JPH05265160A - Processing method and processing device for photosensitive material - Google Patents

Abstract

PURPOSE:To improve restoration processing efficiency and photographic processing efficiency by using liquid which contains a chelating agent of a specific value or above of mol.wt. and metal ions and is specific mole or above in the theoretical metal ion chelatability of the chelating agent with respect to the metal ions and energizing. CONSTITUTION:The development processing device is arrayed with a developing tank 2, a bleaching tank 4, a fixing tank 6 and a washing tank 8 in this order and an energizing chamber 12 segmented by a cation exchange membrane 10 is provided in the developing tank 2. A cathode 16 is provided in the developing tank 2 and an anode 18 in the energizing chamber 12. Both electrodes 16, 18 are connected to a power source 20 and are energized. The chelating agent is generally preferably incorporated into the electrolyte soln. used therein. The chelating agent which is >=1.1mol in the theoretical metal ion chelatability with respect to the metal ions is preferably incorporated therein in such a case. Namely, the chelating agent preferably exists in the excess amt. of the metal ions. The mol.wt. of the chelating agent is preferably large and is more preferably >=400.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention improves the processing capacity of the processing liquid by installing at least one electrode in the processing chamber of a photosensitive material development processing apparatus and energizing the processing liquid to improve the processing capacity of the processing liquid. The present invention relates to a method of processing a photographic light-sensitive material which reduces the amount of replenisher supplied to the photographic material.

[0002]

Wet processing of photographic light-sensitive materials, such as silver halide color photographic light-sensitive materials, comprises respective processing steps such as color development, bleach-fixing, washing with water, and stabilizing. Of these, bleach-fixing includes bleaching and fixing. Or combined with these, and if necessary, a water washing step or the like is inserted between each step. A color developing solution and a bleach-fixing solution are used for color developing and bleach-fixing, respectively, but as the photosensitive material is processed, the developing agent in the color developing solution is consumed and oxidized, Alternatively, silver ions and halogen ions accumulate in the fixing solution due to the fixing action, and the bleaching agent and halogens are consumed and decreased in the bleaching solution, so that their processing ability decreases, so
It has been practiced to supply a replenisher liquid having a composition close to that of the treatment liquid and containing necessary components to each treatment liquid so as to maintain the treatment ability thereof without lowering.

However, if the replenishing liquid is supplied to each liquid to such an extent that the processing capacity of the liquid does not decrease, the overflow liquid is discharged in an amount substantially close to the supply amount, and this liquid becomes a waste liquid. Waste liquids are usually dumped deep into the sea, minimizing pollution of the global environment. However, in recent years, the idea of protecting the global environment has increased, and the dumping of photographic processing waste liquid into the ocean is being reviewed. Although there is a method to incinerate the photographic processing waste liquid instead of dumping into the ocean, the generation of carbon dioxide gas results in another global environmental pollution. Therefore, there is a demand for a technique for detoxifying waste liquid and a technique for reducing the amount of waste liquid, which are alternatives to these methods.

Examples of the detoxifying technique include an activated sludge method by biological treatment and a wet oxidation method. However, since these have large processing devices, it is necessary to collect waste liquid and collectively process the waste liquid. In addition, low replenishment system,
An on-site liquid recycling system (a device in which an automatic processor and a processing liquid recycling device are integrated) and an on-site waste liquid processing system (a device in which an automatic developing device and a waste liquid processing device are integrated) are known. .. However, these are effective technologies only for large processing laboratories.

On the other hand, photographic processing is processed at a large laboratory level, a medium laboratory level, a small laboratory level, and further at a minilab level and a microlab level due to technological progress, and the photographic processing is becoming more and more dispersed, particularly at the minilab and microlab levels. Now, the problem of waste liquid has been highlighted. In other words, at the minilab level, it is difficult to process waste liquid with the automatic processor, and the cost of waste liquid collection increases sharply due to traffic congestion.
Waste liquid processing costs are high, and it is difficult to collect waste liquid, and it is becoming difficult to perform processing at the minilab level.

Under such circumstances, there is a demand for a technical development capable of reducing the waste liquid by regenerating the processing liquid in the main body of the automatic processor of the minilab. In response to such a demand, the inventors of the present invention have disclosed JP-A-3-209471 and JP-A-3-2732.
No. 37 and No. 3-293661 propose a method of energizing a photographic processing solution. According to these techniques, when a color developing tank is provided with a cathode and electricity is applied to cause a reduction action on the cathode surface, the oxidized color developing agent is reduced to some extent to return to the original color developing agent, and anion exchange is performed. Halogen can be removed through the membrane. Further, when a cathode is provided in the fixing tank and electricity is applied, silver can be reduced and deposited on the cathode, and halogen can be moved and removed to the anode through the anion exchange membrane. The bleaching agent is oxidized and regenerated on the anode surface by providing an anode in the bleaching tank and energizing it depending on the processing of the light-sensitive material.

On the other hand, since the halogen moves toward the anode of the bleaching tank through the anion exchange membrane, it is not necessary to supplement the halogenating agent. In the bleaching tank, it is possible to prevent reduction deterioration of the bleaching agent by bringing in a developing solution by applying a little extra electricity. Moreover, since acid is also generated at the anode, the increase in pH due to the carry-in of the developer can be suppressed, and the addition of acid is unnecessary.
Since the bleach-fix solution has both bleaching and fixing functions,
In the electric current treatment, an anode is provided in the first half of the bleaching treatment tank, a cathode is provided in the latter half, and an anion exchange membrane is placed in the center of the treatment tank.
In some cases, the anode and the cathode may be replaced with each other in a photosensitive material having poor developing efficiency.

In this method, for example, in a color developing tank, an anion exchange membrane is used as a diaphragm, an anode is installed in a current-carrying chamber, an electrolyte solution is put therein, and a cathode is installed in a color-developing solution chamber to conduct current. The halogen ions eluted in the color developing solution by the process move toward the anode and selectively pass through the anion exchange membrane to enter the energization chamber, so that excess halogen ions in the color developing solution can be removed. ,
Further, the color developing solution is subjected to a reducing action by the cathode installed in the chamber, and the oxidized color developing agent is reduced to some extent, whereby the performance of the color developing solution can be restored. The same effect can be obtained with the bleach-fix solution depending on the method of energization. According to this method, it is possible to significantly reduce the amount of replenisher liquid to each processing tank.

[0009]

However, if an electrolyte solution for the energization chamber is separately prepared and used, a new waste solution based on it is produced, which is not preferable. Use as a solution is preferable because the amount of waste liquid does not increase. However, when a processing solution was regenerated by using an overflow solution of washing water as an electrolyte solution to process a light-sensitive material, fog was remarkably increased, gradation was lowered, and the image became soft. Further, due to the treatment for several months, considerable precipitation occurred at the four corners of the inner wall of the treatment tank.

