JPH09278487A - Production of conductive particle, production of color filter using the particle, and color filter, display panel and electronic device using the particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain conductive particles showing stable disperslbility with time which does not cause mixing of foreign matter when the conductive particles and pigments are precipitated by micelle electrolysis, by making hydrophilic surfaces of conductive particles into hydrophobic in a specified process. SOLUTION: In the production process of conductive particles, hydrophobic groups are introduced into hydrophilic surfaces of the conductive particles by hydrophobic treatment, and the following means is used. (1) Conductive particles are pulverized in an org. solvent. (2) Hydrophobic reaction is carried out at 110 to 130 deg.C. (3) The conductive particles after the reaction are dried in a reduced pressure. In the pulverizing process (1), the conductive particles are pulverized and dispersed preferably by an ultrasonic device or a high rotation type dispersing machine. In the processes (1) and (2), the solvent used for pulverization and the reaction is an aromatic material, and a single or mixture of two or more aromatic compds. are preferably used. The drying process (3) is preferably carried out in a reduced pressure at <=120 deg.C. The diameter of the conductive particles having hydrophobic surfaces is preferably between >=25Å and <=1000Å.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing conductive particles, a color filter using the same, a method for producing a color filter using the same, an active and passive color display panel having the color filter, and a method for producing the same. The present invention relates to an electronic device having a display panel, such as a liquid crystal television or a personal computer.

[0002]

2. Description of the Related Art A color filter (hereinafter referred to as CF) using a method of forming a pigment film on a substrate by colloidally dispersing pigment particles in a micelle aqueous solution of a redox-reactive surfactant and then electrolyzing the micelle aqueous solution. The present inventor has invented a method for producing the same) and co-depositing the electrically conductive particles hydrophobized on the CF (JP-A-2-267298). Further, a method for forming an inorganic film by hydrophobizing a substance whose surface of inorganic particles is hydrophilic has been invented and filed.

Here, the hydrophobic treatment of the conductive particles is performed as follows. Benzoyl peroxide / isopropyl alcohol is added to conductive ITO particles (average primary particle size of 300 to 400 angstroms) finely pulverized in advance with a ball mill, and the mixture is refluxed for 50 hours. The particles were Soxhlet extracted with chloroform to remove unreacted benzoyl peroxide, and then the particles were dried. The thus obtained conductive ITO particles having an alcoholic hydroxyl group introduced therein are placed in a toluene solution of a titanate coupling agent, and a coupling treatment is carried out at room temperature for 1 hour with stirring. After the reaction, the particles are washed with methanol and then dried to obtain the target hydrophobic conductive ITO particles.

[0004]

SUMMARY OF THE INVENTION The above-mentioned JP-A-2-267
The proposal in Japanese Patent Publication No. 298 is to develop conductivity by dispersing hydrophobicized conductive particles in a CF (hereinafter referred to as micelle CF) layer produced by a micelle electrolysis method. is there.

A patent has already been filed for the method of hydrophobizing, but the conductive ITO obtained by the method described in the prior art.
When an aqueous micellar colloid solution was prepared using particles,
It was possible to disperse more stably than conductive ITO particles that were not hydrophobized, and to make conductive CF. However, its conductivity is 1 × 10 ^7.8 Ωcm, which is less than 1 × 10 ^7.0 Ωcm which is considered necessary for driving with 1/240 DUTY which is generally used for personal computers and word processors. Further, the dispersion stability of the colloidal solution can maintain such characteristics for about 3 days, and the colloidal solution has a very short life.

Further, the conductive IT obtained by this hydrophobizing method
It was found that when a micellar colloidal solution was prepared using O particles, a film-like foreign substance different from the pigment or ITO particles was present in the liquid. Furthermore, a CF layer was formed using this micelle solution and the film surface was observed with a microscope.
It was found that the foreign matter adhered to or mixed with the foreign matter, or the traces of the foreign matter, similar to those existing in the liquid of about 00 microns. This is the following fatal defect in the case of a liquid crystal panel.
1) Adhesion of foreign matter causes a short circuit between electrodes through the foreign matter, a short circuit between substrates, a liquid crystal alignment defect due to uneven surface roughness, etc. 2) A trace of the foreign matter is a point defect when the panel is turned on. Becomes

That is, the CF layer is formed by the conventional method,
Conductive IT that can be made conductive to some extent but has the desired conductivity with excellent dispersion stability without the inclusion of foreign matter
There was no means to make O particles.

[0008]

The above-mentioned problems can be solved by the following means.

The method for producing conductive particles of the present invention comprises (1) a step of pulverizing conductive particles in an organic solvent in the method for producing conductive particles in which a hydrophobic group is introduced into the hydrophilic surface of the conductive particles by a hydrophobic treatment. It is characterized in that it comprises a step of performing a hydrophobizing reaction between 110 ° C. and 130 ° C., and a step of drying the conductive particles after the reaction under reduced pressure.

(2) In the pre-reaction pulverization treatment step of the above-mentioned means 1, the method is characterized in that it is dispersed and pulverized by an ultrasonic system device or a high speed rotation type disperser.

(3) In the crushing step and the step of carrying out the hydrophobizing reaction of the means 1 or 2, the solvent used during the crushing / reaction is an aromatic system, and these are used alone or in combination of two or more kinds. It is characterized by

(4) In the step of carrying out the hydrophobizing reaction of the above-mentioned means 3, the hydrophobizing reaction is carried out in a single solvent of an aromatic solvent such as toluene, xylene or styrene, or in a mixed solvent. .

