JP3086361B2 - Manufacturing method of 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 thin film and a color filter, and more particularly, to a method for producing a thin film and a color filter having high transparency and spectral transmittance and excellent adhesion.

[0002]

2. Description of the Related Art In recent years,
In order to improve the spectral characteristics of a thin film (color filter) or the like, studies have been made to increase the dispersion of a hydrophobic substance to be used (JP-A-4-68301, JP-A-4-335602, JP-A-1-316492). Gazette). But,
It is impossible to improve transmittance, which is one of the spectral characteristics, by the conventional high dispersion technology. That is, even if the maximum dispersion particle size of the hydrophobic substance used is 200 nm (2000 °) or less, transparency and spectral transmittance are low when the average dispersion particle size is 100 nm or more. When 50% or more of dispersed particles having a size of 100 nm or more (that is, aggregates of primary particles in which primary particles are aggregated and dispersed in a dispersion) are present, the dispersion becomes non-uniform. A thin film formed by the micellar electrolysis method using the above dispersion liquid is a film forming method utilizing physical deposition, and therefore has poor adhesion of the thin film to the substrate. Thus, a technique has been disclosed in which the obtained thin film is baked to enhance the bonding between particles of a hydrophobic substance to increase the adhesion (see JP-A-2-101194 and JP-A-2-104697). However, there is a problem that such baking treatment causes aggregation and deterioration of the particles, and causes a reduction in spectral transmittance. There is also a method of naturally drying the thin film without performing the baking treatment. However, it takes a long time to produce a target thin film, and there is a problem that productivity is significantly reduced. Therefore, the present inventors have intensively studied to develop a method of manufacturing a thin film and a color filter having excellent spectral characteristics and excellent adhesion.

[0003]

As a result, the average dispersion particle size of the hydrophobic substance in the dispersion or solubilizing solution is 100 n.
m and controlling the particle size distribution to within ± 50 nm of the average dispersed particle size, and further drying the thin film formed using the same at 140 ° C. or lower,
We found that we achieved our goal. The present invention has been completed based on such findings.

That is, the present invention provides an average dispersion particle diameter (r) of dispersed particles of a hydrophobic substance in a micelle dispersion or a micelle solubilization solution in which a hydrophobic substance and a ferrocene derivative surfactant are dispersed in an aqueous medium. While controlling the particle size to less than 100 nm, and adjusting the particle size distribution of the dispersed particles to within r ± 50 nm, inserting a conductive substrate into the micelle dispersion or micelle solubilizing solution, and conducting an electric current to the substrate. An object of the present invention is to provide a method for producing a thin film, which comprises drying the thin film at 140 ° C. or lower after forming the thin film. Further, the present invention provides a micellar dispersion or micellar solubilization solution obtained by using at least one kind of hydrophobic substance having red, green, and blue primary color spectral characteristics and using a ferrocene derivative surfactant in an aqueous medium. While controlling the average dispersed particle size (r) of the dispersed particles of the hydrophobic substance to less than 100 nm, and adjusting the particle size distribution of the dispersed particles to be within r ± 50 nm, the dispersed particles are transparent to the micellar dispersion or the micelle solubilizing solution. Inserting a substrate for producing a color filter having a conductive thin film, applying a current to the substrate to form a dye film on the electrode, and then drying the dye film at 140 ° C. or lower, producing the dye film. It also provides a method.

[0005] The hydrophobic substance used in the present invention includes various substances. For example, phthalocyanine, metal complexes of phthalocyanine and derivatives thereof,
Colors of naphthalocyanine, naphthalocyanine metal complexes and their derivatives, porphyrin, porphyrin metal complexes and their derivatives, perylene, perylene derivatives, quinacridone, isoindolinone, disazo, dioxazine, viologen, sudan, and derivatives thereof 1,1 'including filter pigments and organic dyes
Electrochromic materials such as -diheptyl-4,4'-bipyridinium dibromide, 1,1'-didodecyl-4,4'-bipyridinium dibromide, 6-nitro-1,3,3-trimethylspiro- (2'H -1 '
Photosensitive materials (photochromic materials) such as -benzopyran-2,2'-indoline) (commonly known as spiropyran), photosensor materials, liquid crystal display dyes such as p-azoxyanisole, and "Color Chemical Encyclopedia" CMC Co., Ltd. Electronics Dyes, Recording Dyes, Environmental Chromism Dyes, Photographic Dyes, Energy Dyes, Biomedical Dyes, Food / Cosmetic Dyes, listed on pages 542 to 717, issued March 28, 1988, Examples include dyes, pigments, and hydrophobic compounds among special coloring pigments. Also, 7,7,8,8-tetracyanoquinonedimethane (TCNQ) and tetrathiafluorene (T
Organic conductive materials and gas sensor materials such as 1: 1 complex with TF), photocurable paints such as pentaerythritol diacrylate, insulating materials such as stearic acid, and diazo type photosensitive materials such as 1-phenylazo-2-naphthol And paints. Further, water-insoluble polymers such as polycarbonate, polystyrene,
General-purpose polymers such as polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polyacrylonitrile (PAN), and polyphenylene, polypyrrole,
Polyaniline, polythiophene, acetylcellulose,
Examples include various kinds of polymers (such as polyvinyl pyridine) and copolymers (such as a copolymer of methyl methacrylate and methacrylic acid), such as polyvinyl acetate and polyvinyl butyral.

