JPS6113579B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for improving the fixing performance of a photographic fixer that has good stability, excellent processing efficiency, and can be recycled and used repeatedly. More specifically, it can accelerate the fixing speed of photographic fixers and significantly improve processing capacity, and it does not deteriorate even when silver is recovered and recycled, and it can be used after silver is recovered. The present invention relates to a method for improving the fixing performance of a photographic fixer, which can be recycled and used repeatedly without being discarded by adding a regenerating agent or a replenisher as appropriate. Generally, in order to develop a silver halide photographic material that has been exposed to light to obtain a silver image or a color dye image, a fixing process is performed after the developing process. That is, when the silver halide photographic material is for black and white use, a silver image is obtained through a development process, and then unexposed silver halide is dissolved and removed through a fixing process, and only the silver image is transferred to the photosensitive material. to be recorded. on the other hand,
When the silver halide photographic light-sensitive material is for color use, a first development process is carried out for positives, and a color development process is used for negatives. ) to convert the material into soluble silver salts, followed by desilvering by dissolving and removing all the soluble silver salts in a fixing process to record color dye images on light-sensitive materials. In either case, the remaining silver salt is dissolved and removed in the fixing process by a compound that reacts with silver halide, such as sodium thiosulfate, as a component of the fixing solution to form a soluble complex salt. For example, a reaction example using ammonium thiosulfate as a fixer component is as follows. AgX+n(NH ₄ ) ₂ S ₂ O ₃ → Ag(S ₂ O ₃ ) _o ^(2n-1) +2nNH ₄ +X (However, n represents 2 or 3, X or halogen.) As seen in this reaction example As silver halide photographic light-sensitive materials are fixed, silver complex salts and halogen ions accumulate in the fixing solution, and free components of the fixing agent decrease. As a result, the fixing efficiency gradually decreases, and if the fixing process is continued as it is, a fatigue phenomenon will eventually appear and the device will become unusable. Therefore, in order to activate this fatigued fixer, a method has been adopted in which an appropriate amount of new fixer (regenerant or replenisher) is replenished and the fatigued wave fixer is discharged to the outside as an overflow. Disposal as is is contrary to resource conservation as it contains silver and other valuable components, is extremely disadvantageous economically, and is not desirable from the perspective of environmental pollution. Treatment must be taken to completely render waste liquid harmless. In this regard, in the past, the silver ions in the overflow fixer solution were often collected and then disposed of, but recently, the fixer solution has gone even further and has been recycled and used again after the silver has been recovered. It's here. For example, when silver is recovered by electrolysis, which is the most advantageous method for silver recovery, the thiosulfate ions that were bound to the silver ions become free ions again, so the fixing solution is 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 is small enough to not overflow. Generally, the fixer is regenerated and used repeatedly while being replenished with a new fixer (regenerant or replenisher) having a concentration that maintains the fixer components. However, even if the fixer is used repeatedly by such a replenishment method, as the frequency of use increases, the fixing performance gradually changes and the fixing speed decreases, even though the concentration of free thiosulfate ions is sufficiently high. This will eventually lead to 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 fixing solution, and fixing-inhibiting components accumulate significantly. As a solution to this problem, methods have been proposed such as adding a fixing accelerator to improve the fixing power and removing halogen oin, which is considered to be a fixing inhibiting component. That is,
An example of the former is the promotion of fixation by a sulfur compound described in Japanese Patent Publication No. 1983-35754, or
Although there are methods to promote fixing using polyethylene glycol compounds described in Publication No. 39173, these methods are still insufficient as a fundamental solution to fixing defects caused by the accumulation of halogenoin, etc., which are considered to be fixing-inhibiting components. There is a drawback that, after being repeatedly recycled and used, poor fixing may occur in the end. Therefore,
