JPH06186718A - Photosensitive material processing device - Google Patents

Abstract

PURPOSE:To provide the processing device for a photosensitive material having a processing liquid regenerating device capable of efficiently regenerating the processing liquid. CONSTITUTION:The processing liquid regenerating device is constituted by installing electrodes 12, 14, 16 in respective chambers of three storage chambers 6, 8, 10 successively provided by partitioning the device with two diaphragms 2, 4, connecting the electrode group in order of the first electrode 12, the second electrode 14 and the third electrode 16 and having power sources 18, 20 for impressing voltages by setting the potentials of the electrode group in this order. The photographic processing liquid is packed into the first chamber 6 and the third chamber 10 and an electrolyte soln. is packed in the second chamber 8. The processing liquid is regenerated by energizing these liquids. As a result, the processing liquid regenerating device is constituted to a small size and low cost while the regeneration of the processing liquid at two points is possible.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for processing a photographic light-sensitive material for developing a silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive 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.However, as the photosensitive material is processed, the developing agent in the color developing solution is consumed and oxidized, Alternatively, silver ion accumulates in the bleach-fixing solution due to the desilvering action, and the bleaching agent is consumed and reduced, so that the processing ability thereof is lowered. Therefore, it has been practiced to supply a replenishing liquid having a composition close to that of the processing liquid and containing necessary components to each of the processing liquids so as to maintain the processing 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. In order to discard this waste liquid, a detoxification process is required, and a processing device therefor becomes large-scale and large and expensive. Therefore, a photosensitive material processing apparatus has been developed which produces a small amount of waste liquid even when a photographic photosensitive material is processed instead of treating the waste liquid to be harmless.

For example, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 3-209
No. 471, No. 3-273237, No. 3-293661.
No. 4, No. 4-243253, No. 4-249242, No. 4-250449, No. 4-276746, No. 4-3.
No. 20265, No. 4-323650, No. 4-3285
No. 45 proposed a method for regenerating electric current of a photographic processing solution. According to these techniques, when an electrode is provided in the color developing tank and the developer is reduced by energizing, the oxidized color developing agent is reduced to some extent and returned to the original color developing agent,
The halogen eluted from the light-sensitive material is removed. In addition, when an electrode is provided in the bleach-fixing tank to energize it, JP-A-4-4-2
According to the method of No. 76746, silver is deposited on the cathode to reduce the concentration of silver ions in the bleach-fixing solution, and at the anode, the reduced bleaching agent is oxidized and returns to the original bleaching agent. As described above, according to the above method, the processing ability of the color developing solution or the bleach-fixing solution can be considerably restored, and the amount of the replenishing solution for replenishing the components can be remarkably reduced.

[0005]

However, in order to further enhance the regenerating effect of each processing solution such as a developing solution, a bleaching solution, and a fixing solution, an energizing tank or an electrode pair for filling each processing tank with an electrolyte solution is provided. If provided, there is a problem that the processing device becomes large and expensive. In order to increase the regeneration effect when the treatment liquid is energized to restore the performance, it is conceivable to increase the unit area of the electrode and the energization amount per unit time, or increase the electrode area. However, if the amount of electricity per unit area and unit time is significantly increased, water in the electrolyte solution is electrolyzed, oxygen gas is generated at the anode in contact with the electrolyte solution, and the pH of the electrolyte solution decreases. Go.

When the cathode is brought into contact with the developing solution and the developing solution is reduced by energization, bromine ions move from the developing solution to the anode side, but the electrolytic solution generates oxygen gas while energizing. Then, it becomes acidic (H ⁺ is generated), and bromine gas is generated as the bromine ion is accumulated.
If the generated bromine gas is diffused as it is to the outside of the apparatus, there is a problem in that the operator feels an unpleasant odor or feels a throat irritation.

An object of the present invention is to provide a photographic material processing apparatus provided with a processing liquid regenerating device which can regenerate the processing liquid efficiently without adversely affecting the processing performance of the photographic photosensitive material.

[0008]

The above objects of the present invention are achieved by the following items (1) to (6). (1) An electrode is installed in each of the three liquid storage chambers, which are partitioned by two diaphragms and are connected in series, and the electrode groups are serially connected in the order of the first chamber, the second chamber, and the third chamber, and in that order. A treatment liquid comprising a power source for applying a voltage by setting the potential of the electrode group low and filling the first chamber and the third chamber with a photographic treatment liquid and filling the second chamber with an electrolyte solution and energizing. A photographic light-sensitive material processing device equipped with a reproducing device.

(2) The processing apparatus according to (1), further comprising a flow path for the processing liquid to overflow from the first chamber to the third chamber.

(3) The first electrode is brought into contact with the treatment liquid or washing water which is brought into contact with the electrolyte solution through the diaphragm to be regenerated by the reduction reaction, and the second electrode is brought into contact with the electrolyte solution, and through the other diaphragm. The third electrode is brought into contact with a treatment liquid or washing water that is brought into contact with the electrolyte solution and regenerated by an oxidation reaction, and the first electrode, the second electrode, and the third electrode are connected in series in this order, and A method for regenerating a photographic processing solution, characterized in that the electric potential of the electrode group is set low and a voltage is applied to regenerate the processing solution or rinsing water.

