JPH03126030A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the decreasing in the flow rate of a permeated liquid and the clogging of a reverse osmosis membrane by adopting a multistage counter current system of >=3 tanks, taking-in a washing liquid or stabilizer from the tank just before the final tank, subjecting the liquid to a reverse osmosis membrane treatment under specific conditions and returning the permeated liquid to the final tank. CONSTITUTION:The silver halide photographic sensitive material is processed in a bath 2 having fixability and is subjected to washing and/or stabilizing processing in the multistage counter current system having >=3 tanks. The washing liquid or stabilizing liquid is taken-in from the tank just before the final tank 5 and is subjected to the reverse osmosis membrane treatment under <=10kg/cm<2> liquid feeding pressure and <=0.30 recovery rate of the flow rate of the permeated liquid with respect to the flow rate of the feed liquid. The permeated liquid is returned to the final tank 5. The decreasing in the flow rate of the permeated liquid and the clogging of the reverse osmosis membrane are prevented in this way even if the processed liquid of the washing and/or stabilizing processing is subjected to the regeneration treatment continuously for a long period of time by the reverse osmosis membrane.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing silver halide photographic materials, and further relates to a method for processing silver halide photographic materials, and further relates to a method for processing a processing solution in a washing tank and/or a stabilizing tank using a reverse osmosis membrane. The present invention relates to a processing method that reduces the amount of fresh liquid to be newly supplied to these processing tanks by purifying and reusing it. In particular, even if the washing liquid and/or stabilizing liquid in a multi-stage countercurrent method is continuously processed using a reverse osmosis membrane for a long period of time, the i3 permeate flow rate will not decrease and the reverse osmosis membrane will not be clogged, resulting in stable images with excellent performance. The present invention relates to a method for processing silver halide photographic materials that can be obtained by The present invention also relates to a method for processing silver halide photographic materials that reduces environmental pollution and processing costs.

(Prior art) The development process of photographic light-sensitive materials involves the process of forming a silver image (
Commonly used processes include black and white development (black and white development), or development to form a single color image (color development), and black and white negative development, fogging and color development to obtain an inverted color image. The black-and-white development process generally includes a development process, a fixing process, a water washing process, and/or a stabilizing process. The color development process includes a color development process, a desilvering process, a water washing process, and/or a stabilization process. Here, the washing step is a step of washing away chemicals and the like adhering to the photosensitive material, and the stabilizing step is a step of imparting an image stabilizing function that cannot be obtained in the washing step. In order to carry out such a water washing process in one bath and to stably obtain images with good performance, it is necessary to sufficiently wash away chemicals and the like, and a large amount of washing liquid is required. Similarly, one stabilization step can be performed without substantially any water washing step.
A large amount of stabilizing solution was required in order to stably obtain images with good performance during bath processing. Such a large amount of treatment liquid ultimately produces a large amount of waste liquid, which has become a problem from the viewpoint of increased waste liquid treatment cost and increased environmental pollution load.

Therefore, from the viewpoint of reducing environmental pollution load and processing costs including waste liquid processing costs, there is a need for a method that maintains images with good photographic performance and reduces the amount of processing liquid in the washing and/or stabilization process. As one of the effective means for this purpose, a multistage countercurrent water washing and/or stabilization process has been used.

("Photograph Inc.") "Rosensing 41979"
(Refer to pages 29-32 of the November issue) This multi-stage counter-current method can maintain good photographic performance for a certain period of time by increasing the number of stages, while reducing the amount of processing liquid (in the case of the multi-stage counter-current method, the amount of fresh liquid replenishment). Although it is possible to reduce the number of stages, an increase in the number of stages leads to an increase in processing cost and equipment cost, and the practical number of stages is naturally limited. Also,
Even if such a practical multi-stage countercurrent water washing and/or stabilization process is used, it is often impossible to maintain good photographic performance if continuous processing is continued for a long period of time, such as an increase in yellow stain. Problems such as this occur.

Recently, by using a reverse osmosis membrane to treat the contaminated washing liquid and/or stabilized liquid through continuous processing in a multi-stage countercurrent system and reusing it as a fresh liquid replenisher, the amount of fresh liquid replenishment can be further reduced while improving the quality of the cleaning liquid. Attempts are being made to find ways to maintain good photographic performance.

For example, in JP-A No. 58-105150, the overflow liquid from the washing tank is treated with a reverse osmosis membrane, the purified permeate is returned to the washing tank and reused, and the concentrated liquid is stored in the prebath of the washing tank. By returning the bleach-fixer from the bleach-fix tank to the washing tank along with the photosensitive material, the bleach-fixer is reused in the bleach-fix tank, reducing the amount of fresh solution refilled to the washing tank and improving the bleach-fixing process. It is described that it improves desilvering performance in a bath and prevents edge seepage contamination of photosensitive materials.