(5) A method for producing electrically conductive particles, which is characterized in that the drying step after the reaction according to any one of the means 1 to 4 is carried out at a reduced pressure of 120 ° C. or less.

(6) The conductive particles having a hydrophobic surface according to any one of the means 1 to 5 have a diameter of 25 angstroms or more and 1000 angstroms or less.

(7) R ₁ O--Ti-(O--X--R ₂ ) ₃ X: a carboxyl group, a sulfonyl group or a phosphoric acid ester group R ₁ , R ₂ : A coupling agent represented by alkyl and alkenyl which may contain a side chain and oxygen, phosphorus, sulfur, cyclohexyl or phenyl is used.

Further, the color filter according to the present invention includes (8) conductive particles produced by any one of the means 1 to 7 on a transparent electrode having a predetermined pattern formed on a transparent substrate, It is characterized in that a colored layer in which pigment particles are mixed is formed.

Further, the method of manufacturing a color filter according to the present invention comprises: (9) forming a transparent electrode on a transparent substrate, processing the transparent electrode into a predetermined pattern, and then using the transparent electrode as an anode by a wet electrolysis method. In a method for producing a color filter in which a pigment film is formed on a transparent electrode, water-soluble or sparingly soluble pigment particles in water and conductive particles produced by any one of the means 1 to 7 are redox-reactive. Having a surfactant and a supporting salt as a basic component, preparing a micellar colloid aqueous solution of a pigment in which the pigment particles and the conductive particles are surrounded by the surfactant, and destroying the micelle by electrolysis,
It is characterized in that pigment particles and conductive particles are deposited on the transparent electrode.

Furthermore, the display panel of the present invention is (10) characterized by having the color filter described in (8) above.

(11) The present invention is characterized by having a color filter obtained by the manufacturing method described in (9) above.

In addition, the electronic device of the present invention has the above (1)
It is characterized by having the display panel described in 0) or (11).

[0021]

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

(Example 1) 100 g of Sumitomo Metal Mining's ITO particles (average primary particle diameter of 300 to 400 angstroms), which are conductive particles, are placed in a separable flask (500 ml, 3 necks) and vacuum dried at 120 ° C for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and the mixture was mixed with a high-speed homogenizer at 6000 r.
Grind with stirring at a speed of pm for 90 minutes. After grinding, the average particle size of the ITO particles in the solution was measured and found to be 815 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is held for 3 hours while controlling the temperature of the oil bath so that the rotation speed is 250 rpm and 113 ± 2 ° C. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Vacuum-dry the TO at 100 ° C for 3 hours and mash it in an agate mortar. At this point, the contact angle of pure water when the ITO particles were formed into a tablet was θ = 48 °. The contact angle is about 0.2g ITO particles are compressed at 200kg / cm2 into a tablet with a diameter of 1cm and a thickness of about 1mm, and the contact angle after 30 seconds when pure water with a diameter of 2mm is dropped on the mirror surface. Was measured by a contact angle meter.

Using the thus obtained ITO particles and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4700 angstroms.

Here, the amount of film-like foreign substances existing in the micelle colloid solution was counted. It is known that many foreign substances are generated when the micelle colloid liquid is strongly stirred. Therefore, the amount of foreign matter was measured after a small amount of micellar colloid solution was placed in a sample tube and shaken for 1 minute. Spread about 1 ml of the prepared micellar colloid solution on the slide to about 2 × 2 cm,
Count the foreign material present when scanning end-to-end with a microscope (x200).

As a comparative example, 108 ° C. (toluene solvent)
A micelle colloid solution was prepared in the same manner using ITO that had been hydrophobized for 5 hours, and the amounts of foreign substances were compared. The characteristic data are shown in Table 1.

[0027]

[Table 1]

As can be seen from Table 1, when a micelle colloidal solution is prepared using the ITO particles of the present invention, the amount of foreign matter is drastically reduced.

A glass substrate having the above-mentioned electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelles, and a constant potential of +0.8 V was applied for 15 minutes.
Electrolysis was performed. This glass substrate was applied with a silver paste on an electrode for establishing electrical continuity with a power source, connected to the power source, and immersed to a water level at which the electrode to be the color filter layer and the counter electrode as the anode were completely submerged in the liquid. As a result, a red pigment film was formed on the ITO electrode.

After washing this substrate with water, it was baked at 180 ° C. for 30 minutes. When the thickness of the red pigment was measured, there was no difference in thickness between the peripheral portion and the central portion of the electrode, and the thickness within the substrate surface was 1.05.
Micron. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.5 ohm cm, and it was electrically conductive to a desired value. After leaving this solution for 1 week, a CF layer was formed by the same method and the characteristics were measured. As a result, the film thickness was 0.92 μm and the conductivity was 1 × 10 ^5.8 ohm cm, which was stable over time.

Here, the preferable range of the conductivity is judged by the variation of the threshold voltage Vth (voltage when the light transmittance is 10%) when the panel is formed. As a result, 1 × 10
^If it exceeds ⁷ ohm cm, the dielectric constant of the pigment for each color will be slightly different, and the Vth will vary among the colors of the panel (about 1 × 1).
0 ⁸ ohm 0.12V at cm) for 1 / driving is difficult in 240DUTY commonly used for personal computers and word processors. If it is less than 1 × 10 ⁷ ohm cm, the Vths between the colors will be uniform, so the upper limit is 1 × 10 ^{7 for} practical use.
Ohms cm are considered good.

