JP2001004823A - Color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide color characteristic and excellent reliability (resistance to heat and light) by coloring a blue part with specified azaphthalocyanines having the sulfonic group. SOLUTION: A blue part is colored with azaphthalocyanines having the sulfonic group, that is represented by formula I. In formula I, A-D independently represent aromatic 6-membered rings, at least one of which contains at least one pyridine ring. R1 represents hydrogen atom, methyl group, ethyl group, hydroxy group, or carboxy group; X represents a hydroxy group, amino group, carboxy (1-3C) alkylamino group or sulfo (1-3C) alkylamino group or a group represented by formula II; and (p) represents an integer of 1-14. M represents copper, zinc, cobalt, nickel, titanium oxide or two hydrogen atoms. In formula II, R2 represents hydrogen atom, methyl group, ethyl group, hydroxy group or carboxy group; (r) represents an integer of 1-4; and (s) represent an integer of 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a color filter. More specifically, the present invention relates to a color filter having excellent optical characteristics used for a liquid crystal display device, a color separation device, a sensor, and the like.

[0002]

2. Description of the Related Art Conventionally, a method of combining three primary color filters of red, green, blue or yellow, magenta, and cyan has been adopted in order to color a liquid crystal display device or a solid-state imaging device. Although there are several methods for forming these color filters, the most basic method is a so-called dyeing method.

[0003] A method of producing a color filter by a dyeing method is as follows.
A synthetic resin film having a transparent cationic group in the form of a thin film such as a stripe or mosaic (referred to as a pattern) on the surface of glass or silicon wafer as a substrate, or a protein-based natural polymer such as gelatin, casein, glue, etc. The basic principle is that a film to be colored is provided by forming a film, and then dyed (colored) with a dye. The following three methods are known as specific manufacturing processes of a color filter.

(1) 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. Next, a non-colored 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, a colored layer is sequentially formed as needed.

(2) After a film to be colored is provided on the substrate surface, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and the dye is fixed and prevented with tannic acid or the like. Apply dyeing treatment. A second coating to be colored is provided by a similar operation. Hereinafter, a colored layer is formed on the same substrate surface as necessary.

(3) A film to be colored (film to be colored) is provided on the surface of the substrate. After a positive resist layer is provided thereon, exposure and development are performed through a mask to dye the pattern-exposed coating film, and then the positive resist layer is peeled off to form a colored portion. The operations after the formation of the positive resist layer are repeated, and the same colored film is dyed into a plurality of colors in a desired pattern.

[0007] In recent years, with the demand for cost reduction by lowering the cost of color filters, a production method using an ink jet printer has been proposed for the above-mentioned dyeing method. The manufacturing process of the color filter by the inkjet method will be specifically described below.

(1) An ink-receiving layer having high dyeability is formed on a substrate, and this is cured as required by using, for example, a heat treatment. (2) A desired colored pattern is formed by selectively jetting a dye ink onto the ink receiving layer by an inkjet method. (3) A fixation process is performed on the formed colored pattern as necessary using, for example, a heat treatment.

Except for special ones, the color filters manufactured by the above-mentioned processes are usually three primary colors of primary colors R (red), G (green), B (blue) or three primary colors of Y. (Yellow), M (magenta), C (cyan), and (M may be omitted) colored layers. The most important characteristic required for the color filter is the optical characteristic, and the spectral characteristic of each colored layer largely determines the value of the final product. In addition, it has a high degree of resistance to heat treatment encountered in the process of manufacturing a liquid crystal display device equipped with a color filter, for example, a sputtering process for providing a transparent electrode layer, and to light applied during use as a final product. And the predetermined optical properties must not be impaired. Also, of course, the applied dye has good solubility and solubility in water,
It must be stable for a long time in an acidic dyeing bath. Further, when a process requiring a fixing treatment is involved, it is required that the fixing treatment effect be excellent. By the way, gelatin,
Since protein-based natural high molecular substances such as casein and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye.

When a photocurable synthetic resin substrate is used in place of these, a cationic group is retained in the resin component so that a water-soluble anionic dye can be formed in the same manner as a protein-based natural polymer. To be stained.

[0011]

Numerous water-soluble anionic dyes have been investigated, alone or in combination, to obtain the desired optical properties. However, for the primary color blue, especially when a synthetic resin having a photocurable cationic group is used as a substrate to be colored, it has desired color characteristics and sufficient resistance to heat and light, and It is particularly difficult to select a dye with excellent fixing performance,
At present, no satisfactory dye has been found.

