JP3147979B2 - Method for producing thin film and method for producing color filter using the method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a thin film and a method for producing a color filter using the method.

[0002]

2. Description of the Related Art As a method of manufacturing a thin film such as a dye layer of a color filter, a printing method of printing three primary colors of RGB ink on a glass substrate using a printing machine, and an ultraviolet curable resist in which a pigment is dispersed are usually used. Apply on a glass substrate, mask exposure by photolithography and heat curing
B. A dispersion method for forming a dye layer three times repeatedly, a resist method as a dye-preventing film formed on gelatin by photolithography, a dyeing method for dyeing each color of RGB with a dye, a dispersion of an electrodeposited polymer and a pigment, There are known an electrodeposition method of performing electrodeposition coating using an electrode formed thereon, and a micelle electrolysis method of dispersing a surfactant and a pigment and performing electrolysis using an electrode formed on a substrate. .

[0003] Among them, a micellar electrolysis method (JP-A-63-24329)
No. 8) discloses a method in which a micellizing agent composed of a ferrocene derivative and a dye material (hydrophobic dye) are added to an aqueous medium in which electric conductivity is adjusted by adding a supporting electrolyte or the like to water as needed. When dispersed by mixing and stirring, micelles having the coloring material taken therein are formed. When this is electrolytically treated, the micelles are attracted to the anode, and the ferrocene derivative in the micelles loses the electron e− on the anode (transparent electrode) (Fe ^{2+ in} ferrocene is oxidized to Fe ³⁺ ),
At the same time, the micelles collapse and the internal dye material is deposited on the anode to form a thin film. On the other hand, the oxidized ferrocene derivative is attracted to the cathode, receives the electron e-, and forms a micelle again. In the process in which the formation and collapse of such micelles are repeated, the particles of the dye material are projected onto the transparent electrode to form a thin film, and a desired dye thin film is formed.

[0004]

However, in the above-mentioned conventional method for producing a thin film or a color filter by the micelle electrolysis method, when performing electrolysis using a patterned electrode, for example, a striped or mosaic electrode. However, since only a constant potential is applied to the target electrode, the natural convection of the electrolytic solution determines the deposition rate of the pigment thin film, and the pigment thin film formed by electrolysis has a film thickness distribution and a nonuniform film thickness. become. For this reason, there is a problem that shading (color spots) occurs in the pigment thin film, and smoothness is lost due to unevenness of the film surface.

The present invention has been made in view of the above-mentioned problems, and has as its object to provide a method of manufacturing a thin film having a uniform film thickness and free from color unevenness and unevenness, and a method of manufacturing a color filter using the method. And

[0006]

In order to achieve the above object, a method for producing a thin film according to the present invention comprises dispersing or solubilizing a hydrophobic substance in an aqueous medium using a surfactant comprising a ferrocene derivative. In a method of manufacturing a thin film in which an electrode-forming substrate is inserted into a dispersion or micellar electrolyte to be formed, and a current is applied to the electrode on the substrate to form a thin film of a hydrophobic substance on the electrode, a periodically changing voltage or current is used. Is applied to the electrode to perform electrolysis. Preferably, the periodically changing voltage or current applied to the electrode is at least one selected from a rectangular wave, a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave. When conducting an electric current to the electrodes on the substrate, a potential other than the target electrode for electrolysis is applied to the electrodes other than the oxidation-reduction potential of the ferrocene derivative surfactant. It is constituted to be applied.

Further, the method for producing a color filter according to the present invention uses a surfactant comprising a ferrocene derivative to produce red,
A substrate for producing a color filter in which a patterned transparent electrode is formed on each of a dispersion or micellar electrolyte obtained by dispersing or solubilizing a pigment or dye having three primary colors of green and blue in an aqueous medium. Are sequentially inserted, a current is applied to the transparent electrode on the substrate, and a method of manufacturing a color filter for forming a dye thin film on the transparent electrode,
At least one waveform selected from a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave as a periodically changing voltage or current;
Alternatively, electrolysis is performed by applying a composite waveform of these waveforms to the transparent electrode, or when performing energization processing by applying a periodically changing voltage or current to the transparent electrode on the substrate. In this method, a potential lower than the oxidation-reduction potential of the ferrocene derivative surfactant is applied to a transparent electrode other than the electrode.