In order to reduce the accumulated convergence concentration of halogen ions, a portion of the overflow fixer is discarded and reused repeatedly, but this approach has not yet solved the pollution problem and uneconomical problem. It's not on. On the other hand, examples of the latter include the halogen olefins described in U.S. Patent Publication No. B-391509, Japanese Patent Publication No. 43-30167, Japanese Patent Application Laid-open No. 18191-1981, or Japanese Patent Application Laid-Open No. 49-53438, etc. There are techniques for removing this, which are effective in improving fixing power, but all of them have drawbacks such as requiring devices with complex structures and high equipment investment and operating costs. The present invention has been made in order to solve the above-mentioned drawbacks.The first object of the present invention is to increase the fixing speed, shorten the processing time, and to obtain a good silver image or a color dye image. An object of the present invention is to provide a method for improving fixing performance in a fixer. A second object of the present invention is to provide a photographic fixer that recovers silver in the fixer using an electrolytic method or other silver recovery method, and that does not cause deterioration of the fixer even when used repeatedly, increasing the frequency of use. An object of the present invention is to provide a method for improving fixing performance in a method of improving fixing performance. A third object of the present invention is to recycle silver without discarding all of the fixer by simply replenishing new fixer (regenerating agent or replenisher) and improving fixing performance. An object of the present invention is to provide a method for improving the fixing performance of a photographic fixer that can be used. A fourth object of the present invention is to provide a method for improving the fixing performance of a photographic fixer in which the fixing accelerator used is less toxic and meets the requirements for pollution prevention. The fifth object of the present invention is that the fixing fluid components used are extremely stable, with no precipitation, and the fixing performance does not deteriorate even after repeated reuse and storage over a long period of time. An object of the present invention is to provide an inexpensive and economical method for improving the fixing performance of a photographic fixer without any problems. The inventors have found that the above object can be achieved by incorporating at least 0.5 mole of bromide or iodide ions into a photographic fixer containing a silver halide fixer. That is, the photographic fixer according to the present invention is characterized in that it contains a silver halide fixing agent and the above specified amount of halogen ion, and only by containing the above specified amount of the specific halogen ion can the above-mentioned effect be achieved. The objects of the present invention can be effectively achieved. The silver halide fixing agent used in the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiosulfate, such as
Typical examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These typical fixing agents can be used alone or in a suitable combination of two or more, and when used in combination, the mixing ratio of the combinations is arbitrary. Although alkali metal or ammonium halides may exhibit a fixing effect, the silver halide fixing agent of the present invention is defined herein as not containing these halides. The amount of such silver halide fixing agent used is not limited, but generally 15
The purpose of the present invention can be fully achieved by using more than 60 to 200 g/g/
You can use The halogen ion contained in the fixing solution according to the present invention is limited to bromide ions and iodide ions, and examples of halogen compounds used to contain this halogen ion in the fixing solution include hydrobromic acid and lithium bromide. , sodium bromide,
Examples include bromides such as potassium bromide and ammonium bromide, and iodides such as sodium iodide, potassium iodide, and ammonium iodide. Among these halides, ammonium salts are particularly effective in terms of processability. be. These halides can be used alone or in an appropriate combination of two or more, and when used in combination, the mixing ratio of the combinations is arbitrary. Note that even if it is a halogen compound, for example, a halogen compound with a chlorine atom or a fluorine atom cannot achieve the desired effect of the present invention and is therefore excluded from the present invention, but the fixer according to the present invention As long as bromide ions or iodide ions are contained, even if these chloride ions and fluoride ions are contained together, the operation and effects of the present invention are not affected.
The bromide ion or iodide ion of the present invention is required to be contained in an amount of at least 0.5 mol per fixing solution, so that the above-mentioned objects of the present invention can be fully achieved, but it is particularly desirable to maintain the viscosity of the solution at a low level. At the same time, in order to maintain a high diffusion rate of fixer components and increase processing efficiency, the amount is preferably 1.5 to 2.5 mol/in the case of bromide ions, and 1.4 to 6 mol/in the case of iodide ions. As mentioned above, in the present invention, bromide ions and iodide ions may be contained in a mixture, but in the case of mixed use, it depends on the amount of the combination, and the total amount is at least 0.5 mol. / It is sufficient if it is contained. Note that, from an economic point of view, it is not necessary to use an amount exceeding 2.5 mol/in the case of bromide ion and 6 mol/in the case of iodide ion. It is generally preferable to use the fixer according to the present invention at a pH of 4 or higher, particularly preferably at a pH of 4.5 to 10.
