JPH11248923A - Manufacturing device for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the device for manufacturing a color filter which is applicable sufficiently to an active and a passive type color liquid crystal panel and free from defects and stains. SOLUTION: In a process for circulating an electrolyte 18 in an electrolytic processor, the electrolyte intake and outlet sides in a reservoir tank 12 are partitioned by more than one couple of alternate upper and lower partition plates 15, the part between the lower and upper partition plates is covered with meshes 16, and the intake-side pipe opening position of the reservoir tank 12 is formed in the liquid while the reservoir outlet-side pipe opening position is formed on the bottom surface of the reservoir tank. Further, the pore diameter of the filter 14 is made larger than the size of particles dispersed in the electrolyte in use and smaller than 100 μm and the filter is formed right in front of an electrolyte tank 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for manufacturing color filters used for active and passive color panels used in displays for liquid crystal televisions and personal computers.

[0002]

2. Description of the Related Art After colloidally dispersing pigment particles insoluble or hardly soluble in water in an aqueous micelle solution of a surfactant having redox reactivity, a predetermined pattern shape used as an anode is obtained by electrolyzing the aqueous micelle solution. The present inventors have already filed a patent application for a method of manufacturing a color filter using a method of forming a pigment film on a transparent electrode having a color filter. In addition, an application has been filed for a method for producing a conductive micelle color filter in which hydrophobized conductive particles are codeposited on the color filter (Japanese Patent Application Laid-Open No. Hei 2-267298).
No.). In addition, an application has been filed for a method for forming an inorganic film by subjecting a substance having a hydrophilic inorganic particle surface to a hydrophobic treatment. In addition, an application has been filed regarding the purity of the pigment used. Thus, we have invented a method of manufacturing a conductive micelle color filter. Here, regarding the film forming apparatus, the electrolytic tank 21 and the reserve tank 22, as shown in FIG.
Pump 24 and filter 2 for circulating electrolyte 23
5. The piping 26 and the upper part of the electrolytic cell are formed by an overflow structure 27. This configuration is common in a cleaning apparatus, a plating apparatus, and the like. Here, the filter can be formed at any position where a differential pressure is generated at the inlet and the outlet of the filter. For example, it is common to form it immediately before or immediately after the pump formation position. The electrolytic cell 21 is filled with an electrolytic solution, a substrate 28 having a transparent electrode is used as an anode, and a counter electrode 29 is inserted as a cathode. Here, in the electrolytic cell, the electrolytic solution in the electrolytic cell is circulated during the film formation and before or after the film formation. This aims to stabilize the in-plane thin film thickness distribution and the film forming speed at the time of forming the thin film by circulating the electrolytic solution. The present inventors have already applied for a patent for a configuration for suppressing foaming of the electrolytic solution in the reserve tank when circulating the electrolytic solution.

[0003]

However, the above-mentioned prior art has the following problems.

When a micelle aqueous solution is poured into an electrolytic cell and circulated after preparing a micelle colloid solution using the conventional technique, fine bubbles having a diameter of 1 mm to 2 mm may be present in the aqueous micelle solution in the electrolytic cell. found. This is a structure in which the overflowed micelle aqueous solution falls into the reserve tank and flows into the reservoir tank.At this time, the entrained air exists in the liquid as air bubbles, or already exists in the reserve tank, the pump, the filter, and the piping connecting them. It is considered to be air bubbles or air mixed in from a connection portion such as a pipe. Further, it was found that these minute bubbles themselves adhered to the substrate. These are the following fatal defects in the case of a liquid crystal panel.

[0005] 1) Since the film-deposited portion is different in the bubble-attached portion, a point defect occurs when the panel is turned on.

2) Bubbles adhering when the substrate is taken out of the electrolytic cell become bubbles and flow down, and when the panel is turned on, traces of the flow of bubbles become spot defects.

That is, although the conductive color filter layer can be formed by the conventional method, generation of minute bubbles is remarkable, and there is no means for producing a color filter free from defects and spots.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide an apparatus for manufacturing a color filter which can be applied to active and passive type color liquid crystal panels and has no defects or spots. It is in.