[0006] 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 the specification of International Publication (WO 89/01939), pyridinium-type ferrocene derivatives as described in JP-A-1-226894, and JP-A-Hei. Various ferrocene derivatives as disclosed in JP-A-88387, JP-A-1-45370, 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 hydrophobic substance and the ferrocene derivative surfactant are dispersed in the aqueous medium to produce a micelle dispersion or a micelle solubilized solution. Here, a supporting salt can be added as needed. As a method for producing a micelle dispersion or micelle solubilized solution of the present invention,
For example, the above-mentioned hydrophobic substance, ferrocene derivative surfactant and supporting salt are put in the above-mentioned aqueous medium, and sufficiently stirred by a mechanical homogenizer, an ultrasonic homogenizer, a pearl mill, a sand mill, a stirrer, a three-roll mill or the like. No. By this operation, the hydrophobic substance is uniformly dispersed or solubilized in the aqueous medium by the action of the surfactant, and becomes 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 hydrophobic substance is 1 to 500.
A range of g / liter is preferred. The stirring operation is performed using an ultrasonic homogenizer (output of 300 W or more, preferably 60 W or more).
(0 W or more, stirring time: 0.5 to 2 hours / liter) is preferable. Further, it is preferable to carry out centrifugal separation and to filter with a filter of about 0.5 μm to adjust the particle size. The particle size of the dispersed particles (primary particle aggregate) of the hydrophobic substance obtained by this operation, that is, the average dispersed particle size (r) is 100 n.
m, preferably 90 nm or less, and the particle size distribution of the dispersed particles is r ± 50 nm, preferably r ± 35 nm. Here, the average dispersed particle size is 100
When the particle size is not less than nm, or when the particle size distribution is out of the range of r ± 50 nm, the dispersion becomes unstable and the formed thin film becomes coarse, resulting in a decrease in spectral transmittance.
Incidentally, the primary particles and dispersed particles of the hydrophobic substance are as shown in FIG. That is, the primary particles a of the hydrophobic substance are dispersed in the micelle dispersion or the micelle solubilization solution to form dispersed particles b.

[0008] The supporting salt which can be used in the method for producing a micelle dispersion or micelle solubilizing solution of the present invention is added to adjust the electric conductivity of an 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 inorganic substance or hydrophobic organic substance, and is usually about 0 to 300 times the concentration of the above micelle agent, preferably 50 to 50 times. A density of about 200 times is a standard. 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 a hydrophobic substance on the electrode. Specifically, sulfates (salts such as lithium, potassium, sodium, rubidium, aluminum, etc.) and acetates (lithium, potassium,
Sodium, rubidium, beryllium, magnesium,
Salts of calcium, strontium, barium, aluminum, etc., halide salts (salts of lithium, potassium, sodium, rubidium, calcium, magnesium, aluminum, etc.), and water-soluble oxide salts (lithium, potassium, sodium, rubidium, calcium, Salts such as magnesium and aluminum) are preferred.

The most important factor in the composition of the micelle dispersion or the micelle solubilization solution is the relationship between the hydrophobic substance and the ferrocene derivative surfactant (micelleizing agent). Normal,
When a hydrophobic substance is put into a surfactant solution, the surfactant is adsorbed on the surface of the hydrophobic 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, for example, completely separating the hydrophobic substance by centrifugation (1,000 rpm or more) and determining the concentration of the surfactant remaining in the aqueous solution by elemental analysis such as plasma emission spectrometry (ICP). Required by The ferrocene derivative surfactant of the present invention may be analyzed for iron.