The silver halide fixing agent may be selected as appropriate depending on the desired pH value. Regarding the meaning of the term "fixer" in the present invention, the processing solution having fixing ability contains a bleaching agent (oxidizing agent) such as an aminopolycarboxylic acid metal complex salt, red blood salt, or ferric salt. There are a so-called bleach-fix solution and a normal fixer that does not have bleaching ability, and the fixer in the present invention refers to the latter, a normal fixer that does not have bleaching ability. A feature of the fixer according to the present invention is that it contains a specific halogen oin in a large amount of 0.5 mol or more. Conventionally, it has been generally accepted that if the fixing solution contains these halogen ions, or if the halogen ions are eluted and accumulated from the emulsion layer of the photosensitive material being processed during processing, the fixing performance is significantly impaired. It was said that In other words, regarding the fixation inhibition caused by such halogen ions,
For example, Photographic Science and Engineering
& Engineering), Vol. 17, No. 2, p. 174 (1973). Therefore, as described above, the current technological trend is that, contrary to the present invention, research and development are being carried out on techniques for removing halogen ions when regenerating the fixer. However, if specific halogen ions, which are generally considered to have fixation-inhibiting properties, are contained in multiple quantities as in the present invention, not only do they exhibit no fixation-inhibiting properties, but they also fail to meet the objectives of the present invention as described above. It was completely unexpected and surprising that a fixer solution with excellent properties that could be fully achieved was obtained. That is, by adding the specific halogen ions as mentioned above, the fixing performance is significantly improved.
Even high-sensitivity silver halide color photographic light-sensitive materials with a high silver content can be sufficiently fixed in a short time, and the coexisting fixing agent is much lower in concentration than conventional fixing solutions. It has an excellent advantage of providing good fixing performance. This advantage is directly reflected in terms of resources and pollution load, and makes it possible to easily supply an inexpensive fixer with less pollution load. The fixer according to the present invention has excellent stability because it is not necessary to significantly increase the concentration of the fixer or to use an expensive and unstable fixing accelerator in order to improve its fixing performance. Although it is inexpensive, it also has the advantage that the main ingredients have high solubility and no precipitation occurs even when the fixer is concentrated prior to use, and the fixer can be easily adjusted. . In particular, the fixing solution according to the present invention does not require the addition of conventional fixing accelerators, so it is extremely stable, and unlike conventional fixing solutions containing fixing accelerators such as sulfur compounds or polyethylene glycol compounds. In addition, it does not cause a decrease in processability or cause precipitation even if a developer or color developer is brought in, mixed with other processing solutions, or diluted, and it is highly stable. It is also easy to recycle and use the liquid repeatedly. As mentioned above, the fixing solution according to the present invention has extremely excellent fixing power, so it can be effectively applied to processing not only low-sensitivity silver halide photographic materials but also high-sensitivity silver halide photographic materials. The types of photosensitive materials include all types of photosensitive materials that require fixing, such as photosensitive materials for black and white or color printing such as photographic paper, photosensitive materials for photography such as negative black and white or color film, and reversal black and white or color film. It can be commonly applied to the processing of silver halide photographic materials of the type. For this reason, in the past, it was not possible to use the same fixer when processing different types of silver halide photographic light-sensitive materials, and it was necessary to adjust fixers using different formulations for each processing line. On the other hand, by using the fixing solution according to the present invention, it becomes possible to apply the same fixing solution to processing lines for all kinds of silver halide photographic materials. This not only saves you the trouble of adjusting the fixer, but also
It is possible to use surplus liquid or waste liquid in other processing lines, which is extremely advantageous in terms of cost, resource conservation, and pollution control. In addition, the fixer according to the present invention allows silver ions dissolved in the fixer to be easily recovered in the same way as conventional fixers, and the stability of the solution is extremely good, so that after recovering the silver ions, After improving the fixing performance by adding a regenerating agent or a replenisher as necessary, it can be used repeatedly. Any known method can be employed as the method for recovering silver from the fixer according to the present invention. Typical specific examples include a silver precipitation method using a precipitant, an electrolytic method using electrolysis, a metal substitution method using ionization tendency, an ion exchange method using an ion exchange resin, etc. The electrolytic method is preferable for recycling and repeated use of the liquid. For information on how to recover this silver, please refer to M.L.