[0009]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems, and comprises the following means.

The apparatus for manufacturing a color filter according to the present invention is a wet type film forming apparatus using an electrolytic solution containing a surfactant, and its structure comprises an electrolytic cell having an overflow structure, a reserve tank, a pump, and a filter. A) a structure having a circulation function, wherein a) the electrolyte inlet side and the electrolyte side inside the reserve tank are separated by at least one or more sets of vertically alternated partition plates; b) the lower partition plate and The space between the upper partition plate and the upper partition plate is covered with at least one or more meshes. C) The pipe position connecting the overflow tank and the reserve tank is at least in the liquid at the reserve tank side pipe opening position. d) the outlet position of the reservoir tank is on the bottom of the reserve tank;
It is characterized by the following.

That is, as shown in a), when there is one or more sets of vertically alternated partition plates, when the electrolytic solution moves up and down between the partition plates toward the outlet, bubbles generated at the inlet of the reserve tank are formed on the lower side. Therefore, only the electrolytic solution can move between the next partition plates. Depending on the flow rate of the liquid, air bubbles may not be removed by one set of the upper and lower partition plates, but the number of the upper and lower partition plates may be selected according to the flow rate range to be applied. Further, the overlap between the partition plates is preferably at least 20 cm so that air bubbles do not easily move between the next partition plates. Further, by forming a mesh as shown in b), it is possible to make it difficult for the electrolyte solution moved to the upper side to entrap bubbles when moving to the lower side, and to make it harder to pass bubbles already existing in the electrolyte solution. It is. However, when the electrolyte is pumped by a pump or the like, the electrolyte can pass through a filter having a mesh of 1.0 μm or less. The present inventors have found that the use of a mesh having a gap of about 1 mm to 2 mm is favorable because it is difficult to pass through. Further, due to the structure of c), since the pipe port is in the electrolyte, the stirring effect of the electrolyte is reduced, and bubbles are hardly generated. It is preferable that the piping port on the reserve tank side is at least 5 cm below the liquid level. Furthermore, by the structure of d),
Only the electrolyte can flow out to the pump without involving air.

Further, in the film forming apparatus, e) the filter is formed by a filter in which the pore diameter of the filter is larger than the particle diameter dispersed in the electrolytic solution to be used and smaller than 100 μm, and f) the filter is at least the electrolytic cell. Is formed immediately before.

That is, by using the filter having the pore diameter shown in e), there is an effect that fine bubbles existing in the electrolyte passing through the filter are trapped and removed from the electrolyte. Bubble that causes spots and defects has a diameter of 1
The present inventors have found that these bubbles pass through a filter having a pore diameter of from 100 mm to 2 mm. The filter is for removing air bubbles, and any filter having the function of the pore diameter can be used. However, in the case of a paper-type filter, for example, filter paper or the like is formed by laminating at least two or three paper-type filters or a cartridge-type or disposable-type filter portion because bubbles may pass through the filter pores. It is preferable to use a filter. If the pore diameter is smaller than the particle diameter in the electrolytic solution, bubbles can be trapped, but the dispersed particles in the electrolytic solution are also removed at the same time. The problem of clogging in time arises. The diameter of the dispersed particles varies depending on the electrolytic solution used, but generally ranges from 200 nm to 50 nm.
In order to use a dispersion having a particle diameter of 0 nm, it is desirable to use a filter having a particle diameter removing ability larger than these particle diameters.

Further, by forming the filter immediately before the electrolytic cell of f), the effect of removing air bubbles existing in the pump, the filter, and the pipes connecting them, or the air mixed in from the connection portion of the pipe or the like can be obtained. Have.
Thereby, only the electrolytic solution is circulated to the electrolytic cell.

Further, water-soluble or poorly water-soluble pigment particles and transparent conductive particles having a hydrophobic surface are added to the electrolyte solution.
It is characterized by using a micelle colloid aqueous solution of a pigment in which the pigment particles containing a surfactant having a redox reaction and a supporting salt as basic components and the transparent conductive particles are surrounded by the surfactant.