The conductivity was measured by the following method.
A CF layer was formed on a glass substrate with ITO (2 × 3 cm), and baked at 180 ° C. for 30 minutes, and then 0.2 as a flattening film.
Apply an acrylic overcoat of μm and re-apply 180 ℃
Bake for 60 minutes. Silver paste (made by Grace Japan)
Is applied in an area having a diameter of 5 mm and connected with a lead wire. I
Connect LCR meter between TO and lead wire
Measure the resistance of the layer and the planarization film. The conductivity is calculated by subtracting the resistance value of the substrate ITO and using the resistance of the CF layer and the planarization film as the resistance of CF. Here, CF made by the same method
A liquid crystal panel using the layers was prepared by the following steps. 1 ITO film is sputtered on Corning 7059 glass.
000 angstroms. This was patterned into a target shape using a photolithography etching process.

A CF substrate was formed on the patterned glass substrate by the micelle electrolysis method as described above to have a thickness of 1 micron. Since the CF layer contains a large amount of pigment and ITO particles, the surface of the CF layer has irregularities, and it is necessary to smooth this in order to stabilize the alignment of the liquid crystal. Therefore, a 0.1-micron planarization layer was formed on the CF layer.

As the flattening film, JS manufactured by Japan Synthetic Rubber Co., Ltd.
S-8 was spin coated. After the flattening film is cured by a predetermined process, polyimide (Toray Co. S
P740) was spin-coated to a thickness of 400 Å and then baked at 180 ° C. for 1 hour.

Rubbing was performed on the substrate as a predetermined alignment treatment. In addition, a predetermined ITO is similarly used as the counter substrate.
After having a pattern and performing a predetermined alignment treatment, a gap material was put in a sealing material so as to have a cell gap of 10 μm and bonded to the CF substrate. Further, a liquid crystal (LCR01 manufactured by Rodick Co., Ltd.) was enclosed in this panel, and a polarizing plate was attached to the liquid crystal panel for the purpose.

Further, as a comparative example, a CF-equipped liquid crystal panel using CF which is not made conductive by the same process,
A liquid crystal panel without CF was prepared and the driving characteristics were compared.
FIG. 1 shows a comparison of the driving characteristics. Driving characteristics 101 of liquid crystal panel without CF, CF not electrically conductive
The driving characteristics 102 of the liquid crystal panel with CF using the above and the driving characteristics 103 of the liquid crystal panel with CF using the ITO particles produced by the processing method of the present invention are shown. The characteristic data are shown in Table 2.

[0038]

[Table 2]

As can be seen from FIG. 1 and Table 2, I of the present invention
A liquid crystal panel in which a CF layer is formed using TO particles has a CF
It has the same drive characteristics as a liquid crystal panel without.

The drive at this time was static drive with a duty of one-half.

Next, using the ITO particles obtained by the same method and the green pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Phthalocyanine Green 6Y 9.0 g / l Disazo Yellow AAMX 2.2 g / l Ferrocenyl PEG 3.9 g / l LiBr (supporting salt) 1.04 g / l Hydrophobized ITO particles 18.0 g / l The above pigment colloid Use an ultrasonic dispersion device to
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4030 angstroms.

The amount of foreign matter was measured by the same method as for the red micelle colloid solution. Similar to the red micelle colloid solution as shown in Table 1,
The amount of foreign matter was reduced by using the ITO of the present invention.

A glass substrate having the above-mentioned electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelles, and a constant potential of +0.6 V was applied to the glass substrate.
Electrolysis was performed. This glass substrate was applied with a silver paste on an electrode for establishing electrical continuity with a power source, connected to the power source, and immersed to a water level at which the electrode to be the color filter layer and the counter electrode as the anode were completely submerged in the liquid. As a result, a green pigment film was formed on the ITO electrode.

After washing this substrate with water, it was baked at 180 ° C. for 30 minutes. When the green pigment film thickness was measured, there was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the film thickness within the substrate surface was uniform and was 0.91 micron. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the green pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. After leaving this liquid for 1 week, a CF layer was formed by the same method and the properties were measured. As a result, the film thickness was 0.82 μm and the conductivity was 1
× 10 ^5.9 ohm cm and stable over time.

Here, when a liquid crystal panel was manufactured by the same method as that for the red pigment film, as shown in Table 1, it has almost the same driving characteristics as the red pigment film.

The drive at this time was static drive with a duty of one-half.

Further, using the ITO particles obtained by the same method and the Blue pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Phthalocyanine blue R 5.2 g / l Dioxazine 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 The above pigment colloid Use an ultrasonic dispersion device to
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloid average particle size of this solution was 3480 angstroms.

The amount of foreign matter was measured by the same method as for the red micelle colloid solution. As shown in Table 1, as with the red micelle colloidal liquid and the green micelle colloidal liquid, the use of the ITO of the present invention reduced the amount of foreign matter.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous micelle solution, and electrolysis was performed at a constant potential of +0.6 V for 15 minutes. This glass substrate is coated with silver paste on the electrodes for electrical continuity and then connected to the power source,
The electrode to be the color filter layer and the counter electrode as the anode were soaked to the water level that they were completely immersed in the liquid. This results in IT
A blue pigment film was formed on the O electrode.

