JPH08206461A - Regeneration of treatment solution for silver halide photosensitive material and replenishing treatment agent therein - Google Patents

Abstract

PURPOSE: To continuously and automatically perform electrodialysis while dispensing with maintenance in the regeneration of a treatment soln. for a silver halide photosensitive material and to provide a replensihing treatment agent used in the regeneration of the treatment soln. CONSTITUTION: Since a dilute aq. soln. of a fixing soln. or a bleaching fixing soln. is introduced into the concn. chambers 21a, 21b, 21c, 21d, 21e of an electrodialytic apparatus 20 and cations (Ag<+> ) and anions (I<-> ) are recovered in the dilute aq. soln., even when a special concn. chamber soln. is not prepared, a treatment soln. such as the fixing soln. or the bleaching fixing soln. is put to practical use to efficiently operate the apparatus as a whole. Further, since cations (Ag<+> ) are not precipitated by using the dilute aq. soln., the maintenance of the electrodialytic apparatus 20 becomes unnecessary and electrodialysis can be performed continuously and automatically.

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 processing solution for silver halide photographic light-sensitive materials by performing electrodialysis using an ion exchange membrane and a replenishing processing agent therefor, and more particularly to efficiently treating halogen ions. The present invention relates to an improved technique for removing.

[0002]

2. Description of the Related Art Conventionally, processing of a silver halide photographic light-sensitive material (hereinafter simply referred to as a photographic light-sensitive material) includes two steps of development and desilvering. That is, when developing a photographic light-sensitive material,
The exposed silver halide is reduced to form an image. At this time, some halogen ions are dissolved in the developing solution. In the processing of color photographic light-sensitive material, silver produced by development is oxidized by a bleaching agent (oxidizing agent) and converted into ions in the desilvering step, and is removed by dissolution with a silver dissolving agent such as thiosulfate. That is, when the photographic light-sensitive material is processed, various anions such as halogen ions contained in the photographic light-sensitive material in advance in the photographic processing liquid are eluted and accumulated in the photographic processing liquid. Then, it is treated by steps such as washing with water and stabilization. In the case of a monochrome photographic light-sensitive material, after black-and-white development, it is directly treated with a fixing solution containing thiosulfate as a main component, and then washed with water. Each of these processing solutions is usually at 20 to 50 ° C.
The temperature is adjusted to 1, and the photographic light-sensitive material is dipped and processed in these processing solutions.

These treatment liquids are successively replenished according to the treatment, and the treatment liquid overflowing from the treatment tank, that is, the overflow liquid, is disposed of as a used liquid or is subjected to pollution control treatment so as not to cause environmental pollution. Later thrown away. However, in the overflow liquid, a large amount of the components of the processing liquid that have not been used up during the processing remain.

Disposal of such a liquid is not preferable in view of the social demand for effective use of resources, and is uneconomical for the user. Further, since it is necessary to perform a special waste liquid treatment for the above-mentioned pollution control treatment, the labor and cost burden required for this treatment is large. On the other hand, there is also known a technique of reusing after removing unnecessary or harmful components from the overflow liquid,
JP-A-52-105820, JP-A-55-14849, JP-A-4-276743, JP-A-5-27401, JP-A-5-53
The ion exchange membrane electrodialysis method disclosed in Japanese Patent No. 259, etc. is one of them. In this method, a direct current voltage is applied by alternately partitioning a plurality of anion exchange membranes and cation exchange membranes between electrodes composed of a cathode and an anode. Here, the anion exchange membrane has the property of transmitting anions such as I- and the like and blocking the cations such as Ag +, and the cation exchange membrane has the opposite property. Therefore, salt is desalted in the chamber with the anion exchange membrane on the anode side and the cation exchange membrane on the cathode side, and the anion and cation are concentrated in the adjacent chamber, resulting in the desalination chamber. Concentration chamber is constructed. After desalting, the processing system is used again as a processing solution.

[0005]

However, according to the above-mentioned electrodialysis, a fixing solution or a bleach-fixing solution is introduced into a desalting chamber, a high-concentration fixing agent is introduced into the concentrating chamber, and the solution is passed through a cation exchange membrane. After moving Ag + ions from the desalting chamber to the concentrating chamber so that the concentration of Ag + ions in the concentrating chamber liquid is above a certain concentration, it is taken out and electrolytic silver recovery is performed to remove silver and return the liquid to the concentrating chamber again. However, in order to recover the electrolytic silver, complicated silver removal maintenance is required to remove silver accumulated in the electrodes, which is troublesome and causes a problem of lowering work efficiency.

Further, in order to perform electrolytic silver recovery efficiently, a dedicated concentrating chamber is required.
Electrolytic oxidative deterioration occurs in the concentrated chamber liquid, and it is necessary to have a concentration management such as partial renewal or addition of preservative, and a PH management device. As described above, by providing the electrolytic silver recovery device, the size of the entire device is increased and the cost is increased. Therefore, there is also a problem that only a part of a large-scale developing station is put into practical use and lacks versatility.

The present invention has been made in view of the above problems, and a method for regenerating a processing solution for a silver halide photographic light-sensitive material and a replenishment thereof, which does not require any troublesome maintenance and can continuously and automatically perform electrodialysis. It is intended to provide a treatment agent.