In addition, JP-A-60-241053 is the aforementioned JP-A-58-241053.
The liquid treated with the reverse osmosis membrane in No. 105150 is simply changed from a washing liquid to a stabilizing liquid, and it is stated that yellow stain after long-term storage and stain immediately after treatment can be reduced.

However, in the methods described in these patent publications, the fit of the fIA-condensed liquid discharged without passing through the reverse osmosis membrane (concentrated liquid It is necessary to reduce the flow rate sufficiently.

This is because the concentrated liquid is returned to the bleach-fix tank, which is the pre-bath of the washing tank, but if the flow rate of the concentrated liquid is higher than the flow rate of the permeate, the treated liquid in the washing tank will pass through the reverse osmosis membrane treatment equipment. The liquid is then transferred to the pre-bath bleach-fix tank, and unless fresh liquid is replenished in an amount equal to the flow rate of the concentrate, the amount of liquid in the washing tank will rapidly decrease and treatment will become impossible. This means that the purpose of reducing the amount of fresh liquid replenishment cannot be sufficiently achieved.

Therefore, in order to sufficiently reduce the flow rate of the concentrate, the reverse osmosis membranes used in these patent publications need to be large in area and have a pressure of 40 to 55 kg/kg.
AI and high pressure were required. For this reason, it requires a large and expensive pressure pump and has the disadvantage of increasing equipment cost, making it difficult to put it into practice except in some large-scale laboratories. Furthermore, such high pressure causes a rise in temperature of the reverse osmosis membrane treatment solution, which has the disadvantage of deteriorating photographic performance.

As a means to improve the drawbacks of reverse osmosis membrane treatment using high pressure, Japanese Patent Application Laid-Open No. 62-254151 discloses that the overflow liquid from the washing tank or stabilization tank is temporarily collected in a storage tank, and the liquid accumulated in this storage tank is treated in a conventional manner. A processing method is described in which the material is concentrated and regenerated while being subjected to repeated VFJ cycles using a low-pressure reverse osmosis membrane. With this method, it has become possible to lower the pressure during reverse osmosis membrane treatment to 14 to 20 kg/cd, which is lower than the conventional pressure (medium pressure).

However, it has been newly discovered that if such high-pressure and medium-pressure reverse osmosis membrane treatment is performed continuously for a long period of time, the reverse osmosis membrane becomes clogged and the permeate flow rate rapidly decreases. .

These high-pressure and medium-pressure reverse osmosis membrane treatments have problems of reduced permeate flow rate and clogging, although the degree of these problems differs, and for example, they are not very noticeable after continuous treatment for 1 to 2 weeks. However, this problem becomes more noticeable during continuous processing over a period of one month, and a fundamental solution has been desired.

There is almost no known technique for preventing such clogging of reverse osmosis membranes other than the method using a chelating agent described in JP-A-62-254151. This method using a chelating agent uses a chelating agent to prevent clogging of a reverse osmosis membrane due to calcium and magnesium originally contained in the washing solution and calcium and magnesium eluted from the photosensitive material.

Although the reduction in permeate flow rate and clogging can be improved to some extent by using this chelating agent, if reverse osmosis membrane treatment is performed continuously for a long period of time, the permeate flow rate will decrease and clogging will occur. It turned out that this was still insufficient.

The same also applies to the photographic performance of the resulting image (in particular, the occurrence of yellow stain). In other words, in both high-pressure and medium-pressure reverse osmosis membrane treatments, the amount of fresh liquid replenishment is reduced, and along with the decrease in permeate flow rate and the occurrence of clogging due to long-term continuous treatment, although there are differences in the degree,
There was a problem in that the photographic performance of the resulting images deteriorated. Therefore, it has been desired to develop a method that can continuously obtain images with excellent photographic performance even after continuous processing for a long period of time.

(Problems to be Solved by the Invention) The first object of the present invention is to solve the problem that even if the treated liquid in multi-stage countercurrent water washing and/or stabilization treatment is continuously regenerated for a long period of time using a reverse osmosis membrane, the permeated liquid 2ii It is an object of the present invention to provide a method for processing a silver halide photographic material, which prevents a decrease in the amount of water and prevents clogging of a reverse osmosis membrane.

A second object is to provide a method for processing a silver halide photographic material, which prevents the occurrence of yellow stain and maintains excellent performance even after continuous processing for a long period of time.

