JP3428603B2 - Optical device and electrolyte - Google Patents

Optical device and electrolyte

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Publication number
JP3428603B2
JP3428603B2 JP08754995A JP8754995A JP3428603B2 JP 3428603 B2 JP3428603 B2 JP 3428603B2 JP 08754995 A JP08754995 A JP 08754995A JP 8754995 A JP8754995 A JP 8754995A JP 3428603 B2 JP3428603 B2 JP 3428603B2
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Japan
Prior art keywords
silver
silver chloride
optical device
solution
acid
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JP08754995A
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JPH08262501A (en
Inventor
融 宇▲だか▼
英治 宮垣
弘一郎 日隈
和宏 野田
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ソニー株式会社
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Description

Detailed Description of the Invention

[0001]

The present invention relates to an optical device (for example, a filter capable of controlling the light transmittance in the visible light region (wavelength: 400 to 700 nm), a numeral or character display, an XY matrix display, etc.). The present invention relates to an optical filter applicable to a display device for performing) and an electrolytic solution used in the device.

[0002]

2. Description of the Related Art Conventionally, electrochromic materials (hereinafter sometimes referred to as EC materials) have been used in voltage-driven display devices, for example, digital clocks for displaying the time.

Electrochromic display element (hereinafter referred to as E
Sometimes referred to as a CD. ) Is a non-emission type display device, which has a merit that it does not cause fatigue even after long-time observation because it is a display by reflected light or transmitted light. It has advantages such as low power consumption. For example, as disclosed in Japanese Patent Laid-Open No. 59-24879, a liquid type ECD in which an organic molecule-based viologen molecule derivative that reversibly forms a colored or decolored state is used as an EC material is known. There is.

With the development of precision optical equipment, there is a need for a fine and low power consumption type light quantity adjusting device which replaces the conventional variable ND filter.
It is necessary to consider whether the CD or its peripheral technology can be applied to it.

However, the conventional EC materials have not been able to meet the above-mentioned requirements because they have been satisfied only by obtaining a single color for display devices. Moreover,
As a light quantity adjusting device (light adjusting element), it is necessary to be able to control the light transmittance in the visible light region (wavelength: 400 to 700 nm), but the EC materials used so far have not been sufficient.

Therefore, although an electrochemical device using silver precipitation and dissolution has been developed, a solvent having a good low temperature characteristic that can dissolve a reducing agent for reversible precipitation and dissolution has been developed. Had not been considered. Furthermore, a system having a good spectral characteristic (spectral characteristic of a deposited silver film) at the time of shielding was not obtained.

Conventionally, regarding the precipitation of silver from a silver complex salt, a cyan-based solution used as a plating bath is well known, but the cyan-based solution is used for ensuring a safe working environment and treating the waste solution. There's a problem.

[0008]

The present inventors have found that when a solution is prepared, the solution has no absorption in the visible light range (400 to 700 nm),
In addition, we investigated the use of a non-cyan-based silver complex salt as a material for the electrochemical light control device, which is capable of shielding almost evenly in the visible light region when colored.

That is, among various silver complex salts, a reversible system was used by using together with a reducing agent. Materials used in this system RED (R eversible E lectro D eposit
Ion) material, which was dissolved in a solvent to prepare a RED solution.

In order to construct a dimming element using a RED material which is an electrochemical material by obtaining a reversible system in which silver is deposited and dissolved on a transparent electrode from a silver complex salt in a non-aqueous system, It was examined whether or not silver thiocyanide or silver halide, which is highly reversible, could be used to form a complex salt thereof and be applied to a light control element. In the systems examined so far, deterioration of temperature characteristics becomes a problem, so for example, a solvent having a low freezing point in low temperature characteristics was investigated.

Up to now, only a solution using silver iodide as a silver halide, ascorbic acid as a reducing agent, and dimethyl sulfoxide (DMSO) as a non-aqueous solvent has been studied as the RED solution. There are problems such as color deterioration of the electrolyte due to generation of iodine when silver is dissolved, and deterioration of image information during shielding, which occurs because the spectral characteristics of the deposited silver film do not have uniform absorption in the visible light range. (This will be described in detail in Comparative Example below).

