JPH05297534A - Photosensitive material processing device - Google Patents

Abstract

PURPOSE:To provide the photosensitive material processing device which can well process the photosensitive materials without generating waste liquids in spite of low replenishment. CONSTITUTION:A cathode 12 is installed in a developing tank 2 of the photosensitive material processing device which executes electrical processing and an anode 14 is installed in an energizing chamber 8. The developing tank 2 and the energizing chamber 8 are segmented by an anion exchange membrane 10. The developer consisting of chelate iron ions as a developing agent is packed into the developing tank 2. The energization quantity to the developer is set in accordance with the potential of the developer measured by a potentiometer 18. The pH of the developer is measured by a pH sensor 22 and the developer is replenished properly with an acidic soln. when the pH increases.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material for recovering the processing ability of the developer by installing electrodes in a developing tank in a developing device for silver halide photographic light-sensitive material and energizing the developer. The present invention relates to a processing device.

[0002]

2. Description of the Related Art The wet processing of, for example, a silver halide black and white photographic light-sensitive material consists of processing steps such as development, fixing and water washing, and a water washing step or the like is inserted between each step if necessary. A developing solution and a fixing solution are used for developing and fixing, respectively, but as the photosensitive material is processed, the developing agent in the developing solution is oxidized to be consumed and halogen ions are accumulated. Alternatively, silver ions and halogen ions are accumulated in the fixing solution due to the fixing action, and the processing ability thereof is lowered. Therefore, a replenisher having a composition close to that of the treatment liquid and containing necessary components is supplied to each treatment liquid so that the treatment ability of the replenishers is maintained so as not to decrease.

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 of incinerating the photographic processing liquid instead of dumping it 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.

In order to reduce the amount of waste liquid, it is necessary to reduce the amount of replenisher as much as possible. However, since the performance that should be recovered by the replenisher cannot be recovered, it is necessary to recover the performance by other means. .. Therefore, the present inventor has proposed a method for recovering the performance of the developer by energizing a developer containing a metal compound capable of reducing silver halide as a developing agent (Japanese Patent Application No. 3-24137). According to this method, for example, a chelate metal compound is used as a developing agent, and the developing tank is partitioned into two parts by an anion exchange membrane. One chamber contains a developing solution and the other chamber contains an electrolyte solution. It is filled. Further, a cathode is installed in contact with the developing solution, and an anode is installed in contact with the electrolyte solution so that both electrodes are energized.

By the development processing of the light-sensitive material, the chelating metal compound as a developing agent is oxidized by reducing silver halide in the light-sensitive material, and the chelating metal ion becomes a more expensive ion. That is, the chelate metal ion increases the ionic valence by participating in the development. For example, when chelate Fe (II) is used as the chelate metal compound, the chelate Fe ²⁺ becomes the chelate Fe ^{3+ as} the development process is performed, and the chelate Fe ³⁺ increases in the developing solution. However, when the current is applied, electrons are given from the cathode to the chelate Fe ³⁺ , the trivalent chelate iron ion returns to divalent, and the chelate Fe ^{2+ as the} developing agent is regenerated. In this way, since the developing agent used for development is regenerated by the energization process, the performance of the developer does not deteriorate if the energization is performed. Therefore, the developer needs to be replenished only by the amount reduced by evaporation or carry-out by the photosensitive material (carry over), and the replenishment amount can be extremely small.

Further, the developing tank partition by anion exchange membrane, by placing the electrodes on either side of the anion-exchange membrane, Br eluted from the photosensitive material ^- depending on the nature of the electrolyte solution on the anode side is concentrated in the anode Becomes 2Br ⁻ → Br _{2 and} bromine gas is discharged from the liquid into the air. Therefore,
Br ⁻ which is an unnecessary substance is not accumulated in the developing solution, an overflow for removing such an unnecessary substance is not necessary, and the waste liquid can be eliminated.

[0009]

However, since the chelating metal compound which is the developing agent is oxidized not only by the development treatment of the photosensitive material but also by contact with air, it is only necessary to control the energization based on the development treatment state. However, the developer performance cannot be sufficiently restored. That is, chelate Fe ²⁺ as a developing agent is oxidized by oxygen in the air to become chelate Fe ³⁺ , and chelate iron ions are more stable when they are trivalent rather than divalent. Even if it does not exist, chelate Fe ³⁺ tends to increase. Therefore, in order to recover the performance of the developing solution, it is necessary to carry out the energization processing in consideration of the performance deterioration due to air oxidation in addition to the development processing state. Since the oxidation state of the chelate Fe ²⁺ changes depending on the contact area of the developer with the air and the degree of sealing above the developer, it is necessary to control energization in consideration of all such oxidation factors.

An object of the present invention is to solve the above problems, and it is possible to satisfactorily recover the performance of a developer which has been deteriorated by air oxidation or development processing of a light-sensitive material. Can be treated well for a long time,
Another object of the present invention is to provide a light-sensitive material processing apparatus that does not generate waste liquid.

[0011]

The above objects of the present invention are achieved by the following items (1) to (6). (1) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolytic solution which is in contact with the developing solution through a diaphragm are filled. An apparatus for processing a silver halide photographic light-sensitive material, comprising an energization tank, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, a means for energizing both electrodes, and a pH controller for controlling the pH of the developing solution. ..

