JPH10288829A - Method for regenerating processing agent for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To greatly decrease a waste processing liquid in processing of photosensitive materials by forming the waste processing liquid to powder, adding the components decreased by processing thereto and forming the liquid again to a solid processing agent. SOLUTION: The waste developer and waste fixer, from which silver ions or halogen ions are removed and which are sent to a secondary regenerated liquid layer 5, are sent to an evaporation pipe 10 where the pressure is reduced by a vacuum pump 11. These liquids are cooled in a cooling tower 12 under a reduced pressure and water is recovered. On the other hand, the evaporation residues formed in the evaporation pipe 10 pass a transporting pipe 7 and is heated and dried by the heat sent from a heat source 16 by a heating pipe 9, by which the powder is formed. The powder is recovered into a powder transporting pipe 17 and a regenerated processing agent powder receiving tank 18. The powdered residues after the moisture is removed by the vacuum evaporation from the waste processing liquid are replenished with the constitution components consumed by the processing in accordance with the results of the analysis of the components included therein and are again solidified to the processing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating a solid processing agent for a silver halide photographic material (hereinafter, simply referred to as a "photosensitive material").

[0002]

2. Description of the Related Art Processing of a black-and-white light-sensitive material is generally performed by exposing the light-sensitive material to light, developing, fixing, washing and drying. In these processing methods using an automatic developing machine, the developing solution used in the developing process and the fixing solution used in the fixing process are replenished with a fixed amount of a developing replenisher and a fixing replenisher for each processing of a fixed amount of photosensitive material. And processed.

In recent years, in the processing method of photosensitive materials, the use of processing replenishers has been rapidly reduced from the standpoint of reducing the pollution load. Reducing the amount of replenishment has the advantage that the amount of waste liquid generated during processing of the photosensitive material can be reduced.

[0004] However, even if the amount of waste liquid is reduced, the amount of waste liquid increases in recent large-scale processing of photosensitive materials, and the waste liquid recovery cost increases due to laws and regulations related to the Pollution Control Law. On the other hand, even if the amount of waste liquid is small, if the waste liquid cannot be flowed into the sewer under the provisions of the Sewerage Law, it is necessary to store the waste liquid until it is handed over to a collection company, and it is necessary to secure a storage space for the waste liquid.

From such a point, a method of regenerating and using the waste liquid to further reduce the waste liquid is known. However, when the developer is regenerated, it is difficult to perform a stable treatment. There are drawbacks such as the need for skilled labor.

[0006] Processing agents for photosensitive materials are changing from conventional concentrated liquid processing agents to solid processing agents in view of easiness of storage and improvement of workability.
Since there is a restriction that a solid raw material is used as the component, there is a disadvantage that the raw material cost is higher than that of a liquid raw material.

[0007] Therefore, in the processing of photosensitive materials, there has been a demand for a processing method capable of greatly reducing the processing waste liquid and reusing the processing liquid.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing method and a method for regenerating a processing agent, which can greatly reduce processing waste liquid in processing of a photosensitive material.

[0009]

The object of the present invention is achieved by the following constitution.

[0010] 1. After processing a silver halide photographic light-sensitive material with a processing solution prepared by dissolving a solid processing agent, in a method of regenerating the processing agent, the processing waste liquid is powdered, the components reduced by the processing are added, and the solid processing agent is added again. A method for regenerating a treatment agent, characterized in that:

2. The method for regenerating a processing agent according to claim 1, wherein after removing halogen ions from the developing waste liquid, water is removed by distillation under reduced pressure to powderize the waste liquid.

3. The method for regenerating a fixing agent according to the above method, wherein after removing silver ions and halogen ions from the fixing waste liquid, water is removed by distillation under reduced pressure to powderize the waste liquid.

[0013] The method for regenerating a treating agent according to 4.2 or 3, wherein the water collected by distillation under reduced pressure is reused as water for dissolving, diluting and / or washing the migrating rack.

The present invention will be specifically described.

The treating agent used in the present invention requires that the solid treating agent or the components in the treating agent be solid at room temperature. That is, if the waste liquid contains components that are liquid at normal temperature, it cannot be powdered even if the water in the waste liquid is completely removed.