(4) The first electrode is brought into contact with the bleach-fix solution which is in contact with the electrolyte solution through the diaphragm, and the second solution is added to the electrolyte solution.
The third electrode is brought into contact with the bleach-fixing solution which is brought into contact with the electrode and is brought into contact with the electrolyte solution through another diaphragm, and the first electrode, the second electrode
A photographic processing liquid regenerating characterized in that the electrode group and the third electrode are connected in series in this order, the potential of the electrode group is set low in this order, and a voltage is applied to regenerate the bleach-fixing solution. Method.

(5) In two adjacent processing tanks filled with the photographic processing solution, the liquid level of the upstream processing tank in the photosensitive material conveying direction is set higher than that of the downstream processing tank to process each processing liquid. The tank is filled with a photosensitive material passage from the upstream processing tank to the downstream processing tank so that the photosensitive material can pass above the liquid surface of the upstream processing tank and above the liquid surface of the downstream processing tank. A processing device characterized by being densely provided.

(6) In two adjacent processing tanks filled with the photographic processing solution, the liquid level of the upstream processing tank in the photosensitive material conveying direction is set lower than that of the downstream processing tank to process each processing liquid. A process in which a photosensitive material is filled in a tank and a photosensitive material passage from the upstream processing tank to the downstream processing tank is provided liquid-tight below the liquid surface of the upstream processing tank so that the photosensitive material can pass therethrough. apparatus.

In the above configurations (1) to (4), when three electrode groups are connected in series and a voltage is applied, the highest potential electrode among these is the anode, the lowest potential electrode is the cathode, and the intermediate potential electrode is the intermediate potential electrode. It can be regarded as a neutral pole. Therefore, in the following description, they may be referred to as an anode, a neutral electrode, and a cathode in descending order of potential. The first electrode of the first chamber is a cathode, and the third electrode is
If the third electrode of the chamber is the anode, the first electrode has the lowest potential, the third electrode has the highest potential, and the second electrode connected between them has the third potential and the third potential. The potential is between that of the electrodes.

The second chamber is filled with the electrolyte solution, but the photographic processing liquids filled in the first chamber and the third chamber may be the same or different. A suitable processing solution for filling with the same solution is a bleach-fix solution. As a combination of processing solutions in which different solutions are preferably filled, enumerating the liquid species in the order of the cathode side and the anode side, a negative developing solution and a negative bleaching solution, a negative fixing solution and a negative bleaching solution, and a negative fixing solution. Rinsing water, etc. In addition,
Neither the first chamber nor the third chamber is filled with washing water for regeneration treatment.

In the configuration of the above (5), the above (1) to
It is more preferable to apply the treatment liquid regenerator or method of (4). It is particularly preferable to apply the configuration of (5) above between the developing tank and the fixing tank. Further, it is particularly preferable for the treatment within 60 seconds in one tank.

Particularly preferred by applying the configuration of the above (6) is a step of treating with a multistage cascade such as a water washing tank, a rinse tank and a stabilizing tank. Further, it is particularly preferable for the treatment within 60 seconds in one tank. When a light-sensitive material is processed by this kind of multi-stage cascade, it is preferable to introduce a part of the processing liquid into a reverse osmosis membrane device for regeneration.

[0018]

In the treatment liquid regenerator according to the present invention, the electrodes provided in each chamber of the three liquid storage chambers, which are partitioned by two diaphragms and are connected in series, are connected in series, and the electrodes (cathode) of the first chamber and the second chamber are connected. The electrode (neutral electrode) and the electrode (anode) of the third chamber are set to a lower potential in this order, the first and third chambers are filled with the photographic processing liquid, and the second chamber is filled with the electrolytic solution to conduct electricity. By doing so, the second chamber filled with the electrolyte solution can be used as a common energization chamber for the first chamber and the third chamber, and the regenerator can be downsized. Further, since the three chambers are simply partitioned by the partition walls, the number of parts does not significantly increase and the cost can be reduced.
Further, when a bleach-fixing solution is applied, the solution can be efficiently regenerated by energization.

When the treatment liquid regenerated by the reduction reaction is filled in the first chamber and the second chamber is filled with the electrolyte solution and electricity is applied, the oxidized component in the treatment liquid is given electrons from the cathode in the first chamber. It is regenerated and the performance of the processing liquid is restored. Examples of the processing solution regenerated by the reduction reaction include a developing solution and a fixing solution. Examples of the treatment liquid regenerated by the oxidation reaction include bleaching liquid and washing water.

