JP2001011331A - New phthalocyanine compound and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new phthalocyanine compound that can provided a color filter on which a blue color coating film having both good color characteristics and good durability against light and heat is loaded, by sulfonating an azaphthalocyanine compound. SOLUTION: This sulfonated azaphthalocyanin is obtained by sulfonating an azaphthalocyanine compound. The sulfonation reaction is preferably carried out in sulfuric acid containing fuming sulfuric acid. The azaphthalocyanine compound is a compound which has a skeleton structure of the formula (A to D are each an aromatic six-membered ring among which one to three rings are pyridine rings) and is obtained by reacting one mole of a phthalic acid compound [preferably phthalic acid (anhydride), a phthalate salt or phthalimide] with 0.2 to 5 moles of a pyridine dicarboxylic acid compound (preferably pyridine dicarboxylic acid). When the sulfonated azaphthalocyanine is used as a blue dye, a color filter having excellent color characteristics, excellent durability, and so on, can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phthalocyanine and a color filter. More specifically, the present invention relates to a novel phthalocyanine for 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 around 600 nm is 1% or less needs to have a top transmittance as high as possible in the region of 440 to 460 nm. It is said. In order to satisfy such optical characteristics, C.I.
I. Acid Blue 83 or C.I. I. Acid
A triphenylmethane dye represented by 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. 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.

[0013]

The present inventors have made intensive efforts to find a color filter having both optical characteristics and durability as described above. As a result, a color filter colored (blue) with a specific phthalocyanine 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 phthalocyanine obtained by sulfonating an azaphthalocyanine compound, (2) a phthalocyanine according to (1), wherein the sulfonation is performed in sulfuric acid containing fuming sulfuric acid, and (3) an azaphthalocyanine compound. Is obtained by reacting a phthalic acid with a pyridinedicarboxylic acid, the phthalocyanine according to (1) or (2). (4) The phthalocyanine according to (3), wherein the phthalic acid and the pyridine dicarboxylic acid are used in an amount of 0.2 to 5 mol of the pyridine dicarboxylic acid per 1 mol of the phthalic acid.

(5) The phthalocyanines according to (3) or (4), wherein the phthalic acids are phthalic acid, phthalic anhydride, phthalic acid salts or phthalimide; and (6) the pyridinedicarboxylic acids are pyridinedicarboxylic acid, pyridinedicarboxylic acid. It is colored with the phthalocyanine according to any one of (3) to (5) and (7) the phthalocyanine according to any one of (1) to (6), which is an anhydride or pyridinedicarboxylic imide. Color filters,
(8) An image display device having the color filter according to (7).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanines of the present invention are obtained by sulfonating an azaphthalocyanine compound. The azaphthalocyanine compound as a raw material is, for example, represented by the following formula (1)

[0016]

Embedded image

(Wherein A, B, C, and D in the formula (1) are each independently a 6-membered aromatic ring, and 1 to 3 of them are pyridine rings.) And may have a substituent. As the substituent,
Examples include a methyl group, an ethyl group, a hydroxyl group, a carboxyl group and the like. Further, the azaphthalocyanine compound may have a metal atom coordinated at its center.
Examples of the metal atom include copper, zinc, cobalt, nickel, titanium oxide and the like.

Representative azaphthalocyanine compounds include, for example, monoazaphthalocyanine, diazaphthalocyanine, triazaphthalocyanine and the like, with monoazaphthalocyanine and diazaphthalocyanine being preferred. Also, a mixture of monoazaphthalocyanine and diazaphthalocyanine, and a mixture of these and a small amount of phthalocyanine (about 10%: based on the peak intensity ratio of mass spectrometry) are azaphthalocyanine compounds which are starting materials used in the present invention. include.