In the method for regenerating the treating agent of the present invention, an electrolyzer (hereinafter referred to as an electrolyzer) and an electrodialyzer are used to remove silver ions and halide ions before removing water from the waste liquid.

These electrolyzers and electrodialyzers may be of any equipment and conditions as long as they are used in the art for this purpose.
No. 42, No. 51-8143, No. 51-84636,
Nos. 51-85772, 51-97432, 51
-98027, 52-56082 and 52-14
No. 6236, No. 53-7239, No. 53-37015
No. 53-46732, No. 53-60371, No. 53-14933, No. 54-9692, No. 54-1
No. 7341, No. 54-19741, etc.
Processing conditions are mentioned.

In the processing of the light-sensitive material, the suppression of development and fixing of the light-sensitive material can be prevented by removing silver ions and halogen ions.

The method for removing silver ions and halogen ions used in the method for regenerating the processing agent for a light-sensitive material of the present invention will be described with reference to FIG.

This apparatus comprises a treatment waste liquid receiving tank 1, an electrolysis apparatus 2, a primary regenerating liquid tank 3, an electrodialysis tank 4, a secondary regenerating liquid tank 5, a heating pipe 9, an evaporating pipe 10, a vacuum pump 11, a cooling pipe 12, Trachea 13, creeping tower 14, water tank 15, heat source 1
6, a powder transport pipe 17, and a regenerating agent powder receiving tank 18, which are connected as a series of lines by a pump 6, a transport pipe 7, and a valve 8.

The electrodialysis apparatus 4 includes an ion exchange membrane, and halogen ions are selectively removed by applying a constant voltage to the ion exchange membrane.

That is, the processing waste liquid overflowing from the processing tank of the automatic developing machine is temporarily stored in the processing waste liquid receiving tank 1,
The solution is sent to the electrodialysis device 4 via the pump 6, the transport pipe 7 and the bubble 8, the electrolytic device 2 via the primary regenerating solution layer 3, and the halogen ion and silver ion are removed and sent to the secondary regenerating solution layer 5.

The electrolytic device 2 is equipped with a carbon as an anode and a stainless steel rotating drum as a cathode. The rotating speed of the drum is usually 50 to 100 rpm, and 1.5 to 2.0 V in order to prevent decomposition of a fixing solution component. Voltage is loaded. The liquid temperature is maintained at 20 to 25 ° C. Usually, the concentration of residual silver in the fixing solution after silver recovery is 0.5 to 1.0 g / liter.

The developing waste solution and the fixing waste solution from which silver ions or halogen ions have been removed are sent to the secondary regenerating solution layer 5 and sent to the evaporating tube 10 where they are decompressed by the vacuum pump 11 and cooled under reduced pressure. Water is collected by cooling in the tower 12.

On the other hand, the evaporation residue generated in the evaporating pipe 10 passes through the transport pipe 7 and is heated and dried by the heat sent from the heat source 16 in the heating pipe 9 into the powder. The powder transport pipe 17 and the regenerating agent powder receiving tank Collected at 18.

Prior to treating the developing and fixing waste liquid with the above-mentioned electrolyzer and electrodialysis apparatus, it is preferable to filter and remove dust contained in the waste liquid.

In the present invention, the means for removing water from the treatment waste liquid is preferably the above-mentioned vacuum evaporation. As the vacuum device, an arbitrary device such as an ejector can be used in addition to a vacuum pump.

The water vapor generated by vacuum evaporation is cooled,
It is preferably taken out again as water and used as washing water and / or migrating rack washing water. As a result, the amount of water required for processing the photosensitive material can be reduced.

The residue obtained by removing water from the treatment waste liquid by vacuum evaporation and pulverized is re-solidified by replenishing the constituent components consumed by the treatment based on the analysis results of the components contained therein. To make a treatment agent.

The components contained in the pulverized processing waste liquid can be analyzed by using a usual analysis method such as high performance liquid chromatography, electrotitration, and spectral analysis to analyze development waste and fixing waste. . In this component analysis, it is important to analyze a developing agent, a fixing agent, an antifoggant and a pH adjuster. That is, these components are important for development and fixing performance.

The developer and fixer regenerated according to the present invention can be used in the same manner as a new developer and fixer, and can be used in various processing apparatuses and techniques well known by those skilled in the art.