The present inventors have invented the use of the reserve tank and the filter having the above structures, and have succeeded in suppressing the entry of bubbles into the electrolytic cell and further suppressing the adhesion of bubbles to the substrate.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail using embodiments.

(Example 1) Red pigment particles (Disuanthraquinonyl Red: particle diameter 1000 Å) and yellow pigment particles (Disazo Yellow HR:
A red pigment colloid aqueous solution having the following composition was prepared by using ITO (Indium Tin Oxide) as the conductive particles and a particle diameter of 3000 Å. The pigment particles used were manufactured by Dainichi Seika.

18. Dianthraquinonyl Red 8.0 g / l Disazo Yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l (* surfactant) LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18. 0 g / l The above aqueous pigment colloid solution was dispersed in an ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected as a pigment micelle colloid aqueous solution.

FIG. 1 shows the structure of the electrolytic processing apparatus of the present invention in the first embodiment. Electrolysis tank 11, reserve tank 12, pump 13, filter 1 with overflow structure
4 has a circulation function. Here, one set of partition plates 15 was formed alternately between the inlet and outlet sides of the electrolyte inside the reserve tank. The overlap between the partitions is 20c
m, the electrolyte inlet side is formed 5 cm below the liquid level,
The electrolyte outlet side was formed on the bottom of the reserve tank. Further, the space between the lower partition plate and the upper partition plate was covered with a mesh 16 having a gap of 1 mm. Further, a filter 14 having a pore diameter of 80 μm was used, and was formed immediately before the electrolytic cell 11. Then, using the pump 13, the liquid flow rate is 8 to 10 L / mi.
The liquid was circulated for 2 minutes at n. Thereafter, the generation of bubbles in the electrolytic cell was compared. Table 1 shows the characteristic data.

[0021]

[Table 1]

As can be seen from Table 1, when the electrolyte is circulated using the conditions of the present invention, the generation of bubbles in the reserve tank is suppressed, and the bubbles existing in the electrolyte are trapped in the filter portion. No bubbles of about 1 to 2 mm were generated in the electrolytic cell.

Further, a glass substrate (30 × 4) having the above-mentioned electrode pattern as an anode was placed in the aqueous micelle solution.
0 cm), a substrate obtained by plating platinum on a titanium plate was immersed on the cathode side, and electrolysis was performed at a constant potential of +0.6 V for 15 minutes. As a result, a red pigment film was formed on the ITO electrode. This substrate was washed with water and baked at 180 ° C. for 30 minutes. When the red pigment film thickness was measured, there was no difference in film thickness between the electrode peripheral portion and the central portion, and the film thickness was uniform on the substrate surface and was 1.05 μm. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data. From Table 1,
When a thin film was formed using the electrolyte circulated under the conditions of the present invention, a uniform film surface without stains was obtained. Therefore,
Good results were obtained under the conditions of the present invention.

(Example 2) Blue pigment particles (phthalocyanine blue R: particle diameter 2000 Å), purple pigment particles (dioxane violet: particle diameter 600 Å) and ITO as conductive particles
Was used to prepare a blue pigment colloid aqueous solution having the following composition. The pigment particles used were manufactured by Dainichi Seika. Phthalocyanine blue R 5.2 g / l Dioxane violet 0.9 g / l Ferrocenyl PEG 3.7 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l 9
Ultrasonic dispersion was performed for 0 minutes. Here, the inside of the reserve tank was formed immediately before the electrolytic cell 11 using the same structure as in Example 1 and using a filter 14 having a pore diameter of 1 μm. Then, using the pump 13, the liquid flow rate is 8 to 10 L / mi.
When the electrolyte was circulated using the conditions of the present invention, as shown in Table 1, the generation of bubbles was suppressed when the electrolyte was circulated using the conditions of the present invention. In order to capture air bubbles existing in the electrolytic solution at the filter portion, the pressure in the electrolytic cell is reduced from 1 mm to 2 mm.
There was no generation of bubbles of about mm. Furthermore, using this micelle aqueous solution, a blue pigment film was formed on an ITO electrode of a glass substrate (30 × 40 cm) having the electrode pattern in the same manner as in Example 1, washed with water, and then at 180 ° C. for 30 minutes. Fired. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data. When a thin film was formed using the electrolyte circulated under the conditions of the present invention, a uniform film surface without stains was obtained. Therefore, good results were obtained under the conditions of the present invention.