A third object is to provide a method for processing silver halide photographic materials in which the environmental pollution load is significantly reduced and equipment costs and processing costs are reduced.

(Means for Solving the Problems) As a result of intensive studies, the present inventor has discovered that a silver halide photographic light-sensitive material is processed in a bath having fixing ability, and then washed and/or stabilized in a multi-stage countercurrent system. In the treatment method, the multistage countercurrent system is a multistage countercurrent system with three or more tanks, and the washing liquid or stabilizing liquid is taken in from the tank just before the final tank, and the liquid feeding pressure is 10 kg/C (less than or equal to the weight of the liquid being fed). It has been found that the above objectives can be achieved by a method for processing silver halide photographic materials, which is characterized by performing reverse osmosis membrane treatment at a recovery rate of 0.30 or less for the flow rate of the permeate, and returning the permeate to the final tank. Ta.

The present invention will be explained in more detail below.

As mentioned above, the problems when repeatedly regenerating the washing solution and/or stabilizing solution using a reverse osmosis membrane are a decrease in the flow rate of the permeate, clogging of the reverse osmosis membrane, and deterioration of photographic performance due to long-term continuous processing. It is deterioration.

Reverse osmosis membranes are originally molecular-level filtration membranes, so they require high pressure to pass through the treatment liquid, and are prone to clogging due to adhesion and accumulation of components that are filtered and separated when used for long periods of time. It is something. In addition, the cause of the decrease in permeate flow rate cannot be said to be due to physical clogging of the reverse osmosis membrane pores, but is due to changes in the composition of the membrane itself, such as changes in the membrane surface due to long-term use. It is also conceivable that the flow rate of the permeate decreases due to a decrease in the diameter of the membrane pores (for example, the degree of polymerization changes, crosslinking of the membrane surface progresses, and the diameter of the pores decreases).

Various factors can be considered to cause clogging of reverse osmosis membranes. For example, gelatin eluted from light-sensitive materials (
Especially calcium and magnesium contained in gelatin)
may adhere to the reverse osmosis membrane and cause clogging, and various compounds with fairly large molecular weights such as sensitizing dyes added to photosensitive materials may elute and adhere to the reverse osmosis membrane and cause clogging. Alternatively, chemicals in processing tanks for developing, bleaching, fixing, etc. may be brought into the washing solution or stabilizing solution with the photosensitive material, causing clogging, or furthermore, large amounts of bacteria may occur in the washing solution or stabilizing solution, causing clogging. etc. are possible.

As a result of careful study by the present inventor, the multistage countercurrent system is changed to a multistage countercurrent system with three or more tanks, and the washing liquid or stabilizing liquid is introduced into the reverse osmosis membrane treatment device from the tank immediately before the final tank, and the liquid feeding pressure is increased. 10
kg/aj or less, which is extremely low compared to conventional methods, and by performing reverse osmosis membrane treatment with a recovery rate of permeate flow rate of 0.30 or less per 2 liters of liquid sent, and returning the i3 filtrate to the final tank, it can last for a long period of time. It was found that continuous regeneration treatment also prevented a decrease in the permeate flow rate and clogging of the reverse osmosis membrane.

The reverse osmosis membrane treatment of the present invention reverses the concept of conventional reverse osmosis membrane treatment.

In other words, in conventional reverse osmosis membrane processing, the flow rate of permeate is increased relative to the flow rate of liquid fed by high liquid feeding pressure, and the flow rate of concentrated liquid is decreased. It has been thought that this method increases over-separation efficiency. This is certainly true at the start of reverse osmosis membrane treatment, but as the treatment progresses and the reverse osmosis membrane becomes clogged, in order to obtain the same permeate flow rate as at the start, it is necessary to increase the flow rate. Pressure is required, and unless the liquid feeding pressure is increased, the permeate flow rate will suddenly and drastically decrease.

On the other hand, in the present invention, by reducing the permeate flow rate relative to the liquid feed flow rate and increasing the concentrate flow rate by using a low liquid feed pressure, although the filtration separation efficiency at the start decreases, it is possible to perform continuous regeneration treatment for a long period of time. Even if the filtration rate is low, a decrease in the amount of permeate and clogging of the reverse osmosis membrane can be prevented, making it possible to maintain the filtration separation efficiency at the start. This is because the flow rate of the concentrated liquid is larger than the flow rate of the permeated liquid, and it is presumed that this large amount of concentrated liquid washes away the surface of the reverse osmosis membrane and has the effect of preventing clogging of the membrane.

