JP2659638B2 - Method for producing micelle dispersion or micelle solubilizing solution, thin film and color filter - Google Patents

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 a micelle dispersion or micellar solubilizing solution, a thin film and a color filter, and more particularly, to the production of a thin film and a color filter by optimizing the equilibrium concentration of coarse particles. The present invention relates to a method for producing a micelle dispersion or micelle solubilizing solution, a thin film, and a color filter capable of suppressing generation and controlling chromaticity.

[0002]

2. Description of the Related Art
Production method of thin film and color filter by micellar electrolysis method (JP-A-63-243298, JP-A-63-505384)
Japanese Patent Application Laid-Open No. 129602/1990 only discloses a method for simultaneously forming a film of a plurality of hydrophobic organic substances (eg, pigments).
In the description, the composition ratio of the mixture is not specifically defined, but is expressed in molar concentration. That is, even if it refers to the β-type copper phthalocyanine described in the examples, the specific surface area differs depending on the production method, the copper phthalocyanine contains at least one chlorine, and the pigment has a high dispersion. Since the dispersing agent and the vehicle are added, the molecular weight is unclear, and from this publication, it was impossible to produce an effective thin film or color filter.

On the other hand, when two kinds of hydrophobic organic substances are dispersed in an aqueous solution and micelle electrolysis is performed, a method of simply mixing the two kinds of dispersion liquids and a method described in JP-A-2-129602 are used. From the beginning, two methods of dispersing a mixed powder of two kinds of hydrophobic organic substances can be considered.
However, both methods have problems when controlling fine characteristics (surface smoothness, color uniformity, uniformity of a micro-sized thin film structure) such as a color filter.

[0004] In the former, generally, the optimum equilibrium concentration of a dispersion of a single hydrophobic organic substance differs for each hydrophobic organic substance. Therefore, when two types of dispersions are mixed, one of the interfaces is changed due to the difference in the equilibrium concentration. The activator is desorbed from one hydrophobic organic and adsorbed on the other, and the equilibrium concentrations of the two liquids tend to be constant. At this time, since the surfactant is eliminated from the one hydrophobic organic substance, the dispersion becomes unstable, and the aggregation of the dispersed particles is performed according to the thin film formation mechanism formed by the energization processing without performing the energization processing. Occur. When such agglomeration occurs in the solution, the dispersed particles are naturally coarsened, and the thin film formed by the electrolytic treatment using the dispersion cannot have uniformity due to the coarse particles. Specifically, coarse particles of several tens of μm are deposited on a thin film of several μm, which causes problems in transmittance, flatness, uniformity, and reproducibility. In addition, large peeling occurs.

In the latter, a mixture of two hydrophobic organic substances cannot be uniformly dispersed. Specifically, the dispersion is carried out by an ultrasonic homogenizer or a sand mill.In any case, unless the particle size and surface physical properties of the hydrophobic organic material are equal, the conditions for dispersing all the plurality of hydrophobic organic materials under the same conditions are used. Is not satisfied, and the optimal dispersion is not realized. Further, according to the example described in JP-A-2-129602, when different dispersion liquid compositions are mixed, one of the hydrophobic organic substances (eg, pigment) precipitates or aggregates as described above during mixing. Therefore, problems such as generation of coarse particles, color separation, and peeling of a thin film occur at the time of film formation by the micelle electrolytic method. This is a problem that, when a color filter is manufactured, this phenomenon not only causes inconsistencies such as uneven color, or misregistration, white spots, and loss of smoothness, but also makes it impossible to adjust to a desired chromaticity. there were. Further, when peeling occurs, there is a problem that a color filter cannot be manufactured. Therefore, the present inventors have intensively studied to develop a method that can freely form a thin film and a color filter without generating coarse particles, color separation, and peeling of the thin film during film formation.

[0006]

As a result, it has been found that the object can be achieved by adjusting the equilibrium concentration of the micelle dispersion or the micelle solubilization solution in an aqueous medium to a specific range. The present invention has been completed based on such findings.

That is, the present invention relates to a method for producing a micelle dispersion or micelle solubilization solution in which an inorganic substance or a hydrophobic organic substance and a ferrocene derivative surfactant are dispersed in an aqueous medium. To provide a method for producing a micelle dispersion or micelle solubilized solution by adjusting the equilibrium concentration of 0.05 to 2.8 mmol / L, and to disperse the inorganic substance or the hydrophobic organic substance and the supporting salt in aqueous solution. When a conductive substrate is inserted into a micelle dispersion or micelle solubilized solution obtained by dispersing or solubilizing a ferrocene derivative surfactant in a medium, and applying a current to the substrate to produce a thin film, A method for producing a thin film using a dispersion or solution obtained by adding a supporting salt to a micelle dispersion or micelle solubilization solution, A color filter with a transparent conductive thin film patterned in a micelle dispersion or micelle solubilization solution obtained by using a ferrocene derivative surfactant in an aqueous medium with a pigment or dye having three primary colors of red, green and blue. When a production substrate is inserted and the substrate is subjected to an electric current treatment to produce a color filter for forming a dye film on an electrode, the equilibrium concentration of the micelle dispersion or the micelle solubilizing solution is adjusted to 0.05 to 2.8. An object of the present invention is to provide a method for producing a color filter using a micelle dispersion or a micelle solubilization solution of at least one color adjusted to a range of mmol / liter.

