JPS6015060B2 - 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 more particularly to a method for processing a silver halide color photographic light-sensitive material, which uses an organic acid metal complex 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 fixer. 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 has excellent stability.
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-fix solution used in the bleach-fix process is generally an aqueous solution containing a bleach 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 dish salt as a bleaching agent releases cyan due to photodecomposition and poses a pollution problem, so measures must be taken to completely render the treated simulated solution 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 materials in the processing machine that is filled with them are easily corroded, and they also This method has the disadvantage that iron hydroxide is precipitated in the emulsion layer of the photographic material to be processed during the processing step, 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 lead salt of ethylenediaminetetraacetate are less toxic and more advantageous in terms of pollution control, so it has been recommended in recent years to use them as bleaching agents. It started to be done. However, organic acid metal salts have relatively low oxidizing power and insufficient bleaching power, so products using this as a bleaching agent are, for example, low-sensitivity silver halide colors based on silver chlorobromide emulsions. When bleach-fixing photographic materials, it is possible to achieve the desired purpose, but
For example, a high-sensitivity silver halide color photographic light-sensitive material that is mainly composed of silver chloroiobromide or silver iodobromide emulsion and is color sensitized, especially a silver halide color reversal photographic light-sensitive material for reversal that uses a high silver content emulsion, is processed. In some cases, the bleaching action is insufficient and desilvering is insufficient, making it difficult to achieve the goal of achieving a bleach-fixing efficiency of 4. If this point is resolved,
Organic acid metal rust salts 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 is not necessarily 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. AgX+n(NH4)2S2
03 → Ship (s2o3) Tei L (2 elbows) 10 or NH4 10 x e (where n is 2 or 3, and X represents halogen) As seen in this reaction example, the bleach-fix solution is silver halide. As the photographic light-sensitive material undergoes bleach-fixing processing, silver salts and halogen ions accumulate, and the free components of the fixing agent 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 overflow, but disposing of this overflow solution as it is is contrary to resource conservation as it contains silver and other valuable components. However, since this is extremely disadvantageous economically and is also undesirable from the standpoint of environmental pollution, 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 due to this electrolytic reaction, and thiosulfate ions are also reduced due to air oxidation or so-called carry over during processing, so the liquid volume must be kept at a level that does not overflow. 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. The fixing speed decreases, eventually resulting in poor fixing.
The cause 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 accumulate. 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. Namely, examples of the former include the promotion of fixation by a sulfur compound described in Japanese Patent Publication No. 45-35754;
Alternatively, there is a fixing promotion Z-axis method using a polyethylene glycol compound described in Japanese Patent Publication No. 48-39173, etc.
Both methods are unfortunately 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 have the disadvantage that fixing defects will eventually occur after repeated reuse and repeated use. There is. Therefore, in order to reduce the accumulated concentration of halogen ions, the overflow bleach-fix solution is currently recycled and used repeatedly while discarding a portion 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. 43-3
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 often used as a fixing agent, does not cause environmental pollution as long as it is used as a fixing agent in bleach-fix solutions, where silver ions and halogen ions, which are fixation-inhibiting components, tend to elute and accumulate from the emulsion layer of processed photographic materials. It can be said to be a serious problem in terms of pollution prevention. On the other hand, thiocyanates and halogen salts, which are known as fixatives other than the thiosulfates mentioned above, have low stability as silver complex salts, so if the fixative concentration becomes low during the next water washing process, the decomposition of the silver complex salts will be delayed. 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 (BOO) and chemical oxygen demand (C
OD), there is dust that pollutes the environment, and 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 preservative for the thiosulfate. Since the sulfite is also a reducing agent, the oxidation-reduction potential of the bleach-fix solution becomes moderately base, and the oxidizing power of the coexisting bleach (oxidizing agent) is increased.
