JPH07104114A - Production of color filter - Google Patents

Abstract

PURPOSE:To enhance the fineness of the color filters having high light resistance and to improve quality, such as flattening, and production efficiency (yield). CONSTITUTION:Plural colors of dyestuff are separated and arranged by using either a stage group A or stage group B on an insulating substrate 101 laminated and formed with.a transparent conductive thin film 102. The stage group A: a1) a stage for forming a dyestuff layer of one color U by a micelle electrolysis method. a2) stage for arranging the dyestuff layer of one color by laminating a transparent photosetting resist 130 on the dyestuff layer of one color, exposing the resist and removing the photosetting resist and dyestuff layer of the unexposed parts. The stage group B: b1) a stage for laminating a photosoluble type resist 140, exposing and developing the resist and removing the photosoluble type resist of the exposed parts. b2) a stage for arranging the dyestuff layer of one color by the micelle electrolysis method on the transparent conductive thin film exposed by removing the photosoluble type resist. b3) The stage for removing all the remaining photosoluble type resists.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter. For more details, see PCs, word processors,
Color TVs such as wall-mounted TVs, pocket LCD TVs, liquid crystal projectors, aurora vision, solid-state image sensor (CCD), audio, vehicle-mounted instrument panel, clock, calculator, VCR, fax machine, communication device,
The present invention relates to a method for manufacturing a color filter that can be suitably used for a color display of games, measuring instruments and the like.

[0002]

2. Description of the Related Art The prior art of a color filter will be described below with reference to the case where it is used in a color liquid crystal display. 2. Description of the Related Art Recently, color liquid crystal displays have been used as displays for liquid crystal televisions, liquid crystal projectors, laptop personal computers, notebook personal computers and the like. This color liquid crystal display uses a color filter in which a dye layer is planarly patterned, that is, separated and arranged on an insulating substrate.

FIG. 59 shows the structure of a general color liquid crystal display. This color liquid crystal display has a liquid crystal sandwiched between two substrates. That is, a color filter is used as the one substrate, and the color filter substrate 1
A liquid crystal 30 is sealed between 0 and the drive substrate 20. After encapsulating the liquid crystal 30, adhesives (sealing materials) 40a, 40b
It is sealed with. The color filter substrate 10 has a plurality of colors, for example, three primary colors, that is, three primary colors, on a glass substrate as an insulating substrate or a substrate 1 in which a conductive thin film is laminated on the glass substrate.
Red (red, R), green (green, G), blue (blue,
B) (hereinafter, simply referred to as R, G, B if necessary)
The dye layers 5a, 5b and 5c are repeatedly formed. Further, between the dye layers 5a to 5c, in order to prevent deterioration of contrast and color purity due to leakage light there, a black matrix (hereinafter referred to as BM as necessary) is provided.
2a, 2b, 2c, 2d are repeatedly provided.

Further, the black matrices 2a to 2d,
A protective film 6 is formed on the dye layers 5a to 5c and planarized, and a liquid crystal driving transparent electrode is provided on the upper surface thereof. On the other hand, the drive substrate 20 includes an insulating substrate 21 and a drive transparent electrode 22.
It is configured by repeatedly forming a, 22b, and 22c. The dye layer of such a color filter is usually printed by using a printing machine to print an ink prepared by kneading R, G, B three primary color pigments or dyes (dyes) and resin on an insulating substrate such as a glass substrate. Is formed by. Further, an ultraviolet curable resin (resist) in which a pigment or a dye (pigment) is dispersed is applied on a glass substrate, and mask exposure by photolithography, development, and heat curing are repeated three times for each R, G, and B. Dispersion method to form a dye layer, or by coating a photosensitive natural polymer such as gelatin on a glass substrate,
After mask exposure and development by photolithography method,
A dyeing method is used in which the step of dyeing gelatin patterned with a dye of one of R, G, and B and thermosetting is repeated for the remaining two colors in the same manner to form a dye layer.

Furthermore, an electrodeposition polymer and a pigment or dye (colorant) are dispersed in a liquid, and R, G, B are formed on the electrode by using a pattern (electrode) of a conductive thin film formed on a substrate. Of the pigment layer is sequentially subjected to electrodeposition coating to form a pigment layer composed of a pigment or dye (pigment) and an electrodeposition polymer, or a surfactant and a pigment or dye (pigment) are dispersed in a liquid. , R of pigment or dye on the previous electrode,
A micellar electrolysis method is used in which the dyes of G and B are sequentially formed into a film to form a dye layer.

In any of the above methods for forming the dye layer of the color filter, a thermosetting resin or the like may be laminated as a protective film on the dye layers of a plurality of colors arranged in a plane. . In the color filter manufacturing method described above, the dye layer formed by the micelle electrolysis method is known to have excellent light resistance because of its high content of pigment or dye (Japanese Patent Application No. 4-031905). issue). Here, in the case of manufacturing a color filter having excellent light resistance by the micelle electrolysis method, for example, step 1 (Japanese Patent Laid-Open No. 3-10
2302), step 2 (JP-A-4-110901),
Step 3 (JP-A-5-142418) can be mentioned. First, a transparent conductive thin film such as indium and tin oxide (ITO) is patterned on an insulating transparent substrate such as glass to form an electrode for forming a dye layer, and further a black dye (black pigment or dye mixture) is contained. Of the acrylic acid-based photocurable resist cured product (Japanese Patent Laid-Open No. 4-13106) and a black matrix layer were patterned and laminated at the same time, and pigments of RGB three primary colors were formed by a micelle electrolysis method to form a dye layer. Formed, forming a protective film with a protective film agent containing acrylic resin or siloxane resin as a main agent,
There is a step of again laminating a transparent conductive thin film such as an oxide of indium or tin (ITO) on one surface or partially to form a liquid crystal driving electrode (step 1, FIGS. 60, 61).

Further, a black matrix in which a metal or metal oxide thin film such as metal chromium and oxide chromium is patterned on an insulating transparent substrate such as glass, an insulating film such as silica or acrylic resin, an oxide of indium and tin. An electrode for dye layer formation in which a transparent conductive thin film such as (ITO) is patterned is sequentially laminated, and a dye (pigment or dye) -containing acrylic acid-based photocurable resist cured product or acrylic acid-based photocurable resist cured After forming an electrode extraction layer made of a material, a pigment layer of RGB three primary colors is formed by a micelle electrolysis method to form a dye layer, and a protective film is formed with a protective film agent containing an acrylic resin or a siloxane resin as a main component, and again. There is a step of laminating a transparent conductive thin film such as indium and tin oxide (ITO) on one surface or part thereof to form a liquid crystal driving electrode (step , As shown in FIG. 62 and 63).

Furthermore, on an insulating transparent substrate such as glass,
An electrode for dye layer formation is formed by patterning a transparent conductive thin film such as indium and tin oxide (ITO), and a dye (pigment or dye) -containing acrylic acid photocurable resist cured product or acrylic acid photocurable product is formed. After laminating an electrode extraction layer consisting of a hardened cured resist, a pigment layer of RGB three primary colors is formed by a micelle electrolysis method to form a pigment layer, and a protective film is formed by a protective film agent containing an acrylic resin or a siloxane resin as a main agent. Then, again, a transparent conductive thin film such as indium and tin oxide (ITO) is laminated on one surface or partially to form a liquid crystal driving electrode, and metal or metal oxide thin film such as metal chromium and chromium oxide is patterned. There is a process using a black matrix (process 3, FIGS. 64, 6).
5). In addition, in the step 3, there is also one in which the order of laminating the liquid crystal driving electrode and the black matrix is reversed.

[0009]

As a problem of the above three steps, in any case, it is indispensable that the electrode for forming a dye layer in which a transparent conductive thin film is patterned (the same as in the electrodeposition method) and the electrode extraction layer are indispensable. Was becoming. Further, patterning of the transparent conductive thin film (mainly ITO) requires fine processing by a photolithography method, and defects due to short circuit and disconnection of the transparent conductive thin film are likely to occur. On the other hand, the electrode extraction layer also needs to be patterned similarly.
The process was complicated. As a result, it is inevitable that the yield of the color filter is finally lowered.

Further, in forming a film of one of the RGB dyes by the micelle electrolysis method, it was necessary to continuously connect the dye layer forming electrodes of the one color. At that time, as the pattern arrangement of the dye layer, in addition to the stripe arrangement, there is a diagonal arrangement, a triangle arrangement, etc., but if the line-and-space of the dye forming electrode pattern is a diagonal and triangle arrangement, it becomes small, Compared with the stripe pattern, the increase in the probability of defects due to the short circuit and the disconnection, that is, the decrease in the yield was remarkable.

Further, by continuously connecting the fine dye layer forming electrodes, a voltage drop is generated due to the resistance of the transparent conductive thin film, and the film thickness difference between the dye layer near the electrode extraction layer and the remote portion, that is, the color filter. There was a case where it caused the color spot of. Especially for diagonal and triangle arrangements, color spots tend to occur for the above reasons. The above problems generally existed not only in the micelle electrolysis method but also in the electrodeposition method.

When the color filter is manufactured by the electrodeposition method, the resist electrodeposition method (JP-A-4-24740) is used.
No. 2) has solved the above problems. That is, (a) a step of forming a transparent conductive layer on a transparent substrate,
(B) a step of forming a specific positive photosensitive resin composition (photosoluble resist) on the transparent conductive layer, (c) after placing a mask having a desired pattern on the photosensitive resin layer Exposing and developing to expose a part of the transparent conductive material,
(D) a step of forming a colored layer of a desired color on the exposed transparent conductive layer by electrodeposition, and (e) the above (c) and (d)
There is disclosed a method for manufacturing a multicolor display device (color filter), which comprises the step of repeating the above step for the required number of times. However, as described above, the dye layer (colored layer) of the color filter produced by this production method contains a considerable proportion of the electro-deposited polymer (water-soluble acrylic resin, epoxy resin, etc.), and contains no pigment or dye. Since the ratio is low, there is a problem that the light resistance of the formed color filter is deteriorated due to the deterioration of the electrodeposition polymer.

On the other hand, also in the micelle electrolysis method, Japanese Patent Laid-Open No.
In Japanese Patent Publication No. 342205, the above problem is solved by a method similar to the resist electrodeposition method (the dye layer is formed by a micelle electrolysis method instead of the electrodeposition method). Since the filmed dye layer is porous and cannot be electrically insulated, when the multicolored dye layer is repeatedly formed, the dye layer formed earlier is contaminated with the dye layer formed later, and the color filter is formed. The problem of not being able to obtain the required color spectrum has not been solved.

On the other hand, there are various 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 dispersion method color filter uses a photo-curable resist in which a dye (pigment or dye) is dispersed, the exposure sensitivity and the fineness (resolution) of the pattern of the dye layer are higher than those of the transparent resist due to the light absorption of the dye. Further, the dye-containing resist is applied by a spin coater and a roll coater, but a film thickness difference of the dye-containing resist occurs at the center part and the end part of the color filter, which causes color unevenness. Was there. The printing method color filter is difficult to align when sequentially printing RGB, and a high-resolution (high-definition) dye pattern cannot be currently desired. In the dyeing method, since only the dye is used as the dye, there is a problem in heat resistance in post-processing of the color filter and chemical resistance in the cleaning process. Further, in any of the dispersion method, the printing method, and the dyeing method, the pigment layer coexists with the pigment (pigment) and the resin (organic substance),
Since the proportion of the resin is higher than that of the pigment, the formed color filter has difficulty in light resistance. The present invention has been made in view of the above problems, and it is possible to achieve high definition while maintaining high light resistance, and to improve quality such as flattening and improve production efficiency (yield). An object of the present invention is to provide a method of manufacturing a color filter that can be used.

[0015]

To achieve the above object, according to the present invention, dye layers of a plurality of colors are separated and arranged on an insulating substrate by a micelle electrolysis method to form a predetermined dye pattern. In the method for manufacturing a color filter, a transparent conductive film is formed on a region corresponding to a continuous pattern including a region where dye layers of at least a plurality of colors are arranged or a region where dye layers of a plurality of colors are arranged on an insulating substrate. Layer is formed by laminating and forming a transparent thin film, and a plurality of dye layers are formed on the insulative substrate on which the transparent conductive thin film is formed by laminating and forming the following process group A (a1 and a2) or process groups B
(B1, b2, and b3), and as an aggregate of dye layers of a plurality of colors, the following process group A (a1 and a
2) and the process group B (b1, b2, and b3) are used to provide a method for manufacturing a color filter, which is characterized by separating and arranging. In addition, in the case of the present invention, when the respective dye layers are separately arranged, all the dye layers are processed by the process group A (a
1 and a2) are not used separately. Step group A a1) Step of forming a dye layer of one color selected from a plurality of colors on the whole or a part of the transparent conductive thin film by film formation by a micelle electrolysis method a2) On the dye layer of one color Is laminated with a transparent photo-curable resist, exposed using a mask corresponding to the dye layer of one color, and before and / or after the heat treatment of the exposed part,
Remove the photo-curable resist and dye layer in the unexposed area,
Step of arranging dye layer of one color Process group B b1) A photosolubilization type resist is laminated on the whole surface or a part of the transparent conductive thin film to correspond to the dye layer of one color selected from a plurality of colors. Exposing using a mask with a pattern,
Then, a step of developing and exposing the exposed portion of the photosolubilizing resist to remove b2) The dye layer of one color is exposed by removing the photosolubilizing resist by film formation by a micelle electrolysis method. Step of disposing on the conductive thin film b3) Step of removing all the photosolubilizing resist remaining on the transparent conductive thin film

Before the step of laminating and forming a transparent conductive thin film on a predetermined region of the insulating substrate, a metal or metal oxide thin film patterned in a black matrix shape is laminated on the insulating substrate. A method for manufacturing a color filter is provided.

Further, a color filter is manufactured by further laminating and forming an insulating film on the metal or metal oxide thin film formed by patterning and laminating on the insulating substrate in a black matrix shape. A method is provided.

Further, a plurality of dye layers are formed on the insulating substrate on which the transparent conductive thin film is laminated and formed, and the following process groups A (a1 and a2) or process groups B (b
1, b2 and b3), and the following process group A (a1 and a2) is used as an aggregate of dye layers of a plurality of colors.
And using both process group B (b1, b2 and b3),
Provided is a method for producing a color filter, which comprises patterning a photocurable resist containing a black dye into a shape of a black matrix and stacking and forming it before, in the middle or after the steps of separating and arranging.

At least after the step of laminating and forming the transparent conductive thin film in a predetermined region on the insulating substrate and before the step of separating and arranging the dye layers of a plurality of colors, A step of laminating and forming a metal or metal oxide thin film in a region where a pigment layer of a plurality of colors and a black matrix are arranged, and patterning and laminating a photocurable resist or a photosolubilizing resist into a black matrix shape. A method of manufacturing a color filter is provided, which comprises a step of forming a black matrix by forming a black matrix by etching a metal or metal oxide thin film having an exposed underlayer.

In the method of manufacturing the color filter, the step of separating and arranging the dye layers of the plurality of colors includes
A method for manufacturing a color filter is provided, which uses only the process group B (b1, b2, and b3).

Further, a protective film may be laminated and formed on a portion other than the portion where the dye layers of the plurality of colors are separated and arranged, before or in the step of separating and placing the dye layers of the plurality of colors. A method for manufacturing a color filter is provided.

Further, there is provided a method of manufacturing a color filter, which comprises laminating and forming a protective film and / or a liquid crystal driving electrode after the step of separating and arranging the dye layers of a plurality of colors.

Further, the dyes (pixels) of the plurality of colors are
There is provided a method of manufacturing a color filter, which corresponds to the three primary colors of red, blue, green, or the three primary colors and black.

In separating and arranging the dye layers of the plurality of colors, a dye layer of one color is formed by a micelle electrolysis method, and then washed with ultraviolet rays. A manufacturing method is provided.

Further, there is provided a method of manufacturing a color filter, characterized in that the method of laminating and forming the photocurable resist and / or the protective film is a micelle electrolysis method or an electrodeposition method. .

Hereinafter, the conventional color film manufacturing process and the specific manufacturing process of the present invention will be briefly described.
The materials used will be described in detail.

1. Conventional Color Filter Manufacturing Process Step 1: FIG. 61 is a front view showing a configuration of a color filter having a stripe type dye pattern, and FIG. 60 is a sectional view taken along line XY of FIG. 61 showing the manufacturing process. (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 by micellar electrolysis film formation. (E): A protective film is formed. (F): Cut at line A in FIG. (G): A liquid crystal driving transparent electrode is formed. Hereinafter, steps 2 to 3 and steps 14 to 16 will be simply described in the same manner.