In the present invention, the recovery rate refers to the flow rate of permeate that permeates through the reverse osmosis membrane and is purified, relative to the amount of liquid sent from the washing tank or stabilization tank to the reverse osmosis membrane device via piping. Indicates the winning percentage. That is, per reverse osmosis membrane, the flow rate of the permeate that has passed through the reverse osmosis membrane and been purified is fmffi/min.
The flow rate of the concentrated liquid that is discharged without passing through the reverse osmosis membrane is Cl1lI! /m! n, the liquid flow ffl (R) sent to the reverse osmosis membrane device is (r + c
) d/win, and the recovery rate is (r/f +
c).

In the present invention, a recovery rate of 0.30 or less means that the amount of concentrated liquid discharged from the reverse osmosis membrane processing device without passing through the reverse osmosis membrane exceeds 70% of the liquid flow rate,
It is presumed that this large amount of concentrated liquid washes away the surface of the reverse osmosis membrane and prevents the membrane from clogging.

In the present invention, the lower limit of the recovery rate is not particularly limited, but it is preferably 0.02 or more depending on the liquid feeding flow rate and the like.

In this way, the recovery rate can be controlled to 0.30 or less by adjusting the three valves shown as valves 14 to 16 in FIG. 1, for example.

In the present invention, the recovery rate is preferably 0.20 to 0.05, particularly preferably 0.10 to 0.05.

Further, in the present invention, it is preferable that the permeate flow rate per reverse osmosis membrane is 110 m1/win or more.

By increasing the permeate flow rate in this manner, a sufficient absolute amount of the processing liquid to be purified and reused can be obtained, and the amount of fresh liquid to be newly replenished can be sufficiently reduced.

In the present invention, the permeate flow rate per 1 nl of reverse osmosis membrane is
More preferably 110Id/min to 500m/sin
and more preferably 120d/1Iin to 300a
+1! /nin.

Particularly preferably 130 relatives/min to 250 relatives/5
It's hin.

In the present invention, the liquid flow rate per reverse osmosis membrane is preferably 10,000 d/min to 400 m/sin, more preferably 5,000 d/sin to 800 d/wi.
n, particularly preferably 3000a+t/m1n-100
0d/+min.

In the present invention, treating the washing liquid or stabilizing liquid with a reverse osmosis membrane means that the liquid in at least one tank used for the washing and/or stabilization process is brought into contact with the reverse osmosis membrane, and the liquid is permeated through the reverse osmosis membrane. Refers to returning the liquid (permeate) to the final tank.

In the present invention, the multistage countercurrent water washing and/or stabilization step is composed of 3 or more tanks, preferably 3 to 9 tanks.
tank, more preferably 3 to 5 tanks. All of these constituent tanks may be water washing baths, or all of them may be stabilization baths. Furthermore, these constituent tanks may be composed of a combination of a washing bath and a stabilizing bath, for example, a plurality of washing baths followed by at least one stabilizing bath.

When a multi-stage countercurrent system is configured with three washing tanks, the bath with fixing ability is followed by the first washing tank, the second washing tank, and the third washing tank, and the photosensitive material is stored in the first washing tank, the second washing tank, and the third washing tank. Washing tank, 3rd
It will pass through the washing tank at one tilt. For this reason, the liquid in the first washing tank has a high concentration of pre-bath components brought in together with the photosensitive material, and the concentration becomes higher in the order of the second washing tank and the third washing tank.

When the intake port for the liquid supplied to the reverse osmosis membrane device is installed in the first washing tank, the concentration of the pre-bath components is high, so in order to obtain a sufficient permeate flow rate, a large-area reverse osmosis membrane and high pressure are required. However, a low-pressure reverse osmosis membrane such as the one of the present invention inevitably suffers from insufficient pressure, making it impossible to obtain a sufficient flow rate of permeate, and at the same time, clogging is likely to occur. Therefore, in the present invention, the liquid intake port is the front tank of the final tank. Furthermore, the permeate is returned to the final tank.

Further, the concentrated liquid discharged from the reverse osmosis membrane treatment device is returned to the same tank as the tank in which the liquid intake port is installed or to the previous tank. Preferably, it is the same tank as the one in which the liquid intake is installed. When returning the concentrated liquid to the tank, use
A storage tank as described in No. 2-254151 may be provided, or the water may be returned directly to the tank, but from the viewpoint of increased equipment cost and running cost and complexity of operation, It is preferable to return it.

More specifically, the configuration of the water washing and/or stabilization step in the present invention includes the following.

