JPH07128519A - Production of color filter - Google Patents

Abstract

PURPOSE:To produce a color filter capable of forming a highdefinition display picture having high light resistance and quality when used in a color liq. crystal display, etc., with high efficiency (yield). CONSTITUTION:A black matrix is formed with metal or metal oxide, then a pigment film of one color is formed by micelle electrolysis, a photo-curing resin is laminated thereon and patterned, the resist and pigment film on the unexposed part are removed by etching to form a pigment layer of one color, the process is repeated to form the layers of other colors, and a pigment pattern of plural colors is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color liquid crystal display, an indoor / outdoor large screen image such as an aurora vision, an information display device, a method for manufacturing a color filter used for a solid-state image pickup device (CCD), etc. The present invention relates to a method for manufacturing a color filter capable of improving image quality and high definition and improving production efficiency (yield).

[0002]

2. Description of the Related Art In recent displays for liquid crystal televisions, liquid crystal projectors, laptop personal computers, notebook personal computers, etc., an insulating substrate or a conductive thin film laminated on the insulating substrate is formed. Further, a color filter formed by planarly patterning, that is, separating and disposing the dye layer is used.

FIG. 11 shows the structure of a general color liquid crystal display. In this color liquid crystal display, liquid crystal 30 is enclosed between the color filter substrate 10 and the driving substrate 20. After the liquid crystal 30 is sealed, it is sealed with adhesives (sealing materials) 40a and 40b. The color filter substrate 10 has three primary colors, that is, red (red, R) green (green, green, green, green, green, etc. on a glass substrate 1 as an insulating substrate or a conductive thin film laminated on a glass substrate.
G), blue (blue, B) (hereinafter, simply R,
Dye layers 5a, 5b and 5c) (referred to as G and B) are respectively formed. Further, a black matrix (hereinafter referred to as BM or BL, if necessary) 2a, 2b, 2c, 2d which plays a role of preventing the contrast and the color purity from being deteriorated due to the leaked light between the dye layers 5a to 5c.
Are repeatedly provided. After that, a protective film 6 is formed on the black matrices 2a to 2d and the dye layers 5a to 5c to be flat, and a liquid crystal driving transparent electrode is provided on the upper surface thereof. On the other hand, the driving substrate 20 includes a transparent driving electrode 22a, 22b, 22c, an insulating substrate 21 such as a glass substrate.
22d is formed.

The dye layer of such a color filter is usually an ink obtained by kneading a resin or a pigment (dye (pigment)) of three primary colors of R, G, and B on an insulating transparent substrate such as a glass substrate using a printing machine. It is formed by a printing method for printing.

Further, an ultraviolet curable resin (resist) containing dispersed pigments or dyes (colorants) is coated on a glass substrate, and R, G, A dispersion method in which a dye layer is formed by repeating three times for each B, or a photosensitive natural polymer such as gelatin is coated on a glass substrate, exposed to a mask by a photolithography method, and after development, R, G, and B are selected. A dyeing method is used in which the step of dyeing gelatin patterned with a dye of one color and heat curing is repeated in the same manner for the remaining two colors to form a dye layer.

Further, a substrate on which an electrodeposition polymer and a pigment or dye (colorant) are dispersed in a liquid such as water, a conductive thin film is formed on the substrate and patterned to form the pattern (electrode) is used. An electrodeposition method in which R, G, and B dye layers are sequentially electrodeposited on the lever electrode to form a dye layer composed of a pigment or paint (dye) and an electrodeposition polymer, or a surfactant and a pigment or A micellar electrolysis method is used in which a dye (pigment) is dispersed in a liquid such as water, and a pigment or each dye of R, G, B of the dye is sequentially formed on the above electrode to form a dye layer. ing.

In any of the above methods for forming the dye layer of the color filter, a thermosetting resin or the like may be laminated and formed as a protective film on the dye layers of a plurality of colors arranged in a plane. Good. In the manufacturing method of the above color filter, the dye layer formed by the micelle electrolysis method,
It is known that since the pigment content is high, it is excellent in light resistance (Japanese Patent Application No. 4-31905). Here, as a method for producing a color filter having excellent light resistance by the micelle electrolysis method, mainly, Step 1 (Japanese Patent Laid-Open No. 3-102302) is used.
No.), step 2 (JP-A-4-110901), step 3
(JP-A-5-142418) is disclosed. The details will be described below.

Step 1: FIG. 13 is a front view showing the structure of a color filter having a stripe type dye pattern, and FIG.
FIG. 14 is a cross-sectional view taken along the line XY of FIG. 13 showing the manufacturing process thereof. (A): A transparent conductive thin film is formed on an insulating substrate. (B): The transparent conductive thin film is patterned. (C): A BL (black) dye-containing photocurable resist cured product pattern is formed to form a black matrix and an electrode extraction layer. (D): R, G, B dye layers are formed and formed by the micelle electrolysis film formation. (E): A protective film is formed. (F): The substrate is cut along the line A in FIG. (G): A transparent conductive thin film (electrode) for driving a liquid crystal is formed. Hereinafter, steps 2 to 3 and steps 6 to 8 will be simply described in a similar manner.

Step 2: FIG. 15 is a front view showing the structure of a color filter having a diagonal type dye pattern, and FIG. 14 is a sectional view taken along the line XY of FIG. 15 showing the manufacturing process. Patterning by forming a metal or metal oxide thin film on an insulating substrate (black matrix formation) → insulating film formation → transparent conductive thin film deposition → transparent conductive thin film patterning →
Photocurable resist cured product patterning (electrode extraction layer formation) → micelle electrolysis film formation R, G, B dye layer formation → protection film formation → substrate cut at line A in FIG. 15 → transparent conductive thin film for driving liquid crystal (electrode ) Formation

Step 3: FIG. 17 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 16 is a sectional view taken along the line XY of FIG. 17 showing the manufacturing process. Deposition of transparent conductive thin film on insulating substrate → Patterning of transparent conductive thin film → Photocurable resist cured product (dye may be included)
Patterning (electrode extraction layer formation) → micelle electrolysis method film formation R, G, B dye layer formation → protection film formation → substrate cut at line A in FIG. 17 → liquid crystal driving transparent conductive thin film (electrode) formation → metal or metal Oxide thin film patterning (black matrix formation)

Step 6: FIG. 19 is a front view showing the structure of a color filter having a triangle type dye pattern, and FIG. 18 is a sectional view taken along the line XY of FIG. 19 showing its manufacturing process. Metal or metal oxide thin film on insulating substrate, pattern formation (black matrix formation) → R, G, B dye-containing photocurable resist cured product pattern formation (color pattern formation) → protective film formation → liquid crystal driving transparent conductive Thin film (electrode) formation

Step 7: FIG. 21 is a front view showing the construction of a color filter having a diagonal type dye pattern, and FIG. 20 is a sectional view taken along the line XY of FIG. 21 showing its manufacturing process. Patterning of metal or metal oxide thin film formation on insulating substrate (black matrix formation) → transparent conductive thin film formation → <photosolubilization type resist pattern formation → electrodeposition method film formation dye layer formation> (repeat RGB 3 times) -> Photosolubilization type resist stripping-> Transparent conductive thin film (electrode) formation for liquid crystal drive

Step 8: FIG. 23 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 22 is a sectional view taken along line XY of FIG. 23 showing the manufacturing process. Transparent conductive thin film deposition on insulating substrate → <Photosolubilizing resist (patterning) → Micelle electrolysis film-forming dye layer formation (RGB 3 times repeated) → Photosolubilizing resist stripping →
Protective film formation → transparent conductive thin film (electrode) formation for liquid crystal driving

[0014]

However, in any case, as a problem of the above-mentioned steps 1 to 3 of the prior art, the transparent conductive thin film is patterned, and the dye layer continuously connected for each color of RGB. There is a problem that the forming electrode and the electrode take-out layer are indispensable (same for the electrodeposition method). In addition, patterning of the transparent conductive thin film, which is mainly ITO, requires high-definition patterning such as a triangle or diagonal array, and microfabrication by a photolithography method corresponding to a complicated dye (pixel) array pattern. Except for simple patterns such as stripes, defects due to short-circuiting or disconnection of the transparent conductive thin film were likely to occur. That is, the widths of the lines of the dye forming electrode pattern and the gaps between the lines were smaller in the case of the diagonal and triangle arrangements, and the probability of defects due to short circuit or disconnection was increased as compared with the stripe pattern. Next, the electrode extraction layer also needs to be patterned similarly, and the process is complicated. As a result, the yield of color filters in production has been unavoidable.

Furthermore, by continuously connecting the fine dye layer forming electrodes, a voltage drop occurs due to the resistance of the transparent conductive thin film, and the dyes formed by the micelle electrolysis method in the vicinity of the electrode extraction layer and the remote portion. In some cases, a difference in film thickness between layers, that is, a color spot on the color filter occurs. Especially in the case of diagonal and triangle arrangements, the frequency of occurrence was high. Further, since the dye layer is formed on the pattern of the fine transparent conductive thin film, a difference in film thickness of the dye layer, that is, a step difference in the pixel may occur between the central portion and the end portion of the pattern line. As a result, the contrast of the color filter may be deteriorated and the image quality may be deteriorated.

The above problems are not unique to the micelle electrolysis method, and there are similar problems in the electrodeposition method. In the case of manufacturing the color filter by the electrodeposition method,
In order to solve the above-mentioned problems by a resist electrodeposition method (JP-A-61-272720 and JP-A-4-24740), (a) a step of forming a transparent conductive layer on a transparent substrate,
(B) a step of forming a specific positive photosensitive resin composition (photosolubilizing resist) on the transparent conductive layer, (c) placing a mask having a desired pattern on the photosensitive resin layer, and then exposing・ Developing to expose a part of the transparent conductive material, (d)
A multicolor display device including a step of forming a colored layer (dye layer) of a desired color on the exposed transparent conductive layer by electrodeposition, and (e) a step of repeating the steps (c) and (d) a required number of times. A method of manufacturing a (color filter) is disclosed (for example, the step 7). However, in the dye layer (coloring layer) of the color filter formed by this manufacturing method, as described above, the electrodeposition polymer (water-soluble acrylic resin, epoxy resin, etc.) is present in a considerable proportion, and the pigment content is high. Therefore, there is a problem that the light resistance of the formed color filter is lowered by the electrodeposition polymer.

On the other hand, in the micelle electrolysis method, the method disclosed in Japanese Patent Laid-Open No.
No. 342205, an attempt is made to solve the above problems by a method similar to the resist electrodeposition method (the dye layer is formed by a micelle electrolysis method instead of the electrodeposition method) (for example, the step 8). Since the dye layer formed by the micelle electrolysis method is porous and cannot be electrically insulated, the dye layer formed earlier is repeatedly formed when the multi-color dye layer is repeatedly formed. There has been a problem that the color spectrum required for the color filter is not recognized due to the contamination.

On the other hand, there are the following problems when the dye layer is formed not only by the micelle electrolysis method and the electrodeposition method but also by other manufacturing methods. That is, since the color filter by the dispersion method contains a dye, that is, a photocurable resist in which the dye is dispersed, the light absorption of the dye causes the exposure sensitivity and the fineness (resolution) of the dye pattern to be higher than that of the transparent resist. It had to get worse. Further, the dye-containing resist is applied by a spin coater or a roll coater, but a difference in film thickness of the resist occurs between the center part and the end part of the color filter, and this film thickness difference causes color unevenness ( For example, the above step 6). With the printing method color filter, it is difficult to align the R, G, and B when printing sequentially, and it has been difficult at present to obtain a high-resolution (high-definition) dye pattern. In the dyeing method, since the dye is a dye, there is a problem in heat resistance in post-processing of the color filter and chemical resistance in the washing process. Further, in any of the dispersion method, the printing method, and the dyeing method, the color filter formed because the pigment layer has a structure in which the pigment (pigment) and the resin (organic substance) coexist (the ratio of the resin is higher than that of the pigment). There was a problem in light resistance.

The present invention has been made in view of the above problems, and has high light resistance when used in a color liquid crystal display or the like, and can improve the definition of a displayed image, and improve the image quality thereof. An object of the present invention is to provide a method for manufacturing a color filter that can improve the production efficiency (yield).