Hereinafter, the present invention will be described in detail. FIG. 1 is a diagram showing a manufacturing process of a thin film of the present invention. The method for manufacturing a color filter of the present invention using the method for manufacturing a thin film of the present invention will also be described.

In the method for producing a thin film of the present invention, a dispersion or micellar electrolyte obtained by dispersing or solubilizing a hydrophobic substance in an aqueous solvent using a surfactant comprising a ferrocene derivative is used.

(1) A ferrocene derivative surfactant (micelleizing agent) can very efficiently disperse or solubilize a hydrophobic substance in an aqueous medium. Here, there are various types of ferrocene derivatives, for example, the general formula

[0011]

Embedded image [Wherein, R ¹ and R ² each represent an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an amino group, a dimethylamino group, a hydroxyl group, an acetylamino group, a carboxyl group, a methoxycarbonyl group, an acetoxy group, Represents an aldehyde group or a halogen, and R ³ represents hydrogen or a group having 4 to 4 carbon atoms.
18 represents a linear or branched alkyl group or alkenyl group, R4 and R5 each represent hydrogen or a methyl group, Y represents oxygen, an oxycarbonyl group or an acyloxy group, a is an integer of 0-4, b is 0 An integer from 4 to m
Represents an integer of 1 to 18, and n represents a real number of 2.0 to 70.0.] As a typical example (Japanese Patent Application No. 1-24108).

(2) As the hydrophobic substance, for example, red,
And hydrophobic pigments such as green, blue and black. Here, examples of the hydrophobic red pigment include, for example, perylene pigments, lake pigments, azo pigments, diazo pigments, quinacridone pigments, anthraquinone pigments, dianthraquinone pigments, and anthracene pigments. Are perylene pigments, lake pigments (Ca, Ba, S
r, Mn), quinacridone, naphthol AS, shicomin pigment, anthraquinone (Sudan I, II, III, R), disazo, benzopyran, cadmium sulfide pigment, Fe (II
I) Oxide pigments and the like. Examples of the hydrophobic green dye pigment include halogen-substituted phthalocyanine pigments, halogen-substituted copper phthalocyanine pigments, and triphenylmethane-based basic dyes, and more specifically, chloro-polysubstituted phthalocyanines, copper complexes thereof, and the like. And barium-triphenylmethane dyes. Examples of the hydrophobic blue pigment include copper phthalocyanine pigments, indanthrone pigments, indophenol pigments and cyanine pigments, and more specifically, chlorocopper phthalocyanine, chloroaluminum phthalocyanine, vanadate phthalocyanine, and magnesium phthalocyanine. And phthalocyanine metal complexes such as zinc phthalocyanine, iron phthalocyanine, and cobalt phthalocyanine; phthalocyanine, merocyanine, and indophenol blue.

In the case of producing color filters, dianthraquinone pigments as red pigments, bromo-chlorocopper phthalocyanine-based and isoindolinone-based mixed pigments as green pigments, and copper phthalocyanine- and dioxazine-based pigments as blue pigments are used. It is preferable to use a mixed pigment or the like.

(3) Next, the above-mentioned ferrocene derivative surfactant (micelleizing agent), a hydrophobic substance and, if necessary, a supporting salt are added to an aqueous medium, and these are mixed, and the mixture is mixed with an ultrasonic wave (homogenizer) or The dispersion is sufficiently dispersed by a stirrer or the like to form micelles, and then, if necessary, excess dye material is removed to obtain a micelle solution (or dispersion).

The concentration of the surfactant of the fersen derivative at this time may be not less than the critical micelle concentration (0.1 mM), but is preferably about 2.0 mM. Further, the concentration of the hydrophobic substance may be not less than the saturation concentration.
１００100 g / l.

The supporting salt (supporting electrolyte) is added as needed to adjust the electric conductivity of the aqueous medium. The amount of the supporting salt to be added may be within a range that does not hinder the precipitation of the solubilized or dispersed coloring material. Usually, the concentration is about 0.05 to 200 mM. The electrolysis can be performed without adding the supporting salt, but in this case, a thin film with high purity free of the supporting salt can be obtained. When a supporting salt is used, the type of the supporting salt is not particularly limited as long as the electric conductivity of the aqueous medium can be adjusted without hindering formation of micelles and precipitation of the coloring material on the electrode. . Specifically, sulfates (salts such as lithium, potassium, sodium, rubidium and aluminum) and halide salts (lithium, potassium, sodium, rubidium,
Salts of calcium, magnesium, aluminum, etc.),
Ammonium salts (salts such as boron tetrafluoride) and water-soluble oxide salts (lithium, potassium, sodium, rubidium,
Salts of calcium, magnesium, aluminum, etc.),
Acetates (salts of lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.) are preferred.

