JPS6010303B2 - Silver halide color photographic material processing method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which includes a step of processing with a bleach-fixing solution, and particularly to a method using an organic acid metal rust salt as a bleaching agent (oxidizing agent) and a specific halogen ion as a fixing agent. The present invention relates to a method for processing a silver halide color photographic material, which includes a step of processing with a bleach-fix solution. More specifically, it meets the demands of preventing environmental pollution, has excellent bleach-fixing efficiency, and does not cause opacity or staining of the finished film even if the photographic material to be processed is a high-sensitivity silver halide color photographic material. It is possible to obtain excellent color dye images, and the bleach-fix solution is stable,
Bleach (oxidizing agent) without making the redox potential of the liquid base
The present invention relates to a method for processing a silver halide color photographic light-sensitive material that can fully utilize the oxidizing ability of an organic acid metal complex salt used as an organic acid metal complex salt. Generally, in order to obtain a color image by developing a silver halide color photographic material that has been exposed to light, the developed silver image is bleached with a bleaching agent (oxidizing agent) after the color development process, and then desilvered with a fixing agent and fixed. A process is performed. In contrast to this type of method in which bleaching and fixing are performed in separate processing steps, a method called bleach-fixing is a method that simplifies the processing steps and completes bleaching and fixing simultaneously in one step for the purpose of speeding up processing and saving labor. A processing method has also been adopted. The bleach-fixing solution used in the bleach-fixing process is generally an aqueous solution containing a bleaching agent and a fixing agent as main ingredients. As the fixing agent for the latter, a fixing agent commonly used for fixing silver halide photographic light-sensitive materials such as thiosulfate, thiocyanate or thiourea is used. . Red blood salt and ferric chloride as bleaching agents are good bleaching agents in that they have high oxidizing power. However, a bleach-fix solution using red blood salt as a bleaching agent releases cyan due to photolysis and poses a pollution problem, so measures must be taken to completely render the treated solution 9E harmless. In addition, bleaching agents using ferric chloride have a very low pH and extremely high oxidizing power, so they have the disadvantage that the parts of the processing machine that is filled with them are easily corroded. This process has the disadvantage that iron hydroxide is precipitated in the emulsion layer of the photographic material to be processed, resulting in so-called staining. For this reason, not only is it necessary to carry out a cleaning step using an organic chelating agent after the bleach-fixing process, but there are also problems in terms of pollution control. Compared to these red blood salts and ferric chloride,
Organic acid metal salts such as iron salts of ethylenediaminetetraacetate have low toxicity and are advantageous in terms of pollution control, so their use as bleaching agents has recently been recommended. However, since organic acid metal salts have a relatively small oxidizing power and insufficient bleaching power, products using them as bleaching agents cannot be used, for example, in low-sensitivity silver halide colorants mainly based on silver chlorobromide emulsions. - When bleach-fixing photographic light-sensitive materials, it is possible to achieve the desired purpose, but for example, high-sensitivity silver halide that is mainly composed of silver chloroiodobromide or silver iodide emulsion and is color sensitized. When processing color photographic materials, especially silver halide color reversal photographic materials that use emulsions with a high silver content, the bleaching action is insufficient, resulting in poor desilvering, and the bleach-fixing efficiency is low, making it difficult to achieve the purpose. be. If this point is resolved,
Organic acid metal salts used as bleaching agents can be said to be excellent bleaching agents that are extremely advantageous in terms of pollution control. On the other hand, as a fixing agent in a bleach-fixing solution, thiosulfate is used in most cases due to the stability and cost of silver salt. However, this thiosulfate cannot be said to be a preferable treatment agent in terms of pollution control. That is, for example, when sodium thiosulfate is used as a fixing agent, the fixing reaction mechanism is as follows. *X+n(NH4)2s2o3 one touch (
s2Q) Q (state,) ten is NH$+Xe (however, n is 2
or 3, X represents halogen. ) As seen in this reaction example, as the silver halide photographic light-sensitive material is bleach-fixed in the bleach-fix solution, silver salt and halogen ions accumulate, and the free components of the fixer decrease. Correspondingly, the fixing efficiency gradually decreases, and if the bleach-fixing process is continued as it is, a fatigue phenomenon will eventually appear, making it unusable. Therefore, in order to revitalize this tired bleach-fix solution, add an appropriate amount of new bleach-fix solution (regenerant or replenisher).
At the same time, a method is adopted in which the exhausted bleach-fix solution is discharged outside as an overflow.However, it is recommended to dispose of this overflow solution as it is, as it contains silver and other valuable components, so it is better to conserve resources. This goes against the grain, is extremely disadvantageous economically, and is also undesirable from the standpoint of environmental pollution. Therefore, treatment must be taken to completely render the treated waste liquid harmless. In this point,
In the past, the silver ions in the overflow bleach-fix solution were often collected and then disposed of, but recently, the bleach-fix solution after silver recovery has also been recycled and reused. Ta. For example, when silver is recovered by electrolysis, which is the most advantageous method for recovering silver, the thiosulfate ions that were bound to the silver ions become free ions again, so the bleach-fix solution does not react with the fixing agent. In other words, the fixing ability is restored, but thiosulfate ions are reduced by this electrolytic reaction, and thiosulfate ions are also reduced by air oxidation or so-called carryover during processing, so the amount of liquid that does not overflow is sufficient. Generally, the bleach-fix solution is regenerated and used repeatedly while being replenished with a new bleach-fix solution (regenerant or replenisher) having a concentration that maintains the bleach-fix components. However, even if the bleach-fix solution is used repeatedly by such a replenishment method, the fixing performance of the fixing agent gradually changes as the fixing agent is used more frequently, even though the free thiosulfate ion concentration is sufficiently high. As a result, the fixing speed decreases, eventually causing fixing failure. The cause of this is said to be that soluble components contained in the emulsion layer of the photosensitive material to be processed are eluted into the bleach-fixing solution, and fixing-inhibiting components are accumulated. As a solution to this problem, methods have been proposed such as adding a fixing accelerator to improve fixing power and removing halogen ions, which are considered to be fixing inhibiting components. In other words, an example of the former is
There is a method for promoting fixation using a sulfur compound as described in Japanese Patent Publication No. 135754, or a method for promoting fixation using a polyethylene glycol compound as described in Japanese Patent Publication No. 481-39173.