The pH of the developer used in the present invention is 9.5.
If the pH is lower than 9.5, the developability is poor and sufficient density and gamma cannot be obtained.
If it exceeds 10.5, pH fluctuation with the passage of time is large, processing stability is deteriorated, and fog is increased.

As a method of replenishing the developing and fixing solutions, it is preferable to replenish the developing replenisher prepared by dissolving the solid developing replenisher by adding dilution water in a replenishing tank based on the processing amount information. The replenishment rate is preferably 50 to 200 ml / m ² .

To solidify the developing and fixing solution, a concentrated solution or a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is temporarily attached to the surface of the developing and fixing agent. Any means such as forming a coating layer by spraying an agent can be adopted (Japanese Patent Application Laid-Open Nos. 4-29136 and 4-29136).
-85535, 4-85536, 4-8553
No. 3, 4-85534 and 4-172341).

A preferred method for producing a tablet is a method in which a powdery solid developing and fixing agent is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and storage properties are improved and the photographic performance becomes stable as compared with a solid development and fixing agent formed by simply mixing a solid development and fixing agent component and forming a tablet.

As the granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
In the tablet formation, when the obtained granules are mixed with those having an average particle size and compressed under pressure, those having a particle size of 100 to 800 μm are used in that non-uniformity of components, that is, so-called segregation does not easily occur. Preferably, more preferably, 200 to 750
μm. Further, the particle size distribution is preferably such that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm.
Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pricketting machine can be used. The solid developer and the fixing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling, or from the problem of dust when used on the user side, a cylindrical type, so-called, Tablets are preferred.

More preferably, at the time of granulation, the above-mentioned effect is further remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

The methods for producing tablet developers and fixing agents are described, for example, in JP-A-51-61837 and JP-A-54-155038.
No. 52-88025 and British Patent No. 1213808. Further, granulating agents are described, for example, in JP-A Nos. 2-10942 and 2-1-1.
No. 09043, No. 3-39735 and No. 3-3993
It can be produced by a general method described in No. 9, etc. Furthermore, powder processing agents are described, for example, in JP-A-54-133332.
And British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861.

The bulk density of the solid developing and fixing agents is as follows:
From the viewpoint of the solubility and the effect of the present invention, the tablet is preferably 1.0 to 2.5 g / cm ^3, more preferably 1.0 g / cm ^3.
In terms of the strength of the solid obtained when it is less than ³ cm 2,
If it exceeds 5 g / cm ³ , it is not preferable in terms of solubility of the obtained solid. When the solid developing and fixing agent is a granule or a powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

Solid tablets are used for photographic processing agents such as rinsing agents in addition to developers and fixing agents. Developers have a great effect of stabilizing photographic performance.

Further, there are a solid developer and a solid fixing agent.
Although it is possible to solidify only the components of the developing agent, all the components of the developing and fixing agent are more preferably solidified. Preferably, each component is molded as a separate solid development and solid fixer and packaged identically. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly charged.

In the replenishment method for replenishing the processing liquid in accordance with the processing amount information, it is preferable that all the processing liquid replenished in each processing tank besides the developing tank be formed as a solid processing agent. When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. In other words, when there are two or more types of processing tanks that need replenishment,
By sharing the replenishing water, only one tank is required to store the replenishing liquid, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

In the developer of the present invention, dihydroxybenzenes, aminophenols and the like described in JP-A-4-15641 and JP-A-4-16481 are used as developing agents.
In addition to pyrazolidones, reductones described in JP-A-5-165161 are used. Particularly, reductones (eg, ascorbic acid (salt), ersorbic acid (salt), etc.)
Is preferred.

In the developer, an organic reducing agent can be used as a preservative in addition to the sulfite described in JP-A-6-138591 as a preservative. In addition, Japanese Patent Application Hei 4-
A bisulfite adduct of a hardener described in 586323 can be used. Also, as a silver sludge inhibitor, Japanese Patent Laid-Open No.
It is also preferable to add compounds described in JP-A-289255 and JP-A-6-308680 (general formulas [4-a] and [4-b]). Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound can be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferred.

It is necessary to use a buffer for the developer. Examples of the buffer include sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

Examples of the development accelerator include known thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, Mesoionic compounds, ionic compounds, imidazoles and the like can be added as needed.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine, such as 1-phenyl-5-mercaptotetrazole.