Therefore, these techniques are still only basic processing liquid recycling techniques, and there is a demand for the development of more specific processing liquid recycling techniques that do not deteriorate the photographic processability. This application is based on the following three viewpoints. First, it is important to recycle the processing liquid to reduce the amount of waste liquid, but it is also important to reduce the components in the photographic processing liquid. It is a viewpoint that can eliminate.
Secondly, regarding the electrolyte solution necessary for the energization treatment, the electrolyte solution can be reused or the waste liquid can be reduced as much as possible.

Thirdly, from the viewpoint of efficiently controlling and managing the energization for efficiently performing the energization process, by doing so, the energizing device can be made compact and the electric capacity can be reduced. Therefore, if the energization process makes the size larger than that of the processor of the main body, the feasibility becomes poor, so that the energization process can be performed as compactly and efficiently as possible. The present invention relates to a method of processing a photosensitive material in which a processing solution performance is recovered by installing electrodes in an energization chamber attached to a processing chamber and energizing the development chamber in a development processing apparatus, thereby promoting recovery processing efficiency and photographic processing efficiency. It is intended to provide a processing method for promoting the above.

[0012]

The above objects of the present invention are achieved by the following items (1) to (9). (1) A photographic photosensitive member in which one electrode is installed in a processing chamber containing a processing liquid, the other electrode is installed in a current-carrying chamber defined by the processing tank and a diaphragm, and the performance of the processing liquid is restored by energizing both electrodes. In the material treatment method, a chelating agent having a molecular weight of 400 or more and a metal ion are included as a solution in the energization chamber,
A method for processing a light-sensitive material is characterized in that the chelating agent is energized with a liquid having a theoretical metal ion chelating ability of 1.1 mol or more with respect to the metal ion.

(2) A cathode is installed in a color developing tank and a fixing tank, an anode is installed in a bleaching tank, and a counter electrode for both electrodes is installed in a common energization chamber defined by each tank and a diaphragm. An apparatus for processing a photographic light-sensitive material, which is characterized by recovering processing liquid performance by energizing.

(3) In a method of processing a photosensitive material in which two or more kinds of processing solutions for processing a photosensitive material are energized to restore the performance of the processing solution, energization processing is performed by shifting the energization timing of each processing solution. A method for processing a photosensitive material.

(4) The processing tank for the photosensitive material is divided into two processing chambers by a diaphragm, the processing liquids having different functions are contained in the respective processing chambers, and a substantially liquid-tight photosensitive material passage is provided in a part of the diaphragm. An apparatus for processing a photosensitive material, which is formed, has an anode installed in one processing chamber and a cathode installed in the other processing chamber, and is energized to both electrodes to restore processing liquid performance.

(5) The processing tank for the photosensitive material is divided into two processing chambers by a partition wall, each of the processing chambers is provided with an energization chamber partitioned by a diaphragm, and the processing liquids having different functions are accommodated in the respective processing chambers.
An electrolyte solution is contained in the energization chamber, a liquid-tight photosensitive material passage is formed in a part of the partition wall, an anode is installed in one energization chamber, and a cathode is installed in the other energization chamber, and both electrodes are installed. A photosensitive material processing device that restores the performance of processing liquids by applying electricity.

(6) Processing of the light-sensitive material as described in (4) or (5) above, wherein the anode is installed in a bleaching tank and the cathode is installed in a fixing tank to conduct electricity. apparatus.

(7) In a photosensitive material processing apparatus in which an electrode is immersed in a processing solution of a photosensitive material and electricity is applied to restore the performance of the processing solution, the electrode is a flexible strip electrode and can be immersed in the processing solution. An apparatus for processing a light-sensitive material, comprising: an electrode winding mechanism for suspending the electrode from the processing solution by winding the electrode after energization.

(8) A photosensitive material processing apparatus having means for recovering the processing solution performance by energizing the processing solution of the photosensitive material, wherein the current processing tanks are arranged in multiple stages in a cascade. ..

(9) An energizing chamber partitioned by a diaphragm is provided in a processing tank containing a processing solution for processing a photosensitive material, one electrode is installed in the processing chamber, and the other processing chamber is installed in the energizing chamber. Energize both electrodes to vaporize the halogen in the liquid,
A method of processing a light-sensitive material, characterized in that halogen is captured from an atmosphere above an electrolyte solution.

The present invention will be described in detail. First, as the processing tank for energizing, it is suitable to carry out each processing such as color development, bleach-fixing or bleaching, fixing as described above. May be performed only for the one process, or may be performed for two or more processes. When electricity is applied to the color developer, the color developing agent and preservative that have undergone air oxidation during processing pauses are electrodes (cathode).
The reaction that is reduced on the surface occurs and the developing power is restored. As a result, a sufficient image density can be obtained, and a decrease in sensitivity and a soft gradation can be prevented.

When the bleaching solution is energized, the bleaching agent in the reduced state is oxidized again by the processing of the light-sensitive material, and the bleaching power is restored. As a result, it is possible to prevent color restoration defects and desilvering defects. When the fixing solution is energized, a reaction occurs in which the fixing agent and preservative that have undergone air oxidation are reduced on the electrode (cathode) surface, the formation of sulfides is prevented, and the fixing stability is increased. Further, since silver in the liquid is deposited at the cathode, the fixing agent is regenerated. This prevents defective desilvering. Further, in some cases, a small amount of fixing agent can be used.

Further, it is preferable to use an anion exchange membrane as the diaphragm. By providing an anion exchange membrane between the developing solution and the electrolyte solution, since halide ions such as Br ⁻ accumulated in the color developing solution by the development process selectively pass through the anion exchange membrane, color development The solution prevents unnecessary accumulation of halide ions and prevents development inhibition. As a result, unnecessary halide ions do not have to be removed by overflow or the like, and the amount of waste liquid and the amount of replenishment can be reduced. Further, by providing an anion exchange membrane between the fixing solution and the electrolyte solution, halide ions such as Br ⁻ accumulated in the fixing solution during the fixing process selectively pass through the anion exchange membrane. The liquid prevents unnecessary halide ions from accumulating and prevents fixing inhibition. On the other hand, silver deposits from the fixing solution and disappears from the system, so that the fixing agent is regenerated.

It is generally preferred that the electrolyte solution used for the current application process contains a chelating agent. This is preferable for preventing the precipitation of components due to the transfer of substances and for preventing the precipitation due to the water quality of the liquid (for example, containing calcium). Furthermore, it is more effective to contain a metal ion that easily causes redox, in order to prevent unnecessary reaction at the electrode. In this case, it is preferable to include a chelating agent having a theoretical metal ion chelating ability of 1.1 mol or more with respect to the metal ion. The theoretical metal ion chelating ability is preferably 1.5 mol or less, more preferably 2.0 mol or less. That is, it is preferable that the chelating agent is present in an excessive amount with respect to the metal ion. This is to prevent the precipitation of metals, the precipitation of calcium in the liquid, and the precipitation of substances that move through the anion exchange membrane.