Step 2: FIG. 63 is a front view showing the structure of a color filter having a diagonal dye pattern.
62 is a cross-sectional view taken along the line XY of FIG. 63, showing the manufacturing process. Metal or metal oxide thin film patterning (black matrix formation) on insulating substrate → insulating film formation → transparent conductive thin film formation → transparent conductive thin film patterning → photocurable resist cured product patterning (electrode extraction layer formation ) → Micelle electrolysis film formation R, G, B dye layer formation → protective film formation → substrate cut →
Liquid crystal driving electrode formation

Step 3: FIG. 65 is a front view showing the structure of a color filter having a diagonal type dye pattern, and FIG. 64 is a sectional view taken along the line XY of FIG. 65 showing its manufacturing process. Transparent conductive thin film formation on insulating substrate → Transparent conductive thin film patterning → Photocurable resist cured product patterning (electrode extraction layer formation) → Micelle electrolysis film formation R, G, B dye layer formation → Protective film formation → Substrate cut → Transparent electrode formation for liquid crystal drive →
Metal or metal oxide thin film patterning (black matrix formation)

Step 14: FIG. 67 is a front view showing the structure of a color filter having a triangle type dye pattern,
66 is a cross-sectional view taken along the line XY of FIG. 67, showing the manufacturing process. Metal or metal oxide thin film pattern formation (black matrix formation)-> R dye-containing (dispersion) resist pattern formation (R-dye layer formation)-> G dye-containing (dispersion) resist pattern formation (G-dye layer formation) on an insulating substrate → Formation of resist pattern containing B dye (dispersion) (formation of B dye layer) → Formation of protective film → Formation of transparent electrode for liquid crystal drive

Step 15: FIG. 69 is a front view showing the structure of a color filter having a diagonal dye pattern.
68 is a cross-sectional view taken along the line XY of FIG. 69, showing the manufacturing process. Metal or metal oxide thin film patterning (black matrix formation) on insulating substrate → transparent conductive thin film formation → photosolubilization type resist pattern formation (for R dye pattern) → electrodeposition method R dye containing (dispersion) electrode Deposition polymer pattern formation → Photosolubilization type resist pattern formation (for G dye pattern) →
Electrodeposition method G Dye-containing (dispersion) electrodeposition polymer pattern formation →
Photosolubilizing resist pattern formation (for B dye pattern)
→ Electrodeposition method B Dye-containing (dispersion) electrodeposition polymer pattern formation → Photosolubilization type resist removal → Protective film formation → Liquid crystal driving transparent electrode formation

Step 16: FIG. 71 is a front view showing the structure of a color filter having a stripe type dye pattern, FIG.
0 is a cross-sectional view taken along the line XY of FIG. 71, showing the manufacturing process. Transparent conductive thin film formation on insulating substrate → photo-solubilization type resist pattern formation (for G dye pattern) → micelle electrolytic film formation G dye layer formation → photo-solubilization type resist pattern formation (B
Dye pattern) → Micelle electrolysis film formation B dye formation → Photosolubilization type resist pattern formation (for R dye pattern) → Micelle electrolysis film formation R dye layer formation → Photosolubilization type resist removal → Protective film formation → Liquid crystal driving Transparent electrode formation

2. Manufacturing Process of Color Filter and the Like 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 has a striped dye pattern,
FIG. 1 is a front view showing the configuration of the color filter, 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): An R dye layer is formed by a micelle electrolysis method (b). (C) A transparent photocurable resist is laminated (c). (D): forming a photocurable transparent resist laminated pattern,
The unnecessary portion of the R dye layer is also removed by etching. (R
Formation of dye layer) (d). (E): A B dye layer is formed by a micelle electrolysis method, then a transparent photocurable resist laminated pattern is formed, and an unnecessary portion of the B dye layer is also removed by etching (B dye layer formation) (e). (F): A photosolubilizing resist pattern is formed (for G dye layer formation) (f). (G): A G dye layer is formed by the micelle electrolysis method.
(G dye layer formation) (g). (H): The photosolubilizing resist is removed (h). Here, in addition to the above, (I): a protective film (i) and / or (J): an electrode (j) of a transparent conductive thin film for driving a liquid crystal is laminated on at least the R, B and G dye layers. Good. Also,
The laminated patterning of the third color (here, G) photo-solubilizing resist may be applied only to the dye layer region of the third color, or a plurality of colors of the color filter including the regions of the dye layers of the first color and the second color. It may be a portion (display portion) where the dye layer is formed.
Further, a protective film may be laminated on a portion of the color filter other than the portion (display portion) where the pigment layers of a plurality of colors are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers. Hereinafter, similarly, the steps 5 to 13 will be simply described.

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. Formation of transparent conductive thin film on insulating substrate and patterning (a) → micelle electrolysis method B dye layer formation (b) → photo-curable resist lamination (c) → photo-curable resist patterning and unnecessary portion B dye The layer is removed by etching (B dye layer formation) (d) → (b), (c) and (d) are repeated for the R dye (R dye layer formation) (e) → photosolubilization type resist lamination patterning ( f) → Micelle electrolysis method G dye layer formation (G dye layer formation) (g) → photosolubilization type resist removal (h) Here, in addition to the above, at least a protective film and / or a liquid crystal driving transparent electrode are provided. It may be laminated on the R, B, and G dye layers, but in the liquid crystal driving method of the STN method and the MIM method, it is possible to drive the liquid crystal by forming a transparent conductive thin film pattern (stripe). / Or a transparent conductive thin film for driving liquid crystal It does not necessarily have to be laminated. Further, the laminated patterning of the photosolubilizing resist of the third color (here, G) may be performed only in the dye layer region of the third color,
It may be a portion (display portion) where the dye layers of a plurality of colors of the color filter are formed, including the areas of the dye layers of the first color and the second color. Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers.

Step 6: FIG. 10 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 9 is a sectional view taken along the line XY of FIG. 10 showing its manufacturing process. Metal or metal oxide thin film formation and patterning (formation of black matrix) on an insulating substrate (a) → transparent conductive thin film formation (b) → micelle electrolysis method G dye layer formation (c) → photocurability Resist lamination (d) → removal by photocurable resist patterning and unnecessary portion by G dye layer etching (G dye layer formation) (e) → (c), (d), (e)
Is repeated for B dye (B dye layer formation) (f) → photosolubilization type resist lamination patterning (g) → micelle electrolysis method R dye layer formation (h) → photosolubilization type resist removal (i) In addition to the above, a protective film and / or a liquid crystal driving transparent electrode may be laminated on at least the R, B, and G dye layers. Further, the laminated patterning of the photosolubilizing resist of the third color (here, R) may be performed only in the dye layer region of the third color, or in the color filter including the regions of the dye layers of the first color and the second color. It may be a portion (display portion) where a plurality of dye layers are formed. Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers.

Step 7: FIG. 12 is a front view showing the structure of a color filter having a triangle type dye pattern, and FIG. 11 is a sectional view taken along the line XY of FIG. 12 showing its manufacturing process. Metal or metal oxide thin film formation and patterning (formation of black matrix) on insulating substrate (a) → insulating film stacking (b) → transparent conductive thin film formation and patterning (c) → micelle electrolysis method B Dye layer formation (d) → photocurable resist stack (e) → photocurable resist patterning and removal of unnecessary portions by B dye layer etching (B dye layer formation) (f) → (d), (e), (F) is repeated for G dye (G dye layer formation) (g) → photosolubilization type resist lamination patterning (h) → micelle electrolysis method R dye layer formation (i) → photosolubilization type resist removal (j) → Formation of protective film (k) Here, in addition to the above, a transparent electrode for driving a liquid crystal may be laminated on at least the R, B, G dye layers, but in the liquid crystal driving method of the STN method and the MIM method, Transparent conductive thin film pattern (stra Since it is possible to drive the liquid crystal by performing the step (1), it is not always necessary to laminate the protective film and / or the transparent electrode for driving the liquid crystal. Also, the third color (here,
The lamination patterning of the photosolubilizing resist of R) may be performed only in the dye layer region of the third color, or a plurality of dye layers of the color filter including the regions of the dye layers of the first color and the second color are formed. It may be a part (display part). Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers 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.

Step 8: FIG. 6 is a front view showing the structure of a color filter having a triangle type dye pattern.
FIG. 5 is a sectional view taken along the line XY of FIG. 6 showing the manufacturing process. Transparent conductive thin film formation on an insulating substrate (a)-> BL dye-containing photocurable resist patterning (black matrix formation) (b)-> micelle electrolysis method R dye layer formation (c)-> photocurable resist lamination ( d) → Removal by photo-curable resist patterning and R dye layer etching of unnecessary portions (R dye layer formation) (e) → (c), (d) and (e) are repeated for B dye (B dye layer formation) ) (F) → Photosolubilizing resist laminated patterning (g) → Micelle electrolysis method G dye layer formation (h) → Photosolubilizing resist removal (i) → Protective film formation (j) → Transparent electrode for driving liquid crystal Formation (k) Here, the laminated patterning of the photosolubilizing resist of the third color (here, G) may be performed only in the dye layer region of the third color, or may include the regions of the dye layers of the first color and the second color. In addition, the multi-color dye layers of the color filter are formed. Part (display part). Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers.

Step 9: FIG. 8 is a front view showing the structure of a color filter having a triangle type dye pattern.
FIG. 7 is a sectional view taken along the line XY of FIG. 8 showing the manufacturing process. Forming and patterning a transparent conductive thin film on an insulating substrate (a)-> BL dye-containing photocurable resist patterning (black matrix formation) (b)-> micelle electrolysis method B dye layer formation (c)-> photocurable resist Lamination (d) → removal by photocurable resist patterning and B dye layer etching of unnecessary portions (B dye layer formation) (e) → (c), (d),
(E) is repeated for R dye (R dye layer formation)
(F) → Photosolubilization type resist laminated patterning (g) → Micelle electrolysis method G dye layer formation (h) → Photosolubilization type resist removal (i) Here, in addition to the above, a protective film and / or a liquid crystal The driving transparent electrode may be laminated on at least the R, B, and G dye layers, but in the liquid crystal driving method of the STN method and the MIM method, it is possible to drive the liquid crystal by forming a transparent conductive thin film pattern (stripe). Therefore, the protective film and / or the liquid crystal driving transparent electrode do not necessarily have to be laminated. Further, the laminated patterning of the third color (here, G) photosolubilizing resist may be performed only in the dye layer region of the third color, or in the color filter including the regions of the dye layers of the first color and the second color. It may be a portion (display portion) where a plurality of dye layers are formed. Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking is performed before the R, B, G dye layer forming step or
It may be between the steps of forming the B and G dye layers. Further, in steps 8 and 9, the BL dye-containing photo-curable resist patterning, that is, the formation of the black matrix is performed by R, G,
It may be before the step of forming the B dye layer, during the step of forming each of the R, B, and G dye layers, or after the step of forming the R, G, and B dye layers.

Step 10: FIG. 14 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 13 is a sectional view taken along line XY of FIG. 14 showing the manufacturing process. Transparent conductive thin film deposition (a) → metal or metal oxide thin film deposition (b) → photo-curable resist patterning and metal and metal oxide thin film etching (formation of black matrix) (c) on insulating substrate -> Photosolubilization type resist laminated pattern (d)-> Micelle electrolysis method R dye layer formation (R dye layer formation) (e)-> Photosolubilization type resist patterning (f)
→ Micelle electrolysis method G dye layer formation (g) → photo-solubilization type resist patterning (h) → micelle electrolysis method B dye layer formation (i)
→ Photosolubilization type resist removal (j) → Protective film formation (k) →
Formation of transparent electrode for driving liquid crystal (l) Further, the photosolubilizing resist may be removed each time each dye layer is formed.

Step 11: FIG. 16 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 15 is a sectional view taken along the line XY of FIG. 16 showing its manufacturing process. Transparent conductive thin film formation (a) → metal or metal oxide thin film formation (b) → photo-curable resist patterning and metal or metal oxide thin film etching (formation of black matrix) (c) on an insulating substrate → Micelle electrolysis method R dye layer formation (d) → photocurable resist layering (e) → photocurable resist patterning and R dye film etching (R) of unnecessary portions
Dye layer formation) (f) → (d), (e), (f) is repeated for B dye (B dye layer formation) (g) → photosolubilizing type resist lamination patterning (h) → micelle electrolysis method G Dye layer formation (i) → photosolubilizing resist removal (j) → protective film formation (k) → liquid crystal driving transparent electrode formation (l) Here, the third color (here, G) photosolubilizing resist The layered pattern may be formed only in the dye layer region of the third color, or in a portion (display unit) in which a plurality of dye layers of the color filter are formed, including the regions of the dye layers of the first color and the second color. Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers.

Step 12: FIG. 18 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 17 is a sectional view taken along the line XY of FIG. 18 showing its manufacturing process. Transparent conductive thin film formation on an insulating substrate (a) → metal or metal oxide thin film patterning (formation of black matrix) (b) → photo-soluble resist patterning (c) → micelle electrolysis method R dye layer formation ( R dye layer formation) (d) → photosolubilization type resist patterning (e) → micelle electrolysis method G dye layer formation (G dye layer formation) (f) → photosolubilization type resist patterning (g) → micelle electrolysis Method B Dye layer formation (B dye layer formation) (h) → photosolubilization type resist removal (i) → protective film formation (j) → liquid crystal driving transparent electrode formation (k) In addition, for each dye layer formation, The photosolubilizing resist may be removed.

Step 13: FIG. 20 is a front view showing the structure of a color filter having a diagonal dye pattern, and FIG. 19 is a sectional view taken along the line XY of FIG. 20 showing its manufacturing process. Transparent conductive thin film formation on an insulating substrate (a) → metal or metal oxide thin film patterning (formation of black matrix) (b) → micelle electrolysis R dye layer formation (c) → photocurable resist lamination ( d) → Photocurable resist patterning and R dye film etching of unnecessary portions (R dye layer formation)
(E) → (c), (d), (e) are repeated for B dye (B dye layer formation) (f) → photo-solubilizing resist patterning (g) → micelle electrolysis method G dye layer formation (h ) → Photosolubilization type resist removal (G dye layer formation) (i) → Protective film formation (j) → Transparent liquid crystal drive electrode formation (k) Here, the third color (here, G) photosolubilization type The resist may be laminated and patterned only in the dye layer region of the third color, or in a portion (display unit) in which a plurality of dye layers of the color filter are formed, including the regions of the dye layers of the first color and the second color. . Further, a protective film may be laminated on a portion of the color filter excluding a portion (display portion) where a plurality of dye layers are formed. The stacking may be performed before the step of forming the R, B, G dye layers or during the step of forming the R, B, G dye layers.

2. Materials Used and Methods of Using the Same Hereinafter, various materials used in the present invention and methods of using the same will be described in detail. (1) Insulating Substrate The insulating substrate used in the present invention is not particularly limited,
A glass plate or a plastic plate can be used. Specifically, as the glass plate, low expansion glass, non-alkali glass (7059 manufactured by Corning, NA4 manufactured by HOYA)
5), quartz glass, soda lime glass and the like. Examples of the plastic plate include plastic plates such as polyethylene terephthalate. Of these, a glass plate is preferable, and a polished product thereof is particularly preferable, but a non-polished product may be used.

(2) Transparent Conductive Thin Film The transparent conductive thin film may be a metal or a conductor having a noble potential higher than the oxidation potential of the ferrocene derivative of the micellizing agent. Specific examples thereof include mixed oxides of indium and tin (ITO), tin dioxide, and transparent conductive polymers. It is preferable that the transmittance is 95% or more (only a thin film), the film thickness is 100 to 2000 ⌒, and the sheet resistance is 500 Ω / □ or less. The forming method is not particularly limited, and the sputtering method, vapor deposition method, CVD method, coating method,
By a pyrosol method or the like, it is formed on an insulating substrate in a region where dye layers of at least a plurality of colors are formed or in a region corresponding to a pattern including a region where dye layers of a plurality of colors are formed. Specifically, it may be the entire surface of the insulating substrate when viewed two-dimensionally, or masking (example: FIG. 3).
By the method of 6), it is formed in at least the region of the color filter where the pigment layers of a plurality of colors are formed. In addition, this transparent conductive thin film, through a predetermined mask (example: FIG. 25),
By a photolithography method or the like, for example, it is formed in a region corresponding to a pattern including at least regions in which color dye layers of plural colors are formed.

