KCl or KBr and /
Alternatively, an organic electrolyte such as cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, or tetrabutylammonium perchlorate was dissolved in water or an organic solvent such as acetonitrile, propylene carbonate, dimethylformamide, N-methyl-2-pyrrolidone, or dimethylsulfoxide. As the solid electrolyte medium, a conventionally known polymer electrolyte obtained by adding an alkali metal salt to polyalkylene oxide, polyphosphazene, polyethyleneimine or the like can be preferably used as the solid electrolyte medium.

<Effects of the Invention> In the ECD element of the present invention having the above-mentioned configuration, both electrodes serve as display electrodes, as compared with a conventional element in which one electrode (counter electrode) does not directly contribute to color development. That is, when a voltage is applied so that the display electrode A becomes the anode and the display electrode B becomes the cathode, both electrodes develop color, and conversely, the display electrode A becomes the cathode and the display electrode B.
When a voltage is applied so that becomes an anode, both electrodes are decolorized. For this reason, although the power consumption is almost the same as the conventional element, the color is extremely vivid,
The contrast between color development and color erasure is large. Furthermore, the resin used for modifying the 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 great.

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

Example 1 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 transparent electrode.

When this transparent electrode was heated at 180 ° C. for 1 hour in a nitrogen atmosphere, the coated resin was cured. (This is referred to as display electrode A.) On the other hand, 2,2'-m-phenylenebis (2-oxazoline) 31.2 parts, ethylene glycol 4.5 parts, n-butyl iodide 12 parts, cetyltrimethylammonium bromide 17.1
And 4.5 parts of 4,4'-dipyridyl were put into 1500 parts of chloroform and dissolved.

Then, a portion of the solution was evenly coated on NESA glass,
After heating to ℃ to remove chloroform, the resin was cured by heating at 160 ℃ for 15 minutes. (This is referred to as display electrode B) Display electrodes A and B are immersed in an electrolyte solution prepared by previously dissolving 322 parts of cetyltrimethylammonium bromide in 7900 parts of acetonitrile, and then the display electrode A side is the anode and the B side is the When a voltage of 1.5 V was applied as the cathode, the anode changed from colorless or pale yellow to blue or pale green,
The cathode was colored from colorless to reddish purple. When the polarity of voltage application was reversed, both electrodes rapidly discolored. When the above-mentioned coloring and decoloring operations were repeated, the color of the electrode repeatedly and reversibly changed.

Example 2 2.0 parts of 4,4'-diaminodiphenylmethane and epoxy equivalent
180g / eq phenol novolac type epoxy compound 3.6g, tetrabutylammonium perchlorate 3.0
Parts were dissolved in 40 parts of 1,1,2,2-tetrachloroethane.
Then, this solution was cast on a glass substrate transparent electrode,
It was cured when heated at 200 ° C. for 45 minutes in a nitrogen atmosphere. (This will be referred to as display electrode A) 2,2'-m-phenylene bis (oxazoline) 31.2 parts,
12.6 parts of adipic acid, 0.7 parts of p-toluenesulfonic acid, 16.1 parts of tetra-n-butylammonium perchlorate and 3 parts of N, N'-dimethyl-4,4'-dipyridinium dibromide were dissolved in 1000 parts of methanol. Then, a part of the solution was placed on NESA glass, cast, heated to 100 ° C. to remove methanol, and then left standing at 165 ° C. for 30 minutes to cure. (As Display Electrode B) The display electrodes A and B were immersed in an electrolyte solution prepared by dissolving 300 parts of tetra-n-butylammonium bromide in 1000 parts of methanol in advance, and the voltage was changed by the same operation as in Example 1. Upon application, the colorless and transparent display electrodes A and B were colored blue at the same time. Further, when the direction of voltage application was reversed, the color was rapidly decolorized and the original colorless and transparent state was restored.

By repeating the above coloring and decoloring operations, the color of the electrode changed reversibly.

Example 3 1.0 part of 4,4'-diaminodiphenylmethane and epoxy equivalent
195g / eq bisphenol A type epoxy compound 3.4
Part, tetrabutylammonium perchlorate 1.0 part
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.
(This will be referred to as display electrode A.) As the display electrode B, the one used in Example 1 was used, and a voltage was applied in the same manner as in Example 1. When the display electrode A was used as an anode and B was used as a cathode, it was colored. When the direction of voltage application was reversed, the color was rapidly decolorized. By repeating this operation, the colors of both electrodes reversibly changed.

Claims (1)

[Claims] 1. An electrochromic display device comprising a pair of conductive transparent substrates, on which a display electrode having a polymer conductive thin film is arranged via an electrolyte medium, wherein one of the color layers of the display electrode is a structural unit shown below. (I) [Here, R is a hydrogen atom or a hydrocarbon group. X and Y are the same or different and each is a halogen atom or a hydrocarbon group. m and n are the same or different and each is an integer of 0-4. R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is a hydrogen atom, a monovalent aliphatic group, an alicyclic group or an aromatic group, and at least one is a hydrogen atom or an epoxy group-containing fat. Group, alicyclic and aromatic groups. ] As a part of the constitutional component, and the above structural unit (I)
An electrochromic display device characterized in that at least a part of the amino group of the above is made of an epoxy resin obtained by quaternization treatment, and the other is made of a quaternized product of 4,4'-dipyridyl or a resin containing the same. .