The cause of this is that the standard redox potential of iodine is lower than that of bromine or chlorine, as shown below. (Hydrogen standard)

[Chemical 1]

[0013]

The object of the present invention is that it can be driven with low power consumption, the light transmittance can be controlled in the visible light region, and the spectral characteristics when light is shielded are good. It is to provide an optical device and an electrolytic solution used for the optical device.

[0014]

That is, the present invention is configured such that a solution in which silver chloride is dissolved in a solvent is arranged between opposed electrodes, and silver is deposited or dissolved by controlling the driving of these electrodes. It has been Oite the optical device, thiourea, allyl
Thiourea, mercaptobenzimidazole and coumarin
Or Ranaru at least one brightener from selected group, off
Consists of Talic Acid, Succinic Acid, Salicylic Acid and Glycolic Acid
At least one complexing agent selected from the group
The other one is characterized in that it is added to the solution.
The present invention relates to an optical device .

According to the present invention, silver chloride having a high standard oxidation-reduction potential is used as a silver salt to reduce the coloring side reaction gas as described above which is generated when silver is dissolved, and the deposited silver film is uniformly distributed in the visible light region. It has acquired a system with a strong absorption. As a result, it is possible to realize a system in which the deposited silver film has good spectral characteristics, and it is possible to avoid deterioration of optical information due to color unevenness during shielding.

Not to mention the RED solution according to the present invention, when a solution is prepared, the solution has no absorption in the visible light region (wavelength: 400 to 700 nm), and when colored, a substantially uniform shield is provided in the visible light region. Possible silver chloride (complex salt) is used as a material. Moreover, this silver chloride (complex salt) is highly reversible in precipitation-dissolution by controlling the drive.

As described above, the present invention uses a reversible system in which silver is deposited and dissolved from silver chloride (complex salt) on the electrode, so that an optical device of low power consumption and suitable for a non-emission type visible light region. , For example an optical filter can be provided.

The optical device of the present invention is provided with a solution in which silver chloride is dissolved in water or a non-aqueous solvent, particularly a non-aqueous solution, and is arranged to be colored or decolored by the precipitation or dissolution of silver.

In this case, the silver chloride concentration is 0.03 to 2.0 mol /
It is desirable to use a RED solution that is L.

It is preferable that at least one additive selected from the group consisting of brightening agents and complexing agents is added to the solution.

For example, at least one brightener selected from the group consisting of thiourea, allylthiourea, mercaptobenzimidazole and coumarin may be used.

Further, at least one complexing agent selected from the group consisting of phthalic acid, succinic acid, salicylic acid and glycolic acid may be used.

Further, dimethylamine borane (DMA
B), trimethylamine borane (TMAB), tartaric acid,
At least one reducing agent selected from the group consisting of oxalic acid and gluconolactone may be added to the solution .

As the RED solution which can be used in the present invention, it is desirable to dissolve silver chloride and use it in combination with a reducing agent to prepare a system having a high reversibility. However, as such a RED solution, ascorbic acid has been used as a reducing agent, while dimethyl sulfoxide (DM) has been used as a solvent.
It has been studied to use only a non-aqueous solvent consisting of SO), but such a RED solution has a problem in low-temperature characteristics because DMSO itself has a freezing point at 18 ° C. It is easy to occur. Therefore, the solvent that can be used is limited.

Therefore, the present inventor, especially in a reversible system in which silver is deposited and dissolved from a silver complex salt on a transparent electrode in a non-aqueous system, prevents deterioration of low temperature characteristics and has a low freezing point that can withstand use at low temperature. Using a solvent, a reducing agent applicable to this was investigated.

From this result, as a reducing agent applicable to a solvent having a low freezing point, which has not been studied at all,
Any of the above-mentioned reducing agents such as DMAB and TMAB can be sufficiently used even if a solvent having a low freezing point is used to improve low temperature characteristics, and is more easily dissolved in such a solvent than ascorbic acid. is there. That is, since it becomes an electrolytic solution that solidifies at a lower temperature than the DMSO-based electrolytic solution, this electrolytic solution does not freeze even in use in cold regions.

In this case, the reducing agent is preferably added in the range of 1/150 times to 1 times the concentration of silver chloride.

