JPH0583899B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, the present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"). For long-term storage,
The present invention relates to a method for processing a light-sensitive material capable of forming a dye image with excellent storage stability. [Prior art] In general, photosensitive materials undergo color development and color development after image exposure.
It is processed through processing steps such as bleaching, fixing, stabilizing, bleach-fixing, and washing with water, but in the washing step that follows the processing with a processing solution that has fixing ability, it reacts with silver halide to form a water-soluble complex salt. If the compound thiosulfate, other water-soluble silver complex salts, and preservatives such as sulfite and metabisulfite are contained or adhered to the photosensitive material and are brought into the photosensitive material, and the amount of water used for washing is small, image storage stability may be affected. is known to have a negative impact on Therefore, in order to eliminate these drawbacks, the current situation is to use a large amount of running water to wash away the above-mentioned salts from the photosensitive material after processing with a processing solution having a fixing ability. However, in recent years, the amount of flushing water has been reduced due to economic reasons such as lack of water resources, rising sewerage and utility costs, and pollution reasons.
Moreover, a treatment process that takes measures against pollution is desired. Conventionally, as a countermeasure against these problems, for example, a method was proposed in West Germany patent no.
No. 2920222 and SRGoldwasser, “Water Flow Late in Immersion Watching of
Motion picture film (Water Flow)
Rate in Immeraion−Washing of
Motionpicture Film)” SMPTE.Vol.64, 248~
Page 253, May, (1955), etc. A processing method is also known in which preliminary washing is provided immediately after the fixing bath to reduce the amount of pollutants contained in or attached to the photosensitive material that enter the washing process and to reduce the amount of washing water. However, these techniques are not treatment methods that do not use washing water at all. Therefore, in recent years, the depletion of water resources and the rising cost of washing due to rising crude oil prices are becoming increasingly serious problems. On the other hand, there is a processing method in which stabilization processing is performed immediately after photographic processing without washing with water. For example, U.S. Patent No.
Silver stabilization treatment using thiocyanate as described in 3335004 is known. However, this method has the disadvantage that the formed image dye is easily converted into a leuco form because the stabilizing bath contains a large amount of sulfite, which has a large effect on the deterioration of color photographic images. Furthermore, as a method of omitting the washing process or extremely reducing the amount of washing water, there is a multi-stage countercurrent stabilization treatment technology as described in JP-A-57-8543, and as a method of JP-A-58-134636. A treatment technique using a stabilizing liquid containing a bismuth complex salt as described is known. However, although these techniques reduce the amount of stabilizing liquid replenished and reduce pollution, the storage stability of photographic images over time is extremely insufficient, and they are particularly susceptible to deterioration in high temperature and high humidity environments. I understand. Furthermore, it was also found that the above-mentioned problems and yellow stains are more likely to occur due to changes in the amount of replenishment of the stabilizing solution, seasonal variations, concentration of the processing solution due to changes in the processing amount, etc. [Object of the Invention] Accordingly, an object of the present invention is to provide a method for processing photosensitive materials that does not use the technique of flowing washing water indefinitely and that reduces energy cost and pollution load. Another object of the present invention is to provide a method for processing a photosensitive material that can form stable color photographic images during long-term storage without using any washing water. [Structure of the Invention] As a result of extensive research, the inventor of the present invention has discovered that after a photosensitive material is subjected to color development processing, it is processed with a processing solution having fixing ability, and then processed with a stabilization processing step as a substantial final processing step. In the method for processing a photosensitive material, the photosensitive material contains at least one kind of polymer coupler, and the concentration of thiosulfate in the final bath of the stabilization treatment step is 2 x 10 ^-5 to 5.0 x 10 ^-3 mol. /
