JPH07159610A - Production of color filter - Google Patents

Abstract

PURPOSE:To produce a color filter having blue, green and red parts excellent in spectral transmitting characteristics and a black part of high density without blurring by a simple method. CONSTITUTION:This filter is produced in the following steps. A direct positive photosensitive material is exposed for a pattern. The photosensitive material has at least three inner latent image-type silver halide emulsion layers of different color sensitivities on a light-transmitting supporting body. Each silver halide emulsion layer contains one of cyan coupler, magenta coupler or yellow coupler. Then the photosensitive material is developed with a developer containing a developing agent after or while the photosensitive material is subjected to fog treatment with light or a nuclei-producing agent. Then the photosensitive material is bleached, fixed and washed with water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter, and more particularly to a blue region, a green region and a red region having excellent spectral transmittance and a black region having excellent spectral absorption characteristics in a mosaic or stripe pattern. The present invention relates to a method of manufacturing arranged color filters.

[0002]

2. Description of the Related Art Color filters are color face plates for CRT display, photoelectric conversion element plates for copying,
It is used in filters for single-tube color TV cameras, flat panel displays using liquid crystals, color solid-state image sensors, and the like. The commonly used color filters are
The three primary colors of blue, green and red are arranged regularly, but if necessary, there are also four or more hues. For example, a color filter for an image pickup tube or a color filter for a liquid crystal display device requires a black pattern for various purposes.

Conventionally known methods for producing a color filter include a vapor deposition method, a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method and a resist electrodeposition transfer method. However, the color filters obtained by these methods have drawbacks such as requiring complicated manufacturing steps, being prone to pinholes and scratches, and being poor in yield.

In order to solve these drawbacks, an inner type developing method (for example, JP-A-63-261361) and an outer type developing method (for example, JP-A-55-6342) using a silver halide color photographic light-sensitive material are used. The method of manufacturing a color filter by However, since these methods are negative methods, high exposure is required to give high optical density to the black pattern portion or the black stripe portion, and as a result, bleeding occurs in the adjacent blue portion, green portion, or red portion. become.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention has been made to solve the above-mentioned drawbacks and to provide a method of manufacturing a color filter having a black portion without requiring a complicated process. That is, a first object of the present invention is to provide a method for easily producing a color filter by using internal color development in photographic technology, and a second object thereof is blue, green and red without bleeding. Another object of the present invention is to provide a method for producing a color filter having a color filter part and a high density black part.

[0006]

As a result of intensive studies, the inventors of the present invention have found that this can be effectively achieved by performing an internal color development process using a positive type silver halide color light-sensitive material. I found it. That is, an object of the present invention is to have at least three internal latent image type silver halide emulsion layers having different color sensitivities on a light-transmissive support, each of the silver halide emulsion layers being a cyan coupler, Magenta coupler,
After pattern exposure of the emulsion layer of a direct positive light-sensitive material containing any of yellow couplers, after or while performing fogging treatment with light or a nucleating agent, color development with a developer containing a developing agent and bleaching It was achieved by a method for producing a color filter, which comprises fixing and washing with water.

In the internal latent image type silver halide emulsion used in the present invention, the surface of silver halide grains is not previously fogged,
Moreover, it is an emulsion containing silver halide that forms a latent image mainly inside the grain. More specifically, the silver halide emulsion is silvered on a transparent support and coated in an amount of 0.5 to 3 g / m ^2. Then, this was exposed to light for a fixed time of 0.01 to 10 seconds, and the following developer (internal developer) was used at 5 ° C. at 5 ° C.
The maximum density measured by an ordinary photographic density measuring method when developed for a minute was 6 times at 20 ° C. in a developing solution B (surface type developing solution) described below in a developing solution B (surface type developing solution) coated with the same amount as above and similarly exposed. The maximum density obtained when developed for a minute,
Those with a concentration of at least 5 times greater are preferred, more preferably those with a concentration of at least 10 times greater.

Internal developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added to 1 liter Surface developer B Metol 2.5 g L-ascorbin Acid 10g NaBO ₂ .4H ₂ O 35g KBr 1g Add water 1 liter

Specific examples of the inner latent type emulsion include, for example, US Pat. No. 2,592,250 and JP-B-58-54379.
No. 58-3536, No. 60-5582, No. 52-156614, No. 57-79940, and No. 58.
Conversion type silver halide emulsions described in the specification of -70221, and emulsions having shells attached thereto, US Pat. Nos. 3,761,276 and 3,850,6.
No. 37, No. 3,923,513, No. 4,035,18
No. 5, No. 4,395, 478, No. 4,431, 730
No. 4,504,570, JP-A-53-60222.
No. 56-22681, No. 59-208540,
No. 60-107641, No. 61-3137, No. 62
-215272, JP-A 1-282545, Research Disclosure No. 23510 (issued in November 1983), P236, and No. 18155 (issued in May, 1979), P265 to 268. Mention may be made of core / shell type silver halide emulsions internally doped with a metal.