(3) Black Matrix As the black matrix, a metal or metal oxide thin film, a black dye-containing photocurable resist cured product, a black dye layer formed by a micelle electrolysis method, or the like can be used. Specifically,
Examples of the metal or metal oxide thin film include metals such as chromium (Cr), nickel (Ni), and copper (Cu), oxides thereof, and mixtures of the above metals or metal oxides. Optical density is 3.0 or more (film thickness 0.05-
0.5 μm) is preferable. There is no particular limitation on the forming method, and the sputtering method, vapor deposition method, C
The above-mentioned metal or metal oxide thin film is formed on the entire surface of the insulating substrate as viewed in a plane by the VD method or the like, or on the entire surface including at least a region where a black matrix and dye layers of a plurality of colors are formed by a masking method. After that, patterning is performed by a photolithography method (generally, photo-solubilization type resist application → exposure (using a mask for forming a black matrix) → development → post bake → metal or metal oxide thin film etching → photo-solubilization type). A method of removing the resist can be mentioned.

The following can be used as the black dye-containing photocurable resist cured product. Examples of the black pigment include carbon black, titanium black, aniline black, cobalt or iron, or oxides thereof, a pigment and a pigment mixture (A) obtained by mixing at least two of them, and black, red, Blue, green,
A quasi-blackening pigment mixture (B) formed by mixing at least two or more of purple, cyanine, and magenta organic pigments (mainly pigments used in the micelle electrolysis film-forming dye layer may be used), and ( A mixture of A) and (B) (JP-A-4-13106, JP-A-4-190362) can be mentioned.

Examples of the photocurable resist include a mixture of an acrylic or methacrylic acid derivative and its copolymer (binder). An epoxy group, a siloxane group, or a polyimide precursor may be introduced into the acrylic or methacrylic acid derivative. Examples of the photoinitiator include triazine-based, acetophonone-based, benzyne-based, benzophenone-based, thioxanthone-based and the like. As the dispersant, nonionic, ionic surfactant,
Examples include organic pigment derivatives, polyester-based single products, and mixtures of two or more thereof. Examples of the solvent include ketones such as cyclohexanone and esters such as cellosolve acetate, and mixtures of two or more thereof.

After mixing, dispersing, and filtering the above, patterning is performed by the photolithography method. Generally, the above resist is applied, an oxygen barrier film (polyvinyl alcohol) is applied if necessary, exposed (using a mask for forming a black matrix), developed, and post-baked.
In addition, by exposing from the back surface of the substrate (back exposure),
In some cases, it is not necessary to use a black matrix forming mask. For example, RGB dye layer (dye pattern)
In the case where the black matrix is already formed, the RGB dye layer can be used as a mask for forming the black matrix.
The optical density is preferably 2.0 or more (film thickness 1.0 μm). As a concrete product name, CK-2000
(Made by Fuji Hunt Electronics Technology Co., Ltd.), V
-259 black (manufactured by Nippon Steel Co., Ltd.) and the like.

Examples of the black dye layer formed by the micelle electrolysis method include the following. As the black pigment, carbon black, titanium black, aniline black, or a single product of cobalt, iron, or an oxide thereof, and a pigment and a pigment mixture (A) formed by mixing at least two kinds, and black, red, and blue. , Green, purple, cyanine, and magenta organic pigments (mainly pigments used in the micelle electrolysis film-forming dye layer may be used), a pseudo black pigment mixture (B) obtained by mixing at least two or more thereof, and A mixture of (A) and (B). The above is formed into a film by the micelle electrolysis method.

The dye layer is formed by forming a black dye layer on the conductive thin film by the micelle electrolysis method, further laminating a photocurable resist, and patterning the resist in the shape of a black matrix by the photolithography method and dye. It can be obtained by etching the layer (Japanese Patent Application No. 4-2654).
22, No. 5-144320)). Further, a photosolubilizing resist is laminated on the conductive thin film, the resist is patterned in the shape of a black matrix by the photolithography method, and a black dye layer is formed on the exposed conductive thin film by the micelle electrolysis method. Can be obtained (Japanese Patent Application No. 5-
91996). Further, if the RGB dye layers are already formed, a black dye film can be formed in the gaps by the micelle electrolysis method (Japanese Patent Application No. 4-265422).
issue). The optical density is preferably 2.5 or more (film thickness 1.0 μm).

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 leakage light between the dye layers of a plurality of colors. More preferably, each dye layer partially overlaps the black matrix. 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) Transparent Photocurable Resist The transparent photocurable resist used in the present invention is one in which the exposed portion of ultraviolet light (i-line, g-line, h-line) is polymerized, cross-linked and cured. The higher the transparency, the better. Specifically, for example, a mixture of acrylic or methacrylic acid derivative and its copolymer (binder) can be mentioned. As the acryl or methacrylic acid derivative, those introduced with an epoxy group, a siloxane group, or a polyimide precursor can be preferably used. As the photoinitiator, triazine-based, acetophenone-based, benziyne-based, benzophenone-based, thioxanthone-based and the like can be preferably used. Examples of the solvent include ketones such as cyclohexanone and esters such as cellosolve acetate, and mixtures of two or more thereof. These are mixed, dispersed, and filtered to prepare a resist.

Specific product names are CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) and V-259P.
A (manufactured by Nippon Steel), JNPC06, JNPC09, JN
PC16 (made by JSR), CFGR (made by Tokyo Ohka),
And Photo Nice UR3100 (manufactured by Toray). The film thickness and transmittance of the transparent photocurable resist cured product are 0.1 to 4.0 μm, and the transmittance is 90% or more /
460 nm is preferred. The transmittance is the value of the resist film only.

(5) Photosolubilizing Resist The photosolubilizing resist used in the present invention is not particularly limited, and the exposed portion of ultraviolet rays (i-line, g-line, h-line) or the like is eluted with a developing solution. Anything will do. Specifically, a photosensitive resin composition containing a diazonium salt and a condensation product of paraformaldehyde (Japanese Patent Publication No. 38-11365).
, U.S. Pat. No. 1,762,033), ortho-quinonediazides, or ortho-diazooxides in a photosensitive resin composition (JP-B-37-3627, JP-B-43-28403, JP-B-45-9610) Etc.), a photosensitive resin composition containing an alkali-soluble azide polymer (Japanese Patent Publication No. 40-28499, Japanese Patent Publication No. 45-22).
No. 085, 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, Japanese Patent Publication No. 45-22082), and tert-butyl ester of carboxylic acid or ter of phenol.
Examples thereof include a positive photosensitive resin composition containing a polymer of t-butyl carbonate having an acid-labile branched group and a photopolymerization initiator (onium salt) that produces an acid upon exposure. Specific product names include, for example, HPR204, FH2130 and the like (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) and OFPR (manufactured by Tokyo Ohka Co., Ltd.).

(6) Micelle electrolysis film-forming dye layer The red (R) dye layer includes perylene pigments, lake pigments, azo pigments, disazo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments and isoindoline. Examples thereof include single pigments such as pigments and isoindolinone pigments, or a mixture of at least two kinds.
As the green (G) dye layer, halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments,
Examples thereof include triphenylmethane-based basic dyes, isoindoline-based pigments, isoindolinone-based pigments, azo pigments, disazo pigments, and the like, or a mixture of at least two or more thereof. Examples of the blue (B) dye layer include a copper phthalocyanine-based pigment, a phthalogenine-based pigment, an indanthrone-based pigment, an indophenol-based pigment, a cyanine-based pigment, and a dioxazine-based pigment, or a mixture of at least two or more thereof. it can. As the black (BL) dye layer, those mentioned in the above description of the black matrix can be used. The dye layer is formed into a film by the micelle electrolysis method.

The film thickness and transmittance of each dye layer are preferably set as follows. Red (R) has a film thickness of 0.5-
1.5 μm (transmittance 60% or more / 610 nm), green (G) has a film thickness of 0.5 to 1.5 μm (transmittance 60%
> / 545 nm) and blue (B) have a film thickness of 0.2 to
1.5 μm (transmittance of 60% or more / 460 nm). The transmittance depends on the value of only the dye layer.

The conditions of the micelle electrolysis method are as follows. The dye (pigment or dye), the photocurable resist or the thermosetting resin described below is added to an aqueous medium using a surfactant (micellating agent) composed of a ferrocene derivative. Disperse to prepare a micelle dispersion. As the aqueous medium used at this time,
Various media such as water, a mixed liquid of water and alcohol, a mixed liquid of water and acetone, and the like can be mentioned. The following can be mentioned as typical examples of the micellizing agent (ferrocene derivative surfactant).

[0058]

[Chemical 1]

Further, as the ferrocene derivative, other than the above, WO 89/0193, JP-A-1-4.
What is manufactured by the method described in 5370 gazette, Unexamined-Japanese-Patent No. 1-2226894, 2-83387, 2-250892 etc. can be used. In the method of the present invention, one kind of the ferrocene derivative may be used as the surfactant (micelling agent), or two or more kinds thereof may be combined, and, if desired, the ferrocene derivative and another surface active agent You may use it combining with an agent. Other surfactants include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, alkyl sulfates, polyoxy Examples thereof include cationic and anionic surfactants such as ethylene alkyl ether sulfate, alkyl trimethyl ammonium chloride, and fatty acid diethylaminoethylamide.

The micelle dispersion is prepared, for example, as follows. A mechanical homogenizer or ultrasonic homogenizer containing the ferrocene derivative, another surfactant optionally used and the desired dye (pigment or dye), a photocurable resist, or a thermosetting resin in an aqueous medium. , Mix well with a ball mill, sand mill, stirrer, etc. 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 other surfactant optionally used is not less than the critical micelle concentration, preferably 0.1 mmol / mol.
It is selected in the range of 1 to 1 mol / liter. on the other hand,
The pigment 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 in a range that does not hinder the precipitation of the dispersed pigment, and is usually 0.05 to 1
It is selected in the range of 0 mol / liter.

Electrolysis can be carried out without adding the supporting salt, but in this case, a thin film (dye layer) having a high purity and containing no supporting salt can be obtained. 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 or the deposition of the pigment on the electrode.

Specifically, sulfates (lithium, potassium, sodium, etc.) which are widely used as supporting salts are widely used.
Rubidium, aluminum salts, etc., Acetates (lithium, potassium, sodium, rubidium, beryllium,
(Salts of magnesium, calcium, strontium, barium, aluminum, etc.), ammonium salts, and the like are preferable, and examples thereof include LiBr, KCl, Li ₂ S.
Examples thereof include O ₄ and (NH ₄ ) BF ₄ .

In this way, four kinds of micelle dispersion liquids in which the red pigment (pigment or dye), the green pigment (pigment or dye), the blue pigment (pigment or dye) and the black pigment (pigment) are dispersed, respectively. To prepare. The micellar dispersion of mixed pigments may be prepared by adding the pigment to be mixed in an aqueous medium together with a micelle-forming agent once and dispersing it, or micellar a single pigment to be mixed in an aqueous medium. It may be prepared by adding together with the agent and mixing the respective micelle dispersions obtained by dispersion.

The film formation by the micelle electrolysis method is performed as follows, for example. In any one of the micelle dispersions described above, for example, an insulating substrate in which a transparent conductive thin film is formed in the region where the dye layers of at least a plurality of colors are formed is inserted, and this is energized to perform micelle electrolysis. A desired dye layer is formed on the transparent conductive thin film of this substrate.

The electrolysis conditions may be appropriately selected according to various situations, but the liquid temperature is usually 0 to 90 ° C., preferably 10 to 70.
Can be selected in the range of ℃, voltage is 0.03 ~ 1.5
V, preferably 0.1 to 0.9 V can be selected. The current density is usually 10 mA / cm ² or less, and preferably 50 to 300 μA / cm ² can be selected. When this electrolytic treatment is performed, the reaction according to the principle of the micelle electrolysis method proceeds. This is the ferrocene derivative F
Focusing on the behavior of e-ions, the ferrocene Fe at the anode
²⁺ becomes Fe ³⁺ , the micelles are disintegrated, and pigment particles or dyes are deposited on the anode (transparent conductive thin film). On the other hand, at the cathode, Fe ³⁺ oxidized at the anode returns to the original micelle when it is reduced to Fe ²⁺ , so that the film forming operation can be repeated with the same solution. The film thickness and transmittance of each dye layer can be controlled by manipulating the electrolysis time within the above voltage range. Next, the 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, heat-treated in a temperature range up to 200 ° C. May be.

Further, a substrate on which a dye layer is formed is inserted into the micelle dispersion liquid of the photocurable resist or the thermosetting resin, and this is energized to carry out micelle electrolysis to obtain a desired dye layer on the substrate. A photocurable resist film or a thermosetting resin film (protective film) is laminated. The dye layer is porous, and since the underlying transparent conductive thin film and the micelle dispersion liquid of the photocurable resist or the thermosetting resin are conducted, the photocurable resist film or the thermosetting resin film is formed by the micelle electrolysis method. It can be laminated on the dye layer. The electrolysis is performed under the same conditions as for the coloring matter (pigment or dye), and the principle of the micelle electrolysis method can be applied. However, when a photo-curable resist or a thermosetting resin film is laminated to fill the voids in the dye layer, the conductivity of the dye layer is gradually lost. As a result, when the sheet resistance of the photocurable resist film including the dye layer and the thermosetting resin film is 10 ⁹ Ω / □ or more, the film cannot be formed. Therefore, the film thickness of the photocurable resist film or the thermosetting resin film including the dye layer is controlled by the film thickness of the dye layer. 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 going, 150-300 ℃
Then, it is completely heat-cured. The photo-curable resist or the thermosetting resin can be laminated by the electrodeposition method as well as the micelle electrolysis method. Alternatively, the light resistance of the formed color filter is not deteriorated due to the large proportion of (or dye).

(7) Formation of a plurality of color dye layers of a color filter The above-mentioned substrate (insulating substrate in which a transparent conductive thin film and a black matrix are laminated), a micellar electrolytic method film, a transparent photocurable resist, and a photosolubilizing type. It is possible to form a pigment layer of a plurality of colors of a color filter by using a resist. First, the process group A used in the present invention will be described. That is, a transparent conductive thin film formed on an insulating substrate at least in a region where color layers of a plurality of colors of a color filter are formed, or a pattern including at least a region where color layers of a plurality of colors of a color filter are formed. On the transparent conductive thin film formed in the region corresponding to (1), one dye (for example, R) of a plurality of colors is formed on the transparent conductive thin film by the micelle electrolysis method (a1). Then, a photo-curable resist is spin-coated and roll-coated, the above-mentioned micelle electrolysis method, and an electrodeposition method using a photo-curable electrodeposition polymer (Japanese Patent Laid-Open No. Hei.
No.-104102) and laminated coating on the R dye layer,
Exposure through a mask corresponding to the R dye layer is performed to etch the photocurable resist and the dye layer in the unexposed portion (a
2). Here photo-curable resist (same for thermosetting resin)
In the case of spin coating and roll coating, the film thickness is controlled by the viscosity of the resist and the spin coating rotation speed and rotation time. In the case of the micelle electrolysis method and the electrodeposition method, the time of insulation is the lamination. Will be the end point of.
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 layer of the resist from the sum of the film thickness of the dye layer and the photocurable resist, In the case of the micelle electrolysis method or the electrodeposition method, it is almost close to the thickness of the dye layer. 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, 20 to 60 in the case of i-line (365 nm).
0 mJ / cm ² is common. Next, a developing solution is sprayed to dissolve the photo-curable resist in the unexposed portion, and the lower dye layer is further subjected to a method such as pure water shower, high pressure pure water shower, brush scrub, and ultrasonic pure water shower. Etching is performed at the same time as the rinsing, leaving the photo-curable resist laminated with the dye layer in the exposed area,
The photocurable resist laminated with the dye layer is completely cured by heating in an oven or a hot plate at 0 ° C. As a developing solution, a general developing solution corresponding to a resist is used. For example, as an organic type, an aqueous solution of a quaternary amine such as tetramethylammonium hydroxide (TMAH) is used, and as an inorganic type, a sodium carbonate, water is used. An aqueous solution of an alkali metal hydroxide such as sodium oxide or potassium hydroxide or an alkali metal salt is used, and the temperature is from room temperature to 80 ° C. Further, only the photocurable resist is patterned by the development and rinse treatment after the exposure of the photocurable resist of the upper layer, and the dye layer exposed after being cured by the above heat treatment is treated with an organic solvent in addition to the above developer. (Ethanol, acetone) or may be treated with a surfactant or the like for etching. Here, as the method for etching the dye layer, not only the wet etching described above but also dry etching using UV / ozone, plasma, sputtering, ion beam, or the like is possible, and wet etching and dry etching may be appropriately used in combination. Good. Such a process is similarly performed for another dye (for example, BG) of a plurality of colors.

