KR100345510B1 - Electrochromic composition - Google Patents

Abstract

PURPOSE: Provided is an electrochromic composition used for car mirrors, window glass for controlling permeability, and displays, which dose not generate the separation of layers though the composition is used for a long time and can prevent characteristic degradation. CONSTITUTION: The electrochromic composition contains: a cathodic reduction component containing a cation comprising the formula I and/or II and an anion selected from the group consisting of Cl-, Br-, I-, BF4-, ClO4-, wherein the cathodic reduction component has a concentration of 0.01-0.1M; an anodic oxidation component containing ferrocene(formula I), which has a concentration of 0.01-0.1M; a solvent containing propylene carbonate and gamma-butyrolactone. In the formula, R21 and R22 are C1-C10 alkyl, phenyl or benzyl substituted by a group selected from Cl, Br, cyano, C1-C4 alkyl, and R31 is C1-C10 alkyl.

Description

Electrochromic Composition

[Industrial use]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic composition, and more particularly, to an electrochromic composition for an electrochromic device used as a mirror for automobiles, a window glass for controlling transmittance, and a display device.

[Private Technology]

Conventionally, a viologen compound is used as a cation of a cathode reduction component that changes color when electrons are obtained, and BF _4- , PF _6- , AsF _6- , ClO _4- , and NO ₃ -are used as the cathode reduction component. It is used as an anion, water or propylene carbonate, butyrolactone, by using one or more compounds selected from the group consisting of KBr, KCl, NiCl ₂ and phenazine derivatives as electrolyte or anodizing component The electrochromic composition was prepared by dissolving in an organic solvent such as ethylene carbonate.

Injecting and encapsulating the electrochromic composition between glass substrates coated with an indium tin oxide (ITO) film on the inner side thereof, and then a cathode reduction component is formed when current flows between the glass substrates coated with a conductive film (ITO). The cation of gets electrons, the color changes, and the anodization component gives electrons to the anode, which facilitates the flow of electric current, resulting in an electrochromic reaction that changes color (transmittance). Is being used. U.S. Patent No. 4,902,108 describes the electrochromic composition and a device using the same.

However, in the conventional electrochromic device, as the time passes or as the number of operations increases, a separation phenomenon occurs in which the components in the electrochromic composition do not have a uniform distribution but are separated from each other. According to such a layering phenomenon, the color is not uniform and the color is not well colored, and there is a problem that the characteristic deterioration occurs that the reaction time required for the foot and the color is also long.

[PROBLEMS TO BE SOLVED BY THE INVENTION]

The present invention has been made to solve the problems of the prior art as described above, the object of the present invention relates to an electrochromic composition that can be prevented from deteriorating characteristics even after long-term use.

[Means for solving the problem]

In order to achieve the above object, the present invention provides an electrochromic composition for an electrochromic device comprising the following components.

1) Cathode reduction component containing the following cation and anion

① cations consisting of the following structural formulas I and / or II

Wherein R ₂₁ and R ₂₂ are a phenyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, 1 to Is selected from the group consisting of benzyl groups substituted with groups selected from the group consisting of four alkyl groups.)

Wherein R ₂₁ and R ₂₂ are a phenyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, carbon number Is selected from the group consisting of a group substituted benzyl group selected from the group consisting of 1 to 4 alkyl group, R ₃₁ is an alkyl group having 1 to 10 carbon atoms.)

② anion selected from the group consisting of Cl-, Br-, I-, BF _4- , ClO _4-

2) Anodizing Component Containing Ferrocine of Formula

3) propylene carbonate, solvent containing r-butyrolactone

EXAMPLE

Referring to the configuration of the electrochromic composition according to the present invention in detail.

Electrochromic composition for electrochromic devices containing the following component.

1) Cathode reduction component containing the following cation and anion

① a cation consisting of the following structural formulas I and / or II, preferably 1

Wherein R ₂₁ and R ₂₂ are phenyl groups substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, and an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, 1 carbon atom. Is selected from the group consisting of benzyl groups substituted with a group selected from the group consisting of 4 to 4 alkyl groups.)

Wherein R ₂₁ and R ₂₂ are a phenyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, carbon number Is selected from the group consisting of benzyl groups substituted with a group selected from the group consisting of 1 to 4 alkyl groups, R ₃₁ is an alkyl group having 1 to 10 carbon atoms.)