Configuration (1): A configuration in which three washing baths are provided after a processing bath (fixing bath or bleach-fixing bath, the same applies hereinafter) having fixing ability (
(a first washing tank, a second washing tank, and a third washing tank). In this case, the replenisher is supplied to the third washing tank, and the overflow liquid of each tank is led to each front tank (here, the overflow liquid of the first washing tank is also supplied to the processing bath having fixing ability, which is the front tank). (The same applies to the following configuration), and the reverse osmosis membrane treatment device is installed in the second washing tank. That is,
The washing liquid in the second washing tank is led to the reverse osmosis membrane treatment device by piping, the permeated liquid is supplied to the third washing tank, and the 4iii liquid is returned to the second washing tank.

Configuration (2): A configuration in which four washing baths are provided after the processing bath having fixing ability (first washing tank, second washing tank, third washing tank, and fourth washing tank). In this case, the replenisher is supplied to the fourth washing tank, and the overflow liquid of each tank is led to each front tank. Further, the reverse osmosis membrane treatment device is installed in the third washing tank. That is, the washing liquid in the third washing tank is led to the reverse osmosis membrane treatment device through piping, and the permeate is supplied to the fourth washing tank,
The concentrated liquid is returned to the third washing tank.

Configurations (3) and (4): The above configurations (1) and (2)
) in which the washing bath, washing tank, and washing liquid were changed to a stabilizing bath, a stabilizing tank, and a stabilizing liquid, respectively.

In the above, preferred configurations include configuration (1) and configuration (
2).

The treatment liquid (washing liquid or stabilizing liquid) may be supplied from the tank in which the reverse osmosis membrane is installed to the reverse osmosis membrane by supplying the overflow liquid from the tank in which the reverse osmosis membrane is installed to the reverse osmosis membrane. However, the treatment liquid in the reverse osmosis membrane installation tank may be forcibly supplied through a pipe provided separately from the overflow liquid, and the latter forcible supply form is preferable.

In either case, pressure is required in order for the treatment liquid supplied to the reverse osmosis membrane to permeate through the reverse osmosis membrane.

There are various types of reverse osmosis membranes, such as high-pressure reverse osmosis membranes, medium-pressure reverse osmosis membranes, and low-pressure reverse osmosis membranes. However, high-pressure reverse osmosis membranes (pressure is 40 to 55 kg/c++I) are expensive, and there are problems such as high equipment costs such as high-pressure pumps to obtain high pressure, and high energy consumption. When applied to a processing liquid (washing liquid or stabilizing liquid), the processing liquid generates heat and its temperature rises, which has a negative effect on photographic performance and furthermore generates noise.

Therefore, it has been desired to use a low-pressure reverse osmosis membrane, but as mentioned above, low-pressure reverse osmosis membranes are extremely sensitive to clogging and have the problem of quickly decreasing the permeate flow rate. could not be used stably for a long period of time. In the present invention, even if such a low-pressure reverse osmosis membrane is used, clogging and permeate 2! It has the remarkable effect of preventing a decrease in image quality and making it possible to obtain images with excellent performance in a stable manner for a long period of time.

Therefore, the reverse osmosis membrane used in the present invention may be a high-pressure reverse osmosis membrane or a medium-pressure reverse osmosis membrane, but is preferably a low-pressure reverse osmosis membrane.
0pp-containing aqueous solution at 25'C, pressure 5 kg/c
NaCl in the permeate when reverse osmosis membrane treatment was performed under the conditions of d.
Reverse osmosis membranes with a rejection rate of 30 to 90% are preferred. When a loose reverse osmosis membrane is used, the permeate flow rate is large even at low pressure, and E
DTA-Fe can also be sufficiently removed.

These reverse osmosis membranes consist of a skin layer that controls membrane performance such as permeate flow rate and rejection rate, and a support layer that supports this layer.There are asymmetric membranes in which both are made of the same material and composite membranes in which they are made of different materials. Examples of asymmetric membranes include cellulose acetate membranes and polyamide membranes, and composite membranes include those in which a skin layer is formed by coating a polysulfone support layer with polyethyleneimine and tolylene diisocyanate, and those in which furfuryl alcohol is polymerized. There are synthetic composite membranes using synthetic materials such as those with a skin layer formed on them.The details are described in "Beppu Kagaku Kogyo 29-7r Development and Practical Application of Advanced Separation Technology" published by Kagaku Kogyo Co., Ltd., pages 156-172. These synthetic composite membranes are preferably used in the present invention in terms of rejection rate, permeate flow rate, and durability to EDTA-Pe.

As the structure of the reverse osmosis membrane, any of a spiral module type, a tubular type, a hollow fiber type, a pleated type, and a rondo type can be used, but the spiral module type is preferable.