There are various kinds of inorganic substances or hydrophobic organic substances used in the present invention. For example, phthalocyanine, phthalocyanine metal complexes and their derivatives, naphthalocyanine, naphthalocyanine metal complexes and their derivatives, porphyrin, porphyrin metal complexes and their derivatives, perylene, perylene derivatives, quinacridone, isoindolinone, disazo, 1,1′-diheptyl-4,4′-bipyridinium dibromide, 1,1′-didodecyl-4,4′-bipyridinium dibromide, including color filter pigments and organic dyes such as dioxazine, viologen, sudan and derivatives thereof Electrochromic materials such as 6-nitro-1,3,3-trimethylspiro-
Photosensitive materials (photochromic materials) such as (2'H-1'-benzopyran-2,2'-indoline) (commonly referred to as spiropyran), photosensor materials, dyes for liquid crystal display such as p-azoxyanisole, and "color chemicals" Encyclopedia "
Dyes for electronics, recording dyes, dyes for environmental chromism, photographic dyes, energy dyes, biomedical dyes, foods listed on pages 542 to 717 of CMC Co., Ltd., published on March 28, 1988. -Cosmetic dyes, dyes, pigments, and hydrophobic compounds among special coloring dyes. And 7,7,8,8
An organic conductive material such as a 1: 1 complex of tetracyanoquinonedimethane (TCNQ) and tetrathiafluorene (TTF), a gas sensor material, a photocurable paint such as pentaerythritol diacrylate, an insulating material such as stearic acid, Examples thereof include diazo-type photosensitive materials such as 1-phenylazo-2-naphthol and paints. Furthermore, water-insoluble polymers, for example, general-purpose polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polyacrylonitrile (PAN), and polyphenylene, polypyrrole, polyaniline, and polythiophene Acetylcellulose, polyvinyl acetate, polyvinyl butyral, and various other polymers (eg, polyvinyl pyridine) or copolymers (eg, a copolymer of methyl methacrylate and methacrylic acid).

[0009] Ferrocene derivative surfactants (hereinafter also referred to as micellizing agents or surfactants) are surfactants containing a ferrocene derivative as an active ingredient, and include various surfactants such as nonionic, cationic and anionic. There are things. Specifically, ammonium-type ferrocene derivatives as described in JP-A-63-243298,
Ether-type ferrocene derivatives and ester-type ferrocene derivatives as described in International Publication WO 89/01939, pyridinium-type ferrocene derivatives as described in JP-A-1-226894, and further JP-A-2-88387. Gazette, JP-A-1-45370,
Various ferrocene derivatives as disclosed in JP-A-2-96585 and JP-A-2-250892 can be exemplified.

Next, examples of the aqueous medium include various media such as water, a mixed liquid of water and alcohol, and a mixed liquid of water and acetone. In the present invention, the above-mentioned inorganic substance or hydrophobic organic substance and a ferrocene derivative surfactant are dispersed in the above-mentioned aqueous medium to produce a micelle dispersion or a micelle solubilization solution. In addition, you may use a supporting salt as needed.

The method for producing the micelle dispersion or micelle solubilizing solution of the present invention includes, for example, the above-mentioned inorganic substance or hydrophobic organic substance, a ferrocene derivative surfactant, and, if necessary, a supporting salt in the aqueous medium. In a water-based medium, sufficient stirring may be performed using a mechanical homogenizer, an ultrasonic homogenizer, a pearl mill, a sand mill, a stirrer, a three-roll mill, or the like. In this operation, inorganic substances and hydrophobic organic substances are acted on by surfactants.
It is uniformly dispersed or solubilized in an aqueous medium to form a micelle dispersion or a micelle solubilized solution. Here, the total concentration of the micellizing agent is preferably selected in the range of 0.1 mmol / L to 1 mol / L. The concentration of the inorganic substance or the hydrophobic organic substance is preferably in the range of 1 to 500 g / liter.

In the method for producing a micelle dispersion or micelle solubilizing solution of the present invention, a supporting salt (supporting electrolyte) may be used as necessary. This supporting salt is added to adjust the electric conductivity of the aqueous medium. The addition amount of the supporting salt may be within a range that does not hinder the precipitation of the solubilized or dispersed inorganic substance or hydrophobic organic substance, and is usually about 0 to 300 times the concentration of the micellizing agent,
Preferably, the concentration is about 50 to 200 times. The electrolysis can be carried out without adding the supporting salt, but in this case, a thin film having a high purity containing no supporting salt can be obtained. Also,
When a supporting salt is used, the type of the supporting salt is not particularly limited as long as it can control the electric conductivity of the aqueous medium without hindering formation of micelles and precipitation of an inorganic substance or a hydrophobic organic substance on an electrode. There is no.

More specifically, sulfates (lithium, potassium, sodium,
Salts such as rubidium and aluminum), acetates (lithium, potassium, sodium, rubidium, beryllium,
Salts of magnesium, calcium, strontium, barium, aluminum, etc., and halide salts (lithium, potassium, sodium, rubidium, calcium,
Salts such as magnesium and aluminum) and water-soluble oxide salts (salts such as lithium, potassium, sodium, rubidium, calcium, magnesium, and aluminum) are preferred.