In order to stably and easily disperse the hydrophobic substance, it is preferable to adjust the equilibrium concentration to 0.05 mmol / L or more. According to the principle of micellar electrolysis, the surfactant is oxidized electrochemically, and as a result, the surfactant adsorbed on the hydrophobic substance is desorbed. When this operation is repeated, finally, the hydrophobic substance cannot be dispersed only by the adsorbed surfactant, and some of the hydrophobic substance particles aggregate to reduce the surface area. However, finally, the particles cannot be completely dispersed and the hydrophobic substance particles are deposited. Therefore, in order for this principle to work, on the contrary, if the concentration of the surfactant, that is, the equilibrium concentration, is too high, sufficient surfactant exists even if oxidized by electrolysis, and aggregation of the hydrophobic substance may occur. It will not happen, and will not be able to achieve its purpose.

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 obtained by adding the above-mentioned supporting salt to a micelle dispersion or a micelle solubilizing solution, and subjecting it to an electrolytic treatment using a conductive substrate (transparent electrode) while standing or with slight stirring. can get. Further, during the electrolytic treatment, the hydrophobic substance may be supplementarily added to the micelle dispersion or the micelle solubilization solution, or the micelle dispersion or the micelle solubilization solution near the anode is extracted out of the system,
A hydrophobic circuit may be added to the extracted micellar dispersion or micellar solubilizing solution, sufficiently mixed and stirred, and then a circulation circuit for returning the solution to the vicinity of the cathode may be provided. 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 not lower than the oxidation-reduction potential of the agent and not higher than the hydrogen generation potential, specifically 0.1-1.5 V, preferably 0.3-1.0.
V, and the current density is 10 mA / cm ² or less, preferably 50 to 300 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 ferrocene becomes Fe ³⁺ at the anode,
Micelles collapse, hydrophobic particles become anode (transparent electrode)
Precipitates on top. 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 forming operation can be repeatedly performed with the same solution.

The thin film formed in this way is 140
The drying treatment is performed at a temperature of not more than ℃ Here, when the drying treatment is performed at a temperature exceeding 140 ° C., the thin film is deteriorated, and as a result, the spectral transmittance is lowered, which is not preferable. Next, the dried thin film is preferably subjected to a cleaning treatment such as high-pressure water cleaning, high-pressure water spray, ultraviolet cleaning, ultrasonic cleaning, brush scrub, and surfactant cleaning. By such a micellar electrolytic treatment, a desired thin film containing a hydrophobic substance is formed.

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.

As the conductive substrate used here, a plate of aluminum or the like, or glass (low-expansion glass (70
59, manufactured by Corning Incorporated), non-alkali glass (NA4
5/300 mm square, width 1.1 mm; manufactured by HOYA), quartz glass, soda lime glass, etc.), thin film of ITO, platinum, graphite, Nesa film, chromium, nickel, antimony oxide, etc. on insulating substrate such as polymer, ceramic, etc. It is preferable to use a transparent electrode added as a material. This transparent electrode has a transmittance of 95% or more and a thickness of 1000 to 2000.
Å, those having a surface resistance of 500Ω / □ or less are preferable.
The material of the transparent electrode is the oxidation potential of the ferrocene derivative (+0.
A metal or a conductor that is nobler than 15 to 0.30 V (saturated electrode) is formed by a sputtering method, a vapor deposition method, or a pyrosol method. Specific examples include ITO, tin dioxide, and conductive polymer films. Note that when forming a thin film on these conductive substrates, it is preferable that the conductive substrates be washed with ultraviolet light in advance.

Further, R, G,
To form a dye film of B, BL (R: red dye, G: green dye, B: blue dye, BL: black dye)
At least one of R, G and B hydrophobic substances (dyes);
Alternatively, a hydrophobic dye of BL is further added to the aqueous medium,
A thin film having a desired color tone may be formed in a desired pattern by the above-described operation (similar to the formation of a thin film), and the above-described operation may be repeated by changing the type of the hydrophobic dye. 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. When preparing the micelle dispersion or the micelle solubilizing solution, the average dispersed particle size of the dispersed particles of the hydrophobic substance in the micelle dispersion or the micelle solubilizing solution (similar to the above-described method for producing a thin film) r) is 100
nm, and the particle size distribution of the dispersed particles is r
It is necessary to adjust within ± 50 nm. The drying temperature of the formed dye film should be adjusted to 140 ° C. or lower in the same manner as in the above-mentioned thin film manufacturing method.