Next, the process group B used in the present invention will be described. That is, on the insulating substrate, at least the transparent conductive thin film formed in the region where the dye layers of the plurality of colors of the color filter are formed, or at least the region where the dye layers of the plurality of colors of the color filter are formed is included. For example, on a transparent conductive thin film patterned in a stripe shape, a photosolubilizing resist is laminated and applied by spin coating and roll coating, and one dye (for example, R) layer of a plurality of colors is further applied. The transparent conductive thin film exposed through a mask, the exposed portion of the photo-solubilizing resist is developed and rinsed by a conventional method and removed (b1), and the R dye layer is exposed by removing the photo-solubilizing resist. An R dye layer is formed by forming a film on the above by a micelle electrolysis method (b
2). This process is performed by adding another dye of multiple colors (for example, B
The same applies to G). Here, exposure and development are the same as those for the photocurable resist. Finally, a resist stripper that is commonly used for all remaining photosolubilized resist,
For example, a solution of amines such as quaternary amines, a solvent such as dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) is used at room temperature to about 160 ° C. to remove (remove) (b3). Further, the photosolubilizing resist may be peeled off each time each dye layer is formed. It should be noted that 20 to 800 mJ / cm before exposure to the resist stripping agent so that the photosolubilized resist can be removed more easily.
More preferably, the ^second exposure such as i-line exposure is performed on the photosolubilizing resist.

In the present invention, the above-mentioned two dye layer forming methods (process group A, process group B) can be combined to obtain a color filter in which dye layers of desired plural colors are arranged in a plane. In this case, each monochromatic dye layer is formed using either process group A or process group B, and all the dye layers are
It is not formed only by the process group A. Further, on the insulating substrate, a transparent conductive thin film is formed at least in a region of the color filter where the pigment layers of a plurality of colors are formed, and then at least a region where the black matrix of the color filter and the pigment layers of a plurality of colors are formed. A metal or metal oxide thin film is formed on. 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 or metal oxide thin film is etched with a mixed aqueous solution of cerium ammonium nitrate and perchloric acid. , Forming a black matrix. In addition, a photosolubilization type resist is patterned on the metal or metal oxide thin film in the form of a black matrix by a conventional photolithography method, and the metal or metal oxide thin film with the exposed underlying layer is cerium ammonium nitrate and perchlorine. The black matrix is formed by etching with a mixed aqueous solution of an acid and using the above-described resist stripping agent to strip the photosolubilizing resist in the same manner. When the substrate manufactured in this manner is used, the aggregate of the pigment layers of a plurality of colors is repeatedly used in the step group A and the step group B, or only the step group B, and a desired pigment layer of a plurality of colors is planarized. It is possible to obtain a color filter that is arranged physically.

(8) Insulating Film The insulating film is used to prevent electrical conduction between the transparent conductive thin film and the metal or metal oxide thin film (black matrix). For example, the transparent conductive thin film patterned in a stripe shape. And black matrix to provide electrical insulation. Black matrix of photocurable resist containing an insulative black dye (JP-A-4-1-1)
No. 3,106, JP-A-4-190362), no insulating film is required. As the insulating film used in the present invention, a cured product of a transparent photocurable resist, a transparent thermosetting resin, or the like can be preferably used, and an insulating film and a transparent conductive thin film, an insulating film and a metal or a metal oxide. It is more preferable to interpose a thin film of a transparent inorganic oxide such as silica, alumina, or titania on the adhesive surface in order to enhance the adhesion to the thin film. Here, as the photocurable resist, the above-mentioned ones can be used. As the thermosetting resin, for example, a mixture of an acrylic or methacrylic acid derivative and its copolymer (binder) can be mentioned. In addition, the above acrylic and methacrylic acid derivatives have an epoxy group,
A material having a siloxane group or a polyimide precursor introduced therein can be preferably used. Examples of the initiator include triazine type, acetophenone type, benzyne type, benzophenone type, thioxanthone type and the like. Examples of the solvent include ketones such as cyclohexanone and esters such as cellosolve acetate, and mixtures of two or more thereof. The above is mixed, dispersed, and filtered to prepare a transparent thermosetting resin. Such a photo-curable resist or thermosetting resin is applied to the entire surface including at least a metal or metal oxide thin film patterned in the shape of a black matrix by roll coating, spin coating, or offset printing, and an oven or a hot Heat and heat cure at 150-300 ° C with a toe plate,
An insulating film is formed. Specific product names include Optomer SS7265, JHR-8484, JSS-819,
JSS715 (manufactured by JSR), OS-808 (manufactured by Nagase & Co., Ltd.), LC2001 (manufactured by Sanyo Kasei), V-259P
A (made by Nippon Steel Chemical Co., Ltd.), CT (made by Fuji Hunt Electronics Technology Co., Ltd.), etc. can be mentioned. The transparent photocurable resist cured product or transparent thermosetting resin cured product has a film thickness and a transmittance of 0.1 to 4.0 μm and a transmittance of 90.
% Or more / 460 nm is preferable. The transmittance is a value only for the cured product. Regarding the film thickness, the transparent photocurable resist can be controlled by the viscosity of the transparent thermosetting resin agent and the rotation speed and rotation time of spin coating.

Examples of the inorganic oxide thin film include alumina, silica, titania and the like. The transparent thermosetting resin may be dispersed and applied as described above, or may be independently formed by a sputtering method, a vapor deposition method, or a CVD method. The thickness and the transmittance of the inorganic oxide thin film are 0.01 to
It is preferably 3.5 μm and the transmittance is 90% or more / 460 nm. The transmittance is a value only for the thin film.

(9) Protective film The protective film is for reducing the adhesiveness of the dye layers to the substrate and the film thickness difference between the dye layers (improving the flatness) after the dye layers of a plurality of colors are arranged in a plane. Or, in order to form a dye layer in a desired place only by the micelle electrolysis method, it is preferable to form a laminate. The protective film used in the present invention can be formed using, for example, a transparent photocurable resist and a transparent thermosetting resin agent. As the transparent photocurable resist, those mentioned above can be used. To form a protective film by roll-coating, spin-coating, offset-printing, etc., by laminating and coating on a region where at least pigment layers of plural colors are formed, and heating and curing at 150 to 300 ° C. in an oven or a hot plate. You can Alternatively, by roll coating, offset printing, or the like, at least the region (display unit) in which the multi-color dye layers are formed of the color filter is removed before or during the multi-color dye layer forming process. It is also possible to form a protective film by laminating and coating on a portion and heating and curing at 150 to 300 ° C. in an oven or a hot plate. Further, by roll coating, spin coating, offset printing, or the like is applied to the entire surface of the substrate including the area where the dye layers of multiple colors are formed, and the area where the dye layers of at least multiple colors are formed by the photolithography method or the multiple colors Before the step of forming the dye layer or during each step, patterning is performed so as to be laminated on at least a portion of the color filter excluding the area where the dye layers of a plurality of colors are formed. 150 ~
The protective film can be formed by heating and thermosetting at 300 ° C.

As the transparent thermosetting resin, those mentioned above can be used. Roll coat or spin coat,
It is possible to form a protective film by applying a laminated coating on at least a portion of the color filter where the pigment layers of a plurality of colors are formed by offset printing or the like and heating and curing at 150 to 300 ° C. in an oven or a hot plate. Alternatively, by roll coating, offset printing, or the like, before the step of forming the pigment layers of a plurality of colors or between the forming steps, at least a portion of the color filter excluding the area where the pigment layers of a plurality of colors are formed is laminated and applied. Then in the oven or hot plate
It is also possible to form a protective film by heating and curing at 50 to 300 ° C. In addition, in the case where it is on the dye layer (the dye layer in which the photo-curable resist is not laminated and is not insulated) (for example, (7) Step group B in forming dye layers of a plurality of colors of the color filter) , A photo-curable resist and a thermosetting resin dispersed in a micelle dispersion liquid are formed into a film by a micelle electrolysis method, or a photo-curing property is obtained even in an electrodeposition method using a photo-curable electrodeposition polymer described in JP-A-4-104102. A protective film of an electrodeposited polymer can be laminated on at least a portion of the color filter where the dye layers of a plurality of colors are formed.

(10) Liquid crystal driving transparent electrode For the liquid crystal driving transparent electrode, the same material and forming method as those for the transparent conductive thin film can be used.

[0076]

EXAMPLES The present invention will be described in more detail below with reference to examples. Production Example 1 1. Preparation of transparent conductive thin film deposition substrate Approximately 1300 Å of ITO thin film was vapor-deposited on a mirror-polished white glass substrate of 300 mm square (Corning 7059) using a sputtering device (ULVAC SDP-550VT). It was At this time, the substrate temperature is set to 25
The surface resistance of the ITO film was adjusted to 0Ω / □ at 0 ° C.

2. Patterning of transparent conductive thin film (ITO) On the substrate on which the ITO thin film is formed, a photosolubilizing resist FH2130 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is applied to the entire surface of the substrate with a roll coater to a film thickness of 1.5 μm. Prebaked on a hot plate at 110 ° C. for 5 minutes. Common part (Micelle electrolysis film formation electrode extraction part)
Through a mask (FIG. 25) for forming an ITO pattern having a stripe pattern and having a stripe pattern (proximity gap 60 μm).
m) after i-line exposure at 100 mJ / cm ² and then a room temperature organic alkaline aqueous solution developer (2.38% TMAH aqueous solution:
Fuji Hunt Electronics Technology FHD-
5) was spin-developed for 2 minutes, washed with pure water, and post-baked in an oven at 150 ° C. for 30 minutes. Then, this substrate is immersed in an equal amount mixture of ferric chloride aqueous solution (Boume 42) and 12N hydrochloric acid aqueous solution at 37 ° C. for 5 minutes to etch the ITO film on the part where the resist is not laminated and wash with pure water. And dried by air blow. Then, the substrate is immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature for 5 minutes, washed with pure water and dried by air blow to completely remove the remaining photosolubilizing resist. Removed to
The patterning of ITO was completed.

3. 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 The mixture was mixed at a concentration of 1 liter, disazo yellow (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a pigment, the pigment concentration was 12.45 g / liter, the FPEG was 2.00 mmol / liter, and lithium bromide was 0.1%. After mixing at a concentration of mol / liter and dispersing each mixed solution for 30 minutes with an ultrasonic homogenizer, each pigment dispersion was mixed at a weight ratio of 9: 1, and this mixed solution was ultrasonicated. The mixture was dispersed for 30 minutes with a homogenizer to prepare a mixed micelle dispersion liquid of R.

Further, in 1 liter of pure water, a halogenated copper phthalocyanine (manufactured by BASF) was used as a pigment, the pigment concentration was 14.85 g / liter, and the above-mentioned FPEG was used as 3.00 mmol / liter. Lithium bromide was mixed at a concentration of 0.1 mol / liter, and disazo yellow (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a pigment, the pigment concentration was 12.45 g / liter, and the FPEG was 2.00. Mmol / l and lithium bromide were mixed at a concentration of 0.1 mol / l, and each mixed solution was dispersed for 30 minutes by an ultrasonic homogenizer, and then each pigment dispersion was mixed at a weight ratio of 6: 4. Was mixed, and this mixed solution was dispersed for 30 minutes by an ultrasonic homogenizer 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, and the FPEG was used.
1.25 mmol / l, lithium bromide was used as a supporting salt and mixed at a concentration of 0.1 mol / l, and dioxazine violet (manufactured by Sanyo Dye Co., Ltd.) was used as a pigment, and the pigment concentration was 4.88 g. / Liter, the FP
EG was mixed at a concentration of 3.00 mmol / liter and lithium bromide at a concentration of 0.1 mol / liter, and each mixed solution was dispersed for 30 minutes by an ultrasonic homogenizer, and then the weight ratio was 7: 3. Mix the pigment dispersion of
Furthermore, this mixed solution was dispersed for 30 minutes with an ultrasonic homogenizer to prepare a mixed micelle dispersion of B.

Further, in 1 liter of pure water, an acrylic acid resist CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was used as a photocurable resist, and the solid content concentration of the resist was 10.00 g / liter.
Was mixed at a concentration of 1.50 mmol / l and lithium bromide as a supporting salt at a concentration of 0.1 mol / l, and the mixture was dispersed for 30 minutes with an ultrasonic homogenizer.
A micelle dispersion of photocurable resist was prepared.

Example 1 The ITO film-formed substrate prepared in Production Example 1 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 to give 0. .4V, 1
Constant-potential electrolysis was carried out for 8 minutes to form an R dye layer on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in a 100 ° C. oven. JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) as a transparent photocurable resist
The dye layer was spin coated at 1500 rpm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through an R dye layer pattern forming mask (for stripe: FIG. 26), i-line exposure was performed at 300 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then an organic alkali system at room temperature Aqueous developer (0.5%
TMAH aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the R dye layer in the unexposed area and a photocurable resist Was etched. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the R dye layer was arranged. 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 0.5 V for 5 minutes of potentiostatic electrolysis was performed. A dye layer of B was formed on the transparent conductive thin film other than the above, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. JNPC06 (manufactured by Japan Synthetic Rubber Co., Ltd.) as a transparent photocurable resist
The dye layer and the B dye layer were spin-coated at 1500 rpm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, a mask for forming the B dye layer pattern (for stripes:
(Fig. 28) through a proximity type exposure device (proximity gap 60 μm) of 300 mJ /
After i-line exposure at cm ² , a room temperature organic alkaline aqueous solution (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute, and scrubbed with an acrylic bristle brush. After that, the substrate was washed with pure water to etch the unexposed portion of the B dye layer and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Next, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked on a hot plate at 110 ° C. for 5 minutes.
300 mJ / cm ^{2 with a} proximity type exposure machine (proximity gap 60 μm) through a mask for forming the G dye layer pattern (for stripe: (FIG. 27))
After i-line exposure, the solution was spin-developed for 2 minutes with a developer (0.5% TMAH solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at room temperature for 2 minutes, and washed with pure water. Then, this substrate 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 obtain 0.7V, 1
Constant-potential electrolysis was carried out for 0 minutes to form a G dye layer on the transparent conductive thin film exposed in the exposed portion, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. Next, the substrate is placed at room temperature in an organic alkaline stripping solution (N
-303: manufactured by Nagase & Co., Ltd.) for 5 minutes, and then washed with pure water to completely remove the remaining photosolubilizing resist and form RGB dye layers. Next, a transparent thermosetting resin agent LC2001 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) was spin-coated on this substrate as a protective film at 900 rpm, and 220
It was completely thermoset in an oven at 0 ° C. 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 / □. The color filter was manufactured as described above (process 4, FIG. 1).

