JPH04323650A - Photographic processing method - Google Patents

Abstract

PURPOSE:To substantially stop discharge of a processing solution due to overflow caused by replenishing of the processing solution and to obtain the processing method small in waste processing solution and superior in photographic performance. CONSTITUTION:A color developing solution 110, a bleaching solution 120, and a fixing solution 140 are brought into contact with a solution containing electrolytes through anion exchange membranes A1, A2, and A3 and an anode and a cathode are immersed into both solutions across the membranes A1, A2, and A3 and electric current is passed, thus permitting processing ability the processing solution to be regenerated, halogen ions and the like to be removed from the processing solution, an amount to be replenished to the processing solution to be reduced or made needless or further the processing solution to come to require some amount of replenishing solution in accordance with decrease of the solution by a proper replenishing means, and therefore discharge of the processing solution due to overflow to be substantially stopped.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a silver halide photosensitive material (hereinafter sometimes abbreviated as "photosensitive material" or "photosensitive material").
This invention relates to a photographic processing method for processing.

0002

[Prior Art] Black and white photosensitive materials are processed through steps such as black and white development, fixing, and water washing after exposure, while color photosensitive materials are processed through steps such as color development, desilvering, washing, and stabilization after exposure. Ru. Black and white developer for black and white development, fixer for fixing, color developer for color development, bleach, bleach-fix, fixer for desilvering, tap water or ion exchange water for washing, Stabilizing solutions are used in each stabilization process. The temperature of each processing solution is usually adjusted to 20 to 50 DEG C., and the photosensitive material is immersed in these processing solutions.

Among these processing steps, the development step is a step in which a developing agent serving as a reducing agent acts on exposed silver halide grains in a photographic emulsion to reduce Ag+ to Ag. In black-and-white photography, a silver image is formed in this way, and in color photography, the oxidized product of the color developing agent reacts with the coupler to form a dye image corresponding to the silver image.

[0004] This developing solution deteriorates due to air oxidation when it is not processed, and its developing power decreases. This decrease in developing power is thought to be mainly due to oxidation of preservatives and developing agents.

Conventionally, such deterioration of the developer solution has been dealt with by increasing the amount of developer replenishment. However, increasing the amount of replenishment increases the amount of chemicals and water used, which is undesirable because in recent years there has been a strong desire to save resources and reduce the amount of waste liquid from the standpoint of environmental conservation. Further, in particular, color developing agents are expensive, and increasing their consumption is disadvantageous in terms of cost.

Furthermore, the desilvering process that is carried out subsequent to the color development process in color photography includes a method in which the bleaching process and the fixing process are performed in the same bath, a method in which they are performed in separate baths,
Alternatively, there is a method in which the bleaching step and the bleach-fixing step are performed in separate baths. Among these methods, a method in which the bleaching step and the fixing step are performed in separate baths has the advantage that stable processing can be performed. In addition, a method of combining a bleaching process and a bleach-fixing process and performing each process in separate baths is attracting attention as a method that promotes desilvering (Japanese Patent Laid-Open No. 61-7
No. 5352).

Among these, the bleaching solution used in the bleaching process contains a bleaching agent, which is an oxidizing agent. Examples of bleaching agents include ferric complexes such as aminopolycarboxylic acids, aminopolyphosphonic acids, and their salts. Typically, ferric complex salts of ethylenediaminetetraacetic acid are commonly used, and in addition to highly oxidized 1,3 as something with power
-diaminopropanetetraacetic acid ferric complex salts, and the like.

[0008] In this bleaching step, a reaction occurs in which the silver produced in the color development step is oxidized by the action of the bleaching agent as described above, and as a result, the oxidizing agent, the bleaching agent, is reduced. Therefore, the bleaching power (oxidizing power) of the bleach solution decreases as the photosensitive material is processed. This decrease in oxidizing power is particularly significant when a large amount of photosensitive material is processed.

[0009] In order to restore the oxidizing power of the bleaching agent, for example, a method has been adopted in which the bleaching solution is oxidized by aeration of air.

However, when such a method is adopted, bubbles are generated in the solution, and the solution spills from the bleaching tank and contaminates the surrounding area, and the droplets generated by the foaming enter the front tank and cause damage to the inside of the front tank. There is a problem of contaminating the processing liquid. In particular, since the processing liquid in the front tank is often a color developer, the problem is serious because the color developer deteriorates and the developing power decreases.

On the other hand, the fixing solution contains a fixing agent that dissolves silver oxidized by a bleaching agent. This fixer is used when the photosensitive material is unprocessed and over time, the preservatives and fixing agents become susceptible to air oxidation, and these agents decompose due to oxidation, producing sulfides, which can contaminate the surface of the photosensitive material. Causes sulfurization trouble. Furthermore, if hyposilver is used as a fixing agent, hyposilver accumulates in the solution during processing, and a certain amount or more must be replenished to keep the hyposilver concentration in the solution low. , fixing failure (desilvering failure) occurs. Further, the above-mentioned troubles due to oxidation are accelerated by contamination of the bleaching solution carried by the photosensitive material. The above-mentioned sulfurization troubles and poor fixing are also problems that occur in fixing solutions for black and white photography.

[0012] In order to solve such problems, a method has conventionally been adopted for both black-and-white photography and color photography to increase the amount of fixer replenishment. However, increasing the amount of replenishment is undesirable from the viewpoint of resource saving, waste liquid treatment, etc., as described above.

The above-mentioned problems in the desilvering process are common to processing solutions containing bleach or fixing agents.