The dyes having spectral characteristics of R, G, B, and BL used herein, that is, the hydrophobic dyes of R, G, B, and BL include the following. As R,
There are perylene pigments, lake pigments, azo pigments, dianthraquinones, quinacridone pigments, anthraquinone pigments and anthracene pigments, for example, perylene pigments, lake pigments (Ca, Ba, Sr, Mn), quinacridone, naphthol AS, There are shicomin pigments, anthraquinone, disazo (Sudan I, II, III, R), benzopyran, cadmium sulfide pigments, Fe (III) oxide pigments and the like, of which perylene pigments and lake pigments are preferred. Examples of G include halogen-substituted phthalocyanine pigments, halogen-substituted copper phthalocyanine pigments, and triphenylmethane-based basic dyes.
And triphenylmethane dyes. Examples of B include copper phthalocyanine pigments, indanthrone pigments, indophenol pigments and cyanine pigments, such as chlorocopper phthalocyanine, chloroaluminum phthalocyanine, vanadate phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, and cobalt. Examples include phthalocyanine metal complexes such as phthalocyanine, phthalocyanine, merocyanine, and indophenol blue. BL includes black organic pigments, organic pigments, inorganic pigments, etc., such as perylene black, R and cyanine, B and G and magenta, and B
Of carbon black (grade: MT, FT, SRF, GP)
F, FET, HAF, ISAF, SAF, MPC, etc.),
Examples include chromium, nickel, copper, Pr, Pt, praseodymium, platinum, ruthenium, titanium and their oxides, reactive black, aniline black, acid first black, direct first black, titanium black, platinum black, and the like. Also, disazo pigments, isoindoline pigments, isoindolinone pigments and the like can be used as yellow pigments for adjusting chromaticity, and dioxazine pigments can be used as purple pigments.

Next, a procedure for manufacturing a color filter will be described. There are various methods for producing the color filter of the present invention, and specific examples here include a method comprising a protective layer / dye film / ITO film / silica film / black matrix (BM) / glass substrate. . First, in order to form a BM, a Cr thin film is formed on a glass substrate by a sputtering method or the like, and a photo-curing resist agent (a photo-solubilizing resist agent is also applicable) is applied thereon after the film formation. Exposure is performed using an appropriate mask on the resist surface of the obtained resist / Cr thin film / glass substrate. The photocurable resist agent used here is, as a monomer or an oligomer,
Acrylics, methacrylic acid derivatives, copolymers of acrylic and methacrylic acid derivatives, and mixtures of these compounds with epoxy groups, siloxane groups, and polyimide precursors introduced therein. Photoinitiators include triazine-based compounds and acetophenone-based compounds. , Benzyne compounds, benzophenone compounds, thioxanthone compounds and the like.
Examples of the stabilizer include nonionic surfactants, organic pigment derivatives, polyester compounds, and mixtures thereof. Examples of the solvent include cellosolve compounds, cyclohexanone, methyl isobutyl ketone, diethylene glycol ether, ester compounds, and the like. And the like. When applying such a photocurable resist agent, it is preferable to previously wash the dye film or the like to be applied with ultraviolet rays. After exposing the applied resist agent, the uncured resist is washed away with a developing solution, and the exposed C
r The thin film is etched. After etching, the BM can be formed by removing unnecessary resist. Here, instead of the Cr thin film, a colored resist (color mosaic CK; manufactured by Fuji Hunt Electronics Technology Co., Ltd.) obtained by coloring a photocurable resist with a black pigment may be used.

Next, after spin-coating, for example, silica as an insulating material to be used for the insulating layer on the obtained BM, ITO is sputtered thereon so as to have an appropriate surface resistance. After forming the photocurable resist on the ITO surface of the formed ITO film / silica film / BM / glass substrate, the film is appropriately prebaked. Obtained resist / ITO film / silica film / B
Exposure is performed on the resist surface of the M / 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 etching, unnecessary resist is stripped off to remove IT
A substrate with O-patterned BM can be created.

Next, the obtained ITO patterned BM
After a film of an ultraviolet-curable resist is formed on the substrate with the film, it is appropriately prebaked. 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. In this manner, a dye film can be produced on a substrate by performing the same micellar electrolysis operation as described 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 is introduced into the holes 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 epoxy polymers or copolymers. Examples of the solvent for melting the structural reinforcing resin include cellosolve compounds, cyclohexanone, methyl isobutyl ketone, diethylene glycol ether, ester compounds, and mixtures thereof. Specific structural reinforcing resins include Optmer SS7265 (manufactured by JSR), JHR-
8484 (manufactured by JSR), JSS-819 (manufactured by JSR),
Examples include protective films such as JSS-715 (manufactured by JSR) and OS-808 (manufactured by Nagase Sangyo). In addition, the protective film
It is preferable to perform baking (baking) as necessary, and the baking temperature at that time is 150 to 260 ° C., preferably 18 ° C.
0-240 ° C.