The most important factor in the composition of the micelle dispersion or micelle solubilizing solution is the relationship between the inorganic substance or hydrophobic organic substance and the micellizing agent (surfactant). Usually, when an inorganic substance or a hydrophobic organic substance is put into a surfactant solution, the surfactant is adsorbed on the surface of the inorganic substance or the hydrophobic organic substance. This adsorption lowers the surfactant concentration in the solution. After a sufficient time, the adsorption reaches equilibrium, and the concentration of this surfactant in the aqueous solution becomes constant. The concentration of the surfactant in the aqueous solution in this state is called an equilibrium concentration. The equilibrium concentration is measured by centrifugation (1,000 rpm).
pm or more) to completely separate the inorganic substance or the hydrophobic organic substance, and determine the concentration of the surfactant remaining in the aqueous solution by elemental analysis such as plasma emission analysis (ICP). The ferrocene derivative surfactant of the present invention may be analyzed for iron.

By adjusting the equilibrium concentration to 0.05 mmol / L or more, inorganic substances or hydrophobic organic substances can be stably and easily dispersed. According to the principle of micellar electrolysis, a surfactant is electrochemically oxidized, and as a result, the surfactant adsorbed on an inorganic substance or a hydrophobic organic substance is desorbed. When this operation is repeated, finally, the adsorbed surfactant alone cannot disperse the inorganic substance or the hydrophobic organic substance, and some of the inorganic substance or the hydrophobic organic substance particles aggregate to reduce the surface area. I do. However, finally, the inorganic substance or the hydrophobic organic substance particles cannot be completely dispersed and are deposited. Therefore, in order for this principle to work, conversely, if the concentration of the surfactant, that is, the equilibrium concentration, is too high, sufficient surfactant exists even if oxidized by electrolysis, and inorganic substances or hydrophobic organic substances are present. Agglomeration of the substance does not occur, and the object cannot be achieved. In the present invention, the optimum value of the equilibrium concentration is 0.05 to 2.80 mmol / liter.

In the present invention, a thin film is produced using the micelle dispersion or the micelle solubilizing solution obtained above. In the present invention, the thin film is prepared by adding the above-mentioned supporting salt to a micelle dispersion or a micelle solubilizing solution and subjecting it to electrolysis using a conductive substrate (transparent electrode) while standing or while slightly stirring. can get. In addition, the above-mentioned inorganic substance or hydrophobic organic substance may be supplementarily added to the micelle dispersion or the micelle solubilization solution during the electrolytic treatment, and the micelle dispersion or the micelle solubilization solution near the anode is extracted out of the system. Alternatively, a circulation circuit may be provided in which an inorganic substance or a hydrophobic organic substance is added to the extracted micelle dispersion or micelle solubilizing solution, mixed and stirred sufficiently, and then the liquid is returned to the vicinity of the cathode. The electrolysis conditions at this time may be appropriately selected according to various situations, but are usually at a liquid temperature of 0 to 90 ° C., preferably 20 to 70 ° C., and the voltage condition is a ferrocene derivative which is a micellizing agent. A voltage equal to or higher than the oxidation-reduction potential of the agent and equal to or lower than the hydrogen generation potential, specifically 0.1 to 1.5 V, preferably 0.3 to 1.0 V;
The current density is 10 mA / cm ² or less, preferably 50 to 3
00 μA / cm ² . When this electrolytic treatment is performed, a reaction proceeds according to the principle of the micelle electrolytic method. Focusing on the behavior of Fe ions in the ferrocene derivative, the Fe ²⁺ of the ferrocene becomes Fe ³⁺ at the anode, micelles collapse, and particles of an inorganic substance or a hydrophobic organic substance are deposited on the anode (transparent electrode). Precipitates out. On the other hand, at the cathode, Fe ³⁺ oxidized at the anode is reduced to Fe ²⁺ and returns to the original micelle, so that the film formation operation can be repeatedly performed with the same solution.
It is preferable that the thin film formed in this manner is subjected to baking (baking), pure water cleaning, and electric field cleaning as necessary. When a micelle dispersion or a micelle solubilizing solution is prepared, when a supporting salt is used, it is not necessary to newly add a supporting salt. By such micellar electrolysis, a desired thin film containing an inorganic substance or a hydrophobic organic substance is formed on the anode (transparent electrode).

As the conductive substrate used here, ITO, platinum, graphite, Nesa film, chromium, nickel, antimony oxide or the like is added as a thin film to a plate made of aluminum or the like or an insulating substrate made of glass, polymer, ceramic or the like. It is preferable to use a transparent electrode. The material of the transparent electrode is the oxidation potential of the ferrocene derivative (+0.15 to 0.3).
Any metal or conductor that is nobler than 0 V versus a saturated sweet potato electrode may be used. Specific examples include ITO, tin dioxide, and conductive polymer films.

In the present invention, a thin film can be produced using two or more kinds of micelle dispersions or micelle solubilization solutions. This production method may be based on the case where one kind of the micelle dispersion or the micelle solubilizing solution is used. However, it is preferable that the equilibrium concentration of at least one of the micelle dispersion or the micelle solubilizing solution is adjusted to 0.1 mmol / L or more, and the difference between the equilibrium concentrations is adjusted to 1.2 mmol / L or less. The mixing method for mixing the micelle dispersion or the micelle solubilizing solution is ultrasonic dispersion (5 to 1000 at 100 to 10 kW).
Minutes), stirrer stirring (1 to 500 at 5-200 rpm)
Min), mechanical homogenizer (1 to 30,000 rp)
m is 1 to 1000 minutes).