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, resulting in disadvantages in repeated reuse. 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 lead salt as a bleaching agent and a specific halogen salt, i.e., bromide or iodide, as a fixing agent, To complete a method for processing silver halide color photographic materials that can solve the above-mentioned drawbacks of organic acid metal complex salts as bleaching agents used in bleach-fix solutions and bromide ions or iodine ions as fixing agents. It has arrived. That is, the first object of the present invention is to provide a bleach-fixing solution that has low biological oxygen demand (80D) and chemical oxygen demand (COD) loads, is low in toxicity, and meets the requirements for preventing environmental pollution. An object of the present invention is to provide a method for processing a halogenated synthetic fiber color photographic material. 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 too low 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. The inventor has discovered that exposed c. After the iron genide color photographic light-sensitive material is developed, it is treated with a bleach-fix solution containing at least 0.01 mole of the organic acid metal salt and at least 3 mole of the bromide ion or at least 1.3 mole of the iodide ion. It has been found that the above object can be achieved by bleach-fixing and treating with an anti-sedimentation solution containing at least 0.03 mol of thiosulfate ion in the processing step after the bleach-fixing. That is, the method for processing a silver halide color photographic light-sensitive 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 exhibit the oxidizing ability of the metal key salt, post-treatment is performed with a processing solution containing thiosulfate ions in the processing step after bleach-fixing using the bleach-fixing processing solution. This method solves the drawbacks of the above-mentioned specific halogen ions. 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 complex salt decomposes and remains as halogen silver in the emulsion layer of the processed material, making the finished film opaque when processing negative or positive films. As mentioned above, this drawback is solved by including a specific amount or more of thiosulfate ion in the processing solution used in any processing step after the bleach-fixing step, and the present invention as described above can be solved. can achieve the objectives of Moreover,
Bleach-fix solutions, which elute and accumulate large amounts of silver ions and halogen ions as fixation-inhibiting components, do not contain any thiosulfate ions, which have a high pollution load, and the elution and accumulation of these ions is more extreme than in bleach-fix solutions. Since thiosulfate ions are contained in a small amount of the treatment liquid, the pollution load can be significantly reduced. In particular, the main purpose of the processing solution containing thiosulfate ions is not to improve the fixing ability, but rather to prevent the precipitation phenomenon of non-stainable silver halide during the water washing process. Therefore, even if the processing amount increases and the amount of accumulated halogen ions and silver ions increases, the processability for preventing silver halide from folding will not deteriorate, and the accumulated silver ions will be recovered. If recycled, the processing solution can be used repeatedly semi-permanently without being discarded, and the above-mentioned pollution load caused by the bleach-fix solution containing thiosulfate ions does not occur. As the organic acid metal key salt as a bleaching agent contained in the bleach-fix solution used in the present invention, any metal salt of an organic acid can be used as long as it acts as an oxidizing agent for silver. Examples of this organic acid include aminopolycarboxylic acids represented by the following general formula [1] or [b]. General formula [1] HOCO-A, 1Z-A2-COO General formula [B] [In each of the above general formulas, A, A2, A3, &, A6 are each substituted or unsubstituted hydrocarbon group, Z represents a hydrocarbon group, an oxygen atom, a sulfur atom, or >N-A7 (A7 is a hydrocarbon group or a lower 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. '11
Ethylenediaminetetraacetic acid [2] Ethylenetriaminebentaacetic acid (3) Ethylenediamine-N-(B-oxyethyl)-N・N'・N
'-Triacetic acid' 41 Propylenediaminetetraacetic acid [51 Nitrilotriacetic acid side Cyclohexanediaminetetraacetic acid {7' iminodiacetic acid■ Dihydroxyethylglycine side Ethyl etherdiaminetetraacetic acid column Glyco-etherdiaminetetraacetic acid (11) Ethylenediaminetetrapropionic acid ( 12) Phenylenediaminetetraacetic acid (13) Ethylenediaminetetraacetic acid disodium salt (1 core Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (15) Ethylenediaminetetraacetic acid tetrasodium salt (16) Diethylenediaminetetraacetic acid pentasodium salt (17)
Ethylenediamine-N-(8-oxyethyl)-N・N
'.N'-Triacetic acid sodium salt (18) Propylene diamine tetraacetic acid sodium salt (19) Nitrilotriacetic acid sodium salt (20) Cyclohexanediamine tetraacetic acid sodium salt The above-mentioned organic acid metal complex salt used in the present invention is a bleach-fixing solution 1. The requirement is that the content be at least 0.01 mol per mole, and thereby the above-mentioned object of the present invention can be fully achieved, but if the amount added is too large, the processability may deteriorate, so it is preferable that the content be 0.01 mol. .01-2.5 mol/
It's a 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 supplied to 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, but when bromide and iodide are used in combination, 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 caused by chloride and fluoride cannot have the desired action and effect of the present invention, but bromide ions or iodide ions at the above concentration are excluded. As long as they are contained, even if these chloride ions and hydrogen ions are contained together, there is no effect on the action and effect of the present invention. 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 1 kg of the bleach-fix solution, thereby sufficiently achieving the above-mentioned purpose of the present invention. However, due to solubility, the upper limit for bromide ions is about 7.5 mol/l, and the upper limit for iodide ions is about 12 mol/l. 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, in the case of bromide ions, the addition amount is 4 to 6 mol/so.