[0008]

Therefore, according to the invention described in claim 1, the desalination of the electrodialyzer having a desalination chamber and a concentration chamber which are arranged between electrodes and separated by an ion exchange membrane. After desalting the treated fixer or bleach-fixer introduced into the chamber, while collecting the desalted salt in the concentrating chamber,
In the method of regenerating the desalted solution as a processing solution for a silver halide photographic light-sensitive material, a diluting aqueous solution of the fixing solution or the bleach-fixing solution is introduced into the concentrating chamber for electrodialysis.

Here, the invention according to claim 2 is configured so that the dilution ratio of the diluted aqueous solution is ½ concentration or less. Further, the invention according to claim 3 is configured such that the diluted aqueous solution is a treatment solution of one of a washing step, a rinsing step and a stabilizing step or a diluted aqueous solution diluted with an overflow solution.

Further, the invention according to claim 4 is configured such that the diluted aqueous solution is an aqueous solution obtained by diluting an overflow liquid or a waste liquid in the fixing step or the bleach-fixing step. Further, the invention according to claim 5 is configured so that the ion exchange membrane closest to the cathode among the electrodes provided in the electrodialysis device is the anion exchange membrane. In the invention according to claim 6, an anode chamber and a cathode chamber are provided in the electrodialysis device, and a plurality of the ion exchange membranes composed of a cation exchange membrane and an anion exchange membrane are provided between the anode chamber and the cathode chamber. The membranes are arranged in an alternating manner and are configured to form a desalination chamber and a concentration chamber.

Further, the invention according to claim 7 is configured so that an aqueous solution containing no silver ion component is introduced into the cathode chamber. According to the invention of claim 8, the concentration of thiosulfate contained in the fixing solution or the bleach-fixing solution is 1/2.
It is configured so that the concentration is adjusted to be equal to or lower than that of the concentration and then introduced into the concentration chamber.

Further, the invention according to claim 9 is an electrodialysis apparatus having an electrode chamber, a desalting chamber and a concentrating chamber which are arranged between electrodes and are separated by an ion exchange membrane, and are used as processing solutions for silver halide photographic light-sensitive materials. In the desalting chamber, the fixing solution or the bleach-fixing solution treated with the silver halide photographic material is desalted, and the cathode chamber of the electrode chamber is treated with the processing solution for silver halide photographic material. It is configured to guide the developed developer.

Further, the invention according to claim 10 is an electrodialyzer having an electrode chamber, a desalting chamber and a concentrating chamber which are arranged between electrodes and separated by an ion exchange membrane, and which is a silver halide photographic light-sensitive device of an automatic developing device. In the method for regenerating a processing solution for materials, the processing solution for silver halide photographic light-sensitive material is introduced into a distillate obtained by evaporation and concentration into at least the concentration chamber or the electrode chamber of the electrodialysis device. .

Further, the invention according to claim 11 is an electrodialyzer having an electrode chamber, a desalting chamber and a concentrating chamber which are arranged between electrodes and separated by an ion exchange membrane. In the method of regenerating the processing solution for materials, a distillate obtained by evaporating and concentrating the processing waste solution of the silver halide photographic light-sensitive material is used to replenish at least diluting water of the reprocessing processing solution or the processing solution for the silver halide photographic light-sensitive material. It is configured to be used as dilution water for the processing liquid.

The twelfth aspect of the present invention is configured to obtain a distillate by adding the processing waste solution from the electrodialysis device to the processing waste solution of the silver halide photographic light-sensitive material and evaporating and concentrating the solution. Further, the invention according to claim 13 is a processing solution for a silver halide photographic light-sensitive material, which is desalted and regenerated by an electrodialysis device having a desalting chamber and a concentrating chamber which are separated by an ion exchange membrane arranged between electrodes. In the replenishing processing agent to be replenished with, the replenishing agent and the dilution water of the replenishing agent are added to the processing solution for the silver halide photographic light-sensitive material, and the replenishing agent amount, the dilution water amount and the processing solution introduced from the previous step. When the total amount of the mother liquor is used as the mother liquor, sulfite is added to produce a concentration of 0.25 mol / liter or more.

Further, in the invention according to claim 14, the processing solution for the silver halide photographic light-sensitive material is a fixing solution or a bleach-fixing solution.

[0017]

Therefore, according to the first aspect of the present invention, a dilute aqueous solution of the fixing solution or the bleach-fixing solution is introduced into the concentrating chamber of the electrodialysis device, and the cation (Ag +) and the anion ( Since Br-, I-) is collected, the entire apparatus can be efficiently operated by utilizing a processing solution such as a fixing solution or a bleach-fixing solution without preparing a special concentrating chamber solution. Furthermore, the use of a diluted aqueous solution makes it difficult for cation (Ag +) precipitation to occur, so that maintenance is not required and electrodialysis can be continuously and automatically operated.