Here, when an anion exchange membrane is used as the diaphragm, the anions in the treatment liquid move into the electrolyte solution,
Unwanted anions are removed from the processing liquid in the first chamber. For example, when the developer having deteriorated performance is filled in the first chamber and electricity is applied thereto, bromine ions in the developer pass through the anion exchange membrane and move into the electrolyte solution. Furthermore, since the electrode of the third chamber has a higher potential than the electrode of the second chamber, if an anion exchange membrane is used as a partition wall that separates the second chamber and the third chamber, the bromine ions that have moved into the electrolyte solution are It further moves through the anion exchange membrane into the liquid in the third chamber.

Therefore, bromine ions are not accumulated in the electrolyte solution in the second chamber. When bromine ions accumulate in the electrolyte solution, electrons are exchanged at the electrode surface to generate bromine gas, but since bromine ions move into the liquid in the third chamber, No bromine gas is generated. It is considered that bromine gas is similarly generated even if bromine ions are accumulated in the liquid in the third chamber. However, when the third chamber is filled with a bleaching solution and the light-sensitive material is brought into contact with the bleaching solution for processing, the developed silver in the light-sensitive material is bleached and rehalogenated.
Incorporation of halogen in the bleaching solution into the light-sensitive material,
Since the pre-bath is a developer and an alkaline solution is brought into the bleaching solution, the halogen content in the bleaching solution does not increase, and p
Since H also does not decrease, bromine gas is not generated in the third chamber.

It is preferable that the processing liquid regenerator is connected to a photosensitive material processing device through a pipe or the like. First
If each of the chamber and the third chamber is connected to the corresponding processing tank of the photosensitive material processing apparatus, the photosensitive material can be processed and the processing liquid can be regenerated. The structure for connecting the processing liquid regenerating apparatus and the photosensitive material processing apparatus is not limited, and the processing liquid regenerating apparatus may be a separate type or an integrated type from the photosensitive material processing apparatus.

The first chamber and the third chamber of the treatment liquid regenerator are also provided.
The chamber is filled with the photographic processing liquid, but the photosensitive material may be directly conveyed into the processing liquids of the first chamber and the third chamber to process the photosensitive material. That is, an energization tank filled with an electrolyte solution may be installed between the processing tanks connected in series in the photosensitive material processing apparatus, and the energization processing may be performed between the energization tank and the processing tank.

As the combination of the treatment liquids for filling the first chamber and the third chamber with different treatment liquids and conducting the electric current treatment, there are the following combinations. 1st chamber 3rd chamber Light-sensitive material conveying direction Color developer Bleach 1st chamber → 3rd chamber Fixing solution Bleaching chamber 3rd chamber → 1st chamber Fixing water Rinse water 1st chamber → 3rd chamber

A bleach-fixing solution is suitable as a processing solution when the same photographic processing solution in the first chamber and the third chamber is filled and an electric current is processed. However, the bleach-fixing process from the first chamber to the third chamber is preferable. It is preferable that the liquid overflows. In the first chamber, the bleach-fix solution is reduced by the cathode and ATS · Ag ⁺ + e ⁻ →
ATS (ammonium sulfite) as a fixing agent is regenerated by the reaction of Ag + ATS, and silver is deposited on the cathode and collected. Further, in the third chamber, the bleach-fixing solution is oxidized by the anode, and EDTA.Fe ²⁺ −e ⁻ → EDTA ·
EDTA.Fe ³⁺ as a bleaching agent is regenerated by the reaction of Fe ³⁺ .

If the bleach-fixing solution of the third chamber is made to flow into the first chamber from the bleach-fixing tank of the light-sensitive material processing apparatus and the bleach-fixing solution of the third chamber is made to flow into the bleach-fixing tank of the processing apparatus, Reproduction processing such as bleach-fix processing can be performed at the same time as the processing of the photosensitive material.

The energization treatment according to the present invention means that a part of the treatment tank is substantially partitioned by an anion exchange membrane, a cathode and an anode are provided through the anion exchange membrane to energize, and no electricity is required 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 anion exchange membrane of an electrode reaction or an ionic compound is proportional to the amount of current flowing through the electrode surface according to Faraday's law. A voltage is applied to cause 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, an unnecessary electrode reaction occurs and the reaction efficiency (current efficiency) with respect to the target is lowered.

Therefore, if a constant current power supply is used, the energization process can be properly controlled only by the time control, but in the case of a power failure or when the power is temporarily cut off, the current is not supplied as set, so this method is used. Is not suitable, and since such a constant current power source is expensive, it is preferable to use a power source that is as inexpensive as possible (battery or secondary battery).

When a battery or a secondary battery is used as a power source, a current decrease due to a voltage decrease occurs and it is difficult to manage the current. 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. To measure current value x time, use an integrating 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 it is sufficient to integrate only the time when the ammeter flows. 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 supply can be reduced if the energization is not performed simultaneously and the time is staggered. 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 rise, which may be undesirable. In order to prevent such a case, it is necessary to keep the film resistance below a certain level. On the contrary, 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 instrument 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 the publication.

For example, in the case of a developing solution, energization is controlled so that the oxidation-reduction potential is within a predetermined range, and when the oxidation-reduction potential exceeds a set upper limit value, the 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 value, energization is started to oxidize the developing solution and raise the potential.

