JPH06104819B2 - 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 study on a method of obtaining a display with clearer and higher contrast by the same electric power as that of ECD using a conventional viologen, the present inventor found that a specific amine compound and a cyclic iminoether were selected. The resin made to react is
It has been found that the above object can be achieved by developing a color by one-electron oxidation and also erasing by reduction, and by using a display electrode modified with a transparent electrode and the above viologen display electrode in combination. Reached

<Structure of the Invention> That is, the present invention provides an electrochromic display device in which a display electrode having a polymer conductive thin film is disposed on a pair of conductive transparent substrates via an electrolyte medium, and one of the polymer thin films is provided. Is the following formula (I) or (II) [However, in the formulas (I) and (II), n is an integer of 1 to 4. R'represents an n-valent aliphatic, alicyclic or aromatic hydrocarbon group, and when n = 2, R'may be a direct bond. Ra, Rb, Rc, Rd, Re and Rf are hydrogen atoms which may be the same or different, an alkyl group having 3 or less carbon atoms or an aryl group having 7 or less carbon atoms. ] The cyclic imino ethers represented by the following formula (III) [Wherein, in the formula (III), R, R ₁ and R ₂ may be the same or different and each is an aliphatic group, an alicyclic group or an aromatic group which may have a hydrogen atom or a substituent. is there. ] And a diamine compound represented by the above, and optionally at least one selected from the group consisting of a polyhydroxy compound, a polycarboxylic acid compound, and a polyamine compound other than the above formula (III), in the presence of a catalyst by heating The electrochromic display device is characterized in that it is made of a resin thus obtained, and the other is made of a quaternized product of 4,4'-dipyridyl or a resin containing the quaternized product.

The present invention will be described in detail below.

The cyclic imino ethers used in the present invention can be represented by the following general formula (I) or (II).

In these formulas, n represents an integer of 1 to 4. Of these, n = 2 is preferable. R'represents an n-valent aliphatic, alicyclic or aromatic hydrocarbon group, and when n = 2, R '
May be a direct bond.

Examples of R ′ include methyl, ethyl when n = 1,
Propyl, butyl, amyl, hexyl, decyl, cyclopentyl, cyclohexyl, phenyl, substituted phenylnaphthyl, substituted naphthyl, etc. can be exemplified. When n = 2, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, p-phenylene, m -Phenylene, cyclohexylene and the like can be exemplified, and when n = 3 Etc., if n = 4 Etc. can be given.

Ra, Rb, Rc, Rd, Re and Rf are each a hydrogen atom, an alkyl group having 3 or less carbon atoms (eg, methyl group, ethyl group), an aryl group having 7 or less carbon atoms (eg, phenyl group,
Tolyl group), which may be the same or different from each other. It is preferable that all of Ra, Rb, Rc, Rd, Re and Rf are hydrogen atoms, or any one of them is a methyl group and the rest are hydrogen atoms.

Specific examples of the cyclic iminoethers (oxazoline derivatives) represented by the above formula (I) include 2-methyl-2.
-Oxazoline, 2-ethyl-2-oxazoline, 2-
Phenyl-2-oxazoline, 2-tolyl-2-oxazoline, 2-phenyl-5-methyl-2-oxazoline, 2-nitrophenyl-2-oxazoline, 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-cyclohexylenebis (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-phenylene bis (2-oxazoline), 2,2'-m-phenylene bis (4-methyl-2-
Oxazoline), 2,2'-m-phenylenebis (5-methyl-2-oxazoline, 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-
Phenylene bis (4-methyl-2-oxazoline), 2,
2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (5-methyl-2-oxazoline), 1,3,5-tris (2-oxazolinyl) -2) Benzene etc. can be illustrated.

Of these, 2,2'-bis (2-oxazoline), 2,2 '
-Tetramethylene bis (2-oxazoline), 2,2'-
m-phenylene bis (2-oxazoline), 2,2'-p
-Phenylenebis (2-oxazoline), 2,2'-m-
Phenylene bis (5-methyl-2-oxazoline), 2,
2'-p-phenylene bis (5-methyl-2-oxazoline) is preferred.