(Comparative Example 1) Pigment similar to that of Example 1, IT
Using O, using the micelle aqueous solution prepared under the same conditions,
No partition plate and no mesh were formed between the electrolyte inlet and the outlet inside the reserve tank, the liquid inlet was formed above the liquid surface, and the electrolyte outlet was formed at the liquid interface. Further, the filter was formed immediately before the electrolytic cell 11 using a filter 14 having a pore diameter of 100 μm. The liquid was circulated at a liquid flow rate of 8 to 10 L / min for 2 minutes using the pump 13, and the state of foam generation was compared. As can be seen from Table 1, when the electrolyte was circulated using the above conditions, the reserve was A large amount of air bubbles were generated in the tank portion, and air bubbles existing in the electrolytic solution were not caught in the filter portion.
Many bubbles of about 2 mm to 2 mm were generated. Further, using this micelle aqueous solution, the same method as in Example 1 was applied to a glass substrate (30 × 40 cm) having the electrode pattern.
A red pigment film was formed on the TO electrode, washed with water, and baked at 180 ° C. for 30 minutes. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data. When a thin film is formed using the electrolyte circulated under the above conditions, when the formed substrate is taken out of the electrolytic bath, it is confirmed that bubbles adhere to the substrate surface as bubbles and flow down, and this portion is stained as a film surface. Was confirmed within. In addition, a large amount of points to which bubbles adhered were generated as point defects. In the case of a liquid crystal panel, a portion where air bubbles adhere becomes a point defect when the panel is turned on.

(Comparative Example 2) Pigment similar to that of Example 2, IT
Using O, a micelle aqueous solution prepared under the same conditions was used.
Here, a partition plate and a mesh were not formed between the inlet side and the outlet side of the electrolyte inside the reserve tank, the liquid inlet side was formed above the liquid surface, and the electrolyte outlet side was formed at the liquid interface.
Further, a filter having a pore diameter of 80 μm was used, and the filter 14 was formed between the reserve tank 12 and the pump 13. Then, using the pump 13, the liquid flow rate is 8 to 10L.
The liquid was circulated at a rate of / min for 2 minutes, and the state of generation of bubbles was compared. As can be seen from Table 1, when the electrolyte was circulated using the above conditions, bubbles existing in the electrolyte in the filter portion were Although it is caught, since there are more air bubbles from the filter part to the electrolytic cell,
Some bubbles of about 1 mm to 2 mm were generated in the electrolytic cell. Further, using this micelle aqueous solution, a glass substrate (30
A blue pigment film was formed on an ITO electrode of (× 40 cm), washed with water, and baked at 180 ° C. for 30 minutes. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data.
Shown in When a thin film is formed using the electrolyte circulated under the above conditions, when the formed substrate is taken out of the electrolytic bath, it is confirmed that bubbles adhere to the substrate surface as bubbles and flow down, and this portion is stained as a film surface. Was confirmed within. Further, a portion to which air bubbles adhered slightly occurred as a point defect. In the case of a liquid crystal panel, a portion where air bubbles adhere becomes a point defect when the panel is turned on.

Comparative Example 3 Pigment similar to that of Example 1, IT
Using O, a micelle aqueous solution prepared under the same conditions was used.
Here, the inside of the reserve tank had the same structure as that of Example 1, and a filter having a pore diameter of 0.25 μm was used. The filter 14 was formed immediately before the electrolytic cell 11. Then, using the pump 13, the liquid flow rate of 8 to 10 L / min
After performing liquid circulation for a minute and comparing the situation of foam generation,
As can be seen from Table 1, the filter clogged immediately after the circulation started and could not be circulated. This catches bubbles existing in the electrolyte in the filter part,
At the same time, the dispersed particles in the electrolytic solution are also removed. The dispersed particle diameter of this electrolyte was measured to be 350 nm on average.