In the present invention, the energization is preferably performed during the processing, and by doing so, the development activity can be maintained during the processing. Then, when the processing is completed and, for example, a signal indicating the completion of the processing of the photosensitive material is received, the energization may be terminated.

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 permeating halide ions such as Br ⁻ accumulated in the developing solution, an anion exchange membrane selectively permeating 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 electricity.
Examples include anion exchange membranes and other permeable membranes. Of these, an anion exchange membrane is preferably used, but 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. . Such anion exchange membranes 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 may 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-
It is preferable to use a commercially available product such as No. 7, Neosepta ACS (manufactured by Tokuyama Soda).

As the permeable membrane, a Yumicron diaphragm (made by Yuasa Battery) used in a storage battery; Torio Higaki, "Fine Electronics and Highly Functional Materials" (CMC, 198).
3rd year), pages 125-132; solid polymer walls; porous polymer plates (for example, xanthone porous film or fiber cloth), porous polyester fiber cloths (for example, Toray Welkey); urethane, polyethylene, polypropylene, etc. A permeable membrane such as a foam wall is used. These can be used instead of the composite porous membrane.

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 having a thickness of μm.

As the electrode used for energization, the cathode, which is one of the electrodes, 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 made of 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 meshed 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 as the electrolyte, NaCl, KCl, LiCl, N
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. Further, a developing solution, a fixing solution, and a waste water of washing water may be diverted.

Even when ion-exchanged water is used as the rinse liquid itself, the rinse liquid after use should be
Salt, which is a fixer component brought into the photosensitive material, is mixed. Therefore, there is no problem in using the waste liquid even with the rinse liquid,
As a result, the amount of waste liquid can be reduced.

As the above-mentioned rinse solution, a usual one may be used, and preferably, one to which antibacterial agents, antifungal agents, dye eluting agents, decolorizing agents and the like are added. Regarding electrolysis conditions, electrode materials, types of exchange membranes, etc., JP-A-3-273237
Those described in Japanese Patent Publication No.

In the present invention, the following photosensitive materials and processing agents can be used. First, the photosensitive material will be described.
The silver halide light-sensitive materials that can be used in the present invention include amateur, industrial, medical, and scientific processing methods such as black and white development, color development, ordinary negative-type processing methods, and positive / negative reversal processing methods. A method, a positive method by chemical inversion, a positive method in which an emulsion has an inversion mechanism, a positive method by diffusion transfer or the like can be used.

The support may be a transparent support, an opaque support or a semitransparent support, and the support has a thickness of 30 to 500 μm.
Level ones can be used. Emulsions include various halogen species and combinations of halogen species, that is, one-component, two-component, and three-component emulsions, those in which the distribution of halogen is changed in the grain formation process, and grains are laminated. Any of the above-mentioned grain structures, those having different core / shell ratios, emulsions with conversion, and junction type emulsions can be used.

Further, as the form of particles, hexahedron, octahedron,
A tetrahedral structure, a mixture thereof, a twin crystal, a flat plate, or a spherical one can be used. As the flat plate, those having various aspect ratios, a mixture thereof or a mixture with other particles can be used. Further, the particle size may be uniform or may have a distribution. For example, less than 0.1 μm, 0.1 to 0.4 μm, 0.4 to 1 μm
m, 1 μm or more and the like, or a single combination.

The emulsion may contain a binder other than gelatin. For example, it is preferable that a natural polymer, a synthetic polymer, or these are dispersed and mixed in various particle sizes.
Also, the allocation may be changed for each layer. These silver halide grains may be made to coexist during the preparation by adsorbing various sensitizing dyes, desensitizing dyes, stabilizers, chemical sensitizers and physical sensitizers. Further, the emulsion mixture may contain various dyes, surfactants, hardeners, oils and the like. An anti-fading agent, an anti-color mixing agent, a nucleating agent, a matting agent, a slip agent, a mordant, a toning agent, a development aid, and a developer may be contained directly or in oil.

Various metals may be added during the grain formation process, or may be added directly to the emulsion. Suitable metals are gold, platinum, rubidium, palladium, iron, cobalt, nickel, iridium, rhodium, silver and the like, but they may be mixed with various chelating agents and used.

The color light-sensitive material may further contain various couplers. Examples thereof include pivaloyl-type / benzoyl-type Y couplers, pyrazolone-type / pyrazoloazole-type M couplers, and phenol-type / naphthol-type C couplers. Furthermore, various DIs as functional couplers
R couplers, colored couplers, polymer couplers, and couplers having various leaving groups can be used.

The light-sensitive material layer can be formed by combining the above-mentioned emulsion and various additives, and in the case of a color light-sensitive material, further combining various couplers. Even if it is a black-and-white light-sensitive material, the functions may be divided into two layers or three layers. In the case of a color light-sensitive material, three layers may be used, and in some cases, the layers may be assembled so that the light is divided into 4 to 5 colors. Good.