The silver halide grains used in the present invention have a regular crystal form such as a cube, an octahedron, a dodecahedron and a tetradecahedron, an irregular crystal form such as a sphere, and the like. length/
Tabular grains having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide. The silver halide preferably used in the present invention contains no silver iodide or contains 3% mol or less of a salt. It is (iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide.

The average grain size of silver halide grains is 2
It is preferably 0.1 μ or more and less than μ, and particularly preferably 1 μ or less and 0.15 μ or more. The particle size distribution may be narrow or wide, but in order to improve graininess, sharpness, etc., the average particle size ± 4 of the number of particles or weight
It is preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution so that 90% or more of all grains fall within 0%, preferably ± 20%. In an emulsion layer having the same color sensitivity, two or more kinds of monodisperse silver halide emulsions having different grain sizes or a plurality of grains having the same size but having different sensitivities may be mixed in the same layer or multi-layered coated in different layers. It Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or laminated and used.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. For specific examples, see Research
Disclosure magazine No. 17643-III (issued in December 1978) P23, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. For specific examples, see Research
Disclosure magazine No. 17643-IV (issued in December 1978) P23-24, etc.

The photographic emulsion used in the present invention contains an antifoggant or stabilizer for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can Detailed examples are, for example, Research Disclosure No. 1
7643-VI (published December 1978) pages 24-25 and "Stabilization of Photographic Silv" by EJBirr.
er Halide Emulsions "(Focal Press), 1974.

A variety of color couplers can be used to directly form a positive color image. Useful color couplers are compounds that produce or release dyes, preferably substantially non-diffusible dyes, by a coupling reaction with a developing agent, especially an oxidant of an aromatic primary amine color developing agent, As such, it is a substantially non-diffusible compound. Typical types of useful color couplers are naphthol or phenolic compounds, pyrazolone or pyrazolone azole compounds and open chain or heterocyclic ketomethylene compounds. These cyans that can be used in the present invention,
Specific examples of magenta and yellow couplers are “Research Disclosure” magazine No. 17643 (published December 1978), P25VII-D, No. 18717 (1).
(Published November 997) and JP-A-62-215272.
JP-A-3-152530 and the patents cited therein.

Among them, as the yellow coupler which can be used in the present invention, an oxygen atom-releasing type or nitrogen atom-releasing type yellow two-equivalent coupler can be mentioned as a representative. In particular, α-pivaloylacetanilide type couplers are excellent in fastness of color forming dyes, particularly light fastness.
Benzoylacetanilide type couplers are preferred because a high color density can be obtained.

The 5-pyrazolone magenta couplers preferably used in the present invention are 5-pyrazolone couplers in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler). Is.

More preferred are pyrazoloazole type couplers, and among them, US Pat. No. 3,725,067.
Preferred are pyrazolo [5,1-c] [1,2,4] triazoles and the like described in U.S. Pat. No. 4,500,500 in view of low yellow sub-absorption of a coloring dye and light fastness.
The imidazo [1,2-b] pyrazoles described in US Pat. No. 630 are more preferable, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferable. .

Cyan couplers which can be preferably used in the present invention include US Pat. Nos. 2,474,293 and 4,4,293.
Naphthol-based and phenol-based couplers described in No. 052,212, and phenol-based cyan couplers having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in US Pat. No. 3,772,002,
Other 2,5-diacylamino-substituted phenol couplers are preferable in terms of color image fastness.

Specific examples of particularly preferable yellow, magenta and cyan couplers are shown below, but the present invention is not limited to these compounds.

[0022]

[Chemical 1]

[0023]

[Chemical 2]

[0024]

[Chemical 3]

A colored coupler for correcting unnecessary absorption in the short wavelength region of the dye formed, a coupler in which the coloring dye has an appropriate diffusibility, a non-coloring coupler, and a development inhibitor released in association with the coupling reaction. DIR couplers or development accelerator releasing couplers and polymerized couplers can also be used. The standard amount of color coupler used is 0.001 per mol of photosensitive silver halide.
It is in the range of 0.01 to 1 mol, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.5 mol for the magenta coupler, and 0.002 to 0.5 mol for the cyan coupler. .