According to the second aspect of the present invention, the dilution ratio of the diluted aqueous solution is set to 1/2 concentration or less,
It is possible to set the molar ratio of the fixing agent to silver such that the fixing agent (thiosulfate) stably dissolves the cation (Ag +) as a complex and the precipitation of the cation (Ag +) does not occur. Further, as in the invention according to claim 3, the diluted aqueous solution is diluted with a treatment liquid or an overflow liquid in one of the washing step, the rinsing step and the stabilizing step. By using the diluted aqueous solution as an aqueous solution obtained by diluting the overflow liquid or the waste liquid in the fixing step or the bleach-fixing step, the aqueous solution used in the processing of the photographic light-sensitive material can be used, and the entire apparatus can be operated more efficiently. In addition, the final amount of waste liquid in the device can be reduced.

According to the fifth aspect of the invention, the ion exchange membrane closest to the cathode among the electrodes provided in the electrodialysis device is the anion exchange membrane, so that the cation (A
The permeation of g +) is blocked by the anion exchange membrane, and cations (Ag +) can be prevented from depositing on the cathode.
Further, as in the invention according to claim 6, since a plurality of desalting chambers and concentrating chambers are alternately formed between the two electrode chambers of the electrodialysis device, the number of electrodes is the same even if the treatment amount is the same. The amount of current can be reduced, and the redox reaction at the electrode can be reduced.

In addition, by introducing an aqueous solution containing no silver ion component into the cathode chamber as in the invention of claim 7, it is possible to prevent cations (Ag +) from being deposited particularly on the cathode side. Maintenance can be unnecessary for a long period of time. Further, according to the invention of claim 8, the concentration of the thiosulfate contained in the fixing solution or the bleach-fixing solution is adjusted to be 1/2 concentration or less and introduced into the concentrating chamber. Since the precipitation of ions (Ag +) does not occur, the device can be used for a long time without maintenance.

Further, according to the invention of claim 9, the fixing solution or the bleach-fixing solution is desalted in the desalting chamber and the developing solution is guided to reduce the oxidant in the cathode chamber.
Both the fixing solution or the bleach-fixing solution and the developing solution can be regenerated in the same apparatus. Further, as in the invention of claim 10, at least the aqueous solution introduced into the concentrating chamber or the electrode chamber is a distillate of the processing waste liquid of the silver halide photographic light-sensitive material, or according to the invention of claim 11, At least diluting water of the regenerating processing solution or diluting water of the replenishing processing solution of the processing solution for the silver halide photographic light-sensitive material is a distillate obtained by evaporating and concentrating the processing waste solution of the silver halide photographic light-sensitive material. Further, since it does not contain metal ions or silica at all, the durability of the electrode, the ion exchange membrane, etc. can be enhanced.

According to the twelfth aspect of the invention, since the processing waste solution from the electrodialyzer is added to the processing waste solution of the silver halide photographic light-sensitive material and evaporated to obtain a distillate, The processing waste liquid of the automatic developing device and the electrodialysis device can be processed together. Further, according to the invention of claim 13, a replenisher and dilution water of the replenisher are added to the processing solution for a silver halide photographic light-sensitive material, and further 0.25 mol /
Since sulfite having a concentration of liter or more is added, the sulfite decomposed by electrodialysis can be compensated, and stable regeneration treatment can be performed for a long period of time. Further, as in the invention described in claim 14, the invention can be applied to the one in which the processing solution for silver halide photographic light-sensitive material is a fixing solution or a bleach-fixing solution.

[0023]

Embodiments of the present invention will be described below. Figure 1
FIG. 1 is a schematic configuration diagram showing an automatic developing device and an electrodialysis device used for processing a photographic light-sensitive material, particularly for processing a color photographic light-sensitive material according to this embodiment. First, the automatic developing device will be described.

In the automatic developing apparatus 10, color developing processing, bleach-fixing processing, and stabilizing processing are performed on color paper among color photographic light-sensitive materials, and the following steps of bleaching processing are performed on color negative films, though not shown. There is a fixing process, and a plurality of processing tanks containing processing liquids for performing each processing are provided in the order of processing, and the photographic light-sensitive material is sequentially passed through these processing tanks so that a series of development processing can proceed. Has become.

Here, since each processing solution becomes fatigued by the processing of the photographic light-sensitive material, the color development replenisher, the bleach-fix replenisher, the bleach replenisher, the fixing replenisher, which are the processing components at certain intervals.
Tap water is generally replenished as well as supplemented with a stabilizing replenisher. The processing tank 11 is a color development processing tank, the processing tank 12 is a bleach-fixing processing tank, and the processing tanks 13a to 13c are stabilization processing tanks. These are three tanks that gradually overflow from the processing tanks 13c to 13a in the arrow direction. It is a counter current method.

The photographic light-sensitive material 40 such as exposed color paper or color negative film is developed by being sent to the processing tank 11, the processing tank 12, and the processing tanks 13a, 13b, 13c in this order as shown by the arrow. Processing in each step of fixing and stabilizing is performed, and after the stabilizing processing in the processing tank 13c, a drying processing is performed by a configuration not shown, and the developing processing of the photographic light-sensitive material 40 is completed. The bleach-fixing step or the step following the fixing step is preferably a multi-stage countercurrent method,
In general, washing and stabilization are carried out, and a chelating agent, antifungal agent, surfactant, image stabilizer and the like can be added.