The spectral characteristics required for a desired blue dye are such that a colored film dyed so that the transmittance near 600 nm is 1% or less, the top transmittance in the region of 440 to 460 nm must be as high as possible. It is said. In order to satisfy such optical characteristics, CIAcid Blue 83
Alternatively, a triphenylmethane dye represented by CIAcid Blue 90 is used. The spectral transmittance curves of these dyes are sharp and clear in color, and when the substrate to be colored is a natural protein such as gelatin, casein or glue or a polyimide-based synthetic resin, the color characteristics and light and Although heat resistance is insufficient, it is not impossible to use. On the other hand, when the base material to be colored is a synthetic resin having a photocurable cationic group, and when the main chain polymer is composed of acrylic acid or a derivative thereof, it has a remarkable resistance to heat and light and is not practically used. I can't get it. Anthraquinone structure is known as a blue dye relatively excellent in heat resistance and light resistance, but there are few dyes satisfying the required optical characteristics, and even those satisfying the optical characteristics can be used in the aforementioned photocurable acrylic synthetic resin. When applied, heat resistance and light resistance are extremely poor. For example,

[0013]

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The colored film using the anthraquinone compound is extremely red-colored in a short time upon exposure to light and cannot be put to practical use. Thus, there is a demand for the development of a color filter having a blue colored film having both light and heat resistance and color characteristics.

[0015]

The present inventors have made intensive efforts to find a color filter having both the above-mentioned optical characteristics and durability, and as a result, a color filter dyed (blue) with a specific phthalocyanine compound has been developed. The inventors have found that they have the color characteristics and excellent reliability (resistance to heat and light) as described above, and have reached the present invention. That is, the present invention provides: (1) a color filter in which the blue portion is colored with an azaphthalocyanine having a sulfonic acid group; (2) the following formula (1)

[0016]

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[In the formula (1), A, B, C and D are independently aromatic.
A six-membered ring having at least one
Contains a gin ring. Also, R₁Is a hydrogen atom, a methyl group,
X represents a hydroxyl group, an ethyl group, a hydroxyl group or a carboxyl group;
Group, amino group, carboxy (C ₁-C_Three) Alkylamino
Group, sulfo (C₁-C_Three) Alkylamino group or formula
(2)

[0018]

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[In the formula (2), R ₂ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a carboxyl group, and r represents 1
４4, s indicates the number of ４1４4. And p represents an integer of 1 to 14. M represents copper, zinc, cobalt, nickel, titanium oxide, or two hydrogen atoms. And a color filter colored with azaphthalocyanines. (3) Among A, B, C and D, two or three positions are a benzene ring, one or two positions are a pyridine ring, R1 is a hydrogen atom, X is a hydroxyl group, p is 12, p is 12, and q is 2 Or 3, the color filter according to (2), wherein M is copper; (4) an image display device having the color filter according to any one of (1) to (3); (5) (1) to (3). (3) An image input device having the color filter according to any one of (1) to (3).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The color filter of the present invention has a blue portion colored with a specific azaphthalocyanine, preferably an azaphthalocyanine having a sulfonic acid group. The azaphthalocyanines include, for example, the compound represented by the above formula (1). In the present invention, for example, this compound is used as a blue component dye. That is, in the present invention, in a color filter in which a film colored in a pattern with a plurality of hues is mounted on a substrate, at least one pattern has an azaphthalocyanine represented by the above formula (1) or a mixture thereof, preferably sulfonic acid. It is colored with azaphthalocyanines having a group.

In the above formula (1), A, B, C, and D are each independently a 6-membered aromatic ring containing at least one pyridine ring. R1 is a hydrogen atom,
A methyl group, an ethyl group, a hydroxyl group, or a carboxyl group, and X represents a hydroxyl group, an amino group, a carboxy (C1-C3)
An alkylamino group, a sulfo (C1-C3) alkylamino group, or a group represented by the formula (2). In the formula (2), R2 is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a carboxyl group, p is 1 to 4, and q is 1
-3 and r are 1-4 and s is an integer of 1-4. Also, M
Is copper, zinc, cobalt, nickel, titanium oxide, or two hydrogen atoms.

Two or three of A, B, C and D are a benzene ring, one or two is a pyridine ring,
R1 is a hydrogen atom, X is a hydroxyl group, p is 12,
Compounds in which q is 2 or 3 and M is copper are preferred.