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, solid dispersion method, alkali dispersion method, latex dispersion method, preferably oil-in-water dispersion method (emulsion dispersion method). Can be mentioned as a typical example.

The light-sensitive material used in the present invention contains a hydroquinone derivative as a color fog preventing agent or a color mixing preventing agent.
Aminophenol derivatives, amines, gallic acid derivatives,
It may contain a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol derivative and the like. Representative examples of color fog preventing agents and color mixing preventing agents are described in JP-A-62-215272.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Typical examples thereof include ethers or ester derivatives in which the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines and these compounds are silylated or alkylated. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In order to prevent deterioration of the yellow dye image by heat, humidity and light, a compound having both partial structures of hindered amine and hindered phenol in the same molecule as described in US Pat. No. 4,268,593 is used. Give good results. In order to prevent the deterioration of the magenta dye image, especially the deterioration by light, spiroindanes described in JP-A-56-159644 and JP-A-55-89835.
The hydroquinone diether or monoether substituted chromans described in US Pat.

Representative examples of these anti-fading agents are disclosed in JP-A-62-62.
No. 215,272. These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding them to the photosensitive layer. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan color developing layer. Further, an ultraviolet absorber can be added to the hydrophilic colloid layer such as the protective layer and also to the photosensitive layer by co-emulsifying with the cyan coupler. Representative examples of the compounds are described in JP-A-62-215273.

Another method of preventing fading is disclosed in JP-A-63-26.
The method described in JP-A No. 1361 and a method of emulsifying and dispersing as a mixed solution in which at least one of a coupler and a water-insoluble organic solvent-soluble homopolymer or copolymer are dissolved can be preferably used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. The coating amount of the hydrophilic colloid is preferably 10 g / m ² or less, more preferably 7 g / m ² or less.

The light-sensitive material of the present invention contains dyes, ultraviolet absorbers, plasticizers, fluorescent whitening agents, matting agents, antifoggants, coating aids, hardeners and antistatic agents for preventing irradiation and halation. Agents and slipperiness improvers can be added. Typical examples of these additives are "Research
Research Disclosure magazine No.17
643 VIII-XIII (issued December 1978) p25-
27 and 18716 (issued in November 1979) p
647-651.

The light-sensitive material used in the present invention comprises at least three emulsion layers (usually a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer) having different color sensitivities on a light-transmissive support.
Each has at least one. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. Sensitivity, infrared sensitivity, etc.) can also be taken.

In the light-sensitive material of the present invention, in addition to the silver halide emulsion layer, it is preferable to appropriately provide auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer and a white reflective layer. .

The other layers of the photographic emulsion layer in the photographic light-sensitive material of the present invention are No. 1 of Research Disclosure Magazine.
No. 7643XVII (issued December 1978) p28 and the supports described in European Patent Nos. 0,182,253 and JP-A 61-97655. Also, Research Disclosure No.17643XV section p
The coating methods described in Nos. 28 to 29 can be used.

The preferred support for use in the present invention has no absorption in the visible light region and is excellent in heat resistance and weather resistance. Specifically, it is glass or PET (polyethylene terephthalate).
And PEN (polyethylene naphthalate). The surface of these supports is generally subbed to improve adhesion with the photographic emulsion layers. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

To prepare color filters of three colors of B, G and R, for the light-sensitive material of the present invention, for example, B, G and R are used.
A surface containing an aromatic primary amine-based color developing agent after being exposed through a mask having a three-color dye and a black portion as a stripe or mosaic pattern, and after or while being subjected to a fogging treatment with light or a nucleating agent. Develop with developer,
A color filter can be obtained by a single operation by bleaching and fixing.

The fogging treatment in the present invention is carried out in the presence of a so-called "light fogging method" for giving a second exposure to the entire surface of the photosensitive layer and a nucleating agent called "chemical fogging method" as described above. Either of the developing methods may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

The entire surface exposure, that is, the fog exposure in the "light fog method" of the present invention is carried out after the pattern exposure, before the developing treatment and / or during the developing treatment. The pattern-exposed light-sensitive material is immersed in a developing solution or in a pre-bath of the developing solution, or is taken out from these solutions and dried before being dried, but exposure in the developing solution is most preferable.