Further, in the automatic developing apparatus of the present embodiment, the replenishment of the processing components corresponding to the fatigue of each processing solution in the processing tank is used in the form of an aqueous solution replenisher or recently because of the ease of replenishing work. The solid tablet type replenisher is introduced into the processing tanks 11 to 13c at certain intervals according to the processing area of the photographic material 40. Here, a replenisher and a diluting water for the replenisher are added to the bleach-fixing solution or the fixing solution, and further added in a range of 0.25 mol / liter or more, preferably in the range of 0.25 to 1.0 mol / liter (in this case, the bleach-fixing solution or the fixing solution). The main component, thiosulfate, has been added with a concentration of sulfite (antioxidant) in the range of 0.4 to 2.0 mol / liter) to compensate for sulfite that is decomposed by electrodialysis, which will be described later, for a long period of time. Therefore, stable and stable regeneration processing can be performed. As the antioxidant, sulfite, bisulfite, sulfinic acid or carbonyl bisulfite adduct is preferable.

The bleach-fixing solution and the replenisher for the fixing solution are photographic materials.
It may be added to any part of the processing unit of 40 or the liquid circulation system of the automatic developing device 10 and the electrodialysis device 20 described later, and may be replenished to prevent deterioration over time. Since the temperature of each processing tank is controlled at constant temperature, the water content evaporates and the concentration of the processing solution becomes high.

Of the above-mentioned processing tanks, the overflow liquid from the processing tank 12, that is, the bleach-fixing processing tank is diluted with the overflow liquid from the processing tank 13a, which is the receiving tank for the final overflow of the stabilizing processing liquid, and is passed through the pipe 14. Is introduced into the overflow receiving tank 15 and becomes a diluted diluted aqueous solution. The dilute aqueous solution may be a dilute aqueous solution obtained by diluting the bleach-fixing solution with tap water or the like, or a dilute aqueous solution diluted with an aqueous solution introduced from the electrode chamber stock solution tank 38 described later.

The dilute aqueous solution output from the overflow receiving tank 15 passes through the pipe 16 and the electrodialyzer described later.
They are introduced into the 20 concentrating chambers 21a, 21b, 21c, 21d, and 21e, respectively, and are led again to the overflow receiving tank 15 via the pipe 17. That is, the pipes 16 and 17 form a circulation path for the diluted aqueous solution. When processing a color negative film, instead of the bleach-fixing solution, the fixing solution is guided to the overflow receiving tank 15.

Next, the electrodialysis apparatus 20 will be described. The principle of electrodialysis using the anion exchange membrane 25 and the cation exchange membrane 26 is already known as described in the prior art and is omitted for brevity. explain. Automatic developing device 10 mentioned above
From the bleach-fixing solution and waste solution of the fixing solution through the pipe 18,
Desalination chambers 22a, 22b, 22c, 22 of the electrodialysis device 20 in which negative and positive electric fields are applied to the cathode 23 and the anode 24, respectively.
Introduced into d and 22e and subjected to electrodialysis treatment, cations (Ag +) are removed in the case of a bleach-fixing solution, and cations (Ag +) and anions (I-) are removed in the case of a fixing solution. It is removed and collected in the concentration chambers 21a, 21b, 21c, 21d, 21e. Then, the desalted bleach-fixing solution and the fixing solution are regenerated and returned to the processing tank of the automatic developing device 10 through the pipe 19 for reuse.

Here, the material of the cathode 23 is iron, nickel, lead, zinc, stainless steel, titanium, hastelloy steel and the like, and the material of the anode 24 is platinum, ruthenium, iridium, palladium and other white metals and palladium. A material in which the oxidant is coated on titanium, graphite, ferrite,
Nickel and the like are used, and they are used in a plate shape, a mesh shape, or the like.

Further, the treatment liquid is subjected to ion exchange membrane electrodialysis.
The current density that is passed in order to determine the characteristics of the ion exchange membrane and the treatment liquid
Generally 0.1 A / dm, depending on characteristics²~ 10A /
dm ², More preferably 0.2 A / dm²~ 5 A / dm²
Is. In addition, when the treatment liquid is regenerated, the treatment liquid is placed in the desalting chamber 22.
Immediately before or simultaneously with the introduction of Japanese Patent Laid-Open No. 53-46732,
JP-A-52-146236, JP-A-54-9626 and JP-A-
54-19741, JP 53-132343, JP 56-3
Polymers, resins, as described in 3644 publication, etc.
Various ion exchange resins (for example, DIAION SA-10
A, SA-20A, PA-316, PA-418, WA-11,
WA-20, CR-10, PK-220, PK-208, Juo
Light S-37, Amber Light IR-410), porous
The treatment liquid is applied to an adsorbent such as a chilendivinyl berzene copolymer.
Contact treatment of the ion-exchange membrane also prolongs the life of the ion-exchange membrane.
It is effective for

The ion exchange membrane used in this embodiment is NEOSEPTA (Tokuyama Soda Co., Ltd.), Selemi.
on (Asahi Glass Co., Ltd.), Aciplex (Asahi Kasei Co., Ltd.), Nafion (DuPont), etc. can be used,
Preferably, a cation exchange membrane or anion exchange membrane that selectively permeates monovalent ions is used. On the other hand, the cation (Ag +) recovered in the concentrating chamber 21 is dissolved by forming a complex with thiosulfate by the bleach-fixing solution introduced into the concentrating chamber 21 or the main agent in the fixing solution, but the cation ( When the concentration is high in relation to the molar ratio with Ag +), a precipitate is likely to be formed, which causes a device failure. In this embodiment, paying attention to this point, the diluted aqueous solution is introduced into the concentrating chamber 21 to prevent the generation of precipitates.