(4) Next, the electrode-formed substrate is inserted into the micelle electrolyte (or dispersion) prepared as described above. Here, the electrode forming substrate is not particularly limited as long as electrodes are formed on the substrate, and the pattern of the electrodes is not particularly limited. Examples of the electrode forming substrate include platinum, gold, carbon, and a color filter manufacturing substrate in which a transparent electrode for forming a dye layer (ITO electrode) is formed on a transparent glass substrate.

(5) After the electrode-formed substrate is inserted into the micelle electrolyte (or dispersion), the electrodes on the substrate are subjected to an electric treatment to perform electrolysis, and a thin film of a hydrophobic substance is formed on the electrodes (FIG. 3). .

In the method of the present invention, in this electrolysis,
Electrolysis is performed by applying a periodically changing voltage or current to the electrode. That is, the voltage or current applied to the electrode during electrolysis is not a constant voltage or current,
Electrolysis is performed while periodically controlling the electrolysis conditions by changing the voltage or current.

The voltage or current that changes periodically includes:
As shown in FIGS. 2A to 2E, a rectangular wave (pulse wave)
(FIG. 2 (a)), trapezoidal wave (FIG. 2 (b)), triangular wave (FIG.
(C)), sine wave (FIG. 2 (d)), sawtooth wave (FIG. 2 (e))
And the like. These waveforms may be used alone or in combination of two or more.

When a rectangular wave pulse is used as a periodically changing voltage or current, for example, the pulse width a is set to 0.
01 to 5 seconds, the interval b between the pulses is 0.05 to 30 seconds, and the pulse height c is 0.3 to 1.5 V or 10 μA.
１1 mA / cm ² , and the bias (voltage or current) d is 0０〜0.25 V or 0 又 は 100 μA / cm ² . The temperature of the electrolyte is 0 to 90 ° C, preferably 20 to 70 ° C. To generate a periodically changing voltage or current,
For example, as shown in FIG. 3, a function generator 15 is connected to a potentiostat 14 connected to the electrode 1 on the electrode forming substrate 10, the sweet pepper electrode (SCE) 12 and the counter electrode 13.
Should be connected.

As described above, by performing electrolysis using a periodically changing voltage or current, the film forming speed of the thin film formed on the electrode is not affected by the natural convection of the electrolytic solution. The film formation rate is determined only by the concentration gradient of the hydrophobic substance, and the film thickness is uniform over the entire surface of the substrate, and a thin film with less color spots and unevenness can be obtained.

When performing electrolysis, it is preferable to apply a potential equal to or lower than the oxidation-reduction potential of the ferrocene derivative surfactant to electrodes other than the target electrode for performing electrolysis, as shown in FIG. Specifically, in addition to the potentiostat 14 used for electrolysis of the target electrode, a potentiostat 16
Is connected to an electrode other than the target electrode, and a potential lower than the oxidation-reduction potential of the ferrocene derivative surfactant is applied. By doing so, Examples 7 to 10 and 1 in Table 1 were obtained.
As shown in Examples 2 and 14 and Table 16 in Example 16, thin films with few white spots can be obtained.

For example, in the production of a color filter, a micelle electrolyte of each color of RGB is used on a red (R), green (G), and blue (B) dye forming electrode (mosaic or stripe). , R, G, and B, a thin film of dye is formed. In this electrolysis, a potential equal to or lower than the oxidation-reduction potential of the ferrocene derivative surfactant is applied to electrodes of two colors other than the one-color target electrode for electrolysis.

(6) After the formation of the thin film by the above-mentioned electrolysis, washing with pure water or electrolytic washing is performed to remove the electrolytic solution, and baking is performed to complete the thin film. In the case of manufacturing a color filter, after performing a conductivity adjusting liquid cleaning (for example, E = −0.8 V. vs. SCE for 3 minutes) in addition to pure water cleaning and electrolytic cleaning, drying with hot water, and post-baking (for example, 100 ° C.,
(15 minutes) to complete the dye thin film.