Specific examples of the cyclic iminoethers (oxazine derivatives) represented by the above formula (II) include 2-methyl-5,6.
-Dihydro-4H-1,3-oxazine, 2-ethyl-5,6-
Dihydro-4H-1,3-oxazine, 2-phenyl-5,6-
Dihydro-4H-1,3-oxazine, 2-phenyl-6-
Methyl-5,6-dihydro-4H-1,3-oxazine, 2,2 '
-Bis (5,6-dihydro-4H-1,3-oxadi), 2,2 '
-Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-tetramethylenebis (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-cyclohexylenebis ( 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-phenylene bis (5,6
-Dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (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-phenylene bis (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-phenylenebis ( 5-methyl-
5,6-dihydro-4H-1,3-oxazine), 2,2'-p-
Phenylene bis (6-methyl-5,6-dihydro-4H-1,3
-Oxazine) and the like.

Of these, 2,2'-bis (5,6-dihydro-4H-1,3-
Oxazine), 2,2'-tetramethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine ), 2,2 ′
-P-Phenylenebis (5,6-dihydro-4H-1,3-oxazine) is preferred.

In the present invention, it is of course possible to use the cyclic iminoethers (oxazoline derivative) represented by the above formula (I) and the cyclic iminoethers (oxazine derivative) represented by the above formula (II) together.

As the cyclic imino ethers, the oxazoline derivative represented by the formula (I) is preferable because of its high reactivity.

Next, the diamino compound represented by the following formula (III) to be reacted with the above cyclic imino ethers in the present invention will be described in detail.

In the formula (III), R, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. , Methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl group such as heptyl, aralkyl group such as benzine,
Examples thereof include cycloalkyl groups such as cyclohexyl and aryl groups such as phenyl, tolyl and diphenyl. R is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group or an aralkyl group.

Specific examples of such diamino compounds 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-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-propylamino) Phenyl) propane, 1,1-bis (4-N-benzylaminophenyl) propane, bis (4-aminophenyl) -phenylmethane, bis (4-N-methylaminophenyl)-
Examples include phenylmethane and bis (4-N-ethylaminophenyl) -phenylmethane. Among these,
4,4'-diaminodiphenylmethane is preferred.

Further, the above diamino compounds can be used alone or in combination of two or more.

The diamino compound is preferably used in an amount of 0.01 to 100 mol% as the amine equivalent of the diamino compound with respect to the iminoether equivalent of the cyclic imino ether.
80 mol% is particularly preferred.

In the present invention, only the cyclic imino ethers and the diamino compound may be reacted by heating in the presence of a catalyst, but if necessary, the system may further include a polycarboxylic acid compound, a polyhydroxy compound, and the above formula. It is possible to add and react at least one selected from the group consisting of polyamine compounds other than the diamino compound represented by (III).

Here, the polycarboxylic acid compound is an aliphatic, alicyclic or aromatic compound having two or more carboxylic acid groups in the molecule, and specifically, as an aliphatic polycarboxylic acid, a succinic group, adipic acid, Sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, dimer acid, glutaric acid, maleic acid, fumaric acid, propane-1,2,3-
Tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, etc., as cycloaliphatic polycarboxylic acid cyclohexane-1,
4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, tetrahydrophthalic acid, dihydrophthalic acid, 1,2- or 1,3-cyclopentanedicarboxylic acid, etc. Examples of the carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, trimellitic acid, trimesic acid, diphenyldicarboxylic acid, methylterephthalic acid and methylisophthalic acid.

In the present invention, a part of the polycarboxylic acid compound is salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid,
It is also possible to replace it with an oxycarboxylic acid such as 6-oxy-2-naphthoic acid, 3-oxy-2-naphthoic acid, ω-oxycaproic acid and the like.