The bleach-fixing solution and the fixing agent used for the fixing solution may contain thiosulfate as a main component and thiocyanate, thioether compounds, and thioureas. Sodium thiosulfate and ammonium thiosulfate can be used most widely. The thiosulfate contained in the diluted aqueous solution in the overflow receiving tank 15 is diluted with the above-mentioned stabilizing solution overflow solution, tap water or the aqueous solution introduced from the electrode chamber stock solution tank 38, and the dilution rate at that time is ½. Concentration, preferably 1/3 ~
By setting the concentration range to 1/50, cations (Ag
+) Does not precipitate.

Since the cation (Ag +) and the anion (I-) are collected in the diluted aqueous solution as described above, the fixing solution or the bleach-fixing can be performed without preparing a special concentrating chamber solution as in the conventional case. The entire device can be efficiently operated by utilizing the processing liquid such as liquid. Furthermore, by introducing the fixing solution or the dilute aqueous solution of the bleach-fixing solution into the concentrating chamber, precipitation of cations (Ag +) does not occur, maintenance becomes unnecessary, and electrodialysis can be continuously and automatically operated.

The dilute aqueous solution may be a dilute aqueous solution obtained by diluting the overflow solution of the bleach-fixing step or the fixing step with a processing solution or overflow solution of a water washing step or a rinsing step (not shown), or overflow of the bleach-fixing step or the fixing step. It is possible to use the aqueous solution used in the process of processing so-called photographic materials such as waste liquid instead of the liquid, and the entire device can be operated more efficiently, and the final waste liquid amount of the device can be reduced. .

Anode 23 and anion exchange membrane of electrodialysis device 20
An anode chamber is formed between the cathode 24 and 25a, and a cathode chamber is formed between the cathode 24 and the anion exchange membrane 25f. In particular, in the present embodiment, the ion exchange membrane closest to the cathode is an anion exchange membrane, so that cations (Ag +) moving due to the negative charge of the cathode can be blocked, and the silver on the cathode 24 can be prevented. Can be prevented.

Further, as another embodiment, the electrodialysis device 20
The bleach-fixing solution may be circulated through the anode chamber of No. 1, in which case the aminocarboxylic acid iron salt used as the bleaching agent in the bleach-fixing solution may be oxidized and regenerated from divalent to trivalent. It is possible. Particularly, since a plurality of desalting chambers and concentrating chambers are formed alternately between the anode chamber and the cathode chamber, the amount of current flowing through the electrodes 23 and 24 is reduced, and the oxidative deterioration of the bleach-fix solution can be suppressed.

The waste liquid stock tank 31 is connected to the waste liquid from the overflow receiving tank 15 via the pipe 30 and the pipe.
Overflow liquid from the electrode chamber stock liquid tank 38, which will be described later, via 42 and 30, and overflow liquid from the processing tank 11, that is, the color development processing tank, are led via the pipe 41 and accumulated. Then, the waste concentrate 34 and the distillate, which are guided to the waste liquid evaporative concentrator 32 through the pipe 32 and are subjected to the evaporative concentration processing and the cooling condensation processing by the reduced pressure heat pump system, are obtained. In this way, the waste liquid evaporative concentrator 32 is used to dilute the component concentrations of the concentrating chamber liquid and the electrode chamber liquid,
Even if the amount of waste liquid increases, the amount of the waste concentrate 34 will eventually be a problem, so that it is possible to treat the treatment waste liquids of the automatic developing device and the electrodialysis device together.

The obtained distillate is temporarily accumulated in the distillate tank 35 through the pipe 36, and is used as a diluting solution for the bleach-fixing replenisher and the stabilizing replenisher through the pipe 37, and the stock solution for the electrode chamber is also used. It is stored in the tank 38, is introduced into the cathode chamber and the anode chamber of the electrodialysis device 20 through the pipe 39, and is returned to the electrode chamber stock solution tank 38 through the pipe 40. In this way, in particular, since the distillate containing no cation (Ag +) is introduced into the cathode chamber, the cation (A
g +) is prevented from precipitating, and maintenance of the cathode can be made unnecessary for a long period of time. In addition, the pipes 30, 41, 32, 36,
The entire processing system can be operated efficiently in the distillate manufacturing process connected by the circulation route of 37. Further, tap water has been conventionally used as a conditioning liquid for each treating agent, but tap water is
g, Ca, Fe, etc.) ions and silica.

These components are related to the durability of the ion exchange membrane. On the other hand, the waste liquid distillate contains ammonium ions, carbonate ions, and sulfite ions as the main components and does not contain the above metal ions or silica at all, so that the diluting water of the reprocessing liquid or the silver halide photographic light-sensitive material is used. Replenishment of treatment liquid By using it as dilution water for the treatment liquid, the durability of the electrode and the ion exchange membrane can be enhanced. Further, although the cost of distilling tap water is high, the distillate from the waste liquid evaporative concentrator 32 is suitable because it costs little.