Other stain inhibitor, sludge inhibitor,
Various additives such as a layering effect promoter can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal such as KBr, an organic inhibitor, and a development accelerator are used.

As the fixing solution used in the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate and ammonium thiosulfate can be used. Among these, ammonium thiosulfate and thiosulfate are preferable in terms of fixing speed. A 70/30 weight ratio of sodium sulfate is preferred. These fixing agents are generally used in an amount of about 0.1 to 6 mol / l.

The fixing agent may contain a water-soluble aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

Malic acid, tartaric acid, citric acid,
Gluconic acid or a derivative thereof can be used alone or in combination. It is effective to contain these compounds in an amount of 0.01 mol or more per liter of the fixing solution.
0.05 to 0.3 mol is particularly effective.

The pH of the fixing solution is preferably 3.8 or more, and more preferably 4.2 to 7.0.
Considering the fixed hardening film or sulfurous acid odor, 4.3-4.
8 is more preferred.

In addition, known compounds can be added to the fixing agent. A pH buffer, a hardener, a preservative, and the like can be added. In addition, a bisulfite adduct or a known fixing accelerator can be used as a hardener.

The photosensitive material which has been developed and fixed is subsequently washed or stabilized. Washing or stabilizing treatment
Not only is it possible to save water with a replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide photographic material (including 0, that is, it can be carried out by pooled water washing), and the piping for installing an automatic developing machine is unnecessary. can do.

When the washing is performed with a small amount of water, a method disclosed in
It is more preferable to provide a squeeze roller washing tank described in -18350 and 62-287252.

Further, in order to reduce the pollution load which becomes a problem when washing with a small amount of water, various oxidizing agents may be added or a filter may be combined. Further, by replenishing the washing or stabilizing bath with water subjected to antifungal means according to the treatment, part or all of the overflow water from the washing or stabilizing bath is described in JP-A-60-235133. As described above, it can also be used for a processing solution having a fixing ability, which is the preceding processing step.

In addition, a treatment agent component which is liable to prevent water bubble unevenness and / or easily adheres to a squeeze roller when a small amount of water is washed,
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. Japanese Patent Application Laid-Open No. 63-1 / 1988 describes prevention of contamination by dyes eluted from a photosensitive material.
The dye adsorbent described in No. 63456 may be installed in a washing tank. In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-1
No. 32435, No. 1-125553, JP-A-46-4
A bath containing the compound described in No. 4446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, a film pH regulator, a hardener, a bactericide, an antifungal agent, an alkanolamine, or a surfactant may be added to the stabilizing bath. Can be.

As the water used in the washing step or the stabilizing step, tap water, deionized water, halogen, ultraviolet germicidal lamp and various oxidizing agents (ozone, hydrogen peroxide,
For example, water sterilized by chlorate or the like can be used.

[0061]

EXAMPLES The present invention will now be described in detail with reference to examples. It goes without saying that the present invention is not limited to the examples described below.

Example 1 Preparation of solid processing agent Next, tablets for solid development were prepared according to the following operations (A) and (B).

Procedure (A) 3000 g of erythorbic acid is ground in a commercially available bantam mill to an average particle size of 10 μm. 3000 g of sodium sulfite and 2000 g of potassium sulfite are added to this fine powder.
g, 1-phenyl-3-pyrazolidone, 1000 g, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirring granulator. The material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the water content of the granulated material. The granules thus prepared were added to polyethylene glycol 6000
Was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, and the resulting mixture was mixed with Kikusui Seisakusho Co., Ltd., Tough Presto Collect 152.
7HU was compressed and compressed using a modified tableting machine at a filling amount per tablet of 3.64 g to prepare 2500 tablets A for development.

Operation (B) 77.5 g of diethylenetriaminepentaacetic acid (DTPA)
4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of potassium hydroxide, N-acetyl-D, L-penicillamine 3
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 300 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture thus obtained was compressed and compressed into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being set to 1.77 g, and 2500 tablets were developed. Tablet B was prepared.