Specifically, the synthetic composite membrane is D manufactured by Daicel Chemical Industries.
RA-40, DRA-80, DRA-89 and Toshi 5
Examples include O-200, 5O-210, 5tl-220, and the like.

In the present invention, the feeding pressure of the treatment liquid supplied to the reverse osmosis membrane is preferably 2 to 10 kg/cd, more preferably 30 kg/cd.
~8 kg/cd, Q also preferably 3-6 kg
/c4.

The usual fresh liquid replenishment in a multi-stage countercurrent system is introduced into the last tank of each bath, washing bath and stabilizing bath.

Conventionally, the amount of replenishment of this fresh liquid is generally 800 d or more per rrl of light-sensitive material. In addition, even if a multistage countercurrent method and a reverse osmosis membrane are combined, conventional photosensitive materials In? Hit 40
It is 0d or more. However, in the present invention, even if the amount of fresh liquid replenishment was significantly reduced to 200 d or less, a remarkable effect was obtained in that images with excellent performance could be stably obtained for a long period of time.

This is because in the present invention, clogging of the reverse osmosis membrane is effectively prevented, so there is no decrease in the amount of permeate and it is possible to return a stable amount of permeate to the treatment bath. This makes it possible to use the permeated liquid (regenerated replenisher) together with the fresh liquid, and the amount of fresh liquid can be reduced accordingly.

Therefore, in the present invention, the amount of fresh liquid replenished may be 200 Id or less per photosensitive material, more preferably 30 to 200 ml per photosensitive material, and even more preferably 50 to 150 ml per rrr of photosensitive material. It is.

The present invention will be explained in more detail below with reference to FIGS. 1 to 4.

In FIGS. 1 to 4, the meanings of symbols in the figures are described below.

1: Color developing tank L1 2: Bleach-fix tank L2 3: First washing tank W1 4: Second washing tank W2 5: Third washing tank W.

6: Fourth washing tank W4 7: Liquid pump P 8: Pressure-resistant device R with built-in reverse osmosis membrane.

9: a Condensed liquid C 10: Permeated water f 11: Replenishment fresh water 12: 13 Ni bar flow water 0F in counter-current washing piping 14-16: Pulp Figure 1 shows the second A method is shown in which washing water is collected from the washing tank Wt, subjected to reverse osmosis membrane treatment, permeated water f is supplied to the third washing tank W, and concentrated liquid C is returned to the second washing tank Wz. This method has the advantage of simple piping and can be implemented at low cost. The pressure device is made of metal or plastic and has a reverse osmosis membrane loaded inside. As the material for the pressure-resistant device, reinforced plastic containing glass fiber is preferably used from the viewpoint of both corrosion resistance and pressure resistance. Through such reverse osmosis membrane treatment, the amount of replenishment fresh water required is significantly reduced, and the amount of overflow water OF from the first washing tank W is also reduced by that ratio.
All of this overflow water OF can also be introduced into the bleach-fix tank L2.

Figure 2 shows a four-tank countercurrent washing system in which washing water is collected from the third washing tank W, subjected to reverse osmosis membrane treatment, permeated water r is supplied to the fourth washing tank W, and concentrated liquid C is supplied to the fourth washing tank W. 3 shows the method of returning to the washing tank W. In this method, as compared to the case shown in FIG. 1, the washing water with a lower concentration of components brought in from the pre-bath along with the photosensitive material is treated, and as a result, the permeated water f becomes more highly purified water and the final washing tank W4. The washing water can be kept cleaner. Furthermore, the amount of fresh water to be replenished can be further reduced than in the case of FIG.

However, since the number of tanks is increased by one compared to FIG. 1, the cost of the device increases slightly.

The methods shown in Figures 1 and 2 are countercurrent water washing methods with 5 or more tanks,
It can also be effectively carried out in the case of a countercurrent stabilization system for a tank or more.

Furthermore, it is also possible to add a stabilizing tank after the systems shown in FIGS. 1 and 2. Addition of such a stabilizing tank can provide an image stabilizing function that cannot be obtained by water washing alone.

Figure 3 shows a comparative method used for running Nα2 in Example 1 (a method based on the method shown in Figure 5 of JP-A-58-105150), in which the first Rinsing water is collected from the rinsing tank W, and subjected to reverse osmosis membrane treatment, and the permeated water f is transferred to the second rinsing tank W! and concentrate C to the first
A method of returning the water to the washing tank W1 is shown.

Figure 4 shows a comparative method used for running Nα22 in Example 2. In the 4-tank countercurrent washing method, washing water is collected from the second washing tank W, and the permeated water is treated with a reverse osmosis membrane. A method is shown in which f is supplied to the third washing tank W, and concentrated liquid C is returned to the second washing tank W.