In the case of iodide ions, it is 1.5 to 6 mol/s. A processing solution used in a processing step after the bleach-fixing process using the above bleach-fix solution, which prevents the precipitation phenomenon of silver ions (herein, this solution is referred to as a hypo-precipitation prevention solution). The thiosulfate ion contained in the anti-folding compound used in the treatment process is referred to as an anti-folding compound) is supplied to the liquid by the thiosulfate. Any type of thiosulfate can be used to incorporate the thiosulfate ion into the precipitation prevention solution. Typical thiosulfates include sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, lithium thiosulfate, etc. Ammonium salts and potassium thiosulfates are particularly preferred because they have a high diffusion rate into the gelatin layer of processed photographic materials. Salt is effective. These thiosulfates can be used alone or in an appropriate combination of two or more. The thiosulfate ion used in the present invention is
The content is required to be at least 0.03 mol per unit, thereby making it possible to prevent the precipitation of silver ions, which is the original purpose of the precipitation prevention liquid. In the present invention, the desirable addition amount is 0.05 mol/l or more, particularly preferably 0-2 mol/l or more, in order to further improve the stability and processing efficiency of the liquid. However, since the anti-sedimentation liquid of the present invention does not have fixing ability as its main purpose as described above, it may be added in an amount that does not have fixing ability. It is preferable to add a thiosulfate ion antioxidant to the hypo-precipitation prevention liquid used in the present invention. Typical antioxidants include sulfites, hydroxylamine, hydrazine, bisulfite adducts of aldehydes, and the like alone or in combination of two or more. As mentioned above, the original purpose of the precipitation prevention liquid used in the present invention is to prevent the precipitation phenomenon of silver ions.
This anti-sedimentation liquid may also have fixing ability. In other words, if the running process 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-sedimentation solution is carried out after the bleach-fixing process, the amount of ion elution and accumulation is smaller than with the bleach-fix solution, so the fixing process can be completed without hindering the fixing performance. It will be done. Further, it is preferable that the antisedimentation liquid used in the present invention contains an appropriate amount of the above-mentioned organic acid metal complex salt. In other words, when the photographic material to be processed is a particularly highly sensitive silver halide color photographic material, silver ions are rapidly and in large quantities bleached, so even if aeration is performed for the purpose of air oxidation, Depending on the type of coupler used in the photographic material, the oxidation may become insufficient and the dye image formed may become a leuco substance, reducing the degree of color recovery. It is desirable to add an organic acid metal salt to the preventive solution in an amount sufficient to prevent the above-mentioned phenomenon, thereby imparting bleaching ability to the solution. The bleaching agent added to this precipitation prevention solution is preferably an organic acid metal tin salt from the viewpoint of pollution prevention, but the amount added may be quite small, and the precipitation prevention solution can be discarded as described above. Other bleaching agents may be used as they can be recycled and used again without any bleaching. 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 in the processing bath, which is also advantageous in repeated reuse. Although processing is preferable, 60 qo or more may generally be undesirable 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 at a temperature in the range of 20 to 55°C. The pH of the bleach-fix solution and hypo-precipitation prevention solution used in the present invention is arbitrary, but the lower the pH of the bleach-fix solution, the shorter the clearing time, so it is better to lower the pH of the bleach-fix solution. 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 4-8.5, preferably 5.5-8.5.