Hereinafter, the color filter of the present invention will be described in detail. The dye component used in the color filter of the present invention is a compound known, for example, from British Patent No. 784843 (1957) and the like, and is obtained, for example, by condensing pyridinedicarboxylic acid and sulfophthalic acid by an ordinary method of phthalocyanine synthesis. . Further, it can also be obtained by condensing pyridinedicarboxylic acids and phthalic acids by an ordinary method for synthesizing phthalocyanine and then sulfonating.

An example of the color filter of the present invention will be described with reference to the drawings. FIGS. 1A to 1H are views showing a method of manufacturing a color filter by a lamination method in which colored layers of different colors are laminated on a base (glass plate). In FIG. 1, 1 is a glass plate, 2 is a thin film of a photocurable resin or the like provided by spin coating, 2 'is a film to be colored by photocuring 2 through a mask, 2 "is a colored layer, and 3 is a colored layer. Stain-resistant protective layer, 4
Denotes a photomask, 5 denotes a second colored layer, and 6 denotes a non-staining protective film.

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 on a glass plate 1 Is applied by a method such as spin coating or roller coating to provide a photocurable thin film 2 having a thickness of 0.2 to 2 μm (FIG. 1B). Next, the thin film is irradiated with ultraviolet light through a photomask 4 having a predetermined pattern to cure the exposed portion (FIG. 1C). Next, development with water or the like is performed to remove the unexposed portions, thereby forming a colored layer 2 'having a predetermined pattern.
(D)) Dyeing is performed using a dye having predetermined optical properties to obtain a first color 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) 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 the layer to be colored in a predetermined pattern is exposed and developed through a mask. Is formed and dyed with a dye having predetermined optical properties to obtain a second color to form a second colored layer 5 (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 present invention, as a substrate on which a film to be dyed is provided, glass, a silicon wafer or the like may be used as necessary or provided with a flattening layer. Examples of the substrate include a glass plate and a plastic sheet. Direct mount color separation color filters for solid-state imaging devices or color sensors include those provided with a flattening layer on a silicon wafer provided with a photodetector, etc., and those pretreated with a silane coupling agent. It becomes a base. The same material as the non-staining protective film can be used for the flattening layer.

Examples of the photocurable film-forming composition capable of dyeing an anionic dye to be a colored layer include the above-mentioned gelatin,
Examples thereof include those obtained by adding a dichromate such as ammonium bichromate to an aqueous solution of a protein-based natural polymer substance such as casein or glue, or a synthetic resin having a cationic group. Examples of the synthetic resin having a cationic group include a resin composition comprising a polymer having a photoreactive unsaturated group and a quaternary ammonium base in a side chain, a photopolymerization initiator and a solvent, or chalcone, cinnamic acid , Azide, stilbazole group, a resin composition in which a cationic group-containing polymer in which a photocrosslinking group such as an epoxy group is previously introduced into a polymer is dissolved in water or an organic solvent, or a nitrogen-containing monomer as one of the essential components. A resin composition obtained by adding a photocrosslinking agent, for example, a diazo compound, an azide or a diazide compound to a polymer obtained by polymerization and diluting the polymer with an organic solvent may be used. These anionic dye-dyeable photocurable film-forming compositions are uniformly coated on a substrate by spin coating, roller coating, or the like, and then irradiated with ultraviolet rays through a mask and developed to be colored in a predetermined manner. The coating layer cures,
A water-insoluble film is formed.

As the film to be colored in the present invention, a film containing a water-soluble polymer can also be used. In this case, dyeing is usually performed by a method such as an inkjet method. Examples of the resin composition for a film containing a water-soluble polymer include resin compositions such as an acrylic resin, an imide resin, a polyvinyl alcohol, a polyurethane, a polyurethane, and a polyester containing a cellulose-based water-soluble polymer. After uniformly applying these resin compositions on a substrate by spin coating, roller coating, or the like, a heat treatment or the like is performed as necessary, thereby forming a predetermined dyed layer to be colored.

In the present invention, the above-mentioned azaphthalocyanines having a sulfonic acid group are used as a dye for obtaining a colored layer of primary color B (blue). In order to dye (color) the film, for example, an immersion method, a printing method, or an inkjet method is used. For example, the immersion dyeing method will be described. Usually, 0.1 to 30 g, more preferably 1 to 10 g of the phthalocyanine compound of the formula (1) is dissolved in 1 liter of water. Wood,
After immersion for 10 seconds or more and 60 minutes, take out, wash and dry. The thus-obtained blue-colored film shows preferable optical characteristics as a color filter.