[0021]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 Ferrocene derivative micellizing agent FPE in 4 liters of pure water
G (11-ferrocenylundecyl polyoxyethylene ether), lithium bromide and copper phthalocyanine were each made into a solution of 2 mmol, 0.1 mol, and 9 g / liter, and dispersed with an ultrasonic homogenizer for 30 minutes to form a dispersion. . The average particle size of the dispersed particles in the dispersion is 68 nm, and the particle size distribution is 68 ± 24.6 nm (light scattering particle measuring device, EL
S-800, measured by Otsuka Electronics Co., Ltd.). IT
A glass substrate (blue glass, polished, silica decup product: Matsuzaki Vacuum) having a sheet resistance of 20Ω / □ as an O film was inserted into the dispersion, and a potentiostat was connected. 0.5
V (based on SCE (saturated sweet potato electrode potential)) and constant potential electrolysis for 25 minutes to obtain a thin film of copper phthalocyanine. After the obtained thin film is washed with pure water, it is heated in an oven at 50 ° C. for 30 minutes.
Baking for minutes. FIG. 2 shows the result of measuring the spectral transmittance of the thin film before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking, and the lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Example 2 The same operation as in Example 1 was performed except that the baking temperature was changed to 100 ° C. FIG. 3 shows the results of measuring the spectral transmittance before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking, and the lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Example 3 The same operation as in Example 1 was performed except that the baking temperature was 130 ° C. FIG. 4 shows the result of measuring the spectral transmittance of the thin film before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking,
The lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Example 4 The same operation as in Example 1 was performed except that the baking temperature was 140 ° C. FIG. 5 shows the result of measuring the spectral transmittance of the thin film before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking,
The lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Example 5 The same operation as in Example 1 was carried out except that drying was carried out under vacuum at room temperature without baking. FIG. 6 shows the results of measuring the spectral transmittance of the thin film before and after vacuum drying. 2 showing this spectral transmittance
Among these curves, the upper curve shows the spectral transmittance before vacuum drying, and the lower curve shows the spectral transmittance after vacuum drying.
Table 1 shows the change in transmittance and pencil hardness of the thin film after vacuum drying.

Comparative Example 1 The same operation as in Example 1 was performed except that the baking temperature was 150 ° C. FIG. 7 shows the result of measuring the spectral transmittance of the thin film before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking,
The lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Comparative Example 2 The same operation as in Example 1 was performed except that the baking temperature was set to 200 ° C. FIG. 8 shows the result of measuring the spectral transmittance of the thin film before and after baking. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before baking,
The lower curve shows the spectral transmittance after baking. Table 1 shows the change in the transmittance of the thin film after baking and the pencil hardness.

Comparative Example 3 The same operation as in Example 1 was performed except that baking was not performed. FIG. 9 shows the results of measuring the spectral transmittance of the thin film before and after drying. Of the two curves showing the spectral transmittance, the upper curve shows the spectral transmittance before drying, and the lower curve shows the spectral transmittance after drying. Table 1 shows the change in transmittance of the thin film after drying and the pencil hardness.

[0029]

[Table 1]

* 1: The maximum value of the change in transmittance at the top peak of each of R, G, and B is described. * 2: Measured after creating a resist pattern. The pencil hardness in the table is based on the thin film after baking or drying.
The determination was performed according to K5400. The adhesiveness of the thin film of the present invention is determined by pencil hardness and may be any hardness B or more. Example 6 (1) Preparation of ITO Patterned Substrate UV curable resist agent (FH22130; Fuji Hunt Electronics Technology) on a glass substrate (blue glass, polished, silica-dipped product; manufactured by Matsuzaki Vacuum) having a surface resistance of 20Ω / □ as an ITO film Was spin-coated at a rotation speed of 1,000 rpm, and prebaked at 80 ° C. for 15 minutes. Next, this resist / ITO / glass substrate was placed in a contact exposure machine (exposure capacity: 120 mW / cm).
² · s) and patterning was performed. The used mask has a line width of 100 μm, a gap of 20 μm, and a line length of 23.
This is a 1920 mm vertical stripe pattern of 0 mm. As a light source, a 2 kW high-pressure mercury lamp was used. After alignment, take a proximity gap of 70 μm and
After exposure to J / cm ² , development was performed with a developer (FHD-5; manufactured by Fuji Hunt Electronics Technology).
After the development, the substrate was rinsed with pure water and post-baked at 180 ° C. Next, 1 mol of FeCl _3.
6N HCl, 0.1N HNO ₃ , 0.1N Ce (NO
₃ ) The mixed aqueous solution of 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 and remove the resist with 1N Na
It was peeled off with OH and further washed with pure water to prepare an ITO patterning substrate.