Conventionally, in order to suppress drainage due to overflow as much as possible, a replenishment means has been adopted in which the concentration of the replenisher is increased and components can be replenished or recovered with a small amount of replenishment. However, in order to reduce the amount of liquid drained due to overflow to zero, it is desirable to be able to replenish only the reduced amount of the processing solution to replenish the consumed components, etc. However, if only the reduced amount is replenished, the consumed components and fatigue components of the processing solution can be refilled. There was a problem in that the liquid could not be sufficiently replenished, and if replenishment was carried out to the extent that the processing capacity was not reduced, the waste liquid had to be discharged. Furthermore, in developing tanks, for example, if halide ions eluted from the sensitive material accumulate in the developing tank, it will have an adverse effect on the developing process. In order to discharge the process liquid, it is necessary to discharge the processing liquid.

[0015]

[Problems to be Solved by the Invention] An object of the present invention is to provide a photographic method in which it is easy to maintain and manage the processing performance of a processing solution, eliminate drainage due to processing solution overflow, and obtain images with good photographic performance. The purpose is to provide a processing method.

[0016]

[Means for Solving the Problems] Such objects are achieved by the following present inventions (1) to (3). That is,

0
(1) The tank is filled with a treatment solution so as to be in contact with the electrolyte-containing solution at least through an anion exchange membrane, and the anode is immersed in the electrolyte-containing solution and the cathode is immersed in the treatment solution. and a photographic processing method in which the silver halide photosensitive material after exposure is processed by applying electricity to the anode and the cathode, the tank for processing the silver halide photosensitive material after the exposure has a reduced amount of liquid. 1. A photographic processing method characterized in that a replenishing means is provided for replenishing liquid in accordance with the liquid replenishment, and the amount of liquid drained due to liquid replenishment is reduced to substantially zero.

(2) Among the replenishment means, the replenishment means for replenishing the developer includes a processing component replenishment system that replenishes processing components in accordance with the amount consumed, and a processing component replenishment system that replenishes processing components in response to water loss. The process liquid replenishment system consists of a processing liquid replenishment system and a processing liquid replenishment system described above (1).
) Photo processing method described in .

(3) A treatment liquid having bleaching ability is filled in the tank so as to be in contact with the electrolyte solution through at least an anion exchange membrane, and a cathode is placed in the electrolyte solution and an anode is placed in the treatment liquid having bleaching ability. A photographic processing method in which the silver halide photosensitive material after exposure is processed by immersing the anode and the cathode in each case, the bath for processing the exposed silver halide photosensitive material includes a liquid. 1. A photographic processing method characterized in that a replenishing means is provided for replenishing liquid in accordance with the amount of decrease in the liquid, and the amount of drained liquid caused by liquid replenishment is reduced to substantially zero.

[0020]

[Function] In the present invention, for example, in processing a color photosensitive material, after exposure, the material is subjected to the following steps: development, bleaching, fixing, washing, and stabilization.

At this time, an anion exchange membrane is installed to separate the developer and the electrolyte-containing solution, and a cathode is placed in the developer.
The anodes are each immersed in a solution containing an electrolyte, and electricity is applied to both electrodes for treatment. In this case, halide ions such as Br- generated by the development process move from the developer solution to the electrolyte-containing solution via the anion exchange membrane.

[0022] This prevents halide ions such as Br- from accumulating in the developer and inhibiting development, and there is no need to discharge the halide ions by overflow. Furthermore, the cathode reduces preservatives, developing agents, and the like that have been oxidized by oxygen in the air, thereby regenerating processing capacity. Therefore, it is sufficient to replenish the developer by replenishing only the developer components consumed during the development process and the moisture reduced by the carry-out and evaporation of the photosensitive material. Less is enough. In this case, the liquid containing the electrolyte is, for example, KCl, K2 CO
3. A solution prepared by adding an electrolyte such as Na2 CO3 can be used, and in some cases, a water-saving overflow bleaching solution can be used.

Furthermore, an anion exchange membrane is installed to separate the bleaching solution and the electrolyte solution, and the anode and the cathode are immersed in the bleaching solution and the electrolyte solution, respectively, and electricity is applied to both electrodes for treatment. In this case, as the electrolyte solution, for example, Cl-, Br
- Those containing halide ions such as - are used. For example, a developing solution, a fixing solution, an overflow solution thereof, and an overflow solution for water-saving washing can also be used.

[0024] By the electricity supply, halide ions such as Br- are transferred from the electrolyte solution into the bleaching solution through the anion exchange membrane. Therefore, there is no need to replenish halide ions, and a reaction occurs at the anode in which the bleaching agent, which is once in a reduced state due to the bleaching treatment, is oxidized and the bleaching power is restored. Therefore, when replenishing the processing solution, it is only necessary to replenish only a small amount of the bleaching agent component that is reduced due to the removal of the photosensitive material and the amount of water that is reduced due to evaporation.

In the above, a solution containing an electrolyte may be brought into contact with the developing solution and the bleaching solution through an anion exchange membrane. The treatment may be carried out by bringing the two electrodes into contact with each other, immersing the cathode in a developer and the anode in a bleaching solution, and energizing both electrodes.

In order to restore the processing performance of the fixer, the cathode is immersed in the fixer and the anode is immersed in a solution containing an electrolyte (including a bleaching solution, etc.) through an anion exchange membrane. The same applies to the case where both poles are energized.

[0027]

[Specific Structure] The specific structure of the present invention will be explained in detail below.

In the photographic processing method of the present invention, in particular, the processing solutions such as the developer and fixer are brought into contact with a solution containing an electrolyte through an anion exchange membrane, and a cathode is connected to the processing solution, and the electrolyte is connected to the processing solution. The anodes are respectively immersed in the liquid contained therein, and electricity is applied to both electrodes to process the photosensitive material.

