JP3050350B2 - Processing method and processing apparatus for silver halide photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for processing a silver halide light-sensitive material.

[0002]

2. Description of the Related Art A silver halide light-sensitive material (hereinafter, referred to as a light-sensitive material) is subjected to processes such as development, desilvering, washing with water, and stabilization after exposure. A developing solution is used for development, a bleaching solution, a bleach-fixing solution, and a fixing solution are used for desilvering, tap water or ion-exchanged water is used for washing, and a stabilizing solution is used for stabilizing processing. The temperature of each processing solution is usually adjusted to 30 to 55 ° C., and the photosensitive material is immersed in these processing solutions for processing.

In such processing, a processing apparatus such as an automatic developing machine is usually used, and the photosensitive material is sequentially transported between processing tanks filled with the above-mentioned processing solution and processed.

Among such processes, in a desilvering process using a processing solution having a fixing ability such as a bleach-fixing solution or a fixing solution, a silver complex salt, or a bromide ion or iodide is contained in the processing solution during the processing. A phenomenon occurs in which halide ions such as ions are accumulated, the activity of the fixing component is reduced, and fatigue occurs.

In order to prevent this, a method has been adopted in which a replenisher of a processing solution having a fixing ability is replenished during processing, and a used processing solution is discharged from a processing tank as an overflow solution.

In the processing of such photosensitive materials, miniaturization and space saving have been demanded in recent years due to the rise of mini-labs and the like. It is desired to reduce the amount.

[0007] This is also desired in recent years because environmental conservation and resource saving have been desired.

Above all, it is particularly desirable from such a viewpoint that silver is recovered from the overflow solution and regenerated at the same time.

In fact, various attempts have been made for such a silver recovery method. 1) A method in which a metal having a higher ionization tendency than silver is brought into contact with a liquid (metal replacement method); 2) An inert silver salt is formed. 3) a method using an ion exchange resin (ion exchange method), 4) a method of depositing silver on a cathode of an electrolyzer (electrolysis method), and the like. .

[0010] Details of these methods can be found in MLScherl.
`` Present Status of Siver Recovery in Motion-Pi '' by bo
cture Laboratories. J. SMPTE., 74, pp. 504-514, 19
65 years).

More specifically, in the method 1), a method is known in which iron or aluminum is replaced with silver using, for example, steel wool or aluminum wool.

As the method 2), for example, a method is known in which silver sulfide is precipitated by adding sodium sulfide to recover silver.

In the reduction precipitation method, a method using hydrosulfite or the like is known.

The electrolysis method 4) itself is a method which has been known for a long time, and many examples of these prior arts are described in, for example, the description of M-L, Schreiber (J. of the SMPTE 74, p. 505, 1965). You can see. Further, in this method, various improvements have been made in improving the current efficiency and controlling the current density and the like during electrolysis.
Such an improved method is disclosed in Japanese Patent Application No. 63-25338.
It is described in the literature cited in the issue.

However, in the above method 1), silver can be recovered from the discharged fixing solution, but a fixing solution containing a large amount of iron ions and aluminum ions is formed, and precipitation of hydroxide and the like is generated. There were difficulties in reusing.

In the method 2), sodium sulfide has a strong odor, and silver particles are hardly filtered and hardly reused. On the other hand, in the reduction precipitation method, silver particles are finely filtered and collected. It takes a long time, it takes time to collect,
There is a practical problem in that the characteristics of the processing solution change.

The above method 3) has no problem in regenerating or reusing the processing solution, but the silver complex salt adsorption capacity of the resin is extremely small and is not practical. Furthermore, since the ion exchange resin is expensive, it has been attempted to regenerate and reuse the ion exchange resin, but the regeneration operation was complicated.

Further, in the method 4), although silver can be recovered efficiently, the fixing solution components sodium thiosulfate and the preservative are oxidatively decomposed to a considerable extent, and the above-mentioned chemicals are replenished when reused. And the operation was complicated. In addition, the size of the apparatus is large, and it is not suitable for installation in a minilab or the like.

Accordingly, the applicant of the present invention has disclosed in
As described in Japanese Patent Publication No. 656, first, silver elements accumulated in a processing solution having a fixing ability can be efficiently and easily removed, and as a result, the use of a processing solution having a fixing ability can be achieved. Another object of the present invention is to provide a method for processing a silver halide light-sensitive material in which the amount can be reduced and silver can be easily recovered. The purpose of the present invention is to provide a processing apparatus for a silver halide light-sensitive material capable of developing a silver halide light-sensitive material after exposure and processing it with a processing solution having a fixing ability. Contacting to form a water-insoluble polymer silver complex and removing silver element from the processing solution. " C that performs processing with fixing ability An apparatus for processing a silver genide photosensitive material, comprising: a processing tank filled with a processing solution having a fixing ability; and a circulation path connected to the processing tank, wherein a polymer silver complex is formed in the circulation path. A silver halide light-sensitive material processing apparatus characterized by providing a silver element removing means containing a complexing agent. "