In this case, it is not preferable for the electrolyte solution to move to the treatment solution side, so that the chelating agent used preferably has a large molecular weight. Moreover, metal ions and stable chelating agents are preferred. The molecular weight of the chelating agent is 40
It is preferably 0 or more and 1,000,000 or less. It has a molecular weight of 10
If it is larger than 0,000, it will not dissolve in water, and if it is smaller than 400, it will pass through the anion exchange membrane. Stability constant indicating the stability of chelating agents with metal ions (generation constant; l
As ogK), 2.0 to 40.0 is preferable. As a metal that can be used as a chelating agent, iron, aluminum, titanium, as an easily available and relatively stable metal,
There are nickel and cobalt. Further, when the electrolyte solution is used as the anode side, it is better to add an alkaline buffer solution because a little acid is generated by energization. On the contrary, when it is used as the cathode side, it is better to add an acid buffer solution because it produces an alkali.

The energization treatment according to the present invention means that in a treatment tank in which a part of the treatment tank is partitioned by an anion exchange membrane, and one has a treatment solution and the other has an electrolyte solution, the cathode is treated with respect to the treatment solution. Alternatively, an anode is provided, and a counter electrode is provided for the electrolyte solution, electricity is applied depending on the processing of the photosensitive material, unnecessary substances or necessary substances are moved to a desired side through the anion exchange membrane, and liquid components are generated by electrode surface reaction. Is a treatment method of oxidizing or reducing The number of ions that move through the electrode reaction or the anion exchange membrane of the ionic compound is proportional to the amount of current flowing on the electrode surface according to Faraday's law. A voltage is applied in order to generate this current, but the voltage must be appropriate, and is usually 0.1 to 10 V, preferably 0.3 to 5 V.
It is V. If the voltage is lower than this value, the current does not flow, and if the voltage is higher than this value, unnecessary electrode reaction occurs and the reaction efficiency (current efficiency) with respect to the target is lowered.

Therefore, if a constant current power source is used, the energization process can be properly controlled only by time control, but when a power failure or temporary power interruption is performed, the current is not energized as set, so this method is used. Is not suitable, and since such a constant current power source is expensive, it is preferable to employ a power source (battery or secondary battery) that is as inexpensive as possible.
When a battery or a secondary battery is used as a power source, a current drop due to a voltage drop occurs and current management is difficult. In this case, it is necessary to energize so that the current value × time becomes constant with respect to the predetermined processing amount of the photosensitive material. In order to measure the current value × time, an integrated ammeter (ammeter) may be used to measure the integrated amount of the current value. As the ammeter, when a constant current power supply is used, various commercially available ammeters can be used, and only the time when the ammeter flows is integrated.
When it is not a constant current power source, a commercially available coulomb meter or an integrating ammeter can be used.

For example, the treatment liquid can be properly regenerated by energizing the treatment liquid so that an electric quantity of a predetermined coulomb is applied to the treatment liquid for processing one film for photographing. In an automatic developing apparatus that has many processing tanks to be energized, the cost of the power source can be reduced by performing the energizing processing at the same time and staggering the times. Further, when the anion exchange membrane is continuously used, the membrane resistance may increase due to clogging or the like. In this case, if an attempt is made to flow a constant current value, the applied voltage may increase, which is not preferable. In order to prevent such a case, it is necessary to keep the film resistance below a certain level. Conversely, in this case, when a constant voltage is applied, the current value gradually decreases. Also at this time, energization processing becomes possible by controlling so that current × time for a predetermined processing amount of the photosensitive material becomes constant.

As described above, the energization process may be controlled by the amount of current according to Faraday's law, but in some cases, the change in the bulk potential of the treatment liquid is detected and this data and the amount of current are combined to obtain the amount of energization. May be determined. The control means at this time may make a fuzzy decision. When arranging a plurality of energization treatment tanks in a cascade, the plurality of energization treatment tanks may be arranged in parallel and the liquid may be moved by overflow, but preferably a diaphragm such as an anion exchange membrane is used as a wall member of the energization treatment tank. The combined use also makes it possible to make the energization treatment tank compact. When the means for sending the washing wastewater from the washing tank to the energization chamber is adopted, for example, washing is 4 times.
When performing cascade water washing in a stage, it is preferable to send the overflow liquid in the first stage of water washing into the energizing chamber.

Further, as the processing tank for the next stage and thereafter, which outputs the overflow liquid to be sent to the energizing chamber, a stabilizing tank may be selected. Also in this case, the stabilizing effect cannot be sufficiently achieved if the amount supplied to the stabilizing tank is too small, so it must be prevented from becoming too small. The water washing tank and the stabilizing tank are not limited to those at the final stage in the development processing step, but may be those after the color developing tank or after the bleach-fixing tank. The treatment bath of the next stage and subsequent stages is preferably a treatment bath of the next bath. However, it is not preferable to send the waste solution of the bleach-fixing tank to the current-carrying chamber of the color developing tank because this solution contains a high concentration of the oxidizing agent. However, if the anion exchange membrane is doubled or the liquid level in the current-carrying chamber is lowered, these concerns can be eliminated.

The measurement of the redox bulk potential of the treatment solution has already been conducted in JP-A-60-195544 and 60-60.
The redox potential measuring device described in Japanese Patent Laid-Open No. 195545 can be used. Moreover, this potential may be detected and controlled by the control method described in this publication. For example, in the case of a bleach-fixing solution, energization is controlled so that the oxidation-reduction potential is within a predetermined range, and when the oxidation-reduction potential exceeds the set upper limit value, energization is interrupted to interrupt the oxidation of the processing solution. Although the redox potential of the processing solution decreases as the photosensitive material is processed during the interruption of energization, when the redox potential falls below the lower limit value, energization is started to oxidize the processing solution and raise the potential.

In the present invention, a cation exchange membrane is used as the diaphragm for partitioning the current-carrying chamber for conducting current.
Examples include anion exchange membranes and other permeable membranes. Of these, an anion exchange membrane is preferably used, and any anion exchange membrane may be used as long as it selectively permeates anions, and a commercially available one can be used as it is. .. Examples of such anion exchange membrane include Selemion AWV / AMR (manufactured by Asahi Glass), Aciplex A201, A172 (manufactured by Asahi Kasei), Neosepta AM-1 to 3 (manufactured by Tokuyama Soda), Ionac MA-3148 (Ionac Ch).
manufactured by E.Malicals), Nepton AR103PZL
(Made by Ionics) or the like can also be used, but Br is preferably used when an energization chamber is provided in the color developing tank for energization.
^- in order to the transmission of a halide ion such as, Selemion AS that selectively transmit monovalent anion
V / ASR (Made by Asahi Glass), Neosepta AFN-
7, it is preferable to use a commercially available product under the trade name such as Neosepta ACS (manufactured by Tokuyama Soda).