As the solvent having a low freezing point, dimethylformamide (DMF) and diethylformamide (D
EF), N, N-dimethylacetamide (DMAA),
N-methylpropionamide (MPA), N-methylpyrrolidone (MP), propylene carbonate (P
C), acetonitrile (AN), 2-methoxyethanol (MEOH) and 2-ethoxyethanol (EEO).
A solvent (non-aqueous solvent) consisting of at least one selected from the group consisting of H) is desirable.

All of these non-aqueous solvents have a lower freezing point than DMSO (especially DMF, DEF, MEOH, E).
With EOH, it is as low as 70 ° C. or higher), and the RED liquid prepared by dissolving silver chloride has excellent low-temperature characteristics, and is sufficiently durable for use in cold regions, for example.

In order to increase the conductivity of the RED liquid,
The supporting salt is preferably added to the solution in a concentration of 1/2 to 5 times that of silver iodide.

A supporting salt (supporting electrolyte) capable of supplying chlorine in order to increase the conductivity of the RED solution and dissolve silver chloride.
Is preferably added to complex silver chloride. Examples thereof include sodium chloride, potassium chloride, calcium chloride and quaternary ammonium chloride.

The supporting salt is preferably added in a concentration range of 1/2 to 5 times that of silver chloride.

Further, for example, a silver deposition potential is applied to a transparent electrode (particularly an ITO electrode: one obtained by doping indium oxide with tin) which serves as a working electrode for depositing or dissolving silver for operating as a filter material. By a chemical or physical surface treatment for reducing
It is possible to lower the deposition potential of silver on the transparent electrode, facilitate the deposition and dissolution of silver, and reduce the electrical damage to the transparent electrode and the solution itself.

As a chemical surface treatment method in this case, it is preferable to perform surface treatment (chemical plating) of the ITO electrode with palladium or the like by a two-liquid treatment method of a tin solution and a palladium solution. That is, as the surface activation treatment of the ITO electrode with palladium, the activity on the surface of the ITO electrode is enhanced by depositing palladium nuclei on the ITO single substrate.

In this case, as the tin solution, 0.10 to 1.0 g of tin chloride (SnCl 2 ) is added to 0.010 to 0.10% HCl.
What was dissolved in 1 L, the palladium solution, palladium chloride (PdCl 2 ) 0.10 ~ 1.0 g 0.010 ~ 0.10%
A solution dissolved in 1 L of HCl can be used.

As a physical surface treatment method, a method of vapor-depositing a metal, which is more precious than silver, on the ITO electrode can be adopted.

In the optical device of the present invention, the solution has no absorption in the visible light region in the decolored state, and the coloring and decoloring substrate electrodes are in the visible light region in order to operate as an optical device. It is desirable to use an ITO electrode that does not absorb light.

When the colored and decolored states are repeated using the RED solution, the solution system cannot be stirred because the device is minute. Therefore, it is preferable to drive by current control which makes it easy to quantify the electrochemical deposition dissolution of silver.

As a coloring-decoloring driving method by such current control, in order to increase the coloring-decoloring speed (silver deposition, dissolution rate), a current that changes from a high current value to a low current value in a rectangular shape. It is preferable to use the driving method according to. Alternatively, in order to reduce damage to the substrate due to repeated deposition and dissolution of silver, it is also possible to use a driving method using a current that changes into a rectangular shape from a low current value to a high current value. When the constant current drive is used, it is desirable to control with a limiter or the like at the potential generated by the side reaction product (to maintain the balance of the system electrolyte).

In the present invention, numeral or character display, or X-
The present invention can be widely applied to an ECD capable of performing Y matrix display and the like, and an optical device such as an optical filter capable of controlling the light transmittance in the visible light range (wavelength: 400 to 700 nm).

The present invention also provides, as an electrolytic solution usable in such an optical device, an electrolytic solution comprising a solution of the above-described silver chloride dissolved in a solvent.

This electrolytic solution consists of a solution of silver chloride dissolved in water or a non-aqueous solvent, preferably at a concentration of 0.03 to 2.0 mol / L, and becomes a colored or decolored state by the precipitation or dissolution of silver. The same brightening agent, complexing agent, reducing agent, supporting salt, and solvent as described above can be contained in predetermined amounts.

[0043]

EXAMPLES Examples of the present invention will be described below.

First, referring to FIGS. 6 and 7, an optical filter 10 according to an embodiment of the present invention is schematically shown.