(2) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolytic solution which is in contact with the developing solution through a diaphragm. Halogenation having an energization tank to be filled, a cathode in contact with the developer, an anode in contact with the electrolyte solution, means for energizing both electrodes, and a redox potential controller for controlling the redox potential of the developer. Processing device for silver photographic light-sensitive materials.

(3) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolytic solution which is in contact with the developing solution through a diaphragm. Halogen having a current tank filled therein, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes, and the developing tank having a low opening degree or a substantially closed type halogen. Processing device for silver halide photographic light-sensitive material.

(4) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. An energization tank to be filled, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes, the developing tank having a low opening degree or a closed type, and the developing tank A photosensitive material processing device for processing a silver halide photographic photosensitive material with a small amount of developing solution.

(5) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolytic solution which is in contact with the developing solution through a diaphragm. An energization tank to be filled, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes are provided, and the emulsion surface of the light-sensitive material to be processed faces the diaphragm, A light-sensitive material processing device in which a cathode is located between the emulsion surface and the diaphragm.

(6) A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. An emulsion tank is provided which has an energization tank filled therein, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes, and the developing tank is provided over the entire photosensitive material conveying path in the developing solution. An apparatus for processing a light-sensitive material, which is divided into two chambers by a diaphragm disposed on the surface side, and the cathode is installed in a chamber on the emulsion surface side of the diaphragm and the anode is installed in another chamber.

When a current is applied to the developing solution, a developing agent or preservative which has undergone aerial oxidation during the rest of the processing is given a electron at the electrode (cathode) surface to be reduced and a developing power is generated. Will recover. As a result, a sufficient image density can be obtained, and a decrease in sensitivity and a soft gradation can be prevented.

Since the developing agent and preservative that have undergone air oxidation are preferably reduced and regenerated at the start of the development process, it is preferable that the energization process is performed before the start of the development process. Since the oxidation-reduction potential also changes when the energization process is performed, by detecting the oxidation-reduction potential, it is possible to detect whether the developer has been regenerated sufficiently for the development process. In addition, by detecting the redox potential during the energization process and controlling the energization amount, proper energization can be performed. To control the redox potential, an electrometer, voltage control means, current control means, or the like is used.

Although bromine ions become bromine gas at the anode due to the energization treatment and are diffused from the liquid, it is necessary to capture the bromine gas so as not to diffuse into the air for environmental protection. In order to generate a large amount of bromine gas, it is sufficient to increase the amount of energization, but since the pH of the developing solution rises due to the energization process, it is preferable to properly control the pH of the developing solution. The pH of the developing solution is preferably 2 to 8, more preferably 3 to 7, and an acidic solution or an alkaline solution is appropriately supplied so that the pH of the developing solution is in this range.

For such control of the redox potential and pH, when the processing tank used for the development processing has a low opening degree or a closed type, the developer is less oxidized by air and good processing can be performed for a long time. For example, Japanese Patent Laid-Open No. 2-84642
No. 2-68548 and No. 2-69744 can be used. Further, when the amount of the liquid is small, the redox potential control and the pH control can be accurately performed. From this point of view, the present invention is suitable for the slit processing, for example, in which the cross-sectional shape of the processed portion of the photosensitive material is a narrow slit-like path.

Further, it is preferable that the developing tank has a contact area with the air as small as possible.
The low-openness or closed-type processing tanks described in Japanese Patent Nos. 9744 and 2-84642 are preferable. The low opening degree referred to here is log K ≦ -1.8 × 10 ⁻⁵ V-1.5 S: surface area of liquid surface portion (cm ² ), V: volume K: opening degree S / V (cm ⁻¹ ). S / V that satisfies the above condition.

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 improved. Will increase. 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. The fixer can be regenerated for black and white or for color.
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. Therefore, in the fixing solution, unnecessary halide ions are prevented from accumulating and the inhibition of fixing is prevented. On the other hand, silver deposits from the fixing solution and disappears from the system, so that the fixing agent is regenerated.

The developer used for the main energization treatment is as follows.
It is generally preferred to include 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 more, more preferably 2.0 mol or more. That is,
It is preferred that the chelating agent be present in excess 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 that the electrolyte solution moves to the developing 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 a part of the treatment tank is substantially partitioned by an anion exchange membrane, the cathode and the anode are provided through the anion exchange membrane to energize, and there is no need to pass through the anion exchange membrane. In this treatment method, a substance or a necessary substance is moved to a desired side, and a liquid component is oxidized or reduced by a reaction on an electrode surface. 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 to generate this current, but the voltage must be appropriate,
Usually, it is 0.1-10V, preferably 0.3-5V. 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 developer can be properly regenerated by energizing the developer so that an electric quantity of a predetermined coulomb is applied to the developer 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 developer 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. To measure the redox bulk potential of the developer, the redox potential measuring device described in JP-A-60-195544 and 60-195545 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 developing solution, energization is controlled so that the redox potential is within a predetermined range, and when the redox potential exceeds a set upper limit value, energization is interrupted to interrupt the oxidation of the developing solution. .. The redox potential of the developing solution decreases as the photosensitive material is processed during interruption of energization, but when the redox potential falls below the lower limit, energization is started to oxidize the developing solution and raise the potential. In the present invention, it is preferable that the energization is performed before or during the processing, and by doing so, the development activity can be maintained during the processing. Then, when the processing is completed and the signal of the processing completion of the photosensitive material S is received, the energization may be terminated.