In addition, RGB which constitutes a color filter
(R: red pigment, G: green pigment, B: blue pigment)
In order to form the dye film, for example, the three primary color dyes are dispersed or solubilized using a ferrocene derivative surfactant to prepare respective dye-containing micelle dispersion solutions or micelle solubilization solutions.

The pigments or dyes having the spectral characteristics of RGB used here, that is, the hydrophobic pigments of RGB include the following. Examples of the red pigment include perylene pigments, lake pigments, azo pigments, dianthraquinone, quinacridone pigments, anthraquinone pigments, and anthracene pigments. For example, perylene pigments, lake pigments (Ca, Ba, Sr, Mn), There are quinacridone, naphthol AS, shicomin pigment, anthraquinone, disazo (Sudan I, II, III, R), benzopyran, cadmium sulfide pigment, Fe (III) oxide pigment and the like, and among them, perylene pigment and lake pigment are preferable. Examples of the green colorant include halogen-substituted phthalocyanine pigments, halogen-substituted copper phthalocyanine pigments, and triphenylmethane-based basic dyes, such as chloro-polysubstituted phthalocyanines, copper complexes thereof, and barium-triphenylmethane dyes. Blue pigments include copper phthalocyanine pigments, indanthrone pigments, indophenol pigments and cyanine pigments, such as chlorocopper phthalocyanine, chloroaluminum phthalocyanine, vanadate phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, and the like. Examples include phthalocyanine metal complexes such as iron phthalocyanine and cobalt phthalocyanine, phthalocyanine, merocyanine, and indophenol blue. Also,
Disazo pigments and isoindolinone pigments can be used as yellow pigments for adjusting chromaticity, and dioxazine pigments can be used as purple pigments. The shape and size of the hydrophobic organic substance are not particularly limited, but powder having a particle size of 10 μm or less is preferably used.

In order to form an RGB hydrophobic dye thin film constituting a color filter, one of R, G and B hydrophobic dyes is added to an aqueous medium, and a thin film having a desired color tone is formed by the above operation. The above operation may be repeated by forming a desired pattern and then changing the type of the hydrophobic dye. Also,
Here, a desired dye-containing micelle dispersion or micelle solubilization solution may be prepared using two or more kinds of micelle dispersions or micelle solubilization solutions. For example, a micelle dispersion or a micelle solubilization solution containing R and Y (yellow dye) is prepared, and a mixing method in the production of a thin film using the two or more micelle dispersions or micelle solubilization solutions is used. I just need. However, the equilibrium concentration in this case is also preferably within the above range. Here, a procedure for manufacturing a color filter will be described. As a method for producing the color filter of the present invention, various methods can be mentioned,
Here, a specific example includes a protective layer / dye film / ITO film / silica film / black matrix (BM) / glass substrate. First, in order to form a BM, Cr is formed on a glass substrate by a sputtering method or the like, and a UV curable resist agent is formed thereon and then appropriately prebaked after forming the film.
Exposure is performed on the resist surface of the obtained resist / Cr / glass substrate using an appropriate mask. After the exposure, the uncured resist is washed away with a developing solution, and the exposed Cr is etched. After etching, the BM can be formed by removing unnecessary resist. Then
After spin-coating, for example, silica as an insulating layer on the obtained BM, ITO is sputtered thereon so as to have an appropriate surface resistance. ITO film / silica film / BM /
A UV curable resist is formed on the ITO surface of the glass substrate and then appropriately prebaked. Obtained resist / ITO
Exposure is performed on the resist surface of the film / silica film / BM / glass substrate using an appropriate mask. After exposure, the uncured resist is washed away with a developing solution, and the exposed ITO is etched. After the etching, an unnecessary resist is peeled off, whereby a substrate with an ITO patterned BM can be formed. Next, a UV curable resist is formed on the obtained substrate with the ITO patterning BM and then appropriately prebaked after forming the film. Exposure is performed on the resist surface of the obtained resist / ITO film / silica film / BM / glass substrate using an appropriate mask corresponding to a portion corresponding to an electrode. After the exposure, the uncured resist is washed away with a developing solution to form an electrode take-out site. Then, a color filter thin film can be manufactured on a substrate by performing the same micellar electrolysis operation as above using each of the dye-containing micelle dispersions or micelle solubilizing solutions. Thereafter, it is preferable to form a protective film on the color filter by spin-coating the color filter thin film substrate with a structural reinforcing resin. Thereby, the structural reinforcing resin particles are introduced into the pores of the hydrophobic dye thin film of the color filter, and the film strength of the hydrophobic dye thin film is improved. Examples of the structural reinforcing resin used here include acrylic, ester, polyimide, cyclized rubber, siloxane, and the like.
Epoxy polymers or copolymers are exemplified.

Further, the obtained color filter is preferably subjected to baking, baking, pure water cleaning and electric field cleaning as required. In particular, if baking is performed, a more stable color filter can be obtained. This is presumably because the heat treatment causes sintering of the above-mentioned particles, thereby obtaining a denser film having a stronger bonding force between the particles and increasing the stability of the film. This heat treatment is performed, for example, in an electric furnace, but is not particularly limited as long as the thin film can be heated. The heating temperature and the heating time are different depending on the kind of the hydrophobic substance, but may be within a range in which the membrane formed by the micellar electrolysis method is not closed and the bonding strength is strong, preferably 80 to 200 ° C, more preferably. Is 80
The temperature is preferably in the range of from 5 minutes to 10 hours, more preferably from 30 minutes to 2 hours.