As the permeable membrane, the Yumicron diaphragm (made by Yuasa Battery) used in storage batteries; Torio Higaki, "Fine Electronics and Highly Functional Materials" (CMC, 198).
Solid electrolyte wall described on pages 125-132 of 3 years); porous polymer plate (for example, xanthone porous film or fiber cloth), porous polyester fiber cloth (for example, Toray Welkey); urethane, polyethylene, polypropylene, etc. A permeable membrane such as a foam wall is used.

In the present invention, the above-mentioned anion exchange membrane is a generic term for membranes that selectively permeate anions. In this sense, the pore diameter is 0.2 to 20.
It also includes a film of a porous ceramic of μm. As the electrode used for energizing, the cathode on the other hand may be any electric conductor or semiconductor that can withstand long-term use, for example, stainless steel, aluminum, silver, nickel, copper, zinc, brass. Metal materials such as titanium and the like are mentioned, and stainless steel is particularly preferable. Further, the anode may be made of an insoluble material and an electric conductor, and specifically, carbon (graphite), lead dioxide, platinum,
Examples thereof include gold and titanium steel, and stainless steel may be used depending on the case. The shape of both electrodes is preferably a plate shape that is easy to install in the tank, a mesh-like plate shape or a plate shape with protrusions. The size may be appropriately selected depending on the tank capacity. Furthermore, by forming the plate-shaped electrode extremely thin to have flexibility, the plate-shaped electrode can be easily wound and the operation of immersing it in the liquid or taking it out in the air becomes easy. Further, with such a configuration, it is possible to adjust the immersion depth of the electrode in the liquid to adjust the substantial electrode area.

As the electrode provided in the energizing chamber, the opposite electrode is provided depending on whether the anode is provided on the processing chamber side or the cathode is provided. As described above, in the case of the color developing tank, the anode is provided in the energizing chamber also in order to move the halogen ions in the color developing solution to the energizing chamber side. Similarly, in the fixing tank, a cathode is provided on the processing liquid side and an anode is provided on the energizing chamber side. On the contrary, in the bleaching tank, an anode is provided on the treatment liquid side and a cathode is provided on the current-carrying chamber side.

The photographic emulsion layer after color development is usually bleached. Examples of bleaching agents include iron (III), cobalt (II
I), compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (I
II) or cobalt (III) complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,
Use of aminopolycarboxylic acids such as 3-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, ethylenediaminetetraacetic acid iron
(III) Iron (III) aminopolycarboxylates including complex salts
Complex salts and persulfates are preferable from the viewpoint of rapid processing 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.

If necessary, a bleaching accelerator can be used in the bleaching solution and the pre-bath. Specific examples of useful bleaching accelerators are, in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,63.
The compounds described in No. 0 are preferable. Examples of the fixing agent used after bleaching include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, and the use of thiosulfates is common, Ammonium thiosulfate can be used most widely. As the preservative for the fixing solution, sulfite, bisulfite, sulfinic acid, or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, and further the temperature of rinsing water, the number of rinsing tanks (number of stages), countercurrent,
It can be set in a wide range depending on the replenishment method such as normal flow and various other conditions. The light-sensitive material used in the present invention includes a black-and-white light-sensitive material as well as a color light-sensitive material. For example, in addition to color paper, color reversal paper, color negative film for photography, color reversal film, negative or positive film for motion picture, direct positive color photosensitive material, X ray film, photosensitive material for printing, micro film, black and white film for photographing. And so on.

[0039]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. <Example 1> (Photosensitive material): Photosensitive material of Example 1 of JP-A-3-273237 (color negative film) (Processing): Processing liquid of Example 1 of JP-A-3-273237 (Process): Process of Example 1 of JP-A-3-273237 in which washing with water between bleaching and fixing is omitted (processor): Fuji Photo Film FNCP-40B, a color negative automatic processor, is shown in FIG. Modified machine

FIG. 1 is a schematic view of a developing processing apparatus, in which a developing tank 2, a bleaching tank 4, a fixing tank 6 and a washing tank 8 are arranged in this order, and the developing tank 2 is an anion exchange membrane 10. A current-carrying chamber 12 partitioned by the cathode is provided in the developing tank 2.
6 and the anode 18 is provided in the energization chamber 12, and both electrodes 1
6 and 18 are connected to a power source 20 to be energized.

(Electrification conditions): Anode: Carbon sheet (Kureha Chemical Industry Kure sheet) Cathode: Molybdenum-containing stainless steel sheet (Nippon Metal Industries NTK316) Energization amount: 2.3 V, 1 A (0.5 A / dm ² ). 35
Energization for 18 seconds per mm film 24Exp Anion exchange membrane: Anion exchange membrane AM-3 manufactured by Tokuyama Soda

(Treatment 1A) As an electrolyte solution, NTA ^*
-Fe (III) salt 0.01M and NTA-Na salt 0.
012M was used. The film was processed at a rate of 40 films per day, and this was run for 1 month. * = Tolyltriacetic acid Na salt (molecular weight MW257)

(Treatment 1B) As the electrolyte solution, DTPA was used.
^**・ Fe (III) salt 0.01M and DTPA ・ Na salt
0.012 M was used. The film was processed at a rate of 40 films per day, and this was run for 1 month. ** = Diethylenetriaminepentaacetic acid Na salt (molecular weight MW503)

(Treatment 1C) As an electrolyte solution, a polymer chelating agent made by Miyoshi Oil and Fat Epofloc L-1 purified product (molecular weight MW 80 to 120,000) L-1.Fe (III) salt 0.01M L-1 as it is 0.03M Was used at a rate of 40 films per day and this was run for 1 month. D of GL (green sensitive coloring layer) as a representative value of photographic property
_It was evaluated by _min (base density + mask density + fog).
The results are shown in Table 1.

[0045]

[Table 1]

From the above table, the chelating agent has a molecular weight MW of 400.
It can be seen that fog rise does not occur when the above items are used. In treatment 1B, the DTPA / Na salt was added to 0.
Precipitation was observed when the treatment was performed at 01M and 0.101M. As a result, it was found that if the theoretical metal ion chelating ability of the chelating agent is 1.1 mol or more with respect to the metal ion, good treatment without metal precipitation can be performed.