According to the method and apparatus for processing a silver halide light-sensitive material proposed above, complexing occurs when a silver halide light-sensitive material (hereinafter, light-sensitive material) is developed and then processed with a processing solution having a fixing ability. Agent, preferably a polymer ligand is brought into contact with the treatment liquid, and a silver element contained in the treatment liquid and the complexing agent form a polymer silver complex and are removed as precipitates. The silver element in the processing solution can be efficiently and easily removed. This improvement in the removal efficiency is considered to be due to the fact that the complexing agent is water-soluble, resulting in a high silver capture rate, and such a complexing agent is also inexpensive. For this reason, the replenishment amount of the processing solution can be reduced, and silver recovery becomes easy. In addition, since the silver element removing means configured so that the processing solution having the fixing ability and the water-soluble complexing agent come into contact with each other is provided in the circulation path of the processing tank, the processing apparatus can be downsized. it can.

[0021]

According to the above-mentioned method and apparatus for processing a silver halide photosensitive material, as described above, the silver element can be effectively removed from the processed processing solution. Since the silver element removed from the silver element removing means is a precipitate of a high molecular silver complex, the liquid content was extremely high and it was difficult to handle. In particular, the collected precipitate is generally transported to another factory or the like, where the silver element is recovered from the precipitate. However, since the precipitate is almost liquid, general transport is performed. Since the trader does not want to handle it, it has to be transported specially, and there is a problem that this transport is costly.

Further, it is desired to more effectively recover the elemental silver from the processed processing solution and regenerate the processing solution.

Therefore, the present invention firstly eliminates the above-mentioned conventional drawbacks by efficiently removing the polymer silver complex precipitate in a liquid state to obtain a recovered product having a reduced liquid content. It is an object of the present invention to provide a processing method and a processing apparatus for a silver halide light-sensitive material which can be performed.

A second object of the present invention is to provide an apparatus for processing a silver halide light-sensitive material capable of more efficiently regenerating a processing solution and recovering a silver element in addition to the above objects. It is.

[0025]

Means for Solving the Problems] Such objects have been achieved by the present invention described below (1) to (5) described. (1) When the exposed silver halide light-sensitive material is developed and processed with a processing solution having a fixing ability, the processing solution after the fixing process is brought into contact with a complexing agent to form a water-insoluble silver complex. In the method for processing a silver halide light-sensitive material, a precipitate slurry formed by precipitation of the silver complex is removed, and silver is recovered from the precipitate slurry.
While applying pressure at a pressure of not less than Kg / m ^{2 and not} more than 15 kg / m ²
Use a current applying pressurizing means for applying a current, and
0.3 A to 6 at a voltage of 1 V to 30 V in the pressing means
A method for processing a silver halide light-sensitive material, wherein a current of A or less is applied to drain a precipitate slurry. (2) when the silver halide photosensitive material is developed and processed with a processing solution having a fixing ability, the processing solution after the fixing process is brought into contact with a complexing agent to form a water-insoluble silver complex; A precipitate slurry formed by precipitation of the silver complex is taken out, and in a silver halide photosensitive material processing apparatus for recovering silver from the precipitate slurry, the precipitate slurry formed of the conductive material and introduced into the silver halide light-sensitive material is used in the following manner. A current applying pressurizing means for applying a current while applying a pressure of 5 kg / m ² or more and 15 kg / m ² or less ;
Use, processor silver halide light-sensitive material characterized by comprising a current applying pressure means for applying the following current 0.3A or 6A in 30V or less voltage than 1V on the current application and pressing means . (3) The current applying and pressurizing means includes an endless liquid-permeable conveyor belt having at least a surface formed of a conductor, and at least a surface formed of a conductor, and disposed on the conveyor belt. a pressure roller for pressing the precipitate slurry with the conveyor belt, the silver halide photosensitive above (2) wherein and a power source for applying a current between the conveyor belt and the pressure roller Material processing equipment. (4) An apparatus for processing a silver halide photosensitive material which performs a process having a fixing ability on the developed silver halide photosensitive material,
It has a processing tank filled with a processing solution having a fixing ability, and a circulation path connected to the processing tank, and includes a silver element removing unit containing a complexing agent that forms a polymer silver complex in the circulation path. A silver halide light-sensitive material processing apparatus, wherein the silver element removing means contains the complexing agent and causes the complexing agent to contact a fixing-processed processing solution;
A silver halide light-sensitive material processing apparatus, comprising: a second tank formed so as to surround the first tank and receiving an overflow solution from the first tank. (5) (2) or (3) above and a current applying pressure means described (4) processing apparatus of the silver halide light-sensitive material as described.