All of these methods are still insufficient as a fundamental solution to fixing defects caused by the accumulation of halogen ions, etc., which are considered to be fixing-inhibiting components, and they have the drawback of causing fixing defects after repeated reuse and repeated use. be. Therefore, in order to reduce the accumulated yield concentration of halogen ions, the overflow bleach-fix solution is currently recycled and used repeatedly while discarding a part of it, which poses pollution problems and is uneconomical. It has not been resolved yet. On the other hand, examples of the latter include U.S. Patent Publication No. B-391509, Japanese Patent Publication No. 4313
There are technologies for removing halogen ions, such as those described in Publication No. 0167, which are effective in improving fixing power, but all of them require devices with complex structures and have high capital investment and operating costs. There are drawbacks. In any case,
Thiosulfate, which is frequently used as a fixing agent in bleach-fix solutions, can be said to have a serious drawback in terms of pollution prevention, as it is highly likely to hide environmental pollution. On the other hand, thiocyanates and halogen salts, which are known as fixatives other than the above-mentioned thiosulfates, have low stability as silver complex salts, so if the fixative concentration becomes low in the next water washing process, the silver rust salts will decompose. It occurs and remains as silver thiocyanate or silver halide in the emulsion layer of photographic materials to be processed, and when processing negative or positive films, the finished film becomes opaque. The current situation is that it has not been put into practical use. It is known that in order to compensate for this drawback, it is sufficient to coexist a certain amount of thiosulfate, but the amount of thiosulfate used is usually around 0.2 mol/about. As mentioned above, when silver is repeatedly used while being recovered, if a portion is disposed of as overflow, biological oxygen demand (SOD) and chemical oxygen demand (C
OD), and there is a risk of environmental pollution.Furthermore, since thiosulfate itself is a reducing agent, the fixing agent is susceptible to oxidative decomposition, resulting in extremely disadvantageous results for reuse and repeated use. . Furthermore, when the above-mentioned thiosulfate is made to coexist with a thiocyanate or a halide as a fixing agent component of a bleach-fix solution, the thiosulfate itself is a reducing agent and is necessary as a guarantee agent for the thiosulfate. Since sulfite is also a reducing agent, the oxidation-reduction potential of the bleach-fix solution becomes very base, and the oxidizing power of the coexisting bleach (oxidizing agent) is impaired.
This results in the disadvantage that it becomes difficult to regenerate and use the liquid repeatedly. Such adverse effects caused by thiosulfate are also serious problems that occur when it is used alone as a fixing agent component in a bleach-fix solution. At present, there is a strong demand for the development of a treatment method. In this respect, thiocyanates and halogen salts, which are known as fixing agents for bleach-fix solutions, have low reducing properties and are difficult to oxidize. It has an excellent property of being able to fully demonstrate its abilities. However, the use of the former of these fixatives, thiocyanate, not only has high biological oxygen demand (BOD) and chemical oxygen demand (COD) loads, but also causes environmental pollution. This is not preferable because there is a risk of decomposition and release of toxic cyanide, and it is also susceptible to the accumulation of halogen ions, which are fixing-inhibiting components, and has drawbacks in terms of reuse and repeated use. On the other hand, the latter fixing agent, halogen salt, is not affected by fixing-inhibiting components such as halogen ions that elute from the emulsion layer of the photographic material to be processed and accumulate in the bleach-fix solution, and is environmentally friendly. It can be said that it is an extremely preferable fixing agent from the viewpoint of pollution control as it is not subject to contamination. Therefore, it is extremely preferable to use a halogen salt as a fixing agent in a bleach-fixing solution, as long as the above-mentioned drawbacks can be overcome. The inventor is
As a result of research on a method for processing silver halide color photographic materials, which includes a process of processing with a bleach-fix solution using an organic acid metal salt as a bleaching agent and a specific halide, i.e., bromide or iodide, as a fixing agent, at least 3 moles/bromine ion or at least 1.3
It is possible to solve the above-mentioned drawbacks of the organic acid metal complex coexisting as a bleaching agent by incorporating iodine ions per mole as a fixing agent in a bleach-fixing solution. It has been discovered that by incorporating a polymer having a pyrrolidone nucleus in its molecular structure into the processing solution used, it is possible to prevent the above-mentioned drawbacks of bromide or iodide ions as fixing agents, that is, the opacity of the finished film. It was proposed as Tokuiso Sho 51-49875 (see Hakama Seki Sho 52-134433). As a result of continuing research on the processing method for silver halide color photographic light-sensitive materials according to the above proposal, the present inventors have discovered that a method for processing silver halide color photographic light-sensitive materials using the bleach-fix solution (and a post-processing solution containing the above polymer) can be used to produce a silver halide color photographic material. When a photographic light-sensitive material is subjected to a large amount of running processing, a large amount of silver ions eluted from the emulsion layer of the light-sensitive material accumulates in the processing solution, especially the bleach-fix solution. When silver ions accumulate in a processing solution containing a polymer, or when a processing solution containing the above polymer is stored for a long period of time even if the accumulated amount of silver ions does not normally cause any problems, viscosity may be added to the processing solution. It has been found that unrelated precipitates are generated and contaminate photographic materials to be processed. Furthermore, it has been found that the insoluble precipitate adheres to the members of the processing machine filled with the processing liquid, particularly the temperature-adjusting liquid circulation system members, causing mechanical failure. This precipitate is thought to be a reaction compound between the above polymer and silver, and it has been found that the above-mentioned adverse phenomenon occurs particularly when bromine ions are used as a fixing agent. The inventor of the present invention has continued diligent research to eliminate these drawbacks, and as a result has completed an excellent method for processing silver halide color photographic materials free of such drawbacks. That is, the first object of the present invention is to provide a color photograph of halogenated synthetic