Example 2 A black dye (carbon black) -containing photocurable resist (CK-200) was formed on the ITO film-forming substrate prepared in Production Example 1.
0: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 500 rpm and prebaked on a hot plate at 85 ° C. for 5 minutes. Further, a polyvinyl alcohol aqueous solution containing 10% ethanol (CP: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 500 rpm, and prebaked on a hot plate at 85 ° C. for 5 minutes. Next, using a black matrix forming mask (FIG. 29) corresponding to the triangle dye layer pattern in a proximity type (proximity gap 60 μm) exposure machine, i-line exposure was performed at 100 mJ / cm ² , and then an inorganic alkali system at room temperature was used. Spin developing with an aqueous solution (0.1N sodium carbonate aqueous solution: CD manufactured by Fuji Hunt Electronics Technology Co., Ltd.) for 2 minutes, brush scrub cleaning with pure water, and heat treatment (post-baking) for 60 minutes in an oven at 220 ° C., The black dye-containing resist cured product was embedded to form a black matrix. Next, the substrate on which the black matrix was formed was inserted into the micelle dispersion liquid of R prepared in Production Example 1, and the transparent conductive thin film and the anode of the potentiostat were connected to each other,
Constant-potential electrolysis was performed at 0.4 V for 18 minutes to form an R dye layer on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in a 100 ° C. oven. As a transparent photo-curable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) 1500r on the R dye layer
It was spin-coated with pm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through an R dye layer pattern forming mask (triangle: FIG. 30), i-line exposure was performed at 100 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure machine, and then an organic alkali system at room temperature was used. Aqueous developer (0.5% TMAH aqueous solution:
Fuji Hunt Electronics Technology FHD-
5) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the R dye layer and the photocurable resist in the unexposed area. Finally 200 ℃
The substrate was inserted into the oven, and the photocurable resist in the exposed area was completely thermoset, and the R dye layer was arranged. 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,
Conducting constant potential electrolysis at 0.5 V for 5 minutes to form the B dye layer on the transparent conductive thin film other than the R dye layer forming part, washing with pure water, draining water by air blow, and then in a 100 ° C. oven. Dried. CT as a transparent photocurable resist
R (made by Fuji Hunt Electronics Technology Co., Ltd.)
Spin coat on dye layer and B dye layer at 700 rpm,
It was prebaked on a hot plate at 80 ° C. for 5 minutes. next,
Through a mask (triangle: FIG. 31) for forming the B dye layer pattern, 100 mJ / cm ^{2 with a} proximity type (proximity gap 60 μm) exposure machine
After i-line exposure, a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute and scrubbed with an acrylic bristle brush. Further, it was washed with pure water to etch the unexposed portion of the B dye layer and the photocurable resist. Finally, the substrate is inserted into an oven at 200 ° C. to completely thermoset the photocurable resist in the exposed area,
The B dye layer was placed. Next, the HP of the photosolubilization type resist
R204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 1500 rpm on the entire surface of the substrate, and 1
It was prebaked on a hot plate at 10 ° C. for 5 minutes. Mask for forming G dye layer pattern (for triangle: Fig. 3
2) via i-line exposure at 100 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure machine, and then a developer of an organic alkaline aqueous solution at room temperature (2.38% TMAH aqueous solution: Fuji Hunt Electronics Technology) It was spin-developed for 2 minutes with FHD-5) manufactured by Co. and washed with pure water. Then, this substrate 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 obtain 0.7V, 1
Constant-potential electrolysis was carried out for 0 minutes to form a G dye layer on the transparent conductive thin film exposed in the exposed portion, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. Next, the substrate is placed at room temperature in an organic alkaline stripping solution (N
-303: manufactured by Nagase & Co., Ltd.) for 5 minutes, and then washed with pure water to completely remove the remaining photosolubilizing resist and form RGB dye layers. Next, as a protective film, a transparent photocurable resist V-259PA (manufactured by Nippon Steel Chemical Co., Ltd.)
Spin coat at 500 rpm and 1 in 80 ° C oven
Prebaked for 5 minutes. Then, it is exposed at 300 mJ / cm ² through a mask capable of exposing only the black matrix of the color filter and the RGB dye layer, and a 0.1N sodium carbonate aqueous solution at room temperature (CD pure water diluted product of Fuji Hunt Electronics Technology Co., Ltd.) Immersion development was carried out, followed by washing with a pure water shower, drying by air blow, and heating in an oven at 200 ° C. for 60 minutes to form a protective film only on the black matrix and RGB dye layers. Finally, an ITO thin film was sputtered using a sputtering device (SDP-550VT manufactured by ULVAC, Inc.) at a thickness of about 1200 to form a transparent conductive thin film for driving a liquid crystal. At this time, the substrate temperature is 200 ° C,
The surface resistance of the ITO film was adjusted to 20Ω / □. The color filter was manufactured as described above (step 8, FIG. 5).

Example 3 The ITO patterned substrate prepared in Production Example 1 was inserted into the micelle dispersion B prepared in Production Example 1, and the transparent conductive thin film (common portion of ITO) and the anode of the potentiostat were inserted. Is connected to perform a constant potential decomposition at 0.5 V for 8 minutes to form a dye layer of B on the transparent conductive thin film, wash with pure water, and then remove water by air blow, 1
Dried in a 00 ° C oven. Next, as a transparent photocurable resist, V259PA (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on the B dye layer at 500 rpm, and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through a mask (for triangle: FIG. 31) for forming a B dye layer pattern, i-line exposure was performed at 300 mJ / cm ² with a proximity method (proximity gap 60 μm) exposure machine, and then an organic alkali system at room temperature was used. Aqueous developer (0.5% T
MAH aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the B dye layer in the unexposed area and a photocurable resist Was etched.
Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Then, the mixture was inserted into the R micelle dispersion prepared in Production Example 1, the transparent conductive thin film (the common part of ITO) was connected to the anode of the potentiostat, and potentiostatic electrolysis was performed at 0.4 V for 15 minutes. The R dye layer was formed on the transparent conductive thin film other than the B dye layer forming portion, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. As a transparent photocurable resist, V259PA (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on the B dye layer and the R dye layer at 700 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through a mask (triangle: FIG. 30) for forming the R dye layer pattern, a proximity method (proximity gap 60 μm) exposure device 3 was used.
After i-ray exposure at 00 mJ / cm ² , a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronic Technologies Co., Ltd.) was sprayed for 1 minute, and then applied to an acrylic bristle brush. Scrub,
Further, it was washed with pure water to etch the R dye layer and the photocurable resist in the unexposed area. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the R dye layer was arranged. Next, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked for 5 minutes on a 110 ° C. hot plate. Through a mask (for triangle: FIG. 32) for forming a G dye layer pattern, 100 mJ / in a proximity type (proximity gap 60 μm) exposure device.
After i-line exposure at cm ² , the solution was spin-developed for 2 minutes with a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronic Technologies Co., Ltd.) at room temperature for 2 minutes and washed with pure water. Next, this substrate was inserted into the micelle dispersion of G prepared in Production Example 1, the transparent conductive thin film (common part of ITO) and the anode of the potentiostat were connected, and a constant potential of 0.7 V for 10 minutes was set. Electrolyze,
A G dye layer is formed on the transparent conductive thin film exposed in the exposed portion, washed with pure water, and then drained by air blow,
Dried in a 100 ° C. oven. Next, the substrate is immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature.
After dipping for a minute, it was washed with pure water to completely remove the remaining photosolubilizing resist, and the RGB dye layers were formed.
Finally, cut the common ITO (conductive part) and
Color stripes were completed by making O stripes independent (process 5, FIG. 3)

Example 4 On the ITO patterned substrate produced in Production Example 1, as a resin black matrix forming resist, the same color CR, CG, and CB were added to the color mosaic CK manufactured by Fuji Hunt Electronics Technology Co., 3: 1:
A mixture of 1: 1 parts by weight (JP-A-4-13106)
Using a spin coater at 500 rpm,
Prebaked for 15 minutes in an oven. Next, a polyvinyl alcohol (PVA) aqueous solution (CP:
Fuji Hunt Electronics Technology Co., Ltd.) was applied in the same manner as the resist. Next, using a mask for forming a black matrix (FIG. 29) corresponding to the triangle dye layer pattern in an exposure system of a proximity system (proximity gap 60 μm), after exposing at 80 mJ / cm ² , an inorganic alkaline aqueous solution at room temperature was used. Developer (0.1
Aqueous sodium carbonate solution: CD developed by Fuji Hunt Electronics Technology Co., Ltd.), spin-developed for 2 minutes, brush scrubbing with pure water, and then in an oven at 220 ° C. for 6 minutes.
After heat treatment (post-baking) for 0 minutes, a black dye-containing resist cured product was embedded, and a black matrix was formed. Next, the substrate on which the black matrix was formed was inserted into the micelle dispersion liquid of B prepared in Production Example 1, the transparent conductive thin film (the common part of ITO) and the anode of the potentiostat were connected to each other. Constant-potential electrolysis at 5 V for 8 minutes was performed to form a B dye layer on the transparent conductive thin film, and after washing with pure water, the water was removed by air blow, and 1
Dried in a 00 ° C oven. Next, as a transparent photocurable resist, V259PA (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on the B dye layer at 500 rpm, and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through a mask (for triangle: FIG. 31) for forming a B dye layer pattern, i-line exposure was performed at 300 mJ / cm ² with a proximity method (proximity gap 60 μm) exposure machine, and then an organic alkali system at room temperature was used. Aqueous developer (0.5%
TMAH aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the B dye layer in the unexposed area and a photocurable resist Was etched. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Then, the mixture was inserted into the R micelle dispersion prepared in Production Example 1, the transparent conductive thin film (common part of ITO) and the anode of the potentiostat were connected to each other, and 0.4 V, 1
Constant-potential electrolysis was carried out for 5 minutes to form an R dye layer on the transparent conductive thin film other than the B dye layer forming portion. The R dye layer was washed with pure water, drained by air blow, and dried in a 100 ° C. oven. As a transparent photocurable resist, V259PA
(Nippon Steel Chemical Co., Ltd.) 700r on the B and R dye layers
It was spin-coated with pm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through an R-dye layer pattern forming mask (triangle: FIG. 30), i-line exposure was performed at 300 mJ / cm ² with a proximity type (proximity gap 60 μm) exposure machine, and then an organic alkaline aqueous solution at room temperature was used. Developer (0.5% TMAH aqueous solution: FHD- manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
5) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the R dye layer and the photocurable resist in the unexposed area. Finally 200 ℃
The substrate was inserted into the oven, and the photocurable resist in the exposed area was completely thermoset, and the R dye layer was arranged. Next, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is applied on the entire surface of the substrate at 1500 rp.
m and spin-coated at 110 ° C. on a hot plate for 5 minutes. I-line exposure at 100 mJ / cm ² with a proximity method (proximity gap 60 μm) exposure machine through a mask (for triangle: FIG. 32) for forming a G dye layer pattern, and then development of an organic alkaline aqueous solution at room temperature The solution (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-developed for 2 minutes 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 (common part of ITO) and the anode of the potentiostat are connected to each other, and constant potential electrolysis is performed at 0.7 V for 10 minutes, and the G dye layer is formed on the transparent conductive thin film exposed in the exposed portion. Was formed, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. Next, the substrate was 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. , RGB dye layers were formed. Finally, the common ITO film (conductive portion) was cut to separate the ITO stripes to complete the color filter (step 9, FIG. 7).

Production Example 2 Preparation of Transparent Conductive Thin Film Deposition Substrate on Metal Thin Film (Black Matrix) Mirror-polished white glass substrate 300 mm square (NA4)
5: HOYA), a Cr thin film was vapor-deposited 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. Then, a photo-solubilizing positive resist (HPR204: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied on the vapor-deposited Cr thin film with a roll coater to a thickness of 1.5 μm.
The film is coated with a film thickness, prebaked in an oven at 110 ° C. for 30 minutes, and passed through a mask (FIG. 33) for forming a black matrix corresponding to the diagonal dye layer pattern, in a proximity method (proximity gap 60 μm).
The exposure was performed at 60 mJ / cm ² with the exposure machine of m). Next, a room temperature organic alkaline aqueous solution developer (2.38% TMAH
Aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. was spin-developed for 2 minutes, washed with a pure water shower, and further heat-treated (post-baked) for 60 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. Etching the Cr thin film in the non-existing portion, further immersing in a resist stripping material (N-303: Nagase & Co., Ltd.) of an organic alkaline aqueous solution at room temperature for 5 minutes and washing with a pure water shower,
A black matrix of a metal thin film (Cr) was formed.
Next, a sputtering device (made by ULVAC: SDP-
550 VT) was used to deposit an ITO thin film at about 1300 Å. At this time, the substrate temperature was adjusted to 250 ° C. and the surface resistance of the ITO film was adjusted to 20 Ω / □.

Example 5 The transparent conductive thin film (ITO) was inserted into the above-mentioned micelle dispersion of G prepared in Production Example 1 on the substrate prepared in Production Example 2.
Connect the anode of the potentiostat to 0.7V,
Constant-potential electrolysis was carried out for 15 minutes to form a dye layer of G on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in an oven at 100 ° C. Next, as a transparent photocurable resist, JNPC16 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated on the G dye layer at 1500 rpm,
It was prebaked on a hot plate at 80 ° C. for 5 minutes. next,
Mask for G dye layer pattern formation (for diagonal:
34) through a proximity type exposure device (proximity gap 60 μm) to 300 mJ / cm.
After i-line exposure at ² , the 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.) is sprayed for 1 minute and scrubbed with an acrylic bristle brush. Further, it was washed with pure water to etch the G dye layer and the photocurable resist in the unexposed area. Finally, the substrate is inserted into an oven at 200 ° C. to completely thermoset the photocurable resist in the exposed area,
The G dye layer was placed. 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 for 0.5 V for 5 minutes to form a G dye layer forming portion. A dye layer of B was formed on the transparent conductive thin film other than the above, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. As a transparent photocurable resist, JNPC16 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated on the G dye layer and the B dye layer at 1000 rpm, and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, through a mask (for diagonal: FIG. 35) for forming a B dye layer pattern, a proximity exposure device (proximity gap 60 μm) is used to perform 30
After i-line exposure at 0 mJ / cm ² , a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was sprayed for 1 minute, and an acrylic bristle brush was used. Scrub,
Further, it was washed with pure water to etch the unexposed portion of the B dye layer and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Next, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked on a hot plate at 110 ° C. for 5 minutes. Next, through a mask (FIG. 36) capable of exposing the entire black matrix and RGB dye layer regions including the electrode extraction portion, 300 mJ / cm ^{2 with a} proximity type exposure device (proximity gap 60 μm).
After i-line exposure, the solution was spin-developed for 2 minutes with a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at room temperature and washed with pure water. Next, this substrate was inserted into the R micelle dispersion prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected to each other, and 0.5 V, 1
A constant potential electrolysis was carried out for 5 minutes to form an R dye layer on the transparent conductive thin film exposed in the exposed area, and after washing with pure water, the water was removed by air blow and drying was performed in a 100 ° C. oven. Next, after exposing the entire surface of the substrate by i-line exposure at 600 mJ / cm ² , an organic alkaline stripping solution (N-303:
After being immersed in Nagase & Co., Ltd.) for 3 minutes, it was washed with pure water to completely remove the remaining photosolubilizing resist, and the RGB dye layers were formed. Next, a transparent thermosetting resin agent Optomer SS7265 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated on this substrate as a protective film at 900 rpm, and 220 ° C.
Completely cured in an oven. 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 / □. The color filter was manufactured as described above (process 6, FIG. 9).

Production Example 3 Preparation of Transparent Conductive Thin Film (ITO) Patterned Substrate on Metal Oxide Thin Film (Black Matrix) In Production Example 2, the metal thin film Cr was changed to the metal oxide Cr ₂ O ₃ and a black matrix for triangle was formed. A transparent thermosetting resin agent JSS819 (manufactured by Japan Synthetic Rubber Co., Ltd.) as an insulating film was spin-coated at 1000 rpm on a substrate on which a black matrix was formed in the same manner except that a mask for masking (FIG. 37) was used, and the temperature was 220 ° C. After completely heat-curing in an oven, a sputtering device (SDP-550VT manufactured by ULVAC, Inc.) was used to further deposit a silica (SiO ₂ ) thin film of about 500 ⌒ and a transparent conductive thin film of an ITO thin film of 1300 ⌒ in order. It was sputtered on and laminated. Next, a photosolubilizing resist FH2130 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was coated on the entire surface of the substrate on which an ITO thin film had been formed by a roll coater to a film thickness of 1.5 μm, and a hot plate at 110 ° C. I prebaked it for 5 minutes. 10 through a proximity type exposure machine (proximity gap 60 μm) through a mask (FIG. 25) for forming an ITO pattern having a common part and patterned in stripes.
After i-line exposure at 0 mJ / cm ² , spin development was carried out for 2 minutes with a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at room temperature and washed with pure water. Post-baked in an oven at 150 ° C. for 30 minutes. Then, this substrate is immersed in an equal amount mixture of ferric chloride aqueous solution (Boume 42) and 12N hydrochloric acid aqueous solution at 37 ° C. for 5 minutes to etch the ITO film on the part where the resist is not laminated and wash with pure water. And dried by air blow. Then, the substrate is immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature for 5 minutes, washed with pure water and dried by air blow to completely remove the remaining photosolubilizing resist. Then, the ITO patterning was completed.