(7) In the case of producing a color filter, a protective film (smooth film or top coat film) is formed on the dye layer after forming the dye layer. The protective film is formed by spin-coating or roll-coating a polymer such as a top coat agent and then post-baking the same. Here, examples of the top coat agent include an acrylic resin, a polyester resin, a polyolefin resin, a phosphazene resin, and a polyphenylene sulfide resin. A conductive thin film layer such as an ITO thin film or tin oxide is formed on the protective film. A conductive thin film such as an ITO film is formed by a sputtering method, an evaporation method, a biosol method, or the like. The ITO thin film or the like is patterned by a photolithography method to form a liquid crystal driving electrode (post-ITO electrode).
The patterning of the ITO thin film by the photolithography method consists of (a) resist coating, (b) exposure, (c) development,
(D) Etching of the ITO thin film and (e) stripping of the resist. Through the above-described process, an RGB color separation color filter is manufactured by the micellar electrolysis method.

The above-described color filter of the present invention includes a color liquid crystal display such as a personal computer, a word processor, a wall-mounted television, and a pocket liquid crystal television, an aurora cavitation, a color filter such as a solid-state imaging device (CCD), an audio, an instrument panel for a vehicle, It is suitably used in the field of color displays such as watches, calculators, video decks, fax machines, communication devices, games, and measuring instruments.

[0028]

The present invention will be described below in more detail with reference to examples. Reference Example 1 Formation of ITO Electrode (Dye Layer Forming Electrode) A UV-curable resist agent was applied to a glass substrate (manufactured by Matsuzaki Vacuum Co., Ltd .: blue plate glass, surface polished, silica dip product) having a sheet resistance of 20Ω / □ as an ITO film. A solution obtained by diluting (Fuji Hunt Electronics Technology: IC-28 / T3) twice with xylene is spin-coated at a rotation speed of 1000 rpm. After spin coating, pre-bake is performed at 80 ° C. for 15 minutes. After that, this resist / ITO
The film substrate is set on the exposure machine. The mask has a line width of 100μ
m · gap 20μm, line length 230mm, number 1920
It is a stripe vertical pattern of a book. A 2 kW high-pressure mercury lamp (exposure intensity: 10 mw / cm ² ) is used as a light source. After setting the proximity gap to 70 μm and exposing for 60 seconds, development is performed with a developer. After the development, the substrate is rinsed with pure water and post-baked at 180 ° C. Next, as an etchant, 1N FeCl ₃ .1N HCl.0.1N
An aqueous solution of HNO ₃ .0.1N Ce (NO ₃ ) ₄ is prepared, and the ITO film is etched. The end of the etching was determined by electric resistance measurement. This etching required about 20 minutes. After the etching, the resist is rinsed with pure water, and the resist is peeled off with 1N NaOH. Thus, an ITO patterned glass substrate is obtained.

Formation of resist black matrix As a resist material for forming a black matrix, color mosaic C of Fuji Hunt Electronics Technology Co., Ltd.
A mixture of K, CR, CG, and CB at a weight ratio of 3: 1: 1: 1 is used. The ITO patterned glass substrate produced in the previous step is rotated at 10 rpm, and 30 cc of the resist is sprayed on the rotating substrate. Next, the rotation speed of the spin coating is set to 2,500 rpm, and the resist is uniformly coated (formed) on the substrate. After coating, the substrate is pre-baked at 80 ° C. for 15 minutes. Next, exposure is performed using a black matrix and a design mask (90 × 310 mm square, 20 mm line width) for forming an electrode extraction window while performing alignment with an exposure machine having an alignment function. A 2 kW high-pressure mercury lamp is used as a light source (light quantity: 100 mJ / cm ² ). After setting the proximity gap to 70 μm and exposing for 200 seconds, development is performed with an alkaline developer. After electrolysis for 20 minutes, the developer (Fuji Hunt Electronics Technology: C
Develop for 30 seconds using D) diluted 4 times with pure water. Further, it is rinsed with pure water and post-baked at 200 ° C. for 100 minutes. Silver paste (P-28, manufactured by Tokurika Chemical Co., Ltd.)
0) was applied to the electrode extraction window frame using a dispenser,
After connecting the R (red), B (blue), and G (green) rows of the electrodes, baking is performed at 150 ° C. for 100 minutes. By the above,
An insulating protective film is formed on a portion other than the effective display portion on the substrate, and at the same time, an electrode extraction window frame is formed.