② anions containing C ₂ B ₉ H ₁₂

2) Anodizing Component Containing Ferrocine of Formula

3) propylene carbonate, solvent containing r-butyrolactone

In the present invention described above, the concentration of the cathode reduction component is preferably 0.01 to 0.1 M, and the concentration of the anodization component is 0.01 to 0.1 M. If the concentration of the cathode reduction component and the concentration of the anodization component is smaller than the above range, the color concentration is lowered.

In the present invention described above, R ₂₁ , R ₂₂ and R ₃₁ are preferably methyl groups.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples and comparative examples are only preferred embodiments of the present invention for the purpose of better understanding of the present invention, and the present invention is not limited to the following examples.

(Example 1)

1 is a schematic cross-sectional view of an electrochromic device, in which two corners of 10 × 5 cm glass coated with ITO are coated with a thermosetting agent on each corner except for the solution inlet, and then placed in a 100 ° C. drying furnace and cured for 30 minutes. ) Was prepared.

0.01M of a dimethyl dipyridine negative electrode reduction component with ClO ₄ − was dissolved in a propylene carbonate solvent, and 0.01M of tetramethylbenzidine was dissolved as an anodizing component to prepare an electrochromic composition. This electrochromic composition was injected into the cell by a vacuum injector (Shindo-Yeki Co., Ltd.). Subsequently, the inlet is sealed using a silicone sealant, and after 3 to 4 hours, a thermosetting agent is applied on the silicone sealant and cured at room temperature for 8 hours to encapsulate the inlet. Ag was applied to form an electrode as in the first diagram.

When the current of 1.0 volt was supplied to the electrode manufactured by the above method, the transmittance of the colorless cell changed to blue, and when the supply of current was cut off, a reversible reaction of returning to colorlessness occurred.

[Comparative Example]

Each corner except for the solution inlet was applied to two sheets of 10 × 5 cm sized glass coated with ITO with a thermosetting agent and placed in a 100 ° C. drying furnace to cure for 30 minutes to prepare a cell.

Dibenzyl bipyridinium difluoroborate was dissolved in 0.02 M of a dibenzyl bipyridinium difluoroborate in a propylene carbonate solvent, and 0.02 M of dihydro dimethylphenazine anodized component was dissolved to prepare an electrochromic composition. . This electrochromic composition was injected into the cell by a vacuum injector (Shindo-Yeki Co., Ltd.). Subsequently, the inlet is sealed using a silicone sealant, and after 3 to 4 hours, a thermosetting agent is applied on the silicone sealant and cured at room temperature for 8 hours to seal the inlet. Then, Ag is applied to the corners of both ITO surfaces. Electrodes were formed as in the first diagram.

The results of measuring the insecticidal phenomenon according to the increase in the number of operation of the electrode prepared in the above Examples and Comparative Examples are shown in Table 1.

TABLE 1

[effect]

As described above, when the electrochromic composition according to the present invention is used as a material for the electrochromic device, the effect of separation in the composition may be reduced as time passes and as the number of repeated operations increases. It is possible to obtain stable properties which are easily caused by blocking and feeding.

1 is a structural diagram showing an electrochromic device.

Explanation of symbols on the main parts of the drawings

1: glass substrate

2: ITO membrane

3: adhesive

4: electrode

5: electrochromic solution

Claims (3)

Electrochromic composition for electrochromic devices containing the following component. 1) Cathode reduction component containing the following cation and anion ① cations consisting of the following structural formulas I and / or II Wherein R ₂₁ and R ₂₂ are a phenyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, 1 to Is selected from the group consisting of benzyl groups substituted with groups selected from the group consisting of four alkyl groups.) Wherein R ₂₁ and R ₂₂ are a phenyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, Cl, Br, cyano, an alkyl group having 1 to 4 carbon atoms, and Cl, Br, cyano, carbon number Is selected from the group consisting of benzyl groups substituted with a group selected from the group consisting of 1 to 4 alkyl groups, R ₃₁ is an alkyl group having 1 to 10 carbon atoms.) ② anion selected from the group consisting of Cl-, Br-, I-, BF _4- , ClO _4- 2) Anodizing Component Containing Ferrocine of Formula 3) propylene carbonate, solvent containing r-butyrolactone The electrochromic composition according to claim 1, wherein the concentration of the cathode reduction component is 0.01 to 0.1M and the concentration of the anodization component is 0.01 to 0.1M. The electrochromic composition of claim 1, wherein R ₂₁ , R ₂₂ and R ₃₁ are methyl groups.