(2) Preparation of Black Matrix (BM) Substrate Color mosaic CR, color mosaic CG, color mosaic CB are applied to color mosaic CK (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) as a BM forming resist agent.
(Manufactured by Fuji Hunt Electronics Technology) in a weight ratio of 3: 1: 1: 1. The ITO patterned substrate prepared in (1) of Example 6 was rotated at 10 rpm, and 30 cc of the BM forming resist was sprayed thereon. Next, the number of rotations of the substrate
At 0 rpm, the resist material on the substrate was uniformly formed.
After pre-baking the substrate at 80 ° C. for 15 minutes, the BM was applied using a 2 kW high-pressure mercury lamp having an alignment function.
Design mask (pixel size: 90 × 310 μm square,
Exposure with a line width of 20 μm; see FIG. 10) was performed. After alignment, a proximity gap of 70 μm was taken, exposure was performed at 120 mJ / cm ² , alkali development was performed, and the developing solution (Fuji Hunt CD) was diluted 4 times with pure water to obtain 3
It was developed for 0 seconds. Furthermore, after rinsing with pure water, 200
Post-baking was performed at 100 ° C. for 100 minutes. (3) Preparation of electrode extraction zone An acrylic resist (CT; manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was used for electrode extraction. The ITO patterning B prepared in (2) of the sixth embodiment.
The substrate with M is rotated at 10 rpm, and the resist is sprayed on the substrate at 30 cc.
At 1500 rpm, a uniform film was formed on the substrate. This substrate was pre-baked at 80 ° C. for 15 minutes, and a high-pressure mercury lamp 2k
While aligning with a contact exposure machine having an alignment function of W, exposure was performed using a mask (FIG. 10: a portion not exposed to light in a bold line) designed to form only an electrode extraction band. 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. The electrodes are electrically connected with silver paste for each row taken out, and R, G, and
Column B (see FIG. 11).

(4) Preparation of Dispersion The following was used as the dispersion of R. A solution of ferrocene derivative micellizing agent FPEG (11-ferrocenylundecylpolyoxyethylene ether), lithium bromide and copper phthalocyanine in 4 liters of pure water at 2 mmol / L, 0.1 mol / L and 10 g / L, respectively. And dispersed with an ultrasonic homogenizer for 30 minutes to obtain a dispersion. As the dispersion of G, the dispersion of the above R using 15 g / l of a copper halide phthalocyanine instead of copper phthalocyanine was used. As the dispersion of B, the dispersion of the above R using 9 g / liter of copper phthalocyanine instead of 10 g / liter of copper phthalocyanine was used.

(5) Production of Dye Film 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 0.5 V (SCE standard) for 25 minutes to obtain a color filter R thin film. Then, after washing with pure water, prebaking was performed in an oven (at 100 ° C. for 10 minutes). Next, this substrate was inserted into the micellar solution of G, and the potential was similarly electrolyzed at 0.5 V (SCE standard) for 20 minutes to obtain a thin film of the color filter G. After film formation, R
The post-treatment was performed under the same conditions as for the film formation. Finally, the substrate was inserted into the micelle solution of B, and subjected to a constant potential electrolysis of 0.5 V (SCE standard) for 15 minutes.
Was obtained. 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.

(6) Production of Protective Film 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 was slowly rotated at a rotation speed of 10 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 7 (1) Preparation of black matrix (BM) Non-alkali glass substrate (HOYA: NA45 / 300 ×
300 μm square, thickness 1.1 mm) was set in a sputtering device (SDP-550VT) manufactured by ULVAC, Inc.
The thin film was sputtered at about 2000 °. A positive resist agent (FH2130, manufactured by Fuji Hunt Electronics Technology) was spin-coated on the Cr thin film at a rotation speed of 1000 rpm. After spin coating, the positive resist layer /
The laminate of the Cr layer / substrate was prebaked at 80 ° C. for 15 minutes and set in a stepper exposure machine. Here, a grid pattern with a pixel size of 90 × 310 μm square and an effective area of 160 mm × 155 mm square is used as a BM design mask.
The divided one was used. Exposure was 100 mJ / cm ² ,
After 60 seconds at a scan speed of 5 mm / sec, development was performed with a dedicated developer. After development and rinsing with pure water, 15
Post-baked at 0 ° C. for 15 minutes. Then, 1N HCl, 0.1N HNO ₃ , 0.1N C as an etching agent
A mixed aqueous solution of e (NO ₃ ) ₄ was prepared, and the Cr
The thin film was etched. The end point of the etching was measured by electric resistance. The etching required about 20 minutes. After etching, rinsing with pure water, removing the resist with 1N NaOH, washing with pure water,
M was created.