In the above, the metal constituting the metal compound used as the developing agent is a transition metal such as Ti, V, Cr, Fe, etc., and has a property that it can take several different oxidation states. Therefore, when it is used as a developing agent, theoretically, it is sufficient to use one in an oxidation state less than the maximum oxidation state and utilize its reducing power.
In Ti Ti ^3+, the V V ^2+, the Cr Cr ^2+, the Fe Fe ²⁺ is used. Among them, Ti ³⁺ , Fe ^{2+ and the} like are preferably used.

Such metal compounds may be not only ordinary salts but also complexes. As salts, chlorides, bromides, halides such as iodides, oxalates, sulfates,
Examples thereof include acetate and citrate. Specifically, Ti
Cl ₃ , TiBr ₃ , TiI ₃ , FeCl ₂ , FeBr
₂ , VCl ₂ , V (SO ₄ ), Fe (COO) ₂ , Fe
SO ₄ , Fe (CH ₃ COO) ₂ , iron (II) citrate and the like can be used. Further, the complex has Ti ³⁺ or Fe ²⁺ as a central metal, and the ligand is preferably a multidentate ligand. Specific examples of such a ligand include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) or salts thereof, ethylenediamine-N, N,
Aminopolyphosphoric acids such as N ', N'-tetramethylenephosphoric acid and 1,3-diaminopropanol-N, N, N', N'-tetramethylenephosphoric acid or salts thereof, nitrilotriacetic acid, oxalic acid, citric acid, etc. Carboxylic acids or salts thereof, nitrilo-N, N, N-trimethylenephosphoric acid, propylamino-N, N-dimethylenephosphoric acid or the like, or salts thereof.

Among these, EDTA and DTPA
A complex having, for example, as a ligand is preferably used. Further, such a complex can be formed in a developing solution by adding a metal salt and a ligand compound, and such a method is also preferable in the present invention. For details of such metal compounds, reference can be made to JP-B No. 54-41899 and the references cited therein. The content of such a metal compound in the developer is 1 to 100 g.
/ Liter, preferably 5 to 50 g / liter.

Further, such a developing solution may contain various additives such as a pH buffering agent and an antifoggant, and such additives are disclosed in JP-B-54-41.
No. 899 and the like. The pH of the developer is 0.5 to 11, more preferably 1 to 11, and preferably 2.5 to 11.
Used in the range of 9.

The cathode used in the present invention may be any electric conductor or semiconductor that can withstand long-term use, but stainless steel is particularly preferable. The anode may be made of an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, titanium and copper, and stainless steel may be used depending on the case. The shape of the both electrodes is preferably a plate shape that is easy to install in the tank, a mesh plate shape or a plate shape with protrusions. The size may be appropriately selected depending on the tank capacity.

As the anion exchange membrane used in the present invention, any one can be used as long as it selectively permeates anions, and a commercially available one can be used as it is. In this case, the anion exchange membrane to be used can be selected according to the valence of the anion which is preferably transferred through the anion exchange membrane. For example, for the purpose of transmitting halide ions such as Br ⁻ accumulated in the developing solution, an anion exchange membrane that selectively transmits only monovalent anions may be used.

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, a Yumicron membrane (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.

The cathode, which is one of the electrodes used for energization, may be any electric conductor or semiconductor capable of withstanding long-term use, such as stainless steel, aluminum, silver, nickel, copper, Examples of the metal material include zinc, brass and titanium, and stainless steel is particularly preferable. The anode may be an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, and titanium steel. In some cases, stainless steel may be used. Good. 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.

The electrolyte solution used in the present invention is not limited, but the electrolyte may be NaCl, KCl, LiCl, N 2.
HaBr such as aBr, KBr, KI, Na ₂ S
Sulfates such as O ₄ , K ₂ SO ₄ , KNO ₃ , NaN
O _3, NH ₄ NO _3, etc. _{nitrate, Na 2 CO 3, K 2} C
It is preferable to use a carbonate such as O ₃ or the like. The concentration of the electrolyte in the electrolyte solution at this time is 0.01 to 30.
%, Preferably 0.01 to 20%. In addition, a diluting solution of the fixing solution can be used.

In the above, the electrolyte solution is newly prepared and used, but the rinse liquid may be used as the electrolyte solution. Even when ion-exchanged water is used as the rinse liquid itself, the rinse liquid after use contains a salt which is a fixing liquid component brought into the photosensitive material S. Therefore, there is no problem in using it as an electrolyte solution, and it is possible to reduce the amount of waste liquid.

As the above-mentioned rinse solution, a usual one may be used, and preferably, one to which antibacterial agents, antibacterial agents, dye eluting agents, decolorizing agents and the like are added. Further, in the present invention, a part of the present invention may be applied not only to a developing solution containing a metal compound as a developing agent but also to processing using an ordinary black and white developing solution. That is, if hydroquinone is semiquinone generated during development of air or silver halide,
It is thought that it is regenerated to hydroquinone by energization. Furthermore, in the case of oxidation from semiquinone to quinone, it is considered that a part is also oxidized to hydroquinone by energization. Furthermore, in the black-and-white developer, silver stain is particularly likely to occur due to the relatively large amount of the sulfite preservative, but silver deposit is prevented on the cathode because silver is deposited on the cathode. It On the other hand, even in the fixing solution, silver is deposited on the cathode, and the silver can be recovered.

