JPH0376353B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an electrochromic material that electrochemically develops and fades color or exhibits a color change. Conventional configurations and their problems Compared to liquid crystal displays, electrochromic displays have no viewing angle dependence, and their colors are bright and clear. As electrochromic materials, WO ₃ is well known as an inorganic material, viologen is the most well known as an organic material, and other pigments such as pyrazolines and anthraquinones are also known. A thin film of WO ₃ is formed on a transparent electrode by vapor deposition or the like, and an electrolytic solution, a dielectric film, etc. are provided between the counter electrodes to form an element. WO ₃
In addition to the display life, practical problems include:
The color unevenness between the display segments is due to the type of coloring or a single blue color. In addition, due to the reaction of the counter electrode, there are problems in that the counter electrode material must be specially designed and reflectors must be incorporated into the element. When oxidized, it returns to its decolored state.
The problem with viologen-based dyes is that they use dyes that become insolubilized in the coloring state, but in that case, there is a problem with the reversibility of soluble and insoluble, which means that the display life is short. .
Further, halogen ions are involved in the reduction and oxidation reactions of these dyes, and there are problems in that these ions may have an adverse effect on the transparent electrode and that power consumption is large. OBJECTS OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks, and aims to provide an electrochromic material that can be easily multicolored and consumes low power. Structure of the Invention The present invention has been made to achieve the above object, and has the general formula (In the formula, R ₁ and R ₂ are lower alkyl groups, R ₃ is hydrogen, and R ₄
is an alkylsulfonyl group, an alkylcarbonyl group, an unsubstituted benzoyl group, an unsubstituted benzenesulfonyl group, Z is an unsubstituted alkylene group having 2 carbon atoms, and A represents an aromatic aldehyde. ) The present invention provides an electrochromic material characterized by containing a substance represented by: Description of Examples Examples of the present invention will be described below. An electrochromic material that is an embodiment of the present invention has the general formula (In the formula, R ₁ and R ₂ are lower alkyl groups, R ₃ is hydrogen, and R ₄
is an alkylsulfonyl group, an alkylcarbonyl group, an unsubstituted benzoyl group, an unsubstituted benzenesulfonyl group, Z is an unsubstituted alkylene group having 2 carbon atoms, and A represents an aromatic aldehyde. ), and examples of the aromatic aldehydes include benzaldehyde, P-acetaminobenzaldehyde, and P-acetaminobenzaldehyde.
-bromobenzaldehyde, m-bromobenzaldehyde, O-bromobenzaldehyde, P-dimethylaminobenzaldehyde, P-diethylaminobenzaldehyde, P-dibutylaminobenzaldehyde, O-chromebenzaldehyde, P
-Chlorbenzaldehyde, P-anisaldehyde, O-anisaldehyde, P-tolualdehyde, m-tolualdehyde, O-tolualdehyde,
O-ethoxybenzaldehyde, P-ethoxybenzaldehyde, P-fluorobenzaldehyde, O-fluorobenzaldehyde, P-nitrobenzaldehyde, m-nitrobenzaldehyde, O-nitrobenzaldehyde, P-cyanobenzaldehyde, O- cyanobenzaldehyde,
2,4-dichlorobenzaldehyde, 2,6-dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 3,5-dichlorobenzaldehyde, 2,4-dimethquinenzaldehyde, 2,
5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde,
3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, veratraldehyde (3,4-dimethoxybenzaldehyde), 4-isopropylbenzaldehyde, O-(2-chloroethyl)benzaldehyde, 2,4,6 -trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde (mesicaldehyde), 2,4,
6-triethoxybenzaldehyde, 3,4-dimethyl-P-anisaldehyde, 2,5-dimethyl-P-anisaldehyde, 2-chloro-5-nitrosobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 2 -chloro-3-nitrobenzaldehyde, 6-chloro-2-nitrobenzaldehyde, vanillin, O-vanillin, isovanillin, 5-bromo-vanillin, 2-chloro-4-
Dimethylaminobenzaldehyde, 2-chloro-
6-fluorobenzaldehyde, 5-bromoveratraldehyde, 6-bromoveratraldehyde, 5-bromo-2-methoxybenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, P-dimethylaminocinnamaldehyde, P
-diethylcinnamaldehyde, P-nitrocinnamaldehyde, O-nitrocinnamaldehyde, 2-chlorocinnamaldehyde, 9-anthraaldehyde, O-chloro-9-anthraaldehyde, 9-phenanthrenecarboxaldehyde,
Examples include fluorene carboxaldehyde. Examples of aromatic nitroso compounds include P-dimethylaminonitrosobenzene, P-diethylaminonitrosobenzene, P-methylnitrosobenzene (P-nitrosotoluene), P-nitronitrosobenzene, P-methylnitronitrosobenzene, O- Examples of the heterocyclic aldehydes include nitronitrosobenzene, 3-nitroso-2-nitrotoluene, etc., and examples of the heterocyclic aldehydes include furfural, 5-methylfurfural, 5-bromofurfural, 4-isopropylfurfural, 2-thioquenecarboxaldehyde, 5-methylthioquenecarboxaldehyde, 3-methoxybenzothioquene-2-carboxaldehyde,
2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, 4-pyridinecarboxaldehyde, 1-ethylindole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde, 1-methyl-2-carboxaldehyde Enylindole-3-carboxaldehyde, N-methylcarbazole-2-carboxaldehyde, N-ethyl-
7-bromocarbazole-2-carboxaldehyde, N-(n-octyl)-7-nitrocarbazole-2-carboxaldehyde, dibenzofuran-
2-carboxaldehyde, pyrrole-2-aldehyde, N-methylpyrrole-2-aldehyde, N
-Phenylpyrrole-2-aldehyde, 3-methylpyrrole-2-aldehyde, 2-ethylpyrrole-5-aldehyde, benzothiazole-2-aldehyde, 6-methylbenzothiazole-2-aldehyde, 6-chlorobenzothiazole- 2-aldehyde, 5-chlorobenzothiazole-2-aldehyde, 6-methoxybenzothiazole-2-
Aldehyde, 5,6-dichlorobenzothiazole-2-aldehyde, benzoselenazole-2-aldehyde, 6-methoxybenzozelenazole-2
-aldehyde, 2,4-dimethylpyrrole-2-
Aldehyde, 4,6-dichloropyrimidine-5-
carboxaldehyde, 2-formyl-4,6-dimethylpyrimidine, quinoline-2-aldehyde,
Acridine-10-aldehyde, 2,4-diphenyl-5,6,7-hexahydrobenzopyran-
8-carboxaldehyde, 2,4-diphenyl-
6-methyl-5,6,7-pentahydrobenzopyran-8-carboxaldehyde, and the like. In addition, examples of heterocyclic nitroso compounds include 3-nitrosoindole, 2-methyl-3-nitrosoindole (3-nitrosomethylketol)
3-nitroso-2-phenylindole, etc. The characteristics of the electrochromic material shown in this example are listed below. (1) Multicolors can be easily created by changing the pigment structure. (2) Coloring and fading reactions occur due to the oxygen reduction reaction of the dye, but the current consumption at this time is small. (3) It is stable against moisture and oxygen in the air, and is easy to use when used as an element. (4) Because the distribution of color light absorption spenotle is narrow,
High color freshness. Next, the basic structure of an electrochromic display element using the electrochromic material of this example is shown in the figure. 1 is a glass substrate, 2 is a display electrode, 3 is a counter electrode, 4 is an adhesive, 5 is a sealing material, and 6 is a displayable substance. The glass substrate 1 may be made of a material in which at least one side is transparent. As electrode materials for the display electrode 2 and the counter electrode 3, transparent electrodes such as In ₂ O ₃ and SnO ₂ are used. In terms of area, the display electrode 2 is smaller than the counter electrode 3. As the sealing material 4 and the pore sealing material 5, epoxy resin, low melting point glass, solder, etc. are used. As the displayable substance 6, a solution consisting of an electrochromic material represented by the above general formula, a supporting electrolyte, and a non-aqueous solvent is used. This display element has a simple structure as shown in the figure, so it is advantageous in terms of manufacturing cost. As an electrochromic material, it has a narrow light absorption width for color development and fading, resulting in sharpness and high contrast. Furthermore, the potential when coloring and fading is performed electrochemically is low, at less than ±1.5V. Furthermore, in such a device structure, information is selectively displayed by dividing the display electrodes into appropriate segments and applying a potential between the appropriate electrodes in order to generate color in the desired area. . Next, specific examples will be shown. <Example 1> A dye having the following structural formula was used as an electrochromic material. Add this dye to dimethylformamide at 0.02M/
, Tetrabutylammonium perchlorate was dissolved as a supporting electrolyte to a concentration of 0.3M/.
After injecting the solution into the display element as shown in the figure, apply a DC voltage of 1.5V between display electrode 2 and counter electrode 3,
The phenomenon of color development and fading was observed. With no voltage applied, 270
It has light absorption in the vicinity of 300 nm, but when voltage is applied with display electrode 2 on the + side, the dye oxidizes and color appears. The light absorption peak of this coloring is
It is located at 550nm and shows red color. Decoloring can be performed by reversing the polarity of voltage application. Example 2 In the structure of the dye in Example 1, -
The coloring and fading characteristics of the dyes with -COCH ₃ groups instead of SO ₂ CH ₃ groups were exactly the same. Example 3 Instead of _-SO2CH3 group of _the dye in Example 1