Next, the present invention will be described in more detail with reference to examples. Example 1 A ferrocene derivative micellizing agent FPE represented by the following formula (I) was added to 15.65 g of lionogen red GD in an aqueous solution with an addition amount of lionogen red GD of 15.65 g.
G (made by Dojin Chemical Co., Ltd.)
Rionogen Red GD15.65 in 0ml pure water
g, concentration of FPEG 2.0 mmol, 10.4 g of LiBr
(0.1 mol), and pure water was further added to make up to 1 liter. The mixture was stirred with a stirrer for 3 days so as to obtain a sufficient equilibrium, and allowed to stand for 1 day. Then 50,000
Centrifugation was performed at rpm to separate only the pigment. The supernatant was subjected to metal iron elemental analysis using ICP, and the amount of adsorption was measured.

Embedded image As a result, FPE to 15.65 g of Lionogen Red GD
The amount of G adsorbed was 1.05 mmol, and a total of 1.51 mmol / L of FPEG was added in order to bring the equilibrium concentration of the ferrocene derivative micellizing agent FPEG to 0.46 mmol / L. Then, FPEG (manufactured by Dojin Chemical) as a ferrocene derivative micellizing agent was actually added to 1 liter of pure water.
1.51 mmol (1.416 g), LiB as a supporting salt
r (manufactured by Wako Pure Chemical Industries) is 0.1 mol (10.4 g), and 15.6 g of Rionogen Red GD (manufactured by Toyo Ink) as a hydrophobic dye is used.
5 g was added to obtain a micellar dispersion, which was dispersed for 30 minutes with an ultrasonic homogenizer to obtain a micelle dispersion. 100Ω /
Insert the ITO substrate into the micelle dispersion, connect a potentiostat, and use a stainless steel substrate for the counter electrode.
Electrostatic potential electrolysis was performed at 5 V for 10 minutes to obtain a hydrophobic organic substance thin film. Then, after washing with pure water, prebaking (120 ° C. for 10 minutes) in an oven was performed to obtain a thin film. The obtained thin film was evaluated as follows. The unevenness of the surface was measured by Dick Tack (a stylus type contact film thickness meter) by scanning 100 mm. The transmittance of the thin film was measured using an MCPD spectrophotometer manufactured by Otsuka Electronics.

Examples 2 to 56 and Comparative Examples 1 to 4 In the same manner as in Example 1, except that the conditions shown in Table 1 were used. The results obtained are shown in Table 2.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

[0034]

[Table 10]

[0035]

[Table 11]

[0036]

[Table 12]

[0037]

[Table 13]

[0038]

[Table 14]

[0039]

[Table 15]

[0040]

[Table 16]

Example 57 The solutions prepared in Examples 32 to 35 and Examples 14 to 17 were mixed in the combinations shown in Table 3 to form a film under the same conditions as in Example 1. As a result, the stability of the mixed solution and the state of the film formation were observed. Among the solutions, those in which aggregation precipitation was observed were described as aggregation in the combination table. The coarse particles in the thin film were measured with an electron microscope, and those having a particle size of 0.5 μm or less were marked with “○” in the table, and those having a particle size of 0.5 μm or more with a rough surface were marked with “X”. Furthermore, although there were no coarse particles, when the thin film was extremely thin, it was described as "thin", and when it was peeled, it was described as "peeling". As a result, in a mixed dispersion in which at least one of the equilibrium concentrations is not less than 0.1 mmol / l and the difference in the equilibrium concentration is within 1.2 mmol / l,
Coarse particles in the thin film become 0.5 μm or less, peeling of the thin film,
A stable dispersion was obtained without coagulation and precipitation of the solution, and a good thin film was obtained at the same time.

[0042]

[Table 17]

Example 58 (1) Patterning of ITO A glass substrate (polished blue plate glass and immersed in silica: manufactured by Matsuzaki Vacuum) having a sheet resistance of 20 Ω / □ as an ITO film was coated with an ultraviolet curable resist agent (IC). A solution of -28 / T3 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) diluted twice with xylene was spin-coated at a rotation speed of 1,000 rpm. After spin coating, prebaking was performed at 80 ° C. for 15 minutes, and then the resist / ITO substrate was set in an exposure machine. The mask used at this time has a line width of 100 cm, a gap of 20 cm, a line length of 230 mm, and 19 mm.
A 20 kW high-pressure mercury lamp was used as a light source (exposure ability: 10 mW / (cm ^2.
s)). Take the proximity gap 70cm,
After exposure for 2 seconds and development, the substrate was rinsed with pure water and baked at 180 ° C. Next, as an etchant, 1F
A mixed aqueous solution of eCl ₃ .1 N HCl, 0.1 N HNO ₃ .0.1 N Ce (NO ₃ ) ₄ was prepared, and I.sub.
The TO was etched. The end point of the etching was measured by electric resistance. The etching required about 20 minutes. After the etching, the resist was rinsed with pure water, and the resist was peeled off with 1N NaOH.