As the light source for the fogging exposure, a light source within the photosensitive wavelength of the photosensitive material may be used, and generally, a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight or the like can be used. In particular, JP-A-56-137350 and 58
A light source having a high color rendering property (as close as possible to white) as described in No. 70223 is preferable. The illuminance of light is 0.0
1 to 2000 lux, preferably 0.05 to 30 lux, and more preferably 0.05 to 5 lux are suitable. Light-sensitive materials using higher sensitivity emulsions are preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, dimming by various filters, changing the distance between the photosensitive material and the light source, or changing the angle between the photosensitive material and the light source. It is also possible to shorten the exposure time by using weak light at the beginning of exposure and then using stronger light.

It is preferable to immerse the light-sensitive material in a developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the penetration of the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1
Minutes, more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.0
It is 1 second to 2 minutes, preferably 0.1 second to 1 minute, and more preferably 1 second to 40 seconds.

As the nucleating agent which can be used in the present invention, all compounds conventionally developed for the purpose of nucleating an internal latent silver halide can be applied. Two or more nucleating agents may be used in combination. More specifically, examples of the nucleating agent include “Research Disclosure” (Rese
arch Disclosure) No.22,534 (published January 1983, pages 50-54) No.15,162 (January 1976)
Issued in January, pages 76 to 77) and No. 23,510 (1)
, Pp. 346-352, issued in November 983), which are roughly classified into three types: quaternary heterocyclic compounds, hydrazine compounds and other compounds. Details of these compounds are described in the above-mentioned documents and JP-A-63-91337.

Specific examples of the nucleating agent are shown below, but the nucleating agent is not limited to these. (I-1), 6-ethoxy-2-methyl-1-propargylquinolinium bromide (I-2), 2,4-dimethyl-1-propargylquinolinium bromide (I-3), 2-methyl- 1- {3- [2- (4-methylphenyl) hydrazono] butyl} quinolinium iodide (I-4), 3,4-dimethyl-dihydropyrido [2,
1-b] benzothiazolium bromide (I-5), 6-ethoxythiocarbonylamino-2-
Methyl-1-propargylquinolinium trifluoromethanesulfonate (I-6), 2-methyl-6- (3-phenylthioureido) -1-propargylquinolinium bromide (I-7), 6- (5- Benzotriazolecarboxamide) -2-methyl-1-propargylquinolinium
Trifluoromethanesulfonate (I-8), 6- [3- (2-mercaptoethyl) ureido] -2-methyl-1-propargylquinolinium
Trifluoromethanesulfonate (I-9), 6- {3- [3- (5-mercapto-thiadiazol-2-ylthio) propyl] ureido} -2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (I-10), 6- (5-mercaptotetrazole-1-
Yl) -2-methyl-1-propargylquinolinium
Iodide

(II-1), 1-formyl-2- {4-
[3- (2-Methoxyphenyl) ureido] -phenyl} hydrazine (II-2), 1-formyl-2- {4- [3- {3-
[3- (2,4-di-tert-pentylphenoxy) propyl] ureido} phenylsulfonylamino] -phenyl} hydrazine (II-3), 1-formyl-2- {4- [3- (5-mercaptotetrazole -1-yl) benzamido] phenyl} hydrazine (II-4), 1-formyl-2- [4- {3- [3-
(5-Mercaptotetrazol-1-yl) phenyl]
Ureido} phenyl] hydrazine (II-5), 1-formyl-2- [4- {3- [N-
(5-Mercapto-4-methyl-1,2,4-triazol-3-yl) carbamoyl] propanamide} phenyl] hydrazine (II-6), 1-formyl-2- {4- [3- {N-
[4- (3-mercapto-1,2,4-triazole-
4-yl) phenyl] carbamoyl} -propanamide] phenyl} hydrazine (II-7), 1-formyl-2- [4- {3- [N-
(5-mercapto-1,3,4-thiadiazole-2-
Ill) carbamoyl] propanamide} phenyl] hydrazine (II-8), 2- [4- (benzotriazole-5-carboxamido) phenyl] -1-formylhydrazine (II-9), 2- [4- {3- [N- (benzotriazole-5-carboxamido) carbamoyl] propanamide} phenyl] -1-formylhydrazine (II-10), 1-formyl-2- {4- [1- (N-phenylcarbamoyl) thiosemicarbazide] Phenyl}
Hydrazine (II-11), 1-formyl-2- {4- [3- (3-phenylthioureido) benzamido] phenyl} hydrazine (II-12), 1-formyl-2- [4- (3-hexyl) Ureido) phenyl] hydrazine

The nucleating agent used in the present invention can be contained in the light-sensitive material or the processing liquid for the light-sensitive material, and preferably in the light-sensitive material.