[0020]

In order to achieve the above object, according to the present invention, dye layers of a plurality of colors are separately formed and arranged on an insulating substrate to form a predetermined dye pattern. In the method of manufacturing a color filter for forming a black matrix, a) a step of forming a transparent conductive thin film on the entire surface of the insulating substrate including a portion corresponding to a region where dye layers of at least a plurality of colors are formed, b) a step of forming a metal or metal oxide thin film on the entire surface including a region where a dye layer of at least a plurality of colors and a black matrix are formed on the transparent conductive thin film, c) light on the metal or metal oxide thin film A layer of curable resist is laminated, and a photocurable resist pattern is formed in the shape of a black matrix by the photolithography method. Or a step of removing the metal oxide thin film by etching to form a black matrix, d) a step of forming a dye film of one color selected from a plurality of colors on the exposed transparent conductive thin film by a micelle electrolysis method, e ) Laminating a photo-curable resist on a dye film of one color, exposing it using a mask corresponding to the dye layer of one color, and exposing the unexposed part of the light before and / or after the heat treatment of the exposed part. The step of forming and arranging the dye layer of one color by removing the curable resist and the dye film by etching, and f) the steps similar to the steps d) and e) are repeated once or more to obtain a plurality of colors. A method of manufacturing a color filter, comprising: a step of separately forming and arranging the dye layers of the remaining colors on the entire surface or a part of the transparent conductive thin film to form a dye pattern of a plurality of colors. It is subjected.

In the step c) of forming the black matrix, a photosolubilizing resist is laminated on a metal or metal oxide thin film, and a photosolubilizing resist pattern is formed in the shape of the black matrix by a photolithography method. The method for producing a color filter is characterized in that the black matrix is formed by forming a black matrix by removing the metal or metal oxide thin film in the exposed portion of the base by etching. Provided.

Further, there is provided a method of manufacturing a Lar filter, which further comprises laminating and forming a protective film and / or a liquid crystal driving electrode after the step f) of forming the dye patterns of a plurality of colors.

In addition, before or during the steps d), e) and f) of forming and arranging the dye layers of the plurality of colors and forming the dye patterns of the plurality of colors, a plurality of layers on the transparent conductive thin film are formed. An insulating film is laminated on a portion other than the area where the color dye layer is formed,
A method for manufacturing a color filter, which is characterized by being formed.

Further, there is provided a method of manufacturing a color filter, wherein the dye layers of a plurality of colors correspond to the three primary colors of red, blue and green.

Further, there is provided a method of manufacturing a color filter, which comprises washing the dye films with ultraviolet rays after the steps d) and / or f) of forming the dye films of the plurality of colors by a micelle electrolysis method. It

Further, there is provided a method of manufacturing a color filter, wherein the photo-curable resist is laminated and formed by a micelle electrolysis method or an electrodeposition method.

Further, there is provided a method of manufacturing a color filter, characterized in that the protective film is laminated and formed by a micelle electrolysis method or an electrodeposition method.

The manufacturing process of the present invention will be briefly described below, and the materials used and the method of using the materials will be specifically described.

1. Manufacturing Process of Color Filter of the Present Invention Representative examples will be shown below, but the present invention is not limited to the following examples. The order of forming the dye layers R, G, and B is arbitrary. Step 4: FIG. 2 is a front view showing the configuration of a color filter having a diagonal dye pattern, and FIG. 1 is a sectional view taken along line XY of FIG. 2 showing the manufacturing process. (A): A transparent conductive thin film is formed on an insulating substrate (a). (B): Form a metal or metal oxide thin film (b). (C): Photocurable resist is laminated and patterned, and the metal or metal oxide thin film is removed by etching (formation of black matrix) (c). (D): R dye is formed into a film by the micelle electrolysis method (d). (E): Photocurable resist is laminated (e). (F): The photocurable resist is patterned, and the R dye film in an unnecessary portion is removed by etching (R dye layer formation).
(F). (G): (d), (e), and (f) are repeated for the B dye (B dye layer formation) (g). (H): G dye is formed into a film by the micelle electrolysis method (G dye layer formation) (h).

If necessary, the photocurable resist laminated patterning and unnecessary G dye film etching may be performed. The laminated patterning may be performed only on the dye layer region (pixel) of the third color (here, G), or may include the region of the dye layer of the first color and the dye layer of the second color (entire display portion). Further, each step of (I) laminating a protective film (i) and / or (J) forming a transparent conductive thin film (electrode) for driving a liquid crystal (j) on at least the R, B and G dye layers. May be added.
Further, an insulating film may be laminated on a portion of the color filter other than the portion corresponding to the region where the pigment layers of a plurality of colors are formed (however, as in the example of step 4 and FIG. If the photo-curable resist is also laminated on the portion except the portion corresponding to the region where the color dye layer is formed, it is not necessary to laminate the insulating film). The stack is
It may be before the step of forming the R, G, B dye layers or during the step of forming the R, B, G dye layers. Similarly, step 5 will be simply described below.

Step 5: FIG. 4 is a front view showing the structure of a color filter having a triangle type dye pattern.
FIG. 3 is a sectional view taken along the line XY of FIG. 4 showing the manufacturing process. Transparent conductive thin film deposition (a)-> metal or metal oxide thin film deposition (b)-> photo-solubilization type resist patterning, metal or metal oxide thin-film etching, photo-solubilization type resist stripping ( Formation of black matrix)
(C) → Micelle electrolysis method R dye film (d) → photocurable resist laminate (e) → photocurable resist patterning / unnecessary part R dye film etching (R dye layer formation) (f) →
(D), (e), and (f) are repeated for the B and G dyes (B and G dye layer formation) (g) The laminated patterning of the third color photocurable resist is
Only the dye layer region (pixel) of the third color (here, G) may be included, or the regions of the dye layer of the first and second colors (entire display portion) may be included. Further, each step of (H) laminating a protective film (h) on at least the R, B, and G dye layers, and / or (I) forming a transparent conductive thin film (electrode) for driving a liquid crystal (i) May be added. Further, an insulating film may be laminated on a portion of the color filter other than the portion corresponding to the region where the pigment layers of a plurality of colors are formed. The stack is R,
It may be before the step of forming the B and G dye layers or during the step of forming the R, B and G dye layers.

2. Materials Used in Each Step and Methods of Using the Same Next, materials used in the steps of manufacturing the color filter of the present invention described above and methods of using the same will be described. (1) Insulating substrate Glass plate (low expansion glass, non-alkali glass (eg, Corning 7059, HOYA NA45), quartz glass plate, soda lime glass), the glass plate with a microlens, or a plastic plate ( Polyethylene terephthalate etc.) can be used. In this case, a glass plate is suitable and is preferably a polished product, but may be non-polished.

(2) Transparent Conductive Thin Film Any metal or conductor that is noble than the oxidation potential of the ferrocene derivative of the micellizing agent may be used. For example, mixed oxide of indium and tin (ITO), tin dioxide, transparent conductive polymer and the like can be used. However, visible light transmittance 95%
Above (thin film only), it is preferable to set the film thickness to 100 to 2000Å and the sheet resistance to 500Ω / □ or less. This transparent conductive thin film can be formed by a sputtering method, a vapor deposition method, a CVD method, a coating method, a pyrosol method or the like. In this case, the film is formed on the entire surface of the insulating substrate including the portion corresponding to the region where the dye layers of at least a plurality of colors are formed. Specifically, it may be the entire surface when viewed two-dimensionally on the insulating substrate,
It is formed on the entire surface including a portion corresponding to at least a region where the dye layers of a plurality of colors are formed by a masking method.

(3) Black Matrix In the present invention, a metal or metal oxide thin film is used as the material for forming the black matrix. As the metal or metal oxide, for example, chromium (Cr), nickel (Ni), titanium (Ti), copper (Cu), or the like or an oxide thereof can be used. It may be a mixture of metal and metal oxide. Optical density 3.0 or more (film thickness 100 to 3000
Å) is preferred. In this case, the insulating substrate is viewed two-dimensionally by a sputtering method, a vapor deposition method, a CVD method, or the like, and corresponds to the entire surface of the insulating substrate or a region where at least a black matrix and dye layers of a plurality of colors are formed by a masking method. After forming a film on the entire surface including the portion, patterning is performed by a photolithography method. That is, resist coating, exposure (using a mask for forming a black matrix), development, post-baking, etching of a metal or metal oxide thin film, and resist stripping (removal) are sequentially performed to form a pattern.

The above-mentioned shape of the black matrix must exist at least in the gap between the dye layers in order to prevent the deterioration of the contrast and the color purity due to the leaked light between the dye layers of a plurality of colors. It is more preferable that each dye layer partially overlaps the black matrix in order to completely eliminate leakage light. Furthermore, the shape of the black matrix region may be present also in a portion (a peripheral portion outside the display portion of the color filter) where the pigment layers of a plurality of colors are not present on the insulating substrate.

(4) Dye film formed by micellar electrolysis method Red (R) dye film Perylene pigment, lake pigment, azo pigment, quinacridone pigment, anthraquinone pigment, anthracene pigment, disazo pigment, isoindoline pigment Pigments, isoindolinone-based pigments and the like can be used individually or as a mixture of at least two types. Green (G) dye film Halogen polysubstituted phthalocyanine pigment, halogen polysubstituted copper phthalocyanine pigment, triphenylmethane basic dye, disazo pigment, isoindoline pigment, isoindolinone pigment, etc., individually or at least Mixtures of two or more can be used. Blue (B) Dye Film Copper phthalocyanine-based pigments, phthalocyanine-based pigments, indanthrone-based pigments, indophenol-based pigments, cyanine-based pigments, dioxazine-based pigments and the like can be used individually or in a mixture of at least two types. The above is formed into a film by the micelle electrolysis method. Regarding the film thickness and the transmittance of each dye film, R has a film thickness of 0.5 to 1.5 μm (transmittance of 60% or more /
610 nm), G film thickness 0.5-1.5 μm (transmittance 6
0% or more / 545 nm), and the thickness of B is 0.2 to
The thickness is preferably 1.5 μm (transmittance of 60% or more / 460 nm).

Conditions for Micelle Electrolysis Method The above-mentioned dye (pigment or dye) that has been subjected to a hydrophobizing treatment, or a photo-curable resist or thermosetting resin described below is used with a surfactant (micelle agent) composed of a ferrocene derivative. Disperse in an aqueous medium to prepare a micellar dispersion. At this time, as the aqueous medium to be used, various media such as water, a mixed solution of water and alcohol, a mixed solution of water and acetone can be mentioned. For example, the following ferrocene derivative surfactants can be mentioned.

[0038]

[Chemical 1]

As the ferrocene derivative, other than the above, WO 89/0193, JP-A-1-4 can be used.
It is possible to use those manufactured by the methods described in JP-A-5370, JP-A-1-226894, JP-A-2-83387, JP-A-2-250892, and the like. As the surfactant (micelling agent), one kind of ferrocene derivative may be used, or two or more kinds thereof may be combined. Alternatively, the ferrocene derivative and other surfactant may be combined. Other surfactants include, for example, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and alkyl sulfates, Examples thereof include cationic and anionic surfactants such as polyoxyethylene alkyl ether sulfate, alkyl trimethyl ammonium chloride, and fatty acid diethylaminoethylamide.

Preparation of Micelle Dispersion A mechanical homogenizer is prepared by adding a ferrocene derivative, another surfactant optionally used and a desired dye (pigment), or a photocurable resist or a thermosetting resin to an aqueous medium. , Thoroughly mix with an ultrasonic homogenizer, ball mill, sand mill, stirrer, etc. When ultrasonic waves are used, the ultrasonic wave application conditions should be 5 hours /
When it is set to liter or less and centrifugation is used, it is preferable that the centrifugation condition is 4 G or less. By this operation, the pigment is uniformly dispersed or micellized in the aqueous medium by the action of the surfactant to be a dispersion liquid or a micelle solution. The concentration of the micellizing agent at this time is not particularly limited, but usually,
The total concentration of the ferrocene derivative and the other surfactant is selected to be not less than the critical micelle concentration, preferably in the range of 0.1 milmol / liter to 1 mol / liter. On the other hand, the pigment or dye concentration is usually selected in the range of 1 to 500 g / liter.

Further, a supporting salt (supporting electrolyte) can be added, if necessary, in order to adjust the electric conductivity of the aqueous medium. The amount of the supporting salt added may be within a range that does not hinder the precipitation of the dispersed pigment on the electrode, and is usually 0.
Select from the range of 05 to 10 mol / liter. It is also possible to carry out electrolysis without adding this supporting salt. In this case, a highly pure thin film (dye film) containing no supporting salt can be obtained. Further, 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 the formation of micelles and the deposition of the pigment on the electrode. Specifically, sulfates (salts of lithium, potassium, sodium, rubidium, aluminum, etc.) that are generally widely used as supporting salts, acetates (lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, (Salts of barium, aluminum, etc.), ammonium salts, and the like are preferable, and examples thereof include LiBr, KCl, and Li.
₂ SO ₄ , (NH ₄ ) BF _4, etc. can be mentioned. Furthermore, it is preferable to filter with a filter of 0.5 μm or less. In this way, red pigment (pigment or dye), green pigment (pigment or dye), blue pigment (pigment or dye),
Five types of micelle dispersions in which a photocurable resist and a thermosetting resin are dispersed are prepared. The micellar dispersion of mixed pigments may be prepared by adding a pigment or dye to be mixed in an aqueous medium together with a micellizing agent once and dispersing it, or micellar a single pigment to be mixed in an aqueous medium. You may mix and prepare each micelle dispersion liquid obtained by adding and dispersing with an agent.