The phthalocyanines of the present invention can be obtained by sulfonating an azaphthalocyanine compound. Sulfonation is usually performed in sulfuric acid, including fuming sulfuric acid. The concentration of fuming sulfuric acid in the sulfuric acid is about 10-60% by weight, preferably about 20-40% by weight. The reaction temperature is generally about 60-120 ° C, preferably about 80-110 ° C.
The reaction time varies depending on the reaction temperature, but is usually about 1 hour to
10 hours, preferably about 4 to 8 hours. After completion of the reaction, the reaction solution is poured into ice water, salted out, filtered and dried to obtain the compound of the present invention. When a mixture of a small amount of phthalocyanine and a large amount of azaphthalocyanine is used as a raw material, the mixture is obtained as a mixture of both sulfonates. When it is desired to remove the sulfonated phthalocyanine, separation can be usually performed by column chromatography.

The compound thus obtained is in the form of the free acid,
Or it exists in the form of its salt. In the present invention, as a free acid or a salt thereof, an alkali metal salt, an alkaline earth metal salt,
It can be used as an alkylamine salt, an alkanolamine salt or an ammonium salt. Preferably a sodium salt,
Examples thereof include alkali metal salts such as potassium salts and lithium salts, and alkanolamine salts such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts, and triisopropanolamine salts.

The azaphthalocyanine compound used in the present invention is produced, for example, by reacting phthalic acids and pyridinedicarboxylic acids in the presence of a polyvalent metal compound. Examples of the phthalic acids include phthalic acid, phthalic anhydride, phthalates (eg, alkali metal salts such as sodium salts and potassium salts), and phthalimide. Examples of the pyridine dicarboxylic acids include pyridine dicarboxylic acid, pyridine dicarboxylic anhydride, and pyridine dicarboxylic imide. As the polyvalent metal compound, for example, copper chloride, zinc chloride, cobalt chloride,
And the like.

The reaction between phthalic acids and pyridinedicarboxylic acids is carried out in an amount of about 0.2 to 5 times, preferably about 0.5 to 3 times, the moles of pyridinedicarboxylic acids per mole of phthalic acids, and trichlorobenzene and sulfolane are used. About 150 ° C. to 250 ° C., preferably about 180 ° C. to 22 ° C.
At 0 ° C., usually about 2 hours to 10 hours, preferably about 4 hours to
It is obtained by reacting for 8 hours. In this method, a mixture of a small amount of phthalocyanine and a large amount of azaphthalocyanine is obtained. Usually, the next sulfonation reaction is carried out as a mixture. In this method, an azaphthalocyanine compound in which the central portion is usually a complex of a polyvalent metal is obtained. The azaphthalocyanine compound is free of a polyvalent metal by adding an acid or the like, and a free azaphthalocyanine compound is obtained.

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 and 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. To form a second color layer 5 by dyeing with a dye having predetermined optical characteristics to obtain a 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 present invention, examples of a substrate on which a film to be dyed is provided 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 primary color B (blue) colored layer. In order to dye (color) the film, for example, an immersion method, a printing method, or an inkjet method is used. For example, when describing the immersion dyeing method, usually 0.1 to 30 g, more preferably 1 to 30 g
10 g of the phthalocyanine compound of the formula (1) dissolved in 1 liter of water is immersed in a dyeing bath at 10 to 100 ° C. for about 10 seconds to 60 minutes. I do. The thus-obtained blue-colored film shows preferable optical characteristics as a color filter.

As the resin composition used for the non-staining protective film, a negative type photoresist, for example, a resin composition obtained by adding a photocrosslinking agent such as a diazo compound to an acrylic or polyvinyl alcohol-based polymer, or 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 device), 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.

[0032]

Next, the present invention will be described in more detail by way of examples.