Present status of Silver Recovery Motion Picture Your Laboratories
silver recovery motion picture Laboratories)
It is described in Vol. 74, pp. 505-514 (1965). As mentioned above, all known methods can be used to recover silver from the fixing solution according to the present invention, 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 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, the halogen ions of the present invention 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 fixer according to the present invention can contain various additives as necessary. For example, boric acid, borax, sodium hydroxide, potassium hydroxide,
PH buffers such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various fluorescent brighteners, antifoaming agents, or surfactants can be contained. Also, sulfite,
Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol nitrates, methanol,
Organic solvents such as dimethyl sulfonamide and dimethyl sulfoxide may also be included as appropriate. The fixing solution according to the present invention has extremely high fixing power, so there is no need to add any other fixing accelerator, but it is optional to add a conventional fixing accelerator as desired. EXAMPLES Next, the present invention will be illustrated with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A commercially available general black and white film, Konipan SS20 (manufactured by Konishiroku Photo Industry Co., Ltd.), was coated with the following halogen compound in a fixing agent with the following composition without exposing it to light.
Fixer solution [1] to (9) added with (1) to (9), quantified to 1 with water and adjusted to PH8.2

Immerse in [9] (processing temperature
(25°C), and the time required to complete fixing (clearing time) until the silver halide in the film was dissolved and the film became transparent was measured. Next, the clearing time was measured when 150 films were processed. The results are shown in Table-1 below.
Shown below. Fixing agent Sodium thiosulfate 120g Sodium sulfite 20g Halogen compounds (1) None (2) Ammonium chloride 200g (3) Ammonium bromide 50g (4) Ammonium bromide 200g (5) Ammonium iodide 180g (6) Ammonium iodide 200g (7) Sodium bromide 400g (8) Sodium iodide 400g (9) Potassium bromide 75g (10) Potassium bromide 600g (11) Potassium iodide 300g (12) Ammonium bromide 100g Ammonium iodide 180g

[Table] As is clear from Table 1, the fixing solution that does not contain a fixing accelerator requires a clearing time of 95 seconds even in the case of a new solution, but as a fixing accelerator, bromide ions in halogen ions or (and) Fixers [3] to [12] according to the present invention containing 0.5 mol/or more of iodide ions have the same clearing time as short as 42 to 80 seconds. It can be seen that the fixing performance is extremely high. Furthermore, in the case of the fixing solution [2] which is not based on the present invention and which contains chlorine ions as halogen ions, the same clearing time takes a long time of 130 seconds, which may actually cause fixing inhibition. I understand. Furthermore, the clearing time when processing a fairly large amount of film, 150 rolls, in the case of fixers [1] and [2] that are not based on the present invention, compared to the clearing time with the new solution. It can be seen that as the width becomes very long, the processing capacity decreases significantly, and the so-called fatigue phenomenon becomes noticeable. On the other hand, in fixers [3] to [12] according to the present invention, the clearing time with a large amount of processing solution is almost different from the clearing time with a new solution, and no fatigue phenomenon is observed. That is, it can be seen that the fixing solution according to the present invention has substantially