[0026]

In the present invention, while applying a current to the sediment slurry while pressurizing the sediment slurry, the liquid is removed from the sediment slurry, so that the liquid is efficiently removed. Removal can now be performed. As a method of removing the liquid component, it is conceivable to simply pressurize, but according to the experiment of the present invention, the liquid content was reduced by less than 20%. On the other hand, according to the present invention, the liquid content could be reduced by about 75%.

In the double element silver removing means of the present invention, the processing liquid in the first tank can be kept warm by the processing liquid in the outer tank, that is, the second tank. The temperature can be maintained, the reaction can be performed efficiently, and the two-stage treatment with the first tank and the second tank is performed, so that a more accurate recovery operation can be performed.

[0028]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail. In the method for processing a silver halide light-sensitive material of the present invention, when processing a silver halide light-sensitive material after development (hereinafter referred to as a light-sensitive material) with a processing solution having a fixing ability, the processing solution and a complexing agent are used. The contact is carried out to form a water-insoluble polymer silver complex, whereby the treatment is performed while removing the silver element from the treatment liquid.

The complexing agent used in the present invention is usually a high molecular weight ligand. The polymer ligand is a so-called chelate resin, and has a function of forming a complex with the ligand in the polymer and selectively collecting silver ions in the processing solution.

In this case, the formed polymer silver complex is insoluble in water. This is often a chelate polymer in which a silver chelate is formed in or between polymers, but is a polymer in which silver is simply coordinated and added without forming a chelate ring. You may.

In the above-mentioned high molecular ligand, the coordinating atom when forming a complex with silver is preferably N or S. Specific examples of the high molecular ligand having such a coordinating atom are as follows. For details, reference can be made to the description of “Chelate Resin / Ion Exchange Resin”, edited by Hojo Shusei, Kodansha Scientific (1976), pp. 8-20, and the references cited therein.

Among these, in the present invention,
A polymer ligand containing S as a coordinating atom is preferred.

[0033] Specifically, dithiocarbamic group and a group derived therefrom (-NH-CS ₂ M) as a coordinating group, is particularly preferable that a thiol group and a group derived therefrom (-SM).

In this case, the coordinating group is preferably a water-soluble group. In the above, M is H, an alkali metal such as Na, an alkaline earth metal such as Ca, a metal cation such as Al or the like. In some cases, onium ions and the like are preferable.

By having such a water-soluble coordinating group, the reaction with the silver element in the processing solution easily proceeds, and the removal efficiency of the silver element is improved.

Such a polymer ligand is preferably used as an aqueous solution or dispersion. The concentration in the aqueous solution may be about 2 to 100%. As in the present invention, when the solution after the treatment is reused, the concentrated solution does not have to be diluted, so that the concentration is more preferably about 40 to 80%, so that it is easier to use.

The number average molecular weight of the high molecular weight ligand is 1
It is preferably at least 000, more preferably at least 30,000, particularly preferably 30,000 to 300,000.

The number of coordinating groups per molecule is 1 mol or more,
More preferably, the amount is 10 to 250 mol.

Further, the solubility of the polymer ligand in water is 1 g or more, more preferably 40 to 9 per 100 g of water.
It is preferably 00 g.

The use of such a compound makes it easy to precipitate the formed high molecular silver complex, and facilitates the separation from the processing solution to be reused.

Specific examples of the polymer ligand preferably used in the present invention are shown below, but are not limited thereto (M is as defined above, and l, m,
n represents a positive integer).

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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In the present invention, the high molecular ligand may be added in a smaller amount than the equivalent of the silver element accumulated in the processing solution, and the high molecular ligand may be added in an amount of 0.6 to 1.3 per mole of silver. Mole, preferably about 0.8 to 1.0 mole.

Even with such addition, the silver element in the processing solution can be sufficiently removed, and even if the high molecular ligand remains in the processing solution to be reused, the addition in the above range does not occur. It does not affect photographic performance.

The complexing agent in the present invention may be a low molecular polydentate ligand which forms a polymer while coordinating with silver ions to form a polymer silver complex.

In these, the molecular weight of the resulting high molecular silver complex is 1,000 or more, preferably 5,000 to 2
It is good to be 0000. Then, about 1 to 0.7 g of silver is collected in 1 g of the precipitated silver complex.

In the present invention, as described above, 錯 or more, preferably １ ／ or more, of the dissolved silver ions in the processing solution having the fixing ability is removed by using the complexing agent.

Usually, such dissolved silver ions vary depending on the type of the light-sensitive material and the replenishment amount of the processing solution to the light-sensitive material, but are about 2 to 20 g / l as silver, and 0.01 to 4 g / l by removal. About.

Specifically, taking a photographic material as an example, the dissolved silver ion becomes 5 g / l or more as silver, but preferably becomes 2 g / l or less by removal. Further, in the photosensitive material for printing, the dissolved silver ion becomes 2 g / l or more as silver, but preferably becomes 0.5 g / l or less by removal.