Examples of the resin composition used for the non-staining protective film include a negative photoresist such as an acrylic or polyvinyl alcohol-based polymer obtained by adding a photocrosslinking agent such as a diazo compound, or a chalcone or silica. A resin composition in which a photocrosslinking group such as cinnamic acid is previously introduced into an acrylic or polyvinyl alcohol-based polymer may be used. Examples of a method for providing a non-staining protective film using these resin compositions include, for example, a method in which the resin composition is dissolved in water or an organic solvent, applied by a spin coating method, and cured by irradiating ultraviolet rays. Is adopted.

The optical device having the color filter of the present invention includes, for example, an LCD (Liquid Crystal Display), a color separation device, a color sensor and the like. For example,
The image display device having the color filter of the present invention is, for example, in the case of a liquid crystal display device, a backlight portion, a polarizing film portion, a liquid crystal portion, a color filter portion of the present invention, a polarizing film portion and the like are laminated and produced in this order, In the case of an image pickup device that is an image input device, the color filter portion of the present invention is formed on a charge transfer element formed on a semiconductor such as silicon, a phototransistor, a protective layer for protecting a photodiode and the like, and is manufactured. Is done.

[0033]

Now, the present invention will be described in further detail with reference to Synthesis Examples and Examples.

Synthesis Example 1 22.2 g of phthalic anhydride, 2,3-pyridinedicarboxylic acid 25.
1 g, 60.1 g of urea, 20.3 g of anhydrous copper (II) chloride, 1 g of molybdic acid heptahydrate in 200 g of 1,2,4-trichlorobenzene at 140 ° C
After heating for 1 hour at 200 ° C., the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution is cooled to room temperature, and acetone 20
After dilution with 0 g, the precipitate was filtered. The precipitate collected by filtration is
After stirring in 1000 mL of 5% hydrochloric acid for 1 hour, the mixture was filtered. Thereafter, the resultant was washed with 1000 mL of 10% aqueous ammonia and dried to obtain 43 g of azaphthalocyanine. Further, 43 g of the dried and pulverized azaphthalocyanine was added to 900 g of 30% fuming sulfuric acid at room temperature and reacted at 100 ° C. for 4 hours.
After completion of the reaction, the reaction solution was cooled to room temperature, added to 2000 mL of ice water, and the precipitate was filtered. The precipitate collected by filtration was washed with 1000 mL of ice water and dried to obtain 55 g of a sulfonated azaphthalocyanine.

Synthesis Example 2 33.3 g of phthalic anhydride, 2,3-pyridinedicarboxylic acid 12.
6 g, 60.1 g of urea, 20.3 g of anhydrous copper (II) chloride, 1 g of molybdic acid heptahydrate in 200 g of 1,2,4-trichlorobenzene at 140 ° C
After heating for 1 hour at 200 ° C., the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution is cooled to room temperature, and acetone 20
After dilution with 0 g, the precipitate was filtered. The precipitate collected by filtration is
After stirring in 1000 mL of 5% hydrochloric acid for 1 hour, the mixture was filtered. Thereafter, the resultant was washed with 1000 mL of 10% aqueous ammonia and dried to obtain 46 g of azaphthalocyanine. Further, 46 g of the dried and pulverized azaphthalocyanine was added to 900 g of 30% fuming sulfuric acid at room temperature and reacted at 100 ° C. for 4 hours.
After completion of the reaction, the reaction solution was cooled to room temperature, added to 2000 mL of ice water, and the precipitate was filtered. The precipitate collected by filtration was washed with 1000 mL of ice water and dried to obtain 60 g of sulfonated azaphthalocyanine.

Synthesis Example 3 11.1 g of phthalic anhydride, 2,3-pyridinedicarboxylic acid 37.
7 g, 60.1 g of urea, 20.3 g of anhydrous copper (II) chloride, 1 g of molybdic acid heptahydrate in 200 g of 1,2,4-trichlorobenzene at 140 ° C
After heating for 1 hour at 200 ° C., the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution is cooled to room temperature, and acetone 20
After dilution with 0 g, the precipitate was filtered. The precipitate collected by filtration is
After stirring in 1000 mL of 5% hydrochloric acid for 1 hour, the mixture was filtered. Thereafter, the resultant was washed with 1000 mL of 10% aqueous ammonia and dried to obtain 40 g of azaphthalocyanine. Further, 40 g of the dried and ground azaphthalocyanine was added to 800 g of 30% fuming sulfuric acid at room temperature, followed by a reaction at 100 ° C. for 4 hours.
After completion of the reaction, the reaction solution was cooled to room temperature, added to 2000 mL of ice water, and the precipitate was filtered. The precipitate collected by filtration was washed with 1000 mL of ice water and dried to obtain 40 g of sulfonated azaphthalocyanine.