Further, in the same way, since a part of the reaction mechanism has a reproducing action by energization, the light-sensitive material in the present invention may be any of various black and white and color light-sensitive materials. For example, black and white negative film, black and white photographic paper, black and white reversal film, black and white reversal photographic paper, black and white positive film, photographic light-sensitive material for plate making, X-ray photographic light-sensitive material, light-sensitive material for micro, color negative film, color reversal film, color photographic paper. , Color positive film, color reversal photographic paper, and the like.

In the present invention, a developing agent used in an ordinary black-and-white developing solution, which does not use the above metal compound as a developing agent, is mainly composed of hydroquinone such as hydroquinone, but good performance is easily obtained. In this respect, a combination of hydroquinones and 1-phenyl-3-pyrazolidones or a combination of hydroquinones and p-aminophenols is preferable. Also, a color developing agent based on a para-aminophenol derivative may be included.

The hydroquinone developing agent is usually 0.01
~ 1.5 mol / l, preferably 0.05-1.2
Used in an amount of mol / liter. In addition to this, p-
The aminophenol type developing agent or the 3-pyrazolidone type developing agent is usually 0.0005 to 0.2 mol / liter,
It is preferably used in an amount of 0.001 to 0.1 mol / liter.

Preservatives for sulfite used in such black and white developers include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and the like. Sulfite is 0.
It is preferably 2 mol / liter or more, and particularly preferably 0.4 mol / liter or more. The upper limit is preferably 2.5 mol / liter.

The pH of such a black-and-white developing solution is preferably in the range of 8.5 to 13. More preferably p
The range is from H9 to 12. In the present invention, the fixing solution used in the fixing process after the development process of the black-and-white light-sensitive material is an aqueous solution containing a fixing agent and has a pH of 3.8 or more, preferably 4.2 to 7.0. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, and is generally about 0.1
It is about 3 mol / liter.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like. For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 to
0.03 mol / l is particularly effective.

Preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents capable of softening water by water are contained in the fixing solution, if desired. Or the compounds described in JP-A No. 62-78551. In the processing of the black-and-white light-sensitive material, a rinsing process is performed after the fixing process. This rinse solution
It has a function of removing the residual treatment chemicals in the previous step, and is used almost synonymously with washing water and washing water.

In this rinsing process, the photosensitive material 1 m
The replenishing amount can be 3 liters or less per ² parts, and in this case, the rinse liquid is preferably provided with a fungicide-proofing means. As the antifungal means, the ultraviolet irradiation method described in JP-A-60-263939, the method using a magnetic field described in JP-A-60-263940, and the ion exchange resin described in JP-A-61-131632 are used. Pure water method, ozone blowing method, JP-A Nos. 62-115154 and 62-153.
No. 952, No. 62-220951, No. 62-2095.
No. 32 and JP-A-1-91533, the method using the antibacterial agent can be used.

Furthermore, LF West. “Water Quality
Criteria ”Photo. Sci, & Eng. Vol. 9 No.6 (1965), M.
W. Beach, “Microbiological Growths in Motion-pict
ureProcessing ”SMPTE Journal Vol. 85, (1976), R.
O. Deegan, “Photo Processing Wash Water Biocide
s "J. Imaging Tech 10, No.6 (1984) and JP-A-57.
-8542, 57-58143, 58-105.
No. 145, No. 57-132146, No. 58-1863.
No. 1, No. 57-97530, No. 57-157244 and the like can be used in combination with antibacterial agents, antifungal agents, surfactants and the like.

Furthermore, RT Kreiman, J. Image. Te
ch 10, (6) p. 242 (1984), isothiazoline compounds, Research Disclosure Volume 205, No. 20526 (19
1981, May issue), isothiazoline compounds,
Isothiazoline compounds described in Vol. 228, No. 22845 (April, 1983), JP-A-62-209532.
It is also possible to use the compounds described in No. 1 and the like as a fungicide (Microbiocide) in combination.

In addition, as described in "Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) Various compounds may be included. A stabilizing solution may also be used for the processing of the black-and-white light-sensitive material. For details of the processing of the black-and-white light-sensitive material, see JP-A-1-937.
37, JP-A 1-250947, JP-A 2-103
No. 035, JP-A No. 2-103037, and JP-A No. 2-71.
The description of JP-A No. 260, JP-A-61-267559 and the like can be referred to.

The fixing solution and rinsing solution used for processing the color light-sensitive material are also the same as those for the black-and-white light-sensitive material. For details of the processing of this color light-sensitive material, see JP-A-63-70857 and JP-A-1. Reference can be made to the descriptions of JP-A-190889, JP-A-1-198754, JP-A-1-106050 and the like. Further, for details of the black-and-white or color light-sensitive material of the present invention, see JP-A-1.
It is disclosed in the above-mentioned patent documents and the like including No. 259359.