After washing this substrate with water, it was baked at 180 ° C. for 30 minutes. When the blue pigment film thickness was measured, there was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the uniform film thickness within the substrate surface was 0.98 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the blue pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. After leaving this liquid for 1 week, a CF layer was formed by the same method and the characteristics were measured. As a result, the film thickness was 0.85 μm and the conductivity was 1
× 10 ^5.8 ohm cm and stable over time.

Here, when a liquid crystal panel was manufactured by the same method as that for the red pigment film, as shown in Table 1, it has substantially the same driving characteristics as the red pigment film.

The drive at this time was static drive with a duty of one-half.

(Example 2) ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After pulverization, the average particle size of the ITO particles in the solution was measured and found to be 840 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 113 at 250 rpm.
While controlling the temperature of the oil bath to be ± 2 ° C, 1
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Vacuum dry at 0 ° C for 3 hours and mash in agate mortar. At this point, the contact angle when the ITO particles were formed into a tablet was θ = 76 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4750 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 7
There were zero.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the film thickness within the substrate surface was uniform and was 1.10 μm. In addition, there is little adhesion of foreign matter to the film surface, and the microscope (× 2
When the number of foreign matters was counted while scanning about 2 cm in (00), there were 5 foreign matters. Furthermore, the color tone of the red pigment film is ITO
It was similar to when no particles were included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.98 μm and the conductivity was 1
× 10 It became ^5.8 ohm cm.

Example 3 ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle diameter 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After crushing, the average particle size of the ITO particles in the solution was measured and found to be 820 angstroms. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 113 at 250 rpm.
2 while controlling the temperature of the oil bath so that it becomes ± 2 ° C.
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Vacuum dry at 0 ° C for 3 hours and mash in agate mortar. At this point, the contact angle when the ITO particles were formed into a tablet was θ = 60 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4600 angstroms.

The amount of the film-like foreign matter existing in the micellar colloid solution was counted by the same method as in Example 1 and found to be 3
It was seven.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the film thickness within the substrate surface was uniform and was 1.10 μm. In addition, there is little adhesion of foreign matter to the film surface, and the microscope (× 2
When the number of foreign matters was counted while scanning about 2 cm in (00), there were only two. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.96 μm and the conductivity was 1
× 10 ^5.9 ohm cm It became.

Example 4 ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After pulverization, the average particle diameter of the ITO particles in the solution was measured and found to be 805 angstroms. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 113 at 250 rpm.
While controlling the temperature of the oil bath so that it becomes ± 2 ° C, 5
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 31 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4950 angstroms.

Here, the amount of the film-like foreign matter existing in the micellar colloid solution was counted by the same method as in Example 1 and found to be 5
Was individual.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was performed at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral part and the central part of the electrode, and the film thickness within the substrate surface was uniform and 1.00 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.6 ohm cm, and it was electrically conductive to a desired value. After leaving this solution for 1 week, electrolytic film formation was carried out by the same method and the characteristics were measured. As a result, the film thickness was 0.85 μm and the conductivity was 1 × 10 ^6.0 ohm cm.

Example 5 ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After crushing, the average particle size of the ITO particles in the solution was measured and found to be 820 angstroms. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 120 rpm at 250 rpm.
While controlling the temperature of the oil bath to be ± 2 ° C, 1
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 42 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4750 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 6
There were zero.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the film thickness within the substrate surface was uniform and 1.03 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. Further, after leaving this solution for 1 week, electrolytic film formation was carried out by the same method and the characteristics were measured. As a result, the film thickness was 0.93 μm and the conductivity was 1 × 10 ^5.8 ohm cm.

(Example 6) ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After pulverization, the average particle size of the ITO particles in the solution was measured and found to be 850 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 120 rpm at 250 rpm.
While controlling the temperature of the oil bath to be ± 2 ° C, 3
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 28 °.

Using the thus obtained ITO particles and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 5050 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1, and it was 1
There were zero.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was performed at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral part and the central part of the electrode, and the film thickness within the substrate surface was uniform and 1.00 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.6 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.84 μm and the conductivity was 1
× 10 It became ^6.1 ohm cm.

Example 7 ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After grinding, the average particle size of the ITO particles in the solution was measured and found to be 860 angstroms. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 120 rpm at 250 rpm.
While controlling the temperature of the oil bath so that it becomes ± 2 ° C, 5
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 14 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloid average particle size of this solution was 5200 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 4
Was individual.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the uniform film thickness within the substrate surface was 0.82 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.6 ohm cm, and it was conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was carried out by the same method and the characteristics were measured. As a result, the film thickness was 0.69 μm and the conductivity was 1 × 10 ^6.2 ohm cm.

(Example 8) ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After crushing, the average particle size of the ITO particles in the solution was measured and found to be 830 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 128 at 250 rpm.
While controlling the temperature of the oil bath to be ± 2 ° C, 1
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 29 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl Red 8.0 g / l Disazo Yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 5000 Å.

Here, the amount of the film-like foreign matter existing in the micellar colloid solution was counted by the same method as in Example 1 and found to be 1
There were five.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was performed at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral part and the central part of the electrode, and the film thickness within the substrate surface was uniform and 1.00 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.5 ohm cm, and it was electrically conductive to a desired value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.86 μm and the conductivity was 1
× 10 ^6.0 ohm cm.