It has been found that the above object can be achieved by keeping the temperature within the range of . The present invention will be explained in detail below. In the case of a continuous process in which the stabilization process that substantially omits the water washing process is a process in which the stabilization process is performed directly from the fixing or bleach-fixing solution, the fixing solution or bleach-fixing solution components, soluble silver complex salts, and their Large amounts of decomposition products are carried into the stabilizing liquid, which primarily degrades the long-term stability of the photographic image. Therefore, in order to maintain the long-term stability of color images, processing must be carried out to ensure that no fixing solution or bleach-fixing solution components, soluble silver complex salts, or their decomposition products remain in the photosensitive material, and generally sufficient washing with water should be carried out. In the case of stabilization treatment without washing with water, methods of increasing the number of tanks or replenishing a large amount of stabilizing liquid are used. However, these methods contradict the objectives of cost reduction and low pollution as described above, and cannot be said to be preferable methods. Therefore, the stabilization of color images and low-cost, low-pollution stabilization processing seem to have an antinomic relationship, and although many studies have been conducted, sufficient results have not yet been obtained. I haven't reached it yet. The inventors of the present invention conducted intensive research to solve this antinomian characteristic, and found that by using the polymer coupler, which is the coupler of the present invention, the dye image becomes noticeable over time, especially under high temperature and high humidity. Furthermore, in combination with the polymer coupler of the present invention, the presence of a small amount of thiosulfate in the final bath of the stabilization process improves the performance of color images under high temperature and high humidity conditions, rather than the absence of thiosulfate at all. We discovered the surprising fact that stability is improved. This fact was completely unexpected based on conventional knowledge. In the present invention, the stabilization treatment step that does not substantially include a water washing step refers to stabilization treatment using a single tank or multiple tank countercurrent method immediately after treatment with a treatment liquid having fixing ability. Treatment steps other than general water washing, such as rinsing, auxiliary water washing, and known water washing promotion baths, may be included in the pre-steps of the stabilization treatment of the present invention. In the stabilization treatment step of the present invention, the method of bringing the stabilizing liquid into contact with the photosensitive material is preferably to immerse the photosensitive material in a bath in the same way as with general processing liquids.
It may be applied to the emulsion surface of the photosensitive material, both sides of the conveyance leader, and the conveyance belt with a sponge, synthetic fiber cloth, or the like, or it may be sprayed onto the conveyance belt. The case where a stabilizing bath by the immersion method is used will be mainly explained below. In the present invention, the bath or each bath in the stabilization treatment step preferably contains an anti-bacterial agent, a chelating agent, or a metal salt in order to improve image storage stability and prevent liquid spoilage. Depending on the pre-bath components brought into the treatment process, only an anti-vibration agent, an anti-vibration agent and a chelating agent, an anti-vibration agent and a metal salt, or a combination of an anti-vibration agent, a chelating agent and a metal salt, etc. are used. good. Particularly preferably, the stabilizing solution contains an anti-bacterial agent in order to improve the storage durability of the coloring dye made of the coupler of the present invention. As the above-mentioned antibacterial agent, for example, isothiazoline type, benzimidazole type, benzisothiazoline type, thiabendazole type, phenol type, organic halogen-substituted compound, mercapto type compound, benzoic acid and its derivatives, etc. can be used, but isothiazoline type is preferable. Examples include benzisothiazoline, thiabendazole, phenol, and benzoic acid. Particularly preferred are isothiazoline, benzisothiazoline, and thiabendazole. Specific compounds are listed below, but the invention is not limited to these. [Exemplary compounds] (1) 2-methyl-4-isothiazolin-3-one (2) 5-chloro-2-methyl-4-isothiazolin-3-one (3) 2-methyl-5-phenyl-4-isothiazoline -3-one (4) 4-bromo-5-chloro-2-methyl-4-
Isothiazolin-3-one (5) 2-Hydroxymethyl-4-isothiazolin-3-one (6) 2-(2-ethoxyethyl)-4-isothiazolin-3-one (7) 2-(N-methyl-carbamoyl) -4-isothiazolin-3-one (8) 5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-isothiazoline-
3-one(9) 5-chloro-2-(2-phenylethyl)-4
-isothiazolin-3-one (10) 4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one (11) 1,2-benzisothiazolin-3-one (12) 2- (2-bromoethyl)-1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-benzisothiazolin-3-one (14) 2-ethyl-5-nitro-1,2-benzisothiazoline -3-one (15) 2-benzyl-1,2-benzisothiazolin-3-one (16) 5-chloro-1,2-benzisothiazolin-3-one These exemplified compounds are described in U.S. Pat.
No. 2767172, No. 2767173, No. 2767174, No. 2767172, No. 2767173, No. 2767174, No.
2870015, British Patent No. 848130, French Patent No. 1555416, etc., the synthesis method and examples of application to other fields are described. There are also commercially available products such as Topside 300, Topside 600 (manufactured by Permakem Asia),
It can be obtained under the trade names of Fine Inside J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.) and Proxel GXL (manufactured by ICI Corporation). The amount of the above compound used is 0.01 to 1 per stabilizing solution.
Can be used in the range of 50g, preferably
Adding 0.05-20g gives good results. In addition, examples of the chelating agent include polyphosphates, aminopolycarboxylate salts, oxycarboxylate salts, polyhydroxy compounds, organic phosphates, etc. Among them, aminopolycarboxylate salts and organic phosphates are used in the present invention. Good results can be obtained when used. Specific compounds of the chelating agent include, but are not limited to, the following compounds. [Exemplary compounds]