Formation of dye film Ferrocene derivative micellizing agent FPE in 4 liters of pure water
G (manufactured by Dojin Kagaku) 2 mM, LiBr (manufactured by Wako Pure Chemical Industries)
0.1 M and 10 g / l of a dianthraquinone-based pigment (manufactured by Sanyo Dyeing Co., Ltd.) as a red pigment were added, and the mixture was dispersed with an ultrasonic homogenizer for 30 minutes to form a micelle solution.
A TO patterned glass substrate is inserted into the micelle solution, and a potentiostat with an external function generator is connected to the R rows of the stripe. As a voltage applied to the electrodes during this electrolysis, a rectangular wave (a: 0.3
Second, b: 6 seconds, c: 0.5 V, d: 0.2 V). After performing electrolysis for 20 minutes, it is washed with pure water and prebaked (120 ° C.) in an oven. In G, a chlorinated brominated phthalocyanine-based green pigment and an isoindolinone-based yellow pigment were separately placed in separate pure water in place of the red pigment.
After preparing a micelle solution in the same manner as in the case of R except that it was added at a concentration of 5 g / l, each micelle solution was mixed at a ratio of 7: 3, and a film was formed under the same conditions as the film formation of R. .
Electrolysis conditions such as applied voltage and post-treatment after electrolysis are the same as in the case of R. In B, a micelle solution was prepared in the same manner as in the film formation of R, except that a phthalocyanine-based blue pigment and a dioxazine-based violet pigment were added to separate pure water at a concentration of 10.9 g / l instead of the red pigment. Later, 7: 3
And the micelle solutions are mixed at the ratio described above, and a film is formed under the same conditions as the film formation of R. Electrolysis conditions such as applied voltage and post-treatment after electrolysis are assumed to be R cases. By the above electrolytic operation, RG
A B color filter dye thin film is obtained.

Formation of Protective Film The dye thin film forming substrate is set on a spin coater, and OS-808 (Nagase Sangyo) is applied as a flattening agent using a dispenser. The substrate is rotated at 10 rpm and applied evenly to the entire substrate. Further, the film is rotated at 800 rpm for 2 minutes to obtain a uniform thin film. Thereafter, it is baked and cured at 260 ° C. for 2 hours. STN with protective film formed as above
To obtain RGB color filters.

[0032] was carried out measuring physical properties of a color filter fabricated by measurements of physical properties above steps. To measure the transmittance, use a spectrophotometer (MCPD-
1100, manufactured by Otsuka Electronics Co., Ltd.). The transmittance of the glass substrate was normalized to 100%, and the transmittance of ITO / pigment thin film / protective film was used for evaluation. 450 each for RGB
The transmittance was evaluated for wavelengths of nm, 545 nm, and 610 nm. The dirt of RGB is caused by the contamination of the electrode of each color with an electrolytic solution other than the target color. The evaluation (stain ratio) of the stain was evaluated based on the difference between the transmittance of the color filter manufactured here and the transmittance of Comparative Examples 2 to 4. For the white spot rate, use an optical microscope (40
(0x), and the ratio of the white area to the pixel area was evaluated as the white area ratio. Regarding the evaluation of spots, the chromaticity of 9 pixels on the substrate was measured for each of RGB,
The color difference was evaluated as the largest (ΔE). The surface smoothness was measured using a surface unevenness measuring device (Dick Tack).

Example 2 In the electrolysis operation of Reference Example 1, a potential waveform (triangular wave) as shown in FIG. 2C was applied to the R, G, and B films for 25 minutes. Table 1 shows the results.

Example 3 In the electrolysis operation of Reference Example 1, a potential waveform (trapezoidal wave) as shown in FIG. 2B was applied to the R, G, and B films for 25 minutes. Table 1 shows the results.

Example 4 In the electrolytic operation of Reference Example 1, two potential waveforms (saw waves) as shown in FIG.
It was applied for 5 minutes. Table 1 shows the results.