(Example 9) ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle diameter 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After pulverization, the average particle diameter of the ITO particles in the solution was measured and found to be 825 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 128 at 250 rpm.
While controlling the temperature of the oil bath to be ± 2 ° C, 3
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 17 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 5050 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 5
Was individual.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the uniform film thickness within the substrate surface was 0.84 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.5 ohm cm, and it was electrically conductive to a desired value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.67 μm and the conductivity was 1
× 10 It became ^6.1 ohm cm.

(Example 10) Sumitomo Metal Mining's ITO particles (average primary particle diameter 300 to 400 angstrom) 1
500 g of 500 ml is placed in a 3-neck separable flask and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After pulverization, the average particle size of the ITO particles in the solution was measured and found to be 845 Å. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is 128 at 250 rpm.
While controlling the temperature of the oil bath so that it becomes ± 2 ° C, 5
Hold for hours. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Grind in an agate mortar vacuum dried at 0 ° C for 3 hours. At this point, the contact angle when the ITO particles are made into a tablet shape is
θ was 15 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. This supernatant liquid was collected and used as a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 5250 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 5
Was individual.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the uniform film thickness within the substrate surface was 0.81 μm. Further, there was no foreign matter attached to the film surface, and the film surface was uniform and uniform. Furthermore, the color tone of the red pigment film was similar to that when the ITO particles were not included.

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.6 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.67 μm and the conductivity was 1
× 10 ^6.0 ohm cm.

(Comparative Example 1) As Comparative Example 1, a hydrophobizing treatment was performed as follows.

500 g of 100 g of ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size: 300 to 400 angstrom)
ml, 3 necks, place in a separable flask and mix at 120 ° C for 3
Vacuum dry for hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 90 minutes. After crushing, the average particle size of the ITO particles in the solution was measured and found to be 830 Å. Laser particle size distribution meter (LP-31 manufactured by Otsuka Electronics Co., Ltd.)
00). After the pulverization with stirring, the heating reaction is not performed as in Examples 1 to 10, and the process directly proceeds to the next step. After taking out the solution into a flask and distilling off xylene with an evaporator, ITO is vacuum dried at 100 ° C. for 3 hours and mashed with an agate mortar. At this point, the contact angle when the ITO particles were tableted was θ = 91 °.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4700 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 5
It was 50 pieces.

A glass substrate having the above-mentioned electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous micelle colloid solution, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the film thickness within the substrate surface was uniform and 1.12 μm.

When the film surface was observed here, 10 to 10
Foreign matter of about 0 micron adhered to the surface, and a lot of traces of the foreign matter were generated. When the number of foreign matters was counted while scanning for about 2 cm with a microscope (× 200), it was found to be 45. This is because when a liquid crystal panel is used, electrode shorts and substrate shorts may occur due to foreign matter, and liquid crystal alignment defects may occur due to uneven surface roughness. Becomes

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.4 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 1.00 μm and the conductivity was 1
× 10 It became ^5.8 ohm cm.

(Comparative Example 2) As Comparative Example 2, a hydrophobizing treatment was performed as follows.

500 g of 100 g of ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle size: 300 to 400 angstrom)
ml, 3 necks, place in a separable flask and mix at 120 ° C for 3
Vacuum dry for hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of toluene was added to this, and the mixture was stirred and pulverized for 90 minutes at a speed of 6000 rpm using a high-speed homogenizer. After grinding, the average particle size of the ITO particles in the solution was measured and found to be 810 angstroms. Laser particle size distribution meter (LP-31 manufactured by Otsuka Electronics Co., Ltd.)
00). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is kept under reflux at a rotation speed of 250 rpm for 5 hours. At this time, the temperature of the reaction liquid is kept at about 108 ° C. After completion of the reaction, the product is taken out into an eggplant-shaped flask, toluene is distilled off with an evaporator, ITO is vacuum dried at 100 ° C. for 3 hours, and then mashed in an agate mortar. I at this point
The contact angle when tableting TO particles is θ = 91
Was ゜.

Using the ITO particles thus obtained and the pigment for CF, a pigment colloid aqueous solution having the following composition was prepared.

Dianthraquinonyl red 8.0 g / l Disazo yellow HR 1.6 g / l Ferrocenyl PEG 3.4 g / l LiBr (supporting salt) 10.5 g / l Hydrophobized ITO particles 18.0 g / l The above pigments The colloidal aqueous solution was ultrasonic
After ultrasonic dispersion for 0 minutes, the mixture was left for half a day. The supernatant was collected to obtain a pigment micelle colloid aqueous solution. The colloidal mean particle size of this solution was 4650 angstroms.

Here, the amount of the film-like foreign matter existing in the micelle colloid solution was counted by the same method as in Example 1 and found to be 2
It was 50 pieces.

A glass substrate having the above electrode pattern as an anode and a stainless steel substrate as a cathode were immersed in this aqueous solution of micelle colloid, and electrolysis was carried out at a constant potential of +0.8 V for 15 minutes. There was no difference in film thickness between the peripheral portion and the central portion of the electrode, and the uniform film thickness within the substrate surface was 1.11 μm.