The processing with a processing solution having a fixing ability in the present invention is a continuous processing using a replenishing method, even if it is a batch processing for processing a fixed amount of a photosensitive material without replenishment. , But in general,
It is preferable to perform continuous processing. Further, the processing tank in the silver element removing means is composed of a first tank and a second tank surrounding the first tank. The first tank functions as a reaction tank. The second tank receives the overflow from the first tank and keeps the temperature of the first tank with the filled processing liquid, and further takes out the sediment slurry precipitated here, and adjusts the silver content of the regenerated processing liquid. It performs the effect of further lowering.

In the batch treatment, all or a part of the treatment liquid may be appropriately taken out, and a high molecular ligand may be added to the treatment liquid to remove the silver element.

In the continuous treatment, a high molecular ligand may be added to the overflow solution to remove the silver element, and then reused as a part of the replenisher.

However, from the viewpoint of the removal efficiency of the silver element and the miniaturization of the apparatus, it is necessary to provide a circulation path in the treatment tank, and to contact the polymer ligand in this circulation path to remove the silver element. Is preferred.

In the present invention, the treatment is performed while the silver element is removed.
The process may be started or stopped, and there is no particular limitation, but it is preferably performed during the process.

In the present invention, by processing with a processing solution having a fixing ability while removing silver element, the amount of this processing solution can be reduced by about 20 to 80% in batch processing. In continuous processing, the replenishment rate can be reduced by about 20 to 80%.

Even if the amount of the processing solution is reduced in this way, no desilvering failure occurs. In some cases, the processing time can be shortened.

Further, the amount of components in the processing solution having a fixing ability can be reduced.

Specifically, all components such as a fixing agent are added in amounts of 20 to 8
It can be reduced by about 0%. In the present invention,
Further, a method of removing a halogen element with an ion exchange resin or the like can be used together.

The contact between the fixing solution and the aqueous solution of the polymer ligand is desirably performed by mixing with vigorous stirring. In addition, when the precipitate is generated, it is preferable that the precipitate is left still.

As described above, the silver element is initially recovered as a precipitate slurry. The sediment slurry is 40% to 50%.
It is quite liquid containing about% of liquid.

Therefore, in the present invention, a liquid component is removed from the precipitate slurry for the subsequent treatment.

The removal of this liquid component is performed by adding
This is performed by applying pressure and current.

The above pressure may be a weak pressure of about 1.5 to 15 kg / m ² . This is because, as described later, by applying a current to the sediment slurry together with this pressurization, this level is sufficient. Also,
This is because a continuous operation using an endless belt, a roller or the like can be performed at such a pressure.

The current is a voltage of about 1 to 30 V,
A current having a current of about 0.3 to 6 A is used. Since the current used in the present invention is of such a small voltage and current, the danger is extremely low.

When performing continuous work using an endless belt, a roller, etc., the sediment slurry is discharged at a rate of 3 minutes per minute.
It is desirable to process about 100 cc each.

Next, an apparatus for processing a silver halide photosensitive material according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a schematic configuration diagram of an automatic developing machine which is a processing apparatus for a silver halide photosensitive material according to an embodiment of the present invention. In this figure, reference numeral 1 denotes an automatic developing machine. The automatic developing machine 1 includes a fixing tank 2 as one of processing tanks, and the fixing tank 2 is filled with a fixing solution 3 for fixing a photosensitive material (not shown). The replenisher 5 stored in the replenisher tank 4 is automatically replenished to the fixing tank 1 in accordance with the degree of fatigue of the fixer 3.

After the fixing solution 3 having been subjected to the fixing process is taken out of the fixing bath 2 and desilvered,
A circulation path 10 for performing an operation of returning to the replenishment tank 4 is connected.

The circulation path 10 is provided with a silver element removing device 11 for performing a desilvering process of the fixing solution 3. The silver element removing device 11 mainly includes a first element that functions as a reaction tank.
A tank 12 and an annular second tank 13 provided so as to surround the tank 12 are provided.

The processed or fatigued fixing solution 3 from the fixing tank 2 is supplied into the first tank 1 via a pipe 14, preferably at the bottom thereof. A vessel 16 is connected to the pipe 14 via a pipe 15. The vessel 16 contains an aqueous solution (or aqueous dispersion) 17 of a polymer ligand (chelate resin). The aqueous solution 18 of the polymer ligand contained in the container 16 is supplied to the pipe 14 via the pipe 15, where it is brought into contact with the fixing solution 3 flowing in the pipe 14.

In this case, the concentration of the aqueous solution 17 may be 2 to 100%, preferably 40 to 80%, as described above.

With such a concentration, the silver element is efficiently removed.

The first tank 12 is provided with a vertical pipe 19 extending substantially vertically therethrough. The upper end of this vertical pipe 19 is installed at a predetermined position lower than the upper end of the first tank 12 as shown in the figure, and the lower end thereof penetrates the bottom plate of the first tank 12 downward and the second tank 13
, Whereby the supernatant of the processing liquid in the first tank 12 is introduced and supplied into the second tank 13.