fibers that have low biological oxygen demand (80D) and chemical oxygen demand (COD) loads, are low in toxicity, and meet the requirements for preventing environmental pollution. An object of the present invention is to provide a method for processing photosensitive materials. A second object of the present invention is to produce excellent color dye images with excellent bleach-fixing efficiency and without opacity of the finished film, even if the photographic material to be processed is a silver halide color photographic light-sensitive material with a high silver content. An object of the present invention is to provide a method for processing a silver halide color photographic material that can be obtained. A third object of the present invention is to be able to use the bleach-fixing solution without deterioration in its bleach-fixing ability even when the bleach-fixing solution is recycled and used repeatedly, without being affected by fixing-inhibiting components that elute and accumulate from the emulsion layer of the photosensitive material to be processed. An object of the present invention is to provide a method for processing silver halide color photographic materials that can be processed more frequently. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material that does not make the redox potential of the bleach-fix solution base and allows the coexisting bleaching agent (oxidizing agent) to fully utilize its oxidizing ability. The object of the present invention is to provide a processing method. A fifth object of the present invention is to prevent the formation of insoluble precipitates, etc. in a processing solution, especially a processing solution containing a polymer having a pyrrolidone core unit in its molecular structure, and to prevent contamination of the processing film. It is an object of the present invention to provide a method for processing silver halide color photographic materials that does not cause mechanical failure of members of a processing machine that fills the liquid. After the exposed silver halide color photographic light-sensitive material is developed, at least 0.01 mol/the organic acid metal complex salt and at least 3 mol/the bromide ion or at least 1.3 mol/the iodide ion are obtained. A polymer having a pyrrolidone core unit in its molecular structure and at least 3 moles of its bromide ion or at least 1.3 moles of its iodide ion in a processing step after the bleach-fixing process. It has been found that the above object can be achieved by processing with a processing liquid containing fixing ability. That is, the method for processing a silver halide photosensitive material according to the present invention uses an organic acid metal salt, which is advantageous in terms of pollution control, as a bleaching agent in a bleach-fix solution, and an organic acid metal salt, which is also advantageous in terms of pollution control, as a fixing agent. In addition to using a specific halogen ion that can fully demonstrate the oxidizing ability of acid metal complex salts, in order to solve the drawbacks of this halogen ion, a polymer having a pyrrolidone core unit in its molecular structure is used, and the This solves the above-mentioned drawbacks caused by the use of polymers. More specifically, when treated with a bleach-fix solution having the above composition,
When the concentration of the fixing agent decreases in the subsequent washing process, the silver salt decomposes and remains as halogen silver in the emulsion layer of the material to be processed, making the finished film opaque when processing negative or positive films. As mentioned above, this disadvantage arises, and as described above, this disadvantage can be solved by using a polymer having a pyrrolidone nucleus in its molecular structure. However, if processing is carried out after the bleach-fixing step with a treatment that does not contain halogen ions but only contains the above-mentioned polymer, there is no problem at first, but as the running process continues, it becomes possible to As silver ions accumulate in the processing solution, the above-mentioned anti-sedimentation effect is reduced. However, if a specific amount of a specific halogen ion is contained in a treatment solution containing this polymer, such drawbacks will not occur and the above-mentioned objects of the present invention can be achieved. As the organic acid metal salt as a bleaching agent contained in the bleach-fix solution used in the present invention, any metal salt of an organic acid that acts as an oxidizing agent for silver can be used. As this organic acid, for example, the following general formula [1]
Or there is an aminopolycarboxylic acid represented by [B].
General formula [1] HOCO-A, 1Z-A2-COO day general formula [B] Shigeru>NZN〈Maji; [In each of the above general formulas, A,, A2, A3, He, N, and As are respectively A substituted or unsubstituted hydrocarbon group, Z represents a hydrocarbon group, an oxygen atom, a sulfur atom, or >N- (A7 is a hydrocarbon group or an aliphatic carboxylic acid). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The general formula [1] or

Representative examples of the aminopolycarboxylic acid represented by [0] and other aminopolycarboxylic acids include the following. '1'
Ethylenediaminetetraacetic acid {21 Dethylenetriaminebentaacetic acid (3}ethylenediamine-N-(3-oxyethyl)-N・N'・N
′-Triacetic acid■p. Pyrenediaminetetraacetic acid (5) Nitrilotriacetic acid '61 Cyclohexanediaminetetraacetic acid '7} Iminodiacetic acid (8) Dihydroxyethylglycine side Ethyl etherdiaminetetraacetic acid Glycol etherdiaminetetraacetic acid OD Ethylenediaminetetrapropionic acid■ Phenylenediamine Tetraacetic acid 03 Ethylenediaminetetraacetic acid disodium salt 04
Ethylenediamine-N-(3-
Propylenediaminetetraacetic acid sodium salt■ Propylene diamine tetraacetic acid sodium salt■
Nitrilotriacetic acid sodium salt ■ Cyclohexanediaminetetraacetic acid sodium salt The above-mentioned organic acid metal key salt used in the present invention is at least 0.0% per bleach-fix solution.
The above-mentioned purpose of the present invention can be fully achieved by this, but if the amount added is too large, the processability may deteriorate, so it is desirably 0.01 to 2. 5 mol/sleeve. The halogen ions as a fixing agent contained in the bleach-fix solution used in the present invention are limited to bromide ions and iodide ions, which are incorporated into the solution by soluble bromide or soluble iodide. The halogen compound used to contain the halogen ions in the bleach-fix solution may be any bromide or iodide, regardless of whether it is an inorganic salt or an organic salt. Typical bromides and iodides include hydrobromic acid, lithium bromide, sodium bromide,
Potassium bromide, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can be mentioned, and ammonium salts and potassium salts, which have a high diffusion rate into the gelatin layer of the photographic material to be processed, are particularly effective. be. These halogen compounds can be used alone or in an appropriate combination of two or more types, but ``When using a combination of bromide and iodide, at least one of them alone must satisfy the above concentration.
Further, when using this combination, even better effects can be obtained if both bromide and iodide satisfy the above concentrations. In the present invention, even halogen ions are excluded because chloride ions and fluoride ions caused by chloride and fluoride cannot achieve the desired action and effect of the present invention, but bromine ions or As long as iodide ions are contained, even if these chloride ions and fluoride ions are contained together, the action and effects of the present invention are not affected. The bromide ion or iodide ion used in the present invention is required to contain at least 3 moles of the former or 1.3 moles of the latter per evening of the bleach-fix solution, so that the above-mentioned objects of the present invention can be fully achieved. However, due to solubility, the bromine ion is 7.5
The upper limit for iodide ions is about 12 mole/mol. In the present invention, in order to maintain the viscosity of the liquid low and the diffusion rate of the liquid components high to increase the processing efficiency, the particularly desirable addition amount is 4 to 6 mol/s in the case of bromide ions, and 4 to 6 mol/s in the case of iodide ions. In some cases, the amount is 1.5 to 6 mol/s. A processing solution used in any processing step after the bleach-fixing process using the above bleach-fix solution, which prevents the precipitation of silver ions (hereinafter, this solution is referred to as an anti-sedimentation solution). The polymer having a pyrrolidone core unit in its molecular structure (hereinafter simply referred to as the polymer of the present invention or the polymer used in the present invention) is contained in It includes all polymerizable polymers in which the primary mirror or side chain of the polymer is substituted with a pyrrolidone nucleus at any position and in any number, and may be a homopolymer or a copolymer of two or more types. It may also be a copolymer. In the latter case, the monomer unit as a copolymer component having a pyrrolidone core unit in its molecular structure is copolymerized with the monomer unit as the copolymerization component with another monomer that does not have a pyrrolidoso core unit in its molecular structure. In the copolymer obtained by polymerizing the units, 20 mol%
It is desirable that the content be at least 30 mol %, particularly preferably 30 mol % or more. In addition, as other monomer units that do not have a pyrrolidone core unit in the molecular structure that are copolymerized with the monomer unit as a copolymerization component that has a pyrrolidone core unit in the molecular structure, a hydrophilic polymer can be obtained. You can use whatever you have. Typical specific examples of polymers used in the present invention include the following. [1] Poly N-vinyl-2-py. Lydone (*Note・) [2] Poly N-(2-acryloyloxy)ethyl-1-pyrrolidone [3] Poly N-glycidyl-2-pyrrolidone [Rainbow Poly N-Allyl-2-
Pyrrolidone [5] Poly-N・N-dimethyl-N-[3(
1-pyrrolidonyl)-2-hydroxy]propylamine-N'-acryloylmine[6]copolyN-vinyl-2-pyrrolidonono-N-acryloylmorpholine (
Molar ratio 42:58) (7) Copoly-N-vinyl-2-pyrrolidonno-N-acryloylpiberidine (Molar ratio 35
:65)(8) Poly-N-vinyl-2-pyrrolidone/N
-methacryloyl-2-methylimidazole (molar ratio 5
5:45)

[9] Copoly N-(2-acryloyloxy)-ethyl-2-pyrrolidone/acrylic acid diethylamide (molar ratio 60:40) [10] Copoly-N-(2-methacryloyloxy)ethyl-2-pyrrolidonoacrylate sodium (Molar ratio 75:25) [11] Copoly-
N-(3-acryloxy)propyl-2-pyrrolidone/methyl methacrylate (molar ratio 65:35) [12] Copoly-N.
N-dimethyl-N-[3-(1-pyrrolidonyl)-2-
ethyl hydroxy]-propylamine-N'-acryloyliminoacrylate (molar ratio 70:35) [13
] Copoly N-vinyl-2-pyrrolidone/vinyl acetate (molar ratio 70:30) [14 Copoly N-vinyl-
Methyl 2-pyrrolidonoacrylate (molar ratio 70:3
0) [15] Copoly-N-vinyl-2-pyrrolidonnostireso (molar ratio 80:20) [16] Copoly-N
-vinyl-2-pyrrolidone/acrylic acid amide/N-vinyl-2-methylimidazole (molar ratio 50:30:
20) (17) Copoly-N-vinyl-2-pyrrolidono-N-(1,1-dimethyl-2-oxo)-butyl-acrylamide (molar ratio 70:30) [18] Copoly-N-allyl-2-pyrrolidonovinyl acetate (molar ratio 64 :36) [19] Copoly N-vinyl-2-pyrrolidone/4-vinylpyridine (molar ratio 60:40) [
20] Copoly-N-vinyl-2-pyrrolidone/ethyl acrylate/monoethanolamine acrylate (molar ratio 50:45:5) [21] Copoly-N-vinyl-2
-pyrrolidone nopiveridinomaleamic acid piberidic acid (molar ratio 53:47) [22] Copoly-N-vinylpyrrolidone/4-vinylpyridino N-methyliodide (molar ratio 42:58) (23) Copoly-N - Vinylpyrrolidone/thiourea maleate half ammonium salt (molar ratio 60:40) *Exemplary polymer shown in Note 1 [1
] is General Aniline and Film Corporation.
lmCorp. ) to PVPK-1fu K-30, PV
It is commercially available under the trade name PK-60. The polymer used in the present invention can be easily obtained as some of it is commercially available as described above, and can be easily obtained from John Willey & Somms, Inc.
IleryandSoms, Inc. ) Published (1961
year) W. Earl Sorenson, T. D.
Camp Bell (on W.R.Sore ship, T.W.Ca.
Preparative Mented of Polymer Chemistry
Metho ship of PolymerChe
It can be easily synthesized according to the method described in MisUy). The amount of the polymer used in the present invention varies depending on the type of polymer used, the type of photographic material to be processed, the type and concentration of the halogen ion coexisting as a fixing agent in the anti-pillowing liquid, processing temperature, etc. Generally, the amount is 1 ta or more, preferably 5 ta or more per 1 ton of the liquid, and from the viewpoint of solubility, the upper limit can be about 250 ta/ku. If the halogen ion to be coexisting is a bromide ion, it is desirable to add it in a larger amount, generally at least 20 t/k, preferably at least 30 t/k. However, in general, if the amount of the polymer of the present invention added is too small, silver halide coins are likely to be decomposed and silver halide is deposited during the water washing step as a subsequent treatment, and an unnecessarily large amount If this is the case, the viscosity of the processing liquid will increase, affecting the processing speed, and a decrease in liquid components may be observed due to carryover. Therefore, in actual use, without being limited to the above range, halogen It is desirable to appropriately determine the amount by experiment so that silver oxide secondary breakage does not occur. The halogen ions contained as a fixing agent in the anti-sedimentation solution used in the present invention are limited to bromide ions and iodide ions, similar to the halogen ions contained as a fixing agent in the bleach-fixing solution described above, and similar bromide or iodide ions. Iodide is added to the liquid, and when bromide and iodide are used in combination, at least one of them alone must satisfy the above concentration and have fixing ability. It is also true that better effects can be obtained when both bromide and iodide meet the above concentrations, but as for the halogen ions contained in such a precipitation prevention liquid, iodide ions are more preferable than bromide ions. . Note that even if halogen ions are used, chlorine ions and fluorine ions cannot have the desired effects and effects of the present invention.
The fact that they are excluded from the present invention is similar to the explanation regarding the bleach-fix solution, and as described above, these chlorine ions and fluorine ions may also be contained together. Furthermore, regarding the amounts of bromide ions and iodide ions added to the anti-sedimentation liquid, the same can be said as explained for the bleach-fixing liquid above, and it is essential that the anti-sedimentation liquid used in the present invention also has fixing ability. This is one of the features of the invention. In other words, if running processing is continued, silver ions will be eluted from the emulsion layer of the photographic material to be processed, and if a large amount accumulates in the bleach-fix solution, the fixing properties will tend to be insufficient. This is because by allowing it to last, it can be completely fixed. Moreover, since the treatment with this anti-scratch liquid is carried out after the bleach-fixing process, the amount of silver ion elution and accumulation is smaller than that of the bleach-fixing liquid, so the fixing process can be completed completely without interfering with the fixing performance. It will be done. Further, it is preferable that the hypo-deposition prevention liquid used in the present invention contains an appropriate amount of the above-mentioned organic acid metal rust salt. In other words, when the photographic material to be processed is a particularly highly sensitive silver halide color photographic light-sensitive material, silver ions are bleached rapidly and in large quantities, so that even if aeration is performed for the purpose of air oxidation, Oxidation is insufficient,
Depending on the type of coupler used in the photographic material, the dye image formed may become a leuco body and the degree of recoloring may be reduced. To compensate for this, an organic acid metal cap is added to the anti-sinking liquid. It is desirable to add salt in an amount that can prevent the above-mentioned phenomenon and also to have bleaching ability. The bleaching agent added to this anti-precipitation solution is preferably an organic acid metal salt from the viewpoint of preventing pollution, but other bleaching agents may be used since the amount added may be quite small. The higher the processing temperature with the bleach-fix solution and anti-sedimentation solution used in the present invention, the faster the processing speed. The difference in clearing time is small, and it is less affected by fixation-inhibiting components that elute from the photographic material to be processed and accumulate during the processing time, and is advantageous when recycled and used repeatedly. Although it is preferable to process the film, it is generally undesirable to use 60 oo or more in relation to the equipment used for processing, the heat resistance of the photographic material to be processed, especially its support, and the physical properties of the film of the photographic material. Therefore, it is common to process in the range of 20:00 to 55:00. The presence of spots in the bleach-fix solution and anti-sedimentation solution used in the present invention is arbitrary, but for bleach-fix solutions, the lower the pH, the shorter the clearing time, so it is better to lower the pH. However, if the pH is too low, depending on the type of coupler used in the photographic material, a problem may arise in that the dye image formed becomes a leuco body and the degree of color recovery is reduced. Therefore, the pH is generally 4 to 85, preferably 5.5 to 85.
It is better to use 7.5. The pH of the anti-settling liquid is preferably in the range of 3 to 10, and more preferably in the range of 3 to 10.
4 to 9. The bleach-fix solution used in the present invention may be of any composition as long as it contains an organic acid metal armor salt at the above concentration as a bleaching agent and bromide or iodide ions at the above concentration as a fixing agent. can. The simplest bleach-fix solutions include those containing only organic acid metal salts and bromide ions, those containing only organic acid metal rust salts and iodine ions, and those containing only organic acid metal salts, bromide ions, and iodine ions. Examples include those containing. Further, these bleach-fixing solutions may contain one or more types of various photographic additives as required. For example, pH buffering agents such as shelf acid, shelf sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone or in combination of two or more. It can be made to contain. In addition, various optical brighteners, antifoaming agents, surfactants, fixing accelerators,
Alternatively, a securing agent such as sulfurous acid, hydroxylamine/hydrazine, bisulfite adduct of an aldehyde compound, an organic chelating agent such as aminopolycarboxylic acid, or a type of stabilizer such as nitroalcohol nitrate, methanol, dimethylsulfonamide, An organic solvent such as dimethyl sulfoxide can be appropriately contained. Furthermore, in special cases oxidizing salts such as hydrogen peroxide, bromates, iodates, chlorates, perborates, nitrites and the like may be included. Although it is preferable that the bleach-fixing solution used in the present invention does not contain the polymer of the present invention for the reasons mentioned above, it is advisable to include the compound of the present invention within a range that does not impair the effects of the present invention. do not have. The anti-sedimentation liquid used in the present invention may have any composition as long as it contains the military combination of the present invention and bromide or iodide ions at the above concentration and has a fixing ability. The simplest anti-collision liquids include a liquid having a fixing chamber containing the polymer of the present invention and bromide ions, a liquid having a fixing chamber containing the polymer of the present invention and iodide ions, and a liquid having a fixing chamber containing the polymer of the present invention and iodide ions. Examples include liquids containing bromide ions and iodide ions and having a fixing ability. As mentioned above, organic acid metal salts and the like may be present in these liquids. In addition, acids such as acetic acid, phosphoric acid, and shelf acid, and alkalis such as sodium hydroxide and sodium carbonate can be added to these anti-settling solutions. Antioxidants, hardening agents made of various compounds including alum and aldehyde, mother buffers, antioxidants such as sulfites, hydroxylamine and hydrazine, and anti-swelling agents such as sodium sulfate and magnesium sulfate. , an antifoaming agent, a surfactant, an organic acid salt as a free chelating agent, etc. can be contained. In addition, although it is normally unnecessary and it is preferable not to add, if desired, a small amount of thiocyanate, thiosulfate, thioglycols, polyethylene glycols, thioureas, 4 amine salts, aliphatic thiols, aromatic thiols, etc. can also be included in the treatment bath. The method for processing a silver halide color photographic light-sensitive material according to the present invention includes all methods for processing a silver halide color photographic light-sensitive material including a step of processing with a bleach-fix solution. Specific representative examples of the preferred treatment method include the following steps. However, the processing method of the present invention is not limited to this. ■ Black and white first development - stop -
Washing with water - Color development - Bleach fixing - Prevention of precipitation Yuichi Washing with water - Stable ■
Pre-hardening - Neutralization - Black and white 1st development - 1 stop - Water washing - Color development - Stop - Bleach-fixing - Precipitation bath - Water washing - Stable ■ Pre-hardening - Neutralization - Black and white 1st development - 1 stop - Water washing - 1 color development Development - Stop -
Bleach-fixing - Rinse - Prevention of sedimentation Yuichi Washing with water - Stable ■ Black and white 1st development - Washing with water - Yuichi Color development 1 stop - Washing with water - Bleach-fixing - Bleach-fixing - Bleach-fixing - Prevention of sedimentation - Preventing precipitation Yuichi Washing with water - Stable ■ Color development - Bleach fixing - You pray to prevent Yuichi Washing with water - Stable ■ Color development - Washing with water - Bleach fixing - Bleach fixing - Preventing pillow formation Yuichi Washing with water - Stable ■ Color development - Stop constant fixation - Bleach fixing - Anti-sedimentation plate - Washing with water - Stable ■ Removal of packing - Water washing - Black and white first development - Water washing - Red exposure - Cyan color development - Water washing - Blue exposure - Yellow color development - Water washing - Magenta color development - Washing - Bleach fixing - Fixed fixation in anti-collision bath - Water washing - Stable In the processing method according to the present invention, the silver halide color photographic light-sensitive material exposed in the process before the bleach-fixing process is developed, but this development process is similar to black and white (first) development in the case of reversal development process. It may be a combination of and color development, or it may be normal color development. As the developer used in the black-and-white development, any developer called black-and-white first development used in the processing of silver halide color photographic light-sensitive materials for reversal can be used. This developer can contain various additives that are generally added to black and white developers. Typical additives include 1-phenyl-3-pyrazolidone, metol,
Developing agents such as hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, and inorganic agents such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole. Other examples include organic inhibitors, water softeners such as polyphosphates, and surface overdevelopment inhibitors made of natural iodides and mercapto compounds. Furthermore, the color developer used in the above color development step can be of any type used in color development processing of color photographic light-sensitive materials, and includes, for example, an aromatic primary amine color developing agent. An alkaline aqueous solution is preferably used in the present invention, and it can contain a mother conditioning agent and a debuffering agent such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium metashelate, sodium bicarbonate, and shelate acid. In special cases, a fogging agent such as tin chloride or borohydride may be added, and pendyl alcohol or the like may also be included. Examples of color developing agents include N-ethyl-N-methoxyethyl-3-methyl-p-phenylenediamine tosyl salt, 3-methyl-4-amino-N-ethyl[2-(2-methoxyethoxy)] Ethyl] aniline tosyl salt, N.N-jethyl-p-phenylenediamine sulfate,
4-amino-N-ethyl-N-B-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-
Examples include phenylenediamines such as 3-methanesulfamide ethylaniline sesquisulfate monohydrate and 3-methyl-4-amino-N-ethyl-N-8-hydroxyethylaniline sulfate. Further, the developer using these may contain bromides, iodides, carbonates, bisulfites, known antifoggants, known development accelerators, solvents such as diethylene glycol, and the like. The photographic material that can be applied to the present invention may be any silver halide color photographic light-sensitive material, and can be used not only for low-sensitivity silver halide color photographic materials but also for processing high-sensitivity silver halide color photographic light-sensitive materials. It can be effectively applied to any type of photosensitive material that requires bleaching and fixing, such as photosensitive materials for color printing such as photographic paper, photosensitive materials for photography such as negative color film, reversal color film, etc. It can be commonly applied to the processing of silver halide color photographic materials of the type. The silver halide color photographic light-sensitive material applied to the present invention uses an internal development method (in which a coupler is contained in the photographic material).
In addition to U.S. Pat. No. 2,376,679 and U.S. Pat. No. 2,801,171), external development methods in which a coupler is contained in the developer (U.S. Pat. No. 2,252,718 and U.S. Pat. No. 2,592)
No. 243, Specification No. 2590970). Moreover, any couplers generally known in the art can be used. For example, cyan couplers are based on naphthol or phenol structures and form indoaniline dyes through coupling, magenta couplers have a 5-pyrazolone ring with an active methylene group as their backbone structure, and yellow couplers have active methylene groups. Any type of penzoylacetanilide, pivalylacetanilide, or acylacetanilide structure having a group, with or without a substituent at the coupling position, can be used. Thus, as the coupler, both so-called 2-equivalent couplers and 4-equivalent couplers can be applied. Silver halide emulsions used in the photographic material applied to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Any silver halide may be used. In addition, as protective colloids for these silver halides,
In addition to natural products such as gelatin, various synthetically obtained products can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. The bleach-fix solution and anti-folding solution used in the processing method of the present invention can easily recover silver ions dissolved in the solution, and have extremely good stability. After that, if necessary, a regenerating agent or a replenisher is added to improve the fixing or bleach-fixing ability, and then the film can be used repeatedly. For the silver recovery method, ``all known methods can be adopted. Typical specific examples include silver precipitation using a precipitant, electrolysis using electrolysis, metal replacement using ionization tendency, and ionization. These include ion exchange methods using exchange resins, and in the present invention, electrolysis methods are particularly preferred in terms of liquid regeneration and repeated use.These silver recovery methods are described in ML Sehrei, Presents.・Status of Circulation ・Recovery ・Motion Picture Your Laboratories (Present
SPtusofSilverRecovery Mot
ion Pjctme Laboratories)74
Vol. 505-514 (1960 Wang), etc. Silver can be recovered from the bleach-fix solution and anti-sedimentation solution used in the present invention by any known method as described above, but it is more preferable to add the following operation incidentally. That is, when using the metal substitution method, for example, bromide ions and iodide ions as fixing agents are adsorbed on the surface of the metal and act as inhibitors, so it is desirable to lower the pH of the liquid to be treated. Furthermore, when using an electrolytic method, bromine or iodide ions as a fixing agent may be oxidized, so it is desirable to change the pH of the electrolytic solution, the current density, the rotation speed of the cathode, etc. The anti-folding solution used in the present invention can be reused by simply recovering the silver ions, but the bleach-fixing solution can be reused by recovering the silver ions and oxidizing the reduced form of the bleach to the original oxidizing agent. preferable. In other words, when the processing solution is a bleach-fix solution, silver is bleached and oxidized and at the same time itself is reduced, resulting in the production and accumulation of a reduced form of bleach, which reduces the bleach-fix properties of the processing solution and causes so-called fatigue. This is because it causes development. However, the bleach-fix solution used in the present invention does not substantially contain a fixing agent that acts as a reducing agent such as thiosulfate, and does not contain any substances that are oxidized at normal pH, so the reduction produced during processing is The body is only the reduced form of bleach. Therefore, in the present invention, the bleaching agent produced by the treatment can be oxidized using a conventional oxidizing agent. For example, oxidation method using air, oxygen, ozone, etc., hydrogen peroxide, persulfate, chlorate, hypochlorite, bromate, nitrous acid,
Oxidation methods using pershelfate salts, halogen gas, or other inorganic or organic oxidizing agents, anodization methods using electrolysis, oxidation methods using redox resins such as metal chelate series or quinone series, etc. can be used. In addition, even if thiocyanate is used in place of the bromide ion or iodide ion used as a fixing agent in the bleach-fix solution or anti-sedimentation solution in the method of the present invention,
Although the addition of the polymer used in the present invention has the effect of preventing the film from becoming opaque and the aforementioned effect of preventing pillow formation, the use of thiosulfate is unfavorable in terms of pollution control, as described above, and furthermore, the use of thiosulfate is Acid salts are excluded from the present invention because they are undesirable in practice because they are easily affected by fixing-inhibiting components such as halogen ions that accumulate in the processing solution. The present invention will now be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 A red-sensitive silver iodobromide emulsion containing 9 mol % of silver iodide was added with 5-[Q-(2,4-di-t-acylphenoxy)hexamide]-2-(Q- A cyan-forming red-sensitive silver halide emulsion prepared by adding Q・B・8-tetrafluoropropioamide) phenol and emulsifying the emulsion was coated with an amount of silver of 2.
11 (2'.
4'.6-trichlorophenol)-13"-1 [3"-1(
2″・4″-di-t-amylphenoxyacetamide)-
A magenta-forming green-sensitive silver halide emulsion to which penzamide]-5-pyrazolone was added and emulsified was coated so that the silver amount was 2.0 ta', and a sound-sensitive silver iodobromide emulsion containing 7 mol% silver iodide was added. A yellow-forming blue-sensitive silver halide emulsion prepared by adding Q-benzoyl [2-chloro-5-Q-(dodecyloxycarbonyl)propyloxycarbonyl]acetanilide as a yellow coupler and emulsifying the emulsion was coated with a silver amount of 2. Samples of silver halide photographic materials for color reversal (3.
5 skins and length 1) were made. After exposing the obtained sample to a predetermined amount of light through a light sliding door in a conventional manner, an automatic color reversal processor (manufactured by Eastman Kodak Co., Ltd. / Count Ectachrome Film "E-4 Processor, Model E-100") was used. ) was used to perform the following processing. [Processing method]
(Processing temperature 29.yo)'1} Anterior dura mater
3 minutes■ Neutralization 3
Min '3' 1st development 6 min '4i
1st stop 3 minutes [5] Washing with water
6 minutes■ Color development
9 minutes {7) 2nd stop 3
minutes {8' water wash 6 minutes '9}
Bleach fixing 6 minutes'1 佽 Anti-sedimentation bath 6 minutes 0U, washing with water
6 min 02 stable
The composition of the treatment liquid used was as follows. *Note 1 The commercially available product PVPK-15 described above was used. Note that ammonium hydroxide or glacial acetic acid was used to adjust the pH of the treatment solution. In the treatment of the sample according to the above treatment method, combinations of bleach-fix solution and anti-sedimentation solution shown in Table 1 below were used. In addition, each treatment solution used started with a new solution,
For each treatment liquid, the amount of liquid that fluctuates due to so-called carryover, carry-in, evaporation, etc. was only supplemented with new liquid. Table 1: Amount of sample that can be processed without failure by processing samples according to the above processing methods (experiment numbers) 1 to 11 (
(number of pieces), that is, the number of pieces that could be processed. The number of films that can be processed here means that either precipitation occurs in the bleach-fix solution or anti-settling solution, or precipitation development occurs in which insoluble silver halide is precipitated on the processed film and the finished film becomes opaque. This refers to the amount of processing required until one failure occurs. The results are shown in Table 2 below along with the details of the failure occurrence. Table 2*Note 1 No failures occurred even when processing a fairly large amount of 15,000 bottles, indicating that it is possible to process more miles than this. As is clear from the results in Table 2, in the case of the processing methods (No. 1 to 5) that are not based on the present invention, in all cases, even with a small processing amount, solid precipitates are generated in the bleach-fix solution, or the finish is The film was observed to become opaque, and even if the film was processed while replenishing the replenisher, it was found that it was difficult to process the film without failure. On the other hand, in the case of the processing methods according to the present invention (Nos. 6 to 11), it can be seen that no failure occurs even if the processing amount is three times or more of the processing amount not based on the above-mentioned present invention. Separately, the dye density of the finished films was measured using an optical densitometer using a red filter, and it was found that sufficient dye density was obtained for all films processed according to the present invention. Among them, the dye density of the films covered by Experiment Nos. 8 and 11 was the highest, and it was found that this was a particularly desirable processing method. Furthermore, regarding the processing method according to the present invention, when the clearing time of the bleach-fixing process was visually measured from the back side of the film, good results were obtained in all cases. Example
2. Samples of silver halide color photographic light-sensitive materials were prepared by coating each of the following layers on a polyethylene laminated paper support (3.
A length of 1 m) was prepared with 5 skins. [1} Yellow coupler Q-pivalyl-2-chloro-5-[y-(214-G-t-amylphenoxy)
butyramide] acetanilide and pivalyl Q-(4-carboxyphenoxy)2-chloro-5[y
1. Yellow-forming sound-sensitive silver halide emulsion layer containing (204-di-t-amylphenoxy)butyramide]acetanilide (coated silver amount 0.7/l). ■ Gelatin intermediate layer '3} As a magenta coupler, 1-[204-dimethyl-6-chlorophenyl)-31[31]
A magenta-forming green-sensitive silver halide emulsion layer containing -pentadecylphenoxy)butylamide]benzamide]-5-pyrazolone (coated silver amount: 0.8 yen/layer). (4) Gelatin intermediate layer {5} 204-dichlor-3- as cyan coupler
A cyan-forming red-sensitive silver halide emulsion layer containing methyl-6-(Q-204-di-t-amylphenoxybutyramide)phenol (coated silver weight 0.6 y/w). (6) Gelatin protective layer The obtained sample was exposed to a predetermined amount of light through a light sliding door in a conventional manner, and then subjected to the following treatment. [Processing method] (Processing temperature 31℃)'1}
Color development 3 minutes {2} Stop 3 Mouse sand '3-
Bleach fixation Change as shown in Table-3■ Anti-sedimentation rating 1 minute'5) Washing with water
The composition of the treatment liquid used was as follows. *Note 1 The commercial product PVPK-15 mentioned above was used. Note that ammonium hydroxide or glacial acetic acid was used to adjust the pH of the treatment solution. In the treatment of the sample by the above treatment method, the table below-
The combination of bleach-fix solution and anti-sedimentation solution shown in No. 3 was used. Note that each treatment solution used was started with a new solution. For the bleach-fix solution and the anti-precipitation solution, we used a method of replenishing only the decrease in processing solution during processing by using 1 final treatment solution of each processing solution, and processing was performed while replenishing the other processing solutions with new solutions. . Table - 3*Note Experiment number 22-2
The bleach-fixing process in No. 4 was carried out in two stages, meaning that the process before the arrow was carried out, and then the process after the missing mark was carried out. The samples were processed by basket development according to the above processing methods (experiment numbers) 12 to 25, and the amount (area) of the samples that could be processed without causing failure, that is, the processable area was measured. Here, the processable area refers to any one of the following failures: precipitation occurs in the bleach-fix solution or anti-sedimentation solution, or insoluble silver halide piles up on the treated paper and contaminates the maximum exposure area. This refers to the amount of processing required until the occurrence of oxidation, expressed as a sample area. The results are shown in Table 4 below along with the details of the failure occurrence. Table 4 *Note 1 No failures occurred even when processing a considerably large amount of 6.0M2, indicating that it is possible to process larger quantities. As is clear from the results in Table 4, in the case of processing methods (Nos. 12 to 15) that are not based on the present invention, in all cases, permanent precipitates are generated in the bleach-fix solution with a small processing amount, or the finished paper It can be seen that failures occur in which contamination due to secondary folding of insoluble silver halide occurs. On the other hand, the treatment method according to the present invention (Nos. 16 to 25)
In the case of , it can be seen that no failure occurs even if processing is performed about three times as much as the processing method (No. 15) which has the largest processing area among the processing methods based on the present invention. From this, it can be seen that the treatment method of the present invention can continue the treatment semi-permanently without any problem if the treatment is performed while replenishing the replenisher as in the actual treatment. Separately, the dye density at the maximum exposure area of the finished papers was measured with an optical densitometer using a red filter, and it was found that sufficient dye density was obtained for all papers treated according to the present invention. Among them, papers based on Experiment Nos. 17, 1924 and 25 had the highest dye densities and were found to be particularly desirable processing methods. Furthermore, when the clearing time of the bleach-fixing process was visually measured for the processing method according to the present invention, good results were obtained in all cases. Regarding the treatment method of this example, the treatment temperature was set to 40qo.
When the treatment method according to the present invention was carried out in place of the above, good results similar to those described above were obtained. Example 3 The following bleach-fix solution was prepared. The treatment was performed using a treatment step in which the blood anti-fraction bath was removed from the treatment steps. The same ones as in Example 1 were used except for the bleach-fix solution. However, the bleach-fixing process was continued for up to 20 minutes while observing the desilvering state every minute. The bleach-fixing solutions (V) to (x) were treated with a total of 6 types, including cases in which PVP K-15 of exemplified compound m was added for 20 evenings each. The clearing time of each was measured, and the surface condition of the emulsion of the processed photographic material sample was observed, and the presence or absence of precipitation was determined.
5. Furthermore, 100% of the bleach-fix solution after processing is added to 20% of the bleach-fix solution.
The solution was stored in a glass beaker, and the number of days for precipitation to occur in the solution was observed and similarly recorded in Table 5. Table 5 As can be seen from the results in Table 5, when the bleach-fix solution of the present invention contains silver ions as in the continuous processing state,
Compared to conventional bleach-fix solutions, it takes significantly less time to complete desilvering and enables rapid processing, but if it does not have anti-sedimentation properties, it has the disadvantage of generating precipitation during the washing process, making the photographic material opaque. are doing. However, it can be seen that by adding the compound of the present invention, this white precipitation phenomenon in the water washing step is eliminated. It can be seen that desilvering is not promoted by the compounds of the present invention. Even with conventional bleach-fix solutions, addition of the compound of the present invention did not promote desilvering in silver bromide emulsions. On the other hand, the storage stability of the bleach-fix solution is limited. With the conventional bleach-fix solution containing thiosulfate, a sulfurization phenomenon was observed within two weeks and a large amount of yellow precipitate was generated, but with the bleach-fix solution of the present invention, No precipitation occurred at all. Furthermore, the storage stability was not affected by the addition of the compound of the present invention.

Claims (1)

[Scope of Claims] 1. After processing the exposed silver halide color photographic light-sensitive material, at least 0.01 mol/l of an organic acid metal complex salt and at least 3 mol/l of bromide ion or at least 1.3 mol Bleach-fixing is carried out with a bleach-fixing solution containing iodide ions/l, and in a processing step after the bleach-fixing, a polymer having a pyrrolidone core unit in its molecular structure and at least 3 mol/l of bromide ions or at least 1 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution having a fixing ability containing .3 mol/l of iodide ions. 2. The halogenated solution according to claim 1, wherein the processing solution having fixing ability is a bleach-fixing solution that contains a bleaching agent and also has bleaching ability, or a normal fixing solution that does not have bleaching ability. Processing method for silver color photographic materials. 3. Silver halide color photographic photosensitive material according to claim 1 or 2, characterized in that the content of bromide ions in the bleach-fix solution and the processing solution having fixing ability is 4 to 6 mol/l. How materials are processed. 4. The method according to claim 1, 2 or 3, characterized in that the content of iodide ions in the bleach-fix solution and the processing solution having fixing ability is 1.5 to 6 mol/l. A method for processing silver halide color photographic materials.