Example 1 Kayamirror CFR-633DHP (acrylic anion dye-dyeable photosensitive resin composition manufactured by Nippon Kayaku Co., Ltd.) was spun on optical glass (high-purity glass plate excellent in light transmittance). Coating is performed by a coating method, and a film is formed so that the film thickness becomes 0.6 μm. Subsequently, UV irradiation is performed through a mask,
Then, when developed, a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having this coating was placed in a 0.2% aqueous solution of the compound of Synthesis Example 1 at 80 ° C. for 1 hour.
It was immersed for 0 minutes and dyed to provide a blue colored film.

When the spectral transmittance curve of this blue colored portion was measured, the transmittance near 600 nm was 1% or less, and the top transmittance was 90% near 460 nm. The spectral characteristics are shown. The density change (ΔE) when exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 20 hours was 10 or less, indicating extremely excellent light fastness. 3 on a 220 ° C hot plate
The change in concentration (ΔE) after heating for 1 minute was 10 or less, indicating extremely excellent heat resistance. In addition, no elution of the dye was observed in each step, which was favorable.

Comparative Example 1 The spectral transmittance curve of the blue colored portion of the colored glass plate prepared in the same manner as in Example 1 except that the dye was changed to CIAcid Blue 83 was similar to the curve obtained in Example 1. However, when the light resistance and heat resistance tests shown in Example 1 were carried out, the reddish color was remarkably red as shown in the results in Table 1, and the color was no longer blue.

Example 2 A glass plate on which a resin was placed in a pattern obtained by the same operation as in Example 1 was dyed in a 0.2% aqueous solution of the compound of Synthesis Example 2 at 80 ° C. for 10 minutes to give a blue color. A glass plate colored in a pattern was obtained. When the spectral transmittance curve of the blue colored portion was measured, the transmittance in the region of 600 ± 30 nm was 1% or less, and the top transmittance was 90% near 460 nm. The characteristics were shown.
The density change (ΔE) when exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 20 hours was 10 or less, indicating extremely excellent light fastness. In addition, the concentration change (ΔE) after heating on a hot plate at 220 ° C. for 31 minutes
Showed extremely excellent heat resistance at 10 or less. In addition, no elution of the dye was observed in each step, which was favorable.

COMPARATIVE EXAMPLE 2 A blue colored portion of a colored glass plate prepared in the same manner as in Example 1 except that the dye was changed to CIAcid Blue 90 was subjected to a heat resistance test by the method shown in Example 2. As shown in FIG. 1, the color was extremely fading, and the color changed to a color that could not be said to be blue anymore.

Example 3 8% of ammonium bichromate to 4 parts of FCR-500 (manufactured by Fuji Pharmaceutical Co., Ltd., aqueous gelatin solution) on optical glass
An aqueous solution mixed with 1 part of an aqueous solution was applied to a thickness of 1 μm by a spin coating method, pre-baked at 80 ° C. for 10 minutes, and then passed through a mask having a predetermined pattern. Exposure with an energy of 300 mJ / cm2 using a mold (manufactured by Mikasa Co., Ltd.)
In hot water. Then, it was post-baked at 120 ° C. for 10 minutes to harden the gelatin film. Then, it was immersed in a 0.2% aqueous solution of the compound of Synthesis Example 1 adjusted to pH 5 with acetic acid at 80 ° C. for 10 minutes and washed with water to form a desired blue pattern. Next, the fixing conditions are as follows: First, use 0.3% tannic acid at 80 ° C.
For 5 minutes, followed by treatment with 0.1% tartaric acid at 70 ° C. for 5 minutes, and finally by treatment at 180 ° C. for 5 minutes to form a first blue colored layer. next,
A photosensitive gelatin layer was provided in the same manner as described above, exposed, developed, immersed in a 0.5% aqueous solution of PC Red 136P (a color filter dye manufactured by Nippon Kayaku Co., Ltd.) at 60 ° C. for 10 minutes, and dyed. Similarly, a fixation / dyeing treatment was performed to provide a second red colored layer. Next, another part of the gelatin layer is dyed in a 0.5% aqueous solution of PCGreen FOP (a color filter dye manufactured by Nippon Kayaku Co., Ltd.) at 60 ° C. for 15 minutes and then fixed and prevented from dyeing in the same manner as described above. And a third green colored layer. 3
No elution of the blue dye into the tannic acid bath and fixing bath subjected to the fixing and dyeing treatments was observed.