In the present invention, the opening ratio (S/V, where S indicates the air contact area of the liquid in the tank, and ■ indicates the amount of liquid in the tank) of the washing tank and/or stabilization tank used is 0.03. The following are preferred. More preferably 0.02 or less, particularly preferably 0.02 or less.
It is below O1. By lowering the opening ratio of the tank in this way,
This prevents evaporation and air oxidation of the liquid in the tank, making it more effective in preventing concentration of the treated liquid and clogging of the reverse osmosis membrane.

In the present invention, the fresh liquid supplied to the washing tank may be tap water, well water, etc. normally used for washing. In order to prevent this, it is preferable to use water in which the calcium and magnesium contents are reduced to 3 .mu./L or less, and specifically, it is preferable to use water that has been deionized by ion exchange resin or distillation.

It is known that antifungal agents, chelating agents, pH buffering agents, optical brighteners, etc. are added to washing water, and these additives are known to be added to washing water as desired. can. In order not to increase the load on the reverse osmosis membrane, it is preferable not to use large amounts of these additives.

In addition to the above-mentioned compounds that can be added to the washing water, the stabilizing solution also contains compounds that have an image stabilizing effect, such as aldehydes such as formalin, methylols, aldehyde releases such as hexamethylenetetramine, and ammonium salts. used.

Note that if bacteria are generated in the storage tank of the fresh liquid for supply, it is preferable to irradiate the storage tank with ultraviolet rays.

In the present invention, it is preferable to use an anti-sulfur agent in the liquid having fixing ability, the washing liquid and/or the stabilizing liquid.

The development process of the photographic light-sensitive material in the present invention may be either a process for forming a silver image (black and white development process) or a process for forming a color image (color development process). When forming an image by the reversal method, a black and white negative development process is first performed, followed by white exposure or treatment with a bath containing a fogging agent, followed by color development.

The black and white development process includes a development process, a fixing process, and a washing process. If a stopping treatment step is performed after the development treatment step or a stabilization treatment step is performed after the fixing treatment step, the water washing treatment step may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the photosensitive material, and the developing process may be performed using only an alkaline solution. A development process using a lithium developer as a developer may also be performed.

Color development processing is Research Disclosure Nα
17643, pages 28 to 29, and the usual methods described in Nα18716, 615, left column to right column.

For example, a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process are performed. Instead of the process using a bleaching solution and the process using a fixing solution, a bleach-fixing process can be performed using a bleach-fixing solution, or a bleaching process, a fixing process, and a bleach-fixing process can be performed. May be combined arbitrarily. It is also possible to carry out a monobath processing step using a one-bath developing, bleaching and fixing processing solution that allows color development, bleaching and fixing to be carried out in one bath. In combination with these treatment steps, a pre-treatment step, its neutralization step, a stop-fixing treatment step, a post-hardening treatment step, etc. may be performed, and a water washing step may be provided between the above-mentioned steps. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the light-sensitive material and the development process is performed using an activator solution, or a monobath process may be performed for the activator process. It can also be applied.

The black-and-white developer used in the black-and-white development process is commonly used in processing known black-and-white photographic materials, and can contain various additives that are generally added to black-and-white developers.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned.

In the present invention, the color developing solution is 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-phinidine diamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline. , 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-mecnsulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates are mentioned. Two or more of these compounds can also be used in combination depending on the purpose.

In the present invention, in order to prevent a decrease in the flow rate of the permeate, it is particularly preferable that the color developing solution does not substantially contain benzyl alcohol. This is because benzyl alcohol alters the reverse osmosis membrane and promotes the generation of bacteria in the washing water, and the embodiment of the present invention is most effective when used in a system that does not contain such benzyl alcohol. "Substantially no benzyl alcohol is contained" means that the amount of benzyl alcohol per color developer 11 is 1 ml or less, and preferably it is not contained at all.

In addition, various preservatives are used in color developing solutions, but in order to compensate for the decrease in color development caused by removing Hensyl alcohol, they have a competitive reactivity for the coupling reaction between the oxidized color developing agent and the coupler. is small,
Further, it is preferable that the developing activity is low relative to silver halide.

From this point of view, it is preferable to keep sulfites and hydroxylamine, which have been widely used in the past, to a minimum amount, and it is particularly preferable not to use them at all.

In place of such sulfites and hydroxylamine, hydroxylamine derivatives other than hydroxylamine, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, *g, monoamines, diamines It is preferable to use organic preservatives such as polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines.