Next, a fixing tablet was prepared by the following operation.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
After pulverizing, the mixture is uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), granulation is performed with the addition amount of water being 500 ml. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the thus-prepared granules and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture is applied to Tough Presto Collect 15 manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed using a modified tableting machine of 27HU with a filling amount per tablet of 6.32 g, and 2500 fixing tablets C were prepared.

Operation (D): 1000 g of boric acid, 150 aluminum sulfate / hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. After adding 4 g of N-lauroylalanine sodium to the thus prepared mixture and mixing for 3 minutes, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with the filling amount per unit being 4.562 g, and 1250 fixing tablets D were prepared.

Starter for developer 120 g of glacial acetic acid 225 g of KBr Water was added to make up to 1 liter.

Using the solid processing agent for development and fixing described above, a starting solution for development and fixing was prepared in the following manner.

At the start of processing of the developer (start of running), 412 developing tablets A and 824 tablets B are dissolved in water.
It was diluted with dilution water to adjust to 16.5 liters.

330 ml of the above starter with respect to the developer
The developing tank is filled with a solution containing the compound (1), and 1154 tablets C and 721 D are dissolved in water in the same manner as the developer in the fixing tank and diluted with dilution water to 16.5 liters. It was prepared and filled in a fixing tank to be in a start state. Further, one of the developing dissolving tank and the fixing dissolving tank was filled as a replenisher to start processing. The pH of the developer to which the starter was added was 10.00. The pH of the fixing solution is 4.
It was 40.

A medical X-ray film SG-R (manufactured by Konica Corporation) was exposed so that the optical density after the development processing became 1.0, and it was cut into four pieces (245 mm × 305 m).
m) was run. The running was performed using an automatic developing machine TCX-201 (manufactured by Konica Corporation).

During the running, ^two of the above-mentioned agents A and B were added to the developing solution dissolving tank per 0.62 m ² of the photosensitive material, and water was added to the developing solution dissolving tank.
The replenishing amount of the developer from the dissolving tank to the processing tank was 80 ml per 0.62 m ² of the photosensitive material. The pH of Agent A and Agent B dissolved in 38 ml of water was 10.15.

The fixing / dissolving tank contains 20 per m ² of the photosensitive material.
0 ml was replenished. The above C per 0.62 m ^{2 of} photosensitive material
Two agents, one D agent and 74 ml of water were added to the dissolving tank at a ratio of 80 ml to 0.62 m ² of the photosensitive material. Each treatment agent 1
The addition rate of water to the individual was started almost simultaneously with the addition of the treatment agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the treatment agent. The dissolution at this time was circulated by a circulation pump at a speed of 15 liter / min for dissolution. The dissolution time at this time is 7.5 mi for one developer dissolution tank.
n, one fixer dissolving tank was 5.0 min.

Processing conditions Current image 35 ° C. 8.2 sec. Fixation 33 ° C. 5.0 sec. Rinse at room temperature 4.5 sec. Squeeze-1.6 sec. Drying 40 ° C. 5.7 sec. Total 30 sec. When 10 liters were accumulated, the developing waste liquid was pulverized using the processing liquid recovery apparatus shown in FIG. This powder was extracted with a solvent, and erythorbic acid, 1-phenyl-3-
The contents of pyrazolidone, 5-methylbenzotriazole and 1-phenyl-5-mercaptotetrazole were measured using high performance liquid chromatography.

In addition, 17.9 g of the powder was dissolved in 100 ml of water, and the pH was measured to determine the amount of potassium carbonate required to reach a predetermined pH.

On the other hand, when 10 liters of the fixing waste liquid has accumulated, the waste liquid is pulverized using the processing liquid recovery apparatus shown in FIG. 1 and the remaining amount of thiosulfate ions is determined from the powder sample by an iodine titration method. The consumption of ammonium thiosulfate and sodium thiosulfate was calculated from the sodium thiosulfate ratio (7: 3). The consumption was calculated by analyzing the aluminum content by weight.

Further, 64.1 g of the powder was dissolved in 100 ml of water, and the amounts of sodium hydrogen acetate and tartaric acid required to reach a predetermined pH were determined.

Table 1 shows the results of the analysis and the amount of the replenisher.
It is shown in FIG.