In this embodiment, a distillate was used as the electrode chamber liquid, but any aqueous solution containing no cation (Ag +) may be used, for example, sodium sulfate solution can be applied. The electrode chamber liquid of the device used for the ion exchange membrane electrodialysis method includes sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate, sodium bisulfate, sodium bicarbonate. Salts, potassium hydroxide,
An electrolyte solution such as an alkali such as sodium hydroxide or an acid such as sulfuric acid is suitable. It is sufficient if the concentration of these electrolyte solutions is 0.001 N or more, and more preferably 0.01 to 2 N.

If necessary, these electrolyte solutions may contain aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid or its sodium salt, ammonium salt, potassium salt, diethylenetriaminepentaacetic acid or its sodium salt, ethylenediamine-N-β). -Oxyethyl-N, N ', N'-triacetic acid or its sodium salt,
Ammonium salt, nitrilotriacetic acid or its sodium salt, triethylenetetramine hexaacetic acid or its sodium salt, or iminodiacetic acid), aminopolyosphonic acid (for example, 1,3-diaminopropanol-N,
N, N ', N'-tetramethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid or 1- Hydroxy-ethane-1,1 diphosphonic acid, etc.), sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate or 2-phosphoethylimito-N, N-diacetic acid can also be added.

In this embodiment, the distillate was made from the waste liquid of the color developing solution on the premise that the bleach-fixing solution was desalted. However, the fixing solution is desalted and color-developed as in the processing of a color negative film. A distillate may be produced from the waste liquid of the developer and the bleaching solution. FIG. 2 is a schematic diagram showing another embodiment of the automatic developing device and the electrodialysis device when the photographic material 40 to be processed is a color negative film.

Unlike the embodiment shown in FIG. 1, a processing tank 50 for fixing processing is added to the automatic developing device 10. The waste solution of the fixing solution is desalted and circulated through the pipes 51 and 52, the waste solution of the bleaching solution is circulated between the bleaching solution and the anode chamber through the pipes 53 and 54, and the waste solution of the color developing solution is guided to the cathode chamber. As a result, an oxidant such as a developing agent is reduced and circulated through pipes 55 and 56. Therefore, by circulating the bleaching solution between the bleaching solution and the anode chamber, an aeration device, which is a device for returning the divalent to trivalent aminopolycarboxylic acid iron salt, which is generally a bleaching agent, provided in the bleaching tank becomes unnecessary, In particular, the bleaching agent is made to function effectively when using propylenediaminetetraacetic acid iron salt having poor aeration efficiency, and reliable bleaching performance can be obtained only by a simple process of adding a liquid circulation system. .

As described above, the fixing solution or the bleach-fixing solution is desalted, and the developing solution is introduced into the cathode chamber to cause a reduction reaction.
Both can be regenerated and the device can be operated efficiently. In particular, the color developing solution is I-, Br-, C
Even if the halogen such as l- is removed, the organic inhibitor is eluted and accumulated from the photographic light-sensitive material 40, the effect of reducing the replenisher is small, and it is expensive to introduce an electrodialysis device dedicated to the color developer. However, the bleach-fixing solution or the fixing solution has a great effect of reducing the replenisher although the above-mentioned configuration has a low installation cost.

In this embodiment, a circulation path for regenerating the fixing solution and returning it to the fixing processing tank is formed, and the evaporation correction water from the outside is formed.
57 is introduced into each processing tank of the automatic developing device 10. Also,
The waste liquid of the overflow receiving tank 15 and the overflow liquid of the color developing solution and the bleach-fixing solution are used as the waste liquid. As shown in FIG. 1 and FIG.
Since the bleach-fixing solution or the overflowing solution of both the fixing solution and the stabilizing solution is introduced into the concentrating chamber 21, the cation (Ag + ) And anions (I-) had an adverse effect on the bleach-fixing solution or maintenance of the processing performance of the fixing solution, but since it is only discarded in the overflow, it is possible to reach a high concentration just before the precipitation occurs. Ions (Ag +) and anions (I-) can be accumulated in the overflow receiving tank. This can reduce the amount of bleach-fix replenisher and fixing replenisher used.

FIG. 3 is a schematic diagram showing an automatic developing apparatus and an electrodialysis apparatus when the photographic light-sensitive material 40 to be processed is a black and white X photographic film. 1 and 2 in this embodiment.
The configuration of the automatic developing apparatus 10 is different from that of the embodiment shown in FIG. 1, the processing tank 60 is a development processing tank, the processing tank 61 is a fixing processing tank, and the processing tank 62.
a to 62c are washing treatment tanks, which are from the treatment tank 62c
It has a 3-tank counter-current system in which it overflows stepwise in the direction of arrow 62a.

The photographic light-sensitive material 40 of the exposed X photographic film is the processing tank 60, the processing tank 61, and the processing tank as indicated by the arrow.
By sequentially sending 62a, 62b, and 62c, processing in each step of development, fixing, and water washing is performed, and after the water washing processing in the processing tank 62c, a drying processing is performed by a configuration not shown and the development processing of the X photographic film is completed. It is supposed to do.