(2) Preparation of BM As a BM forming resist agent, a color mosaic CK manufactured by Fuji Hunt Electronics Technology Co., Ltd.
A mixture of G and CB in a ratio of 3: 1: 1: 1 parts by weight was used. The ITO patterned crow substrate prepared in (1) was rotated at 10 rpm, and 30 cc of the above-described resist agent was sprayed thereon, and the number of revolutions of spin coating was 2,500 rpm.
m, a film was uniformly formed on the substrate. Then, this substrate was
Prebaked at 0 ° C for 15 minutes. And high pressure mercury lamp 2
BM design (90 × 310 cm square-20 cm) while aligning with an exposure machine with kW alignment function
(Line width) Exposure was performed using a mask. The light source used was a 2 kW high-pressure mercury lamp (exposure ability: 100 mJ / cm ² ). After taking a proximity gap of 70 μm and exposing it for 200 seconds, it is developed with an alkane developer.
D (developer) was diluted 4 times with pure water and developed for 30 seconds. Further, the substrate was washed with pure water and post-baked at 200 ° C. for 100 minutes.

As the mixed micelle dispersion of R, the micellar dispersion of Rionogen Red GD (manufactured by Toyo Ink) prepared in Example 1 and the lionol yellow (manufactured by Toyo Ink) prepared in Example 26 were each subjected to ultrasonic wave. After dispersing with a homogenizer for 30 minutes, the respective liquids were mixed at a ratio of 9: 1 (volume ratio), and the mixed liquid was further dispersed with an ultrasonic homogenizer for 30 minutes. As a mixed micelle dispersion of G, a micelle dispersion of Fastogen Green S (manufactured by Dainippon Ink) prepared in Example 17 and a Similar First Yellow 4GT (manufactured by Dainippon Ink) prepared in Example 29 were subjected to ultrasonic waves, respectively. After dispersing with a homogenizer for 30 minutes, 6: 4
The respective liquids were mixed at a ratio of (volume ratio), and the mixed liquid was further dispersed with an ultrasonic homogenizer for 30 minutes. B
The micellar dispersion of Heliogen-K6902 (manufactured by BASF) prepared in Example 44 and the fast violet 2312 prepared in Example 54
(Manufactured by Sanyo Pigment Co., Ltd.) were dispersed with an ultrasonic homogenizer for 30 minutes, and then mixed at a ratio of 7: 3 (volume ratio).
Dispersed for 0 minutes.

The ITO patterned substrate was inserted into the micelle solution of R, and a potentiostat was brought into contact with the R row of the stripe. Electrostatic potential electrolysis was performed at a voltage of 0.8 V for 15 minutes to obtain a color filter R thin film. Then, after washing with pure water, it was prebaked (at 120 ° C. for 10 minutes) in an oven. Next, the substrate was inserted into the micelle solution of G, and similarly, constant potential electrolysis was performed at a voltage of 0.4 V for 18 minutes.
A thin film of the color filter G was obtained. After film formation, post-treatment was performed under the same conditions as for the film formation of R. Finally, this substrate was inserted into the micelle solution of B, and subjected to constant potential electrolysis at a voltage of 0.7 V for 10 minutes to obtain a color filter B thin film. After film formation, post-processing was performed under the same conditions as for the film formation of R, and an RGB color filter dye thin film was obtained.

The dye thin film substrate was set on a spin coater, and OS-808 (manufactured by Nagase Sangyo) was applied as a flat film-forming agent using a dispenser. At this time, the substrate
The substrate was slowly rotated at a rotation speed of rpm, and the entire substrate was applied without gaps. It was further rotated at 800 rpm for 2 minutes to obtain a uniform thin film. Thereafter, the film was baked and cured at 260 ° C. for 2 hours to form a protective film.

Example 59 (1) Preparation of black matrix Non-alkali glass substrate (NA45 / 300 square-1.1 m
m; HOYA) was sputtered with a Cr thin film at a rate of about 2,000 ° (using SDP-550VT manufactured by Alpac). On top of this, an ultraviolet curable resist agent (IC-28)
/ T3; manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at a rotation speed of 1,000 rpm, and then spin-coated.
Prebaking was performed at 0 ° C. for 15 minutes. Then, the resist / Cr / glass substrate was set on a stepper exposure machine, and a mask (pixel size 90 cm × 310 cm × line width 2) was used.
Exposure (10 mW / c) using a mask that divides a grid pattern of 0 cm and an effective area of 160 mm × 155 mm into four parts
m ² · s scan speed 5 mm / sec). After exposure,
After developing with a special developer and rinsing with pure water,
Post-baked at 0 ° C. Next, 1N HCl · 0.1N HNO ₃ · 0.1N Ce (NO ₃ ) is used as an etchant.
The mixed aqueous solution of No. ₄ was prepared, and Cr of the substrate was etched. The end point of the etching was measured by electric resistance. The etching required about 20 minutes. After the etching, the substrate was rinsed with pure water, the resist was peeled off with 1N NaOH, and sufficiently washed with pure water to prepare a black matrix (BM: see FIG. 1).