When it is contained in the light-sensitive material, it is preferably added to the inner latent type silver halide emulsion layer, but as long as it is diffused during coating or during processing and the nucleating agent is adsorbed on the silver halide, Layer may be added to, for example, an intermediate layer, an undercoat layer or a back layer. When the nucleating agent is added to the processing solution, it may be contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350.

When a nucleating agent is contained in the light-sensitive material, its use
The amount is 10 per mol of silver halide. ^-8-10^-2Mol is good
More preferably, and more preferably 10^-7-10^-3It is a mole.

When the nucleating agent is added to the treatment liquid, the amount used is preferably 10 ^-5 to 10 ^-1 mol, and more preferably 10 ^-4 to 10 ^-2 mol per liter.

The following compounds can be added for the purpose of increasing the maximum image density, decreasing the minimum image density, improving the storage stability of the light-sensitive material, or speeding up the development.

Hydroquinones (for example, compounds described in US Pat. Nos. 3,227,552 and 4,279,987): Chromans (for example, US Pat. No. 4,268,6)
21, JP-A-54-103031, Research Disclosure No. 18264 (issued in June 1979).
Compounds described on pages 333 to 334) Quinones (for example, Research Disclosure No. 21206 (1981)
Compounds described on pages 433 to 434, December 2013: Amines (for example, U.S. Pat. No. 4,150,993 and JP-A-58-1).
74757): Oxidizing agents (for example, JP-A-60-260039, Research Disclosure)
No. 16936 (compounds described on pages 10 to 11 of May 1978): catechols (for example, JP-A-55-2)
1013 and 55-65944, compounds described):
A compound which releases a nucleating agent during development (for example, JP-A-60
-107029): thioureas (for example, compounds described in JP-A-60-95533): spirobisindanes (for example, compounds described in JP-A-55-65944).

The nucleation accelerator which can be used in the present invention includes tetrazaindenes, triazaindenes and triazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. Pentazaindenes and JP-A-61-136948
No. 63-106656 and No. 63-81337.

Specific examples of the nucleation accelerator are shown below, but the invention is not limited thereto. (A-1) 3-mercapto-1,2,4-triazolo [4,5-a] pyridine (A-2) 3-mercapto-1,2,4-triazolo [4,5-a] pyrimidine (A-1) -3) 5-mercapto-1,2,4-triazolo [1,5-a] pyrimidine (A-4) 7- (2-dimethylaminoethyl) -5-mercapto-1,2,4-triazolo [1 , 5-a] Pyrimidine (A-5) 3-mercapto-7-methyl-1,2,4-
Triazolo [4,5-a] pyrimidine (A-6) 3,6-dimercapto-1,2,4-triazolo [4,5-b] pyridazine (A-7) 2-mercapto-5-methylthio-1, Three
4-thiadiazole (A-8) 3-mercapto-4-methyl-1,2,4-
Triazole (A-9) 2- (3-dimethylaminopropylthio)-
5-Mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2- (2-morpholinoethylthio) -5-mercapto-1,3,4-thiadiazole hydrochloride (A-11) 2-mercapto- 5-Methylthiomethylthio-1,3,4-thiadiazole sodium salt (A-12) 4- (2-morpholinoethyl) -3-mercapto-1,2,4-triazole (A-13) 2- [2- ( 2-Dimethylaminoethylthio) ethylthio] -5-mercapto-1,3,4-thiadiazole hydrochloride

In this case, the nucleation accelerator is preferably added in the silver halide emulsion or in the layer adjacent thereto.

The amount of the nucleation accelerator added is preferably 10 ^-6 to 10 ^-2 mol, and more preferably 1 mol, per mol of silver halide.
It is 0 ^-5 to 10 ^-2 mol.

When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, it is preferably 10 ^-8 to 10 ^-3 mol per liter, more preferably 10 ^-7.
It is from 10 to ⁴ mol.

Further, two or more kinds of nucleation accelerators can be used in combination.