Finally, in addition to the emulsion layer, an undercoat layer, an intermediate layer, a protective layer, a peeling layer, a separating layer, a neutralizing layer, a filter layer, a vapor deposition layer, a reflecting layer, a light shielding layer and the like may be provided. Further, a light-sensitive material provided with a back layer for the purpose of curl correction, static prevention, magnetic recording and the like can be used for the back of the support. As a total value of these, the sensitivity is ISO 0.1-IS
O 2000 and gradation of 0.1 to 10 can be used.

The processing agent that can be used in the present invention will be described. As the treatment agent usable in the present invention, any treatment agent such as a treatment agent prepared when a premixed treatment agent is used can be used. Black and white, color developing solution, bleaching solution,
A fixing solution, a bleach-fixing solution, a stabilizing solution, a stop solution, a neutralizing solution, a hardening solution, an intensifying solution, a reducing solution, a supersensitizing solution, a toning solution and the like can be used.

As these treatment liquids, those containing various compounds can be used according to the purpose. For example, in developing solutions, black and white developing agents, color developing agents, development aids, antifoggants, surface development inhibitors, development accelerators, chelating agents, buffers, preservatives, precipitation inhibitors, antisludge agents, tar prevention agents Agents can be added. As a special example, DIR-releasing drug,
A dye developing agent, a color precursor agent, a desensitizer, a ferroe-burn preventive agent, an external coupler, a competitive coupler and the like can also be added.

In addition to these, an alkaline agent for adjusting the pH, an acid agent, various activators for changing the surface tension and the like can be added. These examples may be added in addition to the developer. In addition to these, a fluorescent whitening agent, an image stabilizer, a draining agent, an antifungal agent, an antibacterial agent and the like can be added to the final solution. The processing order of applying these processing agents to the light-sensitive material may be a prescribed order or may be changed depending on the case.

Examples of the processing liquid which can be used in the present invention include those described in JP-A-3-33845, pages 9 to 13. Examples of the light-sensitive material that can be used in the present invention include JP-A-3-33845, No. 13 to
Those described on page 26 can be mentioned.

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 to 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. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, particularly 0.01 to
0.03 mol / l is particularly effective.

Preservatives (eg, sulfite, bisulfite), pH buffering agents (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having the ability to soften water by water are used in the fixing solution, if desired. Or the compounds described in JP-A-62-78551. In the processing of the black-and-white light-sensitive material, the rinsing processing is performed after the fixing processing. This rinse liquid has a function of removing the residual treatment chemical in the previous step, and is used almost synonymously with washing liquid and washing water.

In this rinse treatment, the photosensitive material 1 m
The replenishment amount can be 3 liters or less per ² parts, and in this case, it is preferable that the rinse liquid is provided with a mildew-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. A method of making pure water, a method of blowing ozone, JP-A Nos. 62-115154 and 62-153.
No. 952, No. 62-220951, No. 62-2095.
No. 32 and JP-A-1-91533 can be used.

Furthermore, LF West. “Water Quality
Criteria ”Photo. Sci, & Eng. Vol. 9 No.6 (1965), M.
W. Beach, “Microbiologica1 Growths in Motion-pict
ureProcessing ”SMPTE Journa 1 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.
The compounds described in Japanese Patent Publication No.
It can also be used together as e).

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 in JP-A No. 260, JP-A No. 61-267559 and the like can be referred to.

The details of the black-and-white or color light-sensitive material of the present invention are disclosed in JP-A-1-259359 and the above-mentioned patent documents.

[0063]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment.

FIG. 1 is a schematic plan view of the treatment liquid regenerator, and FIG. 2 is a schematic sectional view. The regenerator comprises three chambers 6 partitioned by two anion exchange membranes 2 and 4 as partition walls,
8 and 10, each of the chambers 6, 8 and 10 has electrodes 12, 14,
16 are installed. The electrodes 12, 14, 16 are connected in series, and the first electrode 12 of the first chamber 6, the second electrode 14 of the second chamber 8 and the third electrode 16 of the third chamber 10 are set in order of lower potential (first One electrode 12 has the lowest potential and the third electrode 16 has the highest potential), and a voltage is applied by the power supplies 18 and 20. Therefore, the first electrode 12 can be regarded as a cathode, the third electrode 16 can be regarded as an anode, and the second electrode 14 can be regarded as a neutral electrode.

The first chamber 6 and the third chamber 10 are filled with a photographic processing liquid for the purpose of regeneration, and the second chamber 8 is filled with an electrolyte solution. Since the second electrode 14 of the second chamber 8 serves as a counter electrode of the first electrode 12 and the third electrode 16, it acts as an anode for the first electrode 12 and a cathode for the third electrode 16. .