According to the optical filter 10 of the present example, a pair of transparent substrates (eg, glass plates) 4 and 5 forming a cell are arranged as a display window with a constant gap, and at least the inner surface of each substrate is at least Working electrodes (for example, ITO electrodes) 2 and 3, one of which serves as a coloring electrode or an erasing electrode, are provided facing each other.

The counter electrode 6 is also provided on the entire peripheries of the substrates 4 and 5 also as a spacer, and for example, a silver plate is used. Although not shown, for example, a silver wire is provided as the reference electrode.

A RED liquid 1 in which silver chloride (complex salt) as a RED material is dissolved in a non-aqueous solvent is enclosed between the counter electrodes 2-3 in contact with these electrodes. One of the counter electrodes 2 and 3 is used as an anode and the other is used as a cathode. By applying a DC drive voltage between them for a predetermined time, silver (complex) salt is formed.

[Chemical 2] Then, a redox reaction is generated on the cathode side, and a transition from transparent to colored state is caused by Ag precipitates.

By thus depositing Ag on the electrode, a specific color due to the Ag deposit can be observed from the display window, and the filter material is obtained. Then, the filter action by this coloring, that is, the transmittance of visible light (or the shade of coloring) changes with the magnitude of the voltage or the application time thereof, and by controlling this, it is possible to function as a transmittance variable filter. .

This optical filter 10 includes counter electrodes 2 and 3
May be provided almost all over the cell, but in reality,
For example, it can be configured as shown in FIGS.

That is, the IT provided on the transparent substrates 4 and 5
The counter electrodes of O are divided into central portions 2a and 3a and ring-shaped electrodes 2b, 3b, 2c, 3c, 2d, 3d, 2e, and 3e, which are concentrically arranged around the central portions 2a and 3a. ing. Around the outermost counter electrodes 2e and 3e, silver counter electrodes 6A and 6B for potential compensation are provided.

Each of these electrodes 2a, 3a, 2b, 3b,
2c, 3c, 2d, 3d, 2e, 3e, 6A and 6B are drive power sources 8A, 8B, 8C, 8D, 8E and 8 respectively.
Wiring 9A, 9B, 9C, 9 made of chrome thin wire or the like for F
They are connected by D, 9E and 9F.

The transparent substrate 4-5 is arranged at a predetermined interval by the spacer 7 (this also serves as the counter electrode 6 in FIG. 6), and the RED liquid 1 is enclosed within the interval.

Since the redox reaction (that is, the concentration) of the RED liquid 1 is controlled according to the magnitude of the applied voltage, the above described divided electrodes 2a-3a, 2b-3b.
Between the divided electrodes on the cathode by the voltage (V 1 , V 2 , V 3 , V 4 , and V 5 , respectively) applied between 2c-3c, 2d-3d, and 2e-3e. RED
The amount of silver deposited from the liquid can be changed (note that
The voltage V 6 for potential compensation is also applied between the counter electrodes 6A and 6B).

Therefore, if all the voltages are made equal (V 1 = V 2 = V 3 = V 4 = V 5 ), the RED liquid 1 can be colored uniformly over the entire area and the voltage can be made uniform. It is possible to uniformly change the degree of concentration according to the above.

If the voltage applied to each electrode is made different, for example, V 1 <V 2 <V 3 <V 4 <V 5 , the coloring density increases from the center to the periphery (in other words If the transmittance is small). This is a CCD such as a TV camera
C, which is useful as an optical diaphragm for (charge coupled device),
It is possible to sufficiently cope with the improvement in the integration degree of CDs. If the applied voltage is set in the reverse order to the above, the transmittance increases from the central portion to the periphery.

As described above, the gradation or gradation can be controlled in various patterns by the voltage applied to the divided electrodes,
It is useful as an optical filter, and the range of its usage is widened.

As described above, according to this embodiment, based on an idea completely different from the conventional EC material, the RED material made of silver chloride is used as the filter material for adjusting the light quantity of the optical device. By controlling the drive of the counter electrode (particularly, the applied voltage), it is possible to change the shade of the RED material at the time of coloring, and by utilizing this feature, it becomes possible to give gradation to the optical filter. Therefore, by using the RED material, it is possible to provide a filter that is fine and consumes less power, and has a capacity higher than that of the conventional variable ND filter that has been mechanically operated as a light amount adjustment device.