(Comparative Example 4) Pigment, IT similar to that of Example 1
Using O, a micelle aqueous solution prepared under the same conditions was used.
Here, only one partition plate 15 was formed between the electrolyte inlet and the outlet inside the reserve tank. The length of the partition plate is 20 cm, and the electrolyte inlet side is 5c from the liquid level.
m, and the electrolyte outlet side was formed on the bottom of the reserve tank. Further, the space between the lower partition plate and the upper partition plate was covered with a mesh 16 having a gap of 1 mm. Further, a filter having a pore diameter of 100 μm was used.
4 was formed immediately before the electrolytic cell 11. Then, using the pump 13, the liquid was circulated at a liquid flow rate of 8 to 10 L / min for 2 minutes, and the state of generation of bubbles was compared. As can be seen from Table 1, when the electrolyte was circulated using the above conditions, Air bubbles generated in the reserve tank cannot be completely removed in the reserve tank, and air bubbles existing in the electrolyte cannot be caught in the filter part.
Some bubbles of about mm were generated. Further, using this micelle aqueous solution, a red pigment film was formed on an ITO electrode of a glass substrate (30 × 40 cm) having the electrode pattern in the same manner as in Example 1, washed with water, and then at 180 ° C. for 30 minutes. Fired. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data. When a thin film is formed using the electrolyte circulated under the above conditions, when the formed substrate is taken out of the electrolytic bath, it is confirmed that bubbles adhere to the substrate surface as bubbles and flow down, and this portion is stained as a film surface. Was confirmed within. In addition, a large amount of points to which bubbles adhered were generated as point defects. In the case of a liquid crystal panel, a portion where air bubbles adhere becomes a point defect when the panel is turned on.

(Comparative Example 5) Pigment, IT similar to that of Example 1
Using O, a micelle aqueous solution prepared under the same conditions was used.
Here, the inside of the reserve tank had the same structure as that of Example 1, and a filter having a pore diameter of 100 μm was used. The filter 14 was formed immediately before the electrolytic cell 11. Then, using the pump 13, the liquid flow rate of 8 to 10 L / min
After performing liquid circulation for a minute and comparing the situation of foam generation,
As can be seen from Table 1, when the electrolyte is circulated using the above conditions, bubbles generated in the reserve tank are removed in the reserve tank, but bubbles present in the pump and the piping are caught in the filter. However, bubbles of about 1 mm to 2 mm were slightly generated in the electrolytic cell only at the beginning of circulation. Further, Example 1 was carried out using this micelle aqueous solution.
A red pigment film was formed on the ITO electrode of the glass substrate (30 × 40 cm) having the electrode pattern in the same manner as described above, washed with water and baked at 180 ° C. for 30 minutes. Further, the appearance was observed with a spotlight. Table 1 also shows the characteristic data. When a thin film is formed using the electrolyte circulated under the above conditions, it is confirmed that when only the substrate formed at the beginning of the circulation is taken out of the electrolytic bath, bubbles adhere to the substrate surface as bubbles and flow down. As in the film surface. In addition, a large amount of points to which bubbles adhered were generated as point defects. In the case of a liquid crystal panel, a portion where air bubbles adhere becomes a point defect when the panel is turned on.

Example 3 Two glass substrates of 30 cm square were prepared, ITO used as a transparent electrode was formed by sputtering, and a substrate for a color filter was formed by photolithography at 0.08 mm.
640 lines with width of 0.1 micron and 3 = 1920
The counter electrode was processed into a stripe pattern composed of 480 stripes at a width of 0.28 mm and a pitch of 0.3 mm in a direction perpendicular to the electrodes of the color filter. The pattern end was patterned into a predetermined shape so that a liquid crystal driving IC could be mounted in a later step. First, a black matrix layer is formed between the transparent electrodes on the color filter side (1920 patterns) by photolithography so as to have a width of 0.2 mm and a thickness of 0.8 to 1.0 μm. Then, using the pigment, composition and apparatus used in Example 1 and Example 2, a conductive dye layer was formed on a predetermined ITO transparent electrode in the order of B, G, and R by an electrochemical method.
0.7-0.9 μm, 0.8-1.0 μm, 0.8-
It was formed to have a thickness of 1.0 μm. Here, the electrochemical method means pigment particles (R: insoluble or hardly soluble in water).
Dianthraquinonyl red, G: phthalocyanine green, B: phthalocyanine blue, Y: disazo yellow, V: dioxazine violet) and hydrophobicized ITO particles, a surfactant (ferrocene PEG) charged by electrolysis and a supporting electrolyte (odor) A pigment and ITO particles are surrounded by a surfactant, and a micelle colloid aqueous solution of the ITO and the ITO is prepared. The micelles are destroyed by electrolysis (0.4 to 1.0 V), and the transparent electrode Pigment particles and ITO particles are deposited thereon to form a conductive pigment thin film.