[0056]

Embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic plan view of an automatic developing device. In the automatic developing device, a developing tank 2, a fixing tank 4, and a washing tank 6 are arranged in this order. The developing tank 2 is filled with a developing solution, the fixing tank 4 is filled with a fixing solution, and the washing tank 6 is filled with washing water. .. The exposed light-sensitive material (black and white) is sequentially dipped in each processing solution for processing, and the light-sensitive material S that has been washed with water is dried in a drying unit (not shown).

Although the developing tank 2 is filled with the developing solution,
An energizing tank 8 is provided adjacent to the developing tank 2, and the developing tank 2 and the energizing tank 8 are partitioned by an anion exchange membrane 10. An electrolyte solution is filled in the energization tank 8, and the electrolyte solution and the developing solution are in contact with each other via an anion exchange membrane 10. Further, the cathode 12 is installed in contact with the developing solution, and the anode 14 is installed in contact with the electrolyte solution.
14 is energized by a power supply 16. Further, the developing tank 2 is provided with an electrometer 18 so that the redox potential of the developing solution can be measured. The electrometer 18 is the control device 2
It is connected to 0, and the power source 16 can be controlled according to the oxidation-reduction potential of the developing solution measured by the electrometer 18 to control the potential and the energization amount.

The timing of energizing the developing solution may be before development processing, during development processing, or after development processing. It is particularly preferable to carry out the energization process before the development process to recover the performance of the developer, and when the development process is actually started, the performance of the developer can be kept in a good state. Deterioration of the developing solution is mainly due to the progress of the developing process and the chelating metal ion which is the developing agent has a high ionic valence.
By immersing the cathode 12 in the developing solution and energizing it, electrons are given from the cathode 14 to the chelate metal ion having a high ionic valence, and the metal ion is reduced and regenerated. Therefore, the energization treatment during the development treatment is preferable in that the development efficiency is improved. Further, the chelate metal ion is also oxidized by oxygen in the air, and as a result, the developing performance is lowered. Therefore, by conducting the energization process in advance before the development process,
It is preferable to regenerate a large amount of chelate metal ions having a low ionic valence in the developer to recover the developing performance.

FIG. 2 is a side view of the developing tank 2 as viewed from the downstream side in the photosensitive material conveying direction. The developing tank 2 can control the energization amount as described above, but also can control the pH of the developing solution. Since the developer has a high valence of chelate metal ions due to air oxidation when untreated, energization is required to reduce the chelate metal ions. However, if the current continues to flow, the developer p
Since H becomes higher than necessary, it is necessary to keep the pH of the developer within a predetermined range. Specifically, a part of the acid is released from the light-sensitive material by processing the light-sensitive material, but it is preferable to replenish the acid solution according to the increase of pH when the amount of alkali is larger than that.

A pH sensor 22 is provided in contact with the developing solution, and the pH sensor 22 is connected to the control device 20. The control device 20 is connected to a pump 24, and the pump 24 can supply the acidic liquid in the tank 26 into the developing tank 2. The pH of the developing solution measured by the pH sensor 22 is supplied to the control device 20.
When the detected pH is equal to or higher than a predetermined value, the pump 24 is driven to supply the acidic solution into the developing solution, and the pH of the developing solution is controlled to be lowered.

Although not shown, a floating lid is provided on the upper surface of the developing solution, or a lid that closes the upper part of the developing tank in a substantially airtight manner is provided to prevent the developing solution from coming into contact with air as much as possible. preferable. By minimizing the contact between the developing solution and air, it is possible to prevent the developing agent or preservative from being oxidized by oxygen in the air. By energizing the developing solution, the chelating metal ion as a developing agent and the preservative are reduced and regenerated. Therefore, replenishment for the purpose of supplementing the components in the developing solution is not particularly required, only replenishing for only the evaporated water is required, and development processing can be performed without replenishment or low replenishment for a long period of time.

Further, bromine ions eluted from the photosensitive material S are accumulated in the developing solution, but the bromine ions in the developing solution are selectively passed through the anion exchange membrane 10 and moved to the anode 14 by conducting an electric current. , Becomes bromine gas at the anode 14. Therefore, since bromine ions, which are an unnecessary component for development processing and which rather hinder development, are removed from the developer by energization, there is no need to overflow the developer from the tank and discharge it, eliminating or reducing waste liquid. Can be made Since the bromine gas generated from the electrolyte solution is harmful if it is released into the air as it is, it is preferable to provide the halogen trapping device shown in FIG.

FIG. 3 is a block diagram of the halogen capturing device,
(A) is a configuration using a solid as a halogen capture medium,
(B) is a configuration using a liquid. Explaining the configuration of (a), this trapping device has a dome-shaped collecting lid 90 that covers the anode 14 where halogen is generated, a tube 92 connected to the central portion of the lid, and a tube 92 in the middle thereof. The medium storage section 94 is provided and a pump 96 for sucking the atmosphere in the medium storage section 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 14 and become bromine gas. Therefore, by appropriately operating the pump 96,
The bromine gas is collected by the collecting lid 90 and is collected in the medium containing portion 94.
Reach the halogen capture medium 98 such as activated carbon, zeolite, etc.
Captured by.

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 14 is discharged into the liquid 98, is dissolved in the liquid 98, and is captured.