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[Formula] The amount of chelating agent added is 0.05g per stabilizing liquid.
Can be used in the range of ~40g, preferably
It ranges from 0.1 to 20g. Furthermore, as metal salts, Ba, Ca, Ce, Co,
In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg,
It is a metal salt of A, Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The amount used is 1×10 ^-4 to 1× per stabilizing liquid.
10 ^-1 mol, preferably 4 x 10 ^-4 to 2
×10 ^-2 mol, more preferably 8 × 10 ^-4 to 1 × 10 ^-2
It is in the molar range. In addition to the above-mentioned compounds, additions to the stabilizing bath of the present invention include optical brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, water droplet prevention agents such as polyethylene oxide derivatives and siloxane derivatives, PH adjusters such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, organic solvents such as methanol, ethanol, dimethyl sulfoxide, dispersants such as ethylene glycol, polyethylene glycol, etc. It is optional to add various additives to improve and extend the processing effect, such as color tone modifiers. When the method for supplying the stabilizing liquid in the stabilization treatment step according to the present invention is a multi-tank countercurrent system, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The above compounds can be added to the stabilizing tank as a concentrated liquid, or the above compounds and other additives are added to the stabilizing liquid supplied to the stabilizing tank, and then added to the stabilizing liquid. There are various methods such as making it into a liquid, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the photosensitive material to be processed.
It may be added by any method. In the present invention, the pH value of the treatment liquid in each of the stabilizing baths is preferably in the range of PH4 to 8. This is because silver sulfide is more likely to occur below PH4.
This causes problems such as filter clogging. Also
Above pH 8, scale and microorganisms are likely to occur, so the stabilizing bath of the present invention is used within the range of PH 4 to 8. Further, the pH can be adjusted using the above-mentioned pH adjusting agent. The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. In addition, the processing time is preferably as short as possible from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes.
It is preferable that the treatment time is shorter in the earlier stage tank and longer in the later stage tank. There is no need for any water washing treatment before or after the stabilization treatment according to the present invention, but the surface cleaning can be done by rinsing with a small amount of water within an extremely short period of time, or by using a sponge, etc. to stabilize the image and adjust the surface properties of the photosensitive material. A treatment tank can be provided for this purpose. As for stabilizing the image and adjusting the surface properties of the photosensitive material,
Formalin and its derivatives and siloxane derivatives,
Examples include activators such as polyethylene oxide compounds and quaternary salts. The final stabilizing tank in the present invention contains 2×10 ⁻⁵ to 5.0×10 ⁻³ mol/thiosulfate. That is, according to the present invention, the stability of dye images is improved by processing a photosensitive material containing a polymer coupler in a stabilization process that does not include a substantial water washing process. The stability of the dye image is further improved by treating the tank with a processing solution containing thiosulfate in an amount of 2 x 10 ^-5 to 5.0 x 10 ^-3 mol/mol. In the present invention, thiosulfate is contained in the final stabilization tank at a concentration of 2 x 10 ^-5 to 5.0 x 10 ^-3 mol/.
Specifically, in the case of a positive photosensitive material (color photographic paper), the amount of thiosulfate is preferably 2 x 10 ^-5 to 5.0 x 10 ^-3 mol, particularly 1.0 x 10 ^-4 to 3.0 x 10 ^-3 mol. / is preferred. In the case of negative photosensitive materials (color films for photography), the amount is preferably 2 x 10 ^-5 to 2 x 10 ^-3 mol/, more preferably 4.0 x 10 ^-5
It is in the range of ~1.0×10 ⁻³ mol/. The thiosulfate in the final stabilization tank in the present invention may be replenished as a single solution or in parts by a known replenishment method, and when thiosulfate is used as a soluble silver complexing agent in the fixer or bleach-fixer, The thiosulfate in the fixing or bleaching solution carried by the light-sensitive material may be adjusted as desired, and the latter case is preferred. In the present invention, a processing solution having fixing ability is a processing solution containing a soluble complexing agent that is solubilized as a silver halide complex salt, and includes not only a general fixing solution but also a bleach-fixing solution and a one-bath developing solution. Also included are fixers, one-bath development, bleach-fix solutions. Soluble complexing agents include, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioethers, Typical examples include bromide and iodide, but in the present invention it is particularly preferable to include thiosulfate for stabilization of dye images over time, chemical stability, and solubility with silver halide. Desirable for its ability to form complexes. The processing method of the present invention can also be used to process color paper, color reversal paper, color positive film, color negative film, color reversal film, color X-ray film, and the like. The polymer coupler used in the present invention is obtained by polymerizing coupler monomers, and the yellow coupler monomer as the monomer of the yellow polymer coupler is preferably one represented by the following general formula [I], and the cyan coupler The monomers are preferably those represented by the following general formula [] or [], and the magenta coupler monomers are preferably those represented by the following general formula ().