When the film surface was observed here, 10 to 10
Foreign matter of about 0 micron adhered to the surface, and a lot of traces of the foreign matter were generated. When the number of foreign matters was counted while scanning with a microscope (× 200) for about 2 cm, there were 20 foreign matters. This is because when a liquid crystal panel is used, electrode shorts and substrate shorts may occur due to foreign matter, and liquid crystal alignment defects may occur due to uneven surface roughness. Becomes

When the conductivity of the pigment film (hereinafter referred to as CF layer) obtained in the above steps was measured, it was 1 × 10 ^5.5 ohm cm, and it was made conductive to a target value. After leaving this solution for 1 week, electrolytic film formation was performed by the same method and the characteristics were measured. As a result, the film thickness was 0.96 μm and the conductivity was 1
× 10 It became ^5.8 ohm cm.

Here, Examples 1 to 10 and Comparative Example 1,
Table 3 shows the contact angle in No. 2, the number of foreign substances in the red micelle colloid solution after strong stirring, the number of foreign substances present in the film after film formation, and the film thickness of the red pigment film.

[0128]

[Table 3]

As can be seen from the table, the number of foreign matters existing in the micelle colloidal solution and in the film after film formation is halved by heating during the reaction. Further, by setting the heating temperature to 110 ° C. or higher, the number of foreign matters is further reduced, and the foreign matters in the film can be eliminated by selecting an appropriate reaction temperature and time. However, when the contact angle is 20 ° or less, the film forming rate tends to be slow, and therefore it is preferable to set the contact angle to 20 ° or more for process control.

(Example 11) In the ITO hydrophobic treatment step, the same experiment was conducted by changing the stirring and pulverizing time before the heating reaction. Sumitomo Metal Mining's ITO particles (average primary particle size 3
100 to 500 m
1, 3 necked, put in a separable flask, and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was added to this, and the mixture was pulverized with stirring using a high-speed homogenizer at a speed of 6000 rpm for 60 and 120 minutes. After pulverization, the average particle size of each ITO particle in the solution was measured and found to be 1706 and 1017 angstroms. The measurement was performed with a laser particle size distribution meter (LP-3100 manufactured by Otsuka Electronics Co., Ltd.). The flask is equipped with a Teflon stirring rod, a reflux tube, and a thermometer, and the reaction is performed in an oil bath. The reaction solution is held for 3 hours while controlling the temperature of the oil bath so that the rotation speed is 250 rpm and 113 ± 2 ° C. After completion of the reaction, the product was taken out into an eggplant-shaped flask and xylene was distilled off with an evaporator.
Vacuum dry TO at 100 ° C for 3 hours and mash in an agate mortar. At this time, the contact angles when the ITO particles were formed into a tablet were θ = 44 ° and 45 °. This value is almost the same as the value of 90 minutes for the high speed homogenizer. When a micelle colloidal solution was prepared from these ITOs in the same manner as in Example 1, the number of foreign matters was the same. In addition, the pigment film-forming surface was free from foreign matter and the like and had a uniform and uniform film surface. Further, the color tone, the specific resistance value and the film thickness of the red pigment film are I
It was the same as when TO particles were not included.

(Example 12) In the ITO hydrophobic treatment step, the same experiment was conducted by changing the stirring and pulverizing method before the heating reaction. Sumitomo Metal Mining's ITO particles (average primary particle size 3
100 to 500 m
1, 3 necked, put in a separable flask, and vacuum dried at 120 ° C. for 3 hours. A solution prepared by dissolving 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate in 200 ml of xylene was put into this, a stirring rod made of Teflon was attached to the flask, and the mixture was placed in an ultrasonic cleaner at 60, 90,
Stir and grind for 120 minutes. After pulverization, the average particle diameter of each ITO particle in the solution was measured to be 1354,
1168 and 1180 angstroms. Laser particle size distribution meter (LP-31 manufactured by Otsuka Electronics Co., Ltd.)
00). Attach a reflux tube and a thermometer to the flask and carry out the reaction in an oil path. The reaction solution is 250 rpm
The temperature of the oil bath is kept for 3 hours while controlling the temperature of the oil bath to be 113 ± 2 ° C. After completion of the reaction, the product is taken out in an eggplant-shaped flask, xylene is distilled off by an evaporator, and then ITO is vacuum dried at 100 ° C. for 3 hours and mashed in an agate mortar. At this time, the contact angles when the ITO particles were formed into a tablet were θ = 44 °, 46 °, and 46 °. This value is almost the same as the value of 90 minutes for the high speed homogenizer. When a micelle colloidal solution was prepared from these ITOs in the same manner as in Example 1, the number of foreign matters was the same. In addition, the pigment film-forming surface was free from foreign matter and the like and had a uniform and uniform film surface. Furthermore, the color tone, specific resistance value, and film thickness of the red pigment film were the same as when the ITO particles were not included.

(Comparative Example 3) In the pulverization process before the ITO hydrophobization reaction, the same experiment was conducted without pulverization. ITO particles manufactured by Sumitomo Metal Mining (average primary particle size 300
~ 400 angstrom) 100g 500ml 3
Place in a separable flask and vacuum dry at 120 ° C. for 3 hours. 1.0 g of isopropyl tris (dioctyl pyrophosphate) titanate was added to 20 g of xylene.
The solution dissolved in 0 ml is put and stirred and dispersed with a Teflon stirring rod. After stirring, the average particle size of the ITO particles in the solution was measured and found to be 2780 angstroms.
Laser particle size distribution meter (LP-Otsuka Electronics Co., Ltd.)
3100). The flask is equipped with a Teflon stirring rod, a reflux tube and a thermometer, and the reaction is carried out in an oil path.
The reaction solution is held for 3 hours while controlling the temperature of the oil bath so that the rotation speed is 250 rpm and 113 ± 2 ° C.
After completion of the reaction, the product is taken out in an eggplant-shaped flask, xylene is distilled off by an evaporator, and then ITO is vacuum dried at 100 ° C. for 3 hours and mashed in an agate mortar. At this point, the contact angle when the ITO particles were formed into a tablet was θ = 40 °. When a micellar colloidal liquid was prepared from this ITO in the same manner as in Example 1, the average particle size was 7590 angstroms, which was about 1.5 times that in Example 1.
In addition, the number of foreign matters existing in the liquid is 150, and the adhesion of foreign matters to the pigment film surface is 2 cm with a microscope (× 200).
After scanning about 15 times, there were 15 foreign substances. further,
The surface roughness of the red pigment film was poor and was about twice as high as usual.