[0080]

[Table 1]

[0081]

[Table 2]

Preparation of Recycled Solid Developer 75 g of erythorbic acid, 500 g of potassium carbonate and 16.5 of 1-phenyl-3-pyrazolidone were added to 3000 g of the developer powder recovered from the waste developing solution based on the replenishment amounts shown in Table 1.
g, 1.65 g of 5-methylbenzotriazole and 1.16 g of 1-phenyl-5-mercaptotetrazole, mix in a mill for 30 minutes, and in a commercially available stirred granulator at room temperature for about 10 minutes at room temperature for 30 minutes. After granulating by adding water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the moisture of the granulated material. Polyethylene glycol # 60 was added to the granules thus prepared.
100 g in a room humidified at 25 ° C. and 40% RH or less using a mixer for 10 minutes, and then the resulting mixture is tough pre-collect 1 manufactured by Kikusui Seisakusho Co., Ltd.
527HU was compressed and compressed using a modified tableting machine with a filling amount per tablet of 5.41 g to produce tablets for regenerative development.

Preparation of Regenerated Solid Fixing Agent Similarly, 10600 g of fixing agent powder recovered from the fixing waste liquid
660 g of ammonium thiosulfate / sodium thiosulfate (70/30 weight ratio), 149 g of aluminum sulfate, 74.3 g of boric acid, and 297 g of sodium hydrogen carbonate were added to the mixture and ground, and then homogenized with a commercially available mixer. Mix. Next, in the same manner as in the operation (A), granulation is performed with the addition amount of water being 500 ml. After granulation, granulate 6
After drying at 0 ° C. for 30 minutes, the water content of the granules is almost completely removed. 4 g of sodium N-lauroylalanine was added to the granules thus prepared, and the mixture was added at 25 ° C. and 40% R
Mix for 3 minutes using a mixer in a room humidified below H. Next, the obtained mixture was mixed with a tableting machine obtained by modifying a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed at a filling amount of 10.88 g per tablet to produce a tablet for regenerating and fixing.

Preparation of Comparative Liquid Processing Agent Comparative Developer Formulation (1 L Formulation) Part-A Potassium Hydroxide 37.5 g Potassium Sulfite (50% Solution) 190 g DTPA / 5Na 5.0 g Sodium Bicarbonate 11 g 5-Methylbenzotriazole 0.1 g 1-phenyl-5-mercaptotetrazole 0.02 g 1,4-dihydroxybenzene or exemplified compound 1-1 30 g Part-B glacial acetic acid 14 g triethylene glycol 15 g 1-phenyl-3-pyrazolidone 1.8 g 5-nitro Indazole 0.03 g Starter solution formulation (1 liter formulation) Glacial acetic acid 120 g Potassium bromide 225 g Add water to make up to 1.0 liter Comparative fixer solution formulation (1 liter formulation) Part-A Ammonium thiosulfate (70 wt / vol%) 333 g sodium sulfite 6 g sodium acetate trihydrate 25 g sodium citrate 2.8 g gluconic acid 3.9 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 1 g Part-B aluminum sulfate 18 hydrate 44 g Using the above-mentioned developer and fixing agent, a starting solution of a developing solution and a fixing solution was prepared by the following method.

Preparation of Comparative Liquid Developer The comparative developer was prepared by adding Part-A and Part-B to water.
At the same time, add water while stirring and dissolving to make up to 1 liter, and adjust the pH to 10.4 with glacial acetic acid or potassium hydroxide.
It was adjusted to 0 to provide a comparative developer, and a comparative developer replenisher was also used.

20 ml of a starter solution was added per liter of the developer, and the pH was adjusted to 10.26 to obtain a working solution.

Preparation of Comparative Liquid Fixing Solution The comparative fixing solution was prepared by adding Part-A and Part-B to water.
Is added simultaneously, water is added while stirring and dissolving to make up to 1 liter, and the pH is adjusted to 4. using sulfuric acid and sodium hydroxide.
4, which was used as a comparative fixing solution. This was also used as a comparative fixing replenisher.

Evaluation of Processing Stability At the start of development processing (running start), the recycled developer 12
Thirty-six pieces were dissolved and diluted in water distilled and collected by the treatment liquid collecting apparatus shown in FIG. 1 to prepare 16.5 liters.