The color developing solution used in the color development processing of the light-sensitive material in the present invention contains substantially no silver halide solvent, and contains a developing agent, preferably an aromatic primary amine color developing agent as the main component. It is a solution. Although aminophenol compounds are also useful as color developing agents, p-phenenediamine compounds are preferred. As typical examples thereof, 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline, 3-methyl-4-amino-N-ethyl-N- (β-
Examples thereof include hydroxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides. Other color developing agents include L.I. F. A. Mason, "Photographic Processing Chemistry," Focal Press, Inc. (1966) (LFA Mason "
Photographic Processing Chemistry ", Focal Press)
226-229, U.S. Pat. No. 2,193,015,
Those described in JP-A No. 2,592,364 and JP-A-48-64933 may be used. If desired, two or more color developing agents can be used in combination.

The amount of color developing agent used is 0.1 to 20 g, and more preferably 0.5, per liter of the developing solution.
g to 15 g.

Further, as a preservative, JP-A-52-498
No. 28, No. 56-46038, No. 56-32140
No. 59-160142 and US Pat. No. 374654.
Aromatic polyhydroxy compounds described in US Pat. No. 4, U.S. Pat.
Hydroxyacetones described in JP 615,503 and British Patent 1,306,176; JP-A-52-143020.
.Alpha.-aminocarbonyl compounds described in JP-A Nos. 57-44148 and 57-53.
Various metals described in 749, etc .; JP-A-52-1027
No. 27, various saccharides; No. 52-27638, hydroxamic acids; No. 59-160141, α-
α'-dicarbonyl compound; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3532; poly (alkyleneimine) s described in No. 56-94349; glucone described in No. 56-75647 An acid derivative etc. can be mentioned. Two or more kinds of these preservatives may be used in combination, if necessary. Especially 4,5-
Addition of dihydroxy-m-benzenesulfonic acid, poly (ethyleneimine), triethanolamine and the like is preferable. Further, it is preferable to add a substituted phenol such as p-nitrophenol. Further, it is also preferable to use the alkylhydroxylamine compound described in JP-A-54-3532. In particular, the alkylhydroxylamine compound is preferably used in combination with the above preservative.

The amount of these preservatives used is 0.1 to 20 g, and more preferably 0.5, per liter of the developing solution.
It is from g to 10 g.

The pH of the color developing solution of the present invention is 9 to 14
The range of 9.5 to 12.
0, particularly preferably 9.8 to 11.5. Above pH
Various buffering agents can be used to retain the. Examples of the buffer include carbonates such as potassium carbonate, phosphates such as potassium phosphate, and the like. JP-A-62-2152
The compounds described in No. 72, pages 11 to 22 can be used.

Further, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium or for improving the stability of the color developing solution.

As the chelating agent, for example, JP-B-48-
030496 and 44-30232 aminopolycarboxylic acids, JP-A-56-97347, JP-B-56-39359 and West German Patent 2,227,639.
Organic phosphonic acids described in JP-A-52-102726
No. 53-42730, No. 54-12127,
Phosphonocarboxylic acids described in JP-A-55-126241 and JP-A-55-69556, and others, JP-A-58-1
No. 95845, No. 58-203440, Japanese Patent Publication No. 53-4
Examples thereof include compounds described in No. 0900. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter.

Any development accelerator can be added to the color developing solution if necessary.

As the development accelerator, Japanese Examined Patent Publication No. 37-160
88, 37-5987, 38-7826, 44-12380, 45-9019, and U.S. Pat. No. 3,813,247; thioether compounds; JP-A-52-49829, and JP-A-52-49829. No. 15554, p-phenylenediamine compounds, JP-A-50-
137726, JP-B-44-30074, JP-A-5
Quaternary ammonium salts described in US Pat. Nos. 6,156,826 and 52-43429; US Pat.
And p-aminophenols described in U.S. Pat. Nos. 4,119,462; U.S. Pat. Nos. 2,494,903 and 3,12.
8,182, 4,230,796, 3,25
3, 919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346; amine compounds described in Japanese Patent Publication No. 37-16088. 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431,
42-23883 and U.S. Pat. No. 3,532,501.
Polyalkylene oxide, etc.,
If necessary, phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, thione compounds, imidazoles, etc. can be added. Particularly, thioether compounds and 1-phenyl-3-pyrazolidones are preferable.

In the present invention, an optional antifoggant can be added to the color developing solution, if necessary. As the antifoggant, alkali metal halides such as potassium bromide, sodium chloride and potassium iodide and organic antifoggants may be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5
Nitrogen-containing heterocyclic compounds such as -nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolidine and , 2-mercaptobenzimidazole, mercapto-substituted heterocyclic compounds such as 2-mercaptobenzothiazole, adenine and mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants may be eluted from the color light-sensitive material during processing and may be accumulated in the color developing solution, but in terms of reduction of emission amount,
It is preferable that the amount of these accumulated is small.

