JPS60239748A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To stop use of rinse water, and to reduce energy cost and cost for controlling environmental pollution by incorporating at least one kind of a polymer coupler in a photosensitive material. CONSTITUTION:It is desirable to add an antimold agent, a chelating agent, or a metal salt to a bath or each bath of a stabilization processing step for the purpose of enhancing image retentivity, preventing putrefaction of the solution, etc., and in accordance with the component of the preceding bath to be brought to this step, only the antimold agent, a combination of the antimold agent and the chelating agent, or a combination of said 3 are used, and, especially preferably, the antimold agent is incoporated in the stabilization soln. in order to enhance the storage stability and durability of a color developing dye made of a coupler. As the antimold agent, e.g., those of isothiazoline type, benzimidazole type, benzoic acid and its derivs., can be used, and it is preferable to use those of an isothiazoline type, a benzisothiazoline type, benzoic acid, etc.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, a method for omitting the water washing step and for long-term storage after processing. On the other hand,
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] Generally, after image exposure, photosensitive materials are processed through processing steps such as color development, bleaching, fixing, stabilization, bleach-fixing, and washing with water. In photosensitive materials, thiosulfates, which are compounds that react with silver halides to form water-soluble complex salts, other water-soluble silver complexes, and preservatives such as sulfites and metabisulfites are used in photosensitive materials. It is known that if the amount of water used for rinsing is small, it will have a negative effect on image storage stability. 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, there has been a desire for a treatment process that reduces the amount of washing water and takes measures against pollution due to economic reasons such as a shortage of water resources, rising sewerage charges and utility costs, and pollution reasons. Conventionally, as a countermeasure against these problems, for example, a method of arranging the washing tank in a multi-stage structure and causing water to flow countercurrently was proposed in West German Patent No. 2, 920.2.
No. 22 and varnish Φ Earl Gold Basser (S, R
, Goldwasser), Water Flow Late In Fist Immersion Watching Op Motion Picture Film (Water Flow
Rate in Immersion-Wa8hi
ngof Motionpictura Film)
J SMPTE, Vol. 64, pages 248-253, May, (1955), etc. In addition, a pre-wash is provided immediately after the fixing bath to reduce the amount of polluting components contained in or attached to the photosensitive material that enter the washing process, and to reduce the amount of water used for washing. Processing methods for reducing this are also known. 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 increase in the cost of washing due to the rise in the price of crude oil are becoming more and more serious. 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. 3.335,0
Silver stabilization treatment using thiocyanate as described in No. 04 specification is known. However, this method has the disadvantage that the formed image dye is easily converted to leuco form because the stabilizing bath contains a large amount of sulfite, which can have a large effect on the deterioration of color photographic images. 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 such as that described in JP-A-57-8543, and JP-A-58.
A treatment technique using a stabilizing liquid containing a bismuth complex salt as described in Japanese Patent No. 134636 is known. However, in the case of ISUNE, although this technology reduces the amount of replenishment of the stabilizing liquid and aims to reduce pollution, the storage stability of photographic images over time is extremely insufficient, and they deteriorate particularly under high temperature and high humidity conditions. I found it easy. Furthermore, it has been found that the above-mentioned problem and yellow stain are more likely to occur due to changes in the replenishment amount of the stabilizing solution, seasonal fluctuations, and concentration and pressure equalization of the processing solution due to fluctuations in the throughput. [Purpose of the Invention] Accordingly, an object of the present invention is to provide a method for processing photosensitive materials that does not use any washing water and has low energy costs and low pollution loads. Another object of the present invention is to provide a method for processing a photosensitive material that can form a color photographic image that is stable during long-term storage without using any washing water. As a result of extensive research, we have developed a method for processing photosensitive materials in which the material is subjected to color development processing, then processed with a processing solution that has fixing ability, and then processed through a stabilization processing step that includes a substantial water washing step. The photosensitive material contains at least 1
It has been found that the above object is achieved by including a variety of polymeric couplers 't-'. Furthermore, in a more preferred embodiment, the treatment liquid having fixing ability contains thiosulfate, and the concentration of thiosulfate in the final tank of the stabilization treatment step is 2×10 to 5.0X.