It is better to use 7.5. The pH of the anti-settling liquid is preferably in the range of 3 to 10, more preferably pH
4 to 9. The bleach-fix solution used in the present invention may have any composition as long as it contains organic acid metal fin 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 mirror salts and bromide ions, those containing only organic acid metal salts and iodide ions, and those containing only organic acid metal complex salts, bromide ions, and iodide 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 sulfite, hydroxylamine, hydrazine, or a bisulfite adduct of an aldehyde compound, an organic chelating agent such as aminopolycarboxylic acid, or a type of stabilizer such as nitroalcohol nitrate, methanol, dimethylsulfoamide, 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. The hypo-precipitation prevention liquid used in the present invention may have any composition as long as it contains thiosulfate ions at the above concentration. The simplest anti-settling liquids include a liquid having a fixing chamber containing only thiosulfate ions, and a liquid having a fixing chamber containing thiosulfate ions and an antioxidant. As mentioned above, a bleaching agent such as an organic acid metal rust salt may be present in these anti-sedimentation solutions. In addition, acids such as acetic acid, phosphoric acid, shelf acid, and alkalis such as sodium hydroxide and sodium carbonate can be added to these anti-folding liquids, and if necessary, precipitates consisting of various chelate compounds can be added. Inhibitors, hardening agents made of various compounds including alum-based and aldehyde-based compounds, pH buffering agents, anti-swelling agents such as sodium sulfate and magnesium sulfate, antifoaming agents, surfactants, free chelating agents It is possible to contain organic acid salts and the like. In addition, although it is normally unnecessary and it is preferable not to add, if desired, a small amount of thiocyanate, thioglycols, polyethylene glycols, thioureas, quaternary 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 - Precipitation bath - Washing with water - Stable■
Prehardening - Neutralization - Black and white first development - Stopping - Water washing - Color development - Stopping - Bleach-fixing - Bleach-fixing - Water washing - Hypo-deposition prevention bath One water wash - Stable ■ Prehardening - Neutralization - Black and white first development - Washing with water - Color development - Stopping - Bleach-fixing - Washing with water - Preventing pillowiness Yuichi Washing with water - Stable■
Black and white 1st development - Stop - Water washing - Fog Yuichi Color development - Rinse Bleach-fixing - Water washing - Pillagination prevention bath - Water washing - Stable ■ Color development - Bleach fixing - Precipitation prevention - Washing - Stable ■ Color development - Water washing - Bleach fixing - Bleach-fixing - anti-sedimentation - washing - stable Color development - stopping - washing - bleach-fixing - washing - anti-sedimentation bath - washing - stable ■ 1-bath color development bleach-fixing - anti-sedimentation bath - washing - stable ■ Packing Removal - 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 - Water washing - Bleach-fixing - Precipitation bath - Water washing - Stability In the processing method according to the present invention The silver halide color photographic light-sensitive material exposed in the step before the bleach-fixing step is developed, and this development is a combination of black-and-white (first) development and color development in the case of reversal development. Ordinary color development may be used. 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, potassium carbonate, inorganic or Examples include organic inhibitors, water softeners such as polyphosphates, and surface overdevelopment inhibitors consisting of natural iodides and mercapto compounds. Furthermore, the color developing solution 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 development agent. Alkaline aqueous solutions are preferably used in the present invention, and can contain adjusting agents, pH buffers, such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium metatrate, sodium bicarbonate, and acid. Also, in special cases, fogging agents such as tin chloride or boro/hydride can be added.