The polyhydroxy compound is an aliphatic, alicyclic or aromatic compound having two or more hydroxyl groups in the molecule. Specifically, as an aliphatic polyhydroxy compound,
Ethylene glycol, propylene glycol, trimethylene glycol, butanediol, hexanediol,
Octanediol, decamethylene glycol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol,
Polyoxyethylene glycol, neopentylene glycol, polyoxytetramethinelen glycol, etc., as alicyclic polyhydroxy compounds, cyclohexanedimethanol, dihydroxycyclohexane, trihydroxycyclohexane, etc., as aromatic polyhydroxy compounds, hydroquinone, resorcinol , Methylhydroquinone, chlorohydroquinone, t-butylhydroquinone, t-amylhydroquinone, fluorohydroquinone, bromhydroquinone, 2,5-dichlorohydroquinone, pyrogallol, catechol, 1,3,5-trihydroxybenzene, 2,2-bis (4-hydroxyphenyl)
Propane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, phenol lid Len, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane, 3,4 ′
-Dihydroxyphenyl ether, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, 2,2
-Bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-
4-hydroxyphenyl) propane, 2,2-bis (4-
Examples thereof include hydroxyphenyl) hexafluoropropane and polyol compounds obtained by condensation of phenols and aldehydes. In the polyol compound obtained by condensation of the above phenols and aldehydes, phenol refers to an aromatic hydroxyl group-containing compound, specifically, phenol, cresol, hydroquinone, resorcin, xylenol, α-naphthol, β-naphthol, Examples thereof include dihydroxynaphthalene, and specific examples of aldehydes include formaldehyde, acetaldehyde, glyoxal, glitalaldehyde, benzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and terephthalaldehyde. it can. Specific examples of the polyol compound include phenol novolac.

The polyamine compound other than the formula (III) is a compound having two or more primary amino groups and / or secondary amino groups in the molecule. Specifically, piperazine, 1-
(2-aminoethyl) piperazine, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3′-diaminobenzophenone, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, diaminonaphthalene, 4,4′-diaminodiphenyl sulfide, 2,4-diaminotoluene, 2 , 6-Diaminotoluene, 1,2-diaminoethane, 3,5-diethyl-2,4-diaminotoluene, 3,5
-Diethyl-2,6-diaminotoluene, 2,4,6-triethyl-m-phenylenediamine, 2,6-dimethyl-4-t
-Butyl-m-phenylenediamine, 4,6-diisopropyl-m-phenylenediamine, 2-chloro-p-phenylenediamine, chlorodiaminotoluene, bis (3,5
Examples thereof include -diisopropyl-4-aminophenyl) methane and polymethylene polyphenyl polyamine. Of these, aromatic polyamine compounds are particularly preferable.

Here, the proportion of these polyhydroxy compounds, polycarboxylic acid compounds, and polyamine compounds used is such that the sum of the equivalents of these compounds and the equivalents of the diamino compounds of the general formula (III) is relative to the iminoether equivalents of the cyclic iminoethers. It is preferably 0.01 to 100%, and particularly preferably 0.1 to 80%.

The thin film used for modifying the display electrode A in the present invention is obtained by heating and reacting each of the above components in the presence of a catalyst.

The catalyst used here is not particularly limited as long as it promotes the above reaction, and examples thereof include protonic acid, protonic acid ester, Lewis acid and its complex, alkyl halide, iodine, and formula (IV). [In the formula, X is a halogen, m represents an integer of 0 to 2, Y represents _{-SO 2 R 1 ', -COR 2} ', -CN, a -NO _2. Here, R ₁ ′ has a carbon number of 1 to 1 which may have a substituent.
10 alkyl group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and shows the -NR ₃ R _4, R ₂ '
Represents an optionally substituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, -OR ₅ and -NR ₆ R ₇ . Also R ₃ , R ₄ ,
R ₅ , R ₆ and R ₇ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms and 6 to 6 carbon atoms.
12 represents an aryl group, and R ₃ and R ₄ , and R ₆ and R ₇ may be different from each other. ] The halogenated phenol compound shown by these, the alkali or alkaline earth metal compound M (Z) l ... (V) shown by Formula (V) [In the Formula, M is an alkali metal or alkaline earth metal, Z is BF ₄ , PF ₆ , SbF ₆ and ClO ₄ , and 1 represents 1 or 2. ] Can be mentioned.