It has also been found that a range of 10 mol provides a very desirable effect for the present invention. 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 solution, which generally deteriorates the long-term stability of the photographic image. Therefore, in order to maintain the long-term stability of color images, it is necessary to carry out treatments such that no fixer or bleach-fixer components, soluble silver complex salts, or their decomposition products remain in the photosensitive material, and generally to perform sufficient washing with water. When performing stabilization treatment without washing with water, a method is used in which a large amount of stabilizing solution is supplemented by increasing the number of times. However, these methods contradict the objectives of reducing costs and reducing pollution, as mentioned above.
This is not a desirable method. Therefore, the stabilization of color images and stabilization processing that achieves low cost and low pollution are considered to be in an antinomic relationship, and although many studies have been conducted, sufficient results have not yet been obtained. It has not reached that point. 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, even if thiosulfate is not present at all, it is better to have some thiosulfate present in the final tank of the stabilization process to improve the performance of color images under high temperature and high humidity conditions. We discovered the surprising fact that the stability of This fact was completely unexpected from conventional knowledge. In the present invention, the stabilization process that does not substantially include a water washing process refers to a stabilization process using a single-tank or multiple-tank countercurrent system immediately after treatment with a treatment liquid having fixing ability. However, it may also include processing steps other than general washing, such as rinsing, auxiliary water washing, and known washing accelerator baths. It is preferable to immerse the photosensitive material in the same processing solution as in the above treatment solution, but it may also be applied to the emulsion surface of the photosensitive material, both surfaces of the transport leader, and the transport belt using a sponge, synthetic fiber cloth, etc., or it may be applied by spraying. In the following, the case where a stabilizing bath by the immersion method is used will be mainly explained. To prevent rot, etc., anti-pyre agent,
Preferably, a chelating agent or a metal salt is included; depending on the pre-bath components brought into the stabilization process, the anti-pie agent alone, the anti-pie agent and a chelating agent, the anti-pie agent and a metal salt, or the anti-pie agent and a chelate. Combinations of agents and metal salts, etc. may be used. Particularly preferably, the stabilizing solution contains an anti-pecking agent in order to improve the storage durability of the coloring dye of the present invention. As the anti-spiking agent, for example, isothiazoline type, benzimidazole type, benzintiazoline type, thiabendazole type, phenol type, organic halogen-substituted compound, mercapto type compound, benzoic acid and its derivatives, etc. can be used, but preferably inthiazoline series, pentinthiazoline series, thiabendazole series, phenol series,
Examples include benzoic acid, etc. 6 Particularly preferred are inthiazoline, pentwinthiazoline, and thiabendazole. Specific compounds are listed below, but the invention is not limited to these. [Exemplary compounds] (1) 2-methyl-4-inchacyly/-3-one (2) 5-chloro-2-methyl-4-inchiazoline-
3-one (3) 2-methyl-5-phenyl-4-thiazolin-3-one (4) 4-bromo-5-chloro-2-methyl-4-ythiazolin-3-one (5) 2- and droxymethyl -4-inthiazoline-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-inthiazolin-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-Benzothiacylin-3-o/(
12) 2-(2-bromoethyl)-1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-penzisothiazolin-3-one (14) 2-ethyl-5-nitro-1 , 2-benzisothiazolin-3-one (15) 2-benzyl-1,2-benzisothiazolin-3-one (16) 5-chloroo-1J-benzisothiazolin-
3-one These exemplary compounds are described in U.S. Pat. No. 2,767.
No. 172, 2.7 ti No. 7,173, 2.76
No. 7゜174, No. 2,870,015, British Patent No. 8
48.130, French Patent No. 1,555,
No. 416 specifications and the like describe its synthesis method and examples of its application to other fields. There are also some commercially available
Topside 300, Topside 600 (manufactured by Permakem Asia Co., Ltd.), Fineside J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.), Proxel GXL (1
, C, I). The amount of the above compound used is 1) per lt of stabilizing solution, 01 to 50
It can be used within the range of g, preferably from 0.05 to
Adding 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. The following margin [Exemplary compounds] H5 (a) H2O5P-C-po5H2 HC,H5 (c) HOOC-C-PO5H2 ■H The amount of chelating agent added is 450.05 g per stabilizing solution 1.