<Example 2> In Example 1, the processor was modified as shown in FIG. (A) and (b) are configurations in which the bleaching tank 4 and the fixing tank 6 are also provided with current-carrying chambers 22 and 24 partitioned by the anion exchange membrane 10, and the bleaching tank 4 is provided with an anode 18 and a fixing tank. The cathode 16 is installed in the 6 and each energization tank 2
The counter electrodes are installed in the Nos. 2 and 24. In the following figures, the power source connected to the electrodes 16 and 18 is not shown, and the electrodes 16 and 18 are indicated by the polarity symbols. (A)
The difference between the configuration shown in (1) and the configuration shown in (b) is the manner of overflow in the energization chambers 12, 22, 24, and the arrows indicate the manner of overflow.

(C) and (d) are a developing tank 2, a bleaching tank 4,
The fixing tank 6 has a common energization tank 26 divided by the anion exchange membrane 10. In the configuration shown in (c), the developing bath 2, the bleaching bath 4, and the counter electrodes 16 and 18 of the electrodes 16 and 18 in the fixing bath 6 are installed in the energizing bath 26, respectively. A common electrode 17, which may be of any polarity, is installed in. (Electrification conditions): Developing tank (N1) 18 seconds at 2.3V, 1A Bleaching tank (N2) 29 seconds at 2.3V, 1A Fixing tank (N3) 90 seconds at 2.3V, 1A

(Treatment 2A) Use the treatment solution of 1A as the electrolyte solution in the treatment machine (Treatment 2B) Use the treatment solution of 1C as the electrolyte solution in the treatment machine of (A) (Treatment process 2C) Electrolyte solution in the treatment machine of b Use treatment 1A as treatment (treatment 2D) b using treatment solution 1C as electrolyte solution (treatment 2E) use treatment machine 1A treatment as electrolyte solution (treatment 2F) treatment c Using the treatment solution of 1C as the electrolyte solution in the machine (Treatment 2G) Using the treatment solution of 1A as the electrolyte solution in the treatment machine (Treatment 2H) Using the treatment solution of 1C as the electrolyte solution in the treatment machine of Example 1 Similarly, the GL fog after one week of running was evaluated. The results are shown in Table 2.

[0050]

[Table 2]

As is clear from the results shown in Table 2, when a high molecular weight chelating agent Fe (III) salt is used as the electrolyte solution (Treatment 2B, 2D, 2F, 2H), development fog does not increase. Moreover, in the processors a and b, since Br ⁻ accumulates in the electrolyte solution in the developing tank 2, it is necessary to replenish the electrolyte solution in order to reduce this, and waste liquid increases, which is irrational for the purpose of reducing waste liquid. Is.

On the other hand, in the processors c and d, Br ⁻ is eluted from the developing tank 2 side into the electrolyte solution corresponding to the developing tank 2.
Since Br ⁻ moves from the electrolyte solution corresponding to the next bleaching tank 4 to the bleaching tank 4, accumulation of Br ⁻ can be prevented. Therefore, the electrolyte solution does not need to overflow. By doing so, the energizing tank can be simplified and liquid circulation is little or unnecessary. Since the chelating agent Fe ³⁺ is present, the reaction at the electrode is chelate Fe ²⁺ ← → chelate Fe
^Replaced with ³⁺ and electrically neutralized. Therefore 2
Generation of bromine gas due to the reaction Br ⁻ → Br ₂ is also small.

<Embodiment 3> In the treatments 2F and 2H of Embodiment 2, the energization treatment was performed according to the sequence shown in FIG. X simultaneously starts the energization process for each of development N1, bleaching N2, and fixing N3, and the energization time is 18 seconds for development N1.
It was 29 seconds for bleaching N2 and 90 seconds for fixing N3. Y starts energization processing for development N1 and bleaching N2 simultaneously, energization for development N1 for 18 seconds, energization for bleaching N2 for 29 seconds, energization for fixing N3 at the end of energization for bleaching N2, energization for fixing N3 for 119 seconds It was done. Z is 1 for development N1
The power is supplied for 8 seconds, the bleaching N2 is started at the same time as the development N1 is completed, and this is performed for 47 seconds, and the fixing N3 is started at the same time as the bleaching N2 is completed for 137 seconds. The results are shown in Table 3.

[0054]

[Table 3] As is clear from the results shown in Table 3, when the energization control is performed as in Z, the processing is stabilized without a trouble such as a short circuit, and only one constant power supply device is required, and the cost is low.

<Example 4> (Photosensitive material): Photosensitive material of Example 1 of JP-A-2-287353 (auto positive paper) (Treatment liquid): Example 1 of JP-A-2-287353
Formulation (described on page 30) (Processing step) Tank capacity Replenishment amount Development P1 38 ° C. 135 seconds 15 liters 300 ml / m ² Bleach-fixing P2 33 ° C. 40 seconds 3 liters 300 ml / m ² Water wash PS (1) 33 ° C. 40 Second 3 liters-Washing PS (2) 33 ° C. 40 seconds 3 liters 320 ml / m ² Drying 80 ° C. 30 seconds- (Treatment machine) Treatment equipment configured as shown in FIGS. 4, 5 and 6.

FIG. 4 is a schematic view of the developing processing apparatus, in which a color developing tank 30, a bleach-fixing tank 32, and two water washing tanks 34 are arranged in order. FIG. 5 is a partially modified version of the device shown in FIG. 4, where (a) is a plan view and (b) is a sectional view. The bleach-fixing tank 32 in FIG. 4 is partitioned by the anion exchange membrane 10, and one is a bleaching tank 36 and the other is a fixing tank 38. An anode 18 is installed in the bleaching tank 36, and a cathode 16 is installed in the fixing tank 38, which are connected to a power source to be energized. A passage 44 that is substantially liquid-tight enough to allow the photosensitive material S to pass through is formed in the lower portion of the anion exchange membrane 10. The term "substantially liquid-tight" means that the photosensitive material S is liquid-tight except when passing through the passage 44.

FIG. 6 is a partially modified version of the apparatus shown in FIG. 4, in which (a) is a plan view and (b) is a sectional view. The bleach-fixing tank 32 in FIG. 4 is partitioned by a partition wall 46,
One is a bleaching tank 36 and the other is a fixing tank 38, and a substantially liquid-tight passage 44 is formed in the lower portion of the partition wall 46 so that the photosensitive material S can pass therethrough. Further, an anion exchange membrane 10 is provided on a part of the partition wall 46, an anode is provided on the bleaching tank side, and a cathode is provided on the fixing tank side, and these are connected to a power source to be energized. Is becoming

If a flexible electrode made of carbon fiber, a stainless thin plate (about 50 μm), or the like is used as the electrode, it can be appropriately wound and discharged from the treatment liquid as shown in FIG. FIG. 7 shows a current-carrying chamber 50 partitioned by the ion exchange membrane 10.
Represents the electrode 52 immersed in the. The electrode 52 is wound around a shaft 56 having a pair of flanges 54, and the shaft 56 is rotated by a motor 58.
The electrode 52 can be immersed in the liquid or taken out in the air by driving in the forward and reverse directions. Electrode 5
In order to energize 2, the connecting electric wire 59 from the power source is connected to the shaft 56 as shown in the figure, or the connecting terminal from the power source is brought into contact with the electrode 52. Motor 5
8 is connected to a control device (not shown) to control rotation,
After the energization for a predetermined time or a predetermined amount of electricity, the electrode 52
Rotate to take out from the liquid. This structure has the advantage of facilitating the cleaning of the electrodes, and especially when energizing in the processing tank without providing an energizing chamber, the electrodes should be protected so as not to hinder the transfer of the photosensitive material. Can be appropriately wound up. Further, with such a configuration, it is possible to adjust the immersion depth of the electrode in the liquid to adjust the substantial electrode area. The processing device using the electrode having the above structure is not particularly limited.