The developing tank is filled with a liquid obtained by adding 330 ml of a starter to the developing solution, and the fixing tank is prepared by dissolving and diluting 1875 tablets of the regenerated fixing agent in water distilled and recovered in the same manner as the developing solution. The solution was adjusted to 16.5 liters, filled in a fixing tank to be in a start state, and each of a developing dissolving tank and a fixing dissolving tank was filled with a replenisher prepared with a regenerated developer and a regenerated fixing agent to start processing. The pH of the developer to which the starter was added was 10.00.

A medical X-ray film SG-R (manufactured by Konica Corporation) was exposed so that the optical density after the development processing became 1.0, and it was cut into four pieces (245 mm × 305 m).
m) Running was performed using 1500 sheets. An automatic processor TCX-201 (manufactured by Konica Corporation) for running
After the running conditions are the same as described above, the washing water used for the cross rack washing mechanism is distilled and recovered water, and then the running conditions are used.
A sensitometric test was performed to evaluate the process variation.

As a comparative treatment method, a liquid treatment agent subjected to a running treatment under the same conditions as the running treatment using the solid treatment agent, and a liquid obtained by removing only silver ions and halogen ions from a waste liquid treated with the liquid treatment agent The liquid processing agent and the solid processing agent were used to compensate for the consumed amount of the processing agent.

[Sensitometry] Fluorescent intensifying screen SRO-
250 (manufactured by Konica Corporation), tube voltage 90 kV
X-rays were irradiated at p, 20 mA for 0.05 seconds, and a sensitometric curve was prepared by the distance method to determine sensitivity, fog and gamma (average gamma of fog + 0.25 to fog + 2.0). The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0. Set the sensitivity at the start of processing to 1
It was expressed by relative sensitivity when it was set to 00.

Evaluation of Residual Silver The above-mentioned treatment was carried out without exposing the above film, and a residual silver evaluation solution (2.6 × 10 ⁻³ mol / 1 liter aqueous solution of sodium sulfide) was dropped on the emulsion side of the film for 3 minutes. After leaving
The dropping solution was wiped off, and left at normal temperature and normal humidity for 15 hours.
5 (manufactured by Konica Corporation) with a spectral filter of 436 ± 10
The transmitted blue light density was measured using an interference filter of nm and the difference was regarded as the degree of residual silver. The larger the measured value, the more residual silver in the film, indicating that the fixability is not excellent.

Table 3 summarizes the results of these evaluations.

[0095]

[Table 3]

From Table 3, it is clear that the processing performance hardly fluctuates even when the regenerated solid processing agent is used.

[0097]

According to the present invention, the developing and fixing waste liquid is powdered and regenerated, so that the processing stability is higher than the conventional method of regenerating the diluted waste liquid, and there is no change in sensitivity, fog, etc. Excellent tormetry performance. Further, in addition to economic effects such as transportation and storage of waste liquid, there is an effect that contributes significantly to prevention of environmental pollution and protection of resources.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a processing liquid recovery apparatus used in an embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Processing waste liquid receiving tank 2 Electrolyzer 3 Primary regenerating liquid tank 4 Electrodialyzer 5 Secondary regenerating liquid tank 6 Pump 7 During transportation 8 Valve 9 Heating pipe 10 Evaporation pipe 11 Vacuum pump 12 Cooling pipe 13 Degassing pipe 14 Cooling tower 15 Water receiving tank 16 Heat source 17 Powder transport pipe 18 Recycling agent powder receiving tank

Claims (4)

[Claims] 1. A method for reprocessing a silver halide photographic material after processing a silver halide photographic light-sensitive material with a processing solution prepared by dissolving a solid processing agent, pulverizing a processing waste liquid and adding a component reduced by the processing. A method for regenerating a treating agent, wherein the treating agent is used again as a solid treating agent. 2. The method of regenerating a processing agent according to claim 1, wherein after removing halogen ions from the development waste liquid, water is removed by distillation under reduced pressure to powderize the waste liquid. 3. The method for regenerating a processing agent according to claim 1, wherein silver ions and halogen ions are removed from the fixing waste liquid, water is removed by distillation under reduced pressure, and the waste liquid is powdered. 4. The method for regenerating a processing agent according to claim 2, wherein the water recovered by distillation under reduced pressure is reused as water for dissolving, diluting and / or washing the crossing rack.