Can be used in the range of 40g, preferably 0.1
~20g ◇ 1. Metal salts include Ha, Ca, Ce,
C. , In, La, Mn, Ni, Pb
, Sn, Zn. Metal salts of Ti, Zr, Mg, Al, Sr 1, halides, hydroxides, sulfates, carbonates,
It can be supplied as an inorganic salt such as phosphate or acetate or as a water-soluble chelating agent. The amount to be used is in the range of 1 x 10 to 1 x 10 mol per stabilizing solution, preferably 4 x 10 to 2 x 10 mol, more preferably 8 x 10 to 1 x 10 mol.
In addition to the above compounds, fluorescent brighteners, organic sulfur compounds, onium salts, 1ifl agents, quaternary salts, polyethylene oxide derivatives, and siloxane derivatives are added to the stabilizing bath of the present invention in a range of 1×10 mol. Water droplet prevention agents such as boric acid, citric acid, phosphoric acid, acetic acid, and sodium hydroxide, sodium acetate, potassium citrate, etc.
Add various additives to improve and extend the processing effect, such as I (M additive), organic solvents such as methanol, ethanol, and dimethyl sulfoxide, dispersants such as ethylene glycol, polyethylene glycol, and other color tone adjusting agents. When the method of supplying the stabilizing liquid in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath.
The above compounds can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives are added to the stabilization liquid supplied to the stabilization tank, and this is added as a supply liquid to the stabilization liquid. There are various ways to add it, such as adding it to the prebath of the stabilization process, or adding it to the photosensitive material to be processed and making it exist in the stabilization tank. good. In the present invention, the pH value of the treatment liquid in each of the stabilizing baths is preferably in the range of pH 4 to 8.
Below this level, silver sulfide is generated, causing problems such as sagging and clogging of filters. Furthermore, since water scale and microorganisms are likely to occur above pH 8, the stabilizing bath of the present invention is used within the pH range of 4 to 8. Further, the pH can be adjusted using the above-mentioned pH adjusting agent. The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, a short treatment time is preferable, but usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes. Preferably, the time is long. 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. Examples of the agent for stabilizing the image and adjusting the surface properties of the photosensitive material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. In order to achieve the purpose of the present invention, it is desirable to contain 2.times.10 to 5.0.times.10 moles of thiosulfate 5 in the bath. That is, according to the present invention, the stability of dye images is improved by processing a photosensitive material containing a polymer cadallar in a stabilization process that does not include a substantial water washing process, but the final stabilization bath The stability of the dye image is improved overnight by processing with a processing solution containing 2 x 10 to 5.0 x 10 moles of thiosulfate. In the present invention, two thiosulfates are added to the final stabilization tank.
X10 ~5. It is desirable to contain QXIO mole, but specifically in the case of positive photosensitive materials (color photographic paper),
The amount of thiosulfate is preferably 2X10'' to 5.OX10 moles, particularly 1.0X10-11 to 3.0X1
In the case of negative photosensitive materials (photographic color films), the amount is preferably 2 x 10 to 2 x 10 mol, but is preferably in the range of 4.0 x 10 to 1.0 x 10 mol. The thiosulfate in the final tank may be replenished as a single solution or in parts by a known replenishment method, or when thiosulfate is used as a soluble silver complexing agent in the fixer or bleach-fixer, it may be brought in by the light-sensitive material. The thiosulfate in the fixing or bleach-fixing solution may be arbitrarily adjusted, and the latter is preferable.The processing solution having fixing ability in the present invention refers to a processing solution that is solubilized as a /S silver halide complex salt. It is carried out with a processing solution containing a soluble complexing agent, and includes not only general fixing solutions but also bleach-fix solutions, -bath development constant N solutions, and -bath development bleach-fix solutions.As a soluble complexing agent, are thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples thereof include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, high concentration bromides, iodides, etc. In the present invention, it is especially preferable to contain thiosulfates. The processing method of the present invention is desirable in terms of stabilization of dye images, chemical stability, and ability to form soluble complexes with silver halide. It can also be used to process color reversal films, color X-ray films, etc. The polymer coupler used in the present invention is obtained by polymerizing coupler monomers, and is is preferably represented by the following general formula [I], and the cyan coupler monomer is preferably represented by the following general formula (I).
I) or [II[) is preferable, and as the magenta coupler monomer, the following general formula [1
v] is preferred. General formula [i]: Yellow coupler monomer (b) (a
) In the formula, R1 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, a sulfonamide group,
Represents a carbamoyl group, sulfamoyl group, or cyan group. R5 represents an alkyl group or an aryl group, and X represents a group that leaves upon coupling with the oxidized product of the aromatic primary at7 developer. For example, a hydrogen atom, a -rogen atom, an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, etc. bonded directly to the coupling position of an oxygen atom or a nitrogen atom. can be mentioned. In addition, U.S. Patent No. 3,471,563,
No. 36894, JP-A-47-37425, JP-A No. 50-1
No. 0135, No. 50-117422, No. 50-117
No. 422, No. 50-130441, No. 51-1088
No. 41, No. 50-120334, No. 52-18315
You may use the leaving group described in No. 53-L52423, No. 53-105226, etc. Segment (b) in the above formula is a yellow color-forming component, and segment (a) represents a group containing a polymerizable vinyl group substituted at any position with respect to (b). ,A
represents a linking group of -NH- or -〇-. General formula [■] Rainbow turnip 2-monomer town X General formula (1) In general formula [1 [), R1+ A + X has the same meaning as general formula [1]. R green and R5 have the same meanings as R1 + R2 shown in general formula [I]. B is a divalent organic group, and n represents O or 1. B is specifically an alkylev group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, 7
It represents an arylenealkylene group having up to 241 wA carbon atoms, an arylenebisalkylene group having 8 to 32 carbon atoms, or an alkylenebisarylene group having 13 to 34 carbon atoms. In the general formula [Otori], each R7r and R9 are the general formula [I]
It has the same meaning as R1 and R2 represented by, and X is the general formula [1
) is synonymous with R6 and R8 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, or a group represented by -NH-L (where L is alkoxycarbonyl, alkylcarbamoyl, aliphatic,
(represents an acyl group such as an aromatic or heterocyclic carboxylic acid or sulfonic acid), and an acryloylamino group, a methacryloylamino group, an acryloyloxy group, a methacryloyloxy group, etc., which may be 119% substituted with other substituents. However, at least one of R6 and Rε must have a polymerizable vinyl group-containing group (a) of the general formula CI) as a terminal substituent. General formula (ff): Magenta coupler monomer general formula ([
In V), X has the same meaning as in general formula CI), and R10 has the same meaning as R2 in general formula CI'). R11 has the same meaning as R6 and R8 in general formula (1). C is R6 or R8 of general formula C1) or R,,A,
B has the same meaning as in general formula (II). m represents an integer of 0 to 3. In general formula [1v], at least one of [C] or R11 is a segment (a
) must have a polymerizable vinyl group-containing group. Specific representative examples of coupler monomers are shown below in the margins, but the compounds used in the present invention are not limited to these. [Exemplary coupler monomer] N=N (28) Ct (29) Ct (30) (31) (33) (34) O (35) CH2-0-CH=CH2 SO2NH-CH2-CH2-0-CH=CH20 =C
-OH ■ 0=C-CH3 0=C-OCHy Next, specific polymer examples of the polymer coupler latex of the present invention obtained from the above-mentioned various coupler monomers will be shown, but the invention is not limited thereto. [Exemplary polymer couplers] (p-1) (P-2) NT (OCIIFi9 t x = 70 weight 9 g 7 = 20 weight jlK z = 10 weight (P-3) (P-4) C) I5! * Q5 Na to 1290 weight y+==5 weight z = 5 weight (P-5) N=N X=60 weight F=40 weight π (P-6) CH U-t x=100 weight ( P-7) CH5 (P-8) r To 1265 weight y = 35 weight (P-9) (P-10) υ To X = 55 weight y = 45 weight (P-11) t X = 80 weight To y=20 weight to X=100 weight (P-13) (P-14) x=85 weight 9r y=5 weight Kz=10 weight (P-
15) 0=C (P-16) H5 ■ x = 70 weight 1cK y = 30 weight (P-17) (P-18) t x = 80 weight jkag y = 20 weight (P-19) (P -20） F=5 in close view (P-24) (P-25) (P-26)? H3 H x = 60 weight y = 40 weight (P-27) CI (5 H (P-28) H3 C direction 0 H5 x = 70 weight y; 25 weight z = 5 weight Used in the present invention The amount of the polymer coupler added is preferably 0.005 to 0.5 mol per 1 mol of silver halide in the emulsion layer. More preferably (1,05
~0.3 moles of one polymeric 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 which may be used in combination, phenolic compounds and naphthol compounds are preferable, such as those described in U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 2.474,293, No. 2,895.826, No. 3.253,924, No. 3.034,892,
3.311.476, 3.386,301, 3,419,390, 3.458,315, 3
．． 476,563, 3,591.383, etc., and methods for synthesizing these compounds are also described in the same publication. Photographic magenta couplers include pyrazolone, pyrazolotriazole, and virazolinobenzi? Examples include compounds such as /j-sol, indacylon, etc. As a pyrazolone macenta coupler, U.S. Patent No. 2,60
No. 0,788, No. 3,062,653, No. 3,127
, No. 269, No. 3,311.476, No. 3,419,
No. 391, No. 3,519,429, No. 3.558, 3
No. 18, No. 3.684,514, No. 3.888.68
No. 0, JP-A-49-29639, JP-A No. 49-11i63
No. 1, Mukai No. 49-129538, Mukai No. 50-13041, Tokukoan No. 53-47167, Mukai No. 54-10491,
Compounds described in No. 55-30615; pyrazolotriazole magenta couplers include couplers described in U.S. Patent No. 1,247.493 and Belgian Patent No. 792.525; As a magenta coupler, a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is generally used, for example, U.S. Pat.
No. 2,983,608, No. 3.005゜712, No. 3,684,514, British Patent No. 937゜621, l
F! f Kai No. 49-123625, No. 49-31448
Examples include the compounds described in No. Furthermore, a colored magenta coupler of the type described in US Pat. No. 3,419,391, in which the dye flows out into the processing solution by reaction with an oxidized product of a developing agent, can also be used. As the photographic yellow coupler, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Historically, two-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction have also been advantageously used. Examples of these are U.S. Pat.
No. 65.506, No. 3,664,841, No. 3.40
8゜194, 3.277,155, 3,447
, No. 928, No. 3,415,652, Special Publication No. 1977-1
No. 3576, JP-A-48-29432, JP-A No. 48-66
No. 834, No. 49-10736, No. 49-12233
No. 5, No. 50-28834, No. 50-132926, etc., together with the synthesis method. The amount of the diffusion-resistant coupler used in the present invention is generally 0 to 1X per mole of silver in the light-sensitive silver halide emulsion layer.
10 moles. Various methods can be used to disperse the coupler, such as the so-called alkaline aqueous solution dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method.1. It can be selected as appropriate depending on the chemical structure of the coupler. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-Open Nos. 49-74538 and 51-59943,
No. 54-32552 and Research Disclosure No. 114850 (August 1976) 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-acrylamido-2-methylpropane sulfo/acid, etc. Oil-in-water vaporization dispersion method is used to incorporate hydrophobic additives such as couplers. Conventionally known methods of dispersing can be applied, i.e., for example, tricresyl phosphate, dibutyl phthalate,
'After dissolving in a single or mixed solvent of a high boiling point organic solvent with an M point of 175°C or higher and/or a low boiling point organic solvent such as ethyl acetate or butyl propionate, it is mixed with an aqueous gelatin solution containing a surfactant, and then a high-speed After emulsifying and dispersing with a rotary mixer or colloid mill, it is added directly to the silver halide emulsion, or the emulsified dispersion is added to the silver halide emulsion after removing the low boiling point solvent by a known method. . Further, as colorless couplers that can be used in combination with the present invention, British Patent No. 861.138, British Patent No. 914,145, British Patent No. 1.1
No. 09,963, Japanese Patent Publication No. 45-14033, U.S. Pat.
Agfa Rebel Kusen Volume 4, pp. 352-367 (
You can choose from those described in (i984) and others. Silver halide emulsions that can be used in the present invention include:
Any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide or mixtures thereof. good. 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 polyethylene coated paper, triacetate film, polyethylene terephthalate film, white polyethylene terephthalate film, or the like. 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 amine phenol and p-phenylene diamine derivatives. Due to their stability in the free state, these compounds are generally used in the form of salts, such as hydrochlorides or sulfates. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per ton of color developer, preferably about 1 g to about 15 g per ton of color developer.
Used in g@summer. Examples of the amine phenol developer include 〇-aminophenol, p-aminephenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like. Particularly useful primary aromatic amino color developers include N, p/
-) is an alkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful examples include N,N'-diethyl-p-phenylenediamine hydrochloride, N-meth-p-phenylenediamine [acid [,N,N'-']mef-p-phenylene Diamine 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-methylanili/-p- ) Rue/
Examples include sulfonates. 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 OpH value of this color developer is usually 7 or more, most commonly about 10.
〜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 bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced by development and converts it into silver halide. It has the effect of coloring the uncolored parts of the coloring agent, and its structure is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarbo/acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such organic acid metal complexes include polycarbo/acids or aminopolycarboxylic acids. choleranopolycarbo/acid or aminopolycarbo/#!
may be an alkali metal salt, an ammonium salt or a water-soluble amine salt. ``Specific representative examples of these include the following. [l] Ethylenediamine/tetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl) -N,
N', N'-) diacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid')

[9] Ethyl ether diamine tetraacetic acid [IO3 glycol ether diamine tetraacetic acid [11] Ethylene diamine tetraacetic acid [12] Phenylene diamine/tetra acetic acid [13] Ethylene diamine/tetra acetic acid ditetrium salt (14) Ethylene diamine tetra acetate tetra(trimethyl ammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriamine be/diacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl) -N, N', N'-) diacetic acid sodium salt [ 18] Sodium propylene diamine tetraacetate salt [19] Sodium nitrilotriacetate salt [20] The bleaching solution used in the order of cyclohexafujiami/sodium tetraacetate contains a metal complex salt of an organic acid as described above as a bleaching agent, and Various additives may be included. As additives, it is particularly desirable to include rehalogenating metal salts such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, and chelating agents. Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
It is possible to appropriately add substances known to be added to ordinary bleaching solutions, such as bleaching agents, alkylamines, and polyethylene oxides. (Fixer and bleach-fixer include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite,
Sulfites such as potassium metabisulfite and sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may contain one or more types of pH moderators consisting of various salts. When carrying out the process of the present invention while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiothia/(@, salt, sulfite, etc.). Alternatively, the bleach-fix replenisher may contain these salts and the like and be replenished into the processing bath. Air or oxygen may be blown into the liquid storage tank as desired, or a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate R salt, etc. may be added as appropriate. In the process of the present invention, silver may be recovered by known methods from processing solutions containing soluble silver complexes such as fixing solutions and bleach-fixing solutions as well as stabilizing solutions.For example, electrolysis method (French Painting Patent No. 2 , No. 299,667 specification &), precipitation method (described in JP-A-52-73037, German Patent No. 2,331.
220 specification), ion exchange method (Japanese Patent Application Laid-Open No. 51-1
7114, German Patent No. 2,548.237 Specification iR) and metal substitution method (British Patent No. 1,353.8)
(described in the specification of No. 05) can be effectively used. [Examples] The present invention will be explained in detail below using Examples, but the embodiments of the present invention are not limited thereto. Example-1 Coating silver iodobromide emulsion for negative image formation on cellulose triacetate film Silver amount 25y/di, gelatin 25++
ht/d, /, 1/2 of the exemplary magenta coupler shown in Table 1 and the following comparative coupler M-(1)-y13+
A green-sensitive silver halide emulsion layer containing 2.0 x 10 mol/di of tricresyl phosphate (TCP) dissolved and dispersed in 100% of
4 g of gelatin per 0III, 51. A gelatin aqueous solution containing 0.3 g of 2-bisvinylsulfonylethane was added to 1 gelatin.
Samples N11L1 to 12
Comparative coupler M - (1) Ct Comparative coupler M -+21 ('I Ct Comparative coupler M -+31 After wedge exposure was applied to the samples of Nal to 12 produced as described above, Noritsu Steel Co., Ltd. Using a modified 5RF-60LI machine, a one-way automatic film processor with a shimmy reader,
The stabilization treatment carried out according to the following treatment steps was carried out in a stabilization bath e341 of an automatic processor. Obtained tLfc
The film was stored at 65°C, humidity 80, and RH for 3 weeks, and the transmission density of the highest density area and unexposed area was measured using a Sakura Photodensitometer P.
Measurement was performed using DA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.) to determine the rate of decrease in dye density and increase in yellow stain after storage. The results are shown in Table-1. Processing process Temperature Time (1) Color development 38°C 3 minutes 15 seconds (2) Bleaching 38°C 6 minutes 30 seconds (3) Fixing 38°C 4 minutes 20 seconds (4) Stabilization treatment 38°C 3 minutes 15 seconds The stabilizing liquid was prepared by dissolving 1.0 g of 5-chloro-2-methyl-4-isothiazolin-3-one and 20 g of ethylene glycol in It water at 7'C. As a comparative treatment, samples subjected to water washing according to the CNK-4 standard processing were used. Compared to Samples N1110-10, which combined the polymer coupler of the present invention and 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 a stabilization treatment. Example-2 Exemplary cyan coupler of the present invention shown in Table-2 and the following comparative coupler (C-1) ggx High boiling point organic solvent tricresyl 7 phosphate (hereinafter referred to as Tcp) 2.0 g and ethyl acetate 20 g 1 and as necessary After heating the mixed solution to which the required amount of dimethylformamide was added to 60°C to dissolve it, this was mixed with 5! The mixture was mixed with 100 flt of v-gelatin aqueous solution and emulsified and dispersed using an ultrasonic fractionator to obtain a dispersion. Next, a dispersion of the cyan coupler shown in Table 2 was added to a silver chlorobromide emulsion (contained in 10 moles of silver chloride) so that the amount of the cyan coupler was 10 moles relative to silver, and 1, 2-bis(
Vinylsulfonyl)ethane per 1g of gelatin, 912+
19 parts and coated on a polyethylene cochide paper support so that the coated silver amount was 7q/100d. In this way, color paper samples with Na 13 to 19 were obtained. This sample was subjected to conventional edge exposure and then subjected to the following development treatment. Standard processing process 8i (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach fixing 38°C 1
Minutes 30 seconds [3] Stabilization treatment 25-30”C3 minutes [4]
] Drying 75-80'C for about 2 minutes Processing solution composition (color developing tank solution) (bleaching tank solution) (stabilizing solution) For stabilization processing, RPV204 manufactured by Norilla Koki Co., Ltd. was modified to have a 3-tank configuration. The same evaluation as in Example-1 was carried out. 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. The same evaluation as above was carried out for the product in which both 0.0g and 0.5g of bismuth chloride as a metal salt were added.As is clear from Table 2, as in Example 1, the polymer coupler of the present invention and the stable It can be seen that the decrease in the cyan dye density after storage is significantly smaller only in combination with the chemical treatment.Also, when ammonium thiocyanate K was used as the fixing component in the bleach-fix solution, ammonium thiosulfate was used as the fixing component. In both cases, the pigment concentration deteriorated after storage, and it can be seen that using thiosulfate as a fixing component in the present invention is more effective in increasing the effect of the present invention. It is also clear that the effect of the present invention is remarkable even when the agent alone or both a chelating agent and a metal salt are added.Example-3 Antihalation layer and gelatin layer on 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 !-sensitive silver halide emulsion layer on which the total amount of silver is 100 CTII equivalent and 980 M. The emulsion was prepared using spherical silver halide grains with an average grain size of 1.5 μm.At this time, an exemplary yellow coupler (P-23) was added to the blue-sensitive silver halide emulsion layer, and a green An exemplary magenta coupler (P-13') was used for the sensitive silver halide emulsion, and an exemplary cyan coupler (P-5) was used for the red-sensitive silver halide emulsion layer. The following were added as inhibitor-releasing couplers (1) IR couplers), and conventional additives such as high-boiling solvents, sensitizing dyes, film-forming agents, and spreading agents were used. The color negative film obtained was mixed with the photosensitive material of the present invention (1
). (DIR coupler) *C00CHCOOC12H25(n)**C00C
HCOOC12H25 (~Next, the yellow coupler used in photosensitive material (1)
P-23) f: Magenta coupler (p
-xa)t-(P~14), cyan coupler (P-5
Photosensitive material (2) was prepared in the same manner as photosensitive material +1) except that (P-2) was substituted for (P-2). Next, a photosensitive material (3) was prepared in the same manner as the photosensitive material (1) except that the yellow, magenta, and cyan couplers used in the photosensitive material (1) were replaced with those shown below. The following margins (yellow coupler) (magenta coupler) Comparative coupler (M-1) used in Example-1 (cyan coupler) It was exposed to light and processed according to the processing steps of Example-1. Note that the standard treatment CNK-4 was used as a treatment comparison. There are four tanks for each stabilization, and the first to fourth tanks are arranged in a cascade system, and a treatment bath to which siloxane and formalin are added is provided after each stabilization.
This prevented the leakage to monks. Furthermore, the amount of replenishment to the fourth tank for each stabilization was set to 9 g/min so that the amount of thiosulfate of the fourth tank per stabilization was 3.0×-10 mots, and the overflow liquid was Let it flow out into the debt, and let it be discharged from the first monk. The amount of refill to the processing bath containing activator and formalin is 30 ml.
/min. However, as the stabilizing liquid, the processing liquid for sample Ugly 19 used in Example-2 was used. Furthermore, photosensitive materials (1) to +31 t1″ each 50rr?/
The solution was treated continuously for 4 weeks at a rate of 1 day, and then the same evaluation as in Example 1 was performed using the solution. Furthermore, the same evaluation as in Example 1 was carried out in the case where the thiosulfate concentration in the fourth situation was changed to 1 x 10 mol and 1.0' x 10 mol by changing the replenishment amount for each stabilization. As is clear from Margin Table 3 below, the samples obtained by combining the light-sensitive material of the present invention and the stabilization treatment are yellow (Y), magenta (
Even in the multilayer structure of M) and cyan (C), the rate of decrease in dye concentration and yellow stain after storage were significantly reduced. It has been found that when the dye density is in the range of 10 to 5×5 10 , the decrease in dye density can be suppressed to 4, and the effects of the present invention can be further enhanced.
Karu. Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (3)

[Claims] (1) A silver halide color photographic light-sensitive material that is subjected to a color development process, then processed with a processing solution having fixing ability, and then processed in a stabilization process without a substantial water-washing process. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material contains at least one kind of polymer coupler'. (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. (3) The concentration of thiosulfate at the R end of the stabilization process is 2
3. The method for processing a silver halide color photographic light-sensitive material according to claim 2, wherein the amount is in the range of x10 to s, oxio moles.