[0029] In this case, the current density is 0.02~
3A/dm2, preferably 0.05-1.2A/dm
It is sufficient to apply a voltage so that the voltage becomes 2. The applied voltage is
Although it varies depending on the liquid used, the form of the processing equipment, the distance between the electrodes, the properties and type of the diaphragm, conceptually it is 0.05 to 10.
0V, preferably 0.1 to 10V.

[0030] The initial value of the membrane voltage is usually 0.5 to 2
0V (membrane resistance 0.5-30Ω).

By applying electricity in this manner during the processing of photosensitive materials, halide ions such as Br-, which accumulate in the developer and fixer during processing, are transferred to the electrolyte solution at the counter electrode through the anion exchange membrane. Therefore, the halide ions in the processing solution can be maintained at a constant level, and further, oxidized processing components such as developing agent are reduced to recover the processing performance, and a certain processing performance can be obtained.

[0032] In the present invention, electricity is applied with a constant current, but in this case, the unit volume of the processing liquid (for example, 1
1) It is best to manage the current (current concentration) per unit so that it is constant. In this case, specifically, time management may be used. Furthermore, when the current is simply being applied (for example, at a constant voltage, with no voltage or current control), it may be managed using an integrating ammeter or the like. This is because the movement of halide ions and oxidation in the bleaching solution act with an efficiency of 80 to 99% relative to the amount of current applied.

[0033] The current concentration at this time is usually 0.5 to 5
0 A/l, preferably 1 to 10 A/l. By performing such management, the amount of movement of anions can be controlled to be more constant.

At this time, the amount of electricity required to restore the developing power of the developer depends on the adjustment of the current application time, but this amount of electricity depends on the amount of silver coated on the photosensitive material, and when the tank is not in the first tank. It may be determined based on the amount of photosensitive material brought in from the pre-bath.

The anion exchange membrane used in the present invention may be any membrane as long as it selectively allows anions to pass therethrough, and commercially available membranes can be used as they are.

As described above, as an anion exchange membrane, Se
lemion AMV/AMR (manufactured by Asahi Glass), Acip
lex A201, A172 (manufactured by Asahi Kasei), Neos
epta AM-1 to 3 (manufactured by Tokuyama Soda), Iona
c MA-3148 (Ionac Chemica
ls), Nepton AR103PZL (Ion
ics) can also be used, but in particular, since the purpose of the present invention is to permeate halide ions such as Br-, Selm, which selectively permeates monovalent anions, can also be used.
ion ASV/ASR (manufactured by Asahi Glass), Neosep
It is preferable to use those commercially available under trade names such as ta AFN-7 and Neosepta ACS (manufactured by Tokuyama Soda).

In the present invention, the above-mentioned anion exchange membrane is a general term for membranes that selectively permeate anions, and in this sense, the anion exchange membrane has a pore size of 0.2 to 20
Porous ceramics of micrometers are also included.

Specifically, processing liquids to which the present invention is applied include, in color photography, a color developer, a first black-and-white developer for reversal processing, a fixer, and the like, and in black-and-white photography, black-and-white These include developing solutions and fixing solutions. In these processing solutions, it is necessary to prevent the accumulation of halide ions eluted from the emulsion layer of the sensitive material as processing progresses.

As already mentioned, energization removes Br-, which accumulates in the developer and fixer during processing.
Halide ions such as
Transfer to the electrolyte-containing solution during processing eliminates the need for overflow to eliminate accumulated halide ions and replenish consumed processing components, including those that are correspondingly lost or removed. It is sufficient to replenish only the amount of liquid reduced due to evaporation or removal of the photosensitive material.

In particular, for color developing agents in color photography, the agents consumed during the development process are replenished,
Further, a water component is separately replenished to adjust the liquid level to a constant level so that the total amount of the replenisher is reduced.

On the other hand, the electrolyte-containing solution in which the anode is immersed may be a treatment solution or a separately prepared solution, and this separately prepared solution is referred to as an electrolyte solution. Examples of the processing liquid include processing liquids having bleaching ability, such as bleaching liquid. In bleaching solutions, halide ions are transferred from the developer and fixing solutions to the bleaching solution by combining with a color developing solution and a fixing solution, and the bleaching solution itself is oxidized at the anode in a reduced state. processing performance can be restored.

In the combination of a color developing solution and a bleaching solution, it is preferable to install two anion exchange membranes between the two solutions, and in the space partitioned by the two anion exchange membranes,
Preferably, it is filled with an electrolyte solution such as KCl. By doing so, it is possible to prevent the bleaching solution from entering the color developing solution through the anion exchange membrane. Such a relationship also applies to the relationship between the bleaching solution and the fixing solution.

On the other hand, the bleaching solution is brought into contact with the electrolyte solution through an anion exchange membrane, the anode is immersed in the bleaching solution, and the cathode is immersed in the electrolyte solution, and electricity is applied to both electrodes to dry the photosensitive material. It can also be processed. In the bleach solution, the developed silver is subjected to oxidative bleaching treatment, and the bleach itself, which has been reduced once, is oxidized and the processing ability is restored. In particular, if the electrolyte solution is a solution containing halide ions, the halide ions will selectively pass through the anion exchange membrane and be contained in the bleaching solution. Therefore, the amount of replenishment of halide in the rehalogenating agent or bleach accelerator is reduced or becomes unnecessary.

[0044] When replenishing the bleaching solution, it is now necessary to replenish only the small amount of bleaching agent lost due to the removal of the sensitive material and the amount of water lost due to evaporation, etc., and there is no need to replenish the bleaching solution to the extent that it overflows. will disappear.

[0045] The electrolyte used in the electrolyte solution is not particularly limited, but NaCl, KCl, LiCl, N
Halides such as aBr, KBr, KI, Na2 SO
4, sulfates such as K2SO4, KNO3, NaN
Nitrates such as O3, NH4 NO3, Na2CO3
, K2 CO3 and the like are preferably used.