(2) Preparation of substrate with ITO patterning BM Next, OCDTYE-7 (silica; manufactured by Tokyo Ohka) is spin-coated as an insulating film on this BM at a rotation speed of 1,000 rpm. After baking for 2 minutes, the mixture was cooled to room temperature, and further, Alpac: SDP-550VT
Set the machine plate on the board and apply ITO about 1,300 機 from above the machine plate.
Sputtered. At this time, the work was set to 200 ° C and the ITO
Was adjusted to 20Ω / □. The obtained ITO film / silica / Cr / glass substrate was spin-coated with an ultraviolet-curable resist agent (IC-28 / T3; manufactured by Fuji Hunt Electronics Technology) at a rotation speed of 1,000 rpm, and then at 80 ° C. for 15 minutes. Pre-baked. Next, this resist / ITO / silica / Cr / glass substrate was placed in a contact exposure machine (exposure ability: 10 mW / cm ^2.
s) and patterning was performed. The mask used was 92 cm in line width, 18 cm in gap, and 155 mm in line length.
Is a vertical stripe pattern. As a light source, a 2 kW high-pressure mercury lamp was used. After the alignment, a 50-cm broximity gap was taken, exposed for 15 seconds, and developed with an alkane developer. After development, rinse with pure water,
Post-baked at 150 ° C. Next, as an etchant, 1N FeCl ₃ .1N HCl, 0.1N HNO ₃
A mixed aqueous solution of 0.1N Ce (NO ₃ ) ₄ was prepared, and the ITO of the substrate was etched. The end point of the etching was measured by electric resistance. The etching required about 20 minutes. After etching, rinse with pure water,
The resist was peeled off with 1N NaOH, and further washed with pure water. After confirming that there was no electric leak between adjacent ITO electrodes, a substrate with an ITO patterned BM was prepared.

(3) Preparation of Electrode Extraction Zone An acrylic resist (CT; manufactured by Fuji Hunt Electronics Technology) was used for electrode extraction. The substrate with the ITO patterning BM prepared in the above (2) is rotated at 10 rpm, and the resist agent IC-28 / T3 is sprayed thereon at 30 cc, and the number of revolutions of the spin coat is set at 1,500 rpm. Into a uniform film. This substrate is pre-baked at 80 ° C for 15 minutes, and a mask is designed to create only the electrode extraction band while aligning with a contact exposure machine with an alignment function of a high-pressure mercury lamp of 2 kW (Fig. (No portion). Then, after developing with a developing solution for 90 seconds, it was washed with pure water and post-baked at 180 ° C. for 100 minutes. Thus, an electrode extraction zone was obtained. Conductivity was given to the extracted electrode rows with a silver paste to form R, G, and B rows in the production of the dye film.

(4) Preparation of Dispersion A micellar dispersion of chromophtal A3B (manufactured by Ciba Geigy) prepared in Example 10 was dispersed as an R mixed micellar dispersion by an ultrasonic homogenizer for 30 minutes. As a mixed micellar dispersion of G, a micelle dispersion of Heliogen Green L9140 (manufactured by BASF) prepared in Example 14 and Irgazine Yellow (manufactured by Ciba Geigy) were dispersed by an ultrasonic homogenizer for 30 minutes, respectively. 6: 4
Mix each micelle dispersion at the ratio of (volume ratio),
Further, the mixture was dispersed with an ultrasonic homogenizer for 30 minutes. As a mixed micellar dispersion of B, the micelle dispersion of Heliogen Blue L7080 (manufactured by BASF) prepared in Example 43 and Fastogen Super Violet (manufactured by Dainippon Ink) prepared in Example 50 were each mixed with an ultrasonic homogenizer. After the dispersion for minutes, the respective liquids were mixed at a ratio of 7: 3 (volume ratio), and the mixture was further dispersed for 30 minutes with an ultrasonic homogenizer.

(5) Production of Color Filter The substrate with the ITO patterning BM was inserted into the mixed micelle dispersion of R, and a potentiostat was connected to the R row of the stripe. Electrostatic potential electrolysis was performed at a voltage of 0.8 V for 15 minutes to obtain a color filter R thin film. Then, after washing with pure water, pre-baking in an oven (at 120 ° C for 10 minutes)
did. Next, this substrate was inserted into the mixed micellar dispersion of G, and subjected to constant potential electrolysis at 0.4 V for 18 minutes to obtain a thin film of the color filter G. After film formation, post-treatment was performed under the same conditions as for the film formation of R. Finally, the substrate was inserted into the micelle solution of B, and subjected to a constant potential electrolysis at 0.7 V for 10 minutes to obtain a color filter B thin film. After film formation, post-treatment was performed under the same conditions as for the film formation of R. Thus, RGB color filters were obtained. Next, the prepared RGB color filter substrate was rotated at 10 rpm, and 30 cc of a JSS7265 top coat agent (manufactured by Nippon Synthetic Rubber) was sprayed thereon, and the spin coat rotation speed was set to 1,000 rpm, and the substrate (RGB color filter) was rotated. ) Was uniformly formed on the film. This substrate is 18
Post-baking was performed at 0 ° C. for 50 minutes. Thus coarse particles 0.
An RGB color filter of 1 μm or less was obtained.

Examples 60 to 63 A film was formed in the same manner as in Example 58 except that the mixed dispersion of RGB was changed to the solution shown in Table 4. Table 5 shows the obtained results. Thus, in each case, since the particles are fine, the spectral characteristics are very excellent, and a good color filter free from problems such as generation of coarse particles, color separation, and peeling of a thin film was obtained.