After forming the three colors, baking is performed at 180 ° C. for 30 minutes. Thereafter, a flattening film of 0.2 μm is applied, and
By baking at 80 ° C. for 1 hour, a conductive micelle color filter having a maximum thickness difference of about 0.2 μm between the conductive dye layer and the black matrix layer was produced.

Using the color filter and the counter substrate, a predetermined liquid crystal panel forming process is performed to obtain the STN.
A color liquid crystal panel was manufactured. As a result of driving the panel at 1/240 Duty and measuring display unevenness and defects of the panel, no point defects or spots were found when the panel was turned on as shown in Table 2.

[0033]

[Table 2]

(Comparative Example 6) An STN color liquid crystal panel was manufactured under the same conditions as in Example 3 using the conductive micelle color filter side substrate manufactured using the pigment, composition and apparatus of Comparative Example 1 and Comparative Example 2. Driven under the same conditions. as a result,
As shown in Table 2, point defects and spots were observed when the panel was turned on.

[0035]

As described above, according to the present invention, the bubbles present in the electrolytic solution when the electrolytic solution is circulated are eliminated, and the stains and point defects generated in the thin film of the color filter produced thereby are eliminated. This makes it possible to manufacture a high-performance color filter free from spot defects and spots even in a simple matrix color panel using STN liquid crystal. Further, the present invention can be applied to a cleaning apparatus and a plating apparatus having the same structure.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a manufacturing apparatus of the present invention.

FIG. 2 is a view for explaining a conventional color filter manufacturing apparatus.

[Explanation of symbols]

 11 electrolytic treatment tank 12 reserve tank 13 circulation pump 14 filter 15 partition plate 16 mesh 17 pipe 18 electrolyte 18 electrolytic treatment tank 22 reserve tank 23 electrolyte 24 circulation pump 25 filter 26 pipe 27 overflow V-shaped groove 28 transparent substrate (color Filter substrate) 29 Counter electrode 30 DC power supply

Claims (3)

[Claims] 1. A wet film forming apparatus using an electrolytic solution containing a surfactant, the constitution of which has a circulation function comprising an electrolytic cell having an overflow structure, a reserve tank, a pump and a filter; The electrolyte inlet and outlet sides inside the reserve tank are separated by at least one or more sets of vertically alternated partition plates. B) The lower partition plate and the upper partition plate are separated from each other. C) a structure that is covered with at least one or more meshes. C) a position of the reserve tank side pipe opening of a pipe connecting the overflow tank and the reserve tank is at least in the liquid. D) a pipe on the outlet side of the reserve tank. An apparatus for producing a color filter, characterized in that the mouth position is on the bottom of the reserve tank. 2. The film forming apparatus according to claim 1, wherein: e) the filter is formed by a filter having a pore diameter larger than the diameter of particles dispersed in an electrolyte used and smaller than 100 μm; The color filter manufacturing apparatus according to claim 1, wherein the apparatus is formed immediately before the electrolytic cell. 3. An electrolytic solution comprising: pigment particles insoluble or hardly soluble in water; transparent conductive particles having a hydrophobic surface; and pigment particles containing a surfactant having a redox reaction and a supporting salt as basic components. 3. The color filter manufacturing apparatus according to claim 1, wherein an aqueous micelle colloid of a pigment in which transparent conductive particles are surrounded by the surfactant is used.