Further, since the RED liquid in which silver chloride is dissolved in a non-aqueous solvent (for example, DMF) is used as the RED material, the freezing point of the non-aqueous solvent is sufficiently low and the low temperature characteristics are excellent. This non-aqueous solvent sufficiently dissolves the reducing agent (for example, DMAB) added to the RED material together with silver chloride.

Next, this embodiment will be described in more detail with reference to a specific example. In the following specific examples, the optical filter configured as in the examples shown in FIGS. 6 and 7 was used.

Example 1 (Silver chloride (AgCl) according to the invention)
Precipitation and dissolution of silver chloride) Silver chloride was used in order to investigate a system of reversible silver precipitation and dissolution. In this specific example, the purpose was to investigate the change in transmittance during precipitation and dissolution of silver.

As the solvent, dimethylformamide (D
MF) was used. The silver chloride concentration was set to 0.05 mol / L, and 0.2 mol / L of quaternary ammonium salt [Tetra-n-butyl ammonium chloride] was dissolved for the purpose of dissolving it and increasing conductivity. Let Furthermore, as a brightener, thiourea [SC (N
H 2 ) 2 ] was dissolved at 1.0 g / L to prepare a RED solution, which was placed in the filter.

The change in transmittance was traced under the following potential conditions. Here, an ITO electrode was used as the working electrode, a silver wire was used as the reference electrode, and a silver plate was used as the counter electrode.

FIGS. 1 and 2 show changes in the spectral characteristics measured using the RED solution (electrolyte solution) described above. FIG. 1 is a spectral characteristic showing a decrease in transmittance when silver is deposited, and FIG. 2 is a spectral characteristic showing a recovery of transmittance when silver is dissolved.

The potential sweep (cyclic voltammetry: CV) method is used for the measurement, and the potential of silver is -2000.
Swept between mV and +2500 mV. The starting point of the sweep was at the same potential as the silver potential, and the measurement was performed from the reducing side at a sweep rate of 50 mV / sec. The data of spectral characteristics are taken in every 200 mV.

From the results shown in FIGS. 1 and 2, by using the electrolytic solution according to the present invention, it was possible to obtain a good change in the transmittance without using the reducing agent. Further, it can be seen that the spectral characteristics of the deposited silver film in this system have uniform absorption in the visible light region, and the transmittance similarly rises and falls both during precipitation and during dissolution. Even if the amount of silver chloride used is as low as 50 mM, a sufficient change in transmittance can be obtained.

Example 2 (Precipitation and dissolution of silver chloride based on the present invention) In Example 1, dimethylamine borane (DMAB) was further added and dissolved as a reducing agent at 500 mM / L in order to improve reversibility. Then, a RED solution was prepared, placed in a filter, and the change in transmittance was measured in the same manner as in Example 1. The results are shown in FIGS. 3 and 4.

From these results, it is possible to obtain a better change in transmittance by adding a reducing agent to the electrolytic solution according to the present invention, and the spectral characteristics of the deposited silver film show a uniform absorption in the visible light region. It can be seen that the transmittance rises and falls in both precipitation and dissolution.

Example 3 (Precipitation of silver iodide according to a comparative example) As a comparative example, a change in the transmittance of a silver iodide-based precipitated silver film having no uniform absorption in the visible light region was determined, and the results are shown in FIG. 5 shows.

In this comparative example, DMSO was used as a solvent, AgI 50 mM / L, NaI (supporting salt) 500 mM / L, ascorbic acid (reducing agent) 100 mM / L, tetrabutyl ammonium perchlorate (Tetra-n-butyl ammonium). perchlo
rate) (supporting salt) A solution in which 300 mM / L was dissolved was used as an electrolytic solution.

Here, although constant current driving was used for the deposition of the silver film, the absorption of the deposited silver film by a driving method such as constant potential or constant current is not so different. From the results shown in FIG. 5, the deposited silver film obtained with the silver iodide system had an absorption at a wavelength of 500 to 600 nm, so that the transmittance was not uniform and the reflection color was dark purple.