The color developing solution of the present invention preferably contains a fluorescent whitening agent. As a fluorescent whitening agent, 4,4-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / liter, preferably 0.1
g-2 g / liter.

If necessary, alkylphosphonic acid,
Various surfactants such as arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be carried out simultaneously with the fixing process by one-bath bleach-fixing process or separately. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used. Aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or the bleach-fixing solution of the present invention. Additives used in the bleaching solution or the bleach-fixing solution of the present invention are described in JP-A-62-215272, No. 2
Various compounds described on pages 2 to 30 can be used. After the desilvering process (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. It is preferable to use softened water as the washing water or the stabilizing solution. Examples of the water softening treatment method include a method using an ion exchange resin or a reverse osmosis device described in JP-A-62-288838.

In order to prevent the mixing of metal ions, alkali metal ions and alkaline earth metal ions into the color filter for liquid crystal display and the filter for solid-state image pickup device, it is necessary to sufficiently wash with water containing almost no such ions. preferable.

It is preferable that the amount of the replenisher in each processing step is small. The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 30 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.

The color filter produced according to the present invention may have an oxygen barrier layer described in JP-A-4-309902 on the surface thereof. Further, when the color filter produced according to the present invention is used as a liquid crystal display, another overcoat and an alignment film can be provided on the color filter.

[0075]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these. Example 1 A transparent borosilicate glass substrate (30 cm × 30 c) having a thickness of 1.1 mm
m) was sequentially coated with the following first to seventh layers to prepare a color filter light-sensitive material. The components and the coating amount (g / m ² unit) are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is the emulsion E described below.
It was prepared according to the production method of M1.

First Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.3 μ, size distribution [variation coefficient] 8%, 8 .Hedron) ... 0.38 gelatin ... 0.95 cyan coupler (ExC-1) ... 0.33 cyan coupler (ExC-2) ... 0.37 anti-fading agent (Cpd-1). ..0.05 Anti-fading agent (Cpd-2) ... 0.12 High boiling point solvent (Solv-1) ... 0.35

Second layer (intermediate layer) Gelatin: 0.57 Color mixing inhibitor (Cpd-3): 0.08 High boiling point solvent (Solv-1): 0.05 High boiling point solvent (Solv) -2) ... 0.13

Third Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.32 μ, size distribution 8%, octahedron) ... 42 Gelatin ・ ・ ・ 1.05 Magenta coupler (ExM-1) ・ ・ ・ 0.41 Anti-fading agent (Cpd-4) ・ ・ ・ 0.46 Anti-stain agent (Cpd-5) ・ ・ ・ 0.02 Stain Inhibitor (Cpd-6) ・ ・ ・ 0.04 Anti-fading agent (Cpd-7) ・ ・ ・ 0.06 High boiling point solvent (Solv-2) ・ ・ ・ 1.11 High boiling point solvent (Solv-3) ・.. 0.29

Fourth layer (intermediate layer) Gelatin: 0.57 Color mixing inhibitor (Cpd-3): 0.08 High boiling point solvent (Solv-1): 0.05 High boiling point solvent (Solv) -2) ... 0.12 UV absorber (Cpd-1) ... 0.01 UV absorber (Cpd-8) ... 0.02 UV absorber (Cpd-9) ... 0. 06 UV absorber (Cpd-10) ... 0.04 Polymer (Cpd-11) ... 0.05 Yellow dye (YF-1) ... 0.15

Fifth Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.45 μ, size distribution 8%, octahedron) ... 0 .54 Gelatin ... 1.14 Yellow coupler (ExY-1) ... 1.02 Anti-fading agent (Cpd-12) ... 0.13 Anti-staining agent (Cpd-7) ... 0.06 Polymer (Cpd-13) ... 0.12 High boiling point solvent (Solv-4) ... 0.36

Sixth Layer (UV Absorbing Layer) Gelatin ... 0.36 UV Absorbing Agent (Cpd-1) ... 0.01 UV Absorbing Agent (Cpd-8) ... 0.02 UV Absorbing Agent ( Cpd-9) ... 0.06 UV absorber (Cpd-10) ... 0.03 Polymer (Cpd-11) ... 0.05 Irradiation prevention dye (Dye-1, 2, 3, 4 in a molar ratio of 10: 10: 13: 15) ... 0.04