[0059] (processing 4A) using the apparatus shown in FIG. 4, the replenisher was treated amount 1 m ² per 300ml refill of the photosensitive material in the bleach-fixing tank, daily light-sensitive material was 4m ² handles this two-week running As a result, no photographic performance problem occurred.

(Process 4B) The apparatus shown in FIG. 5 was used. Further, the bleach-fix solution was divided as follows. _{Bleach: EDTA · 2Na · 2H 2 O} 4g EDTA · Fe (III) NH 4 · 2H 2 O 70g Water to make 500ml fixer: Ammonium thiosulfate (70%) 180ml p- toluenesulfonic acid sodium 20 g 5-mercapto - 1,3,4-triazole 0.5 g Ammonium nitrate 10 g Water was added to 500 ml

(Electrification conditions): Energization is carried out for 10 seconds at 0.5 A per 1 dm ^{2 of the} light-sensitive material. Moreover, the replenisher in the bleach-fixing tank is 300 ml per 1 m ² of the processing amount of the light-sensitive material.
The replenishment was 15 ml / m ² with bleach and 1 with fixer.
Replenish with 5 ml / m ² and add 4 m of light-sensitive material per day.
^{When two} treatments were carried out and this was run for two weeks, no problems occurred in photographic performance. Therefore, by energizing the bleaching solution and the fixing solution, good processing can be performed even if the replenisher is reduced. Further, since the light-sensitive material is not exposed in the air between the bleaching process and the fixing process, rapid processing is possible.
Further, if the treatment is carried out for the same treatment time as in the conventional case, the concentration of the treatment liquid and the concentration of the replenisher can be reduced, and as a result, the concentration of the waste liquid is reduced and the pollution load is reduced. (Process 4C) The same process as in Process 4B was performed using the processor b. As a result, similar to the treatment 4B, there was no problem in photographic performance. Therefore, the same effect as that of the processing 4B can be obtained.

<Example 5> In Example 4, the same test was performed using the color paper of Example 1 of JP-A-2-287353 instead of the auto positive paper. Results were obtained.

<Example 6> In the process 1C of Example 1, the process was carried out by modifying the processing apparatus as shown in FIG. Explaining the modified parts, the developing tank 2 and the bleaching tank 4
Are partitioned by an L-shaped anion exchange membrane 10 so that electricity is supplied between the developing tank 2 and the bleaching tank 4, and an anode 18 is installed in the bleaching tank 4. Anion exchange membrane 1
0 corresponds exactly to the two surfaces that divide the developing tank 2.
The bleaching tank 4 is larger than that of the apparatus shown in FIG. 1, and the area of the anion exchange membrane 10 is about three times that of the apparatus shown in FIG. The electrodes 16 and 18 are L-shaped so as to face two wall surfaces that partition the processing tank, and the electrode area is larger than that of the device shown in FIG. With this configuration,
Since the electrode area was significantly increased and the area of the anion exchange membrane was expanded about three times, the energization time for obtaining a predetermined amount of electricity was about 1/3 (6 seconds).

<Embodiment 7> In Embodiment 2, FIG.
Processing was carried out using an apparatus in which the developing tank, the bleaching tank, and the fixing tank of the processing apparatus having the configuration shown in (a) were modified as shown in FIG. FIG. 9 shows only the developing tank 2, the bleaching tank 4, and the fixing tank 6,
The developing tank 2 and the bleaching tank 4 are L-shaped anion exchange membranes 10.
The bleaching tank 4 and the fixing tank 6 are both partitioned by the L-shaped anion exchange membrane 10, and the electrodes 16 and 18 are also L-shaped. Therefore, as compared with the device shown in FIG. 1, the area of the anion exchange membrane and the area of the electrode are significantly larger. As a result of the processing performed by the processing apparatus having such a configuration, the energization time for obtaining the predetermined amount of electricity was reduced to about 1/3 each, as in Example 6.

<Example 8> In Example 1C, the apparatus shown in FIG. 10 was replaced with an apparatus having a separately installed energization chamber 12 instead of the apparatus shown in FIG. The energization chamber 12 is the anion exchange membrane 10
The developing solution overflows from the developing tank 2 into one chamber, and the bleaching solution overflows from the bleaching tank 4 into the other chamber. A cathode 16 is provided on the developing solution side and an anode 18 is provided on the bleaching solution side so as to be energized. Each liquid in the energization chamber 12 is returned to the developing tank 2 and the bleaching tank 4 by pumps 60 and 62, respectively. When it was processed by such a processing device, it could be processed without any problems.

<Embodiment 9> In Embodiment 8, the separately installed energization chamber 12 was processed with the structure shown in FIGS. 11, 12 and 13. FIG. 11 is a cross-sectional view of the separately installed energization tank 64. The energization tank 64 is composed of three energization chambers 66, 68, 70, and each of the energization chambers 66, 68, 70 is partitioned by the anion exchange membrane 10, and the cathode 16 is provided in each chamber on both sides of the anion exchange membrane 10. And the anode 18 is installed. Each room 66, 6
The cathode-side chambers of Nos. 8 and 70 are filled with the regenerated developer, and the anode-side chambers are filled with the electrolyte solution.

The characteristic of the energizing bath 64 is that the first to third energizing chambers 66, 68, 70 are arranged in a cascade, and the developing tank 2 develops in the cathode side chamber of the first energizing chamber 66. The liquids are allowed to flow by overflow, so that the developer in the first energization chamber 66 overflows into the second energization chamber 68 and the developer in the second energization chamber 68 overflows into the third energization chamber 70. .. The developer in the third energization chamber 70 is the finally regenerated developer and is returned to the developing tank 2 by the pump 72. Further, the electrolyte solution in the first energization chamber 66 goes to the second energization chamber 68, and the electrolyte solution in the second energization chamber 68 goes to the third
The electrolyte solution in the third energization chamber 70 is returned to the first energization chamber 66 by the pump 74. The energizing bath 64 having the above-described configuration has three energizing chambers 66, 68, 70, but the number of energizing chambers is not limited as long as the energizing bath has a multistage cascade configuration.