Example 5 Regarding the electrolytic operation of Reference Example 1, the amplitude was 0.25 V, the period was 5 seconds, and the lower potential was 0.
A sine waveform potential of 2 V and an upper potential of 0.7 V was applied for 20 minutes. Table 1 shows the results.

REFERENCE EXAMPLE 6 Regarding the electrolysis operation of Reference Example 1, 10 μA / cm ² (1 second) and 0 μA /
A constant current pulse of cm ² (10 seconds) was applied for 20 minutes. Table 1 shows the results.

Comparative Example 1 In the electrolytic operation of Reference Example 1, a constant potential of 0.7 V was applied to the R, G, and B films for 10 minutes. Table 1 shows the results.

Example 7 In the electrolysis operation of Reference Example 1, F was applied to electrodes other than the target electrode.
The same operation as in Reference Example 1 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

Example 8 Regarding the electrolytic operation of Example 2, F was applied to electrodes other than the target electrode.
The same operation as in Example 2 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

Example 9 Regarding the electrolytic operation of Example 3, F was applied to electrodes other than the target electrode.
The same operation as in Example 3 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

Example 10 Regarding the electrolytic operation of Example 4, F was applied to electrodes other than the target electrode.
The same operation as in Example 4 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

Example 11 In the electrolysis operation of Example 5, F was applied to electrodes other than the target electrode.
The same operation as in Example 5 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

Example 12 In the electrolysis operation of Reference Example 6, F was applied to electrodes other than the target electrode.
The same operation as in Reference Example 6 was performed, except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. Table 1 shows the results.

REFERENCE EXAMPLE 13 Regarding the electrolytic operation of Reference Example 1, FES was used as a micellizing agent.
T (the redox potential is shown in Table 3) was used at the same concentration,
The same operation as in Reference Example 1 was performed. Table 1 shows the results.

Example 14 In the electrolysis operation of Reference Example 1, FES was used as a micellizing agent.
The same evaluation as in Reference Example 1 was performed, except that T was used at the same concentration and a potential of 0.18 V was applied to electrodes other than the target electrode as a potential lower than the oxidation-reduction potential of FEST. Table 1 shows the results
Shown in

[0047]

[Table 1]

Reference Example 15 Formation of Chromium Black Matrix Non-alkali glass substrate (manufactured by HOYA: NA45 / 30)
A chromium (Cr) thin film is formed on a 0 mm square and 1 mm thick by sputtering using a sputtering apparatus (manufactured by ULVAC, Inc .: SDP-550VT) to a thickness of about 2000 angstroms by a sputtering method. An ultraviolet-curable resist agent (IC-28 / T3, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied on the Cr thin film for 1,0 hours.
Spin coating is performed at a rotation speed of 00 rpm. After spin coating, pre-bake is performed at 80 ° C. for 15 minutes. afterwards,
The resist / Cr / glass substrate is set on a stepper exposure machine (exposure intensity: 10 mW / cm ² ) to perform exposure. The mask has a pixel size of 90 μm × as shown in FIG.
310 μm, line width 20 μm, effective area 160 mm x 1
Using a grid pattern of 55 mm, step exposure is performed four times for one glass substrate. After the exposure is completed, develop
After rinsing with pure water, post-baking is performed at 150 ° C. Next, 1M as an etching solution (etchant)
FeCl ₃ .1N HClO ₄ .0.1N HNO _3.
An aqueous solution of 0.1N Ce (NO ₃ ) ₄ is prepared, and Cr on the substrate is etched. The end of the etching was determined by electric resistance measurement. The etching required about 20 minutes. After the etching, the resist is rinsed with pure water, and the resist is peeled off with 1N NaOH. Wash thoroughly with pure water,
A chrome black matrix (BM) and an extraction electrode were completed.