The first electrode 12 and the second electrode 14 face each other via the anion exchange membrane 2, and the second electrode 14 and the third electrode 16 face each other via the other anion exchange membrane 4. There is. Since it is preferable that a large amount of treatment liquid be present between the pair of electrodes, each electrode is installed apart from the anion exchange membranes 2 and 4. The second electrode 14 has a bent shape as shown in FIG. 1 or is divided into two and connected so as to be installed apart from the anion exchange membranes 2 and 4. Note that FIG.
In FIG. 2, the second electrode 14 is shown as a flat plate for convenience.

The processing solution which can be regenerated by filling the first chamber is of a type in which the components are reduced by the first electrode 12 which is a cathode and the performance is recovered. For example, a color or black and white developing solution or a fixing solution is used. , A bleach-fixing solution, a reversal solution for processing a color reversal light-sensitive material, a conditioner solution and the like. Further, the treatment liquid which can be regenerated by filling the third chamber is of a type in which the components are oxidized by the third electrode 16 which is an anode and the performance is recovered. For example, a negative bleaching solution, a bleach-fixing solution, and a water washing solution are used. water,
Examples include a rinse solution and a stabilizing solution.

Hereinafter, the treatment liquid regenerator having the above structure will be used.
Regeneration processing of each photographic processing solution will be described, but first, the case of regenerating the developing solution will be described. A large amount of bromine ions eluted from the light-sensitive material are accumulated in the developing solution having deteriorated performance. The first chamber 6 is filled with such a developing solution,
The second chamber 8 is filled with an electrolyte solution to fill the first electrode 12 and the second electrode.
A voltage is applied to the electrode 14. Then, the bromine ions in the developer move toward the second electrode 14, which is the anode, through the anion exchange membrane 2 and are removed from the developer, and as a result, the developer is regenerated. In addition, some of the developing agent oxidized by oxygen in the air is also regenerated.

The bromine ions removed from the developing solution move into the electrolyte solution. At this time, by filling the third chamber 16 with another processing solution and applying a voltage to the third electrode 16 as well, Since the third electrode 16 further acts as an anode, bromine ions in the electrolyte solution move into the treatment solution. If the treatment liquid is a bleaching liquid, the bleaching liquid is in a state of being supplemented with bromine. Therefore, the performance of the bleaching liquid can be restored by filling the third chamber 10 with the bleaching liquid and energizing the bleaching liquid. Here, even if bromine ions in the bleaching solution continue to increase, as shown in FIG. 2, the photosensitive material S is conveyed to the first chamber 6 and the third chamber 10,
By processing the photosensitive material S with the bleaching solution in the third chamber 10, the developing solution adheres to the photosensitive material S and is brought in.
The pH of the bleaching solution does not decrease even when electricity is applied. at the same time,
When the developed silver in the light-sensitive material is oxidized, halogen in the bleaching solution is consumed as a rehalogenating agent, so that a large amount of bromine ions are not accumulated and bromine gas is not generated.

Further, the migration of bromine ions in the bleaching solution can reduce the content of bromine contained in the components of the bleaching replenisher. In the bleaching solution with deteriorated performance, E
Although it contains a large amount of DTA.Fe ^{2+, the} bleaching solution is oxidized by the third electrode 16 which is an anode, and EDTA.Fe ²⁺
The reaction of −e ⁻ → EDTA · Fe ³⁺ regenerates EDTA · Fe ³⁺ as a bleaching agent.

Next, the case where the first chamber 12 and the third chamber 16 are filled with the bleach-fixing solution and reproduced is described. The bleach-fixing solution with deteriorated performance contains a large amount of ATS.Ag ⁺ . Therefore, when the bleach-fixing solution is filled in the first chamber 6 and the electric current is applied, the first electrode 12 causes ATS · Ag ⁺ + e
^- → Ag ° + ATS reduction reaction occurs, so ATS which is a fixing agent is regenerated. Further, since silver is deposited on the first electrode 12, it is possible to recover the silver eluted from the photosensitive material S into the bleach-fixing solution. Further, when the bleach-fixing solution is filled in the third chamber 10 and an electric current is applied thereto, the same E
DTA / Fe ²⁺ is oxidized to EDTA / Fe ³⁺ ,
The bleach-fix solution is regenerated.

Here, by arranging piping so that the bleach-fix solution overflows from the first chamber 6 to the third chamber 10, silver is recovered and ATS is regenerated in the first chamber 6, and then the third chamber is recovered. 10, EDTA.Fe ³⁺ can be regenerated, and silver can be recovered from the bleach-fixing solution and the bleach-fixing solution can be efficiently regenerated. For such reprocessing of the bleach-fixing solution, it is preferable that the processing solution reclaiming apparatus is separate from the photosensitive material processing apparatus. Next, a description will be given of a photosensitive material processing apparatus which is suitable for being connected to the processing liquid regenerating apparatus having the above-mentioned configuration or integrally configured.