Micelle Electrolytic Method Film Formation Next, a transparent conductive thin film is formed on any one of the above micelle dispersion liquids over the entire surface including a portion corresponding to the region where the dye layers of at least a plurality of colors are formed, Further, an insulating substrate having a black matrix formed on the transparent conductive thin film is inserted, and this is energized to perform micelle electrolysis, thereby forming a desired thin film (dye film) on the transparent conductive thin film of this substrate.

The electrolysis conditions may be appropriately selected according to various circumstances, but the liquid temperature is usually 0 to 90 ° C., preferably 10 to 10.
Select in the range of 70 ° C. The voltage is 0.03 to 1.5V,
Preferably, it is selected in the range of 0.1 to 0.9V. Also,
The current density is usually 10 mA / cm ² or less, preferably 50 to 300 μA / cm ² . When this electrolytic treatment is performed, the reaction proceeds according to the principle of the micelle electrolysis method. Focusing on the behavior of the Fe ion of the ferrocene derivative, Fe ²⁺ of ferrocene becomes Fe ^{3+ at} the anode, the micelles collapse, and the pigment or dye is deposited on the anode (transparent conductive thin film). 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 repeated with the same solution. The film thickness and transmittance of each dye film (layer) can be controlled by manipulating the electrolysis time within the above voltage range. Next, the thin film (dye layer) formed by the micelle electrolysis treatment may be washed with pure water or the like and then air-dried at room temperature, or if necessary, heated in a temperature range up to 200 ° C. Processing may be performed.

Further, the substrate on which the dye film is formed is inserted into the micelle dispersion liquid of the photo-curable resist or the thermosetting resin, and this is energized to carry out micelle electrolysis to obtain the desired dye film on the substrate. Forming a photo-curable resist film or a thermosetting resin film (protective film). Since the dye film is porous, the underlying transparent conductive thin film and the micelle dispersion liquid of the photo-curable resist or thermosetting resin are conducted, and therefore the photo-curable resist film or thermosetting resin film is used for the micellar electrolysis method. It is possible to form a film on the dye film. Electrolysis is a pigment
The same conditions can be applied, and the principle of the micelle electrolysis method can be applied. However, when a photo-curable resist or a thermosetting resin film is laminated and fills the voids in the dye film, the conductivity of the film is gradually lost. As a result, when the sheet resistance of the photocurable resist film including the dye film and the thermosetting resin film becomes 10 ⁹ Ω / □ or more, the film cannot be formed. Therefore, the film thickness of the photocurable resist film (dye layer) including the dye film or the thermosetting resin film is controlled by the film thickness of the dye film. Next, the resist film formed by the micelle electrolytic treatment may be washed with pure water or the like and then air-dried at room temperature, or if necessary, heat-treated in a temperature range up to 150 ° C. May be. On the other hand, since the thermosetting resin film is used as a protective film, it may be washed with pure water or the like and then air-dried at room temperature.
After heat treatment in the temperature range up to 0 ° C, 150 ~ 3
Heat treatment is performed at 00 ° C. to completely heat cure.

The photo-curable resist or thermosetting resin can be laminated not only by the micelle electrolysis method but also by the electrodeposition method. Since the proportion of the coloring matter (pigment) in the layer is large, the light resistance of the formed color filter is not deteriorated.

(5) Photocurable Resist Cured Product The exposed part of ultraviolet light (i-line, g-line, h-line) or the like is polymerized, cross-linked and cured, and the higher the transparency, the better. For example, a mixture of acrylic or methacrylic acid derivative and its copolymer (binder) can be used. This acrylic, methacrylic acid derivative has an epoxy group,
A material having a siloxane group or a polyimide precursor introduced therein can be preferably used. As the photoinitiator, triazine type, acetophenone type, benzyne type, benzophenone type, thioxanthone type and the like can be used. As the solvent, ketones such as cyclohexanone, esters such as cellosolve acetate, or a mixture of two or more thereof can be used. In addition, JP-A-4-10410
The photocurable electrodeposition polymer described in No. 2 can also be used.

The above is mixed and filtered to prepare a resist,
This resist is laminated and coated on the dye film of the micelle electrolytic film by a roll coater or a spin coater on at least the entire surface of the display portion. Then, photopolymerization and photocrosslinking (exposure) through a mask pattern of a color filter corresponding to a desired dye layer.
After that, for example, the unexposed portion is etched and then completely cured by heat treatment. Further, as a method for applying a photocurable resist (preferably a transparent ultraviolet curable resist), a transparent photocurable resist is prepared by the above-mentioned micelle electrolysis method or electrodeposition method instead of the conventional roll coating or spin coating. By coating, not only the step of drying the substrate after film formation can be omitted, but also foreign matter can be prevented from entering.

Specific product names of these resists are CT (manufactured by Fuji Hunt), V259PA (manufactured by Nippon Steel), JNPC06, JNPC09, JNPC16 (J
SR company), CFGR (Tokyo Ohka company), Photonice UR3100 (Toray company), etc. can be mentioned. The film thickness and the transmittance of the cured transparent photocurable resist are 0.
It is preferable that the thickness is 1 to 4.0 μm and the transmittance is 90% or more / 460 nm. The film thickness of each dye layer depends on the film thickness of each dye film of the micellar electrolysis film formation method, such as the resist viscosity and the rotation speed of spin coating, or the film formation potential and film formation in the micelle electrolysis method or electrodeposition method. It can be controlled by time and the like, and the thickness difference of each dye layer can be minimized to achieve flatness.

(6) Photosolubilizing type resist It is sufficient that the exposed portion is eluted with a developing solution. For example, a photosensitive resin composition containing a diazonium salt and a paraformaldehyde condensation polymer (Japanese Patent Publication No. 38-11365, US Pat. No. 1,762,033, etc.), a photosensitive resin composition containing an ortho-quinone diad (Japanese Patent Publication No. 37-3627).
No. 4, Japanese Patent Publication No. 43-28403, Japanese Patent Publication No. 45-9610
No.), a photosensitive resin composition containing an alkali-soluble azide polymer (Japanese Patent Publication No. 40-28499, Japanese Patent Publication No. 45-
22085, British Patent No. 843541, etc.), a photosensitive resin composition containing an azide compound developable with water or an aqueous alkali solution (Japanese Patent Publication Nos. 41-7100 and 44).
No. 28725, US Pat. No. 2,692,826, and Japanese Patent Publication No. 45-22082), and carboxylic acid tert.
-Positive-type photosensitive resin composition comprising a polymer having an acid-labile branched group consisting of butyl ester or tert-butyl carbonate of phenol and a photopolymerization initiator (onium salt) that produces an acid upon exposure Etc. can be mentioned. As a specific product name, for example, HPR2
04, FH2130 and the like (manufactured by Fuji Hunt Electronics Technology Co.).

(7) Preparation of Substrate for Forming Dye Layers of Multiple Colors A transparent conductive thin film is formed on the entire surface of the insulating substrate, including at least a portion corresponding to the region where the dye layers of multiple colors are formed. Then, a metal or metal oxide thin film is formed on the entire surface including at least a portion corresponding to a region where the black matrix and the dye layers of a plurality of colors are formed. Then, the photocurable resist is patterned in the form of a black matrix by a photolithography method by a conventional method, and the exposed metal and metal oxide thin films are etched with a mixed aqueous solution of cerium ammonium nitrate and perchloric acid. A black matrix is formed, and if necessary, the photocurable resist is heat-treated (post-baked) by heat treatment in an oven or a hot plate at 150 to 300 ° C. In addition, a photosolubilizing resist is patterned on the metal or metal oxide thin film in the form of a black matrix by a photolithography method by a conventional method, and the exposed metal or metal oxide thin film is cerium ammonium nitrate and perchlorine. Etching with an acid-mixed aqueous solution or the like, and further using a resist stripper (for example, a solution of amines such as quaternary amines, a solvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), etc. at room temperature. To 80 ° C. and peeling), the photosolubilizing resist is peeled off in the same manner to form a black matrix. Using the substrate thus created, by the following method,
It is possible to obtain a color filter in which dye layers of desired plural colors are arranged in a plane.

(8) Formation of Dye Layers of Multiple Colors Next, on the substrate prepared above, one dye (for example, R) of a plurality of colors is formed on the transparent conductive thin film by the micelle electrolysis method. Then, a photo-curable resist is spin-coated, roll-coated, the micelle electrolysis method, or an electrodeposition method using a photo-curable electrodeposition polymer (JP-A-4-104102).
Is laminated and coated on the R dye film and exposed through a mask corresponding to the R dye layer to etch the photocurable resist and the dye film in the non-reactive portions. In the case of spin coating or roll coating, the film thickness of the photocurable resist (the same applies to the thermosetting resin) is controlled by the viscosity of the resist, the rotation speed of the spin coating, and the rotation time,
In the case of the micelle electrolysis method or the electrodeposition method, the time point of insulation is the end point of stacking. Therefore, the film thickness of the dye layer of the color filter, in the case of roll coating or spin coating, is the amount obtained by subtracting the amount of permeation into the dye film of the resist from the sum of the film thickness of the dye film and the photocurable resist, In the case of the micelle electrolysis method or the electrodeposition method, it is almost close to the film thickness of the dye film. Next, the exposure may be any of contact exposure, proximity exposure, mirror projection, and stepper, and may be performed according to the spectral sensitivity of the resist used. The exposure energy is, for example, i-line (365n
In the case of m), 20 to 600 mJ / cm ² is general.

Next, the developing solution is sprayed to dissolve the photocurable resist in the unexposed portion, and the lower dye film is further purified water shower, high pressure pure water shower, brush scrub, ultrasonic pure water shower, etc. And the photocurable resist (dye layer) laminated on the dye film in the exposed area are left, and then heated by an oven or a hot plate at 150 to 300 ° C. by the method described in 1. Completely cure the curable resist. As a developing solution, a general developing solution corresponding to a resist is used. For example, as an organic system, an aqueous solution of a quaternary amine such as tetramethylammonium hydroxide (TMAH) is used, and as an inorganic system, sodium carbonate, hydroxide is used. An aqueous solution of an alkali metal hydroxide such as sodium or potassium hydroxide or an alkali metal salt is used, and the temperature is from room temperature to 80 ° C. Further, only the photo-curable resist is patterned by the development and rinse treatment after the exposure of the photo-curable resist of the upper layer, and the dye layer exposed after being cured by the above-mentioned heat treatment is treated with an organic solvent in addition to the above-mentioned developer. (Ethanol, acetone) or a surfactant or the like may be used for etching.

Here, the method of etching the dye film is not limited to the above wet etching, but can be dry etching such as UV / ozone, plasma, sputtering, and ion beam, and wet etching and dry etching can be used in combination. You may. Such a process is similarly performed with respect to a plurality of different color dyes (for example, B and G) (Japanese Patent Application No. 4-265422). It should be noted that for a substrate on which a black matrix is formed by patterning a photocurable resist by a photolithography method in the shape of the black matrix including the peripheral portion of the substrate outside the display area of the color filter, the dye layer of the third color should already be formed. Since the resist frame is left, the photo-curable resist laminated pattern is formed on the portion corresponding to the dye layer of the third color and the unnecessary portion G is formed.
There is no need to perform dye film etching. (For the substrate on which the black matrix is formed of the photo-solubilizing resist, since the resist frame for forming the dye layer of the third color is not left, the photo-curable resist lamination pattern of the portion corresponding to the dye layer of the third color is left. And it is necessary to perform the G dye layer etching of unnecessary portions.)

(9) Protective film After arranging the dye layers of a plurality of colors in a plane, adhesion of the dye layers to the substrate, reduction of film thickness difference between the dye layers (improvement of flatness), or a desired place. In order to form the dye film only by the micelle electrolysis method, it may be laminated. Examples of the protective film include a transparent photocurable resist cured product and a transparent thermosetting resin cured product. Transparent photo-curable resist cured product (the same materials as those mentioned above can be used) Transparent photo-curable resist is roll-coated, spin-coated,
Alternatively, by offset printing or the like, a layer is applied by coating on a region (the entire surface of the display portion) where at least pigment layers of a plurality of colors are formed, and is heated and cured at 150 to 300 ° C. in an oven or a hot plate to form a protective film. Further, by roll coating, spin coating, offset printing or the like is applied to the entire surface of the substrate including a portion corresponding to the area where the dye layers of the multiple colors are formed, and the photolithography method is used to form the dye layer of the multiple colors. Before or during each forming step, patterning is performed so as to be laminated on a portion excluding a portion corresponding to at least a region where the dye layers of a plurality of colors are formed, and heated by an oven or a hot plate at 150 to 300 ° C. It may be cured to form a protective film.