Example 13 In the drying step after the hydrophobizing reaction, the same experiment was conducted by changing the drying method. Up to the reaction step, the same method as in Example 1 was used. After the reaction, xylene was distilled off by an evaporator, and then ITO particles were mixed with 1
It was dried under reduced pressure at 20 ° C. for 3 hours. After grinding with an agate mortar, the contact angle of the ITO particles in the form of tablets was measured. As a result, θ = 45 °, and almost the same results as in Example 1 were obtained. Further, a red micelle colloidal liquid was prepared in the same manner as in Example 1, and the number of foreign matters in the micelle liquid was measured and found to be 16. Furthermore, no foreign matter adhered to the inside of the film after the film formation. The thickness and conductivity of the pigment film obtained in the above steps were measured and found to be 1.02 μm, 1 × 10 ^5.
It was ⁴ ohm cm. Also, after leaving this liquid for 1 week, a CF layer was formed by the same method and the characteristics were measured.
The film thickness is 0.92 micron and the conductivity is 1 × 10 ^5.9 ohm cm, which is stable over time.

(Comparative Example 4) In the drying step after the hydrophobizing reaction, the same experiment was conducted by changing the drying method. Up to the reaction step, the same method as in Example 1 was used. After the reaction, xylene was distilled off with an evaporator, and then ITO particles were mixed with 12
It was dried at 0 ° C. for 3 hours under normal pressure. After grinding with an agate mortar, the contact angle of the ITO particles in the form of tablets was measured. As a result, θ = 0 °, and the ITO particles had no hydrophobicity. Further, when a red micelle colloidal liquid was prepared in the same manner as in Example 1, most of the red pigment was precipitated within 5 hours after preparation, and a stable dispersed state could not be obtained.

(Comparative Example 5) In the drying step after the hydrophobizing reaction, the same experiment was conducted by changing the drying method. Up to the reaction step, the same method as in Example 1 was used. After the reaction, xylene was distilled off with an evaporator, and then ITO particles were mixed with 14
It was dried under reduced pressure at 0 ° C. for 3 hours. After grinding with an agate mortar, the contact angle of the ITO particles in the form of tablets was measured. As a result, θ = 0 °, and the ITO particles had no hydrophobicity. Further, when a red micelle colloidal liquid was prepared in the same manner as in Example 1, most of the red pigment was precipitated within 10 hours after preparation, and a stable dispersed state could not be obtained.

Example 14 In the hydrophobic reaction step,
The same experiment was conducted by changing the reaction solvent. Except for the reaction solvent, the same method as in Example 1 was used. The solvent used was a mixture of toluene and xylene at a ratio of 1: 1. After the reaction, the mixed solvent was distilled off with an evaporator, and then the ITO particles were dried at 120 ° C. for 3 hours under reduced pressure. After crushing with an agate mortar, the contact angle of the ITO particles in the form of tablets was measured. As a result, θ was 50 °, and almost the same results as in Example 1 were obtained. Further, a red micelle colloidal liquid was prepared in the same manner as in Example 1, and the number of foreign matters in the micelle liquid was measured and found to be 16. Furthermore, no foreign matter adhered to the inside of the film after the film formation. The thickness and conductivity of the pigment film obtained in the above steps were measured and found to be 1.06 μm, 1 ×
It was 10 ^5.4 ohm cm. After leaving this solution for 1 week, a CF layer was formed by the same method and the characteristics were measured. As a result, the film thickness was 0.93 μm and the conductivity was 1 × 10 ^5.8 ohm cm, which was stable over time.

(Example 15) In the hydrophobic reaction step,
The same experiment was conducted by changing the reaction solvent. Except for the reaction solvent, the same method as in Example 1 was used. The solvent used was a mixture of toluene and styrene in a ratio of 2: 1. After the reaction, the mixed solvent was distilled off with an evaporator, and then the ITO particles were dried at 120 ° C. for 3 hours under reduced pressure. After grinding with an agate mortar, the contact angle of the ITO particles in the form of tablets was measured. As a result, θ was 46 °, and almost the same results as in Example 1 were obtained. Further, a red micelle colloidal liquid was prepared in the same manner as in Example 1, and the number of foreign matters in the micelle liquid was measured and found to be 16. Furthermore, no foreign matter adhered to the inside of the film after the film formation. The thickness and conductivity of the pigment film obtained in the above steps were measured and found to be 1.02 μm, 1 ×
It was 10 ^5.3 ohm cm. After leaving this solution for one week, a CF layer was formed by the same method and the characteristics were measured. As a result, the film thickness was 0.90 micron and the conductivity was 1 × 10 ^5.8 ohm cm, which was stable over time.