In the second tank 13, the unprecipitated silver complex component in the introduced processing solution is precipitated here to obtain a more pure processing solution.

A processing liquid outlet 20 is provided at a predetermined height of the second tank 13. The outlet 20 is connected to a tank 22 via a pipe 21. A container 24 is connected to the pipe 21 via a pipe 23. The container 24 contains a regenerant solution 25 for activating the processing liquid supplied from the second tank 13.

As the regenerating agent, a fixing agent component reduced by taking out the photosensitive material, for example, a thiosulfate, a sulfite, a chelating agent, or the like can be used. 7 to 3 mol / l, 0.1 to 0.3 mol / l for sulfite, 0.01 to 0.1 for chelating agent
Desirably, it is about 0.05 mol / l.

The regenerant solution 25 from the container 24 is supplied to the pipe 14 through the pipe 23, where it is brought into contact with the fixing solution flowing in the pipe 21.
The fixer 3 is activated by the action of the regenerant solution 25 and is once stored in the tank 22, whereupon the pump 2
The replenishment tank 4 is supplied to the replenishment tank 4 through the pipe 27 by the pipe 6, and is used again.

The bottoms of the first tank 12 and the second tank 13 are each provided with a slanted bottom, and the lower part of the slant is used to discharge the formed slurry of the polymer silver complex precipitate out of the tank. A first discharge unit 28 and a second discharge unit 29 for performing the operation. The first discharge part 28 and the second discharge part 29 are provided with a first on-off valve 30 and a second on-off valve 31, respectively, and the above-mentioned sediment slurry is appropriately discharged from the first tank 12 and the second tank 13. It is designed to discharge.

The discharge part of the sediment slurry from the tank is
A liquid component removing device 40 for removing a liquid component from the sediment slurry is arranged. The liquid removing device 40 includes an anode drum 41 and a cathode belt conveyor 42.

The anode drum 41 may be entirely made of a conductive material, for example, stainless steel, or may be made by applying a carbon paint or the like to the drum surface of a non-conductive material to make only the surface conductive. Is also good.

The cathode belt conveyor 42 is made of, for example, mesh type stainless steel, and has liquid conductivity as well as conductivity. It is desirable that the mesh type stainless steel is provided with an opening having a diameter of about 3 to 30 μm. In this case, when the mesh of the mesh type stainless steel has a diameter of 0.1 to 10 mm, a cloth filter and a paper filter attached to the mesh type stainless steel may be used. The cathode belt conveyor 42 is adapted to move partly around the part of the anode drum 41, and the tension rollers 43, 44 act at this part to operate the anode drum 41.
The pressure is applied to the sandwiched object. The roller 45 is a guide roller.

A liquid collecting hopper 46 is disposed below the portion of the cathode belt conveyor 42 along the anode drum 41, and the collected liquid is replenished through a pipe 48 by the action of a pump 47. It is to be introduced into the tank 4.

A current is applied between the anode drum 41 and the cathode belt conveyor 42 by a DC power supply 49.

In the figure, reference numeral 52 denotes a buffer plate for preventing the sediment at the bottom of the first tank 12 from rising, and has a structure as shown in FIG.

Next, the liquid removing device 4 having the above-described structure.
The operation of 0 will be described.

First, the first and second on-off valves 30, 3
1 is opened or opened by adjusting the opening degree, and the first tank 12,
The sediment slurry accumulated at the bottom of the second tank 13 is discharged out of the tank via the first and second discharge units 28 and 29.

The liquid removing device 40 is driven in advance, and the cathode belt conveyor 42 is driven to rotate in the direction indicated by the arrow. The sediment slurry discharged as described above is transferred to the cathode belt conveyor 4 near the tension roller 43.
2 and moved in the direction of the arrow to apply pressure and current between the anode drum 41 and the cathode belt conveyor 42.

At this time, the throughput of the sediment slurry in the liquid component removing device 40 is desirably 3 to 100 cc / min as described above. ~15kg / m ² approximately, the applied current,
A voltage of about 1 to 30 V and a current of about 0.3 to 6 A is used.

Then, the precipitate slurry is anionic since a part of the functional groups do not capture silver ions, and is thus sucked into the anode drum 41, and at the same time, a liquid component as a processing liquid is removed. Emit a considerable amount. Thereby, the liquid component of the precipitate slurry is removed. Most of the solid side (hereinafter, referred to as cake) of the precipitate slurry from which the liquid component has been removed adheres to the anode drum 41.

The cake adhered to the anode drum 41 is
The cake scraped off by the scraper 50 provided on the anode drum 41 and adhered to the cathode belt conveyor 42 is scraped off by the scraper 51 provided on the cathode belt conveyor 42 and collected. This collected cake has a low liquid content and is in a posaposa state.