Seventh Layer (Protective Layer) Gelatin ... 0.35 Fluorosurfactant (Cpd-14) Hardener (H-1) ... 0.12

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 60 ° C. over 8 minutes with vigorous stirring, and octahedral silver bromide having an average particle size of 0.15 μm was added. The particles were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mol of silver. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were successively added per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the grains thus obtained as a core, the grains were further grown in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.32 μ was obtained. The coefficient of variation of particle size was about 8%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was mixed at 60 ° C. for 6 hours.
The mixture was heated for 0 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
^10-2 wt%, Cpd-15 ^10-2 as nucleation accelerator
Used by weight%. Also, as a stabilizer of silver halide, Cpd
-16 was added. Further, in each layer, sodium dodecylbenzene sulfonate as an emulsification dispersion aid, ethyl acetate as an auxiliary solvent, Cpd-17 as a coating aid, and potassium polystyrene sulfonate as a thickening agent were used.

[0085]

[Chemical 4]

[0086]

[Chemical 5]

[0087]

[Chemical 6]

[0088]

[Chemical 7]

[0089]

[Chemical 8]

[0090]

[Chemical 9]

The light-sensitive material prepared as described above was overlaid with a mask for a color filter composed of a blue portion, a green portion, a red portion and a black portion, and exposed with tungsten light. The exposed light-sensitive material was developed according to the following steps, and B, G, R three colors and black color filters were produced in one operation. (Processing step) (Temperature) (Time) Color development 38 ° C 3 minutes 30 seconds Bleach fixing 38 ° C 1 minute Water wash-1 35 ° C 40 seconds Water wash-2 35 ° C 40 seconds Dry 60 ° C 2 minutes

The composition of each processing solution is as follows. Color developer D-Sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Ethylenediaminetetrakismethylenephosphonic acid 1.5 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.80 g Benzotriazole 0.003 g Sodium sulfite 2.4 g N, N-bis (carboxymethyl) hydrazine 6.0 g D-glucose 2.0 g triethanolamine 6.0 g N-ethyl-N-hydroxyethyl-4-aminoaniline sulphate 4.2 g potassium carbonate 30. 0g Add water 1 liter pH (25 ℃) = 10.5

Bleach-fixing solution Ethylenediaminetetraacetic acid / sodium dihydrate / 4.0 g Ethylenediaminetetraacetic acid / ferric ammonium / dihydrate 70.0 g Ammonium thiosulfate (700 g / liter) 180 ml Sodium p-toluenesulfinate 20. 0 g sodium bisulfite 20.0 g 5-mercapto-1,3,4-triazole 0.5 g ammonium nitrate 10.0 g Water was added to 1 liter pH (25 ° C.) = 6.2

Washing water Deionized water having an electric conductivity of 5 μS or less

When the spectral absorption of the color-developed color image was measured, a color filter having an excellent hue and no bleeding was obtained as shown in FIG. Example 2 The composition of the color developing solution was changed as follows, and the color developing solution was changed to 150
When the same light-sensitive material as in Example 1 was used, except that the second color development processing was carried out, the same processing was carried out. As a result, a color filter excellent in spectral characteristics and free from bleeding was obtained.

Color developer D-Sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Nitrilotris (methylenephosphonic acid) 5 sodium salt 1.80 g Diethylenetriamine 5 acetic acid 0.50 g 1-Hydroxyethylidene-1,1 -Diphosphonic acid 0.15 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.0 g Tri Ethanolamine 6.00 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.00 g potassium carbonate 30.0 g Water was added 1 Li Le pH (25 ℃) = 10.3

[0097]

According to the present invention, blue having excellent spectral transmission characteristics,
A color filter having green and red and a high density black portion and having no blur can be obtained by an extremely simple production process.

[Brief description of drawings]

FIG. 1 shows a spectral transmission characteristic curve of a color filter prepared according to the present invention. In the figure, the vertical axis represents the transmittance and the horizontal axis represents the wavelength.

Claims (1)

[Claims] 1. A light-transmissive support having at least three internal latent image type silver halide emulsion layers having different color sensitivities, each silver halide emulsion layer having a cyan coupler and a magenta coupler. After pattern exposure to the emulsion layer of a direct positive light-sensitive material containing any of the yellow couplers,
After or while performing a fogging treatment with light or a nucleating agent, color development is performed with a developer containing a developing agent, and bleaching / fixing,
A method for producing a color filter, which comprises performing a washing treatment with water.