(2) Preparation of Insulating Film and ITO Thin Film Electrode On the BM obtained in (1) of Example 7, silica (OCDTYPE-7, manufactured by Tokyo Ohka) was used as an insulating film material.
Spin coating was performed at a rotation speed of 000 rpm. After spin coating, the substrate was baked at 250 ° C. for 60 minutes, and then cooled to room temperature. The obtained substrate was set in a sputtering device manufactured by ULVAC, Inc., and ITO was sputtered from the substrate at about 1700 °. At this time, the substrate temperature was adjusted to 180 ° C., and the surface resistance of ITO was adjusted to 20Ω / □. I thus obtained
Positive resist agent (FH21) on TO film / Cr / glass substrate
30, Fuji Hunt Electronics Technology Co., Ltd.)
Was spin-coated at a rotation speed of 1000 rpm. After spin coating, the laminate was pre-baked at 80 ° C. for 15 minutes,
It was set in a contact exposure machine. The mask used here has a line width of 92 μm, a line gap of 18 μm, and a line length of 155.
mm vertical stripes pattern. As a light source for exposure, a 2 kW high-pressure mercury lamp was used. After alignment, take a proximity gap of 50 μm and
J / cm ² exposure, alkali developing solution 2.4% TMAH
Was developed. After development, rinse with pure water,
Post-baking at 1 ° C., and then 1 M FeCl ₃ .1 N HCl, 0.1 N HNO ₃ , 0.1 N as an etchant.
A mixed aqueous solution of specified 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, remove the resist with 1N NaOH, wash with pure water and confirm that there is no electric leak between adjacent ITO electrodes, and create a substrate with ITO patterning BM did.

(3) Preparation of Electrode Extraction Band An acrylic negative resist (CT: manufactured by Fuji Hunt Electronics Technology) was used as an electrode extraction window frame band. The substrate with the ITO patterning BM obtained in (2) was rotated at 10 rpm, and 30 cc of the negative resist was sprayed thereon. Next, the rotation speed is set to 1000 rpm.
Thus, a negative resist agent was uniformly formed on the substrate. This substrate was pre-baked at 80 ° C. for 15 minutes to obtain a high-pressure mercury lamp 2
While aligning with a contact exposure device having an alignment function of kW, exposure was performed using a mask (FIG. 10: a portion to which light is not applied is shown in a bold line) designed to form only an electrode extraction band. After developing with a developer for 90 seconds,
The substrate was washed with pure water and post-baked at 180 ° C. for 100 minutes. Thus, an electrode extraction zone was obtained. The electrodes are electrically connected with silver paste for each row taken out, and R,
G and B columns.

(4) Production of Color Filter The substrate with the ITO patterned BM was inserted into the mixed micelle dispersion of R prepared in Example 1, and a potentiostat was connected to the R rows of the stripe. 0.7V (SCE standard)
For 20 minutes to obtain a color filter R thin film. Then, after washing with pure water, it was prebaked in an oven (at 100 ° C. for 15 minutes). Next, this substrate was inserted into the mixed micelle dispersion of G prepared in Example 1, and 0.4 V was applied.
Electrostatic potential electrolysis was performed for 15 minutes (SCE standard) to obtain a color filter G thin film. 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 dispersion of B prepared in Example 1, and 0.6 V (SCE standard)
Was performed 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.

(4) Formation of Protective Film Next, the prepared RGB color filter substrate was set at 10 rpm.
m, and 30 cc of Optmer SS-7265 topcoat agent (manufactured by Nippon Synthetic Rubber Co., Ltd.) was sprayed thereon, the spin coating rotation speed was set to 1,000 rpm, and a uniform film was formed on a substrate (RGB color filter). . This substrate is
Post-baking was performed at 0 ° C. for 50 minutes.

Example 8 (1) Preparation of Transparent Conductive Thin Film Substrate An ITO thin film was sputtered on a mirror-polished 300 mm × 300 mm square white glass substrate (7059, manufactured by Corning Incorporated) using the above sputtering apparatus by about 1300 °. did. At this time, the substrate temperature was adjusted to 250 ° C., and the surface resistance of the ITO was adjusted to 20Ω / □. (2) Production of color filter Ferrocene derivative micellizing agent FPE in 4 liters of pure water
G, lithium bromide and dianthraquinone were made into solutions of 2 mmol / L, 0.1 mol / L and 10 g / L, respectively, and dispersed with an ultrasonic homogenizer for 30 minutes to form a micelle solution. Next, the I obtained in the above (1)
The substrate on which the TO thin film was formed was inserted into the obtained micelle solution, and a potentiostat was connected. 0.5V vs. S
Perform constant potential electrolysis for 20 minutes with CE,
Was obtained. Then, after washing with pure water, pre-baking (100 ° C. for 15 minutes) in an oven and washing with a 180 W UV lamp. Furthermore, a transparent photo-curable resist (JNP
C06, manufactured by JSR) on the R thin film at 1000 rpm
And prebaked at 80 ° C. for 30 minutes. R
Using a mask for array exposure, taking a proximity gap of 60 μm with a proximity type exposure machine,
After exposure at J / cm ² , immersion development was carried out with a developing solution of 2.38% TMAH (FHD-5, manufactured by Fuji Hunt Electronics Technology) at room temperature. Further, when brush scrubbing was performed with pure water, the exposed R and the transparent photocurable resist remained, and the remaining unexposed resist and R dye could be removed. Next, after the above resist was completely thermally cured at 200 ° C., dry etching was performed for 10 minutes with a UV / ozone asher (ultraviolet cleaning device PL1-907, Sen Special Light Source Co., Ltd.), and the dye in the unexposed portion was The layers were completely disassembled and removed. Thus, an R dye pattern having excellent resolution was formed. Dyes (pigments) used
G (dye: copper halide phthalocyanine 15 g / l), B (dye: copper phthalocyanine 9 g / l), BL (dye:
Carbon black 10 g / l, used to form BM), and R, G, B, BL
Are arranged in stripes.