Suitable protic acids include, for example, methanesulfonic acid,
Organic protonic acids such as ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc .; sulfuric acid, phosphoric acid,
Inorganic protic acids such as phosphorous acid, phosphinic acid, phosphonic acid, perchloric acid and the like can be mentioned. Examples of the protic acid ester include methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate and p-toluenesulfonate.
Examples thereof include sulfonic acid esters such as ethyl toluene sulfonate and the like, inorganic protonic acid esters such as dimethyl sulfate, trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, triphenyl phosphite and the like.

Examples of the Lewis acid and its complex include titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, trifluoroborane, trifluoroborane ether complex and the like, and alkyl halides such as methyl iodide, ethyl iodide, and iodo. Examples thereof include propyl iodide, butyl iodide, benzyl iodide, benzyl bromide and the like.

Specific examples of the halogenated phenol compound represented by the formula (IV) include 3,5-dibromo-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxy-benzonitrile and 3,5-dibromo- 4-hydroxybenzonitrile, 3,5-dichloro-4-hydroxynitrobenzene,
3,5-dibromo-4-hydroxynitrobenzene, bis (3,5-dichloro-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl)
Sulfone, bis (3,5-dichloro-4-hydroxyphenyl) ketone, bis (3,5-dibromo-4-hydroxyphenyl) ketone, methyl 3,5-dichloro-4-hydroxybenzoate, 3,5-dibromo Methyl-4-hydroxybenzoate, 3,5-dibromo-4-hydroxybenzoic acid methyl ester, 3,5-dibromo-4-hydroxybenzoic acid amide, 3,5-dibromo-4-hydroxybenzoic acid N-ethylamide, 3 Examples thereof include 5,5-dichloro-4-hydroxybenzenesulfonic acid amide, 3,5-dibromo-4-hydroxybenzenesulfonic acid amide, and 3,5-dibromo-4-hydroxybenzenesulfonic acid N-methylamide.

Further, as the alkali or alkaline earth metal compound represented by the formula (V), LiBF ₄ , NaBF ₄ , KBF ₄ , LiPF ₆ , NaP
_{F 6, Mg (BF 4)} 2, Ca (BF 4) 2, LiSbF 6, NaSbF 6, NaCl
O _{4 and the} like can be exemplified.

These catalysts can be used alone or in combination of two or more. The amount of these catalysts is not particularly limited, but is preferably 0.01 to the cyclic iminoether compound used.
The amount is about 70 mol%.

The display electrode A of the present invention can be obtained by coating a conductive transparent 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, modifies them, and does not react, but for example, alcohols such as methanol, ethanol, propanol, and isopropanol. , Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, halogen solvents such as methylene chloride, chloroform, trichlene, dichloroethane and tetrachloroethane, esters such as ethyl acetate,
Examples thereof include amide solvents such as dimethylformamide and dimethylacetamide, nitrile solvents such as acetonitrile, nitro solvents such as nitromethane, and hydrocarbon solvents such as tolue 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 varies depending on the type of raw material used, the proportion used, etc., but is preferably 50 to 260 ° C, more preferably 60 to 240 ° C, and particularly preferably 70 to 220 ° C. The reaction time may be a time sufficient for the resin to be sufficiently cured, and this time is preferably 10 seconds to 60 minutes, more preferably 20 seconds, although it varies depending on the type of raw material used, the proportion used, the reaction temperature, etc. -40 minutes, particularly preferably 30 seconds to 20 minutes.

This reaction can be carried out under atmospheric pressure to increased pressure, but in this case, it is preferable to carry out under an inert gas atmosphere such as nitrogen or argon in order to prevent the influence of oxygen or water in the atmosphere.

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, as a quaternary compound of 4,4′-dipyridyl, for example,
For example, the following formula (VI)[Wherein D is a monovalent hydrocarbon group, A Is inorganic or organic
The monovalent anion of is shown. ] A low molecular weight compound represented by the following formula (VII) or (V
III)[In the formula, D ′ represents a divalent hydrocarbon group. A Is the same
Up. ][In the formula, D ″ represents a trivalent hydrocarbon group. D and A Is the same
Up. ] A so-called polymer having a repeating unit represented by
We can mention compound.