(Comparative Example 6) In the ITO hydrophobic treatment step, the same experiment as in Example 1 was conducted by changing the kind of ITO particles. As the ITO particles, ITO particles manufactured by Sumitomo Metal Mining Co., Ltd. (average primary particle diameter of about 1000 Å) were used.

When a red micelle colloidal solution was prepared in the same manner as in Example 1 by using the ITO particles after the hydrophobizing treatment, a large amount of ITO particles were precipitated after 1 day. In addition, the film thickness and conductivity of the pigment film after film formation were measured to be 0.72 micron,
The film thickness was 1 × 10 ^7.6 ohm cm, which was thinner than that of Example 1 by about 0.3 μm, and the electric conductivity was at an unusable level.

[0140]

As described above, according to the present invention, in a method for producing conductive particles in which a hydrophobic group is introduced into the hydrophilic surface of the conductive particles by a hydrophobic treatment, the conductive particles are pulverized in an organic solvent. The hydrophobic conductive particles obtained by the step, the step of performing the hydrophobic reaction between 110 ° C. and 130 ° C., and the step of drying the conductive particles after the reaction under reduced pressure are the foreign substances generated in the micelle liquid and after the film formation. Foreign substances existing in the film can be eliminated. In addition, a stable dispersed state is maintained over time. This is also apparent from the fact that the number of foreign substances existing in the micelle colloid solution and in the film after film formation is reduced by half by heating during the reaction. By setting the heating temperature to 110 ° C. or higher, the number of foreign matters is further reduced, and the foreign matters in the film can be eliminated by selecting an appropriate reaction temperature and time. This is because when a micelle colloidal solution was prepared using the ITO particles of the present invention, no foreign matter was attached to the CF layer deposited by the micelle electrolysis method, and the conductivity was stable at a low value over time. I can judge.

Further, when a CF display (liquid crystal) panel with an electrode underlay is prepared by using the CF prepared by this method, a display (liquid crystal) panel having a driving characteristic equivalent to that of a display (liquid crystal) panel without CF is produced. It was

Further, according to the present invention, a reliable color display panel can be manufactured, and in addition, an excellent electronic device having such a reliable color display panel can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing driving characteristics of a liquid crystal panel using a CF of the present invention.

[Explanation of symbols]

101 driving characteristics of liquid crystal panel without CF 102 driving characteristics of liquid crystal panel using CF under electrode 103 driving characteristics of liquid crystal panel

Claims (12)

[Claims] 1. A method for producing a conductive particle in which a hydrophobic group is introduced into a hydrophilic surface of the conductive particle by a hydrophobic treatment, a step of pulverizing the conductive particle in an organic solvent, 110 ° C. to 1
A method for producing conductive particles, comprising a step of performing a hydrophobizing reaction at 30 ° C. and a step of drying the conductive particles after the reaction under reduced pressure. 2. The method for producing conductive particles according to claim 1, wherein, in the pulverizing step, the particles are dispersed and pulverized by an ultrasonic system device or a high-speed rotating type disperser. 3. In the pulverizing step and the step of carrying out the hydrophobizing reaction, the solvent used during the pulverizing / reaction is an aromatic system, and these are used alone or in combination of two or more kinds. Item 3. A method for producing conductive particles according to Item 1 or 2. 4. The step of carrying out the hydrophobization reaction, wherein the hydrophobization reaction is carried out with a single solvent of toluene, xylene, or styrene as an aromatic solvent, or with a mixed solvent. The method for producing electrically conductive particles. 5. In the drying step after the reaction, 120
The method for producing conductive particles according to any one of claims 1 to 4, wherein the method is performed in a reduced pressure state of not higher than ° C. 6. The method for producing conductive particles according to claim 1, wherein the conductive particles having a hydrophobic surface have a diameter of 25 angstroms or more and 1000 angstroms or less. 7. In the hydrophobization reaction, R ₁ O—Ti— (O—X—R ₂ ) ₃ X: a carboxyl group, a sulfonyl group or a phosphoric acid ester group R ₁ , R ₂ : side chains and oxygen, phosphorus, 7. The method for producing electrically conductive particles according to claim 1, wherein a coupling agent represented by alkyl and alkenyl which may contain sulfur, cyclohexyl or phenyl is used. 8. A colored layer in which conductive particles produced by the method according to any one of claims 1 to 7 and pigment particles are mixed is formed on a transparent electrode having a predetermined pattern formed on a transparent substrate. A color filter characterized by being formed. 9. A color filter, which comprises forming a transparent electrode on a transparent substrate, processing the transparent electrode into a predetermined pattern, and then forming a pigment film on the transparent electrode by using the transparent electrode as an anode by a wet electrolysis method. In the method, water-soluble or sparingly water-soluble pigment particles and conductive particles produced by the method according to any one of claims 1 to 7 are prepared by using a surfactant having redox reactivity and a supporting salt as basic components. Characterized in that an aqueous micelle colloid solution of a pigment in which the pigment particles and the conductive particles are surrounded by the surfactant is prepared, the micelles are destroyed by electrolysis, and the pigment particles and the conductive particles are deposited on the transparent electrode. Color filter manufacturing method. 10. A display panel comprising the color filter according to claim 8. 11. A display panel comprising a color filter obtained by the manufacturing method according to claim 9. 12. An electronic device comprising the display panel according to claim 10.