no difference in fixing ability from that of the new solution even though some silver ions are accumulated in the solution and thiosulfate ions are reduced. Example 2 A sample of a silver halide color negative photographic material was prepared by sequentially coating the following layers on a subbing-treated polyethylene terephthalate film support. (1) Antihalation layer Black colloidal silver was dispersed in an aqueous gelatin solution and coated at a ratio of 3 g/m ² of gelatin and 0.3 g/m ² of silver. (2) Cyan-forming red-sensitive silver halide emulsion layer Silver iodobromide gelatin emulsion (6 mol) prepared by dispersing a mixture of 5 g of colored cyan coupler () and 20 g of cyan coupler () in an aqueous gelatin solution dissolved in tricresyl phosphate. % silver iodide content), gelatin 4.5 g/m ² , silver 3.4 g/m ² ,
Cyan coupler was applied at a rate of 1.4 g/m ² . (3) Intermediate layer An aqueous gelatin solution was applied at a rate of 1.3 g/m ² of gelatin. (4) Magenta-forming green-sensitive silver halide emulsion layer A silver iodobromide gelatin emulsion (6) in which a mixture of 5 g of colored magenta coupler () and 25 g of magenta coupler (2) was dissolved in tricresyl phosphate and dispersed in an aqueous gelatin solution. mol% of silver iodide), gelatin 5.0g/m ² , silver 3.2g/m 2
m ² and magenta coupler at a rate of 1.2 g/m ² . (5) Intermediate layer An aqueous gelatin solution was applied at a rate of 1.3 g/m ² of gelatin. (6) Yellow filter layer Yellow colloidal silver was dispersed in an aqueous gelatin solution and applied at a ratio of 0.1 g/m ² of silver and 1.3 g/m ² of gelatin. (7) Yellow-forming blue-sensitive silver halide emulsion layer Silver iodobromide gelatin emulsion (containing 7 mol% silver iodide) containing 30 g of yellow coupler () dissolved in dibutyl phthalate and dispersed in an aqueous gelatin solution. , gelatin 4.0g/m ² , silver
It was applied at a rate of 1.0 g/m ² and yellow coupler 1.6 g/m ² . (8) Protective layer A gelatin aqueous solution was applied at a rate of 1.3 g/m ² of gelatin. Each layer contained 1,2-bis(vinylsulfonyl)ethane as a hardening agent at a rate of 20 mg/g gelatin. In addition, the following couplers were used. () Colored cyan coupler 1-hydroxy-4-[4-(2-hydroxy-3,6-disulfo-1-naphthylazo)anilinocarbonyloxy]-N-[σ-2,4-di-t-amylphenoxy] Butyl]-2-naphthamide disodium salt () Cyan coupler 2-{4-(2,4-di-t-amylphenoxy)butyl}carbamoyl-1-naphthol () Colored magenta coupler 3-(2-chloro-5-octadecylsuccinimide-anilino)-1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-
5-pyrazolone () Magenta coupler 1-(2,4,6-trichlorophenyl)-3
-(3-octadecylsuccinimidebenzamide)-5-pyrazolone () Yellow coupler α-succinimide-α-pivalyl-6-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyl acid]acetanilide Without exposing the obtained sample, we used a cine strip machine model 35-14KO (automatic developing machine for color negatives made by Paco, USA), and the processing agent was Sakura color processing agent type (Konishiroku Photo Industry Co., Ltd.) except for the fixing solution. Co., Ltd.) for color development, bleaching, washing with water, fixing, washing with water, stabilization, and drying. All treatments were performed at 38°C. The fixing solution is a basic fixing solution with the following composition and Table 2 below.
The halogen compounds shown in the table were added in the amount shown in the same table, and the pH was adjusted to 1 by adding water to the pH of 7.6. Basic fixer Ammonium thiosulfate (60% aqueous solution) 150 ml Ammonium sulfite (50% aqueous solution) 40 ml Clearing time and 1.6 m ² sample (for 50 sheets of the above sample) when the above 320 cm ² sample was treated with the new fixer ) was processed and the clearing time was measured. The results were as shown in Table-2.