FIG. 4 is a sectional view of a modified example of the developing tank 2.
The photosensitive material S is transported by the transport roller 28 in the developing tank 2 through a U-shaped path. The inside of the developing tank 2 is partitioned by an anion exchange membrane 10 provided along the conveyance path of the photosensitive material S,
The outside of the anion exchange membrane 10 is filled with an electrolyte solution, and the inside is filled with a developer. In addition, in the electrolyte solution, the anode 14
However, a cathode 12 is provided between the anion exchange film 10 in the developing solution and the photosensitive material S. The photosensitive material S is conveyed with the emulsion surface Em facing the cathode 12.

A floating lid 30 in which a passage for the photosensitive material S is formed is provided on the upper surface of the developing solution, and the contact area between the developing solution and air is reduced. Therefore, the developing agent and preservative in the developing solution are less likely to be oxidized by oxygen in the air. If a shutter means is provided in the photosensitive material passage of the floating lid 30, it is possible to prevent the opportunity of contact between the developer and air. Furthermore, as shown by the imaginary line, the floating lid 3
It is preferable to provide a lid 32 that closes the upper part of 0 in a substantially airtight manner. The term "substantially airtight" as used herein means the photosensitive material S.
Although there is a slight air movement when the photosensitive material S is passing, it is hermetically closed when the photosensitive material S is not passing, and it is preferable to provide a shutter means or the like in the photosensitive material passage.

[0067]

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): Fuji Photo Film scanner film LS-400 (Treatment liquid): A developing solution has the following formulation-1 A fixing solution uses Fuji Photo Film's plate-making fixing agent GR-F1.

(Formulation-1): Water 800 ml Ammonia water (28%) 100 ml EDTA (4H) * 60 g Citric acid (anhydrous) 38.4 g KBr 1 g Ferrous sulfate (7H ₂ O) 55.6 g Adjusted to pH 6.5-7.0 Add water 1 liter * EDTA (4H): POTITE 4H (EDTA-Free acid, Wako Pure Chemical Industries, Ltd.)

(Processing device): A processing device was used in which nitrogen bubbles were introduced into the developing solution of Formula-1 and stirred in the developing tank having an energizing structure shown in FIG. 3% Na ₂ as electrolyte solution
A CO ₃ aqueous solution was used.

(Process 1-1) Nitrogen bubbles were introduced into 3 liters of the formulation-1 solution, and the mixture was stirred. While energizing at 3.5 V, 5 A for 90 seconds, 0.1 g of KBr was added every 9 seconds of energization to adjust the pH.
Was controlled by a pH controller so as to be 6.5 to 7.0 (the output of the Horiba pH meter model F-13 was taken out, and when pH ≦ 6.5, 10% KOH and pH ≧
At 7.0, control was performed so that 10% H ₂ SO ₄ was added). Exposed film in electrolyzed developer at 38 ℃ 60
Immersion for 2 seconds followed by development treatment, followed by fixing treatment at 38 ° C. for 20 seconds and washing treatment at 38 ° C. for 20 seconds. The obtained photographic performances are D _min = 0.06, D _max = 5.16, gradation of linear part γ = 9.61, and there is little fog and high maximum density.
The gradation was also hard and favorable performance was obtained. From the above, by controlling the pH to 6.5 to 7.0 while energizing the developing solution for 90 seconds, it is possible to recover the fatigue caused by the air oxidation of the developing solution to the state where good photographic performance can be obtained. did it.

(Process 1-2) In Process 1-1, the exposed film was continuously processed while energizing at 3.5 V and 5 A for 40 minutes. Also at this time, if the pH is controlled to 6.5 to 7.0 by adding 0.1 g of KBr every 9 seconds of energization (the output of the Horiba pH meter model F-13 is taken out, and 10% when pH ≦ 6.5). KOH, pH ≧
At 7.0, control was performed so that 10% H ₂ SO ₄ was added), and good performance was obtained as in Treatment 1-1. From the above, by controlling the pH to 6.5 to 7.0 while energizing the developer, the fatigue of the developer due to the continuous processing of the light-sensitive material can be restored to a state where good photographic performance can be obtained. I was able to.

(Process 1-3) In Process 1-1, 3.
When processing was performed without pH control when energizing at 5 V and 5 A for 90 seconds, the pH of the developer decreased to 1.0 or less. When the exposed film was treated with such a developing solution, D _max was remarkably lowered to 0.35, and the developing solution was not practically used at all. (Treatment 1-4) In Treatment 1-3, after adding 10% KOH so that the pH of the developer is 6.5 to 7.0,
The exposed film was continuously processed while energizing at 3.5 V, 5 A for 40 minutes. At this time, KBr 0.1 g every 9 seconds when energized
When the pH controller for controlling the pH to 6.5 to 7.0 was not added, the processing solution was precipitated and no development processing was possible. However, when the pH was controlled to 6.5 to 7.0 by the pH controller, the activity of the developing agent could be maintained and there was no precipitation,
Excellent photographic performance was obtained as in Process 1-1.