On the other hand, the liquid separated from the sediment slurry passes through the cathode belt conveyor 42 and falls. The liquid is collected by the hopper 46 and replenished through the pipe 48 by the action of the pump 47. It is introduced into the tank 4.

The processing solution having a fixing ability according to the present invention comprises:
It contains a fixing agent which is a compound having a fixing action, and specific examples include the above-mentioned fixing solutions and bleach-fixing solutions.

The fixing agent used in the fixing solution or the bleach-fixing solution in the present invention is a known fixing agent, that is, a thiosulfate such as sodium thiosulfate and ammonium thiosulfate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
It is a water-soluble silver halide dissolving agent such as a thioether compound such as 8-octanediol and a thiourea, and these can be used alone or in combination of two or more. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably 0.3 to 2 mol.

The fixing solution or the bleach-fixing solution of the present invention may be a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) or a bisulfite (eg, sodium bisulfite, potassium bisulfite, bisulfite) as a preservative. Ammonium sulfate), metabisulfite (e.g.,
(E.g., sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / liter in terms of sulfite ion, more preferably 0.04 to 0.25 mol / l.
Mol / l. As a preservative, sulfite is generally added, but other ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added.

The bleaching agent used in the bleach-fixing solution used in the present invention may be a ferric ion complex or a ferric ion complex.
A complex of iron ions with a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or a salt thereof. Aminopolycarboxylate or aminopolyphosphonate is a salt of aminopolycarboxylic acid or aminopolyphosphonic acid with an alkali metal, ammonium or a water-soluble amine. Examples of the alkali metal include sodium, potassium, and lithium. Examples of the water-soluble amine include methylamine, diethylamine, triethylamine, alkylamines such as butylamine, finger-like amines such as cyclohexylamine, aryls such as aniline and m-toluidine. Amines and heterocyclic amines such as pyridine, morpholine, piperazine.

Representative examples of these chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetraammonium salt. (Trimethylammonium) salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid trisodium salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid, ethylenediamine-N-
(Β-oxyethyl) -N, N ′, N′-triacetic acid trisodium salt, ethylenediamine-N- (β-oxyethyl) -N, N ′, N′-triacetic acid triammonium salt, 1,2-diaminopropane Tetraacetic acid, 1,2-diaminopropanetetraacetic acid disodium salt, 1,3-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid diammonium salt, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, cyclohexanediaminetetraacetic acid, Cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-
Diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N',
Examples thereof include N′-tetramethylenephosphonic acid and 1,3-propylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid, but are not limited to these exemplified compounds.

The iron ion complex salt may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate. A ferric ion complex salt may be formed in a solution using diiron or the like and a chelating agent such as aminopolycarboxylic acid or phosphonocarboxylic acid. When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used.
On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. In any case, the chelating agent may be used in excess of the amount of the ferric ion complex salt. Among the iron complexes, iron aminopolycarboxylate complexes are preferred.

The addition amount is usually 0.02 to 1 mol /
Liter, preferably 0.06 to 0.6 mol / liter.

The bleach-fixing solution may contain a bleaching accelerator, if necessary. Specific examples of useful bleaching accelerators include U.S. Pat. Nos. 1,290,812, 1,229,812 and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-
No. 95631, No. 53-104232, No. 53-12
No. 4424, No. 53-141623, No. 53-284
No. 26, a compound having a mercapto group or a disulfide group described in Research Disclosure 17129 (July, 1978);
Thiazolidine derivatives as described in JP-A No. 9-85; JP-B-45-8506; JP-A-52-20832;
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715
And iodides described in JP-A-58-16235; polyethylene oxides described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; JP-A-49-424
No. 34, 49-59644, 53-94927
And compounds described in JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940, and iodine and bromine ions. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect, and in particular, US Pat.
No. 8, West German Patent No. 1,290,812,
Compounds described in No. 95630 are preferred.

In addition, the bleach-fixing solution may be a bromide (for example,
Potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, ammonium iodide) rehalogenating agents may be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
One or more inorganic acids or organic acids having a pH buffering capacity such as tartaric acid and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bleach-fixing solution or fixing solution of the present invention
The pH region is preferably from 3 to 10, and more preferably from 5 to 9.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Further, a buffer, a fluorescent whitening agent, a chelating agent, a fungicide and the like may be added as required.

The processing method of the light-sensitive material to which the present invention can be applied is as follows: black-and-white development → fixing → washing → drying Color developing → bleaching → washing → drying Color developing → bleaching → fixing → washing → drying Color developing → bleaching → bleaching / fixing → water washing → drying black and white development → water washing → reversal processing (fogging exposure or fogging bath processing) → color development → bleaching → fixing → water washing → drying black and white development → water washing → color development → bleach fixing → water washing → drying etc. No. Further, a processing method in which intermediate water washing is provided in each processing step may be used.

In addition, various steps such as a pre-hardening bath and a neutralizing bath are combined as needed.

Furthermore, a simple processing method such as performing only a so-called "stabilization process" without providing a substantial water-washing step instead of the water-washing process can be used.