Formation of Insulating Film and ITO Electrode Next, the above BM is spin-coated with insulating silica (SiO ₂ ) (OCDTYPE-7, manufactured by Tokyo Ohka Co., Ltd.) at a rotation speed of 1,000 rpm. After baking at 250 ° C. for 60 minutes, a sputtering device (manufactured by ULVAC, Inc .: SDP-
Using 550 VT), an ITO thin film is sputter deposited to a thickness of about 1,300 angstroms. At this time, the substrate temperature was set to 200 ° C. in order to adjust the surface resistance of the ITO film to 20Ω / □. This ITO thin film / CrB
M / Ultraviolet curable resist on glass substrate (IC-28 / T manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
3) is spin-coated at a rotation speed of 1,000 rpm. After spin coating, pre-bake is performed at 80 ° C. for 15 minutes. Then, the resist / ITO thin film / CrBM /
A glass substrate is exposed to a contact exposure machine (exposure intensity: 10 mW /
cm ² ). The mask used is a vertical stripe pattern having a line width of 92 μm, a gap of 18 μm, and a line length of 155 mm. The light source uses a 2 kW high-pressure mercury lamp.
After alignment preparation, proximity gap 50μ
m, exposure for 15 seconds, and development with an alkali developer. After development, rinse with pure water,
And post bake. Next, 1M as an etchant
FeCl ₃ .1N HCl.0.1N HNO ₃ .0.
Using an aqueous solution of 1N Ce (NO ₃ ) ₄ ,
The O thin film is etched to form an ITO electrode. The end of the etching was determined by electric resistance measurement. The etching required about 20 minutes. After the etching is completed, the resist is rinsed with pure water, and the resist is immersed and peeled off with 1N NaOH. After washing with pure water, it is confirmed that there is no electric leak between adjacent ITO electrodes. Thus, an ITO patterned glass substrate with a BM was completed.

Simultaneous formation of electrode extraction window frame An acrylic resist agent (CT, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is used as a resist agent for forming an electrode extraction window frame. The ITO patterned glass substrate with BM prepared above is rotated at 10 rpm, and 30 cc of the resist agent is sprayed thereon. Next, the number of rotations of the spin coating is set to 1,500 rpm, and the substrate is uniformly coated. After spin coating, the substrate is pre-baked at 80 ° C. for 15 minutes. Then, after alignment with a contact exposure machine having an alignment function using a 20 kW high-pressure mercury lamp as a light source, exposure is performed using a design mask for formation shown in FIG. Thereafter, the film is developed with a developing solution for 90 seconds, rinsed with pure water, and post-baked at 180 ° C. for 100 minutes. Through the above steps, a substrate for manufacturing a color filter is completed. Next, a silver paste (P-280, manufactured by Tokurika Chemical Co., Ltd.) was applied to the electrode extraction window frame using a dispenser, and each R of the electrode was coated.
After connecting the (red), B (blue) and G (green) columns, 15
Bake at 0 ° C. for 100 minutes. As described above, the insulating protective film is formed on a portion other than the effective display portion on the substrate, and at the same time, the electrode extraction window frame is formed.

Formation of Dye Film A ferrocene derivative micellizing agent FPE was added to 4 liters of pure water.
G (manufactured by Dojin Kagaku) 2 mM, LiBr (manufactured by Wako Pure Chemical Industries)
0.1M and 10 g / l of a red pigment dianthraquinone pigment (manufactured by Sanyo Dyeing Co., Ltd.) were added, and 3
After dispersing for 0 minute to form a micelle solution, the ITO patterned glass substrate is inserted into the micelle solution, and a potentiostat with an external function generator is connected to the R row of the stripe. The voltage applied to the electrodes during this electrolysis is a rectangular wave (a: 0.3 seconds, b: 6) shown in FIG.
Second, c: 0.5 V, d: 0.2 V). After performing electrolysis for 20 minutes, it is washed with pure water and prebaked (120 ° C.) in an oven. In the case of G, the micelle solution was prepared in the same manner as in the case of R, except that a chlorinated brominated phthalocyanine-based green pigment and an isoindolinone-based yellow pigment were added to separate pure water at a concentration of 15 g / l instead of the red pigment. Is prepared, the respective micelle solutions are mixed at a ratio of 7: 3, and a film is formed under the same conditions as the film formation of R. Electrolysis conditions such as applied voltage and post-treatment after electrolysis are the same as in the case of R. In B, a micelle solution was prepared in the same manner as in the film formation of R, except that a phthalocyanine-based blue pigment and a dioxazine-based purple pigment were each added to separate pure water at a concentration of 10.9 g / l instead of the red pigment. After that, the micelle solutions are mixed at a ratio of 7: 3, and the film is formed under the same conditions as the film formation of R. Electrolysis conditions such as applied voltage and post-treatment after electrolysis are the same as in the case of R. By the above electrolytic operation, RGB
A color filter dye thin film is obtained.