Further, the overflow solution of the developing solution, the fixing solution and the washing solution is introduced into the overflow receiving tank 15,
It is adapted to circulate with the concentrating chamber 21 of the electrodialysis device 20. As described above, the photographic light-sensitive material 40 has been described as the color paper, the color negative film, and the black and white X photographic film, but the photographic light-sensitive material 40 developed by using the processing liquid can be applied. Examples thereof include color reversal film, color positive film, color reversal photographic paper, photographic light-sensitive material for plate making, black and white paper, black and white negative film, and light-sensitive material for micro.

The color developing solution used for the development processing of the color photographic light-sensitive material used in this embodiment is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-
4-amino-N, N-diethylaniline, 3-methyl-
4-Amino-N-ethyl-N-ρ-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-
ρ-methanesulfonamide ethylaniline, 3-meter-4-amino-N-ether-N-ρ-methoxyetheraniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains an alkali metal carbonate, a pH buffer such as borate or phosphate, a bromide salt,
It generally contains a development inhibitor such as an iodide salt, benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. Further, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2,2]
2] Various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, Typical examples are haplas agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids. Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N,
N-trimethylenephosphonic acid, ethylenediamine-N-
Representative examples include NN′-N′-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid), and salts thereof.

The black-and-white developer used for reversal processing of color photographic light-sensitive materials and development processing of black-and-white photographic light-sensitive materials includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and N-methyl. -P
The known black and white developing agents such as aminophenols such as aminophenol can be used alone or in combination. PH of these color developers and black and white developers
Is generally 9-12.

In the processing of color photographic light-sensitive materials, bleaching processing and bleach-fixing processing are carried out after color development processing. Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution in these treatments include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids and quinones. And nitro compounds are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3. -Use of aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes You can Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution and the bleach-fixing solution. Specific examples of useful bleach accelerators are described in the following specifications; US Pat. No. 3,
893,858, West German Patent 1,290,812, JP-A-53-95630
No., Research Disclosure No. Issue 17,129 (1978
July)) and the like having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in US Pat. No. 3,706,561; JP-A-58-16235. The iodide salts described above; the polyoxyethylene compounds described in West German Patent No. 2,748,430; the polyamine compounds described in Japanese Patent Publication No. 45-8836; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide bond are preferred from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferred.

The bleach-fixing solution and the fixing agent used in the fixing solution may contain thiosulfate as a main component and thiocyanates, thioether compounds and thioureas. The thiosulfate is particularly ammonium thiosulfate. Most widely used. Further, as a preservative, sulfite, bisulfite,
Sulfinic acids or carbonyl bisulfite adducts are preferred.

The fixing solution used for processing the black and white photographic light-sensitive material has a pH of 3.8 or higher, preferably 4.2 to 7.0. As the fixing agent, ammonium thiosulfate is particularly preferably used from the viewpoint of fixing speed. The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum. Further, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds in the fixer. If desired, the fixer may contain preservatives (eg sulfite, bisulfite),
A pH buffer (for example, acetic acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water and a compound described in JP-A-62-78551 can be contained.

[0059]

As described above, according to the first aspect of the present invention, an electrodialysis apparatus is provided with a processing solution such as a fixing solution or a bleach-fixing solution without using a special concentrating chamber solution. The whole can be operated efficiently. Further, maintenance of the electrodialysis device is not required, and electrodialysis can be continuously and automatically operated.

According to the second aspect of the present invention, the fixing agent (thiosulfate) stably dissolves the cation (Ag +) as a complex so that precipitation of the cation (Ag +) does not occur. It can be set to the molar ratio of fixing agent to silver. Further, as in the invention described in claim 3 or the invention described in claim 4, the diluted aqueous solution can use the aqueous solution used in the process of processing the photographic light-sensitive material, so that the entire apparatus can be operated more efficiently. Moreover, the final amount of waste liquid in the device can be reduced.

According to the fifth aspect of the invention, it is possible to prevent cations (Ag +) from depositing on the cathode of the electrodialysis device. Further, as in the invention according to claim 6,
The current amount of the electrode of the electrodialysis device can be reduced, and the redox reaction at the electrode can be reduced. Further, as in the invention according to claim 7, in particular, the cation (A
Since g +) can be prevented from precipitating, maintenance can be unnecessary for a long period of time.

According to the eighth aspect of the present invention, precipitation of cations (Ag +) does not occur in the electrodialysis device, and the device can be used for a long time without maintenance.
According to the invention described in claim 9, both the fixing solution or the bleach-fixing solution and the developing solution can be regenerated by the same apparatus. Further, as in the invention according to claim 10 and the invention according to claim 11, by using a distillate containing no metal ions or silica at all, the durability of the electrode, the ion exchange membrane, etc. can be enhanced.

According to the twelfth aspect of the invention, it is possible to process the processing waste liquid of the automatic developing device and the electrodialysis device together. Further, according to the invention described in claim 13, it is possible to compensate for sulfite which is decomposed by electrodialysis and to perform stable regeneration treatment for a long period of time. Further, as in the invention described in claim 14, the invention can be applied to the one in which the processing solution for silver halide photographic light-sensitive material is a fixing solution or a bleach-fixing solution.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an automatic developing device and an electrodialysis device in this embodiment.

FIG. 2 is a schematic configuration diagram of an automatic developing device and an electrodialysis device in another embodiment.

FIG. 3 is a schematic configuration diagram of an automatic developing device and an electrodialysis device in another embodiment.