embedded image In the formula, R ₁ represents hydrogen or a methyl group. _R2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, a sulfo group, a carboxy group,
Represents a sulfonamide group, carbamoyl group, sulfamoyl group, or cyan group. R ₃ represents an alkyl group or an aryl group, and X represents a group that leaves when coupled with an oxidized product of an aromatic primary amine developer. For example, hydrogen atoms, halogen atoms,
Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, etc., which are directly bonded to the coupling position via an oxygen atom or a nitrogen atom. Additionally, U.S. Patent No.
No. 3471563, Special Publication No. 36894, No. 1971-
No. 37425, No. 50-10135, No. 50-117422, No. 50
−117422, No. 50-130441, No. 51-108841,
No. 50-120334, No. 52-18315, No. 53-52423
The leaving groups described in No. 53-105226 may also be used. Segment (b) in the previous formula is a yellow coloring component,
Segment (a) represents a group containing a polymerizable vinyl group, at least one of which is substituted at any position relative to (b), and A represents a linking group of -NH- or -O-.

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[Formula] In the general formula [], R ₁ , A, and X have the same meanings as in the general formula [I]. R ₄ and R ₅ have the same meanings as R ₁ and R ₂ shown in general formula [I], respectively. B is a divalent organic group, and n represents 0 or 1. B specifically represents an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene alkylene group having 7 to 24 carbon atoms, and 8 to 32 carbon atoms. or an alkylenebisarylene group having 13 to 34 carbon atoms. In the general formula [], R ₇ and R ₉ each have the same meaning as R ₁ and R ₂ shown in the general formula [I], and X has the same meaning as the general formula [I]. R ₆ and R ₈ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a sulfo group, a carbamoyl group, a carboxy group, a sulfamoyl group, -NH-
A group represented by L (where L is alkoxycarbonyl, alkylcarbamoyl, aliphatic, aromatic,
(represents an acyl group such as a carboxylic acid or sulfonic acid having a heterocycle), an acryloylamino group, a methacryloylamino group, an acryloyloxy group, which may be further substituted with other substituents,
Represents a methacryloyloxy group, etc., but R ₆ and R ₈
At least one of the above is (a) of the general formula [I]
It must have a group having a polymerizable vinyl group as a terminal substituent.