The obtained color filter was composed of three colors, blue, red and green, and was suitable for liquid crystal displays. When the spectral transmittance curve of the blue colored portion was measured, the transmittance in the region of 570 to 630 nm was 1% or less, and the top transmittance was 90% near 460 nm. The spectral characteristics are shown. In addition, carbon arc fade meter (manufactured by Suga Test Machine)
In addition, a change in density (ΔE) upon exposure for 20 hours was 10 or less, indicating extremely excellent light fastness.

Comparative Example 3 The blue dye used to obtain the first blue colored portion was CIAc
A color filter was prepared in the same manner as in Example 3 except that id Blue 62 was used. Then, when the spectral transmittance curve of the blue colored portion of the color filter was measured,
Although similar to Example 3, the heat resistance described in Example 1
As a result of the light resistance test, as shown in Table 1, the blue colored portion was noticeably reddish.

Table 1 Samples Light resistance Heat resistance Example 1 9.5 9.3 Example 2 9.3 9.0 Example 3 9.5 9.2 Comparative example 1 160 or more 160 Comparative example 2 120 or more 110 Comparative example 3 55 20

Heat resistance: heat treatment at 220 ° C. for 31 minutes Displayed by concentration change (ΔE) Light resistance: Carbon arc irradiation for 20 hours Displayed by concentration change (ΔE)

Table 1 shows that the examples and the comparative examples are much better than the comparative examples in heat resistance and light resistance.

[0048]

By using azaphthalocyanines having a sulfonic acid group or a mixture thereof as a blue dye for a color filter, a color filter having a blue colored film having both color characteristics, light resistance and heat resistance can be obtained. It became so. That is, since the color characteristics of the blue colored layer are present and the resistance to heat applied in the manufacturing process of the device incorporating the color filter and the light resistance required for the final product are good, the color filter is used as a display color filter. A well-balanced color image can be obtained, and faithful color reproducibility can be obtained as a color filter for color separation. The dye used in the present invention is particularly useful when the substrate to be colored is an acrylic photocurable synthetic resin,
The present invention is not limited to this, and can be applied to natural substrates. Furthermore, there is no elution of the dye from the colored layer into the fixing bath, which is a problem during the production involving the fixing and dyeing treatment in the above-mentioned dyeing production process (2), and the fixing and dyeing resistance is excellent.

[Brief description of the drawings]

FIG. 1A shows a substrate (glass plate), FIG. 1B shows a glass plate provided with a photocurable thin film, and FIG. 1C shows a photocurable thin film irradiated with ultraviolet light via a photomask. Process
(D) shows the glass plate provided on the layer to be colored, (e) shows the step of dyeing the layer to be colored, (f) shows the step of providing a non-staining protective film on the colored layer, and (g) shows the step of coloring. (H) represents a step of providing a second colored layer, and (h) represents a step of providing a second non-staining protective film.

Claims (5)

[Claims] 1. A color filter in which a blue portion is colored with an azaphthalocyanine having a sulfonic acid group. 2. A compound represented by the following formula (1):[In the formula (1), A, B, C, and D each independently represent an aromatic 6
Member ring containing at least one pyridine ring
I do. Also, R₁Is hydrogen atom, methyl group, ethyl group, water
X represents a hydroxyl group, an amino group or a carboxyl group;
Group, carboxy (C ₁-C_Three) Alkylamino group, sulfo
(C₁-C_Three) Alkylamino group or formula (2)[In the formula (2), R_TwoRepresents a hydrogen atom, a methyl group, an ethyl group,
Represents a hydroxyl group or a carboxyl group, r is 1 to 4, s is 1 to
Indicates an integer of 4. And p is 1 to 14
Indicates an integer. M is copper, zinc, cobalt, nickel
, Titanium oxide, or two hydrogen atoms. ]
Color filled with azaphthalocyanines
Tar. 3. A, B, C, D two or three positions are a benzene ring, one or two positions are a pyridine ring,
R1 is a hydrogen atom, X is a hydroxyl group, p is 12, q is 2
3. The color filter according to claim 2, wherein 3, M is copper. 4. An optical device having the color filter according to claim 1. 5. The optical device according to claim 4, which is an image display device or an image input device.