Example 1 22.2 g of phthalic anhydride, 25.1 g of 2,3-pyridinedicarboxylic acid, 60.1 g of urea, and anhydrous copper (II) chloride 2
0.3 g, 1 g of molybdic acid heptahydrate in 200 g of 1,
After heating in 2,4-trichlorobenzene at 140 ° C. for 1 hour, the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with 200 g of acetone, and the precipitate was filtered. The precipitate collected by filtration is 100
After stirring for 1 hour in 0 mL of 5% hydrochloric acid, the mixture was filtered. Then, when washed with 1000 mL of 10% aqueous ammonia and dried, 43 g of azaphthalocyanine was obtained. The azaphthalocyanine was a mixture in which the central metal was copper, about 10% phthalocyanine, about 50% monoazaphthalocyanine, and about 40% diazaphthalocyanine (all of which were peak intensity ratios by mass spectrometry). 43 g of the dried and ground azaphthalocyanine was mixed with 900 g of 30
% Fuming sulfuric acid at room temperature, followed by reaction at 100 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature,
It was added to 0 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 sulfonated azaphthalocyanine.

Example 2 33.3 g of phthalic anhydride, 12.6 g of 2,3-pyridinedicarboxylic acid and 60.1 g of urea, anhydrous copper (II) chloride 2
0.3 g, 1 g of molybdic acid heptahydrate in 200 g of 1,
After heating in 2,4-trichlorobenzene at 140 ° C. for 1 hour, the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with 200 g of acetone, and the precipitate was filtered. The precipitate collected by filtration is 100
After stirring for 1 hour in 0 mL of 5% hydrochloric acid, 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 ground azaphthalocyanine was added to 9 g
100 g of 30% fuming sulfuric acid at room temperature
For 4 hours. After the 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.

Example 3 11.1 g of phthalic anhydride, 37.7 g of 2,3-pyridinedicarboxylic acid, 60.1 g of urea, and anhydrous copper (II) chloride 2
0.3 g, 1 g of molybdic acid heptahydrate in 200 g of 1,
After heating in 2,4-trichlorobenzene at 140 ° C. for 1 hour, the temperature was further raised and reacted at 200 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with 200 g of acetone, and the precipitate was filtered. The precipitate collected by filtration is 100
After stirring for 1 hour in 0 mL of 5% hydrochloric acid, 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 8 g
100 g of 30% fuming sulfuric acid at room temperature
For 4 hours. After the 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 obtained by filtration was washed with 1000 mL of ice water and dried to obtain 40 g of sulfonated azaphthalocyanine.

Example 4 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, irradiation with ultraviolet rays is performed through a mask and then development is performed to form a water-insoluble film having a predetermined pattern to be colored. The optical glass substrate having this coating was immersed in a 0.2% aqueous solution of the compound of Example 1 at 80 ° C. for 10 minutes to be dyed, thereby providing 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. 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 resistance. Further, the concentration change (Δ) after heating on a hot plate at 220 ° C. for 31 minutes.
E) showed very excellent heat resistance at 10 or less. 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 4 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 4 were performed, the color was remarkably changed to red as shown in the results of Table 1, and the color was changed to a color that could not be said to be blue anymore.

Example 5 A glass plate on which a resin was placed in a pattern obtained by the same operation as in Example 4 was dyed in a 0.2% aqueous solution of the compound of Example 2 at 80 ° C. for 10 minutes. A glass plate colored in a blue 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 9% in the vicinity of 460 nm.
0%, indicating good spectral characteristics as a blue portion of the color filter. 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. The density change (ΔE) after heating for 31 minutes on a hot plate at 220 ° C. 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 2 A heat-resistant test was performed on the blue colored portion of the colored glass plate prepared in the same manner as in Example 4 except that the dye was changed to CIAcid Blue 90, according to the method described in Example 5, and the results are shown in Table 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 6 FCR-500 (Fuji Pharmaceutical Co., Ltd.) on optical glass
4 parts of an aqueous gelatin solution), 1 part of an 8% aqueous solution of ammonium dichromate was mixed, and the defoamed photosensitive solution was applied to a thickness of 1 μm by a spin coating method.
After pre-baking for 0 minutes, exposure is performed with an energy amount of 300 mJ / cm 2 using a mask alignment device MA-10 (manufactured by Mikasa Corporation) through a mask having a predetermined pattern, and then developed in warm water at 40 ° C. did. 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 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.
For 1 minute, then treated with 0.1% tartaric acid at 70 ° C. for 5 minutes, and finally treated at 180 ° C. for 5 minutes to fix, thereby providing a first blue colored layer. Next, a photosensitive gelatin layer was provided in the same manner as described above,
After developing, 0.5% aqueous solution of PC Red 136P (a color filter dye manufactured by Nippon Kayaku Co., Ltd.)
After dyeing by immersion for 0 minutes, a fixing and dyeing treatment was performed in the same manner as described above to provide a second red colored layer. Next, another part of the gelatin layer was replaced with PC Green FOP in the same manner as described above.
(Nippon Kayaku Co., Ltd. color filter dye) 0.5
After dyeing in an aqueous solution at 60 ° C. for 15 minutes, a fixation-preventive dyeing treatment was performed to provide a third green colored layer. No blue dye was eluted into the tannic acid bath and the fixing bath which had been subjected to the fixing and dyeing treatment three times.