[0041]

According to the present invention, a thin film and a color filter having excellent transparency, spectral characteristics and adhesion can be manufactured. Therefore, according to the present invention, it can be effectively used for a laptop personal computer, a word processor, a workstation, an aurora vision, a liquid crystal projector, a liquid crystal TV, an OHP, a vehicle-mounted instrument panel, a device monitor, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a thin film formed of primary particles of a hydrophobic substance and a state in which the primary particles are dispersed in a micelle dispersion or a micelle solubilization solution to form dispersed particles.

FIG. 2 shows measurement results of spectral transmittance before and after film formation in Example 1.

FIG. 3 shows measurement results of spectral transmittance before and after film formation in Example 2.

FIG. 4 shows measurement results of spectral transmittance before and after film formation in Example 3.

FIG. 5 shows the measurement results of spectral transmittance before and after film formation in Example 4.

FIG. 6 shows measurement results of spectral transmittance before and after film formation in Example 5.

FIG. 7 shows measurement results of spectral transmittance before and after film formation in Comparative Example 1.

FIG. 8 shows measurement results of spectral transmittance before and after film formation in Comparative Example 2.

FIG. 9 shows measurement results of spectral transmittance before and after film formation in Comparative Example 3.

FIG. 10 shows a BM design mask.

FIG. 11 shows an electrode extraction window and a mask of an effective display unit.

[Description of Signs]: Spectral transmittance curve of thin film before baking or vacuum drying: Spectral transmittance curve of thin film after baking or vacuum drying 1: R row 2: G row 3: B row A: Thin film B: Dispersion liquid a: primary particles b: dispersed particles

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C25D 9/02 C25D 13/04 G02B 5/20

Claims (6)

(57) [Claims] An average dispersion particle diameter (r) of a dispersed substance of a hydrophobic substance in a micelle dispersion or a micelle solubilization solution obtained by dispersing a hydrophobic substance and a ferrocene derivative surfactant in an aqueous medium is reduced to less than 100 nm. While controlling and adjusting the particle size distribution of the dispersed particles within r ± 50 nm, a conductive substrate was inserted into the micelle dispersion or micelle solubilizing solution, and a current was applied to the substrate to form a thin film. Thereafter, the thin film is dried at 140 ° C. or lower. 2. A micellar dispersion or micellar solubilization solution obtained by using at least one kind of hydrophobic substance having three primary colors of red, green and blue spectral properties and using a ferrocene derivative surfactant in an aqueous medium. While controlling the average dispersed particle size (r) of the dispersed particles of the hydrophobic substance to less than 100 nm, and adjusting the particle size distribution of the dispersed particles within r ± 50 nm, patterning the micellar dispersion or the micelle solubilizing solution. Inserting a substrate for producing a color filter having a transparent conductive thin film formed thereon, applying a current to the substrate to form a dye film on an electrode, and then drying the dye film at 140 ° C. or lower. Manufacturing method of membrane. 3. A transparent photo-curable resist is applied on the dye film according to claim 2, and further subjected to an exposure process using a mask pattern corresponding to a pixel or a black matrix.
A method for producing a color filter, comprising removing an uncured photocurable resist and a thin film by etching. 4. The method for producing a thin film according to claim 1, wherein the substrate is cleaned with ultraviolet light before the thin film is formed by the energization process. 5. The method for producing a dye film according to claim 2, wherein the substrate is washed with ultraviolet light before the formation of the dye film by the energization treatment. 6. The method for producing a color filter according to claim 3, wherein the dye film is subjected to ultraviolet cleaning before forming a thin film by applying a current or before applying a photocurable resist.