[Table] As is clear from Table 2, the fixing solution [1] that does not contain halogen ions required a clearing time of 3 minutes and 5 seconds even when processing with the new solution, but the bromine ions in the halogen ions Or (and) the fixing solutions [3] to [11] according to the present invention containing 0.5 mol/or more of iodide ions have a short clearing time of 2 minutes 25 seconds to 2 minutes 50 seconds, and have a high silver content. It can be seen that the fixing solution according to the present invention exhibits excellent fixing performance even for silver halide photographic light-sensitive materials. Furthermore, in the case of the fixing solution [2] which is not based on the present invention and contains chlorine ions as halogen ions, the same clearing time takes a long time of 3 minutes and 55 seconds, which actually hinders the fixing performance. I know it will appear. Furthermore, the clearing time when processing a sample with a high silver content as large as 1.6 m ² exceeds the processing speed limit of the automatic processor in the case of fixers [1] and [2] that are not based on the present invention. However, in the case of the fixing solution according to the present invention, the clearing time with the large amount of processing solution as described above is in the range of 3 minutes 5 seconds to 4 minutes 5 seconds, which is sufficient. It can be seen that the fixing performance is maintained. When ammonium bromide was added in an amount of 0.4 mol/equivalent, the clearing time was 6 minutes and 30 seconds when processing a sample with a high silver content of 1.6 m ² and no fixation could be obtained. Example 3 A commercially available general color negative film, Sakura Color 20-shot (manufactured by Konishiroku Photo Industry Co., Ltd.), was exposed through a step wedge, and a cine strip machine model 35-14KO (same product as in Example 2) was used. The processing agent was Sakura Color processing agent type (same product as in Example 2) except for the fixer.
The same treatment as in Example 2 was carried out using . The fixer was prepared by adding the following halogen compounds (1) to (3) to the same basic fixer as in Example 2, and measuring the amount to 1 with water.
Fixing solutions [1] to [3] whose pH was adjusted to 7.6 were used. Halogen compounds (1) None (2) Ammonium bromide 200g (3) Potassium iodide 250g Processing with the obtained fixer is carried out using an electrolytic silver recovery device (Model 500 manufactured by Rotex).
2) was continuously circulated to recover silver, and the deficient thiosulfate was replenished with a replenisher, regenerated, and used repeatedly. When the above film is processed with a new fixer,
Similarly, the clearing times were measured when 15,000 pieces were processed, when 30,000 pieces were processed, and when 45,000 pieces were processed. The results were as shown in Table 3 below.

【table】

[Table] As is clear from Table 3, the clearing time using the fixer [1] that does not contain halogen ions and is not based on the present invention requires 2 minutes and 5 seconds even when processing with the new solution. When using a solution that has processed 15,000 bottles, the clearing time is more than twice that, and when using a solution that has processed an additional 30,000 bottles, the clearing time is 6 times longer.
With a clearing time of minutes and 30 seconds, stains indicating poor fixation began to remain. On the other hand, the clearing time using the fixing solutions [2] and [3] according to the present invention is extremely short at 1 minute 40 seconds and 1 minute 30 seconds in the case of processing with the new solution. 30000 pieces and
Even if the throughput was increased to 45,000 lines, there was almost no increase in the clearing time, indicating that a constant fixing performance was maintained. In this example, 1,500 films were processed per day, and it took more than 30 days to process 45,000 films. It was found that the fixer according to the above did not deteriorate its processing performance and was stable. Furthermore, no change was observed in the silver recovery efficiency in this case.

Claims (1)

[Scope of Claims] 1. Fixing in a photographic fixer containing a silver halide fixer, characterized in that the fixer contains at least 0.5 mol of bromide ions or iodide ions per unit to improve fixing performance. How to improve performance. 2 Bromine ion content is 1.5 to 2.5 per 1
Claim 1 characterized in that it is molar.
A method for improving the fixing performance of the photographic fixer described in Section 3. 3 Iodine ion content is 1.4 to 6 per 1
Claim 1 characterized in that it is molar.
A method for improving the fixing performance of the photographic fixer described in Section 3. 4 The content of silver halide fixing agent is 60 per 1
A method for improving the fixing performance of a photographic fixer according to claim 1, 2 or 3, characterized in that the amount of the fixer is from 200g to 200g.