FIG. 3 is a schematic sectional view of a developing device for a color negative photosensitive material. The processing equipment is a developing tank N1 and a bleaching tank N.
2, a fixing bath N3, two water washing baths NS, and a stabilizing bath N4 are connected in series, and the photosensitive material S is processed by sequentially dipping it from a developing solution according to the processing steps. The developing tank N1 and the bleaching tank N2 are connected to the processing solution regenerator described above, and the developing solution and the bleaching solution are circulated between the regenerator and the developing solution as shown by arrows. Further, the developing tank is provided with a floating lid 22 for covering the liquid surface of the photosensitive material S other than the passage for the purpose of preventing air oxidation and mixing of the bleaching solution.

The bleaching solution surface is set lower than the developing solution surface, and the photosensitive material S moves to the bleaching tank N2 through the passage 24 formed in the partition between the developing tank N1 and the bleaching tank N2. The passage 24 is formed at a position lower than the developing solution surface and higher than the bleaching solution surface. The passage 24 is liquid-tight so that the photosensitive material S can pass therethrough. FIG. 5 shows an example of the passage structure. A pair of elastic blades 3 are provided in the opening 28 formed in the partition wall 26.
0 is provided, and the tip of the blade 30 elastically contacts to maintain a liquid-tight state.

In the conventional processing apparatus, the photosensitive material S moves from the developing tank N1 to the bleaching tank N2 through the upper part of the partition wall.
In the above structure, the photosensitive material S enters the bleaching solution without passing through the upper part of the partition. Therefore, the crossover time required for the photosensitive material S to exit the developing solution and enter the bleaching solution can be shortened as compared with the conventional case. In a treatment system that performs all treatment steps quickly, the crossover time accounts for a large proportion of all treatment steps, so if the crossover time is shortened, dipping time in the liquid will be maintained as it is and good treatment will be performed. Moreover, the total processing time can be shortened. In particular, the above configuration is effective for rapid processing within 60 seconds in one step.

For the purpose of shortening only the developing time, the passage may be formed below the bleaching liquid surface, but in this case, since the passage is not completely liquid-tight, the bleaching liquid is formed especially when the light-sensitive material S passes through. It gets mixed in the developer. However, since the passage 24 is the boundary between the developing solution and the air as in the above-described configuration, the bleaching solution does not mix with the developing solution through the passage 24.

The fixing liquid surface may be higher than the bleaching liquid surface. The level of the washing water is lower than the level of the fixing liquid, and the passage 2 is located at a position lower than the level of the fixing water and higher than the level of the washing water.
4 are formed. Therefore, as described above, the passage 2
The washing water does not mix with the fixing solution through the step 4, and the fixing solution is not diluted by the washing water. Two flush tanks N
The passage 24 between S is preferably submerged in the liquid, and washing water flows from the washing tank NS on the downstream side in the photosensitive material transport direction to the washing tank NS on the upstream side through the passage 24 to obtain a preferable counterflow state.

The developing processing apparatus shown in FIG. 3 is constructed so that the liquid levels of the developing tank N1 and the bleaching tank N2 are sequentially lowered, but like the developing processing apparatus shown in FIG.
It may be configured such that each liquid surface from the fixing tank to the fixing tank N3 sequentially decreases. According to this structure, the fixing solution is not mixed in the bleaching solution, and the performance of the bleaching solution can be prevented from being deteriorated. Further, the liquid level may be sequentially increased after the washing tank NS. According to this structure, the washing water and the stabilizing liquid are likely to be in a countercurrent state opposite to the conveying direction of the photosensitive material even under the influence of water pressure due to the liquid level difference, and a preferable countercurrent state can be obtained.

The washing tank NS is preferably equipped with a reverse osmosis membrane device 32 for the purpose of regenerating the washing water and reducing the replenisher. The reverse osmosis membrane device 32 introduces the washing water in the upstream side washing tank NS, replenishes the cleaning solution filtered from this into the downstream side processing tank as a replenishing solution, and returns the remaining solution to the downstream side washing tank NS. Is. With this configuration, the replenishing solution for washing can be reduced together with the reduction of the replenishing solution due to the regeneration of the processing solution by energization, so that the waste liquid generated in the photosensitive material processing apparatus can be reduced.

[0080]

EXAMPLES Photosensitive material: Sample 1-1 (color negative film) of Example 1 of JP-A-3-240039 Processing steps and formulation: Same as Example 5 of JP-A-2-250052 (however, N1, The amount of replenishing liquid of N2 was set to 1/5 of the prescription.) Processing machine: A modified machine in which Fuji Photo Film minilab FP-350 was modified as shown in FIG. 4 Energizer: Configuration shown in FIGS. 1 and 2. Anion exchange membrane: AM-3 manufactured by Tokuyama Soda Cathode: Stainless SUS316 plate (thickness 3 mm, area 3 dm ² ) Neutral pole: Stainless SUS316 plate (thickness 3 mm, area 1.5 dm ² 2 wires) Anode : Kureha Chemical's Kureha sheet (5 mm thick carbon sheet, area 3 dm ² ) Applied voltage and current density: 1.2 V between the cathode and the neutral pole, and 0.3 A / dm ² between the neutral pole and the anode. 2V, 0.3A / dm ² color negative film 30 seconds for each developing process

Under the above conditions, 100 color negative films were processed per day and run for 2 weeks. The color negative films and the processing solutions after development had good photographic performance. Moreover, the waste liquids of N1 and N2 were reduced to 1/5.
In this way, stable photographic performance was obtained by shortening the air time from N1 to N2. Moreover, N2
There was no photographic abnormality due to mixing of the processing solution from N1 to N1.