In the present invention, the black-and-white developer used for the development processing includes dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-).
Known developing agents such as pyrazolidone) and aminophenols (eg, N-methyl-p-aminophenol) can be used alone or in combination.

The color developer is generally composed of an alkaline aqueous solution containing a color developing agent.

Color developing agents include known primary aromatic amine developers such as phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline).

The developer may further include an alkali metal carbonate,
It may contain a pH buffer such as borate or phosphate, a development inhibitor or an antifoggant, and the like.

If necessary, water softeners, preservatives,
Organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developing agents, viscosity-imparting agents, polycarboxylic acid-based chelating agents, antioxidants, alkali agents, dissolution aids, surfactants, defoamers And the like.

The processing temperature of the color (color developing) or black-and-white developer in the present invention is preferably 30 ° C. to 50 ° C., more preferably 33 ° C. to 42 ° C. Further, the development processing in the present invention is a replenishment method for replenishing the developer,
Further, a non-replenishment method may be used.

Examples of the bleaching solution in the present invention include those obtained by removing the fixing agent from the above-mentioned bleach-fixing solution.

As the washing water used in the washing step, tap water, ion-exchanged water and the like can be used, and if necessary, known additives can be contained.

For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid and organic phosphoric acid, bactericides for preventing the growth of various bacteria and algae, antibacterial agents, hardening agents such as magnesium salts and aluminum salts, drying agents A surfactant or the like for preventing load and unevenness can be used. Or, L.
E.West, "Water Quality Criteria" Phot.Sci.and Eng.,
vol.9 No.6 P344-359 (1965) and the like.

As the stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image is used. For example, pH 3 ~
A liquid having a buffer capacity of 6, or a liquid containing an aldehyde (for example, formalin) can be used. As the stabilizing solution, a fluorescent whitening agent, a chelating agent, a bactericide, a sunscreen, a hardener, a surfactant, and the like can be used as necessary.

The light-sensitive material of the present invention may be any of various color and black-and-white light-sensitive materials. For example, a color negative film, a color reversal film, a color photographic paper, a color positive film, a color reversal photographic paper, a photographic light-sensitive material for plate making, an X-ray photographic light-sensitive material, a black-and-white negative film, a black-and-white photographic paper, a photosensitive material for micro, and the like can be mentioned.

In the photographic emulsion layer of the light-sensitive material of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide. Preferred silver halide is silver chlorobromide containing 3 mol% or less of silver iodide,
Silver iodobromide or silver iodochlorobromide.

In the present invention, when processing with a processing solution having a fixing function, the processing is carried out while removing the silver element, so that any light-sensitive material having the above-mentioned silver halide composition can be processed efficiently.

Detailed examples of the photosensitive material used in the present invention are as follows.
For example, it may be described on page 10, lower right column, line 14 to page 13, upper right column, line 6 of JP-A-3-132656.

[0133]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. As the color light-sensitive material, a multilayer color light-sensitive material described in the ninth line from the lower right column on page 13 of JP-A-3-132656 was used.

After exposing the above color photographic light-sensitive material, each was processed using an automatic developing machine by the method described below (until the cumulative replenishment amount of the bleach-fix solution became 24 l).

Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C. 45 ml 10 l Bleaching 2 minutes 10 seconds 38 ° C. 7 ml 4 l Fixing 3 minutes 15 seconds 38 ° C. 20 ml 8 l Rinse with water (1) 40 seconds 35 ° C 4 l countercurrent piping system from (2) to (1) Rinse (2) 1 minute 00 seconds 35 ° C 30 ml 4 l Stability 2 minutes 10 seconds 38 ° C 45 ml 4 l Drying 1 minute 15 seconds 55 ℃ Replenishment rate is 35mm width per 1m length.

Next, the composition of the processing solution will be described.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodide Potassium 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 l 1.0 l pH 10.05 10.10

(Bleaching solution) Common to mother liquor and replenisher (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator (shown in the following chemical formula 44) Structure) 0.005 mol

[0139]

Embedded image

Ammonia water (27%) 15.0 ml Add water and add 1.0 l pH 6.3

(Fixing solution) Common to mother liquor and replenisher (unit g) Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 280 ml Ammonia water (27%) 6.0 ml Add water 1.0 l pH 6.7

(Washing solution) A common mixture of mother liquor and replenisher filled with tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Rohm and Haas Co.) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through the bed column to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate and 0.1 mg of sodium sulfate.
15 g / l were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water was added. 1 l pH 5.0 to 8.0

During the above processing steps, the circulation path 1 shown in FIG.
0, the fixing solution having been subjected to the fixing process is passed through this circulation path 10.
Then, the solution was brought into contact with an aqueous solution of a polymer ligand to perform a regeneration treatment of the fixing solution and to recover a silver element.

In this case, the compound represented by the above formula 9 was used as the polymer ligand, and the concentration was set to 80%.