In the above formulas (VI) (VII) (VIII), A Is sometimes
Onions in polyanions such as polystyrene sulfonate
It may be on.

The display electrode B of the present invention can be obtained by coating the above quaternary 4,4'-dipyridyl compound alone or with another resin, and coating this 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 , 818).
(1981), JP-A-59-217787, JP-A-59-217791, JP-A-61-204224, etc.).

The resin containing a quaternized product of 4,4'-dipyridyl is not particularly limited, but among them, epoxy resin, cyclic imino ethers and polycarboxylic acid, polyhydroxy compound and diamine compound represented by the above formula (III) A resin obtained by heating and reacting with at least one compound selected from the group consisting of polyamine compounds other than the above in the presence of a catalyst, and containing the above quaternary 4,4'-dipyridyl compound by blending. , Or cyclic iminoethers, and 4,4′-dipyridyl and optionally a polycarboxylic acid compound, a polyhydroxy compound, the above formula (II
In the resin obtained by heating and reacting at least one compound selected from the group consisting of polyamine compounds other than the diamine compound represented by I) in the presence of a catalyst, the above 4,
It is preferable to use the one containing a quaternized product of 4'-dipyridyl by blending. Here, as the cyclic imino ethers, polycarboxylic acid compounds, polyhydroxy compounds, and polyamine compounds other than the formula (III), 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. The amount of 4,4′-dipyridyl quaternary compound used in this case is preferably 0.01 to 4 with respect to the cyclic imino ethers.
It is 70 mol%, more preferably 0.05 to 60 mol%, and 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 the diamine compounds represented by formula (III) is used in combination,
The total amount of the quaternized product of 4,4'-dipyridyl and these other components is preferably 10 to 120 with respect to the cyclic imino ethers.
Mol%, more preferably 20 to 110 mol%, and particularly preferably 30 to 100 mol%. 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 a solid electrolyte medium for the solution, a so-called polymer electrolyte such as an alkali metal salt of polyalkylene oxide can be preferably mentioned.

<Effects of the Invention> In the EDC 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 that of the conventional element, the coloring is extremely vivid and the contrast between the coloring and the erasing 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 2,2'-m-phenylene bis (2-oxazoline) 31.2
Parts, 4,4'-diaminodiphenylmethane 20.0 parts, methyl p-toluenesulfonate 14.0 parts and tetra-n-butyl-ammonium perchlorate 15.0 parts with chloroform.
It was dissolved in 1500 parts. Then, a part of the solution was cast on NESA glass, heated to 100 ° C. to remove chloroform, and then heated at 150 ° C. for 3 minutes to cure. (This is referred to as display electrode A) On the other hand, 2,2'-m-phenylenebis (2-oxazoline) 31.2 parts, sebacic acid 11.7 parts, p-toluenesulfonic acid 16.2 parts, cetyltrimethylammonium chloride 15.8
And 6.8 parts of 4,4'-dipyridyl were placed in 800 parts of methanol and dissolved and mixed. The solution is then cast on NESA glass and heated to 100 ° C to remove methanol and then at 170 ° C for 30
It was cured when heated for a minute. (This is referred to as display electrode B) The display electrodes A and B are immersed in an electrolyte solution prepared by dissolving 320 parts of cetyltrimethylammonium chloride in 7900 parts of deoxygenated acetonitrile, and then the display electrode A side is an anode, When a voltage of 1.5 V was applied as a cathode on the B side, colorless or pale yellow was colored blue or green at the anode, and colorless to magenta 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 repeatedly and reversibly changed.