From the above results, comparing the silver chloride system according to the present invention with the silver iodide system according to the comparative example, the deposited silver film obtained with the silver chloride system shows a visible light region (λ = 400 to 700 nm). Since it has uniform absorption in, there is no problem that the image information is deteriorated by the color peculiar to the silver film (filter) unlike the system using the silver iodide system. Another advantage is that chlorine gas has a higher standard oxidation-reduction potential (hydrogen standard) than iodine gas, so using a silver chloride system greatly contributes to the reduction of side reaction gas generated during silver dissolution. .

From the above reasons, it is clear that the silver chloride type is superior to the silver iodide type in the light control element using the silver film electrochemically deposited and dissolved.

Example 4 (Low Temperature Storage Test of Non-Aqueous Solvent) The freezing points of various non-aqueous solvents are summarized in Table 1 below.

[0074]

Then, a solvent low temperature storage test was conducted in the same manner as described above using each solvent, and the results shown in Table 2 below were obtained.

[0076]

Thus, the non-aqueous solvent other than DMSO is
Even if it is stored at 40 ° C, it does not solidify and can be practically used in the liquid state, but in the case of DMSO, it solidifies (freezes) completely and becomes unusable.

Although the embodiments of the present invention have been described above, the above-mentioned embodiments can be further modified based on the technical idea of the present invention.

For example, the types of RED materials and RE
The combination and concentration of the D liquid components may be variously changed.

Further, the structure of the optical filter including the ITO electrode pattern, the material of each component, and the driving method are not limited to those described above. For example, as a filter structure, the electrode pattern as shown in FIG. 8 may be variously changed into a stripe shape, a lattice shape, or the like, or different RED liquid cells may be divided and juxtaposed for each divided electrode. You can also In this case, RED liquid and conventional EC
It is also possible to combine liquids.

The optical filter according to the present invention can be combined with other known filter materials (for example, organic electrochromic material, liquid crystal, electroluminescent material). Further, the optical filter according to the present invention can be widely applied not only for an optical diaphragm of a CCD, but also for various optical systems, and also for adjusting a light amount of an electrophotographic copying machine, an optical communication device and the like.

[0082]

The present invention, as described above, is a conventional EC.
Based on an idea completely different from the material, silver chloride and even thio
A RED liquid containing a brightening agent such as urea and / or a complexing agent such as phthalic acid is used for an optical device such as a filter material for adjusting the light amount of an optical device, and silver is controlled by driving the counter electrode (especially applied voltage). Forms a reversible system that deposits and dissolves on the electrode. Therefore, it is possible to provide a non-emission type optical device suitable for the visible light region with low power consumption by using the RED material.

In addition, since the deposited silver film obtained by the electrolytic solution made of silver chloride has uniform absorption in the visible light region (λ = 400 to 700 nm), the silver film like the silver iodide system is used. There is no problem that the image information is deteriorated by the color unique to the film (filter). Further, since chlorine gas has a higher standard oxidation-reduction potential (based on hydrogen) than iodine gas, the use of an electrolytic solution made of silver chloride greatly contributes to the reduction of side reaction gas generated when silver is dissolved.

[Brief description of drawings]

FIG. 1 is a spectrum diagram showing a change in transmittance according to an applied voltage when coloring an optical filter according to the present invention.

FIG. 2 is a spectrum diagram showing a similar change in transmittance when the optical filter is decolored.

FIG. 3 is a spectrum diagram showing a change in transmittance according to an applied voltage when coloring another optical filter according to the present invention.

FIG. 4 is a spectrum diagram showing a similar change in transmittance when the optical filter is decolored.

FIG. 5 is a spectrum diagram showing a change in transmittance due to a drive current when a silver iodide-based optical filter according to a comparative example is colored.

FIG. 6 is a schematic sectional view of an optical filter according to the present invention.

FIG. 7 is a conceptual diagram of the optical filter.

FIG. 8 is an ITO electrode pattern diagram of a specific example of the optical filter.

FIG. 9 is a schematic sectional view of the optical filter.