[Chemical Formula] In the general formula [], X has the same meaning as in the general formula [I], and R ₁₀ has the same meaning as R ₂ in the general formula [I].
R ₁₁ has the same meaning as R ₆ and R ₈ in the general formula []. C
is R ₆ or R ₈ of the general formula [] or

It is represented by [Formula]. Here, R ₁ , A, and B have the same meanings as in the general formula [].
m represents an integer of 0 to 3. In the general formula [], at least one of [C] or R ₁₁ must have a group having a polymerizable vinyl group, which is the segment (a) of the general formula [I]. Specific representative examples of coupler monomers are shown below, but the compounds used in the present invention are not limited to these. [Exemplary coupler monomer]

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[Image Omitted] Specific polymer examples of the polymer coupler latex of the present invention obtained from the above-mentioned various coupler monomers are shown below, but the invention is not limited thereto. [Exemplary polymer couplers]

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[C] The amount of the polymer coupler used in the present invention is:
0.005 per mole of silver halide in the emulsion layer
~0.5 mol is preferred. More preferably, it is 0.05 to 0.3 mol. The polymer coupler of the present invention can be used in combination with commonly known photographic couplers such as those shown below. As the photographic cyan coupler that may be used in combination, phenolic compounds and naphthol compounds are preferable, such as U.S. Pat. Nos. 2,369,929 and 2,434,272.
No. 2474293, No. 2895826, No. 3253924,
Same No. 3034892, No. 3311476, No. 3386301, Same No.
No. 3419390, No. 3458315, No. 3476563, No. 3419390, No. 3458315, No. 3476563, No.
You can choose from those listed in No. 3591383, etc.
Methods for synthesizing these compounds are also described in the same publication. Examples of photographic magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As pyrazolone magenta couplers, US Patent Nos. 2600788, 3062653, and
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558318, No. 3684514, No. 3519429, No. 3558318, No. 3684514, No.
No. 3888680, JP-A-49-29639, JP-A No. 49-111631
No. 49-129538, No. 50-13041, Special Publication No. 53
-47167, No. 54-10491, and No. 55-30615; pyrazolotriazole magenta couplers include US Pat. No. 1247493;
For example, the coupler described in Belgian Patent No. 792525 is mentioned, and as a diffusion-resistant colored magenta coupler, a compound having an arylazo substitution at the coupling position of a colorless magenta coupler is generally used. For example, U.S. Pat.
No. 3005712, No. 3684514, British Patent No. 937621
Examples include compounds described in JP-A-49-123625 and JP-A-49-31448. Further US patents
Colored magenta couplers of the type described in No. 3419391, in which the dye flows out into the processing solution by reaction with the oxidized form of a developing agent, can also be used. As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Furthermore, the carbon atom at the coupling position is substituted with a substituent that can leave during the coupling reaction 2
Equivalent type yellow couplers have also been used advantageously. Examples of these are U.S. Pat.
No. 3664841, No. 3408194, No. 3277155,
No. 3447928, No. 3415652, Special Publication No. 49-13576,
JP-A-48-29432, JP-A No. 48-66834, JP-A No. 49-
No. 10736, No. 49-122335, No. 50-28834, No. 50
-132926, etc., along with the synthesis method. The amount of the diffusion-resistant coupler used in the present invention is generally 0 to 1.times.10.sup.- ¹ mol per mol of silver in the light-sensitive silver halide emulsion layer. Various methods can be used to disperse the coupler, such as a so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., and these methods can be selected as appropriate depending on the chemical structure of the coupler, etc. can do. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have long been well known, and the latex dispersion method and its effects have been described in Japanese Patent Application Laid-open No. 74538/1983.
No. 51-59943, No. 54-32552, and Research Disclosure No. 14850 (August 1976), pages 77-779. Suitable latexes include, for example, styrene, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium metasulfate, 3-
(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-2
- Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like. As the oil-in-water vaporization dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied. That is, for example, high-boiling organic solvents with a boiling point of 175°C or higher such as tricresyl phosphate and dibutyl phthalate and/or ethyl acetate,
After dissolving in a low boiling point organic solvent such as butyl propionate alone or in a mixed solvent, it is mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed in a high-speed rotary mixer or colloid mill, and then directly added to a silver halide emulsion. Alternatively, after removing the low boiling point solvent from the emulsified dispersion by a known method, it is added to the silver halide emulsion. Furthermore, as colorless couplers that can be used in combination with the present invention, British Patent No. 861138, British Patent No. 914145, British Patent No. 1109963