Transparent Thermosetting Resin Cured Material The same materials as those mentioned above can be used. Roll coating, spin coating, or offset printing,
At least a portion corresponding to the area where the dye layers of a plurality of colors are formed is laminated and coated with an oven or a hot plate.
It is heated and cured at 0 to 300 ° C. to form a protective film. In addition, by roll coating or offset printing, etc., it is laminated on a portion excluding a portion corresponding to a region where at least a pigment layer of a plurality of colors is formed before or during a step of forming a pigment layer of a plurality of colors. It may be applied and heated and cured at 150 to 300 ° C. in an oven or a hot plate to form an insulating film. In addition, by forming a film of a photocurable resist or a thermosetting resin dispersed in a micelle dispersion by a micelle electrolysis method, or by an electrodeposition method using a photocurable electrodeposition polymer described in JP-A-4-104102. The protective film can be laminated on at least the dye film (non-insulated dye film).

(10) Transparent conductive thin film (electrode) for driving liquid crystal The same material and forming method as those of the above transparent conductive thin film can be used.

[0057]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. [Production Example 1] Production of transparent conductive thin film deposition substrate An ITO thin film was formed on a 300 mm square white plate glass substrate (Corning Corp., 7059) that had been mirror-polished using a sputtering device (ULVAC Corp .: SDP-550VT). Was evaporated at about 1300Å. In this case, the substrate temperature was adjusted to 250 ° C. and the surface resistance of the ITO film was adjusted to 20Ω / □. Next, a metal (Cr) thin film was further vapor-deposited on the entire surface of the transparent conductive thin film (ITO) film forming substrate by using a spattering device (SDP-550VT manufactured by ULVAC, Inc.) at about 1200Å. At this time, the substrate temperature was adjusted to 250 ° C.

Preparation of Micelle Dispersion In 1 liter of pure water, dianthraquinonyl red (manufactured by Ciba Geigy) was used as a pigment, and the pigment concentration was 1
1.31 g / liter, FPEG (11-ferrocenylundecyl polyoxyethylene ether) as a ferrocene derivative micelle agent, 2.75 mmol / liter, lithium bromide as a supporting salt, 0.1 mol / liter Mixed at a concentration of 1 liter. Disazo yellow (manufactured by Dainippon Ink and Chemicals, Inc.) was used as the pigment, and the pigment concentration was 12.45 g / liter, FPEG was 2.00 mmol / liter, and lithium bromide was 0.1 mol / liter in concentration. Disperse each mixture with an ultrasonic homogenizer for 30 minutes, and then mix the former and the latter in a weight ratio of 9: 1.
The respective pigment dispersions are mixed at a ratio of, and the mixture is further dispersed for 30 minutes by an ultrasonic homogenizer,
A mixed micelle dispersion of R was prepared. Further, in 1 liter of pure water, halogenated copper phthalocyanine (manufactured by BASF) was used as a pigment, the pigment concentration was 14.85 g / liter, the above FPEG was used, 3.00 mmol / liter, and lithium bromide as a supporting salt. 0.1 mol /
Mixed at a concentration of 1 liter. Disazo yellow (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a pigment, and a pigment concentration of 12.45 g / liter, FPEG of 2.00 mmol / liter, and lithium bromide of 0.1 mol / liter were mixed. . Then, after dispersing each mixed solution with an ultrasonic homogenizer for 30 minutes, the respective pigment dispersions are mixed at a weight ratio of the former and the latter of 6: 4,
Further, this mixed solution was dispersed by an ultrasonic homogenizer for 30 minutes to prepare a mixed micelle dispersion of G. further,
In 1 liter of pure water, copper phthalocyanine (manufactured by BASF) was used as a pigment, the pigment concentration was 6.90 g / liter, FPEG was used, the concentration was 1.25 mmol / liter, and lithium bromide was used as the supporting salt. , 0.1 mol / l. Dioxazine violet (manufactured by Sanyo Dye Co., Ltd.) was used as a pigment, and a pigment concentration of 4.88 g / liter, FPEG of 3.00 mmol / liter, and lithium bromide of 0.1 mol / liter were mixed. Then, after dispersing each mixed solution with an ultrasonic homogenizer for 30 minutes, the respective pigment dispersions are mixed at a weight ratio of the former and the latter of 7: 3,
Further, this mixed solution was dispersed for 30 minutes with an ultrasonic homogenizer to prepare a mixed micelle dispersion of B. further,
Acrylic acid resist CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was used as a photocurable resist in 1 liter of pure water to obtain a resist solid content concentration of 1
0.00 g / l, using the FPEG, 1.5
After mixing 0 mmol / l and lithium bromide as a supporting salt at a concentration of 0.1 mol / l and dispersing with an ultrasonic homogenizer for 30 minutes, a micelle dispersion of a photocurable resist was prepared.

[Example 1] The substrate prepared in Production Example 1 was coated with a photocurable resist (V259PA: manufactured by Nippon Steel Chemical Co., Ltd.) by a spin coater at 1500 rpm.
Prebaked in an oven at 80 ° C for 15 minutes, and through a mask (Fig. 24) for forming a black matrix having a shape including a peripheral portion of a display substrate of a color filter corresponding to a diagonal dye pattern (proximity gap). 60 μm) type exposure machine 300
It was exposed with mJ / cm ² i-line. Next, spin development is carried out for 2 minutes with an organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology Co., Ltd.) at room temperature, and pure water shower washing is performed,
Further, a heat treatment (post-baking) was performed for 60 minutes in an oven at 200 ° C. to form a resist pattern. Next, 165 g of ceric ammonium nitrate and 42 ml of perchloric acid
A 1 liter Cr etchant was prepared with pure water and the substrate on which the resist pattern was formed was immersed for 2 minutes at room temperature and washed with a pure water shower to remove C in the portion without the resist pattern.
r After etching the thin film, dry by air blow,
A black matrix of a metal thin film (Cr) was formed.
The substrate prepared in Preparation Example 1 was inserted into the R micelle dispersion prepared in Preparation Example 1, and the electrode terminal portion of the transparent conductive thin film was connected to the potentiostat anode. After this connection, constant potential electrolysis was performed at 0.4 V for 18 minutes. Further, an R dye film was formed on the transparent conductive thin film, washed with pure water, drained with an air blow, and dried in an oven at 50 ° C. Next, as a transparent photocurable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) 1500
Spin coat at rpm, 5 on hot plate at 80 ° C
I prebaked for a minute. Next, a mask for R dye layer formation (for diagonal: 1 through a proximity type exposure device (proximity gap 60 μm) through FIG. 25)
After i-line exposure at 00 mJ / cm ² , a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology Co., Ltd.) was sprayed for 1 minute, and acrylic hair was sprayed. Scrubbing was performed with a brush, and further washing with pure water was performed to etch the dye film and the photocurable resist in the unexposed area. Finally, the substrate was inserted into an oven at 200 ° C., and the photocurable resist in the exposed area was completely heat-cured to obtain an R dye layer. Then, it was inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and
Constant-potential electrolysis was performed at 5 V for 5 minutes to form a B dye film on the transparent conductive thin film other than the R dye layer forming portion, which was washed with pure water, drained with air blow, and dried in a 100 ° C. oven. . CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is used as a transparent photocurable resist.
It was spin-coated at 0 rpm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through a mask (for diagonal: FIG. 26) for forming the B dye layer, a proximity type exposure device (proximity gap 60 μm) is used.
m) after i-line exposure at 100 mJ / cm ² , and a developer of an organic alkaline aqueous solution at room temperature (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
A diluted product of pure water) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist. Finally 2
The substrate was inserted into an oven at 00 ° C., and the photocurable resist in the exposed area was completely thermoset to obtain a B dye layer. Then, the mixture was inserted into the micelle dispersion of G prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and constant potential electrolysis was performed at 0.8 V for 7 minutes to obtain R and B.
A G dye layer was formed on the transparent conductive thin film other than the dye layer forming portion, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. to obtain a G dye layer. Next, 900 rp of transparent thermosetting resin Optomer SS7265 (manufactured by Japan Synthetic Rubber Co., Ltd.) is used as a protective film on this substrate.
m was spin coated and completely thermoset in a 220 ° C. oven. Finally, using a sputtering apparatus (SDP-550VT manufactured by ULVAC, Inc.), the ITO thin film was adjusted to about 1
A transparent conductive thin film (electrode) for driving a liquid crystal was formed by sputtering on the protective film at 200Å. In this case, the substrate temperature was adjusted to 200 ° C. and the surface resistance of the ITO film was adjusted to 20Ω / □. As described above, the color filter according to step 4 shown in FIGS.

Example 2 A metal oxide (Cr ₂ O ₃ ) thin film was used instead of a metal (Cr) thin film on the transparent conductive thin film (ITO) film forming substrate prepared in Production Example 1 by a sputtering device (ULVAC). (Manufactured by SDP-550VT) was used to deposit about 1200Å. At this time, the substrate temperature is set to 2
Prepared at 50 ° C. Next, on the evaporated Cr ₂ O ₃ thin film,
Photosolubilization type resist (HPR204: made by Fuji Hunt Electronics Technology Co., Ltd.) 75 by spin coater
Coat at 0 rpm, pre-bake on a hot plate at 80 ° C. for 5 minutes, and through a mask for forming a black matrix corresponding to the triangle dye pattern (FIG. 27)
Proximity method (Proximity gap 60
of 100 mJ / cm ² i-line.
Next, an organic alkaline aqueous solution developer at room temperature (2.38%
TMAH aqueous solution: spin-developed for 2 minutes with FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd., washed with pure water shower, and dried by air blow. Further 130
Heat treatment (post bake) for 30 minutes in an oven at ℃,
A resist pattern was formed. Next, 1 liter of Cr etchant was prepared with 165 g of ceric ammonium nitrate, 42 ml of perchloric acid and pure water, the substrate on which the resist pattern was formed was immersed at room temperature for 2 minutes and washed with a pure water shower to form the resist pattern. After etching the Cr thin film in the non-existent portion, it is immersed in a resist stripper (N303: Nagase & Co., Ltd.) at room temperature for 3 minutes, rinsed with a pure water shower and dried by air blow to obtain a metal oxide thin film ( Cr
A black matrix of ₂ O ₃ ) was formed. Next, the mixture was inserted into the R micelle dispersion liquid prepared in Production Example 1, and the transparent conductive thin film and the anode of the potentiostat were connected to each other,
A constant potential electrolysis was performed at 0.4 V for 18 minutes to form a dye film of R on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in a 100 ° C. oven.
Next, as a transparent photocurable resist, JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin coated at 1500 rpm, and 8
It was prebaked for 5 minutes on a hot plate at 0 ° C. Then R
Through a mask (for triangle: FIG. 28) for forming a dye layer, i-line exposure was performed at 300 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then a developer (0 .5% T
MAH aqueous solution: Fuji Hunt Electronics Technology Co., Ltd. FHD-5 pure water diluted product) is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the dye film and light in the unexposed area The curable resist was etched. Finally, the substrate was inserted into an oven at 200 ° C. for 30 minutes to completely thermoset the photocurable resist in the exposed area to obtain an R dye layer. Then, it is inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat are connected, and constant potential electrolysis is performed for 0.5 V for 5 minutes to form the R dye layer. The dye film of B was formed on the transparent conductive thin film other than the portion corresponding to the region, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. for 10 minutes. Next, JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as a transparent photocurable resist at 1000 rpm.
Was spin-coated on the plate and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through a mask for B pigment layer formation (for triangle: (FIG. 30), the exposure was carried out by a proximity type exposure machine (proximity gap 60 μm)
After i-line exposure at 0 mJ / cm ² , room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology)
Was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C. for 30 minutes to completely thermoset the photocurable resist in the exposed area to obtain a B dye layer. Then, it was inserted into the micelle dispersion of G prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected,
Constant potential electrolysis at 0.8 V for 7 minutes is performed to form a G dye film on the transparent conductive thin film other than the portions corresponding to the R and B dye layer forming regions, and the water is blown with water after washing with pure water. It was cut and dried in a 100 ° C. oven for 10 minutes. Next, as a transparent photocurable resist, JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1500 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through a mask (for triangle: FIG. 29) for forming the G dye layer,
After i-line exposure at 300 mJ / cm ² with a proximity type exposure machine (proximity gap 60 μm), a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: F manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
HD-5 pure water diluted product) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist.
Finally, insert the substrate into an oven at 200 ° C for 30 minutes,
The photocurable resist in the exposed area was completely heat-cured to obtain a G dye layer. Next, a transparent thermosetting resin material LC2001 (manufactured by Sanyo Kasei Co., Ltd.) 900 was formed on this substrate as a protective film.
After spin coating at rpm, it was placed in an oven at 220 ° C. for 30 minutes for complete heat curing. Finally, using a sputtering device (SDP-550VT manufactured by ULVAC, Inc.),
About 1200Å of ITO thin film was sputtered on the protective film to form a transparent conductive thin film (electrode) for driving liquid crystal.
At this time, the substrate temperature was adjusted to 200 ° C. and the surface resistance of the ITO film was adjusted to 20 Ω / □. As described above, the color filter of step 5 shown in FIGS. 3 and 4 was manufactured.