Formation of Protective Film The RGB color filter substrate obtained by the above process was
It is rotated at 0 rpm, and 30 cc of a JSS7265 top coat agent (Nippon Synthetic Rubber) is sprayed thereon. Next, the rotation speed of the spin coating was set to 1,000 rpm, and the substrate (R
(GB color filter thin film).
After spin coating, post-baking is performed at 180 ° C. for 50 minutes. Through the above steps, an RGB color filter thin film for TFT is obtained.

Measurement was performed in the same manner as in Reference Example 1. Table 2 shows the results.

Example 16 In Reference Example 15, the same electrolytic operation as in Example 7 was performed. Table 2 shows the results.

Comparative Example 4 In Reference Example 15, the same electrolytic operation as in Comparative Example 1 was performed. Table 2 shows the results.

Comparative Example 5 In Reference Example 15, the same electrolytic operation as in Comparative Example 2 was performed. Table 2 shows the results.

[0057]

[Table 2]

As is clear from Tables 1 and 2, the white spot rate, the color spot (ΔE), and the unevenness are better than those of the comparative examples. The transmittances are equivalent.

[0059]

[Table 3]

[0060]

As described above, according to the method for producing a thin film and the method for producing a color filter of the present invention, it is possible to produce a thin film or a color filter having a uniform thickness and no color spots and irregularities.

[Brief description of the drawings]

FIG. 1 is a view showing a manufacturing process of a thin film of the present invention.

FIGS. 2A to 2E are diagrams showing modes of a voltage or a current that changes periodically.

FIG. 3 is a block diagram illustrating an electrolysis process.

FIG. 4 is another block diagram illustrating an electrolysis process.

FIG. 5 is a plan view showing a mask used in the manufacturing process of the color filter of the present invention.

FIG. 6 is a plan view showing another mask used in the manufacturing process of the color filter of the present invention.

[Explanation of symbols]

 Reference Signs List 10 electrode forming substrate 11 electrode 14, 16 potentiostat 15 function generator

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G02B 5/20-5/28 C25D 9/02 C25D 13/04

Claims (4)

(57) [Claims] 1. An electrode-forming substrate is inserted into a dispersion or micellar electrolytic solution obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a surfactant comprising a ferrocene derivative. A thin film of a hydrophobic substance formed on an electrode by applying a current to the electrode, wherein a voltage or a current that changes periodically is applied to the electrode to perform electrolysis, and an electrode other than the target electrode for performing the electrolysis is used. Applying a potential equal to or lower than the oxidation-reduction potential of the ferrocene derivative surfactant. 2. The method according to claim 1, wherein the periodically changing voltage or current is:
2. The method according to claim 1, wherein the waveform is at least one waveform selected from a rectangular wave, a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave, or a composite waveform of these waveforms. 3. A dispersion obtained by dispersing or solubilizing a pigment or dye having spectral characteristics of three primary colors of red, green and blue in an aqueous medium containing a supporting salt using a surfactant comprising a ferrocene derivative. Alternatively, a color filter manufacturing substrate having a patterned transparent electrode formed thereon is sequentially inserted into each of the micellar electrolytes, and a current is applied to the transparent electrode on the substrate to form a dye thin film on the transparent electrode. In the manufacturing method, a voltage or a current that changes periodically is applied to the transparent electrode to perform electrolysis, and the voltage or the current is at least one waveform selected from a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave; Alternatively, a method for manufacturing a color filter, characterized by a composite waveform of these waveforms. 4. A dispersion or micellar electrolyte obtained by dispersing or solubilizing pigments or dyes having three primary colors of red, green and blue in an aqueous medium using a surfactant comprising a ferrocene derivative. In each, a color filter manufacturing substrate on which a patterned transparent electrode is formed is sequentially inserted, a current is applied to the transparent electrode on the substrate, and a method of manufacturing a color filter for forming a dye thin film on the transparent electrode is performed. When a voltage or current that changes periodically is applied to the transparent electrode to perform electrolysis, and when a current is applied to the transparent electrode on the substrate, the ferrocene derivative surfactant is applied to a transparent electrode other than the target electrode for electrolysis. A method for producing a color filter, comprising applying a potential lower than the oxidation-reduction potential of the color filter.