JPH028286A - Electrochromic display material - Google Patents

Abstract

PURPOSE:To obtain the title material having high coloring concentration and decoloring properties and enabling vivid display having high display quality and contrast ratio by forming the material from a specific benzothiazole compound. CONSTITUTION:The aimed display material formed from a benzothiazole compound expressed by formula I or formula II [X is heterocyclic ring, alkyl, (substituted) aryl, (substituted) styryl or hydrazyl; R1 is H, alkoxy, (substituted) aryl, alkyl, aralkyl, nitro, cyano, amino, carboxyl, sulfonic acid or carboxylic amide; R2 is alkyl; Y is anion].

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrochromic display material that reversibly develops and fades in color through a redox reaction upon application of voltage.

BACKGROUND OF THE INVENTION In recent years, as the living environment has become increasingly electronic, display elements for human vision have become increasingly important. Display elements in this field include light-emitting elements,
Those using cathode ray tubes, those using light emitting diodes,
Furthermore, as non-emissive type elements, those using liquid crystal elements are well known, and electrochromic elements are also known. Compared to conventional light-emitting and non-light-emitting devices, electrochromic elements: ■ They fit the eye like printed matter under normal ambient light, and do not become difficult to read due to external light.
The device has no viewing angle dependence and has vivid colors; ■The driving voltage is low at 0.5 to 5 V, allowing direct drive from a unit battery, and is highly compatible with IC circuits. ■Element structure It is generally simple, and there is no need to precisely control the distance between the electrodes like in liquid crystal displays.■ It is easy to make the screen larger.
■It has many advantages such as a wide operating temperature range. Therefore, various electrochromic elements have been proposed in the past, and their materials include tungsten oxide,
Inorganic substances such as iridium oxide and viologen pigments,
Various organic substances have been proposed, including anthraquinone pigments. (For example, JP-A-60-51774
No. 60-55074, No. 60-99188, No. 60-115681, No. f30-22388f3,
60-231782, etc.) Problems to be Solved by the Invention However, conventionally proposed electrochromink display elements have problems with writing time, permissible range of applied voltage necessary for color development, color when decoloring, color density, Usable solvents, etc.
It did not satisfy all of the various demands, and was ultimately insufficient for practical use. As electrochromic display materials, organic materials generally provide more vivid colors than inorganic materials, and have the advantage of being able to express various colors depending on the material selection. At present, the appearance of display elements is awaited.

The present invention has been made in view of the current situation, and its purpose is to provide a new material that can be used in electrochromic display elements.

Means for Solving the Problems The organic electrochromic display material of the present invention has the general formula (I> or (II) (I) (II) (wherein, X
represents a heterocyclic group, an alkyl group, an optionally substituted aryl group, an optionally substituted styryl group, or a hydrazyl group, and R1 is a hydrogen atom, an alkoxy group, an optionally substituted aryl group, or an alkyl group. , an aralkyl group, a nitro group, a cyano group, an amine group, a carboxyl group, a sulfonic acid group, or a carboxylic acid amide group, R2 represents an alkyl group, and Y represents an anion). It is characterized by

The organic electrochromic display material of the present invention will be described in detail below.

In the above general formulas (I) and <II), X represents a heterocyclic group, an alkyl group, an optionally substituted aryl group, an optionally substituted styryl group, or a hydrazyl group; Examples include a thiophene group, a furanyl group, a pyrrole group, a 3-pyrrolinyl group, and a biphenyl group.

As the aryl group, phenyl group, biphenyl group,
Examples include naphthyl group, anthryl group, and phenanthryl group. These aryl groups may have a substituent. Examples of the substituent include a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group and amyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group,
C-substituted amine groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, ditolylamino group, dixylylamino group, diphenylamino group, dibenzylamino group, halogen atoms such as chlorine atom, bromine atom, hydroxy group, carboxy group, etc.

When X represents a styryl group, a substituent such as a nitro group or a dialkylamino group may be present.

Further, R3 represents a hydrogen atom, an alkoxy group, an optionally substituted aryl group, an alkyl group, an aralkyl group, a nitro group, a cyano group, an amino group, a carboxyl group, a sulfonic acid group, or a carboxylic acid amide group, Examples of substituents for the aryl group that may be substituted include alkyl groups such as methyl, ethyl, propyl, butyl, and amyl groups, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, and dimethyl. Di-substituted amino groups such as amino group, diethylamino group, dipropylamino group, dibutylamino group, ditolylamino group, dixylylamino group, diphenylamino group, dibenzylamino group, halogen atom such as chlorine atom, bromine atom, hydroxy group , carboxy group, cyano group, etc.

Furthermore, R2 and Y are groups that form a quaternary salt,
Each represents an alkyl group and an anion.

Examples of anions include halogen atoms such as chlorine atoms.

The above general formula (I>
and benzothiazole compounds represented by (II).

Compound Example 7 N Compound Example 8 The above benzothiazole compound of the present invention is used in a display element having the structure shown in FIG. The display element in FIG. 1 is a solution type cell, and includes a transparent substrate 2 provided with a transparent or translucent display electrode 1, and a counter electrode 1. The 0 display electrode is constructed by sealing an electrochromic display material-containing solution 6 between a support 4 having a back electrode 3 via an insulating spacer 5 such as Mylar or Teflon, and sealing with a seal 7. , indium oxide, tin oxide, indium tin oxide, or the like, and the counter electrode is made of the same material as the transparent electrode material, or a metal such as platinum, gold, or aluminum. Further, the support body is formed of a material such as glass or plastic. The electrochromic display material-containing solution is prepared by dissolving the benzothiazole compound represented by the above general formula (I) or (II) together with a supporting electrolyte in an appropriate solvent.