<Example 2> (Photosensitive material): Laser film PD-F100 manufactured by Fuji Photo Film (Treatment liquid): The developing solution is the following formulation-2. Others are the same as in Example 1 (Treatment process): As in Example 1. the same

(Formulation-2): Water 800 ml EDTA.Fe.NH ₄ 2H ₂ O 79.6 g (Churest FNO manufactured by Chubu Chillest) EDTA · 2Na 2 g citric acid (anhydrous) 12.8 g Ammonia water (28%) 30 ml KBr 1 g pH adjusted to 6.5-7.0 Water added 1 liter

(Processing apparatus): An apparatus having the structure shown in FIG. 1 was used. Cathode side: Developer Anode side: Electrolyte solution (3% Na ₂ CO ₃ aqueous solution) Anion exchange membrane: Tokuyama Soda anion exchange membrane AM-3 Cathode: Tokai carbon carbon electrode Anode: Stainless steel (SUS316) (treatment 2) -1) The developing tank was filled with the developing solution of Formula-2, and the exposed film was processed. The photographic performance (D _max ) obtained by processing immediately after being filled with the developing solution and every 2 hours after standing is shown below.

Aging: New solution 2 hours 4 hours 6 hours 8 hours 10 hours D _max : 5.13 5.10 4.99 4.25 3.43 2.03 As is clear from the above results, the performance was deteriorated after 4 hours, and it could not be used. That is, even if the developing solution was a fresh solution, the fatigue of the developing solution due to air oxidation was large, and a clear deterioration in performance was observed when air developing was carried out for 4 hours.

(Processing 2-2) The potential controller shown in FIG. 1 (pH meter model F-13, manufactured by Horiba) was used in the redox potential measurement mode, and the output was taken out to control the potential. That is, when the potential rises above -230 mV, it is energized at 2 V and 1.5 A, and -230 mV.
The power supply was controlled to stop when the voltage was in the range of to -350 mV (particularly, it stopped after passing -350 mV). However, 0.1 g of KBr is added every minute. Processing 2-1 using such a developer
The same process was performed. As a result, D _max stayed within the range of 5.16 to 5.11 and good performance was obtained after 10 hours from the fresh liquid state. That is, by controlling the potential of the developing solution in the range of -230 mV to -350 mV using a potential controller, the fatigue of the developing solution due to air oxidation can be recovered and the developing solution performance can be favorably maintained, and the redox potential is- It was found that sufficient performance can be obtained by recovering to 350 mV.

<Embodiment 3> In Embodiment 2, Embodiment 1
An additional pH controller was also installed, and the processing of the light-sensitive material was continued from the fresh liquid state for one week in the same manner as in Example 2.
The performance similar to that of the fresh solution was obtained for almost a week. However, when the pH controller operation was stopped and the pH control was not performed, precipitation occurred in the developing solution on the 4th day from the state of the new solution, and the developing performance deteriorates (D _max = 4 on the 4th day).
4.73, D _max = 3.99 at the 5th day). From the above, although the fatigue due to the air oxidation of the developer is recovered by controlling the potential, the effect is limited. However, by using the developer pH control together, the effect could be extended more than twice.

Example 4 TiCl ₃ was added to the formulation-1.
When 15 ml / liter of (20% aqueous solution) was added, the development time for obtaining good results was shortened by about 10%. Therefore, the addition of TiCl ₃ was useful for activating the developing solution and shortening the developing time. Moreover, as in the case of Example 1, by controlling energization and pH, it was possible to recover fatigue of the developing solution due to air oxidation of the developing solution and processing of the photosensitive material.

<Example 5> The following formulation-3 was used as the developing solution, and the other processes were performed in the same manner as in Example 2. (Formulation-3) EDTA · 2Na · 2H ₂ O 97 g CH ₃ COONa 20 g TiCl ₃ (20% aqueous solution) 150 ml Adjusted to pH 4.0 (with NaOH) Water added 1 liter

However, the potential of the developing solution was controlled in the range of -250 mV to -300 mV by the potential controller. That is, when the potential rises above -250 mV, it is energized at 2 V and 1.5 A, and -250 mV to -300 mV.
It was controlled so as to stop the energization in the range of V. As a result, good performance was obtained as in Example 2.
That is, even when TiCl ₃ was used as the developing agent, by controlling the potential during energization, the tired developer could be well recovered and the performance could be maintained, and good processing could be performed.

<Example 6> (Process 6-1) An apparatus having the structure shown in Fig. 1 of Japanese Patent Application Laid-Open No. 2-84642 was treated with the liquid of Formula-1 of Example 1. However, partition the interior of the developing tank with an anion exchange membrane,
The cathode was installed in the chamber having the photosensitive material transport path, and the anode was installed in the other chamber to conduct electricity. ² per 1 dm ^{2 of} photosensitive material
The light-sensitive material was continuously processed for 10 seconds at 10 dm ² per day for ² seconds while being energized at V, 0.5 A for 2 weeks, but there was no change in photographic performance and the performance in a new liquid state was continuously obtained.

(Process 6-2) When the device of Process 6-1 was opened in the same manner and processed in the same manner, the photographic performance deteriorated in the latter half of the first day and deteriorated in the second day. I could not use it violently. As described above, the air oxidization of the developing solution can be effectively prevented by making the opening degree of the developing apparatus extremely small or by preventing the developing solution from coming into contact with air as a closed type. Moreover, by energizing, it was possible to recover the air oxidation of the developing solution and the fatigue of the developing solution due to the processing of the photosensitive material.