[0082]

According to the present invention, in the treatment liquid regenerator, the three chambers partitioned by the diaphragm are continuously provided, and the second chamber filled with the electrolyte solution is energized between the first chamber and the third chamber. In this case, the electrode in the second chamber is shared as the counter electrode of the electrode in the first chamber and the electrode in the third chamber, so that the treatment liquid can be regenerated at two locations, but the treatment liquid can be regenerated. The device can be made compact and inexpensive.

Further, since the treatment liquid can be regenerated satisfactorily even with a low energization amount, the water in the electrolyte solution is not electrolyzed, the pH of the electrolyte solution does not drop significantly, and the developing solution is developed in the first chamber. Even if bromine ions move into the electrolyte solution in the second chamber, the bromine ions move further into the third chamber, so that bromine gas is generated from the electrolyte solution. There is nothing to do. Further, when the photosensitive material is processed by filling the bleaching solution in the third chamber, the developed silver in the photosensitive material is bleached and rehalogenated, so that the halogen in the bleaching solution is taken into the photosensitive material. In addition, since the pre-bath is a developing solution and an alkaline solution is brought into the bleaching solution, the halogen in the bleaching solution does not increase and the pH does not decrease, so bromine gas is not generated in the third chamber. Absent.

[Brief description of drawings]

FIG. 1 is a schematic plan view of a treatment liquid regenerator according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of a treatment liquid regenerator which is an embodiment of the present invention.

FIG. 3 is a schematic sectional view of a photosensitive material processing apparatus that is an embodiment of the present invention.

FIG. 4 is a schematic sectional view of a modified example of the photosensitive material processing apparatus according to the embodiment of the present invention.

FIG. 5 is a configuration diagram of a passage.

[Explanation of symbols]

 S Photosensitive material 2, 4 Anion exchange membrane 6, 8, 10 Chamber 12, 14, 16 Electrode 18, 20 Power supply 22 Float lid 24 Passage 26 Partition wall 30 Elastic blade 32 Reverse osmosis membrane device

Claims (6)

[Claims] 1. An electrode is installed in each chamber of three liquid storage chambers which are partitioned by two diaphragms and are connected in series, and the electrode group is connected in series in the order of a first chamber, a second chamber and a third chamber, and And a power source for applying a voltage by setting the electric potential of the electrode group low in order, the first and third chambers are filled with a photographic processing liquid, and the second chamber is filled with an electrolyte solution to conduct electricity. A photographic light-sensitive material processing apparatus equipped with a processing liquid recycling apparatus. 2. The processing apparatus according to claim 1, further comprising a flow path for a processing liquid to overflow from the first chamber to the third chamber. 3. The first electrode is brought into contact with a treatment liquid or washing water which is brought into contact with an electrolyte solution through a diaphragm and is regenerated by a reduction reaction,
The second electrode is brought into contact with the electrolyte solution, and the third electrode is brought into contact with the treatment liquid or washing water which is brought into contact with the electrolyte solution through another diaphragm and is regenerated by an oxidation reaction, and the first electrode, the second electrode,
Regeneration of the treatment liquid or washing water by connecting the electrode group in series in the order of the third electrode, applying a voltage by setting the potential of the electrode group low in the order, and regenerating the treatment liquid or the washing water. Method. 4. A bleach-fixing solution which is brought into contact with an electrolyte solution through a diaphragm, is brought into contact with a first electrode, a second electrode is brought into contact with the electrolyte solution, and a bleach-fixing solution which is brought into contact with the electrolyte solution through another diaphragm. The bleach-fixing is performed by bringing the third electrode into contact, connecting the electrode group in series in the order of the first electrode, the second electrode, and the third electrode, setting the potential of the electrode group low in this order, and applying a voltage. A method for reclaiming a photographic processing solution, which comprises reclaiming the solution. 5. In two adjacent processing tanks filled with a photographic processing solution, the liquid level of the upstream processing tank in the photosensitive material conveying direction is set higher than the liquid level of the downstream processing tank so that each processing tank can be processed. Liquid passage in the photosensitive material passage from the upstream processing tank to the downstream processing tank so that the photosensitive material can pass through below the liquid surface of the upstream processing tank and above the liquid surface of the downstream processing tank. A processing device provided in the. 6. Two processing tanks adjacent to each other filled with a photographic processing solution are set so that the liquid level of the upstream processing tank in the photosensitive material conveying direction is set lower than that of the downstream processing tank. And a photosensitive material passage from the upstream processing tank to the downstream processing tank is provided below the liquid level of the upstream processing tank in a liquid-tight manner so that the photosensitive material can pass therethrough. .