Example 2 2,2'-m-phenylene bis (2-oxazoline) 31.2
Parts, N, N'-dibenzyl-4,4'-diaminodiphenylmethane 2.5 parts, adipic acid 12.7 parts, benzenesulfonic acid 1
And 15.0 parts of cetyltrimethylammonium chloride were dissolved in 800 parts of methanol. Then, a portion of the solution is
Apply evenly on ESA glass with a bar coater, 100 ℃
After heating to 160 ° C. to remove the methanol, heating at 160 ° C. for 5 minutes resulted in curing. (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. (This is referred to as display electrode B.) Display electrodes A and B were immersed in an electrolyte solution prepared by dissolving 322 parts of cetyltrimethylammonium bromide in 7900 parts of acetonitrile in advance, and the voltage was changed in the same manner as in Example 1 below. When applied, the anode was colored from colorless or pale yellow to blue to pale green, and the cathode was colored from colorless to magenta. When the voltage application was reversed, decolorization occurred. The above coloring and decoloring were reversibly repeated.

Example 3 2,2'-m-phenylene bis (2-oxazoline) 31.2
Parts, N, N'-dimethyl-4,4'-diaminodiphenylmethane 2.3 parts, 1,4-cyclohexanedimethanol 14.0 parts, bis (3,5-dibromo-4-hydroxyphenyl) sulfone 3.0 parts and cetyltrimethylammonium bromide 1
7.1 parts was put into a glass reactor and, after purging with nitrogen, heated to 140 ° C. to melt. Then, a portion of this solution is placed on a transparent conductive film, and roller coating is performed while heating on a 180 ° C hot plate, and in that state.
It was cured when left for 10 minutes. (This is referred to as display electrode A.) On the other hand, 2,2'-m-phenylene bis (5,6-dihydro-4H
-1,3-oxazine) 35 parts, m-xylylene diammine 1
1.7 parts, ethyl benzenesulfonate 6.1 parts, tetra-n-
15.1 parts of butylammonium bromide and 2.3 parts of 4,4'-dipyridyl were put into 1400 parts of chloroform and dissolved. Then, a part of the solution was cast on a transparent conductive film, heated to 100 ° C. to remove the solvent, and then heated at 165 ° C. for 30 minutes to cure. (This is referred to as display electrode B.) These two electrodes were previously prepared by adding 330 parts of tetra-n-butylammonium perchlorate to acetonitrile 6500.
It was immersed in an electrolyte solution prepared by dissolving it in a part of
When a voltage was applied in the same manner as above, coloring and decoloring were reversibly repeated.

Example 4 2,2'-m-phenylene bis (5,6-dihydro-4H-1,3
-Oxazine) 35.2 parts, N, N'-diethyl-4,4'-diaminodiphenylmethane 1 part, 3,3'-diaminodiphenylsulfone 25.0 parts, n-butyl iodide 2 parts and tetra-n-butylammonium bromide 15.1 Section 1,1,2,2-
Dissolved in 1500 parts of tetrachloroethane and stored under nitrogen at 120 ° C for 20
When heating and stirring were performed for a minute, the solution changed into a viscous liquid. Then, a part of the liquid is taken out and placed on NESA glass, uniformly applied by spin coating, and
It was cured by heating at 0 ° C. for 5 minutes. (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 2 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 at 100 ° C. to remove methanol and then left at 165 ° C. for 30 minutes to cure. (Being 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.

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 polymer thin films has the formula (I ) Or (II) [However, n is an integer of 1 to 4 in the formulas (I) and (II). R'represents an n-valent aliphatic, alicyclic or aromatic hydrocarbon group, and when n = 2, R'may be a direct bond. Ra, Rb, Rc, Rd, Re and Rf are hydrogen atoms which may be the same or different, an alkyl group having 3 or less carbon atoms or an aryl group having 7 or less carbon atoms. ] The cyclic imino ethers represented by the following formula (III) [Wherein, in the formula (III), R, R ₁ and R ₂ may be the same or different and each is an aliphatic group, an alicyclic group or an aromatic group which may have a hydrogen atom or a substituent. is there. ] In the presence of a catalyst, a diamine compound represented by: and optionally, at least one selected from the group consisting of a polyhydroxy compound, a polycarboxylic acid compound, and a polyamine compound other than the above formula (III). An electrochromic display element comprising a resin obtained by heating and reacting the other with a quaternary compound of 4,4'-dipyridyl or a resin containing the same.