Example 6 On the substrate prepared in Preparation Example 3, the above micelle dispersion liquid of B prepared in Preparation Example 1 was inserted, and the transparent conductive thin film (ITO common part) and the anode of the potentiostat were connected. hand,
Constant-potential electrolysis was performed at 0.5 V for 5 minutes to form a dye layer of B on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in an oven at 100 ° C. Next, as a transparent photocurable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is applied to the B dye layer by 80.
It was spin-coated at 0 rpm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, a proximity type exposure machine (proximity gap 6) is formed through a mask (for triangle: FIG. 31) for forming the B dye layer pattern.
After i-line exposure at 100 mJ / cm ² at 0 μm), 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) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the unexposed portion of the B dye layer and the photocurable resist. Finally 20
The substrate was inserted into an oven at 0 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Then, it was inserted into the micelle dispersion of G prepared in Production Example 1,
The transparent conductive thin film (common part of ITO) and the anode of the potentiostat are connected to each other, and constant potential electrolysis is performed at 0.5 V for 10 minutes, and the G dye layer is formed on the transparent conductive thin film except the B dye layer forming part Was formed, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. As a transparent photocurable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is applied on the B dye layer and the G dye layer in an amount of 120.
It was spin-coated at 0 rpm and prebaked on a hot plate at 80 ° C. for 5 minutes. Next, a proximity type exposure machine (proximity gap 6) is formed through a mask (for triangle: FIG. 38) for forming a G dye layer pattern.
After i-line exposure at 100 mJ / cm ² at 0 μm), 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) was sprayed for 1 minute, scrubbed with an acrylic bristle brush, and further washed with pure water to etch the G dye layer in the unexposed area and the photocurable resist. Finally 20
The substrate was inserted into an oven at 0 ° C., the photocurable resist in the exposed portion was completely thermoset, and the G dye layer was arranged. Next, HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.), which is a photosolubilizing resist, is applied to the entire surface of the substrate by 150.
It was spin-coated at 0 rpm and prebaked on a 110 ° C. hot plate for 5 minutes. Proximity type exposure device (proximity gap 60 μm) through a mask (for triangle: FIG. 39) for forming the R dye layer pattern.
m) after i-line exposure at 300 mJ / cm ² , and a room temperature organic alkaline aqueous solution developer (0.5% TMAH aqueous solution: FHD- manufactured by Fuji Hunt Electronics Technology Co., Ltd.).
5) was spin-developed for 2 minutes and washed with pure water. Then, this substrate was inserted into the R micelle dispersion prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected, and potentiostatic electrolysis was performed at 0.5 V for 15 minutes to perform the above exposure. R dye layer is formed on the transparent conductive thin film exposed at the part, washed with pure water, then drained by air blow,
Dried in a 100 ° C. oven. Next, the entire surface of the substrate is 600
After i-line exposure at mJ / cm ² , the film was immersed in an organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) at room temperature for 3 minutes, washed with pure water, and left as a photosolubilizing type. The resist was completely removed to form RGB dye layers. Next, a transparent thermosetting resin agent Optomer SS7265 (manufactured by Japan Synthetic Rubber Co., Ltd.) was applied as a protective film on this substrate using an offset printing machine to apply about 2.0 μm on the RGB dye layers,
After completely thermosetting in an oven at 220 ° C., finally, the common (conducting) part of ITO was cut to make the ITO stripes independent, and a color filter was manufactured (step 7, FIG. 11).

Production Example 4 Production of Metal (Cr) Thin Film Black Matrix Forming Substrate on Transparent Conductive Thin Film On the transparent electroconductive thin film (ITO) film-formed substrate produced in Production Example 1, a metal (Cr) thin film is further sputtered. A Cr thin film was vapor-deposited in an amount of about 1200 ℓ using (SDP-550VT manufactured by ULVAC, Inc.). At this time, the substrate temperature was adjusted to 250 ° C. Next, a photocurable resist (V259PA: manufactured by Nippon Steel Chemical Co., Ltd.) was coated on the vapor-deposited Cr thin film by a spin coater at 1500 rpm, and 8
Prebaked in an oven at 0 ° C. for 30 minutes, and through a mask for forming a black matrix corresponding to the stripe and diagonal dye layer patterns (FIG. 40), 300 mJ / cm ^{2 with a} proximity type (proximity gap 60 μm) type exposure machine. Exposed. Next, an organic alkaline aqueous solution at room temperature (0.5% TMAH aqueous solution: F manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
The resist pattern was formed by spin developing with HD-5) for 2 minutes, washing with pure water in a shower, and further heat-treating (post-baking) for 60 minutes in an oven at 200 ° C. next,
Cerium ammonium nitrate 165g and perchloric acid 42
Prepare 1 liter of Cr etchant with ml and pure water,
The substrate on which the resist pattern is formed is immersed at room temperature for 2 minutes, washed with a pure water shower to etch the Cr thin film in the portion without the resist pattern, and then dried by air blow to form a black matrix of the metal thin film (Cr). Formed.

Example 7 On the substrate prepared in Preparation Example 4, H of the photosolubilizing resist was applied.
PR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 750 rpm on the entire surface of the substrate, and 1
It was prebaked on a hot plate at 10 ° C. for 5 minutes. Mask for R dye layer pattern formation (for diagonal: FIG. 4)
1) through i-line exposure at 100 mJ / cm ² with a proximity type exposure machine (proximity gap 60 μm), and then a developer of an organic alkaline aqueous solution at room temperature (2.38% TMAH aqueous solution: Fuji Hunt Electronics Technology) It was spin-developed for 2 minutes with FHD-5) manufactured by Co. and washed with pure water. Next, this substrate was inserted into the R micelle dispersion prepared in Production Example 1, the transparent conductive thin film and the anode of the potentiostat were connected to each other, and 0.5 V, 1
A constant potential electrolysis was carried out for 5 minutes to form an R dye layer on the transparent conductive thin film exposed in the exposed area, and after washing with pure water, the water was removed by air blow and drying was performed in a 100 ° C. oven. Next, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked on a hot plate at 110 ° C. for 5 minutes. Through a mask (for diagonal: FIG. 42) for forming a G dye layer pattern, i-line exposure was performed at 100 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then development of an organic alkaline aqueous solution at room temperature was performed. Liquid (2.38% TMAH
Aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. was spin-developed for 3 minutes 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, and constant potential electrolysis was carried out at 0.5 V for 10 minutes to perform the above exposure. A G dye layer was formed on the transparent conductive thin film exposed in the area, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. Further, a photosolubilizing resist HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked for 5 minutes on a 110 ° C. hot plate. Through a mask (for diagonal: FIG. 43) for forming a B dye layer pattern, a proximity type exposure device (proximity gap 60 μm) is used for 10
After i-line exposure at 0 mJ / cm ² , spin development was performed for 4 minutes with a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) of an organic alkaline aqueous solution at room temperature, 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,
Constant-potential electrolysis at 0.5 V for 15 minutes is performed to form a dye layer of B on the transparent conductive thin film exposed in the exposed area, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. did. Next, 600 mJ / cm over the entire surface of the substrate
^After the i-line exposure of ² , the substrate was immersed in a room temperature organic alkaline stripping solution (N-303: Nagase & Co., Ltd.) for 3 minutes,
The residual photosolubilizing resist was completely removed by washing with pure water to form RGB dye layers. Next, a transparent thermosetting resin agent JSS715 as a protective film is formed on this substrate.
(Manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated at 900 rpm, and completely heat-cured in an oven at 220 ° C. Finally, a sputtering device (made 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 (electrode) for driving a liquid crystal. At this time, the substrate temperature is 200 ° C,
The surface resistance of the ITO film was adjusted to 20Ω / □. The color filter was manufactured as described above (Step 10, FIG.
3)

Example 8 The substrate prepared in Preparation Example 4 was inserted into the R micelle dispersion prepared in Preparation Example 1, and the transparent conductive thin film and the anode of the potentiostat were connected to each other to 0.4 V. 18 minutes of constant potential electrolysis was performed to form an R dye layer on the transparent conductive thin film, and after washing with pure water, the water was removed by air blow, and 1
Dried in a 00 ° C oven. As a transparent photocurable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the R dye film at 1500 rpm,
It was prebaked on a hot plate at 80 ° C. for 5 minutes. next,
Mask for R dye layer pattern formation (for diagonal:
(Fig. 44) through a proximity type exposure device (proximity gap 60 μm) of 100 mJ /
After i-line exposure at cm ² , a room temperature organic alkaline aqueous solution (0.5% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is sprayed for 1 minute, and scrubbed with an acrylic bristle brush. This was performed and further washed with pure water to etch the unexposed portion of the R dye layer and the photocurable resist. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the R dye layer was arranged. 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 0.5 V for 5 minutes of potentiostatic electrolysis was performed. A dye layer of B was formed on the transparent conductive thin film other than the above, washed with pure water, drained by air blow, and dried in an oven at 100 ° C. As a transparent photocurable resist, CT (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the R dye layer and the B dye layer at 1000 rpm, and prebaked for 5 minutes on a hot plate at 80 ° C. Next, through a mask (for diagonal: FIG. 35) for forming a B dye layer pattern, i-line exposure was performed at 100 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then an organic alkali system at room temperature was used. Aqueous developer (0.5%
TMAH aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the B dye layer in the unexposed area and a photocurable resist Was etched. Finally, the substrate was inserted into an oven at 200 ° C., the photocurable resist in the exposed portion was completely thermoset, and the B dye layer was arranged. Next, a photosolubilizing type resist HPR204
(Manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the entire surface of the substrate at 1500 rpm, and prebaked for 5 minutes on a hot plate at 110 ° C. I-line exposure at 100 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm) through a mask for forming a G dye layer pattern (for diagonal: FIG. 45), followed by development of an organic alkaline aqueous solution at room temperature Liquid (0.5% T
MAH aqueous solution: spin-developed for 2 minutes with Fuji Hunt Electronics Technology FHD-5) 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, and a constant potential electrolysis was carried out at 0.7 V for 10 minutes to perform the above exposure. A G dye layer 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. Next, the substrate was 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. , RGB dye layers were formed. Next, a transparent thermosetting resin agent Optomer SS7265 (manufactured by Japan Synthetic Rubber Co., Ltd.) was spin-coated on this substrate as a protective film at 900 rpm, and was completely thermoset in an oven at 220 ° C. 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 for driving a liquid crystal. At this time, the substrate temperature is 200 ° C. and the surface resistance of the ITO film is 20
Adjusted to Ω / □. The color filter was manufactured as described above (process 11, FIG. 15).

Production Example 5 Production of Metal Oxide (Cr ₂ O ₃ ) Thin Film Black Matrix Forming Substrate on Transparent Conductive Thin Film On the transparent electroconductive thin film (ITO) film-forming substrate produced in Production Example 1, metal oxide was further formed. Sputtering apparatus for (Cr ₂ O ₃ ) thin film (manufactured by ULVAC, Inc .: SDP-550V
T) was used to deposit a Cr ₂ O ₃ thin film of about 1200 Å.
At this time, the substrate temperature was adjusted to 250 ° C. Then, on the Cr ₂ 0 ₃ thin film was deposited, light-solubilizing type resist (HPR2
04: Made by Fuji Hunt Electronics Technology Co., Ltd.)
Was coated with a spin coater at 750 rpm, pre-baked on a hot plate at 80 ° C. for 5 minutes, and passed through a mask for forming a black matrix corresponding to the stripe and diagonal dye layer patterns (FIG. 33), a proximity method (proximity gap 60 μm). ) Was used for exposure at 100 mJ / cm ² . Next, a room temperature organic alkaline aqueous solution developer (2.38% TMAH aqueous solution: FH manufactured by Fuji Hunt Electronics Technology Co., Ltd.)
D-5) was spin-developed for 2 minutes, washed with pure water by shower, and dried by 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, 165 g of ceric ammonium nitrate, 42 ml of perchloric acid and 1 liter of C with pure water.
After the r etchant was prepared, the substrate on which the resist pattern was formed was immersed at room temperature for 2 minutes, washed with a pure water shower to etch the Cr thin film in the portion without the resist pattern, and then the resist stripper at room temperature (N303: Nagase & Co., Ltd. (Made by the company)
It was immersed for 3 minutes in water, rinsed with a pure water shower, and dried by air blow to form a black matrix of a metal oxide thin film (Cr ₂ O ₃ ).

Example 9 A color filter was manufactured in the same manner as in Example 7 using the substrate manufactured in Manufacturing Example 5 (step 12, FIG. 17).

Example 10 Using the substrate produced in Production Example 5, a color filter was produced by the same method as in Example 8 (step 13, FIG. 19).

Example 11 A color filter was manufactured by the same method as in Example 8 except that UV cleaning was performed for 60 seconds before spin coating the transparent photocurable resist (Step 11, FIG. 1).
5).

Example 12 Instead of spin-coating the transparent photocurable resist in Example 8, the dye layers of R and B were added to the micelle dispersion of the photocurable resist prepared in Production Example 1 by the micelle electrolysis method. Insert the substrate formed in step 2, connect the transparent conductive thin film and the anode of the potentiostat, and set RB to 0.5.
A potentiostatic electrolysis was performed at V for 10 minutes to laminate a photocurable resist film on each RB dye layer. Then, after washing with pure water, the water was removed with an air blow and dried in a 100 oven. A color filter was manufactured by the same method as in Example 8 except for the above (Step 11, FIG. 15).

Example 13 Instead of spin-coating a transparent photocurable resist in Example 8, a transparent photocurable electrodeposition polymer (Japanese Patent Laid-Open No. Hei.
No. 104102), a substrate on which the dye layers of R and B are formed by the micelle electrolysis method is inserted into this 10% transparent photocurable electrodeposition polymer electrodeposition liquid, and the transparent conductive thin film and the potion are formed. The anode of the stat was connected, and constant potential electrodeposition was performed at 100 V for 1 minute for each RB, and a film of the photocurable electrodeposition polymer was laminated on each RB dye layer. Then, after washing with pure water, the water was removed with an air blow and dried in a 100 oven. A color filter was manufactured by the same method as in Example 8 except for the above (Step 11, FIG. 15).

Example 14 After the RGB dye layers were formed in Example 7, the protective film was inserted into the micelle dispersion of the photocurable resist prepared in Production Example 1 instead of the thermosetting resin to give a transparent conductive film. Connect the thin film and the anode of the potentiostat to 0.5V to 1
A potentiostatic electrolysis was performed for 0 minutes to laminate a photocurable resist film on each of the RGB dye layers. Then, after washing with pure water, drain the water with an air blow and dry in a 220 oven,
Heat cured. A color filter was manufactured by the same method as in Example 7 except for the above (Step 10, FIG. 21).

Example 15 On the substrate on which the ITO film formed in Production Example 1 was formed,
Optomer SS7265 (manufactured by Japan Synthetic Rubber Co., Ltd.) as a transparent thermosetting resin except for the electrode extraction portion, and RG
Other than the portion where the dye layer of B is to be formed (FIG. 46),
By offset printing with a film thickness of 1.5 μm, 2
Heat cured in an oven at 20 ° C. Then, using this substrate, a color filter was manufactured by the same method as in Example 1 (step 4, FIG. 23).

Comparative Example 1 ITO Thin Film Patterning (Formation of Dye Layer Forming Electrode) As a ITO film, a glass substrate having a sheet resistance of 20 Ω / □ (blue plate glass, polished, silica dip product: manufactured by Geomatec) was used as a photosolubilizing resist. (FH2030M: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 1,000 rpm. After spin coating, prebaking was performed at 80 ° C. for 15 minutes. After that, this substrate is set in the exposure device. As the mask, stripe ITO patterning (FIG. 48) was used. Proximity gap 70 μm
After exposure to i-rays at 80 mJ / cm ² , it was developed with an inorganic alkaline developer (LSI developer: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at 25 ° C. After development, the substrate was rinsed with pure water and then post-baked at 180 ° C. Then, as an etchant, 1M FeCl ₃ 6N HCl 0.1NH
An aqueous solution of NO ₃ 0.1N Ce (NO ₃ ) ₄ is prepared, and the IT of the substrate is prepared.
Etch O. The end point of etching was measured by electric resistance. The etching required about 10 minutes. 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 Formation and Electrode Extraction Layer Formation As a black matrix formation resist, the color mosaic CK of Fuji Hunt Electronics Technology Co. was mixed with 3: 1: 1: 1 parts by weight of CR, CG and CB, respectively. 4-13106) was used.
The above resist was coated on the ITO patterned glass substrate prepared above with a spin coater at 500 rpm, and
Prebaked for 15 minutes in 0 ° C oven. Then, a polyvinyl alcohol (PVA) aqueous solution (C
P: Fuji Hunt Electronics Technology Co., Ltd.) was applied in the same manner as the resist. Then, while aligning with an aligner using an aligner having an alignment function, a proximity gap of 80 μm was set using a black matrix corresponding to the stripe dye layer pattern and a mask (FIG. 49) designed to form an electrode extraction layer. After the i-line exposure, it was developed with an inorganic alkaline developer (0.1N sodium carbonate aqueous solution: CD manufactured by Fuji Hunt Electronics Technology Co., Ltd.). In addition, rinse with pure water and
Post-baked in an oven at 20 ° C.

Formation of Dye Layer The ITO patterned substrate with the black matrix (FIG. 50), which is made conductive for each color by silver paste, is inserted into the R micelle solution described in Production Example 1 to make the R row of the stripes conductive. The silver paste and the potentiostat anode were connected. A constant potential electrolysis was performed at 0.8 V for 15 minutes to obtain an R dye layer. Then, it was washed with pure water and prebaked in an oven (100 ° C. × 15 minutes). Next, this substrate was inserted into the G micelle solution, the conductive silver paste was connected to the stripe G row and the anode of the potentiostat was connected, and constant voltage electrolysis was performed for 0.4 V for 18 minutes to obtain the color filter RG. Obtain a thin film of the dye layer. After film formation, post-treatment was performed under the same conditions as the film formation of R. Finally, this board is B
Insert the above micelle solution, connect the silver paste and the potentiostat anode to the stripe B row,
Constant-voltage electrolysis was performed at 0.7 V for 10 minutes to obtain a color filter RGB dye layer. After film formation, post-treatment was performed under the same conditions as the film formation of R.

Formation of Protective Film OS-808 (manufactured by Nagase & Co., Ltd.) was spin-coated on the dye thin film substrate as a protective film at 800 rpm, and then 2
It was baked at 40 ° C. for 1 hour and cured. Thus, the protective film was formed.

Substrate Cutting and Chamfering The substrate on which the protective film was formed was cut with a scriber at an accuracy of ± 0.3 mm or less along line A in FIG. 61, and the cut surface was chamfered and polished by a chamfering machine.

Formation of Transparent Electrode for Driving Liquid Crystal Finally, a sputtering device (made by ULVAC, Inc .: SDP
-550 VT) using an ITO thin film of about 1200 ⌒,
A transparent conductive thin film (electrode) for driving a liquid crystal was formed on the protective film by sputtering. At this time, the substrate temperature is set to 200
The surface resistance of the ITO film was adjusted to 20 Ω / □ at ℃ and the color filter was completed (step 1, FIG. 60).

Comparative Example 2 Metal thin film (Cr) black matrix formation On a non-alkali glass substrate (NA45: HOYA), Cr was applied.
About 1300 ⌒ sputtered thin film (ULVAC: SDP-5
50 VT). On top of this, a photosolubilizing resist agent (HPR20
4: Fuji Hunt Electronics Technology Co., Ltd.)
It was spin coated at 000 rpm. Then 5 at 100 ° C
Prebaked on a hot plate for minutes. Then, this substrate was set in a mirror projection type exposure machine, and 80 mJ was passed through a black matrix pattern mask (FIG. 47) corresponding to the diagonal dye layer pattern.
/ Cm < ² > i-line exposure, and immersion development was carried out with a developer (2.38% TMAH aqueous solution, FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) of an inorganic alkali aqueous solution. Next, after shower rinsing with pure water, post-baking was performed at 150 ° C. Then, as an etchant, Cr was immersion-etched for 3 minutes with a mixed aqueous solution of cerium ammonium nitrate and perchloric acid at room temperature. After etching, the substrate was rinsed with pure water, and the resist was stripped with an organic alkaline aqueous solution stripping agent (N-303: manufactured by Nagase & Co., Ltd.). It was thoroughly washed with pure water to obtain a black matrix (BM).

Formation of Insulating Film and ITO Thin Film Pattern (Formation of Dye Layer Forming Electrode) Next, a silica dispersion (OCD) was formed as an insulating film on the BM.
TYPE-7; manufactured by Tokyo Ohka Co., Ltd.) is spin coated at 1,000 rpm, baked at 250 ° C. for 60 minutes, and then the substrate is set on SDP-550VT manufactured by ULVAC, Inc., and ITO is sputtered on the substrate for about 1300 ⌒. did.
At this time, the work is set to 200 ° C. and the surface resistance of ITO is set to 2
It was adjusted to 0Ω / □. Then, a photosolubilizing resist (FH2030M: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on this substrate at 1,000 rpm,
Prebaking was performed for 15 minutes in an oven. Then, after alignment exposure (exposure energy 60 mJ / cm ² (i-line)) through a diagonal pattern mask (FIG. 51) with a contact exposure machine, a developer of an inorganic alkaline aqueous solution (LSI developer: Fuji Spin development was performed by Hunt Electronics Technology. After development,
After rinsing with a pure water shower, post-baking was performed at 150 ° C. Next, the ITO on the substrate was etched for 3 minutes by using a ferric chloride aqueous solution (Boume 42) at 37 ° C. as an etchant and an equal volume mixture of hydrochloric acid. The end point of etching was measured by electric resistance. After etching, the substrate was rinsed with pure water, and the resist was peeled off with an organic alkaline aqueous solution (N-303: manufactured by Nagase & Co., Ltd.). Further wash with pure water and
It was confirmed that there was no electrical leakage between adjacent TO electrodes, and a substrate with an ITO patterning BM was completed.

Formation of Electrode Extraction Layer Using an acrylic acid type resist (CT: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) as an electrode extraction layer, the above substrate was spin-coated at 850 rpm and prebaked in an oven at 100 ° C. for 45 minutes. Then, while aligning with a proximity exposure device (proximity gap 60 μm), exposure was performed (exposure energy 40 m
J / cm ² (i line)). Then, immersion development was performed for 1 minute with a developer of an inorganic alkaline aqueous solution (0.1N sodium carbonate aqueous solution: CD manufactured by Fuji Hunt Electronics Technology Co., Ltd.). Furthermore, the substrate was rinsed with pure water and post-baked in a 200 ° C. oven for 60 minutes to complete a color filter substrate.

Formation of Dye Layers R, G, and B dye layers were obtained by the same steps as in Comparative Example 1 except that the electrodes were extracted with a silver paste as shown in FIG.

Formation of Protective Film Next, a thermosetting resin agent (Optomer SS7265: manufactured by Japan Synthetic Rubber (JSR)) as a protective film agent was spun at 900 rpm on the substrate on which the dye layer formed previously was formed. It was coated and further post-baked in a 220 ° C. oven for 60 minutes.

Substrate cutting and chamfering The same steps as in Comparative Example 1 were carried out except that the cutting was carried out along the line A in FIGS.

Formation of transparent electrode for driving liquid crystal Finally, a sputtering device (made by ULVAC, Inc .: SDP
-550 VT) using an ITO thin film of about 1200 ⌒,
A transparent conductive thin film (electrode) for driving a liquid crystal was formed on the protective film by sputtering. At this time, the substrate temperature is set to 200
The surface resistance of the ITO film was adjusted to 20 Ω / □ at ℃ and the color filter was completed (step 2, FIG. 62).

Comparative Example 3 ITO thin film patterning (formation of dye layer forming electrode) ITO film / glass substrate (alkali-free glass; ITO: 2)
A photo-solubilizing resist (HPR204: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on 0Ω / □ at 1,000 rpm. After spin coating, 1 in 80 ° C oven
Prebaking was performed for 5 minutes. Then, this substrate was exposed at 80 mJ / cm ² through a diagonal dye layer pattern mask (FIG. 51) with a contact exposure machine, and then a developer of an organic alkali aqueous solution (2.38% TMAH aqueous solution: Fuji Hunt Electronics Technology Co., Ltd.) was used. Immersion development. After development, rinse with pure water, then 15
Post-baked at 0 ° C. Next, 3 as an etchant
The ITO of the substrate was etched for 3 minutes with an equal mixture of a ferric chloride aqueous solution (Boume 42) and hydrochloric acid at 7 ° C. The end point of etching was measured by electric resistance. Then, the resist is rinsed with pure water to remove the resist from an organic alkaline aqueous solution (N-3
03: manufactured by Nagase & Co., Ltd.). Further, the substrate was washed with pure water, and it was confirmed that there was no electrical leakage between adjacent ITO electrodes, and an ITO patterned substrate was completed.

Formation of Electrode Extraction Layer The same steps as in Comparative Example 2 were carried out to form an electrode extraction layer.

Formation of Dye Layers The same steps as in Comparative Example 2 were carried out to form RGB dye layers.

Formation of Protective Film The same process as in Comparative Example 2 was performed to form a protective film.

Substrate Cutting and Chamfering The same steps as in Comparative Example 1 were carried out except that the cutting was carried out at the line A in FIGS.

Formation of transparent electrode for driving liquid crystal Finally, a sputtering device (manufactured by ULVAC, Inc .: SDP
-550 VT) using an ITO thin film of about 1200 ⌒,
A transparent conductive thin film (electrode) for driving a liquid crystal was formed on the protective film by sputtering. 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 substrate by about 1500 Å (SDP-550VT type manufactured by ULVAC, Inc.). Next, a photosolubilizing resist agent (FH2130: manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 1,500 rpm. After spin coating, prebaking was performed in a 90 ° C. oven for 15 minutes. After that, this substrate is set in a proximity type exposure device (proximity gap 80 μm), and a base IT is formed through a black matrix pattern mask (FIG. 47) corresponding to a diagonal dye layer.
I-line exposure was performed at 60 mJ / cm ² in alignment with the O pattern. Then, the substrate was immersed in a developer of an inorganic alkaline aqueous solution (LSI developer: manufactured by Fuji Hunt Electronics Technology Co., Ltd.), rinsed with pure water, and post-baked at 150 ° C. Next, Cr was etched for 3 minutes with a mixed aqueous solution of cerium ammonium nitrate and perchloric acid as an etchant. The end point of etching was measured by electric resistance. Then, it was rinsed with pure water, and the resist was stripped and removed with a stripper (N-303: Nagase & Co., Ltd.) of an organic alkali aqueous solution. It was thoroughly washed with pure water to obtain a black matrix (BM), and a color filter was completed. (Step 3, FIG. 64)

Comparative Example 4 (Dispersion Method Color Filter) Black Matrix Formation The same steps as in Comparative Example 2 were carried out except that a black matrix pattern mask (FIG. 37) corresponding to the triangle dye layer pattern was used.

Dye layer formation Red (R) is formed on the substrate on which the black matrix is formed.
Dye-containing resist CR-2000 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated at 500 rpm, prebaked in an oven at 85 ° C. for 15 minutes, and then an oxygen barrier film (CP: manufactured by the same company) was laminated and coated in the same manner as the above resist. This substrate was set in a contact exposure machine, aligned with the black matrix, and aligned with the black matrix through a mask of R dye layer pattern (for forming triangle dye layer pattern: FIG. 30) to 30 mJ / cm.
² is exposed to i-line, and is developed with a developing solution of an inorganic alkali aqueous solution (0.
Spray development was performed with a 1N sodium carbonate aqueous solution: CD: manufactured by the same company, and rinsed with a pure water shower. Then, it was post-baked in a 200 ° C. oven for 60 minutes to form an R dye layer. Similarly, a mask for forming a dye layer (triangle dye) is coated with a resist containing a green (G) dye (CG-2000: manufactured by the same company) and a resist containing a blue (B) dye (CB-2000: manufactured by the same company). For layer pattern formation: Alignment i-line exposure, development, rinsing, and post-baking are repeated for RGB3 in FIGS.
A color dye layer was formed.

Protective Film Formation / Transparent Electrode Formation for Liquid Crystal Driving The same steps as in Comparative Example 2 were performed to complete a color filter (step 14, FIG. 66).

Comparative Example 5 (Resist electrodeposition method color filter) N, N-diethylaminoethyl methacrylate, styrene, ethyl acrylate, a compound obtained by an equimolar reaction of p-hydroxybenzoic acid and glycidyl acrylate in a molar ratio of 3: A cationic photosensitive resin composition composed of 800 g of an organic polymer binder copolymerized with 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 used as ethylene. The solid content was diluted to 20% with glycol monobutyl ether, neutralized with 0.5 equivalent of acetic acid, and the solid content was adjusted to 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. HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) as a photosolubilizing resist was spin-coated at 1500 rpm on a transparent conductive thin film (ITO) film-forming substrate on a chromium thin film black matrix produced in Production Example 2.
It was prebaked on a hot plate at 110 ° C. for 5 minutes. Mask for R dye layer pattern formation (for diagonal: FIG. 4)
I) at 80 mJ / cm ² with a proximity type exposure machine (proximity gap 60 μm) through 1)
After the line exposure, a developing solution (2.
38% TMAH aqueous solution: FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd. was immersion developed for 1 minute 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. Then, constant potential electrodeposition was carried out for 5 V for 30 seconds to form an R dye layer on the transparent conductive thin film exposed in the exposed area, and after washing with pure water, the water was removed with an air knife and the oven was heated at 100 ° C. Dried. Then G
80 mJ of the above substrate through a proximity type exposure device (proximity gap 60 μm) through a mask (for diagonal: FIG. 42) for forming a dye layer pattern.
/ Cm ² After exposure, it was immersed for 1 minute in a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) of an organic alkaline aqueous solution at room temperature, and washed with pure water. Then, this substrate was inserted into the G-colored cationic electrodeposition solution prepared above, and the transparent conductive thin film and the negative electrode potentiostat were connected to perform constant potential electrodeposition at 5 V for 45 seconds, followed by the above exposure. A G dye layer was formed on the transparent conductive thin film exposed in the area, washed with pure water, drained with an air knife, and dried in an oven at 100 ° C.
Further, the substrate on which the RG dye layer was formed was passed through a mask (for diagonal: FIG. 43) for forming the B dye layer pattern, and the i-line was irradiated at 80 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm). After exposure,
Room-temperature organic alkaline aqueous solution (2.38% TM
AH aqueous solution: immersion development was performed for 1 minute with FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd., and washed with pure water. Then, this substrate was inserted into the B-color cation electrodeposition solution prepared above, the transparent conductive thin film and the negative electrode potentiostat were connected, and constant potential electrodeposition at 5 V for 30 seconds was performed.
A dye layer (thin film) of B was formed on the transparent conductive thin film exposed in the exposed portion, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. Next, after exposing the entire surface of the substrate to 600 mJ / cm ² by i-line, the substrate on which the RGB dye layers are formed is subjected to an organic alkaline stripping solution (N
-303: manufactured by Nagase & Co., Ltd.) for 10 minutes and washed with pure water to completely remove the remaining photosolubilizing resist. Next, a transparent thermosetting resin agent (Optomer SS7265: manufactured by Japan Synthetic Rubber Co., Ltd. (JSR)) was spin-coated on this substrate as a protective film at 700 rpm, and 22
It was heat-treated (post-baked) for 60 minutes in an oven at 0 ° C. to be heat-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,
Substrate temperature is 200 ° C, surface resistance of ITO film is 20Ω / □
Adjusted to. The color filter was manufactured as described above (step 15, FIG. 68).

Comparative Example 6 HPR204 (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) as a photosolubilizing resist was spin-coated at 750 rpm on the substrate prepared in Preparation Example 1 to obtain 110.
It was prebaked for 5 minutes on a hot plate at ℃. After the G-dye layer pattern forming mask (for stripe: (FIG. 27), i-line exposure was performed at 80 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), an organic alkaline aqueous solution at room temperature was used. Developer (2.38%
TMAH aqueous solution: spin-developed for 1 minute with FHD-5) manufactured by Fuji Hunt Electronics Technology Co., Ltd., 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, and constant potential electrolysis was performed at 0.4 V for 18 minutes, and the above exposure was performed. A G dye layer 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. next,
After the mask for B dye layer pattern formation (for stripe: (FIG. 55), i-line exposure was performed at 80 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), an organic alkaline aqueous solution at room temperature was used. A developing solution (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-developed for 2 minutes and washed with pure water, and then this substrate was added to the micelle dispersion of B prepared in Production Example 1. Insert and connect the transparent conductive thin film and the anode of potentiostat, 0.7V, 1
Constant-potential electrolysis was performed for 0 minutes to form a dye layer of B on the transparent conductive thin film exposed in the exposed area, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. Further, the mask for forming the R dye layer pattern (for stripe: (FIG. 54) is used, and the exposure is carried out by a proximity type exposure device (proximity gap 60 μm).
After exposure with mJ / cm ² , the film was spin-developed for 3 minutes with a developer (2.38% TMAH aqueous solution: FHD-5 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) at room temperature for 3 minutes, and washed with pure water. Next, this substrate is manufactured as Example 1.
The transparent conductive thin film and the anode of the potentiostat were connected to each other by inserting into the micelle dispersion liquid of R prepared in
A constant-potential electrolysis was performed for 15 minutes at V to form a dye layer of R on the transparent conductive thin film exposed in the exposed portion, washed with pure water, drained by air blow, and dried in a 100 ° C. oven. Next, the substrate on which the GBR dye layer is formed is immersed in an organic alkaline stripping solution (N-303: manufactured by Nagase & Co., Ltd.) at room temperature for 5 minutes, washed with pure water, and remaining photosolubilized. The mold resist was completely removed. Next, a transparent thermosetting resin agent LC2001 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) was spin-coated on this substrate as a protective film at 900 rpm, and 2
It was completely thermoset in an oven at 20 ° C. Finally, a sputtering device (made by ULVAC: SDP-550V
Using T), an ITO thin film was sputtered on the protective film at a thickness of about 1200 to form a transparent conductive thin film (electrode) for driving a liquid crystal. At this time, the substrate temperature is 200 ° C., IT
The surface resistance of the O film was adjusted to 20Ω / □. The color filter was manufactured as described above. (Step 16, FIG. 7
0)

Reference Example 1 (Japanese Patent Application No. 4-265422) In Example 1, the substrate on which the RB dye layer was formed was inserted into the micelle dispersion of G prepared in Production Example 1 to form a transparent conductive thin film. Connect the anode of the potentiostat,
Constant-potential electrolysis was performed at 0.7 V for 10 minutes to form a G dye layer on the transparent conductive thin film, which was washed with pure water, drained by air blow, and dried in an oven at 100 ° C. 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 G
Mask for forming the dye layer pattern (for stripe: (Fig. 5
6) through i-line exposure at 300 mJ / cm ² with a proximity type exposure device (proximity gap 60 μm), and then a developing solution (0
． 5% TMAH aqueous solution: FHD-5 made by Fuji Hunt Electronics Technology Co., Ltd. is sprayed for 1 minute, scrubbed with an acrylic bristle brush, further washed with pure water, and the G dye layer in the unexposed area and photocuring The positive resist was etched. Finally, the substrate is inserted into an oven at 200 ° C., and the photo-curable resist in the exposed area is completely heat-cured.
The dye layer was placed. Hereinafter, a color filter was manufactured in the same manner as in Example 1 (FIG. 57).

The evaluation results of production yield, color unevenness, definition, heat resistance and light resistance in the above color filter manufacturing process (excluding Comparative Example 6) are shown (Tables 1 and 2). A comparison of the spectral characteristics of the color filters manufactured in Example 1 and Comparative Example 6 is shown in FIG. Production yield: Indicates the ratio (%) of the number of non-defective color filters to 20 insulating substrates (glass substrates). As a condition for a non-defective product, a white defect and a black defect having a diameter of 30 μm or less were determined by visual inspection. 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. In addition, the protrusions on the color filter surface were measured with a surface roughness meter, and those having a protrusion height of 4 μm or more were determined to be good. Color unevenness: The chromaticity of 9 pixels on the substrate was measured for each RGB, and the one with the largest color difference was evaluated as ΔE. ΔE is JIS Z87
24, Z8723. Definition: Shows the dimensional accuracy (μm) of the dye layer pattern with respect to the design mask pattern (50 μm □). Heat resistance: Change in color purity (G dye layer pattern) (%) by heat treatment at 260 ° C. for 1 hour (oxygen atmosphere)
(Difference between color purity before heat treatment and color purity after heat treatment) is shown.
Light resistance: 10 million lux of metal halide lamp
The change (%) in the color purity (for the G dye layer) by irradiation for 00 hours (difference between the color purity before irradiation and the color purity after irradiation) is shown. The color purity is calculated by taking chromaticity coordinates for each color, connecting the C light source and its chromaticity coordinates with a straight line, and assuming that the intersection of the extrapolated line and the outer peripheral portion is 100% in color purity. Shows the ratio (%) of the distance from the C light source.

[0128]

[Table 1]

[Table 2] ────────────────────────────────── Dye layer pattern Production yield Color unevenness Fine Degree Heat resistance Light resistance ────────────────────────────────── Comparative Example 1 Strife 60 <5 ± 2.0 0 0 Process 1 Comparative Example 2 Diagonal 25 <5 ± 2.0 0 0 Process 2 Comparative Example 3 Diagonal 20 <5 ± 2.0 0 0 Process 3 Comparative Example 4 Triangle 60 <5 ± 3.0 10 60 Process 14 Comparative Example 5 Diagonal 60 <3 ± 2.0 10 70 steps 15 ──────────────────────────────────

From Table 1 and Table 2, the color filter manufacturing method of the present invention makes it possible to produce a color filter with good yield even with respect to various dye layer patterns, and reduce color unevenness. It was found that the definition was also good. Furthermore, it was confirmed that the dye layer (pattern) obtained in the present invention is excellent not only in heat resistance but also in light resistance in particular. In addition, it was confirmed from the comparison of the difference between the dye layers of RGB (difference between the maximum value and the minimum value of the thickness of the dye layer) in Table 3 that the flatness between the dye layers was improved by stacking the protective film.

[Table 3] ─────────────────────── Protective film Dye layer step (μm) ───────────── ─────────── Example 2 Yes <0.2 Example 3 No <0.5 ───────────────────────

Further, as can be seen from the comparison diagram (FIG. 72) of the spectral characteristics of the color filters manufactured in Example 1 and Comparative Example 6, in Comparative Example 6, it is clear that the spectral characteristics of the color filters were lowered. . Since the dye layer formed by the micelle electrolysis method is not electrically insulated, when the dye layers of a plurality of colors are formed without insulation as in Comparative Example 6, the dye layer formed earlier is a dye formed later. It was found to be contaminated with layers. Therefore, at least the dye layer formed first must be electrically insulated. Therefore, as in Example 1, a photocurable resist was laminated on the dye layer formed by the micelle electrolysis method to insulate (form a dye layer pattern), and the dye layer formed earlier was formed on the dye layer formed later. It was found that it is necessary to devise a method to prevent the layers from being stacked and contaminated. Further, Table 4 compares Example 1 with Reference Example 1.
In Example 1, after exposing the transparent photocurable resist applied on the dye layer formed by the micelle electrolysis method through a mask corresponding to a desired color, the photocurable resist and the dye in the unexposed portion were exposed. The step of forming a dye layer (pattern) by etching the layer and the dye layer in the micelle electrolysis method on the transparent conductive thin film in the voids of the photosolubilizing resist pattern formed by exposing and developing the photosolubilizing resist A color filter is manufactured by repeating the steps of forming a dye layer of a plurality of colors in combination, and in Reference Example 1, a transparent photocurable resist coated on the dye layer formed by the micelle electrolysis method is formed into a desired color. After exposure through the corresponding mask, the steps of forming the dye layer (pattern) by etching the photocurable resist and the dye layer in the unexposed portion are repeated for the dye layers of multiple colors. To produce a color filter return. From the results in Table 4, when a dye that is difficult to etch as in Reference Example 1 (for example, G dye layer) is selected, a photosolubilizing resist is exposed and developed as in Example 1. It has been found that a color filter can be manufactured with good yield by selecting a step of forming a dye layer on the transparent conductive thin film in the voids of the photosolubilizing resist pattern by the micelle electrolysis method.

[0133]

[0134]

According to the method of manufacturing a color filter of the present invention, it is not necessary to pattern the transparent conductive thin film <1> by microfabrication, and even if microfabrication is performed, it is relatively easy. (Example: stripe) pattern can be used, so that reduction in yield due to short circuit and disconnection can be avoided. Further, in the present invention, the present invention can be easily applied to the conventional technique in which it is difficult to arrange a diagonal pattern and a triangle pattern in the dye layer (pattern of the dye layer) of the <2> color filter. Also, <
3> 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 spots of the color filter due to the voltage drop.
<4> In the present invention, the transparent photo-curable resist applied on the dye film formed by the micelle electrolysis method is exposed through a mask corresponding to a desired color, and then the photo-curing of the unexposed portion is performed. Of a photo-soluble resist and a dye layer to form a dye layer (pattern), and a dye in a micelle electrolysis method in a void of the photo-solubilized resist formed by exposing and developing an almost transparent photo-solubilized resist. Due to the step of forming the layer, there is no reduction in exposure sensitivity and resolution of the resist due to light absorption of the dye of the photocurable resist containing a dye (pigment) such as a dispersion method color filter. As a result, it can be expected that the color filter of the present invention will be applied to a color liquid crystal display with higher definition. In addition to such effects, since the dye layer of the <5> original micelle electrolysis color filter has a particularly large pigment (dye) content, it is possible to take advantage of high light resistance and heat resistance. <6> According to this manufacturing method, there is no need to form an electrode extraction layer, and the color filter manufacturing process can be simplified. Further, in the <7> color filter manufacturing process, in the above-mentioned resist electrodeposition method, the dye layer once formed coexists with the electrodeposition polymer, so that it is electrically insulated,
Although it is possible to form the dye layers of the three primary colors as it is by applying the photosolubilizing resist once, the dye layer formed by the micelle electrolysis method is not electrically insulated. , The dye layers of at least two colors must be electrically insulated. Therefore, it is necessary to laminate a photo-curable resist or a photo-solubilizing resist on the dye layer formed by the micelle electrolysis method to insulate the dye layer so that the subsequent dye layer is not formed on the previously formed dye layer. is necessary. By this device, even in the micelle electrolysis method, it is possible to manufacture a color filter having a desired spectrum without contaminating the dye layer formed earlier with the dye layer formed later. <8> After exposing a transparent photocurable resist applied on a dye layer formed by the micelle electrolysis method through a mask corresponding to a desired color, the photocurable resist and the dye in the unexposed portion are exposed. Multiple steps of forming the dye layer (pattern) by etching the layer and forming the dye layer by the micelle electrolysis method in the voids of the photosolubilizing resist formed by exposing and developing the photosolubilizing resist It is possible to select an arbitrary dye by repeatedly combining the dye layers of (1) and (2) to manufacture a color filter. That is, in the etching of the dye layer, there are some that are difficult to etch depending on the dye, and in wet etching, it is difficult to etch the dye layer in which the agglomerated state of the dye is dense, and in dry etching the molecular structure of the dye becomes an etching gas. Since some resists have resistance, the dyes that can be selected are limited only by etching the dye layer as described above. Therefore, when a dye that is difficult to etch is selected, micelles are formed on the transparent conductive thin film in the voids of the photosolubilizing resist pattern formed by exposing and developing the photosolubilizing resist as in the present invention. If the step of forming the dye layer in the electrolytic method is selected, the color filter can be manufactured with higher yield. <9> In addition to such a color filter manufacturing method, ultraviolet (UV) cleaning is performed on the dye layer formed by the micelle electrolysis method. With this, foreign substances such as oil and fat mixed in the dye layer are decomposed by a slight amount of ozone due to a reaction between ultraviolet light and oxygen in the air, and the wettability of the photocurable resist and the protective film is improved, It is possible to reduce pinholes in the coating film of the photocurable 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 <10> dye layer is a micellar electrolysis method or a film formation method by an electrodeposition method, such as a micelle dispersion liquid and an electrodeposition liquid. However, in the same manner as above, foreign matter is reduced from the atmosphere around the coater and the sliding parts of the coater device, which are generally problematic in dry processes such as spin coaters and roll coaters. It is possible to further improve the manufacturing yield of the color filter. <11> A protective film is provided on a portion of the color filter obtained by such a method for producing a color filter except a portion where the pigment layers of a plurality of colors are formed, before the step of forming the pigment layers of a plurality of colors or each pigment. By forming it during the layer forming step, the film forming range of the dye layer in the micelle electrolysis method is narrowed, and the etching range of the dye layer may be small, so that the dye in the micelle dispersion can be saved. The film forming time and etching time can be shortened, and the efficiency of color filter manufacturing can be improved. Furthermore, since the amount of dye that is etched is small, the dye that has been etched onto the color filter is not mixed as foreign matter, and the yield can be increased. Further, since the protective film and / or the transparent conductive thin film for driving liquid crystal is laminated on the dye layer formed by the <12> micelle electrolysis method, the adhesion of the dye layer to the substrate can be further improved. Furthermore, <1
3> Reduce film thickness step between dye layers (improve flatness)
be able to.

[Brief description of drawings]

1 to 24 are a sectional view schematically showing a manufacturing process of a color filter of the present invention and a schematic plan view when a color filter is completed.

25 to 56 are plan views schematically showing a mask used for manufacturing a color filter.

57 to 58 are a cross-sectional view schematically showing the manufacturing process of the color filter in the reference example and a schematic plan view when the color filter is completed.

FIG. 59 is a cross-sectional view schematically showing a general color liquid crystal display.

60 to 71 are a schematic cross-sectional view of a conventional color filter manufacturing process and a schematic plan view of a completed color filter.

FIG. 72 is an explanatory diagram showing a comparison of spectral characteristics between the color filter of the invention (Example 1) and the conventional color filter (Comparative example 6).

[Explanation of symbols]

 101 ... Insulating substrate 102 ... Transparent conductive thin film 110 ... Black matrix 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 140 ... Light possible Soluble resist 150 ... Protective film 160 ... Transparent electrode for driving liquid crystal

Claims (11)

[Claims] 1. A method of manufacturing a color filter in which dye layers of a plurality of colors are separated and arranged on an insulating substrate by a micelle electrolysis method to form a predetermined dye pattern, wherein at least a plurality of colors on the insulating substrate are provided. The region where the dye layer is arranged, or, a transparent conductive thin film is laminated and formed in a region corresponding to a continuous pattern including a region where at least dye layers of a plurality of colors are arranged, and this transparent conductive thin film is laminated, On the formed insulating substrate, a plurality of dye layers are used, as each of the monochrome dye layers, any one of the following process group A (a1 and a2) or process group B (b1, b2 and b3), and A method for producing a color filter, characterized in that both of the following process group A (a1 and a2) and process group B (b1, b2 and b3) are used as an assembly of a plurality of color dye layers . Step group A a1) Step of forming a dye layer of one color selected from a plurality of colors on the whole or a part of the transparent conductive thin film by film formation by a micelle electrolysis method a2) On the dye layer of one color Is laminated with a transparent photo-curable resist, exposed using a mask corresponding to the dye layer of one color, and before and / or after the heat treatment of the exposed part,
Remove the photo-curable resist and dye layer in the unexposed area,
Step of arranging dye layer of one color Process group B b1) A photosolubilization type resist is laminated on the whole surface or a part of the transparent conductive thin film to correspond to the dye layer of one color selected from a plurality of colors. Exposing using a mask with a pattern,
Then, a step of removing the photosolubilizing resist in the developed and exposed portion b2) A transparent layer in which the dye layer of one color is exposed by removing the photosolubilizing resist by film formation by a micelle electrolysis method. Step of disposing on the conductive thin film b3) Step of removing all the photosolubilizing resist remaining on the transparent conductive thin film 2. A metal or metal oxide thin film patterned in the shape of a black matrix is laminated on the insulating substrate before the step of laminating and forming a transparent conductive thin film on a predetermined region of the insulating substrate. The method of manufacturing a color filter according to claim 1, wherein the color filter is formed. 3. The insulating film is further laminated and formed on the metal or metal oxide thin film formed by patterning and laminating on the insulating substrate in the shape of a black matrix. Of manufacturing color filter of. 4. A plurality of dye layers are formed on an insulating substrate on which the transparent conductive thin film is laminated and formed, and the following process group A (a1 and a2) or process group B (b1,
b2 and b3), and using both of the following step group A (a1 and a2) and step group B (b1, b2 and b3) as an assembly of the dye layers of a plurality of colors, The method for producing a color filter according to claim 1, wherein a photocurable resist containing a black dye is patterned into a shape of a black matrix and laminated and formed before, during or after the step of disposing. 5. At least after the step of laminating and forming a transparent conductive thin film in a predetermined region on the insulating substrate and before the step of separating and disposing the dye layers of a plurality of colors, A step of laminating and forming a metal or metal oxide thin film in a region where a pigment layer of a plurality of colors and a black matrix are arranged, and patterning and laminating a photocurable resist or a photosolubilizing resist into a black matrix shape. 2. The method of manufacturing a color filter according to claim 1, further comprising the step of forming a black matrix by forming a black matrix by etching the metal or metal oxide thin film having an exposed underlayer. 6. The method of manufacturing a color filter according to claim 5, wherein the step of separating and arranging the dye layers of the plurality of colors uses only the step group B (b1, b2 and b3). Method for manufacturing color filter. 7. A protective film is laminated and formed on a portion other than a portion where the pigment layers of the plurality of colors are separated and arranged, before or in the step of separating and placing the pigment layers of the plurality of colors. The method for manufacturing a color filter according to claim 1, wherein the color filter is manufactured. 8. A protective film and / or a liquid crystal driving electrode is laminated after the step of separating and arranging the dye layers of a plurality of colors.
It forms, The manufacturing method of the color filter of any one of Claims 1-7 characterized by the above-mentioned. 9. The dyes (pixels) of the plurality of colors are red,
9. The method for producing a color filter according to claim 1, which corresponds to three primary colors of blue and green, or three primary colors and black. 10. When separating and arranging the dye layers of a plurality of colors, the dye layer of one color is formed by a micellar electrolysis method, and then washed with ultraviolet light. 10. The method for manufacturing a color filter according to any one of 9 above. 11. The method for laminating and forming the photocurable resist and / or the protective film is based on a micelle electrolysis method or an electrodeposition method, according to any one of claims 1 to 10. A method of manufacturing a color filter according to the item.