<Embodiment 7> A slit type automatic developing machine having the construction shown in FIG.
When electricity was processed according to the processing amount of the light-sensitive material, there was no change in photographic performance even after one week from the fresh liquid state. When the amount of developer is very small like a slit type automatic processor and fatigue of the developer due to the processing of the photosensitive material is likely to occur,
By applying the electric current, the fatigue of the developing solution could be effectively recovered.

<Example 8> A developing solution having the formulation-1 of Example 1 was filled in a developing tank having the structure shown in FIG. 4 to process a photographic material. Stable photographic performance was obtained as in Example 6. Was given. Since the cathode is installed on the emulsion surface side of the light-sensitive material and the anode is installed through the partition wall, it is possible to rapidly reduce and regenerate the developing agent near the emulsion surface immediately after fatigued by the processing. The photographic performance can be kept constant.

<Example 9> In Example 1, the anion exchange membrane was replaced by AFN-7 manufactured by Tokuyama Soda, and a developing machine for a photosensitive material was used by using a processor having the structure shown in FIG. 3 (a) or (b). I went. (Processing 9-1) Without using the apparatus of FIGS. 3 (a) and 3 (b),
When 100 dm ^{2 of} electricity was applied per day (with pH control), the concentration of the same exposure started to decrease from the 3rd day, and almost no concentration appeared on the 10th day. This is considered to be a development obstacle due to the accumulation of bromine ions, which is an unnecessary substance, in the developer.

(Treatment 9-2) Using the apparatus of FIG. 3 (a) or (b), the electrolyte solution was replaced with 3% Na ₂ SO ₄ and a current running treatment was carried out, and the photographic performance changed until the 10th day. It could be used without any. (Treatment 9-3) When the halogen-trapping medium was removed in Treatment 9-2 for treatment, a pungent odor was generated (generation of bromine gas) around the treatment machine, and the throat was hurt. But,
Similar to Process 9-2, there was almost no change in photographic performance, and the process could be processed with constant performance.

[0088]

According to the present invention, even when the performance of the developing solution is deteriorated due to air oxidation or processing of the light-sensitive material, the p
By controlling H and the oxidation-reduction potential within a predetermined range, the developer performance can be favorably restored, the processing performance can be favorably maintained for a long time, and the replenishment amount can be extremely small. Bromine ions (unnecessary substances) generated by the development are vaporized and diffused at the anode, so that unnecessary components do not accumulate in the developing solution. Therefore, it is not necessary to overflow the developer in order to discharge bromine ions as an unnecessary component, and no waste liquid is generated. As for the replenishment of the developing replenisher, only the amount reduced by carryover or evaporation of the light-sensitive material needs to be replenished, and good processing performance can be maintained even if replenishment is hardly performed.

[Brief description of drawings]

FIG. 1 is a plan view of a development processing apparatus that is an embodiment of the present invention.

FIG. 2 shows a sectional view of a developing tank.

3A and 3B are configuration diagrams of a halogen capturing device, FIG. 3A is a device using a solid as a halogen capturing medium, and FIG. 3B is a device using a liquid as a halogen capturing medium.

FIG. 4 shows a sectional view of a modified example of the developing tank.

FIG. 5 shows a sectional view of a slit type processing tank which is a modified example of the developing tank.

[Explanation of symbols]

 2 developing tank 4 fixing tank 6 washing tank 8 energizing tank 10 anion exchange membrane 12 cathode 14 anode 16 power supply 18 electrometer 20 controller 22 pH sensor 24 pump 26 tank 28 transport roller 30 floating lid 32 lid

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Tsuji 2-26-30 Nishiazabu, Minato-ku, Tokyo Within Fujisha Shin Film Co., Ltd. In the company

Claims (6)

[Claims] 1. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. Of a silver halide photographic light-sensitive material having an energization bath, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, a means for energizing both electrodes, and a pH controller for controlling the pH of the developing solution. Processing equipment. 2. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. A silver halide having an energization bath, a cathode in contact with the developer, an anode in contact with the electrolyte solution, means for energizing both electrodes, and a redox potential controller for controlling the redox potential of the developer. Photosensitive material processing equipment. 3. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. Halogenation in which the developing tank has a low opening degree or a substantially closed type, which has an energization tank, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes. Processing device for silver photographic light-sensitive materials. 4. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. An energizing bath, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes, the developing tank is of low opening degree or closed type, and in the developing tank Photosensitive material processing equipment for processing silver halide photographic photosensitive materials with a small amount of developer. 5. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. And a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes. The emulsion surface of the light-sensitive material to be processed faces the diaphragm, An apparatus for processing a photosensitive material, wherein a cathode is located between a surface and the diaphragm. 6. A developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and gives electrons to return to a substitution product, and an electrolyte solution which is in contact with the developing solution through a diaphragm. An energizing bath, a cathode in contact with the developing solution, an anode in contact with the electrolyte solution, and a means for energizing both electrodes. A processing apparatus for a light-sensitive material, which is divided into two chambers by a diaphragm disposed on the side, the cathode is placed in the chamber on the emulsion side of the diaphragm, and the anode is placed in the other chamber.