The ratio of contact with the aqueous solution of the polymer ligand was set to 50% of the total circulation amount of the fixing solution.

[0147] The unexposed portion X-ray fluorescence analysis of the processed light-sensitive material was determined the residual silver amount (μg / cm ^2), are both almost completely fixed in 5~8μg / cm ² (desilvering) I was

Further, sensitometric exposure was carried out, and the amount of residual silver was similarly examined at the exposed portions of the light-sensitive material.
It was 10 μg / cm ² , and almost completely desilvered.

Further, when the fixing end time was obtained,
It was 2 minutes and 13 seconds. Since the fixing end time in the conventional case where no operation was performed was measured to be 2 minutes and 45 seconds, 30
Time savings of a little over a second have become possible.

Next, the sediment slurry containing the polymer silver complex accumulated below them is taken out of the first tank 12 and the second tank 13 in the silver element removing device 11, and the liquid component removing device 40 shown in FIG. Thus, the liquid component was removed from the precipitate slurry.

In the above processing, the liquid removing device 4
0 is supplied at 100 cc / min. Performed in

The applied current was a voltage of 3.2 V and a current of 1 A.

The pressure was adjusted to 2.3 kg / m ² by adjusting the pressure of the anode drum 41. With the above conditions,
When the liquid removal of the precipitate slurry was performed, the liquid content was 43%, which was reduced to 11%. As a result, what was in a tapo state with considerable liquid content,
It was collected in a pozaposa state.

For comparison, similarly to the above, using the liquid component removing device 40 having the structure shown in FIG. 1 and simply applying pressure (2.3 kg / m ² as in the above) without applying a current. As a result, the liquid content was only about 35%.

As described above, in the present invention,
Although the liquid content of the recovered material was reduced by 75% from 43% to 11%, the liquid content of 43% to 35
% And less than about 20%. From this, the remarkable features of the present invention can be understood.

[Brief description of the drawings]

FIG. 1 is a schematic structural view showing an apparatus for processing a silver halide photosensitive material of the present invention.

FIG. 2 is a perspective view of a buffer plate in the processing apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Automatic developing machine 11 Silver element removing device 40 Liquid component removing device 41 Anode drum 42 Cathode belt conveyor 49 DC power supply

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 5/00 B01D 21/02

Claims (5)

(57) [Claims] When a silver halide light-sensitive material after exposure is developed and processed with a processing solution having a fixing ability, the processing solution after the fixing process is brought into contact with a complexing agent to form silver insoluble in water. In a method for processing a silver halide photosensitive material, a complex is formed, a precipitate slurry formed by precipitation of the silver complex is taken out, and silver is recovered from the precipitate slurry, the precipitate slurry is subjected to 1.5 kg / m ^2. Using a current applying pressurizing means for applying a current while pressurizing at a pressure of 15 kg / m ² or less ,
In 1V or 30V voltage below the current applying pressure means 0.3
A method for processing a silver halide photosensitive material, wherein a current of A to 6 A is applied to drain a precipitate slurry. 2. When a silver halide photosensitive material is developed and processed with a processing solution having a fixing ability, the processing solution after the fixing process is brought into contact with a complexing agent to form a water-insoluble silver complex. Then, a precipitate slurry formed by precipitation of the silver complex is taken out, and in a silver halide photosensitive material processing apparatus for recovering silver from the precipitate slurry, the precipitate slurry formed of the conductive material and introduced is removed. 1.5 kg / m ² or more and 15 kg
Current mark that applies current while applying pressure at a pressure of / m ² or less
Using a pressurizing means, apply 1 V or more 3
It is applied to 6A less current than 0.3A at voltage less than 0V
Processor of the silver halide light-sensitive material, characterized in that that. 3. The current applying and pressurizing means includes an endless liquid-permeable conveyor belt having at least a surface formed of a conductor, and an at least surface formed of a conductor, and disposed on the conveyor belt. a pressure roller for pressing the precipitate slurry to and from the conveyor belt, the silver halide according to claim 2, wherein and a power source for applying a current between the conveyor belt and the pressure roller Processing equipment for photosensitive materials. 4. A processing apparatus for a silver halide light-sensitive material for performing a process having a fixing function on a silver halide light-sensitive material after development, comprising: a processing tank filled with a processing solution having a fixing function; An apparatus for processing a silver halide photosensitive material, the apparatus comprising a connected circulation path, and a silver element removal means containing a complexing agent for forming a polymeric silver complex in the circulation path. Is formed around the periphery of the first tank for containing the complexing agent and bringing the complexing agent into contact with the processing solution having been subjected to the fixing treatment, and formed around the first tank. An apparatus for processing a silver halide photosensitive material, comprising: a second tank for receiving an overflow solution . 5. The processing apparatus of the silver halide light-sensitive material of claim 4 wherein a current applying pressure means according to claim 2 or 3 wherein.