Example 3 In Example 2, the substrate prepared in Production Example 1 was inserted into the G micelle dispersion prepared in Production Example 1 on the substrate on which the R and B dye layers were formed. The electrode terminal of the transparent conductive thin film was connected to the anode of the potentiostat, and constant potential electrolysis was performed at 0.8 V for 7 minutes.
The G dye film was formed on the transparent conductive thin film other than the portions corresponding to the R and B dye layer forming regions, washed with pure water, drained by air blow, and dried in a 100 ° C. oven for 10 minutes. Next, a transparent photocurable resist (JNPC0
6: manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1500 rpm and heat-treated (pre-baked) for 5 minutes on a hot plate at 80 ° C. Next, through a mask for G dye formation including the regions of the R and B dye layers (FIG. 31: a mask that can expose the entire regions of the R, B, and G dye layers, that is, a mask that can expose the display portion of the color filter). 300m with a proximity exposure machine (proximity gap 60μm)
After i-line exposure at J / cm ² , a developer of an organic alkaline aqueous solution at room temperature (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology Co., Ltd.)
Was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C. for 30 minutes to completely thermoset the photocurable resist in the exposed area to obtain a G dye layer and prepare a color filter. Finally, an ITO thin film of about 1200 Å was sputtered on the protective film using a sputtering device (SDP-550VT manufactured by ULVAC, Inc.) to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature was adjusted to 200 ° C. and the surface resistance of the ITO film was adjusted to 20 Ω / □. As described above, the color filter of step 5 according to the present invention shown in FIGS. 5 and 6 was manufactured.

[Example 4] In Example 2, a transparent photocurable resist CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) as an insulating film was spin-coated at 1500 rpm on the substrate on which the black matrix was formed, and 8
It was prebaked on a hot plate at 0 ° C. for 5 minutes. Then, 100 mJ / c is applied through a mask (FIG. 32) capable of exposing a portion (outside the display portion of the color filter) other than the electrode extraction portion and the portion corresponding to the formation regions of the dye layers of a plurality of colors.
m ^2, in and i-line exposure, a developing solution of an organic alkaline aqueous solution at room temperature (0.5% TMAH aqueous solution: Fuji Hunt Electronics Technology Co., Ltd. FHD-5-pure water diluted product) was sprayed for 1 minute, further with pure water After washing, the photocurable resist was developed. Finally, the substrate was put in an oven at 200 ° C. for 30 minutes to completely heat-cure the photocurable resist in the exposed portion to obtain an insulating film. Next, the transparent conductive thin film was inserted into the R micelle dispersion liquid prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and a constant potential electrolysis was performed at 0.4 V for 10 minutes to obtain a transparent conductive film. After forming the R dye film on the thin film and washing it with pure water, drain the water by air blow and
Dry in a 00 ° C. oven for 10 minutes. Next, as a transparent photocurable resist, JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1500 rpm, and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, a proximity type exposure device (proximity gap 6 is used through a mask for R dye layer formation (for triangle: (FIG. 28)).
I-line exposure at 300 mJ / cm ² at 0 μm), then a developer of an organic alkaline aqueous solution at room temperature (0.5% TMAH aqueous solution: FH manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
D-5 pure water diluted product) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C. for 30 minutes to completely thermoset the photocurable resist in the exposed area to obtain an R dye layer. Then, it was inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and constant potential electrolysis was performed for 0.5 V for 3 minutes to form the R dye layer. The dye film of B was formed on the transparent conductive thin film other than the portion corresponding to the region, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. for 10 minutes. Next, JNPC0 is used as a transparent photocurable resist.
6 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1000 rpm, and prebaked on a hot plate at 80 ° C. for 5 minutes.
Next, a mask for forming the B dye layer (for triangle:
(FIG. 30), 300 mJ / in a proximity exposure machine (proximity gap 60 μm)
After i-line exposure at cm ² , a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute, and then applied to an acrylic bristle brush. Scrubbing, and further washing with pure water to etch the dye film and the photocurable resist in the unexposed area. Finally, put in an oven at 200 ° C for 3
The substrate was inserted for 0 minutes, and the photocurable resist in the exposed area was completely thermoset to obtain a B dye layer. Then, it was inserted into the micelle dispersion of G prepared in Production Example 1, and the transparent conductive thin film and the anode of the potentiostat were connected to each other to give 0.8
V for 5 minutes of constant potential electrolysis to form a G dye layer (film) on the transparent conductive thin film other than the R and B dye layer forming portions,
After washing with pure water, drain the water by air blow to 100
Dried in oven at 10 ° C for 10 minutes. Next, a transparent thermosetting resin agent JSS819 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated on this substrate as a protective film at 900 rpm, and 220
It was placed in an oven at 60 ° C. for 60 minutes to be completely heat-cured. Finally, a sputtering device (manufactured by ULVAC: SDP-5)
An ITO thin film of about 1200 Å was sputtered on the protective film using 50 VT) to form a transparent conductive thin film for driving a liquid crystal. At this time, the substrate temperature was adjusted to 200 ° C. and the surface resistance of the ITO film was adjusted to 20 Ω / □. As described above, the color filter of step 5 shown in FIGS. 7 and 8 was manufactured.

[Embodiment 5] The same method as in Embodiment 1, except that UV cleaning is performed for 120 seconds each time the R, B, and G dye films are formed by the micelle electrolysis method. , 2 was manufactured.

Example 6 Instead of spin-coating the transparent photocurable resist in Example 2, R, R, and M in the micelle dispersion of the photocurable resist prepared in Production Example 1 were used.
Insert the substrate on which the B and G dye films are formed, connect the transparent conductive thin film and the anode of the potentiostat, and apply 0.5V.
Was subjected to potentiostatic electrolysis for 10 minutes, and a photocurable resist film was laminated on each of the R, B, and G dye films. Then, after washing with pure water, the water is removed by air blow,
Example 2 except that it was dried in a 0 ° C. oven for 10 minutes
A color filter according to step 5 shown in FIGS.

[Example 7] In Example 2, instead of spin-coating a transparent photocurable resist, a transparent photocurable electrodeposition polymer (Japanese Patent Laid-Open No. 4-104102) was used, and this 10% transparent photocurable resist was used. A substrate on which dye films of R, B, and G are formed is inserted into the electro-deposition polymer electro-deposition liquid, and the transparent conductive thin film and the anode of the potentiostat are connected to each other,
On both B and G, constant potential electrodeposition was carried out at 100 V for 1 minute, and a film of a photocurable electrodeposition polymer was laminated on each of the R, B and G dye films. Then, after washing with pure water, the step 5 shown in FIGS. 3 and 4 was carried out in the same manner as in Example 2 except that the water was removed by air blow and dried in a 100 ° C. oven for 10 minutes.
The color filter according to the present invention was manufactured.

[Comparative Example 1] ITO thin film patterning (formation of electrode for forming dye layer) ITO film forming glass substrate having a sheet resistance of 20 Ω / □ as an ITO film (blue plate glass, polishing, silica dip product: manufactured by Geomatic) UV soluble type positive resist (F
H2030M: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 1000 rpm. After this spin coating, heat treatment (prebaking) at 80 ° C for 15 minutes
I went. Then, this substrate was set in a proximity exposure machine. As the mask, stripe ITO patterning (FIG. 34) was used. Proximity Gap 7
After taking 0 μm, i-line exposure was performed at 80 mJ / cm ² , and then 2
It was developed with an inorganic alkaline developer (LSI developer: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at 5 ° C. After this development, rinse with pure water and then at 180 ° C for 3
Heat treatment (post-baking) was performed for 0 minutes. Next, as an etchant, 1M FeCl ₃ .6N HCl.O. 1N
HNO ₃ · O. Prepare an aqueous solution of 1NCe (NO ₃ ) ₄ and etch the ITO of the substrate.
Needed 0 minutes time. After etching, the substrate was rinsed with pure water, and the resist was stripped with a stripping agent (N-303: manufactured by Nagase & Co., Ltd.). Thus, an ITO patterned glass substrate was obtained.

Black matrix and electrode extraction
Layer forming process As a black matrix forming resist (black dye-containing resist), a color mosaic CK manufactured by Fuji Hunt Electronics Technology Co., Ltd., mixed with 3: 1: 1: 1 parts by weight of CR, CG and CB, respectively (Japanese Patent Laid-Open No. Hei 4). −
013106) was used. 500r using a spin coater on the ITO patterned glass substrate prepared above.
The above resist was applied by pm and heat-treated (prebaked) in an oven at 80 ° C. for 15 minutes. Next, a polyvinyl alcohol (PVA) aqueous solution (CP: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) for the oxygen barrier film was applied in the same manner as the resist. Then, while aligning with a proximity aligner having an alignment function using a aligner, after performing 80 μm proximity exposure (i-line) using a mask (FIG. 35) having a design for forming a black matrix and electrode extraction layer, Inorganic alkaline developer (0.
1N sodium carbonate aqueous solution: developed by Fuji Hunt Electronics Technology Co., Ltd., CD pure water diluted product). Further, it was rinsed with pure water and heat-treated (post-baked) in an oven at 220 ° C. for 30 minutes.

Dye layer manufacturing process Production example 1 of ITO patterned substrate with black matrix (FIG. 36) in which continuity was established for each color by silver paste.
The R paste was inserted into the R micellar solution described in 1. and the silver paste conducted to the R row of the stripe was connected to the anode of the potentiostat. A constant potential electrolysis was carried out at 0.8 V for 15 minutes to obtain a thin film of R dye. Then, after washing with pure water, prebaking (100 ° C. × 15 minutes) was performed in an oven. Next, this substrate was inserted into a micelle solution of G, and 0.4 V,
Constant-potential electrolysis was performed for 18 minutes to obtain R and G thin films. After film formation, post-treatment was performed under the same conditions as the film formation of R. Finally,
This substrate was inserted into a B micelle solution, the conductive silver paste and the anode of a potentiostat were connected to the stripe B row, and constant potential electrolysis was performed at 0.7 V for 10 minutes.
Thin films of R, G and B were obtained. After film formation, post-treatment was performed under the same conditions as the film formation of R.

[0069] Formation of the protective layer the R, G, as a B dye layer (film) protection formation substrate film O
S-808 (manufactured by Nagase & Co., Ltd.) was spin-coated at 800 rpm and then heat-treated (baked) at 240 ° C. for 1 hour to be cured to form a protective film.

The substrate on which the substrate cutting and chamfering protective film was laminated was cut by a scriber with an accuracy of ± 0.3 mm or less along line A in FIG. 13, and the cut surface was chamfered and polished by a chamfering machine.

Formation of ITO film for driving liquid crystal Finally, a sputtering device (made by ULVAC, Inc .: SDP
-550 VT), an ITO thin film was sputtered on the protective film at about 1200 Å to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature is set to 200
The surface resistance of the ITO film was adjusted to 20Ω / □ at ℃. Thus, the color filter corresponding to step 1 shown in FIGS. 12 and 13 was completed.

[Comparative Example 2] A Cr matrix thin film was sputtered on a non-alkali glass substrate having a black matrix (NA45: manufactured by Hoya Co., Ltd.) at about 1300 Å (made by ULVAC: SDP-550VT). On top of this, a UV solubilizing type positive resist agent (HPR204: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is added at 1000 rpm.
Was spin coated at. Next, prebaking was performed on a hot plate at 100 ° C. for 5 minutes. After that, this substrate was set in a mirror projection type exposure machine, and i-line exposure was performed at 80 mJ / cm ² through a black matrix pattern mask for diagonal (FIG. 33), and a developing solution of an inorganic alkali aqueous solution (2.38) was used. % TMAH aqueous solution Fuji Hunt Electronics Technology Co., FHD-
5) It was immersed in and developed. Next, after shower rinsing with pure water, heat treatment (post-baking) was performed at 150 ° C. for 30 minutes. Next, as an etchant, Cr was immersion-etched for 3 minutes in a mixed aqueous solution of 165 g of cerium ammonium nitrate at room temperature, 42 ml of perchloric acid, and 1 liter of pure water. After this etching, it was rinsed with pure water, and the resist was stripped with a stripper (N-303: Nagase & Co., Ltd.) of an organic alkali aqueous solution. Then, it was thoroughly washed with pure water to obtain a black matrix.