FIG. 12 is a cross-sectional view of another separately installed energization tank 64. This energization tank 64 has three anion exchange membranes 10.
Is divided into four chambers by the first chamber 76 and the third chamber.
The cathode 16 is installed in the chamber 80, and the anode 18 is installed in the second chamber 78 and the fourth chamber 82. Also, the first chamber 76
The third chamber 80 is filled with the developing solution, and the second chamber 78 and the fourth chamber 82 are filled with the electrolyte solution. And
The developer in the first chamber 76 overflows into the third chamber 80, and the electrolyte solution in the fourth chamber 82 flows into the second chamber 7.
It overflows to 8. Also, the first
The developer is supplied from the developing tank 2 to the chamber 76 by overflow, and the electrolyte solution in the second chamber 78 is sent to the fourth chamber 82 by the pump 74.

By applying an electric current between the first chamber 76 and the second chamber 78, the developer in the first chamber 76 is somewhat regenerated. Further, this flows into the third chamber 80 due to overflow, and the third chamber 80 and the second chamber 78 and the third chamber 80 and the fourth chamber 82 are energized, respectively, so that the developer in the third chamber 78 is discharged. Is played further. And the third chamber 78
The finally regenerated developer therein is returned to the developer tank 2 by the pump 72. In this way, by using the anion exchange membrane 10 also as the processing tank wall, the energization tank 64 can be made compact.

FIG. 13 is a vertical sectional view of still another separately-installed type energization tank 64. This energization tank 64 is a partial modification of the configuration shown in FIG. The changed portion of the configuration will be described. The energization tank 64 is sealed, the first chamber 76 and the third chamber 80 are communicated with each other by the lower passage 84, and the second chamber 7 is connected.
8 and the fourth chamber 82 also communicate with each other through the upper passage 86. Then, the first developing liquid is caused by the overflow from the developing tank 2.
The developer in the first chamber 76 is supplied to the chamber 76, and
It moves to the 3rd chamber 80 through 4. Similarly, the electrolyte solution in the second chamber 78 moves to the fourth chamber 82 through the passage 86, and the electrolyte solution in the fourth chamber 82 is sent to the second chamber 78 by the pump 74. The third chamber 80 is energized between the second chamber 78 and the fourth chamber 82, so that the third chamber 80
The developing solution inside is regenerated considerably. Then, the regenerated developing solution is sent to the developing tank 2 by the pump 72. Note that, although FIG. 13 is shown as a vertical cross-sectional view of the energizing tank 64, the energizing tank 64 may have a horizontal sectional structure similar to this vertical section. That is, each passage has an energization tank 6
It may be on the side surface of No. 4.

(Processing 9A) When the process of Example 8 was performed using the apparatus of FIG. 11, the energization time for obtaining the predetermined amount of electricity was 1/3 that of Example 8. (Processing 9B) When the process of Example 8 was performed using the apparatus of FIG. 12, the energization time for obtaining the predetermined amount of electricity was 1/3 that of Example 8. (Processing 9C) When the process of Example 8 was performed using the apparatus of FIG. 13, the energization time for obtaining the predetermined amount of electricity was half that of Example 8.

Example 10 In Example 1, 3% of Na ₂ SO ₄ was used as the electrolyte solution. When the energization treatment was performed, the pH of the electrolyte solution was lowered, and the bromine ions moving from the developing solution were collected at the anode to generate bromine gas. For this reason, the halogen trap having the configuration shown in FIG. When the amount of bromine ions at the anode increases, the migration of bromine ions to the anode becomes poor. That is, when the bromine ion of the anode is more than double the bromine ion of the cathode,
Especially, the migration of bromine ions is reduced. Fortunately, when the pH of the liquid on the anode side is 6 or less, the bromine ions of the anode are released as bromine gas by Br ⁻ + Br ⁻ → Br ₂ to the outside of the system. Therefore, when the pH of the liquid on the anode side is 6 or less, the accumulation of bromine ions disappears,
The liquid on the anode side can continuously take bromine ions on the cathode side without overflowing.

When the electrolyte solution is changed to Na ₂ SO ₄ and the pH is adjusted to 6 or less by applying electricity, bromine ions can be removed from the liquid as bromine gas, and the amount of waste liquid due to overflow can be reduced. Along with this, bromine gas harms the human throat, so it is necessary to provide a trapping device. FIG. 14 is a block diagram of a halogen capture device,
(A) is a configuration using a solid as a halogen capture medium,
(B) is a configuration using a liquid.

Explaining the structure of (a), this trapping device has a dome-shaped collecting lid 90 covering the anode 18 where halogen is generated, and a tube 92 connected to the central portion of the lid.
And a medium containing portion 94 provided in the middle of the pipe 92, and a pump 96 for sucking the atmosphere in the medium containing portion 94. The medium containing portion 94 is filled with activated carbon, zeolite or the like as a halogen capturing medium 98. When the developing solution is energized, bromine ions eluted from the photosensitive material into the developing solution are collected at the anode 18 and become bromine gas. Therefore, the pump 96
By appropriately operating, the bromine gas is collected by the collecting lid 90, reaches the medium containing portion 94, and is captured by the halogen capturing medium 98 such as activated carbon or zeolite.

In the configuration of (b), the medium containing portion 94 in (a) is a container capable of containing a liquid as the halogen capturing medium 94, and the other end of the tube 92 extending from the collecting lid 90 is It has reached the inside of the liquid. As the halogen capture medium 98, 15% NaOH solution, 15% KOH solution, pyrogallol alkaline solution, or the like is used. Liquid 9 in medium container 94
8, an exhaust pipe 99 is provided above the pump 8.
The atmosphere above the liquid is discharged by. Then, the bromine gas generated at the anode 18 is discharged into the liquid 98, is dissolved in the liquid 98, and is captured.
As described above, when the halogen capturing device was provided in the energizing chamber of the processing device, the bromine gas was not emitted in the air, and it was possible to run for one month without exchanging the electrolyte solution. Furthermore, the energization process could be continued without causing the electrolyte solution to overflow, and the amount of waste liquid could be reduced.