Among the various salts mentioned above, when nitrates are used, nitrate ions are replenished, so that the replenishment of corrosion inhibitors and bleach accelerators can be reduced or, in some cases, eliminated.

When sulfate is used, sulfate ions are replenished, so that acid supplementation for pH reduction can be reduced or even eliminated.

When carbonates are used, carbonate ions are replenished, so that pH buffer and acid replenishment can be reduced or even eliminated.

The concentration of the electrolyte in the electrolyte solution at this time may be 0.1 to 30%, preferably 0.5 to 20%.

[0050] The anion exchange membrane may be appropriately selected depending on the electrolyte solution.

[0051] Alternatively, the discharge liquid of a rinsing liquid provided at the rear of the bleaching tank or the fixing tank may be used. Even when ion-exchanged water is used as the rinsing solution itself, the rinsing solution after use is contaminated with salt, which is a component of the bleaching solution and fixing solution carried by the photosensitive material. Therefore, there is no problem in using it as an electrolyte solution, and thereby the amount of waste liquid can be reduced. The above-mentioned rinsing liquid may be a conventional one, preferably one containing an antibacterial agent, a fungicidal agent, a dye eluent, a decolorizing agent, or the like.

The cathode used in the present invention may be made of any electrical conductor or semiconductor as long as it can withstand long-term use, but stainless steel is particularly preferred. The anode may be made of an insoluble material and an electrical conductor, specifically carbon (graphite),
Examples include lead dioxide, platinum, gold, and titanium steel, and stainless steel may be used in some cases. The shape of both electrodes is preferably a plate shape, a meshed plate shape, or a plate shape with projections so that they can be easily installed in the tank. The size may be appropriately selected depending on the tank capacity.

FIG. 1 shows a processing apparatus used in the present invention.
shows an example of its configuration. FIG. 1 is a plan view showing the arrangement of tanks and the like.

As shown in the figure, the processing apparatus 1 includes a color developing tank 11 filled with a color developing solution 110, a bleaching tank 12 filled with a bleaching solution 120, a rinsing tank 13 filled with a rinsing solution R,
Fixing tank 14 filled with fixing liquid 140, first washing liquid W1
A first washing tank 15 filled with the water, a second washing tank 16 filled with the second washing liquid W2, and a stabilizing tank 17 filled with the stabilizing liquid 170.
For example, a photosensitive material S such as a color negative film is transported between processing tanks and subjected to the following treatments: color development → bleaching → rinsing → fixing → washing → washing → stabilization.

Color developing tank 11, bleaching tank 12, fixing tank 14
is provided with liquid tanks 21, 22, and 23 that can freely communicate liquid with each of the above-mentioned tanks. And each liquid tank 21, 22, 23
Anion exchange membranes A1, A2, and A3 are arranged so as to divide the inside of each tank into two chambers.

The first chamber 211 of the liquid tank 21 is filled with an electrolyte solution 210, the second chamber 212 is filled with the color developer 110 in the color developer tank 11, and the second chamber 212 is filled with the color developer 110 in the color developer tank 11. 212 is configured to freely communicate liquid with the color developing tank 11 through a connecting pipe or the like. With this configuration, the color developing solution 110 and the electrolyte solution 210 come into contact with each other via the anion exchange membrane A1. Further, in the liquid tank 21, a cathode 31 is immersed in the color developing solution 110, and an anode 32 is immersed in the electrolyte solution 210.

The liquid tanks 22 and 23 have the same structure as the liquid tank 21, with first chambers 221 and 231 filled with electrolyte solutions 220 and 230, respectively, and a second chamber 222 filled with electrolyte solutions 220 and 230, respectively.
, 232 are filled with a bleaching solution 120 and a fixing solution 140. Bleaching solution 120 and fixing solution 140 pass through anion exchange membranes A2 and A3 to electrolyte solutions 220 and 23, respectively.
It is in contact with 0.

Further, in the liquid tank 22, the cathode 33 is immersed in the electrolyte solution 220, and the anode 34 is immersed in the bleaching solution 120.
A cathode 35 is immersed therein, and an anode 36 is immersed in an electrolyte solution 230.

The electrodes immersed in the liquid tanks 21, 22, and 23 are configured to be energized.

The compositions of the electrolyte solutions 210, 220, and 230 in the processing apparatus of this embodiment will be explained. The electrolyte solution 210 is a sodium carbonate (Na2 CO3) solution. The liquid tank 22 uses the discharged liquid from the rinsing tank 13 as an electrolyte solution 220, and the overflow liquid from the rinsing tank 13 flows into the liquid tank 22.

Furthermore, the liquid tank 23 uses the discharged liquid from the first washing tank 15 as an electrolyte solution 230.

To explain the flow of the electrolyte solution, the flow of the electrolyte solution is as follows:
The first chamber 211 of is replenished with sodium carbonate solution,
Electrolyte solution 21 overflowing from the first chamber 211
0 flows into the first washing tank 15.

On the other hand, the second washing tank 16 includes the liquid tank 21.
Approximately 5-20% of the supply amount of electrolyte solution 210 supplied to
About twice as much washing water is replenished, and the drained liquid from the overflow from the stabilization tank 17 flows in. Drainage liquid due to overflow from the second water washing tank 16 is transferred to the first water washing tank 15.
flow into. In the washing water W1 of the first washing tank 15,
Draining the electrolyte solution 210 that has flowed in from the liquid tank 21;
Since salt, which is a component of the fixer brought by the photosensitive material S, is mixed in, there is no problem in using it as an electrolyte solution. Therefore, the drained liquid due to the overflow of the washing water W1 in the first washing tank 15 is allowed to flow into the first chamber 221 of the liquid tank 22 and used as the electrolyte solution 230.

The electrolyte solution 230 overflowing from the first chamber 231 in the liquid tank 23 flows into the rinsing tank 13 . The rinsing liquid is mixed with the inflow of the electrolyte solution 230 and the halide ions brought in by the photosensitive material S, and there is no problem in using it as an electrolyte solution. The drained liquid due to the overflow of the rinsing liquid R is drained into the liquid tank 2.
2 into the first chamber 221 and used as the electrolyte solution 220. Then, the electrolyte solution 22 from the liquid tank 22
Drainage liquid due to overflow of 0 is treated as waste liquid.

[0065] In this way, by sequentially using the waste liquid from the overflow of each tank as a treatment liquid or an electrolyte solution, the amount of waste liquid can be further reduced.

Furthermore, with the above configuration, the halide ions taken out by the photosensitive material S from the bleaching tank 12 are returned from the rinsing tank 13 to the first chamber 221 of the liquid tank 22, so that a re-halogenating agent, etc. replenishment is no longer necessary, or only a very small amount is required.

[0067] It is preferable that the current be applied during the treatment. That is, it may be done at the same time as the signal to start processing the photosensitive material S is received, or after a predetermined period of time has elapsed, and the energization may be stopped at the end of the processing.

By applying electricity in this manner, the processing performance of each processing solution in the color developing solution 110, bleaching solution 120, and fixing solution 140 is restored. In the color developer 110,
Halide ions eluted from the photosensitive material S move toward the anode 32 through the anion exchange membrane and are removed. Therefore, there is no need to overflow the color developing solution 110, and it is only necessary to replenish the consumed amount of the developing agent and the moisture corresponding to the decrease in the level of the developing solution. Moreover, some of the oxidized color developing agent is reduced at the cathode 31, and some of it is OH-
is generated, so that the acid eluted from the photosensitive material S is neutralized. On the other hand, in the bleaching solution 120, halide ions move from the electrolyte solution 220, so there is no need to add new halide ions, and the oxidizing power of the bleaching agent is also restored. Furthermore, since H+ is generated by the electrode reaction, p due to the color developer 110 brought into the photosensitive material S
H rise is suppressed. Furthermore, in the fixer 140, the fixing power of the fixer is restored, and halide ions are transferred to the electrolyte solution 140.
30 and removed, and furthermore, the formation of sulfide derived from the fixing agent and the deterioration of the preservative are prevented.

Next, replenishment of the processing solution in the color developing tank 11 will be explained.

A processing component replenishment system Rep1 is provided for replenishing the developing agent consumed by the color development processing.

The processing component replenishment system Rep1 performs quantitative replenishment at predetermined intervals depending on the processing amount of the photosensitive material. In the processing component replenishment system Rep1, as described above, since the reduction reaction of the air-oxidized color developing components and preservatives occurs on the cathode surface, only a small amount of processing components can be replenished. The replenishment means of the processing component replenishment system Rep1 may be, for example, a known means such as a metering pump such as a bellows pump.

The amount of processing solution in the first color developing tank is significantly reduced due to swelling and removal of the photosensitive material. For this reason,
In many cases, only the component replenishment described above does not sufficiently replenish the decreased liquid amount, and the insufficient liquid amount is replenished by the liquid replenishment system Rep2, which will be described later.

Next, the means for replenishing the processing liquid provided in the color developing tank 11, the bleaching tank 12, and the fixing tank 14 will be explained.

FIG. 2 is a side sectional view showing the color developing tank and replenishing means.

The replenishing means 4 is composed of a replenisher tank 40 and a supply path 41 connected to the bottom of the replenisher tank 40. The replenisher tank 40 is configured to be airtight and communicates with the outside only through the supply path 41. The replenishment tank 40 is filled with a replenisher 45,
In the case of a replenisher for a color developer, it is filled with water. The replenisher tank 40 and supply channel 41 preferably have sufficient rigidity, and may be made of metal or hard plastic such as vinyl chloride or polyethylene.

FIGS. 3 and 4 are partial side sectional views of the supply path 41. FIG. A replenishment port 42 having a horizontal opening surface is provided at the lower end of the supply path 41 so as to face the processing liquid level;
The refill port 42 is set at an appropriate level of the processing liquid. A first valve 43 is attached to the refill port 42 . The valve 43 allows the replenisher 45 and mother liquor (color developer)
The replenisher 45 is configured to prevent mixing with the replenisher 110 due to diffusion, and to supply a constantly adjusted replenisher 45 with a constant concentration.

The valve 43 is composed of a valve body 430 that is a float, and a fulcrum 431 that is provided at the end of the replenishment port 42 and supports the valve body 430 so as to be openable and closable. The valve body 430 is configured to have a specific gravity smaller than that of the mother liquid 110, and has a fulcrum 431 provided at the end of the replenishment port 42.
It is pivotally supported so that it can be opened and closed. Examples of the material for the valve 43 include polyethylene (specific gravity d=0.91), modified polyolefin (specific gravity d=0.90), and ethylene vinyl acerate (specific gravity d=0.93). Furthermore, it can also have a hollow structure. Note that any resin can be used for the hollow structure. If the buoyancy force of the valve body 430 is the value obtained by subtracting the weight of the valve body 430 from the buoyancy force on the valve body 430, then the buoyancy force of the valve body 430 is 30 g/cm2.
It may be about 50 g/cm2 or more, more preferably about 50 g/cm2 or more. If this levitation force is too small, the refill port 4
This is because the adhesion between the valve body 430 and the replenisher liquid 45 becomes weaker, and mixing of the replenisher liquid 45 and the mother liquid 110 cannot be sufficiently prevented.

In the supply path 41, the first valve 43
A second valve 44 is provided on the replenisher tank 40 side. The second valve 44 includes a narrow portion 441 whose inner diameter gradually decreases within the supply path 41 and a spherical valve body 442. The diameter of the valve body 442 is configured to be larger than the inner diameter of the narrow portion 441, and the material may be the same as that of the valve body 440 of the first valve 43. In addition, the levitation force that has already been defined is
The weight of the valve body 442 may be about 40 g/cm2 or more, more preferably about 50 g/cm2 or more. If this floating force is too small, the narrow portion 441 and the valve body 4
This is because the adhesion force with 42 becomes weak and a sufficient sealing effect cannot be exerted.

Furthermore, an engaging portion 432 made of a magnetic material is provided at the end of the valve body 430. The engaging portion 432 is provided at the outer end of the supply path 41.
A solenoid 411 is installed at a position facing the valve body 430, and is configured to electrically restrict opening and closing of the valve body 430.

To explain the operation of the replenishment means 4 configured as described above when replenishing the replenisher, when the replenishment port 42 is in contact with the surface of the processing liquid, air is generated in the replenisher tank 40. Since the replenisher 45 does not enter the tank, the replenisher 45 is not supplied. At this time, the valve 43 of the replenishment port 42 connects the replenisher 45 and the mother liquor 110.
This prevents the two from coming into contact with each other, thereby preventing the two from mixing due to diffusion. Therefore, the mother liquor 110 is diffused into the replenisher 45,
The concentration of the supplied replenisher 45 does not become diluted. Furthermore, due to leakage from the first valve 43, a small amount of mother liquor 11
Even if 0 diffuses into the supply path 41, the second valve 44 prevents it from diffusing into the replenishment tank 40, and the concentration of the replenisher in the replenishment tank 40 is always maintained constant.

When the processing liquid level is lowered due to the removal of the processing liquid due to the removal of the photosensitive material S or due to evaporation, the liquid level moves away from the replenishment port 42 . Here, the replenisher is replenished from the component replenishment system, and thereafter, the restriction on closing of the valve body 430 by the solenoid 411 is released. Then, as shown by the imaginary line in FIG. 4, the valve body 430 opens. The replenisher 45 flows out from the replenishment port 42, and at the same time, air enters from the replenishment port 42 and accumulates in the replenishment tank 40. At this time, the first valve 43 is opened by the valve body 440 descending following the processing liquid level. At this time, the replenisher 45 flows from the upper replenisher tank 40, the valve body 442 of the second valve 44 is pushed down, and the second valve 44 opens.

When the processing liquid level rises due to the supply of the replenisher 45 and reaches the replenishment port 42, the supply of the replenisher 45 is stopped and the valve body 442 rises due to buoyancy, and the first valve 43 is closed. At the same time, the second valve 44 is also closed due to the buoyancy of the valve body 442. Here, the solenoid 411 is turned on again to regulate the valve body 430 to the closed state.

With this configuration, the replenisher 45 is immediately supplied even when the processing liquid level drops slightly, making it possible to maintain the height of the processing liquid level at a substantially constant level. Furthermore, since the height of the processing liquid level is constant, processing time does not vary and processing unevenness is reduced. moreover,
Dissolved components in the processing liquid are less likely to precipitate on the inner wall of the processing tank, reducing fluctuations in liquid composition and staining of the inner wall of the processing tank. In particular, the device of the above embodiment has the advantage that the replenishing fluid 45 can be replenished accurately and appropriately quickly with a very simple valve structure.

In the case of the bleaching tank 12 and the fixing tank 14, only the liquid replenishing means described above is provided, and the processing liquid is replenished as needed as the processing liquid decreases. Note that the liquid replenishing means provided in the bleaching tank 12 and the fixing tank 14 may not have an opening/closing regulating structure using the solenoid 411.

Specifically, the current concentration is set to 0.5 to 50A.
/l, the replenishment amount of conventional replenisher is 1/l.
It can be reduced by 10 to 1/2.

That is, the amount is 25 to 40 ml per 1 m 2 of the photosensitive material.

Furthermore, the bleaching tank 12 and the fixing tank 14 are provided with only a liquid replenishment system having the above-mentioned structure for replenishing the amount of water that has been reduced due to evaporation or the like. For replenishment in the bleach tank 12, the replenisher may contain about 1 to 5% bleach or the like.

Similarly, when replenishing the fixing tank 14,
The replenisher may contain a small amount of about 1 to 5% of a fixing agent. The bleaching agent and fixing agent added here are used to replenish the amount lost due to removal of the photosensitive material, so only a small amount is needed, and the majority of the replenisher is water.

As described above, the processing apparatus used in the present invention is not limited to the illustrated example, and can have various configurations depending on the processing steps and the like.

In addition to the processing apparatus 1 described above, the processing apparatus 2 shown in FIG. 5 does not have a liquid tank for each processing tank, but has a color developing tank 11,
A liquid tank 24 defined by anion exchange membranes A4 and A5 is provided between the bleach tank 12 and the color developer 1.
It has a structure in which a cathode 37 is immersed in a bleaching solution 10 and an anode 38 is immersed in a bleaching solution 120. And anion exchange membrane A4, A
The liquid tank 24 between 5 and 5 is filled with an electrolyte solution 240.

[0091] By applying electricity in such a configuration, halide ions move from the color developing tank 11 to the bleaching tank 12, and the same effect as in the above embodiment can be obtained. Furthermore, such a structure may also be provided between the bleaching tank 12 and the fixing tank 14.

Next, the processing liquid used in the present invention will be described.

The color developing solution used in the development of color sensitive materials is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but
p-phenylenediamine compounds are preferably used,
As a typical example, 3-methyl-4-amino-N,N-
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4 -amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo[2,2
, 2] octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers. , fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,
N-trimethylenephosphonic acid, ethylenediamine-N,
Representative examples include N,N',N'-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.

The black and white developer used for reversal processing of color sensitive materials and development processing of black and white sensitive materials includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-p - Known black and white developing agents such as aminophenols such as aminophenol can be used alone or in combination. The pH of these color developing solutions and black and white developing solutions is 9.
~12 is common.

[0096] The black and white developer also contains, as a developing agent,
For example, using metal compounds such as complexes with Ti(III) and Fe(II) as central metals, coordinated with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA). (See Japanese Patent Publication No. 54-41899, etc.).

In the processing of color sensitive materials, after color development processing, bleaching processing and bleach-fixing processing are performed. Bleaching agents used in the bleaching solution or bleach-fixing solution in these treatments include, for example, iron (III) and cobalt (III).
, compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. . Among these, aminopolycarboxylic acid iron(III) complex salts including ethylenediaminetetraacetic acid iron(III) complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these iron(III) aminopolycarboxylic acid complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

A bleaching accelerator may be used in the bleaching solution and bleach-fixing solution, if necessary.

Specific examples of useful bleach accelerators are described in US Pat. No. 3,893,858;
West German Patent No. 1,290,812, JP-A-53-956
No. 30, Research Disclosure No. 17,
Compounds having a mercapto group or disulfide bond described in No. 129 (July 1978), etc.; JP-A-1988-1
Thiazolidine derivatives described in US Pat. No. 40129; thiourea derivatives described in US Pat. No. 3,706,561; iodide salts described in JP-A-58-16235;
Polyoxyethylene compounds described in Japanese Patent Publication No. 748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide bond are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-9
The compounds described in No. 5630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834.

[0100] Examples of fixing agents used in bleach-fixing solutions and fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The use is common, especially ammonium thiosulfate, which is the most widely used. Further, as the preservative, sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts are preferable.

[0101] Furthermore, the fixer used for processing black and white sensitive materials is
It has a pH of 3.8 or higher, preferably 4.2 to 7.0. As the fixing agent, ammonium thiosulfate is particularly preferably used from the viewpoint of fixing speed.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potash alum, and the like. In addition, the fixing solution may contain tartaric acid, citric acid, gluconic acid, or their derivatives alone or in combination with two or more of them.
Can be used. Furthermore, the fixer may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (
(e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid),
Chelating agent with hard water softening ability and JP-A-62-78551
It can contain the compounds described in No.

The photosensitive material used in the present invention may be either a color photosensitive material or a black and white photosensitive material. Examples of such materials include those mentioned above, such as color paper, color negative film, color reversal film, color positive film, color reversal photographic paper, photographic material for plate making, X-ray photographic material, black-and-white negative film, and black-and-white photographic photographic material. paper,
Examples include microphotosensitive materials. Among these, it is preferable to apply it to the processing of color photosensitive materials.

In addition to the processing liquid described above, a rinsing liquid and a stabilizing liquid are used for processing the photosensitive material in the present invention. This rinsing liquid has the function of removing residual processing chemicals from the previous process, and is used almost synonymously with washing liquid and washing water. Details of the processing liquid, including the processing liquid mentioned above, processing conditions, etc., can be found in JP-A-63-70857 and JP-A-1-1.
No. 190889, JP-A-2-103035, JP-A-2
-103037, JP-A-2-71260, JP-A-6
1-267559 etc. can be referred to.

[0105]

[Examples] The present invention will be specifically explained below with reference to Examples.

Example 1 Sample 201 of Example 2 of JP-A-1-259359
After exposing this color negative film (coated silver amount: 7.2 g/m2), it was run using a cine-type automatic processor according to the processing steps shown in Table 1 until 3 liters of color developer was replenished. did. Thereafter, the temperature control time per day was set to 10 hours, and running processing was performed for 4 months at a rate of 10 images per day of 24 images of 135 size.

[0107]

[Table 1]

The color developing solution used in the processing steps shown in Table 1 was shown in Table 2, the bleaching solution was shown in Table 3, the fixing solution was shown in Table 4, and the stabilizing solution was shown in Table 5. Each was used.

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

The rinsing liquid was a fixing liquid having the composition shown in Table 4 diluted to 2%.

[0114] Ion-exchanged water was used as the washing water.

[0115] In the above processing, the processing was carried out in the same manner except that the automatic processor was replaced with a modified machine having the configuration shown in Fig. 1. At this time, molybdenum-containing stainless steel (SU
S316 equivalent) sheet [NTK3 manufactured by Nippon Metal Industry Co., Ltd.
16: Size 15 cm x 10 cm (wall thickness 1 mm width)] is installed as an anode in the bleach tank and liquid tank. A carbon sheet [Cresheet manufactured by Kureha Chemical Industry Co., Ltd.: Size 15 cm
m×10 cm (wall thickness: 5 mm)] were used, respectively. In addition, the anion exchange membrane is Neosepta AFN
-7 (manufactured by Tokuyama Soda) was used.

Furthermore, 3wt is added to the liquid tank provided in the developer tank.
% of sodium carbonate as an electrolyte, and was replenished at a replenishment amount of 2 ml per 1 m of 35 mm wide photosensitive material, and the drained liquid due to overflow was allowed to flow into the first washing tank.

[0117] The amount of washing water to be replenished to the second washing tank is 35 m.
The amount of water was 10 ml per meter of photosensitive material having a width of m, and the overflow water was allowed to flow into the first washing tank. Therefore, the first washing tank includes the second washing tank and the first washing tank 21 of the developing tank.
The liquid is replenished from the chamber 211.

[0118] The overflowing liquid from the first washing tank was flowed into the first chamber 231 of the liquid tank 23 provided in the fixing tank, and was used as an electrolyte solution. The inflow amount (replenishment amount) was 32 ml per 1 m of photosensitive material having a width of 35 mm.

Furthermore, a liquid tank 23 provided in the fixing tank
The drained liquid due to the overflow of the electrolyte solution from the first chamber 231 is made to flow into the rinsing tank, and the drained liquid due to the overflow from the rinsing tank is further made to flow into the first chamber 221 of the liquid tank 22 provided in the bleaching tank. and used as an electrolyte solution.

In the developing tank, bleaching tank, and fixing tank, a weight loss replenishment device is provided which replenishes only the amount lost in response to a drop in the liquid level, as shown in FIG. The tank is provided with a processing component replenishment system for replenishing processing components, and replenishment is carried out at a rate of 1.5 ml per 1 m of 35 mm width photosensitive material (Rep 1).

[0121] The current conditions were that a voltage of 2.6 V was applied as an initial voltage in each liquid tank, and a voltage of 0.6 V was applied in color development.
A current was allowed to flow (current density 0.4A/dm
2). Similarly, with bleaching, 0.6A (current density 0.4A/d
m2), 1.2A at fixing (current density 0.8A/dm2)
) was made to flow. Note that color development was replenished using a regular replenishment pump (Rep 1), and water was replenished using the apparatus shown in FIG. Roughly complete replenishment is 1.
It was 5 ml.

Example 2 In a processing apparatus similar to the above-mentioned Example 1, the developing tank, bleaching tank, and fixing tank were each provided with a normal processing tank without an energizing processing tank, and no energizing processing was performed. The treatment was carried out using the replenishment amounts shown in Table 6. Other processing conditions are Example 1
It is similar to

[0123]

[Table 6]

As a result of the above processing, the photographic performance of the light-sensitive material processed with the processing apparatus of Example 1 was improved in terms of green sensitivity and gradation, defective desilvering, defective color restoration, etc., due to the overflow of the processing solution. A processing capacity equivalent to that of the photosensitive material processed with the processing apparatus of Example 2 was obtained. Furthermore, in Example 1, the amount of liquid drained is 32 to 32 per meter of 35 mm width
36 ml, but in Example 2, the drainage volume was 35 mm width x
160 to 165 ml per 1 m, and the drainage volume is 1/4.5
It was found that it can be reduced to ~1/5.

[0125]

Effects of the Invention According to the present invention, there is an advantage that by eliminating the waste liquid of the processing liquid, the amount of waste liquid can be reduced and good photographic performance can be obtained.

[Brief explanation of drawings]

FIG. 1 is a plan view schematically showing a tank arrangement of a processing apparatus used in the present invention.

FIG. 2 is a side sectional view of a developer tank and a replenishing means, showing the structure of a replenishment system.

FIG. 3 is a partial perspective view showing a developing tank and a bleaching tank.

FIG. 4 is a side sectional view of the supply path.

FIG. 5 shows another embodiment of the present invention, and is a plan view schematically showing a tank arrangement of a processing device.

[Explanation of symbols]

1 Processing device 11 Color developer tank 110 Color developer 12 Bleach tank 120 Bleach solution 13 Rinse tank 14 Fixer tank 140 Fixer 15 First washing tank 16 Second washing tank 17 Stabilizer tank 170 Stabilizer 21, 22, 23 Liquid tank 211 , 221, 231 First chamber 212, 222, 232 Second chamber 31, 33, 35 Cathode 32, 34, 36 Anode 4 Replenisher 40 Replenisher tank 41
Supply path 411 Solenoid 42 Replenishment port 43 First valve 430 Valve body 431 Fulcrum 432 Engaging portion 44 Second valve 441 Narrow portion 442 Valve bodies A1 to A3 Anion exchange membrane R Rinse liquid S Photosensitive material W Rinsing water

Claims (3)

[Claims] 1. A treatment liquid is filled in a tank so as to be in contact with a liquid containing an electrolyte through at least an anion exchange membrane, and an anode is immersed in the electrolyte-containing liquid and a cathode is immersed in the treatment liquid. and a photographic processing method in which the silver halide photosensitive material after exposure is processed by applying electricity to the anode and the cathode, the tank for processing the silver halide photosensitive material after the exposure has a reduced amount of liquid. 1. A photographic processing method characterized in that a replenishing means is provided for replenishing liquid in accordance with the liquid replenishment, and the amount of liquid drained due to liquid replenishment is reduced to substantially zero. 2. Among the replenishment means, the replenishment means for replenishing the developer includes a processing component replenishment system that replenishes processing components in accordance with the consumption amount of the processing components, and a processing component replenishment system that performs replenishment in response to a decrease in water content. The process liquid replenishment system consists of a liquid replenishment system, and processing liquid replenishment is
2. The photographic processing method according to claim 1, wherein each of the two replenishment systems is replenished separately. 3. A treatment liquid having bleaching ability is filled in the tank so as to be in contact with the electrolyte solution through at least an anion exchange membrane, and a cathode is provided in the electrolyte solution, and an anode is provided in the treatment liquid having bleaching ability. A photographic processing method in which the silver halide photosensitive material after exposure is processed by immersing the material in each case and applying electricity to the anode and the cathode, the bath for processing the silver halide photosensitive material after exposure includes a liquid. 1. A photographic processing method characterized in that a replenishing means is provided for replenishing liquid in accordance with a decreased amount, and the amount of drained liquid caused by liquid replenishment is reduced to substantially zero.