Insulating film / ITO thin film pattern formation (dye layer
Formation of forming electrode) Next, a silica dispersion (OCDTYPE-7; manufactured by Tokyo Ohka Co., Ltd.) 10 was formed as an insulating film on the black matrix.
After spin coating at 00 rpm and baking at 250 ° C. for 60 minutes, SDP-550V manufactured by ULVAC, Inc.
Set the substrate on T and put ITO on the substrate for about 1300
Spattered with Å. At this time, the work is set to 200 ° C. and I
The surface resistance of the TO film was adjusted to 20Ω / □. Next, an ultraviolet solubilizing type positive resist (FH2030
M: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) by spin coating at 1000 rpm, and 1 at 80 ° C. in an oven.
Heat treatment (prebaking) was performed for 5 minutes. Next, using a contact exposure machine, a diagonal pattern mask (see FIG.
After alignment exposure (exposure energy of i-line is 60 mJ / cm ² ) via 7), spin development was performed using a developer of an inorganic alkaline aqueous solution (LSI developer: manufactured by Fuji Hunt Electronics Technology Co., Ltd.). After this development, the substrate was rinsed with a pure water shower and further heat-treated (post-baked) at 150 ° C. Next, the ITO on the substrate was etched for 3 minutes by using a mixed solution of ferric chloride aqueous solution (Boume 42) at 37 ° C. and hydrochloric acid as an etchant for 3 minutes. After etching,
After rinsing with pure water, the resist was stripped with an organic alkaline aqueous solution stripping agent (N-303: Nagase & Co., Ltd.). further,
After washing with pure water, it was confirmed that there was no electrical leak between adjacent ITO electrodes, and a substrate with an ITO patterning black matrix was completed.

Formation of Electrode Extraction Layer An acrylic acid-based resist (CT: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was used for forming the electrode extraction layer, and the substrate was spin-coated at 850 rpm to form 1
Heat treatment (prebaking) was performed for 45 minutes in a 00 ° C oven.
Next, while aligning with a proximity exposure machine (proximity gap 60 μm), exposure was performed (i-line exposure energy 40 mJ / c through a mask (FIG. 38) of only the electrode extraction layer portion for diagonal).
m ² ). Then, it was developed by immersing it in a developing solution of an inorganic alkaline aqueous solution (0.1N sodium carbonate aqueous solution: CD pure water diluted product manufactured by Fuji Hunt Electronics Technology Co., Ltd.) for 1 minute. Further, the substrate was rinsed with pure water and heat-treated (post-baked) for 60 minutes in a 200 ° C. oven to complete a substrate for producing a color filter.

Dye layer manufacturing process : R, G, and B dye layers were obtained by the same process as in Comparative Example 1 except that the electrodes were extracted with silver paste as shown in FIG.

Formation of Protective Film Next, a thermosetting resin (Optomer SS7265: manufactured by Nippon Synthetic Rubber Co., Ltd.) as a protective film agent was spin-coated at 900 rpm on the substrate on which the above-mentioned dye layer was formed , and further 2
It heat-processed (post-baking) for 60 minutes in a 20 degreeC oven. Substrate cutting and chamfering The same steps as in Comparative Example 1 were carried out except that the cutting was performed along the line A in FIG.

Formation of ITO film for driving liquid crystal Finally, a sputtering device (made by ULVAC, Inc .: SDP
An ITO thin film was sputtered on the approximately 1200Å protective film using -550 VT) to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature is set to 200
The surface resistance of the ITO film was adjusted to 20Ω / □ at ℃. In this way, the color filter according to step 2 shown in FIGS. 12 and 13 was completed.

[Comparative Example 3] ITO thin film patterning (formation of dye layer forming electrode) ITO film / glass substrate (non-alkali glass; ITO film 2)
UV solubilization type positive resist (HPR2)
04: Fuji Hunt Electronics Technology Co., Ltd.)
Was spin coated at 1000 rpm. After this spin coating, heat treatment (prebaking) for 15 minutes in an 80 ° C oven
I went. After that, in this substrate contact exposure machine, 80 m through a diagonal pattern mask (Fig. 37).
After i-line exposure at J / cm ² , it was immersed in a developer of an organic alkali aqueous solution (2.38% TMAH aqueous solution: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) for development. After this development, it was rinsed with pure water and post-baked at 150 ° C. Next, as an etchant, an IT mixture of the ferric chloride aqueous solution (Boume 42) and hydrochloric acid at 37 ° C.
O was etched for 3 minutes. Next, the resist was rinsed with pure water, and the resist was stripped with a stripper (N-303: Nagase & Co., Ltd.) of an organic alkali aqueous solution. Further, wash with pure water and
After confirming that there was no electrical leakage between adjacent TO electrodes, a color filter manufacturing substrate was completed.

Formation of Electrode Extraction Layer This formation was carried out in the same steps as in Comparative Example 2 to form an electrode extraction part. Dye layer formation This formation is performed in the same steps as in Comparative Example 2, and R, G, B are formed.
To form a dye layer. Formation of Protective Film This formation was performed in the same process as in Comparative Example 2. Substrate cutting and chamfering This substrate cutting and chamfering was performed in the same steps as Comparative Example 1 except that the line A in FIG. 17 was cut. Formation of ITO film for liquid crystal drive Finally, sputtering device (made by ULVAC: SDP
The ITO thin film was sputtered on the protective film at about 1200 ℓ using -550 VT) to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature is set to 200
The surface resistance of the ITO film was adjusted to 20Ω / □ at ℃. Formation of Black Matrix A Cr thin film was sputtered on the above-mentioned substrate at about 1500 Å (manufactured by ULVAC, Inc .: SDP-550VT type). Next, an ultraviolet solubilizing type positive resist agent (FH2130: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was added at 1,500 rp.
m was spin coated. After spin coating, heat treatment (prebaking) was performed for 15 minutes in a 90 ° C. oven. afterwards,
This substrate is set on a proximity type exposure machine (proximity gap 80 μm), and the underlying IT is put through a black matrix pattern mask (FIG. 33).
I-line exposure was performed at 60 mJ / cm ² in alignment with the O pattern. Next, an inorganic alkaline aqueous solution (LSI developer:
After immersing in a developing solution of Fuji Hunt Electronics Technology Co., Ltd., rinsing with pure water, and post-baking at 150 ° C. for 30 minutes. Further, Cr was etched for 3 minutes with an aqueous solution of 165 g of cerium ammonium nitrate, 42 ml of perchloric acid, and 1 liter of pure water as an etchant. Next, the resist was rinsed with pure water, and the resist was stripped with a stripper (N-303: Nagase & Co., Ltd.) of an organic alkali aqueous solution. Further, it was thoroughly washed with pure water to form a black matrix. Thus, the color filter according to step 3 shown in FIGS. 16 and 17 was completed.

[Comparative Example 4] (Dispersion method color filter) Black matrix formation The same process as in Comparative Example 2 was carried out except that a triangle black mask (Fig. 27) was used. Red (R) is formed on the substrate on which the dye layer forming black matrix is formed.
Dye-containing (dispersion) resist CR-2000 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 500 rpm and heat-treated (pre-baked) in an 85 ° C. oven for 15 minutes. Next, an oxygen barrier film (CP: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was laminated and coated in the same manner as the resist. This substrate was set in a contact exposure machine, aligned with the black matrix, and exposed to i-line at 30 mJ / cm ² through a mask of R dye pattern (for triangle: FIG. 28).
Spray development was performed with a developer of an inorganic alkaline aqueous solution (0.1N sodium carbonate aqueous solution: CD: manufactured by Fuji Hunt Electronics Technology Co., Ltd.). Further, it was rinsed with a pure water shower and then heat-treated (post-baked) in a 200 ° C. oven for 60 minutes to form an R dye layer. Thereafter, a blue (B) dye-containing (dispersion) resist (CB-
2000: Fuji Hunt Electronics Technology Co., Ltd., green (G) dye-containing (dispersion) resist (CG-2)
000: Fuji Hunt Electronics Technology Co., Ltd. is coated, and alignment exposure is performed using a mask (for triangle: FIGS. 29 and 30) for forming each dye layer.
Development, rinsing and heat treatment (post-baking) were repeated to form R, G and B dye layers. Formation of protective film and formation of ITO thin film (electrode) for driving liquid crystal This formation was carried out by the same steps as in Comparative Example 2, and
The color filter according to step 6 shown in 9 was completed.

[Comparative Example 5] (Resist electrodeposition method color filter) N, N-diethylaminoethyl methacrylate, styrene, ethyl acrylate, and a compound obtained by an equimolar reaction of p-hydroxybenzoic acid and glycidyl acrylate in a molar ratio. Cationic photosensitive resin composition composed of 800 g of an organic polymer binder copolymerized with 3: 2: 4: 1 and a weight average molecular weight of 70,000, 5 g of 2,2-dimethoxy-2-phenylacetophenone, and 145 g of trimethylolpropane triacrylate. Was diluted to a solid content of 20% with ethylene glycol monobutyl ether, neutralized with 0.5 equivalent of acetic acid, and adjusted to a solid content of 10% with pure water. A pigment of each color was mixed with the electrodeposition resin composition prepared as described above as follows to prepare a cationic electrodeposition liquid. That is, the R color cationic electrodeposition liquid is a cationic photosensitive electrodeposition resin composition: azo metal salt red pigment = 995.0: 5.0, and the B color cationic electrodeposition liquid is a cationic photosensitive electrodeposition resin composition. Material: Copper phthalocyanine = 995.0: 5.0, G color cation electrodeposition liquid is
The cationic photosensitive electrodeposition resin composition and the halogenated copper phthalocyanine were mixed in a ratio of 995.0: 5.0. Then, on a mirror-polished 300 mm square white glass substrate (7059, manufactured by Corning Incorporated), a Cr thin film was sputtered at about 1200 Å using a sputtering device (SDP-550VT, manufactured by ULVAC, Inc.). At this time,
The substrate temperature was adjusted to 250 ° C. Next, a photo-solubilizing resist (HPR204: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was coated on the deposited Cr thin film by a spin coater at 750 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. to prepare a diagonal dye pattern. I-line exposure was performed at 100 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure machine through a mask (FIG. 40) for forming a black matrix. Next, spin development was carried out for 2 minutes with a developing solution (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Co., Ltd.) of an organic alkaline aqueous solution at room temperature, followed by washing with pure water shower and drying with air blow. Further, a heat treatment (post-baking) was performed for 30 minutes in an oven at 130 ° C. to form a resist pattern. Next, 1 liter of Cr etchant was prepared with 165 g of ceric ammonium nitrate, 42 ml of perchloric acid and pure water, the substrate on which the resist pattern was formed was immersed at room temperature for 2 minutes and washed with a pure water shower to form the resist pattern. No Cr
After etching the thin film, the resist stripper (N3
03: made by Nagase & Co., Ltd.) for 3 minutes, rinsed with pure water shower, dried by air blow, and dried with a metal thin film (C
A black matrix of r) was formed. Next, an ITO thin film was vapor-deposited on the entire surface of the Cr black matrix-formed substrate by using a sputtering device (SDP-550VT manufactured by ULVAC, Inc.) to form a transparent conductive thin film (ITO). At this time, the substrate temperature was adjusted to 250 ° C. On the transparent conductive thin film (ITO) film-forming substrate on the chromium thin film black matrix thus prepared, HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) 1500r was used as a photosolubilizing resist.
spin coated with pm, 5 on a 110 ° C hot plate
I prebaked for a minute. 80 m with a proximity type exposure machine (proximity gap 60 μm) through a mask for R dye layer formation (for diagonal: FIG. 41)
After i-line exposure at J / cm ² , immersion development was carried out for 1 minute with a developer (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Co., Ltd.) at room temperature and washed with pure water. . Next, the substrate in which a photo-solubilizing resist for forming the R dye layer was patterned was inserted into the R color cation electrodeposition solution prepared above, and was connected to the transparent conductive thin film and the negative electrode of the potentiostat. 50V, 3
Constant potential electrodeposition was carried out for 0 seconds to form a dye layer of R on the transparent conductive thin film exposed in the exposed area, washed with pure water, drained with an air knife, and dried in a 100 ° C. oven for 10 minutes.
Dry for minutes. Next, the above-mentioned substrate is exposed to a proximity type exposure machine (proximity gap 60 μm) through a mask (for diagonal: FIG. 42) for forming a G dye layer.
m) after i-line exposure at 80 mJ / cm ² and then a developing solution of an organic alkaline aqueous solution at room temperature (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Co., Ltd.)
Immersion development for 1 minute and washing with pure water. Then, this substrate was inserted into the G-colored cationic electrodeposition solution prepared above,
The transparent conductive thin film and the negative electrode potentiostat are connected to each other, and constant potential electrodeposition is carried out at 50 V for 45 seconds to form a G dye layer on the transparent conductive thin film exposed in the exposed portion,
After washing with pure water, drain the water with an air knife to 100
C. oven dried. Further, the substrate on which the R and G dye layers are formed is passed through a mask for forming the B dye layer (for diagonal: FIG. 43), and the above substrate is exposed by a proximity type exposure device (proximity gap 60 μm).
After i-line exposure at 0 mJ / cm ² , immersion development was carried out for 1 minute with a developer (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Corporation) at room temperature and washed with pure water. . Then, this substrate was inserted into the B color cation electrodeposition solution prepared above, and the transparent conductive thin film and the potentiostat of the negative electrode were connected to each other.
Constant potential electrodeposition for 30 seconds at V is performed to form a dye layer of B on the transparent conductive thin film exposed at the exposed portion, and after washing with pure water, water is removed by air blow for 10 minutes in an oven at 100 ° C. Dried. Next, the entire surface of the substrate is 800 mJ / c
After i-line exposure with m ² , the substrate on which the R, B, and G dye layers were formed was immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature for 10 minutes and then washed with pure water. The remaining photo-solubilizing resist was completely removed. Next, a transparent thermosetting resin agent (Optomer SS7265: manufactured by Nippon Synthetic Rubber Co., Ltd.) was spin-coated on this substrate as a protective film at 700 rpm, and heat-treated (post-baked) for 60 minutes in an oven at 220 ° C. to heat it. Cured. Finally, using a sputtering device (SDP-550VT manufactured by ULVAC, Inc.), an ITO thin film of about 1200 Å was sputtered on the protective film to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature was adjusted to 200 ° C. and the surface resistance of the ITO film was adjusted to 20 Ω / □. As described above, FIG.
The color filter according to the step 7 shown in FIGS.