Furthermore, pendyl alcohol or the like may be included. As a color developing agent, for example, 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-ethyl-p-phenylenediamine sulfate, 4-amino-N-ethyl-N-3-hydroxyethylaniline sulfate, 3-methyl-4-amino -N-Ethyl-8-methanesulfamide ethylaniline sesquisulfate monohydrate, 3-methyl-4-amino-N-ethyl-N-P-hydroxyethylaniline sulfate, and other phenylenediamines. 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 bleach-fix solution of the present invention is used after developing the exposed silver halide color photographic light-sensitive material, but it does not need to be used immediately after the development, and other treatments such as water washing or rinsing may be involved. It's okay. Further, the bleach-fixing treatment using the bleach-fix solution may be a single step or may be a multi-step process divided into a plurality of steps. This multi-step bleach-fixing process may be a so-called countercurrent method in which each step consists of a continuous processing solution, or a method in which each processing solution consists of an independent step. Further, the treatment with the bleach-fix solution of the present invention may be a treatment with a so-called one-bath color development bleach-fix solution which also contains a color developer. 1 like this
In the case of a bath solution, development is performed first and then bleach-fixing is performed, so that it is included in the processing method of the present invention. The anti-sedimentation liquid of the present invention can be used in any process of bleach-fixing using the above bleach-fixing solution, but from the viewpoint of simplifying the process and processing efficiency, it can be used in the process immediately after the bleach-fixing process. It is preferable to use However, it goes without saying that other treatments such as washing with water may be interposed between the bleach-fixing treatment and the precipitation prevention treatment using the anti-sedimentation liquid. In order to improve processing efficiency, it is desirable to increase the amount of thiosulfate ion added as appropriate. Further, after the pillowing prevention treatment using the anti-sedimentation liquid of the present invention, arbitrary treatments such as water washing treatment and stabilization treatment may be performed. 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 all types of photosensitive materials that require bleaching and fixing, such as photosensitive materials for color printing such as photographic paper, photosensitive materials for photography such as negative color film, and reversal color film. It can be commonly applied to the processing of type silver halide color photographic light-sensitive materials. 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-spinning solution used in the processing method of the present invention can easily recover silver ions dissolved in the solution, and have extremely good stability, so silver ions can be recovered easily. 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. Any known method can be used to recover the silver. Typical specific examples thereof include a silver precipitation method using a precipitant, an electrolytic method using electrolysis, a metal replacement method using ionization tendency, an ion exchange method using an ion exchange resin, etc. In this case, the electrolytic method is preferred for recycling and repeated use of the liquid. For information on how to recover these silvers, see M.L. Sehrei, Present Status of Silver Recovery Motion Picture Your Laboratories.
NetusofSilverRecoveryMooo
n Pictme Laboratories) Volume 74 5
It is described in pages 05 to 514 (King, 1965).
For the recovery of silver from the bleach-fixing solution and anti-folding solution used in the present invention, any of the three methods mentioned above can be employed, but it is more preferable to add the following operation incidentally.
That is, for example, when using the metal substitution method, bromide and iodide ions as fixing agents in the case of a bleach-fix solution, and special addition from the bleach-fix solution or elution from the emulsion layer of the photographic material to be processed in the case of an anti-sedimentation solution. The bromide or iodine ions that accumulate on the surface of the metal become adsorbed and act as inhibitors.
Therefore, it is desirable to lower the pH of the liquid to be treated. Furthermore, when using an electrolytic method, the above-mentioned bromide ions or iodide ions 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-sedimentation 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, producing and accumulating a reduced form of bleach, which reduces the bleach-fixing ability of the processing solution and causes so-called fatigue. This is because it may cause the phenomenon to occur. 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 substances that are oxidized in ordinary meat, so it does not contain the reducing agent that is generated during processing. 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, persherate, halogen gas or other inorganic or organic An oxidation method using an oxidizing agent, an anodization method using electrolysis, an oxidation method using a redox resin such as a metal chelate type or a quinone type, etc. can be used.