[Explanation of symbols]

 10 Automatic development device 11 Processing tank for color development processing 12 Processing tank for bleaching processing 13a, 13b, 13c Processing tank for stabilization processing 15 Overflow receiving tank 20 Electrodialysis equipment 21a, 21b, 21c, 21d, 21e Concentration chamber 22a, 22b , 22c, 22d, 22e Desalination chamber 23 Anode 24 Cathode

Claims (14)

[Claims] 1. Desalination of treated fixer or bleach-fixer introduced into the desalting chamber of an electrodialysis device having a desalting chamber and a concentrating chamber arranged between electrodes and separated by an ion exchange membrane. After that, while recovering the desalted salt in the concentrating chamber, the desalted solution is regenerated as a processing solution for a silver halide photographic light-sensitive material, wherein the condensing chamber contains the fixing solution or the bleach-fixing solution. A method for regenerating a processing solution for a silver halide photographic light-sensitive material, which comprises conducting a dilute aqueous solution for electrodialysis. 2. A method of regenerating a processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the dilution rate of the diluted aqueous solution is ½ concentration or less. 3. The dilute aqueous solution is a dilute aqueous solution diluted with a treatment liquid or an overflow liquid in one of a washing process, a rinsing process and a stabilizing process. Method for reclaiming processing solution for silver halide photographic light-sensitive material. 4. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the diluted aqueous solution is an aqueous solution obtained by diluting an overflow solution or a waste solution in the fixing step or the bleach-fixing step. How to play. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the ion exchange membrane closest to the cathode among the electrodes provided in the electrodialysis device is an anion exchange membrane. Method for reclaiming treatment liquid. 6. The electrodialysis apparatus is provided with an anode chamber and a cathode chamber, and a plurality of the ion exchange membranes composed of a cation exchange membrane and an anion exchange membrane are alternately arranged between the anode chamber and the cathode chamber. 6. A method for regenerating a processing solution for silver halide photographic light-sensitive materials according to claim 1, wherein a desalting chamber and a concentrating chamber are formed. 7. A method of regenerating a processing solution for a silver halide photographic light-sensitive material according to claim 6, wherein an aqueous solution containing no silver ion component is introduced into the cathode chamber. 8. The method according to claim 1, wherein the concentration of the thiosulfate contained in the fixing solution or the bleach-fixing solution is adjusted to be 1/2 or less and introduced into the concentrating chamber. 7
A method for regenerating the processing solution for a silver halide photographic light-sensitive material as described above. 9. A method for regenerating a processing solution for a silver halide photographic light-sensitive material in an electrodialyzer having an electrode chamber, a desalting chamber and a concentrating chamber, which are arranged between electrodes and separated by an ion exchange membrane. It is characterized by desalting the fixing solution or bleach-fixing solution that processed the silver halide photographic light-sensitive material in the salt chamber and introducing the developing solution processed by the processing solution for silver halide photographic light-sensitive material to the cathode chamber of the electrode chamber. And a method for regenerating a processing solution for a silver halide photographic light-sensitive material. 10. A method for regenerating a processing solution for a silver halide photographic light-sensitive material of an automatic developing device with an electrodialyzer having an electrode chamber, a desalting chamber and a concentrating chamber which are arranged between electrodes and separated by an ion exchange membrane. In the method for processing a silver halide photographic light-sensitive material, a distillate obtained by evaporating and condensing a processing waste liquid of the silver halide photographic light-sensitive material is introduced into at least the concentration chamber or the electrode chamber of the electrodialysis device. How to regenerate the liquid. 11. A method for regenerating a processing solution for a silver halide photographic light-sensitive material of an automatic developing device with an electrodialysis device having an electrode chamber, a desalting chamber and a concentrating chamber which are arranged between electrodes and separated by an ion exchange membrane. In, the distillate obtained by evaporating and concentrating the processing waste liquid of the silver halide photographic light-sensitive material is used as at least the diluting water of the regenerating processing liquid or the diluting water of the replenishing processing liquid of the silver halide photographic light-sensitive material processing liquid. A method for regenerating a processing solution for a silver halide photographic light-sensitive material, comprising: 12. The distillate is obtained by adding the processing waste solution from the electrodialysis device to the processing waste solution of the silver halide photographic light-sensitive material, and evaporating and concentrating the solution to obtain a distillate.
11. A method for reclaiming a processing solution for silver halide photographic light-sensitive materials as described in 11. 13. A replenisher replenished to a processing solution for a silver halide photographic light-sensitive material, which is desalted and regenerated in an electrodialysis device having a deionization chamber and a concentration chamber separated by an ion exchange membrane arranged between electrodes. In the processing agent, a replenisher and dilution water for the replenisher are added to the processing solution for the silver halide photographic light-sensitive material, and the total amount of the replenisher, the amount of the dilution water and the processing solution introduced from the previous step is added to the mother liquor. In the case of, the replenishing processing agent for the processing solution for silver halide photographic light-sensitive material is characterized in that it is formed by adding a sulfite so as to have a concentration of 0.25 mol / liter or more. 14. The silver halide photographic material processing solution is a fixing solution or a bleach-fixing solution.
A replenishing processing agent for the processing solution for the silver halide photographic light-sensitive material described above.