[Comparative Example 6] A 300 mm square white plate glass substrate (7059, manufactured by Corning Incorporated) was mirror-polished, and a sputtering device (SDP-550V, manufactured by ULVAC, Inc.) was used.
Using T), an ITO thin film was sputtered at about 1300Å. At this time, the substrate temperature was adjusted to 250 ° C. Next, a photosolubilizing resist (HPR20
4: Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 750 rpm and prebaked for 5 minutes on a 110 ° C. hot plate. After the i-line exposure at 80 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure machine through a mask for forming the G dye layer (for diagonal: FIG. 42), a developing solution of an organic alkaline aqueous solution at room temperature (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Co., Ltd.) was spin-developed for 1 minute and washed with pure water. Then, this substrate was inserted into the micelle dispersion of G prepared in Production Example 1,
The transparent conductive thin film and the anode of the potentiostat were connected to each other, and constant potential electrolysis was performed at 0.4 V for 18 minutes to form a G dye layer (film) on the transparent conductive thin film exposed in the exposed portion. After washing with pure water, drain the water by air blow,
Dry in a 100 ° C. oven for 10 minutes. Next, the above substrate was exposed through a mask (for diagonal: FIG. 43) for forming a B dye layer at 80 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm).
After the line exposure, a developing solution (2.
38% TMAH aqueous solution: spin-developed with Fuji Hunt Electronics Co., Ltd. FDH-5) for 2 minutes, and washed with pure water. Then, this substrate was inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected to each other, and the potential was electrolyzed at 0.7 V for 10 minutes, and the above exposure was performed. A dye layer (film) of B was formed on the transparent conductive thin film exposed at the part, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. for 10 minutes. Further, the above substrate is exposed to a proximity type exposure machine (proximity gap 60 μm) through a mask for R dye layer formation (for diagonal: FIG. 41).
m) after i-line exposure at 80 mJ / cm ² and then a developing solution of an organic alkaline aqueous solution at room temperature (2.38% TMAH aqueous solution: FDH-5 manufactured by Fuji Hunt Electronics Co., Ltd.)
Was spin-developed for 3 minutes and washed with pure water. Then, this substrate was inserted into the micelle dispersion of R prepared in Production Example 1,
The transparent conductive thin film and the anode of the potentiostat were connected to each other, and constant potential electrolysis was performed at 0.8 V for 15 minutes to form an R dye layer (film) on the transparent conductive thin film exposed in the exposed portion. After washing with pure water, drain the water by air blow,
Dry in a 100 ° C. oven for 10 minutes. Next, G, B,
The substrate on which the R dye layer is formed is immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature for 5 minutes and then washed with pure water to completely remove the remaining photosolubilizing resist. Removed. Next, a transparent thermosetting resin material LC2001 (manufactured by Sanyo Kasei Co., Ltd.) 900 was formed on this substrate as a protective film.
After spin coating at rpm, it was placed in an oven at 220 ° C. for 60 minutes to be completely thermoset. Finally, using a spattering device (SDP-550VT manufactured by ULVAC, Inc.), I
About 1200Å of TO thin film was sputtered on the protective film to form a transparent conductive thin film (electrode) for driving liquid crystal. At this time, the substrate temperature is 200 ° C. and the surface resistance of the ITO film is 2
It was adjusted to 0Ω / □. 22 and 23 as described above.
The color filter according to step 8 shown in FIG.

[Reference Example] (Method described in Japanese Patent Application No. 4-265422) A sputtering device (SDP-550VT manufactured by ULVAC, Inc.) was placed on a 300 mm square white plate glass substrate (7059 manufactured by Corning) which was mirror-polished. A Cr thin film of about 1200 Å was used for sputtering. At this time, the substrate temperature was adjusted to 250 ° C. Next, a photo-solubilizing resist (HPR204: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was coated on the vapor-deposited Cr thin film with a spin coater at 750 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. to prepare a triangle dye pattern. Through the mask (FIG. 27) for forming a black matrix, i-line exposure was performed at 100 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure device. Then, a developing solution (2.
38% TMAH aqueous solution: spin-developed for 2 minutes with Fuji Hunt Electronics Technology FDH-5), washed with pure water shower, and dried by air blow. 1 more
A heat treatment (post-baking) was performed for 30 minutes in an oven at 30 ° C. to form a resist pattern. Next, 1 liter of Cr etchant was prepared with 165 g of ceric ammonium nitrate, 42 ml of perchloric acid and pure water, the substrate on which the resist pattern was formed was immersed at room temperature for 2 minutes and washed with a pure water shower to form the resist pattern. After etching the Cr thin film in the non-existing portion, a resist stripper (N303:
Immersed in Nagase & Co., Ltd.) for 3 minutes, rinsed with a pure water shower, and dried by air blow to form a black matrix of a metal thin film (Cr). Next, a transparent conductive thin film (ITO) is further sputtered on the entire surface of the Cr black matrix-formed substrate (ULVAC: S
DP-550VT), using ITO thin film about 1300
Å It was vapor-deposited. At this time, the substrate temperature was adjusted to 250 ° C. The thus-prepared substrate was inserted into the R micelle dispersion prepared in Production Example 1, and the transparent conductive thin film and the anode of the potentiostat were connected to each other.
After performing a constant-potential electrolysis for minutes, an R dye film was formed on the transparent conductive thin film, washed with pure water, drained by air blow, and dried in a 100 ° C. oven for 10 minutes. Next, as a transparent photocurable resist, JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1500 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through an R dye layer forming mask (for triangle: FIG. 28), i-line exposure was performed at 300 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then a room temperature organic alkaline aqueous solution was used. Developer (0.5% TM
AH aqueous solution: FHD-5 pure water diluted product of Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the dye film and light in the unexposed area The curable resist was etched. Finally, the substrate is placed in an oven at 200 ° C. for 30 minutes to completely heat cure the photocurable resist in the exposed area,
An R dye layer was obtained. Then, the mixture was inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and constant potential electrolysis was performed at 0.5 V for 5 minutes to form the R dye layer. Form the dye film of B on the transparent conductive thin film other than the part corresponding to the area, wash with pure water, drain the water by air blow, and put in a 100 ° C oven for 1 hour.
Dry for 0 minutes. Next, as a transparent photocurable resist, J
NPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 1000 rpm and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through a mask for B pigment layer formation (for triangle: FIG. 30), 300 mJ with a proximity type exposure device (proximity gap 60 μm).
/ Cm ² After i-line exposure, room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 pure water diluted by Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute, and acrylic bristle brush is applied. Scrub at
Further, it was washed with pure water to etch the dye film and the photocurable resist in the unexposed area. Finally, the substrate was put in an oven at 200 ° C. for 30 minutes to completely heat-cure the photocurable resist in the exposed portion, and a B dye layer was obtained. Then, Production Example 1
Insert into the micelle dispersion liquid of G prepared in step 1, connect the transparent conductive thin film and the anode of the potentiostat, and
Performing constant potential electrolysis for V and 7 minutes to form a G dye film on the transparent conductive thin film other than the portion corresponding to the RB dye layer forming region, washing with pure water and draining water by air blow,
Dry in a 100 ° C. oven for 10 minutes. Next, as a transparent photocurable resist, JNPC06 (manufactured by Nippon Synthetic Rubber Co., Ltd.) was spin-coated at 1500 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through a mask (for triangle: FIG. 29) for forming a G dye layer, i-line exposure was performed at 300 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then a room temperature organic alkaline aqueous solution was used. Developer (0.5% TMAH aqueous solution: FH manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
D-5 pure water diluted product) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the dye film and the photocurable resist. Finally, the substrate was placed in an oven at 200 ° C. for 30 minutes to completely heat-cure the photocurable resist in the exposed portion to obtain a G dye layer, and the color filter shown in FIGS. 9 and 10 was manufactured.

Next, the evaluation result will be described. Tables 1 and 2 (Tables 1 and 2 show the evaluation results of production yield, color unevenness, definition, heat resistance, and light resistance in the above-described color filter manufacturing process (excluding Comparative Example 6). Is shown in Comparative Example). Each item of the color filter evaluation in this (Table 1 and Table 2) will be described.

The production yield is an insulating substrate (glass substrate).
Is the ratio (%) of the number of non-defective color filters when 20 sheets are loaded. As a condition for this non-defective product, it is assumed that there is no white defect or black defect having a diameter of 30 μm or more by visual inspection. In addition, the protrusions on the color filter surface are measured with a surface roughness meter, and those having a protrusion height of 4 microns or more are regarded as non-defective products.

In this case, in the color filter by the micelle electrolysis method, the defect of the dye layer due to the disconnection of the ITO pattern corresponds to the white defect, and the overlap of the dye layers due to the leakage of the ITO pattern corresponds to the black defect. Color unevenness is ΔE
According to (JIS Z8724, Z8723). The chromaticity of pixels at 9 points on the substrate is measured for each of R, G, and B, and the one having the largest color difference is evaluated as ΔE.

The definition is defined by the design mask pattern (50 μm
Dimensional accuracy (μm) of the dye layer with respect to □).

Heat resistance is a color purity (for G dye pattern) by heat treatment at 260 ° C. for 1 hour (oxygen atmosphere).
Change ratio (ratio of the difference between the color purity before heat treatment and the color purity after heat treatment).

The light resistance is defined as the change% (the ratio of the difference between the color purity before irradiation and the color purity after irradiation) of the color purity (for the G dye pattern) after 1000 hours irradiation of a metal halide lamp of 1 million lux. The color purity is calculated by taking chromaticity coordinates for each color and connecting the C light source and the chromaticity coordinates with a straight line.
This is the ratio of the distance from the C light source of the chromaticity coordinates when the intersection between the extrapolated straight line and the outer peripheral portion is 100% in color purity.

[Table 1] ───────────────────────────────── Dye layer pattern Production yield Color unevenness Fineness Heat resistance Light resistance ───────────────────────────────── Example 1 Diagonal 85 <2 ± 1.0 0 0 Process 4 ───────────────────────────────── Example 2 Triangle 80 <2 ± 1.0 0 0 Process 5 ───────────────────────────────── Example 3 Triangle 80 <2 ± 1.000 Step 5 ── ─────────────────────────────── Example 4 Triangle 85 <2 ± 1.0 0.00 Step 5 ──── ─────────────── ───────────── Example 5 Diagonal 90 <2 ± 1.0 0 0 Step 4 ─────────────────────── ─────────── Example 6 Triangle 90 <2 ± 1.0 0 0 Step 5 ──────────────────────── ───────── Example 7 Triangle 90 <2 ± 1.0 0 0 Step 5 ────────────────────────── ───────

[Table 2] ───────────────────────────────── Dye layer pattern Production yield Color unevenness Fineness Heat resistance Light resistance ───────────────────────────────── Comparative Example 1 Strife 60 <5 ± 2.0 0 0 Process 1 ───────────────────────────────── Comparative Example 2 Diagonal 25 <10 ± 2.0 0 0 Process 2 ───────────────────────────────── Comparative Example 3 Diagonal 20 <10 ± 2.0 00 Step 3 ── ─────────────────────────────── Comparative Example 4 Triangle 70 <5 ± 3.0 0 75 Step 6 ──── ───────────── ─────────────── COMPARATIVE EXAMPLE 5 DIAGONAL 70 <4 ± 2.0 10 85 Process 7 ───────────────────── ─────────────

It can be seen from Tables 1 and 2 that the method for producing a color filter of the present invention can produce with a high yield and can reduce color unevenness even for various dye pattern arrangements. It was also confirmed that the definition was also good. Further, it was confirmed that not only the heat resistance but also the light resistance was excellent in the dye layer obtained by the micelle electrolysis film formation.