No., Special Publication No. 45-14033, U.S. Patent No. 3580722 and Mitsutteilungen Ausden Versiennings Laboratory Endea Agfa
It can be selected from those described in Level Kyusen Vol. 4, pp. 352-367 (1964). Silver halide emulsions that can be used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, or mixtures thereof. Any silver halide may be used. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. Silver halide emulsions include stabilizers, sensitizers, hardeners,
It can contain conventional photographic additives such as sensitizing dyes and surfactants. The support may be anything such as polyethylene coated paper, triacetate film, polyethylene terephthalate film, white polyethylene terephthalate film, etc. In the present invention, the aromatic primary amine color developing agent used in the color developing solution includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds are generally added in a concentration of about 0.1 g to about 30 g per color developer, preferably about 1 g to about 30 g per color developer.
Use at a concentration of approximately 15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. Particularly useful primary aromatic amino color developers are N,N'-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N,N'-dimethyl-p-phenylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching solution or bleach-fixing solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced during development and converts it into silver halide. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. . The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylene diamine Tetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. I can do it. As additives, in particular alkali halides or ammonium halides,
For example, it is desirable to contain a rehalogenating agent metal salt such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, or a chelating agent.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Further, the fixing solution and bleach-fixing solution include ammonium sulfite, potassium sulfite, ammonium bisulfite,
Sulfites such as potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, It may contain one or more PH buffers consisting of various salts such as potassium carbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. The bleach-fixing replenisher may contain these salts and the like and be replenished into the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent,
For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt, such as a fixing solution and a bleach-fixing solution, as well as a stabilizing solution. For example, electrolysis method (described in French patent No. 229967),
Precipitation method (described in JP-A-52-73037, German patent)
2331220), ion exchange method (Japanese Unexamined Patent Publication No. 1983)
-17114, German Patent No. 2548237), metal substitution method (British Patent No. 1353805), etc. can be effectively used. [Examples] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Reference Example 1 Coating silver iodobromide emulsion for negative image formation on cellulose triacetate film Silver amount 25 mg/dm ² , gelatin 25 mg/dm ² , illustrative magenta couplers shown in Table 1 and the following comparative couplers M-(1) ~ (3) is 1/2
A green-sensitive silver halide emulsion layer containing 2.0×10 ^-5 mol/dm ² of tricresyl phosphate (TCP) dissolved and dispersed in 100 g of tricresyl phosphate (TCP) was coated, and on top of that, 4 g of gelatin per 100 ml was applied as a protective layer. A gelatin aqueous solution containing 0.3 g of 1,2-bisvinylsulfonylethane was applied to the sample at a concentration of 15 mg/dm ² of gelatin.
Photosensitive materials Nos. 1 to 12 were produced.

[ka]

[ka]

[C] After applying wedge exposure to the samples Nos. 1 to 12 produced as above, using a modified Noritsu Koki shot leader type automatic film developing machine SRF-60L, they were processed according to the following processing steps. The stabilization treatment was carried out using an automatic processor with a stabilizing bath consisting of three tanks. The obtained film was heated at 65℃ and humidity 80%.
After storage at RH for 3 weeks, the transmission density of the highest density area and the unexposed area was measured using a Sakura Photodensitometer PDA-65 (manufactured by Konishiroku Photo Industries Co., Ltd.), and the rate of decrease in dye density and increase in yellow stain after storage were determined. I asked for The results are shown in Table-1. Processing process Temperature Time (1) Color development 38℃ 3 minutes 15 seconds (2) Bleaching 38℃ 6 minutes 30 seconds (3) Fixing 38℃ 4 minutes 20 seconds (4) Stabilization treatment 38℃ 3 minutes 15 The stabilizing liquid is 5-chloro-2-methyl-4-
A solution prepared by dissolving 1.0 g of isothiazolin-3-one and 20 g of ethylene glycol in 1 part of water was used. As a comparative treatment, a sample subjected to water washing according to the CNK-4 standard treatment was used.

【table】

[Table] Note (1) Expressed as the difference in blue density between before and after storage.
As is clear from the results in Table 1, Samples Nos. 1 to 9 were combined with couplers other than the present invention and water washing treatment.
Compared to Samples Nos. 10 to 10 in which the polymer coupler of the present invention was combined with stabilization treatment, there was a clear decrease in magenta density and yellow staining after storage. Therefore, it can be seen that the effects of the present invention are particularly remarkable when the polymer coupler of the present invention is combined with stabilization treatment. Reference Example 2 8 g of the exemplary cyan coupler of the present invention shown in Table 2 and the following comparative coupler (C-1), 2.0 g of high-boiling organic solvent tricresyl phosphate (hereinafter referred to as TCP), and 20 g of ethyl acetate, A mixed solution to which the required amount of dimethylformamide was added as necessary was heated to 60°C to dissolve it, and then added to 100 ml of a 5% gelatin aqueous solution containing 10 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont). The mixture was mixed and emulsified and dispersed using an ultrasonic dispersion machine to obtain a dispersion liquid. Next, the cyan coupler shown in Table 2 is applied to silver.
The dispersion was added to a silver chlorobromide emulsion (containing 10 mol% silver chloride) at a concentration of 10 mol%, and 1,2-bis(vinylsulfonyl)ethane was added as a hardening agent at a rate of 12 mg per 1 g of gelatin. In addition, the amount of silver coated on the polyethylene coated paper support was 7
It was applied at a concentration of mg/100cm ² . In this way, color paper samples No. 13 to 19 were obtained. This sample was subjected to wedge exposure using a conventional method, and then subjected to the following development treatment. Standard processing steps (processing temperature and processing time) [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 38℃ 1 minute 30 seconds [3] Stabilization treatment 25-30℃ 3 minutes [4] Drying 75 ～80℃ for about 2 minutes Processing solution composition (color developing tank liquid) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5 g 3-methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total volume to 1, and adjust the pH to 10.20. adjust. (Bleach-fix tank solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid. Add water to bring the total volume to 1. (Stabilizing liquid) 1,2-benzisothiazolin-3-one 1 g Ethylene glycol 10 g Stabilization treatment was carried out by modifying RPV204 manufactured by Noritsu Koki Co., Ltd. into a three-tank configuration, and the same evaluation as in Reference Example-1 was conducted. Also, a bleach-fix solution in which ammonium thiosulfate (70%) solution was replaced with ammonium thiocyanate, a stabilizing solution containing 2.0 g of diethylenetriaminepentaacetic acid as a chelating agent, and a stabilizing solution containing 2.0 g of diethylenetriaminepentaacetic acid as a chelating agent and The same evaluation as above was also carried out on a sample in which 0.5 g of bismuth chloride was added as a metal salt.

[Table] As is clear from Table 2, similar to Reference Example 1, only the combination of the polymer coupler of the present invention and the stabilization treatment resulted in a significantly smaller decrease in cyan dye density after storage. Recognize. Furthermore, when the fixing component in the bleach-fix solution was changed to ammonium thiocyanate, the dye density after storage was worse than when ammonium thiosulfate was used as the fixing component. It can be seen that this is effective in enhancing the effects of the present invention. Furthermore, it is clear that the effects of the present invention become even more pronounced by adding a chelating agent alone or both a chelating agent and a metal salt to the stabilizing solution. Example 1 An antihalation layer and a gelalin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer are formed on the triacetate film base. The total amount of silver in the emulsion layer is 100cm ²
It was applied at a dose of 80mg per coat. The emulsion used was prepared from spherical silver halide grains with an average grain size of 1.5 μm. At this time, the exemplary yellow coupler (P-23) was used in the blue-sensitive silver halide emulsion layer, the exemplary magenta coupler (P-13) was used in the green-sensitive silver halide emulsion layer, and the exemplary magenta coupler (P-13) was used in the red-sensitive silver halide emulsion layer. A cyan coupler (P-5) was used in each case.
Each emulsion layer also contains a development inhibitor releasing coupler (DIR).
The following compounds were added as couplers, and conventional additives such as high-boiling solvents, sensitizing dyes, hardeners, and spreading agents were used. The color negative film thus produced is used as the photosensitive material (1) of the present invention.
And so.

[C] Next, the yellow coupler (P-23) used in the photosensitive material (1) is replaced with (P-22), the magenta coupler (P-13) is replaced with (P-14), and the cican coupler (P-14) is replaced with the yellow coupler (P-23) used in the photosensitive material (1). Photosensitive material (2) was prepared in the same manner as photosensitive material (1) except that (P-2) was substituted for (P-2). Next, photosensitive material (3) was prepared in the same manner as photosensitive material (1) except that the yellow, magenta, and cyan couplers used in photosensitive material (1) were replaced with those shown below.
It was created.

[ka]

[Chemical formula] The photosensitive materials (1) to (3) thus prepared were exposed to light in a conventional manner and processed according to the processing steps of Reference Example-1. Note that the reference treatment CNK-4 was used as a treatment comparison. There are four stabilizing baths, the first to fourth tanks are arranged in a cascade system, and a processing bath to which siloxane and formalin are added is provided after the stabilizing bath, and the processing liquid in the processing bath is transferred to the fourth tank of the stabilizing bath. This prevented leakage. Furthermore, the thiosulfate concentration in the fourth tank of the stabilization bath is
3.0×10 ^-4 mo/
The amount of replenishment to the tank was set to 9 ml/min, and the overflow liquid was made to flow into the front tank and be discharged from the first tank. The amount of replenishment to the treatment bath to which the activator and formalin were added was 30 ml/min. However, as the stabilizing liquid, the processing liquid of sample No. 19 used in Reference Example-2 was used. Furthermore, photosensitive materials (1) to (3) are each added at a rate of 50 m ² /day.
The treatment was continued for a week, and then the same evaluation as in Reference Example 1 was performed using the solution. Furthermore, by changing the amount of replenishment of the above stabilizing bath, the thiosulfate concentration in the fourth tank was set to 1×10 ^-6 mol/, 1×10 ^-5 mol/, 2.0× ^{10 -5} mol/, and 3×10 ^-3 mol. /,
The same evaluation as in Reference Example-1 was also performed in the case of 5.0×10 ⁻³ mol/and 1.0×10 ⁻² mol/.

[Table] As is clear from Table 3, even in the multilayer structure of yellow (Y), magenta (M), and cyan (C), the sample obtained by combining the photosensitive material of the present invention and the stabilization treatment after storage The rate of decrease in dye concentration and yellow stain were significantly reduced, and the concentration of thiosulfate in the final stabilization tank was between 2×10 ^-5 and 5×.
It can be seen that when the amount is in the range of 10 ^-3 mol/, the decrease in dye concentration can be further suppressed, and the effects of the present invention can be further enhanced.

Claims (1)

[Claims] 1. After a silver halide color photographic light-sensitive material is subjected to color development processing, it is processed with a processing solution having fixing ability, and then processed in a stabilization processing step as a final processing step without a substantial water washing step. In the method for processing a silver halide color photographic material, the silver halide color photographic material contains at least one polymer coupler, and the concentration of thiosulfate in the final tank of the stabilization treatment step is 2×10 ^-5 ~5.0×10 ^-3
A method for processing a silver halide color photographic material, characterized in that the amount of silver halide is within the range of mol/molar. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing liquid having fixing ability contains a thiosulfate.