In addition, even if thiocyanate is used in place of the bromide or iodide ion used as a fixing agent in the bleach-fix solution in the method of the present invention, the effect of preventing film opacity due to the hypodeposition prevention solution containing thiosulfate ions, and Although the above-mentioned precipitation prevention effect etc. can be obtained, the use of this thiosulfate is not preferable from the viewpoint of pollution control as mentioned above, and furthermore, thiocyanate can prevent fixation-inhibiting components such as halogen ions that accumulate in the processing solution. It is excluded from the present invention because it is not practically desirable because it is susceptible to oxidation. Next, an additional comment will be made regarding the method for recovering silver from the hypo-precipitation prevention liquid used in the present invention. The reuse and reuse of anti-pillowing liquid can be carried out in exactly the same way as the reuse and reuse of ordinary fixer fluids, but especially the reuse and reuse using so-called electrolytic silver recovery in which silver is deposited on the cathode of an electrolytic cell. can be carried out advantageously. In normal reuse and repeated use of the fixer, {1} The fixer replenisher is replenished into the fixer tank as the photosensitive material is developed.
The same amount of tired fixer as the amount of replenisher overflows from the fixer tank, but this overflow solution is led to an electrolytic tank to recover silver, and a regenerating agent is added and mixed to use it again as a fixer replenisher. (hereinafter referred to as the batch method). ■
The electrolytic cell and the fixing tank are directly connected, and silver is recovered while circulating the fixing solution between the two tanks in order to reduce the silver concentration in the fixing solution by bringing the concentrations of silver contained in both the tanks as close as possible. At the same time, a regenerating agent is added to the fixer overflow from the fixer tank and used again as a fixer replenisher (hereinafter referred to as the circulation method). etc. Reuse and repeated use of the fixer can be carried out advantageously by either a batch method or a circulation method. As the fixer is repeatedly recycled and used, halogen ions, silver, and the like, which have the property of reducing the fixing ability, accumulate in the fixer. Among the halogen ions, bromide ions and iodine ions that accumulate during development of silver iodobromide photosensitive materials particularly reduce the fixing ability. Ions must be kept as low in concentration as possible. The amount of processing solution used in the process before the fixing process in which the iodide ions accumulated in the fixer are brought into the fixing tank by the photosensitive material, the amount of iodide ions contained in the photosensitive material as silver iodide or iodide, and the amount of replenisher , it is necessary to control the rate of regeneration, ie, the amount of fixer fatigue liquid that is discarded outside the system before or after adding the regenerant. High-sensitivity photosensitive materials made of ordinary silver iodobromide contain about 2 mol% to 15 mol% of silver iodide, but the fixing process for such photosensitive materials contains 0.2 mol to 1 mol of silver iodide/its thiosulfate. The amount of replenishment is equal to 1 for the photosensitive material.
3 to 30 per 00 is normal. Fatigue fixer overflows from the fixer tank or electrolytic tank during replenishment, but 1/2 of this overflow liquid
Add the same amount of regenerating agent as the overflow liquid that was discarded or a smaller volume and reuse it as a replenisher. By controlling the concentrations of iodide ions and silver in the fixing tank to about 5/min or less when recycled and used repeatedly in this manner, processing can be carried out without impairing the fixing properties. Especially when silver recovery is carried out by circular method,
It is advantageous that the silver concentration in the fixing tank can be maintained at around 0.5% by controlling the current or current density. 0.
When the silver concentration is maintained at 5 m/h or more, silver can be safely recovered without the risk of silver sulfide formation on the cathode. The current density at the cathode is preferably maintained within a range that does not produce silver sulfide, and the higher the silver concentration in the fixing tank, the higher the current density at the cathode can be. There is a close relationship between the silver concentration in the fixing tank and the current density without silver sulfide formation; for example, when the silver concentration in the fixing tank is 0.5 m/at that time, the current density at the cathode is 0.0 m'c. Below the tiger, the silver concentration is 2.0 ta'
So, 5 evenings/At that time, the current density of the cathode was 0. secretion/
C liquid, 0. Silver recovery can be carried out with a current less than I'. The concentration of iodide ions in the fixer tank must be maintained at about 500 ml per hour or less, but this depends on the rate of regeneration of the fixer solution, i.e., the amount of fixer fatigue solution that is discarded outside the system before or after adding the regenerant. In particular, by setting the regeneration ratio to 70 to 95% in order to keep the iodide ion concentration below 30%, i.e., the overflow of the fatigued fixer from the fixer or electrolytic tank is reduced during replenishment. By reusing 70 to 95% again, recycling and repeated use can be advantageously carried out. In the above-mentioned regeneration and repeated use of the fixer, when the tired fixer overflows from the fixer tank or electrolytic tank, a regenerant is added in a regeneration tank other than the fixer tank and used as a fixer replenisher. Exactly the same results can be obtained even if the agent is directly added and mixed into the fixing tank without being added to the regeneration tank. The method for regenerating and repeatedly using the anti-sedimentation solution containing thiosulfate ions described above can be similarly applied to a fixing solution or a bleach-fixing solution when thiosulfate ions are used as a fixing agent. The present invention will now be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 1-Hydroxy-2-n-6-(2,4-di-t-amylphenoxybutyl)naphthamide was added as a cyan coupler to a red-sensitive silver bromide emulsion containing 9 mol% silver iodide and emulsified and mixed. A cyan-forming red-sensitive silver halide emulsion was coated with a coated silver amount of 2.0 ta', and a green-sensitive silver iodobromide emulsion containing 8 mol% silver iodide was coated with a magenta coupler of 1.