The benzothiazole compound represented by the above general formula (I) or (If) is not limited to the so-called solution type cell as described above, and even if it is introduced into the polymer as a pendant group of the polymer compound, electrochromism can be achieved. , and it is also possible to apply it to solid-state cells. Moreover, the above general formula (I
) or (II) by binding a compound of an appropriate size to the benzothiazole compound to increase the molecular weight, it is also possible to control the migration of colored species generated on the electrode surface.

Example Hereinafter, the present invention will be explained by examples.

Example 1 The above exemplified compound No. 1 1011nol and tetrabutylammonium perchlorate (TBAP) were used as a supporting electrolyte.
)0.1 mol was dissolved in N,N-dimethylacetamide 10001 to prepare an electrochromic display material-containing solution 6. The obtained solution was filled and sealed in an electrochromic display element having the structure shown in FIG.

When a DC voltage of -1 to -2 V was applied between the display electrode 1 and the counter electrode 3 of this electrochromic display element, a green to deep green color was observed on the display electrode 1. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 2 10 n1 ol of the above exemplified compound Nα2 and 0.110 tetrabutylammonium perchlorate as a supporting electrolyte.
1 was dissolved in 1000 n, G acetonitrile, and the resulting solution was filled and sealed in the same manner as in Example 1, except that the resulting solution was used as an electrochromic material-containing solution.

As in Example 1, when a DC voltage of -1 to -1.8 V was applied between the display electrode and the counter electrode, a green to deep green color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 3 101lol of the above exemplary compound NQ3 and 0.1io1 of lithium perchlorate as a supporting electrolyte were
In addition to dissolving mj in dimethylacetamide and using the resulting solution as an electrochromic material-containing solution,
It was filled and sealed in the same manner as in Example 1.

As in Example 1, when a DC voltage of -1 V was applied between the display electrode and the counter electrode, a red color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 4 10IIIlol of the above exemplified compound No. 4 and 0.1nol of lithium perchlorate as a supporting electrolyte were
Filling and sealing were carried out in the same manner as in Example 1, except that the solution was dissolved in dimethylacetamide of 0 raj and the resulting solution was used as an electrochromic material-containing solution.

As in Example 1, when a DC voltage of -1.2 cm was applied between the display electrode and the counter electrode, a reddish-purple color was observed on the display electrode. This coloring disappears quickly by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 5 101 nol of the above exemplified compound Nα5 and 0.0 mol of tetrabutylammonium as a supporting electrolyte. IIIol and
Dissolved in 1000 nj dimethylacetamide,
Filling and sealing were carried out in the same manner as in Example 1, except that the obtained solution was used as an electrochromic material-containing solution.

When a DC voltage of -1.2 V was applied between the display electrode and the counter electrode to the same urine as in Example 1, a reddish-purple color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 6 101 iol of the above exemplified compound No. 6 and 0.1 nol of tetrabutylammonium as a supporting electrolyte were mixed into 1
Filling and sealing were carried out in the same manner as in Example 1, except that the solution was dissolved in dimethylacetamide of 000 nj and the resulting solution was used as an electrochromic material-containing solution.

As in Example 1, when a DC voltage of -1 .mu. was applied between the display electrode and the counter electrode, a red color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 7 10 nmol of the above exemplary compound No. 7 and 0.11 ol of tetrabutylammonium as a supporting electrolyte,
Filling and sealing were carried out in the same manner as in Example 1, except that the solution was dissolved in 100011JI dimethylacetamide and the resulting solution was used as an electrochromic material-containing solution.

As in Example 1, when DC voltages -o and ev were applied between the display electrode and the counter electrode, red color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Example 8 The above exemplified compounds No. 8 1QINnol and tetrabutylammonium 0.1TRO+ as a supporting electrolyte were dissolved in 1000 nj of dimethylacetamide, and the resulting solution was used as an electrochromic material-containing solution. It was filled and sealed in the same manner as in Example 1.

As in Example 1, when a DC voltage of -0.45 V was applied between the display electrode and the counter electrode, a red color was observed on the display electrode. This coloring quickly disappeared by removing the applied voltage or by applying a voltage of about 1 V of opposite polarity.

Effects of the Invention When the electrochromic display material of the present invention is used for an electrochromic display, it is possible to produce a display with high color density, clarity, display quality, and contrast ratio, and moreover, it becomes colorless when decolored. Or hardly any coloring.

transparent electrode

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of an electrochromic display element to which the electrochromic display material of the present invention is applied. DESCRIPTION OF SYMBOLS 1...Display electrode, 2...Transparent substrate, 3...Counter electrode, 4...Support, 5...Insulating spacer, 6...
- Electrochromic display material-containing solution, 7... Seal. Patent applicant Tomegawa Paper Mills Co., Ltd. Agent Patent attorney Liquid Department Figure 1 1゜2゜3゜4゜Procedural amendment (voluntary)

Claims (1)

[Claims] (1) General formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X is a heterocyclic group, an alkyl group , represents an optionally substituted aryl group, an optionally substituted styryl group, or a hydrazyl group, and R_1 is a hydrogen atom, an alkoxy group, an optionally substituted aryl group, an alkyl group, an aralkyl group, a nitro group, An electrochromic display material comprising a benzothiazole compound represented by a cyano group, an amino group, a carboxyl group, a sulfonic acid group, or a carboxylic acid amide group, R_2 represents an alkyl group, and Y represents an anion.