[Explanation of symbols]

1 ... RED solution (solution containing silver salt) 2, 2a to 2e, 3, 3a to 3e ... ITO electrode 4, 5 ... Display window (transparent substrate) 6, 6A, 6B ... Counter electrode 7 ... Spacer 8A-8F ... Power supply 10: Optical filter

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichiro Hikuma 6-735 Kitashinagawa, Shinagawa-ku, Tokyo, Sony Corporation (56) Reference JP-A-8-136956 (JP, A) JP-A 8-136957 (JP, A) JP-A-7-5497 (JP, A) JP-A-54-137488 (JP, A) US Patent 4240717 (US, A) J. Duchen et al. , ELECTROLYTIC DISPL AY, IEEE Transactions on Electron Devices, vol. ED-26, No. 8, pp. 1243-1247 I.D. Camlidel et al. , AN EXPERIMENTAL DISPLAY STRUCTURE BASED ON REVERSIB LE ELECTRODEPOSITION, Appl. Phys. Let t. , Vol. 33, no. 9, pp. 793-794 (58) Fields investigated (Int. Cl. 7 , DB name) G02F 1/15-1/19 G09F 9/30-9/46

Claims (15)

(57) [Claims]
1. A solution prepared by dissolving silver chloride in a solvent is disposed between the opposed electrodes, these configured optical device odor to cause silver deposition or dissolution by the drive control of the electrodes
Te, thiourea, allyl thiourea, mercapto benzoimidazol
At least one selected from Lumpur and coumarin or Ranaru group
From one brightener and phthalic acid, succinic acid, salicylic acid and glycolic acid
At least one complexing agent selected from the group consisting of
And one of them is added to the solution.
Optical device .
2. The optical device according to claim 1, wherein a solution in which silver chloride is dissolved in water or a non-aqueous solvent is arranged, and coloring or decoloring is caused by precipitation or dissolution of silver.
3. The silver chloride concentration is 0.03 to 2.0 mol.
The optical device according to claim 1, wherein a solution of / L is used.
4. At least one reducing agent selected from the group consisting of dimethylamine borane, trimethylamine borane, tartaric acid, oxalic acid and gluconolactone ,
It is added to the liquid, the optical device according to claim 1.
5. The non-aqueous solvent is dimethylformamide, diethylformamide, N, N-dimethylacetamide,
The optical device according to claim 2, comprising at least one selected from the group consisting of N-methylpropionic acid amide, N-methylpyrrolidone, propylene carbonate, acetonitrile, 2-ethoxyethanol, and 2-methoxyethanol.
6. The optical device according to claim 1, wherein a supporting salt capable of supplying chlorine is added to dissolve silver chloride, and silver chloride is complexed.
7. The optical device according to claim 6 , wherein the supporting salt is added in a concentration range of 1/2 to 5 times that of silver chloride.
8. A transparent electrode , which serves as a working electrode for depositing or dissolving silver, has a table for reducing the deposition potential of silver.
Surface treatment is facilities, optical device as claimed in claim 1.
9. An electrolytic solution comprising a solution of silver chloride dissolved in a solvent, wherein thiourea, allylthiourea and mercaptobenzimidazo are used.
At least one selected from Lumpur and coumarin or Ranaru group
From one brightener and phthalic acid, succinic acid, salicylic acid and glycolic acid
At least one complexing agent selected from the group consisting of
And one of them is added to the solution.
Electrolyte .
10. The electrolytic solution according to claim 9, which is composed of a solution of silver chloride dissolved in water or a non-aqueous solvent, and is brought into a colored or decolored state by precipitation or dissolution of silver.
11. The concentration of silver chloride is 0.03 to 2.0 mo.
The electrolytic solution according to claim 9 , which is 1 / L.
12. The electrolytic solution according to claim 9 , wherein at least one reducing agent selected from the group consisting of dimethylamine borane, trimethylamine borane, tartaric acid, oxalic acid and gluconolactone is used.
13. The non-aqueous solvent is dimethylformamide,
Diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, propylene carbonate, acetonitrile, 2-
The electrolytic solution according to claim 10 , comprising at least one selected from the group consisting of ethoxyethanol and 2-methoxyethanol.
14. The electrolytic solution according to claim 9 , wherein a supporting salt capable of supplying chlorine is added to dissolve silver chloride, and silver chloride is complexed.
15. The electrolytic solution according to claim 14 , wherein the supporting salt is added in the range of 1/2 to 5 times the concentration of silver chloride.
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EP19950117797 EP0712025B1 (en) 1994-11-11 1995-11-10 Optical apparatus
DE1995630900 DE69530900D1 (en) 1994-11-11 1995-11-10 Optical device
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