<Embodiment 11> Similar effects were obtained by using a fixing solution instead of the developing solution of Example 10. In the developing solution, the halogen in the portion where the development of silver halide in the emulsion has occurred is eluted into the developing solution, which suppresses the development and lowers the softness. However, since the eluted halogen moves to the anode through the anion exchange membrane, it is possible to suppress the low softness.
Similarly, in the fixing solution, all silver halide is eluted in the fixing solution. The eluted silver ions are reduced and deposited on the cathode in accordance with the amount of energization, so that the silver ions disappear and the fixing agent in the fixing solution is regenerated. However, when halogen accumulates, it causes fixing inhibition, but since halogen moves to the anode through the anion-exchange membrane, fixing solution can be completely regenerated without causing fixing inhibition like the developing solution. It was

[0077]

According to the present invention, an electrolyte solution containing a chelating agent having a molecular weight of 400 or more and a metal ion, and the chelating agent has a theoretical metal ion chelating ability of 1.1 mol or more with respect to the metal ion is used. By energizing the electrolytic solution and the treatment liquid, it is possible to perform treatment without increase in fog and deterioration of gradation, and further, since the treatment liquid can be efficiently regenerated, the replenishment amount is reduced, Furthermore, it has become possible to reduce waste liquid. Such an effect becomes more remarkable when the energizing chamber is arranged in a multistage cascade. Further, by providing the processing device with the halogen capturing device, it is possible to eliminate overflow for discharging halogen ions, so that the amount of waste liquid can be reduced.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a development processing apparatus according to a first exemplary embodiment of the present invention.

2A and 2B are schematic diagrams of four types of development processing apparatuses according to Embodiment 2 of the present invention, in which FIG. 2A is a processing apparatus in processing 2A and 2B, FIG. 2B is a processing apparatus in processing 2C and 2D,
(C) is a schematic diagram of the processing apparatus in processing 2E, 2F, (d) is a processing apparatus in processing 2G, 2H.

FIG. 3 shows three kinds of energization sequences in Embodiment 3 of the present invention.

FIG. 4 is a schematic diagram of a development processing apparatus in processing 4A of Example 4 of the present invention.

5A and 5B are schematic views of a development processing apparatus in processing 4B of Example 4 of the present invention, in which FIG. 5A is a plan view and FIG.

6A and 6B are schematic views of a development processing apparatus in processing 4C of Example 4 of the present invention, in which FIG. 6A is a plan view and FIG.

FIG. 7 is a perspective view of a flexible electrode used in an embodiment of the present invention in a rolled-up state.

FIG. 8 is a schematic diagram of a development processing apparatus according to a sixth embodiment of the present invention.

FIG. 9 is a schematic diagram of a developing processing apparatus according to a seventh embodiment of the present invention.

FIG. 10 is a schematic diagram of a development processing apparatus according to an eighth embodiment of the present invention.

FIG. 11 is a schematic diagram of a development processing apparatus in processing 9A of Example 9 of the present invention.

FIG. 12 is a schematic diagram of a development processing apparatus in processing 9B of Example 9 of the present invention.

FIG. 13 is a schematic diagram of a development processing apparatus in processing 9C of Example 9 of the present invention.

14A and 14B are configuration diagrams of a halogen capturing device according to Example 10 of the present invention, in which FIG. 14A is a device using a solid as a halogen capturing medium, and FIG. 14B is a device using a liquid as a halogen capturing medium.

[Explanation of symbols]

 2 Color developing tank 4 Bleaching tank 6 Fixing tank 8 Washing tank 10 Anion exchange membrane 12, 22, 24, 26 Energizing chamber 16 Cathode 18 Anode 20 Power supply 30 Color developing tank 32 Bleaching fixing tank 34 Washing tank 36 Bleaching tank 38 Fixing tank 44 passage 46 partition wall 50 electrification tank 52 flexible electrode 56 shaft 58 motor 59 electric wire 60, 62, 72, 74, 96 pump 64 electrification tank 66 first conduction chamber 68 second conduction chamber 70 third conduction chamber 76 first chamber 78 2nd chamber 80 3rd chamber 82 4th chamber 84, 86 passage 90 collection lid 92 pipe 94 medium accommodating portion 98 halogen trapping medium 99 exhaust pipe

Claims (9)

[Claims] 1. An electrode is installed in a processing chamber containing a processing liquid, the other electrode is installed in an energization chamber defined by the processing tank and a diaphragm, and both electrodes are energized to restore the performance of the processing liquid. In the method of processing a photographic light-sensitive material, a chelating agent having a molecular weight of 400 or more and a metal ion are contained as a solution in the energization chamber, and the chelating agent has a theoretical metal ion chelating ability of 1.1 mol or more with respect to the metal ion. A method of processing a light-sensitive material, which is characterized in that electricity is applied using a liquid. 2. A color developing tank and a fixing tank are provided with a cathode, a bleaching tank is provided with an anode, and a common energization chamber defined by each of the tanks and a diaphragm is provided with a counter electrode for both electrodes, and all electrodes are energized. A processing device for a photographic light-sensitive material, characterized in that the processing liquid performance is recovered. 3. A method for processing a photosensitive material in which two or more kinds of processing solutions for processing a photosensitive material are energized to recover the performance of the processing solution, wherein energization processing is performed by shifting the energization timing for each processing solution. And a method for processing a photosensitive material. 4. A photosensitive material processing tank is partitioned by a diaphragm into two processing chambers, processing solutions having different functions are accommodated in the processing chambers, and a substantially liquid-tight photosensitive material passage is formed in a part of the diaphragm. Then, an anode is installed in one processing chamber and a cathode is installed in the other processing chamber, and both electrodes are energized to restore the performance of the processing liquid. 5. A photosensitive material processing tank is divided into two processing chambers by partition walls, and each processing chamber is provided with an energization chamber partitioned by a diaphragm. Each processing chamber contains a processing liquid having a different function, and the energization is performed. An electrolyte solution is contained in the chamber, a substantially liquid-tight photosensitive material passage is formed in a part of the partition wall, and an anode is provided in one energization chamber,
A processing device for photosensitive materials, in which a cathode is installed in the other energizing chamber and the performance of the processing liquid is restored by energizing both electrodes. 6. The photosensitive material processing apparatus according to claim 4, wherein the anode is installed in a bleaching tank, and the cathode is installed in a fixing tank to energize. 7. A photosensitive material processing apparatus for recovering the processing solution performance by immersing an electrode in a processing solution of a photosensitive material to energize the electrode so that the electrode is a flexible strip electrode and can be immersed in the processing solution. An apparatus for processing a photosensitive material, comprising: an electrode winding mechanism that is suspended and that winds the electrode out of a processing liquid after energization. 8. A processing apparatus for a photosensitive material, which comprises a means for energizing a processing solution for the photosensitive material to recover the processing solution performance, wherein an energization processing tank is arranged in multiple stages in a cascade. 9. A processing tank containing a processing solution for processing a photosensitive material is provided with an energization chamber partitioned by a diaphragm, one electrode is installed in the processing chamber, and the other processing chamber is installed in the energization chamber. A method for processing a light-sensitive material, comprising energizing an electrode to vaporize halogen in a liquid and capturing the halogen from an atmosphere above an electrolyte solution.