-(2', 4', 6-trichlorophenol)-3''-
A magenta-forming green-sensitive silver halide emulsion prepared by adding [3″-(2″・4″-t-t-amylphenoxyacetamide)-penzamide]-5-pyrazolone and emulsifying the emulsion was coated with a coating silver amount of 2.0 μm/day. Then, Q-benzoyl[2-chloro-5-Q-(dodecyloxycarbonyl)propyloxycarbonyl]acetanilide was added as a yellow coupler to the sonic silver iodobromide emulsion containing 7 mol% of silver iodide, and emulsified and mixed. A yellow-forming blue-sensitive silver halide emulsion was coated on a subbed polyethylene terephthalate film at a coating silver amount of 2.0 mm/min to prepare a sample of a silver halide photographic light-sensitive material for color reversal. A sample with a length of 1 and 5 arcs was prepared.The resulting sample was exposed to a predetermined amount of light through a photoacid using a conventional method, and then processed using an automatic processor for color reversal (Viscount Ektachrome manufactured by Eastman Kodak Company). The following treatments were carried out using a film, E-4 film, Rosseter, model E-100). [Processing method] (Processing temperature 29.80)'1} Predural mater 3 minutes ■ Neutralization 3 minutes (3) 1st development 6 minutes {4) 1st stop 3 minutes ■ Washing 6 minutes '6} Color development 9 minutes '7' 2nd stop 3 minutes {8} Washing 6 minutes ■ Bleach fixing 6 minutes (10) Preventing sedimentation 6 minutes (11) Wash with water 6 minutes (12) Stable
The composition of the treatment liquid used was as follows. Pre-hardening solution Neutralizing solution First developer First and second stop solution Color developing solution Stabilizing solution Bleach-fix solution (A) Bleach-fix solution (B) Processing solution (C) ... Comparative processing solution (D) Comparison anti-sedimentation liquid (E) Precipitation prevention liquid (F) Pillow prevention liquid (G) Water was added and left overnight to adjust the concentration to 6.5. Note that ammonium hydroxide or glacial acetic acid was used to adjust the citrus color in 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,
As for the bleach-fix solution and anti-sedimentation solution, the amount of the solution fluctuated due to so-called carry-over, carry-in, evaporation, etc. was only supplemented with new solution, and the other processing solutions were processed while being replenished with new solution. Table 1 Note 1 Processing liquids (■, ■) having fixing ability were used for comparison. Samples were processed according to the above processing methods (experiment numbers) 1 to 10, and the processing amount was measured until a settling phenomenon in which permanent halogen silver precipitated on the processed film and the finished film became opaque appeared. As a result, treatment methods not based on the present invention (Nos. 1 to 4)
In all cases, opacity of the finished film was observed from the beginning of processing. On the other hand, in the case of the processing method according to the present invention (Nos. 5 to 10), no opacity of the finished film occurred at all even when a considerably large number of films, 18,000 or more, were processed. It turned out that more processing than this was possible. 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 of the films processed according to the present invention. Among them, it was found that the dye density of the film was the highest based on Experiment Nos. 6 and 10, and 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.