【formula】

When the group [Formula] is attached, a display element having the same solution composition as in Example 1 exhibits a coloring and fading phenomenon when a voltage is applied. The absorption spectrum of color development and fading is as follows.

[Table] Effects of the invention In summary, the present invention has the general formula (In the formula, R ₁ and R ₂ are lower alkyl groups, R ₃ is hydrogen, and R ₄
is an alkylsulfonyl group, an alkylcarbonyl group, an unsubstituted benzoyl group, an unsubstituted benzenesulfonyl group, Z is an unsubstituted alkylene group having 2 carbon atoms, and A represents an aromatic aldehyde. ) The present invention provides an electrochromic material characterized by containing a substance represented by the following formula, which has the advantage of being easily multicolored, having a long life, and having low power consumption.

[Brief explanation of drawings]

The figure is a sectional view showing the basic structure of a display element to which an electrochromic material is applied, which is an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1...Glass substrate, 2...Display electrode, 3...Counter electrode, 4...Sealing material, 5...Sealing material, 6...Displayable substance.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ and R ₂ are lower alkyl groups, R ₃ is hydrogen, and R ₄
is an alkylsulfonyl group, an alkylcarbonyl group, an unsubstituted benzoyl group, an unsubstituted benzenesulfonyl group, Z is an unsubstituted alkylene group having 2 carbon atoms, and A represents an aromatic aldehyde. ) An electrochromic material characterized by containing a substance represented by: