JP2528306B2 - Color filter - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color filter. More specifically, the present invention relates to a color filter having excellent optical characteristics used for liquid crystal display devices, color separation devices and sensors.

2. Description of the Related Art A conventional method for producing a color filter by a dyeing method is a film of synthetic resin or gelatin having a transparent cationic group in the form of a thin film such as stripes or mosaics (called a pattern) on the surface of a substrate such as glass or silicon wafer. ,
The basic principle is to provide a film of a protein-based natural polymer such as casein or glue to form a film to be colored, and dye (color) this with a dye. The following three methods are known as specific manufacturing processes for color filters.

(1) After providing a film to be colored on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer. Next, a non-coloring protective coat film is provided on the entire surface, and a second film to be colored is provided thereon by the same operation as described above. Hereinafter, if necessary, colored layers are sequentially laminated.

(2) After a film to be colored is provided on the substrate surface, a pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and then a dye fixing and anti-staining treatment is performed with tannic acid or the like. Give. A second coating to be colored is provided by the same operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

(3) A film to be colored (coloring film) is provided on the surface of the substrate. After a positive resist layer is provided thereon, the colored film exposed in a pattern is dyed by exposing and developing through a mask, and then the positive resist layer is peeled off to form a colored portion. The operation after providing the positive resist layer is repeated, and the same colored film is dyed into a plurality of colors in a desired pattern.

The color filter manufactured by the above-described process generally has three primary colors, R (red), G (green), and B (primary).
It has a colored layer colored in (blue) or Y (yellow), M (magenta), C (cyan), and (M may be omitted) which are three primary colors of complementary colors. The most important characteristic required for a color filter is an optical characteristic, and the spectral characteristic of each colored layer largely determines the value of a final product.

Related to this, there is a high degree of resistance to the heat treatment encountered in the process of manufacturing a liquid crystal display device equipped with a color filter and to the light added during use as the final product, and the predetermined optical characteristics are impaired. There should not be. Of course, the dyes applied must also have good solubility and solubility in water and be stable for a long time in acidic dye baths. By the way, since protein-based natural polymer substances such as gelatin, casein, and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye. When a photo-curable synthetic resin substrate is used instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye like a protein-based natural polymer substance. Become so.

Problems to be Solved by the Invention In order to obtain a dye having desired optical properties and reliability (mainly excellent resistance to heat and light) and solubility in water, many water-soluble anionic dyes are used alone. Have been considered in or a combination of them. However, in the case of a complementary yellow dye, it is particularly difficult to select a dye satisfying the above-mentioned desired properties, and no satisfactory dye has been found at present. Also, with respect to the green color obtained by combining the yellow anionic dye with the cyan or green anionic dye, a desired green color cannot be obtained because the desired yellow dye has not been found.

Spectral characteristics required for the desired yellow dye are 400-450
The wavelength (λ _T = 50) that gives 50% transmittance of a colored film dyed so that the transmittance at nm is 1% or less is 520 ± 10n.
It is that the transmittance in the region of wavelength longer than 550 nm is as large as possible.The dye belonging to the color index Acid Orange 149 is conventionally used for such a purpose, but this dye is light fast. It has the disadvantage of poor performance. Further, there is Color Index Acid Yellow 161 as a dye satisfying both the optical characteristics and the light resistance, which has been conventionally used, but this dye has poor solubility in water and the aqueous solution is turbid, which is especially for dyeing. When the dyebath is made acidic, it becomes cloudy and the dye precipitates, the reproducibility of dyeing is poor, and the life of the dyebath is short.

Under these circumstances, there is a demand for development of a dye for a color filter, which has excellent optical properties, solubility in water, and heat resistance and light resistance of a dyed coating thereby.

Means for Solving the Problems As a result of diligent efforts to find a color filter having the above-mentioned optical characteristics and excellent reliability (light resistance, heat resistance), the present inventors have found that a specific metal-containing azo compound The present invention has been found to have excellent solubility in water, whereby a dyed (colored) color filter satisfies the above-mentioned optical characteristics and has excellent reliability. That is, the present invention provides a symmetric or asymmetric 2: 1 chromium complex salt dye of an azo compound represented by the following formula (1) in which at least one pattern is a free acid in a color filter in which a pattern-colored film is placed on a substrate. Color filter characterized by being colored with (In the formula (1), R ₁ is --H, --Cl, --SO ₃ H, --SO ₂ NH ₂ , --S
_{O 2 CH 3, -SO 2 C} 2 H 5, -SO 2 NHCH 3, -SO 2 NHC 2 H 5 or -NO
₂ , R ₇ is --CH ₃ or Respectively. Also representative of the _{R 2, R 3, R 4} , R 5 and -H R ₆ are each _{independently, -Cl, -CH 3, -C 2} H 5, -OCH 3 or -SO ₃ H. ) I will provide a.

The color filter of the present invention will be described in detail. The symmetrical or asymmetrical 2: 1 chromium complex salt dye of the azo compound represented by the formula (1) used in the color filter of the present invention is generally prepared as follows.

First, the azo compound of the formula (1) used for producing a symmetrical or asymmetrical chromium complex dye can be obtained, for example, by reacting a diazonium salt of aminocarboxylic acid with a pyrazole derivative by a conventional method.

A symmetric or asymmetrical 2: 1 chromium complex salt is prepared by first forming a 1: 1 chromium complex salt dye with one of the azo compounds of the formula (1) and a chromium compound, and further acting the same or different azo compound of the formula (1). The conversion of the azo compound of formula (1) into a 1: 1 chromium complex salt dye to obtain a dye is carried out, for example, by adding at least 1 molar equivalent of the azo compound of formula (1) in the presence of an acid medium in a closed or open container. Can be carried out by reacting the chromium donor with the medium at the boiling point of the medium or at a temperature higher than 100 ° C. In this case, a trivalent chromium salt such as chromium formate,
Chromium acetate, chromium fluoride, chromium chloride or chromium sulfate can be used as chromium donors. This 1: 1 chromium complex chloride can be optionally carried out in an aqueous medium in the presence of an organic solvent such as alcohol, butanol or formamide.

Next, the conversion of the 1: 1 chromium complex salt dye to the 2: 1 chromium complex salt is performed as follows. When a symmetrical 2: 1 chromium complex dye is desired, an azo compound of the formula (1) used to prepare the 1: 1 chromium complex dye and asymmetric 2: 1 chromium complex dye is 1 when desired. The azo compound of the formula (1) is different from the azo compound of the formula (1) used for producing the 1 chromium complex salt dye, and the reaction is carried out by acid-bonding in an aqueous solution or suspension. It can be carried out by heating in the presence of the agent. The reaction temperature is preferably 60 to 100 ° C. Examples of acid binders which can be used are alkali metal hydroxides or carbonates or acetates, such as sodium hydroxide, sodium carbonate or sodium acetate or the corresponding lithium, potassium or ammonium salts. The reaction is
Sometimes an organic solvent such as an alcohol or formamide may be added or a surfactant may be added to accelerate. The molar ratio of the azo compound of the formula (1) to the 1: 1 chromium complex salt dye is usually 1: 0.85 to 1: 1.2, preferably 1: 1.

Next, an example of the color filter of the present invention will be described with reference to the drawings. FIGS. 1 (a) to 1 (h) are conceptual diagrams showing a method for producing a color filter by a lamination method in which colored layers of different colors are laminated on a glass plate (base). In FIG. 1, 1 is a glass plate, 2 is a thin film of photo-curable resin or the like provided by spin coating, 2'is a film to be colored which is photo-cured from 2 through a mask, 2 "is a colored layer, 3 ' Is a non-staining protective film, 4 is a photomask, 5 is a second colored layer, and 6 is a non-staining protective film.

A glass plate 1 is spin-coated with a mixture of a protein-based natural polymer such as gelatin, casein, or glue and a dichromate such as ammonium dichromate, or a photocurable synthetic resin composition having a cationic group, and a roller. It is applied by a method such as coating to provide a photocurable thin film 2 having a thickness of 0.2 to 2 μ (FIG. 1 (b)).

Next, the thin film is irradiated with ultraviolet light through the photomask 4 having a predetermined pattern to cure the exposed portion. (FIG. 1 (c)).

Next, it is developed with water or the like to remove the unexposed portion to form a colored layer 2'having a predetermined pattern (Fig. 1 (d)), and a dye having predetermined optical characteristics for obtaining the color of the younger brother 1 is formed. Dyeing is used to form a first colored layer 2 ″ (FIG. 1 (e)).

Next, a non-staining protective film 3 is provided on the entire surface (FIG. 1 (f)).

Next, a photocurable coating layer for obtaining a layer to be colored is provided on the protective film 3 in the same manner as described above, and exposed and developed through a mask to form a layer to be colored in a predetermined pattern. Then, the second colored layer 5 is formed by dyeing with a dye having a predetermined optical characteristic to obtain the second color (FIG. 1 (g)).

Next, a non-staining protective film 6 is provided on the entire surface (FIG. 1 (h)). This operation can be repeated to form a colored layer of the third color and further a colored layer of the fourth color.

In the direct resolution type color filter for a solid-state image sensor, a flattening layer may be provided on a silicon wafer provided with a photodetection section to be a base, and a colored layer may be formed on the flattening layer by the same operation as described above. It is possible to use the same flattening layer as the non-staining protective film.

As the coloring layer, primary color R (red), G (green), B
It may be (blue), or may be Y (yellow), M (magenta), and C (cyan) which are complementary color systems.

Green may be obtained by combining yellow and cyan, and may be formed by stacking a yellow colored layer and a cyan colored layer,
It can also be formed by a double dyeing method of dyeing yellow or cyan and then dyeing again with a cyan or yellow dye.

In the present invention, as a dye for obtaining a complementary color Y (yellow) color layer or a primary color G (green) color layer, the azo compound represented by the general formula (1) is symmetrical or asymmetrical. : 1 It is essential to use a chromium complex salt dye or a mixture thereof, and since the yellow colored layer or the green colored layer has good spectral transmission characteristics and resistance such as light resistance and heat resistance, color separation It is possible to obtain faithful color reproducibility as an application color filter, and to obtain a color image having excellent color durability and excellent color balance as a color display color filter.

The protein-based natural polymer substance such as gelatin, casein, and glue as the film to be colored in the present invention will be described. Gelatin is an animal protein in which collagen is irreversibly changed to water-soluble by boiling with water. It is extracted from animal bones, skin, tendons, etc. by boiling with water. Casein is a phosphoprotein that is the main component of milk. A dichromate such as ammonium dichromate is added to an aqueous solution of these natural proteins, which is applied uniformly on a substrate such as glass by spin coating, roller coating, etc., and then irradiated with ultraviolet rays to cure the coating layer. , A water-insoluble film is formed.

Examples of the synthetic resin having a cationic group as the material to be colored used in the present invention include the following.

That is, a photoreactive resin composition comprising a polymer having an unsaturated group capable of photoreacting in the side chain and a quaternary ammonium salt group, a photopolymerization initiator and a solvent, or a photoreaction in a molecule of the resin composition. A film formed by coating the surface of a substrate with a photoreactive resin composition containing a compound having two or more possible unsaturated groups and then irradiating it with an actinic ray such as ultraviolet rays to cause a reaction. is there. In this case, the polymer having a photoreactive unsaturated group and a quaternary ammonium base in the side chain is, for example, (N, N-dimethylamino) ethyl acrylate, (N, N-diethylamino) ethyl acrylate,
A homopolymer or copolymer obtained by polymerizing a monomer having a tertiary amino group such as (N, N-dimethylamino) propylacrylamide is added to allylpromide,
It is obtained by reacting an unsaturated compound having an active halogen atom such as chloro-2-methylpropene, p-chloromethylstyrene, and 3-chloro-2-hydroxypropyl methacrylate. Examples of compounds having two or more photoreactive unsaturated groups in one molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane trimethacrylate. Can be mentioned. As the photoreaction initiator, 2-ethylanthraquinone, penzophenone or the like can be used. As the solvent, any solvent may be used as long as it can dissolve the polymer, the photoreaction initiator and the like well.
-Methoxyethanol, 2-ethoxyethanol, toluene, xylene and the like are used.

Such a photoreactive resin composition is applied to the surface of a substrate and cured by irradiation with actinic rays such as ultraviolet rays to obtain a film.

The examples of the photocurable anionic dye-dyable synthetic resin are not limited to the above examples, and a polymer containing a quaternary ammonium salt as one component may be used as a photocrosslinking agent such as a diazo compound. , Azide or diazide compound is added, or a resin composition in which a cationic group-containing polymer in which a photocrosslinking group such as chalcone, cinnamic acid, azide or stilbazole group is introduced into the polymer is dissolved in water or an organic solvent. But it's okay.

Symmetrical or asymmetrical 2: 1 of the azo compound represented by the formula (1)
For dyeing (coloring) the film with a chromium complex salt dye, for example, a printing method is used as the dipping method, and the dipping dyeing method using an aqueous solution is particularly convenient. In this case usually 0.1-3
0 g, more preferably 1-10 g of a symmetrical or asymmetrical 2: 1 chromium complex dye of the azo compound of formula (1) is dissolved in water 1
The substrate provided with the film is usually immersed in a dyeing bath at -100 ° C for about 10 seconds or more and about 60 minutes, taken out, washed with water and dried. The cyan-colored film thus obtained exhibits favorable optical characteristics as a color filter.

As a method for providing the non-staining protective film, a negative photoresist such as a resin composition obtained by adding a photo-crosslinking agent such as a diazo compound to an acrylic or polyvinyl alcohol polymer or a photocrosslinking group such as chalcone or cinnamic acid A method in which a resin composition or the like in which is previously introduced into an acrylic or polyvinyl alcohol-based polymer is dissolved in water or an organic solvent, applied by a spin coating method, and irradiated with ultraviolet rays to be cured is used.

In the present invention, the substrate on which the film to be dyed is provided is glass, plastics sheet, silicon wafer, or the like, if necessary, pretreated with a silane coupling agent, or provided with a flattening layer before use. It

"Examples" The present invention will be described in more detail by way of examples.

Example 1. Optical glass (high-purity glass plate with excellent light transmission)
FCR-500 on top (Fuji Pharmaceutical Co., Ltd. gelatin aqueous solution)
1 part of an 8% aqueous solution of ammonium dichromate was mixed with 4 parts and defoamed.
After applying and pre-paking at 80 ℃ for 10 minutes,
A mask alignment apparatus MA-10 type (manufactured by Mikasa Co., Ltd.) was used for exposure through a mask having a predetermined pattern at an energy amount of 300 millijoules / cm ² , and then developed in warm water at 40 ° C. Then, it was post-baked at 120 ° C. for 10 minutes to harden the gelatin film.

Next, CI Acid Bull-185 was adjusted to pH 5 with acetic acid.
It was immersed in a 0.5% aqueous solution at 60 ° C. for 5 minutes, washed with water and dried to form a first cyan colored layer.

Next, FVR-G10 (oil-soluble negative photoresist manufactured by Fuji Pharmaceutical Co., Ltd.) was applied by spin coating so that the film thickness became 0.5 μm, and after prebaking at 120 ° C. for 10 minutes,
Exposure with an energy amount of 55 mW / cm ² using an ultra-high pressure mercury lamp,
After rinsing, post-baking was performed at 150 ° C. for 20 minutes to form a dye-proof layer.

Next, a photosensitive gelatin layer was provided on the dye-proof layer in the same manner as described above, and exposed and developed to form a dyeable layer having a specific pattern, and the pH was adjusted to 5 with acetic acid. A second colored layer was provided by immersing in a 0.2% aqueous solution of the compound of the formula (2) described below for 5 minutes at 60 ° C for dyeing.

This compound had excellent solubility in water, was completely transparent even when acetic acid was added, and no precipitate was formed even when left at 60 ° C. for 2 weeks.

Next, the same photosensitive composition as the above-described anti-dyeing layer was formed to a thickness of 0.5 μm.
, And exposed under the same conditions to form a protective film. The obtained color filter was composed of two colors, yellow and cyan, and was suitable as a color filter for a solid-state image pickup device.

When the spectral transmittance curve of the yellow colored part was measured, it was 400
The transmittance in the region of ~ 450nm is 3% or less, and the transmittance is 50%.
% Wavelength, λ _T = 50, was 512 nm. This value did not change at all when used after leaving the dyeing bath for obtaining yellow color at 60 ° C. for 2 weeks, and the reproducibility and work stability were good.

Standard fade meter (Suga Test Machine FA) via an ultraviolet cut filter (HOYA L-40)
(L-3H type), the reduction rate of the optical density (-logT) at the maximum absorption wavelength of 435 nm of the yellow colored part when exposed to light for 80 hours is 1
Almost no discoloration occurred.

The symmetrical 2: 1 chromium complex salt of the formula (2) used in this example was synthesized as follows.

1: 1 chromium complex salt dye prepared by reacting diazotised 2-aminobenzoic acid-5-sulfonic acid with 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone followed by chromation 0.1 mol, and diazotized 2-aminobenzoic acid-5.sulfonic acid were added to 1- (3'-
0.1 mol of the dyestuff prepared from chlorophenyl) -3-methyl-5-pyrazolone was suspended in 1 of water. pH value is 7
After adding IN sodium hydroxide solution until, the mixture was heated to 80 ° C. The clear yellow solution that forms soon is pH = 7,80 ° C until no metal-free dye is detected
It was stirred at. Then sodium chloride was added to precipitate the 2: 1 chromium complex salt, which was separated and dried.

This complex salt dye Had the structure of

Comparative Example The spectral transmittance curve of the yellow part of the color filter prepared by the same method as in Example 1 except that the dye used to obtain the second colored layer was replaced with CI Acid Yellow 161, the dye bath immediately after preparation was used. When used, it was very similar to the curve obtained in Example 1. But CI Acid Yellow 161
Its solubility in water is poor, the solution is translucent, and when acetic acid is added to adjust the pH, it becomes cloudy and a viscous precipitate is formed over time. Therefore, when the dyebath was left at 60 ° C. for 2 weeks and then dyed, deposits were spotted on the film surface of the material to be dyed. In addition, the spectral transmittance curve of the part where the deposit is not adhered varies depending on the part, resulting in uneven dyeing. At the same time, the wavelength at which the coloring power is reduced and the transmittance is 50%, λ _T = 50,
Was shifted to the short wavelength side of 3 to 10 nm depending on the location of the colored portion, as compared with the case where the dye bath immediately after preparation was used.

Practical example 2 Toluene: 69 parts (N, N-dimethylamino) ethyl methacrylate: 30 parts Azoisobutyronitrile: 1 part A liquid of the above composition is treated in a nitrogen atmosphere at 80 ° C. for 8 hours,
100 parts of poly (N, N-dimethylamino) ethyl methacrylate solution are obtained. Chloromethylstyrene 1 was added to 50 parts of this solution.
After adding 5 parts at room temperature and reacting for 16 hours, this was dissolved in 260 parts of 2-ethoxyethanol. Further Irgacure 6
16 parts (Ciba-Geigy, photopolymerization initiator) were added and dissolved to obtain a cationic group-containing photosensitive resin composition.

Next, after washing the glass surface with acetone and drying,
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 10%
The ethanol solution was applied, air-dried, and then heat-dried at 110 ° C. for 5 minutes, and the surface was washed with acetone and dried to obtain a coating substrate. The photosensitive resin composition is applied to the surface of the coating substrate by spin coating to a film thickness of about 1 micron,
After drying at 100 ℃ for 20 minutes, use a high-pressure mercury lamp to apply 80Wat of UV light.
The coated film was cured by irradiation at t / cm for 4 seconds, and post-baked at 130 ° C. for 30 minutes to form a cured layer to be dyed. Positive resist AZ
111S (manufactured by Hoechst Japan Co., Ltd.) was applied by spin coating to a film thickness of 1 μm, prepaked at 80 ° C. for 20 minutes, and then a mask alignment apparatus MA-10 type (Mikasa) was applied through a mask having a predetermined pattern. (Manufactured by Co., Ltd.)
After exposure with an energy amount of 300 millijoules / cm ² , the positive resist developer AZ303 (manufactured by Hoechst Japan Ltd.) was developed at a room temperature for 90 seconds in a solution diluted 4-fold with water, and then washed with water. Next, "Kayanor Milling Red GRA"
(Nippon Kayaku Co., Ltd., red acid dye) immersed in 0.1% aqueous solution at 50 ° C. for 5 minutes, washed with water, treated with ethyl acetate for 2 minutes, treated with N-methylpyrrolidone for 5 seconds and then positive. The resist was peeled off, washed with water and dried to obtain a patterned first red colored portion.

Next, a positive resist layer is provided in the same manner as described above, and the dyeable resin layer is exposed to light through a mask and developed to expose the dyeable resin layer in a portion different from the first colored portion.

After dipping in a 0.2% aqueous solution of the compound of the following formula (3) at 60 ° C. for 2 minutes, it was placed in a 0.5% aqueous solution of CI Acid Blue 185.
After dipping at 10 ° C. for 10 minutes for dyeing, the positive resist was peeled off to obtain a second colored layer colored in green. The 0.2% aqueous solution of the compound of the following formula (3) for obtaining a yellow color was completely transparent, and no precipitate was formed even when left at 60 ° C. for 1 month.

Next, in the same manner as described above, another portion of the same dyeable resin layer was immersed in a 0.1% aqueous solution of CI Acid Blue 90 at 50 ° C. for 5 minutes for dyeing, and then the positive resist was peeled off to give a blue color. A third colored layer was obtained.

Next, the same photosensitive composition as the anti-dyeing layer of Example 1 was used to obtain a film thickness of 0.
The color filter of the present invention was obtained by spin coating so as to have a thickness of 5 μm, and exposing under the same conditions to form a protective film.

The obtained color filter was composed of three colors, red, green and blue, and was suitable for a liquid crystal color television. When the spectral transmittance curve of the colored part of green is measured, the wavelength showing the maximum transmittance is 520 nm and the wavelength showing the yellow side transmittance is 50%, and λ _T = 50, is the transmittance of 513 nm, 400 to 450 nm region. Was 3% or less. The optical density (-logT) at the maximum absorption wavelength 513nm on the yellow side after 200 hours of exposure to a standard fade meter (Suga Test Instruments FAL-3H type) through an ultraviolet cut filter (HOYA L-40) The rate of decrease was 2%, and almost no discoloration occurred.

The compound of the following formula (3) used in Example 2 was synthesized as follows.

1: 1 chromium complex salt dye prepared by reacting diazotized 2-aminobenzoic acid-5.sulfonic acid with 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone followed by chromation 0.11 mol and diazotised 2-aminobenzoic acid and 1-phenyl-3-methyl-
0.1 mol of the dyestuff prepared from 5-pyrazolone is stirred in 1 part of water. The resulting suspension was then adjusted to pH = 6-7 with aqueous ammonia and warmed to 90 ° C. The yellow solution that forms soon is brought to pH until no metal-free dye is detected.
= 7.90 ° C and stirred. Then add sodium chloride,
The asymmetric 2: 1 chromium complex dye was precipitated, separated and dried. This complex dye has the following structure Had.

Comparative Example The yellow dye used to obtain the second green colored part
The spectral transmittance curve of the green colored portion of the color filter manufactured by the same method as in Example 2 except that CI Acid Orange 149 was replaced was similar to that in Example 1, but the results of the light fastness test described in Example 1 The deterioration rate was 58%, which was markedly fading, and the green-colored part was out of balance between yellow and cyan, and turned into a strong cyan blue.

Examples 3 to 16 Symmetrical or asymmetrical 2: 1 chromium complex salt dyes were synthesized according to Example 1 or Example 2 using the azo compounds shown in Columns I or II of the table as the azo compound of the formula (1). Using this complex salt dye (λmax in water is shown in column III of the table), a color filter consisting of two colors, yellow and cyan, was obtained in substantially the same manner as in Example 1.

Effect of the Invention A color filter used for liquid crystal display devices, color separation devices, sensors, etc., which exhibits excellent reproducibility and excellent optical characteristics and durability, especially in the green region by combination with a yellow or cyan dye. was gotten.

[Brief description of drawings]

 1 (a) to (h), 1 ... glass plate 2 ... photocurable thin film 2 '... colored film 2 "... first colored layer 3 ... non-staining protective film 4 ... photomask 5: second colored layer 6: non-staining protective film 7: development tank 8: dyeing tank 9: irradiation lamp

Claims (1)

(57) [Claims] 1. A symmetrical or asymmetrical 2: 1 chromium complex dye of an azo compound represented by the following formula (1) in which at least one pattern is a free acid in a color filter having a pattern-colored film mounted on a substrate. A color filter characterized by being colored with. (In the formula (1), R ₁ is --H, --Cl, --SO ₃ H, --SO ₂ NH ₂ , --S
_{O 2 CH 3, -SO 2 C} 2 H 5, -SO 2 NHCH 3, -SO 2 NHC 2 H 5 or -NO
₂ , R ₇ is --CH ₃ or Respectively. Also representative of the _{R 2, R 3, R 4} , R 5 and -H R ₆ are each _{independently, -Cl, -CH 3, -C 2} H 5, -OCH 3 or -SO ₃ H. )