5 cm and length 1) was prepared. [11 As yellow couplers, Q-pivalyl-2-chloro-5-[y-(2,4-di-t-amylphenoxy)butyramide]acetanilide and Q-pivalyl-Q-(4-carpoxyphenoxy)2-chlor-5 [
Yellow-forming sound-sensitive silver halide emulsion layer containing y-(2.4-di-t-amylphenoxy)butyramide]acetanilide (at a coated silver amount of 0.6 ta'). ■ Gelatin intermediate layer {3} 11[2,4-dimethyl-6-chlorophenyl)-3-{31[Q1(3-n
-bentadecylphenoxy)butylamide]benzamide}-5-pyrazolone magenta-forming green-sensitive silver halide emulsion layer (coated silver weight 0.75 ta'). [4) Gelatin intermediate layer ■ Cyan-forming red-sensitive silver halide emulsion layer containing 2,4-dichloro-3-methyl-6-(Q-2,4-di-t-amylphenoxybutyramide) phenol as a cyan coupler (coating) Silver amount 0.6 yen/force). (6) Gelatin protective layer The obtained sample was passed through a light tower in a conventional manner to give a prescribed exposure, and then the following treatment was performed. [Processing method] (Processing temperature: 31°C) {1- Color development 3 minutes ■ Stop Stop
3 jobs '3} Bleach fixing
Changes as shown in Table 2 '4'
1 minute'5} Water washing 2 minutes The composition of the treatment liquid used is as follows. Color developer stop solution Bleach-fix solution (H) Bleach-fix solution (1) Bleach-fix solution U) Processing solution (K)... Comparative processing solution (L)... Comparative settling solution Preventing liquid (M) Anti-settling liquid (N) Precipitating liquid (0) Water was added thereto overnight, and the pH was adjusted to 6.4. Pillow prevention liquid (P) *, water is reduced to 1, mottling 9.2'
I made this adjustment. 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 2 below were used. Note that each treatment solution used was started with a new solution. For the bleach-fix solution and anti-sedimentation solution, we adopted a method of replenishing only the decrease in processing solution during processing using 1 final treatment solution of each processing solution, and processing was performed while replenishing the other processing solutions with new solutions. . Table-2 *Note 1. The bleach-fixing treatments of experiment numbers 21 to 23 were carried out in two stages, meaning that the pre-loss processing was carried out followed by the post-loss processing. xNote 2. For comparison, a processing solution with bleach-fixing ability was used.
, mountain) was used. The sample was treated with the above method (experiment number) 11
The processed paper was processed by basket development according to No. 24, and the processing amount until the phenomenon of insoluble silver halide settling on the processed paper and contaminating the maximum exposure area was measured. the result,
In all cases of processing methods not based on the present invention (No. 11-14), stains due to the precipitation of faceless silver halide were observed on the finished paper from the beginning of the processing. On the other hand, the treatment method according to the present invention (No. 15 to 24)
In all cases, no contamination due to the precipitation of insoluble silver halide occurred on the finished paper even when a considerably large amount of treatment was carried out with a treatment area of 10 or more. It turned out that more processing than this was possible. Separately, the dye density in the most exposed area of the finished paper was measured with an optical densitometer using a red filter, and it was found that sufficient dye density was obtained for all vapors processed according to the present invention. Among them, the papers based on Experiment Nos. 17 and 23 had the highest dye concentrations, 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. In addition, regarding the treatment method of this example, the treatment temperature was set to 40q0
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.

Claims (1)

[Scope of Claims] 1. After developing 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 with a bleach-fixing solution containing iodine ions/l, and treatment with an anti-sedimentation solution containing at least 0.03 mol/l thiosulfate ions in the processing step after the bleach-fixing. Characteristic processing method for silver halide color photographic materials. 2. The method for processing a silver halide color photographic material according to claim 1, wherein the content of bromide ions in the bleach-fix solution is 4 to 6 mol/l. 3 Iodine ion content in bleach-fix solution is 1.5~
Claim 1 characterized in that the amount is 6 mol/l.
A method for processing a silver halide color photographic light-sensitive material according to item 1 or 2.