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. 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.

Comparative Example 3 Example 6 except that the blue dye used to obtain the first blue colored portion was changed to CIAcid Blue 62.
A color filter was produced in the same manner as described above. Then, when the spectral transmittance curve of the blue colored portion of the color filter was measured, it was similar to that of Example 6, but the heat resistance and light resistance tests described in Example 4 were performed. The blue colored portion was noticeably reddish.

Table 1 Samples Light resistance Heat resistance Example 4 9.5 9.3 Example 5 9.3 9.0 Example 6 9.5 9.2 Comparative example 1 160 or more 160 Comparative example 2 120 or more 110 Comparative example 3 55 20

Note) Heat resistance: Hot plate heat treated 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 the azaphthalocyanine compound of the present invention as a blue dye for a color filter,
A color filter on which a blue colored film having both color characteristics, light resistance and heat resistance is mounted can be obtained. That is,
It has the color characteristics of a blue colored layer, and has good resistance to heat applied in the manufacturing process of a device incorporating a color filter and good light resistance required for a final product. An obtained 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 base material to be colored is an acrylic photocurable synthetic resin, but is not limited thereto, and is applicable to a natural base material. it can. Further, there is no elution of the dye from the coloring bath into the fixing bath, which is a problem during the production involving the fixing treatment in the above-mentioned dyeing production process (2), and the fixing and dyeing prevention ability is excellent.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating 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).

[Explanation of symbols]

(A) shows a substrate (glass plate), (b) shows a glass plate provided with a photocurable thin film, and (c) shows a step of irradiating the photocurable thin film with ultraviolet light through a photomask. (d) shows the glass plate provided on the coloring layer, (e) shows the step of dyeing the coloring layer, (f) shows the step of providing a non-staining protective film on the coloring layer, and (g) shows the step of dyeing the coloring layer. (H) providing a colored layer
Represents a step of providing a second non-staining protective film.

Claims (8)

[Claims] A phthalocyanine obtained by sulfonating an azaphthalocyanine compound. 2. The phthalocyanine according to claim 1, wherein the sulfonation is carried out in sulfuric acid containing fuming sulfuric acid. 3. The phthalocyanine according to claim 1, wherein the azaphthalocyanine compound is a compound obtained by reacting a phthalic acid with a pyridinedicarboxylic acid. 4. The phthalocyanine according to claim 3, wherein the ratio of the phthalic acid to the pyridinedicarboxylic acid is 0.2 to 5 mol per 1 mol of the phthalic acid. 5. The phthalocyanine according to claim 3, wherein the phthalic acid is phthalic acid, phthalic anhydride, phthalate or phthalimide. 6. The method according to claim 3, wherein the pyridine dicarboxylic acid is pyridine dicarboxylic acid, pyridine dicarboxylic anhydride or pyridine dicarboxylic imide.
The phthalocyanines according to the above. 7. A color filter colored with the phthalocyanines according to claim 1. Description: 8. An image display device having the color filter according to claim 7.