From the comparison of the R, G, and B dye layer steps (difference between the maximum and minimum film thicknesses of the dye layer) shown in Table 3, the flatness between the dye layers was improved by laminating the protective film. I was able to confirm that

[Table 3] ───────────────────── Protective film Dye layer step (μm) ─────────────── ─────── Example 2 Yes <0.1 Reference Example 1 No <0.3 ─────────────────────

Further, Example 1 and Comparative Example 6 shown in FIG.
As is clear from the comparison of the spectral characteristics of the color filters manufactured in 1., in Comparative Example 6, the spectral characteristics of the color filters deteriorate. Since the dye layer (dye film) formed by the micelle electrolysis method is not electrically insulated, when a dye layer (dye film) of a plurality of colors is formed without insulation as in Comparative Example 6, it is formed first. The dye layer (dye film) is contaminated with the dye layer (dye film) to be formed later. Therefore, at least the dye layer (dye film) formed first must be electrically insulated. Therefore, as in Example 1, a photocurable resist is laminated on the dye layer (dye film) formed by the micelle electrolysis method to insulate (form a dye layer), and the dye layer is formed on the dye layer previously formed. It was found that it is necessary to devise a method that does not contaminate the subsequent dye layers (dye film). Further, as shown in Table 4, the production yield was compared between Example 1 and Reference Example 1. In Example 1, a photolithography step was performed once to form a black matrix, a photocurable resist was applied on the dye film formed by the micelle electrolysis method, and then exposed through a mask corresponding to a desired color and then exposed. The process of forming the dye layer (pattern) by etching the photo-curable resist and the dye film in the non-existing portion may be performed for two colors. For the third color, the third color dye is formed by the micelle electrolysis method, A protective film and / or a transparent conductive thin film may be laminated accordingly. Therefore, the photolithography process is performed twice, and the photolithography process may be performed three times in total.

On the other hand, in Reference Example 1, one photolithography step was used to form the black matrix, a photocurable resist was applied on the dye film formed by the micelle electrolysis method, and then a mask corresponding to the desired color was used. After the exposure, the step of etching the photocurable resist and the dye film in the unexposed portion to form the dye layer (pattern) must be performed for three colors.
A total of 4 times is required. From the results shown in Table 4, it was found that the color filter can be manufactured with a higher yield in Example 1 having fewer photolithography steps.

[0097]

[0098]

As described above, according to the method for manufacturing a color filter of the present invention, it is not necessary to pattern the transparent conductive thin film by microfabrication, and it is possible to avoid a decrease in yield due to short circuit or disconnection. it can. Further, in the present invention, it is possible to easily apply the present invention to the conventional technique in which it is difficult to arrange the diagonal pattern and the triangle pattern in the color filter and the dye layer (pattern of the dye layer). Further, since it is not necessary to continuously connect the fine patterns of the transparent conductive thin film for one color having the dye layer, it is possible to reduce the color spot of the color filter due to the voltage drop. Further, in the present invention, after exposing the transparent photocurable resist applied on the dye film formed by the micelle electrolysis method through a mask corresponding to a desired color, the photocurable resist in the unexposed portion and Due to the step of etching the dye film to form the dye film (pattern), the photosensitivity of the resist of the photocurable resist containing the dye (pigment) such as a dispersion method color filter can be improved by the light absorption of the dye. There is no decline. As a result, the use of the color filter obtained by the present invention can be expected to be applied to a higher-definition color liquid crystal display.

In addition to such effects, the dye layer of the micellar electrolysis color filter originally has a high pigment (dye) content, so that the advantages of high light resistance and heat resistance can be taken advantage of. Further, according to this manufacturing method, it is not necessary to form an electrode extraction layer, and the color filter manufacturing process can be simplified. In the color filter manufacturing process, in the previous resist electrodeposition method, the dye layer once formed is electrically insulated because it coexists with the electrodeposition polymer, and if the photosolubilizing resist is applied once, the three primary colors will be used. Although it is possible to form the dye layer of the above, the dye layer (dye film) formed by the micelle electrolysis method is not electrically insulated. Must be electrically isolated. Therefore, it is necessary to devise a photo-curable resist laminated on a dye film formed by the micelle electrolysis method to insulate the dye film so that a subsequent dye layer (dye film) is not formed on the previously formed dye layer. . By this device, even in the micelle electrolysis method,
It has become possible to manufacture a color filter having a desired spectrum without contaminating the previously formed dye layer with the dye layer (dye film) formed later.

Further, in the inventions up to now (Japanese Patent Application No. 4-2
No. 65422), it is customary to form a metal or metal oxide black matrix on an insulating substrate and then stack a transparent conductive thin film by vapor deposition or sputtering to form a dye film by the micellar electrolysis method. However, in this case, unevenness of the black matrix may cause variations in the electric resistance value of the transparent conductive thin film, and sometimes cracks. In the present invention, a transparent conductive thin film is first laminated and then a black matrix of a metal or a metal oxide is formed, thereby eliminating the above problems and stably manufacturing a color filter with a high yield. Became possible. In particular, when forming the black matrix, a photocurable resist is patterned in the shape of the black matrix on the metal or metal oxide thin film, and then the exposed metal or metal oxide thin film of the underlying layer is etched. When a plurality of color dye layers are formed according to the present invention using the substrate manufactured in this manner, the photocurable resist remains in the form of a black matrix while forming a frame in which each dye layer is arranged. Therefore, for example, when sequentially forming dye layers for the three primary colors of red, blue, and green, for any one dye, photo-curable resist coating on the dye layer of the third color, exposure, photo-etching of the dye layer, etc. There is no need to perform a lithography process. As a result, the manufacturing process can be shortened, and the productivity can be improved by turning the dye that is difficult to be etched into the third color. As a result, the production yield of the color filter can be improved and the manufacturing cost can be reduced. Can be expected.

Further, in the present invention, in addition to such a color filter manufacturing method, ultraviolet (UV) cleaning is performed on the dye film formed by the micelle electrolysis method. by this,
Foreign substances such as fats and oils mixed in the dye film are decomposed by a small amount of ozone due to the reaction between ultraviolet light and oxygen in the air, and the wettability of the photocurable resist and protective layer is improved, resulting in photocurability. It has become possible to reduce pinholes in the coating film of the resist and the protective film and further improve the manufacturing yield of the color filter. In addition, a method of laminating a photocurable resist and / or a protective film on a dye film, that is, a method of forming a film by a micelle electrolysis method or an electrodeposition method,
Although it is performed in a wet state such as a micelle dispersion and an electrodeposition liquid, it is generally a problem in a dry process such as a spin coater or a roll coater, the atmosphere around the coater and the sliding part of the coater device. As a result, it is possible to further reduce the amount of foreign matter mixed in and to further improve the manufacturing yield of the color filter as described above.

Before the step of forming a multi-color dye layer, an insulating film is formed in a portion of the color filter obtained by such a color filter manufacturing method, excluding a portion corresponding to a region where multi-color dye layers are formed. Alternatively, by forming during the formation process of each dye layer, the film forming range of the dye in the micelle electrolysis method is narrowed, and because the etching range of the dye film may be small, the dye in the micelle dispersion liquid In addition to saving, the film forming time and the etching time can be shortened, and the efficiency of the color filter manufacturing process can be improved. Further, since the amount of dye that is etched is small, the dye that is etched onto the color filter is less likely to be mixed as a foreign substance, and the yield can be increased. Further, since the protective film and / or the transparent conductive thin film (electrode) for driving liquid crystal is laminated on the dye film formed by the micelle electrolysis method, the adhesion of the dye layer to the substrate can be further improved. Furthermore, it is possible to reduce the thickness difference between the dye layers (improve the flatness).

[Brief description of drawings]

[Figure 1]

FIG. 8 is a cross-sectional view schematically showing the manufacturing process of the color filter of the present invention and a schematic plan view when the color filter is completed.

FIG. 9

FIG. 10 is a cross-sectional view schematically showing a manufacturing process of a color filter, which is cited as a reference example, and a schematic plan view when the color filter is completed.

FIG. 11 is a sectional view schematically showing a general color liquid crystal display.

FIG. 12

FIG. 23 is a cross-sectional view schematically showing a conventional manufacturing process of a color filter, and a schematic plan view when the color filter is completed.

FIG. 24

FIG. 35,

FIG. 37

FIG. 38:

FIG. 40

FIG. 43 is a plan view schematically showing a mask used for manufacturing a color filter.

FIG. 36,

[Fig. 39] Fig. 39 is a plan view schematically showing conduction for each color by the silver paste at the time of manufacturing the dye layer.

FIG. 44 is an explanatory diagram showing a comparison of spectral characteristics between a color filter obtained in the present invention (Example 1) and a color filter obtained in a conventional method (Comparative Example 6).

[Explanation of symbols]

 101 ... Insulating substrate 102 ... Transparent conductive thin film 110 ... Black matrix 115 ... Insulating film 121 ... Micelle electrolysis method R pigment layer 122 ... Micelle electrolysis method G pigment layer 123 ... Micelle electrolysis method B pigment layer 130 ... Transparent photocurable resist 131 ... BL dye-containing resist 132 ... R dye-containing resist 133 ... G dye-containing resist 134 ... B dye-containing resist 140 ... Photosolubilizing resist 150 ... Protective film 160 ... Liquid crystal driving transparent electrode 170 ... Display section 180 ... Electrode extraction Part 181 ... Without mask (exposed part) 182 ... With mask (non-exposed part)

Claims (8)

[Claims] 1. A method for manufacturing a color filter in which a dye layer of a plurality of colors is separately formed and arranged on an insulating substrate to form a predetermined dye pattern, and a black matrix is formed, comprising: a) an insulating substrate. A step of forming a transparent conductive thin film on the entire surface including a portion corresponding to the region where the dye layers of at least a plurality of colors are formed, b) a dye layer of at least a plurality of colors and a black matrix on the transparent conductive thin film A step of forming a metal or metal oxide thin film on the entire surface including a region to be formed, c) A photocurable resist is laminated on the metal or metal oxide thin film, and photocured into a black matrix shape by a photolithography method. Black by removing the metal or metal oxide thin film on the exposed base by etching A step of forming a matrix, d) a step of forming a pigment film of one color selected from a plurality of colors on the exposed transparent conductive thin film by a micelle electrolysis method, e) photo-curing on the pigment film of one color Functional resist is laminated and exposed using a mask corresponding to the dye layer of one color, and the photo-curable resist and the dye film in the unexposed portion are removed by etching before and / or after the heat treatment of the exposed portion. A step of forming and arranging a dye layer of one color, and f) repeating the steps similar to the steps d) and e) one or more times to form the dye layers of the remaining colors of the transparent conductive thin film. A method for producing a color filter, comprising the steps of: separately forming and arranging on the whole surface or a part thereof to form dye patterns of a plurality of colors. 2. The step c) of forming the black matrix comprises laminating a photosolubilizing resist on a metal or metal oxide thin film and forming a pattern of the photosolubilizing resist in the shape of the black matrix by photolithography. 2. The color matrix according to claim 1, wherein the black matrix is formed by removing the metal or metal oxide thin film on the exposed portion of the base by etching and then removing the photosolubilizing resist. Filter manufacturing method. 3. The protective film and / or the liquid crystal driving electrode is further laminated and formed after the step f) of forming the dye patterns of the plurality of colors.
A method for manufacturing the described color filter. 4. Forming and arranging the dye layers of the plurality of colors,
Before or during the steps d), e) and f) of forming a multi-color dye pattern, an insulating film is laminated on a portion of the transparent conductive thin film other than a region where the multi-color dye layer is formed, The method of manufacturing a color filter according to claim 1, wherein the color filter is formed. 5. The dye layers of a plurality of colors correspond to the three primary colors of red, blue and green.
A method for manufacturing a color filter according to any one of 1. 6. The dye film is washed with ultraviolet light after the steps d) and / or f) of forming the dye films of the plurality of colors by a micelle electrolysis method. Item 1. A method of manufacturing a color filter according to item 1. 7. The lamination and formation of the photocurable resist,
The method for producing a color filter according to claim 1, wherein the method is a micelle electrolysis method or an electrodeposition method. 8. The method of manufacturing a color filter according to claim 3, wherein the protective film is laminated and formed by a micelle electrolysis method or an electrodeposition method.