Examples 64 to 68 The procedure of Example 59 was repeated, except that the mixed dispersion of RGB was changed to the solution shown in Table 4. The results are summarized in Table 5. As described above, in each case, since the particles are fine, the spectral characteristics are very excellent. In addition, a good color filter free from problems such as generation of coarse particles, color separation, and peeling of a thin film could be obtained.

[0055]

[Table 18]

[0056]

[Table 19]

[0057]

[Table 20]

[0058]

[Table 21]

[0059]

[Table 22]

[0060]

[Table 23]

[0061]

[Table 24]

[0062]

According to the present invention, by optimizing the equilibrium concentration, it is possible to obtain a safe micellar dispersion or micellar solubilization solution capable of suppressing generation of coarse particles. As a result, it is possible to form a thin film or a color filter having an uneven film thickness, no color separation, and no thin film peeling. Therefore, according to the present invention, a laptop personal computer, word processor, workstation, aurora vision, liquid crystal projector, liquid crystal TV, OH
It can be effectively used for P, car instrument panel, equipment mortar, etc.

[Brief description of the drawings]

FIG. 1 is a diagram showing a part of a cross-sectional view of a color filter.

FIG. 2 is a front view showing a mask for forming an ITO thin film electrode.

[Explanation of symbols]

 1: Black matrix 2: Glass substrate 3: Dye film 4: Protective film 5: R row 6: G row 7: B row

Continuation of front page (56) References JP-A-2-236299 (JP, A) JP-A-2-250892 (JP, A) JP-A-2-250893 (JP, A)

Claims (8)

(57) [Claims] In producing a micelle dispersion or micelle solubilization solution in which an inorganic substance or a hydrophobic organic substance and a ferrocene derivative surfactant are dispersed in an aqueous medium, the equilibrium concentration of the micelle dispersion or micelle solubilization solution is determined.
A method for producing a micelle dispersion or micelle solubilized solution, which is prepared in the range of 0.05 to 2.8 mmol / L. 2. The amount of a ferrocene derivative surfactant adsorbed on an inorganic substance or a hydrophobic organic substance is determined, and the equilibrium concentration is adjusted to 0.05 to 2 by replenishing the ferrocene derivative surfactant in an amount corresponding to the adsorption amount. 2. The method for producing a micelle dispersion or a micelle solubilized solution according to claim 1, wherein the solution is maintained in a range of 0.8 mmol / liter. 3. The concentration of the inorganic substance or the hydrophobic organic substance is in the range of 1 to 500 g / l, and the total concentration of the ferrocene derivative surfactant is 0.1 mmol / l to 1 mol / l.
3. The method for producing a micelle dispersion or micelle solubilized solution according to claim 2, wherein the solution is prepared in a range of 1 liter. Wherein one of said inorganic substance or claim 1 and a hydrophobic organic material a supporting salt is obtained by dispersing or solubilized using ferrocene derivative surfactant in an aqueous medium
A micelle component produced by the method according to any one of claims 1 to 3.
A solution obtained by adding a supporting salt to a liquid dispersion or micelle solubilization solution
Then, a conductive substrate is inserted, and a current is applied to the substrate to perform thinning.
A method for producing a thin film, comprising producing a film. 5. The equilibrium concentration of at least one of the micellar dispersion or micelle solubilizing solution of each of the two or more kinds of inorganic substances or hydrophobic organic substances is not less than 0.1 mmol / L, and the equilibrium concentration of each liquid is not less than 0.1 mmol / L. after preparing the density difference to be within 1.2 mmol / l, those of the inorganic material or a hydrophobic organic each micelles dispersion or micellar solubilization solution of the material was mixed, claim was dispersed
Micelles produced by serial mounting methods either 1-3
Supporting salt added to dispersion or micellar solubilization solution
A method for producing a micelle dispersion or micelle solubilized solution, comprising preparing a liquid. 6. Insert the conductive substrate to the micelles dispersion or micellar solubilization solution containing an inorganic substance or a hydrophobic organic substance produced by the method of claim 5, wherein and the supporting salt,
A method for producing a thin film of an inorganic substance or a hydrophobic organic substance, wherein a current is applied to the substrate. 7. A transparent conductive thin film which is patterned into a micelle dispersion or micelle solubilization solution obtained by using a ferrocene derivative surfactant in an aqueous medium with a pigment or dye having three primary colors of red, green and blue. Inserting a substrate for producing a color filter having, and conducting an electric current to the substrate, in producing a color filter for forming a dye film on the electrode, the equilibrium concentration of the micelle dispersion or micelle solubilizing solution is 0.05 A method for producing a color filter, comprising using a micelle dispersion or a micelle solubilization solution of at least one color prepared in a range of from about 2.8 mmol / L to about 2.8 mmol / L. 8. A transparent conductive thin film which is patterned into a micelle dispersion or micelle solubilization solution obtained by using a ferrocene derivative surfactant in an aqueous medium with a pigment or dye having three primary colors of red, green and blue. In order to produce a color filter for forming a dye film on an electrode by inserting a substrate for producing a color filter having the above and conducting an electric current to the substrate, the concentration of an inorganic substance or a hydrophobic organic substance is 1 to 500 g / l. And the total concentration of the ferrocene derivative surfactant is from 0.1 mmol / L to
3. A method for producing a color filter, comprising using a micelle dispersion or a micelle solubilized solution produced by the method according to claim 2 , wherein the color filter is prepared in a range of 1 mol / liter.