The color developer preferably has a pH of 9 to 11, more preferably 9.5 to 10.5, and may contain other known developer components.

In order to maintain the above pH, it is preferable to use various buffering agents. Examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, Acid disodium, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5 Examples include sodium -sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developing solution is preferably 0.1 mol/1 or more, particularly 0.1 to 0.4 mol/I.
! , is particularly preferable.

In addition, various chelating agents can be used in the color developing solution as anti-settling agents for calcium and magnesium in order to improve stability.

Specific examples of chelating agents are shown below, but the invention is not limited thereto.

・Nitrilotriacetic acid ・Diethylenetriaminepentaacetic acid ・ethylenediaminetetraacetic acid ・triethylenetetraminehexaacetic acid ・N,N,N-trimethylenephosphonic acid ・ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・1.3 -Diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthohydroxy Phenylacetic acid/2-phosphonobutane-1,2,4-1-licarboxylic acid/1-hydroxyethylidene-1,1-diphosphonic acid/N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-di Acetic acid Two or more of these chelating agents may be used in combination, if desired.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

For example, it is about 0.1 g to Log per 12 color developing solutions.

Moreover, any development accelerator can be added to the color developing solution if desired.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 75987, No. 38-7826, No. 44-1238
No. 0, No. 459019 and U.S. Patent No. 3,813,2
Thioether compounds described in No. 47, JP-A-52-4
p-phenylenediamine compounds described in No. 9829 and No. 50-15554, JP-A-50-137726
No. 44-30074, Japanese Patent Publication No. 56-15 (i)
Quaternary ammonium salts described in U.S. Pat. No. 826 and U.S. Pat. No. 52-43429, U.S. Pat.
p-aminophenols described in US Pat. No. 2,494,903, US Pat. No. 3.128.1
No. 82, No. 4,230.796, No. 3,253,91
No. 9, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,48
No. 2,546, No. 2,596.926 and No. 3.58
Amine compounds described in No. 2,346, Japanese Patent Publication No. 3716
No. 088, No. 42-25201, U.S. Patent No. 3.12
8.183, Special Publication No. 41-11431, No. 42-2
3883 and U.S. Pat. No. 3,532.501, and other 1-phenyl-3
- Pyrazolidones, hydrazines, isoionic compounds, ionic compounds, imidazoles, etc. can be added as desired.

Any antifoggant can be added to the color developing solution if desired. As the antifoggant, alkali metal halides such as potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimitasole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-henzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution preferably contains a fluorescent whitening agent.

As an optical brightener, 4,4'-diamino-2,2'-
Disulfostilbene compounds are preferred. The amount added is 0~
5 g/L, preferably 0.1-4 g/j! It is.

If desired, various surfactants such as alkylsulfonic acid, arylsulfonic acid, alkylphosphonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

In the case of color paper, the replenishment amount of the color developer is preferably 30 to 300 d/rd, more preferably 40 to 2 d/rd.
00 d/po, particularly preferably 50 to 120 M/+d, and in the case of color negative film, preferably 100 to
1000af/rrf, more preferably 200-700
m1/rd, particularly preferably 300 to 600 d/po.

The processing temperature of the color developer is 20 to 50°C, preferably 3
It is 0-40°C. The processing time for color development is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

Examples of bleaching agents used in bleaching solutions and bleach-fixing solutions include iron (■), cobalt (■), chromium (rV), and wA.
Examples include compounds of polyvalent metals such as (n), peracids, quinones, nitro compounds, and the like. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobal (Ill), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminotetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfate; bromate; 1J47
7 ganic acid salts; nitrobenzenes and the like. Preferably, the organic acid ferric complex salt described above is preferred.

The amount of these bleaches used is 12 times the bleach solution or bleach-fix solution.
It is 0.05 to 0.5 mol per unit, and 0.1 to 0.3 in particular from the viewpoint of desilvering property, cyan dye recoloring property, and stain prevention.
When using the above organic acid ferric complex salt, which is preferably expressed in molar terms, it is usual to add free organic acid in a molar ratio of about 1/10.

As the periosulfate used in the processing liquid having fixing ability, known ones such as ammonium thiosulfate and sodium thiosulfate are used. As preservatives, sulfites such as sodium sulfite and ammonium sulfite, sulfinic acids such as sodium valatoluenesulfinate, and aldehyde bisulfite adducts such as the adduct of benzaldehyde 0-sulfonic acid and bisulfite can be used. can.

A rehalogenating agent such as ammonium bromide or ammonium chloride is used in the bleach or bleach-fix solution in an amount of 0.5 to 2 to 2 mol, preferably 0.7 to 1.5 mol/l. Further, known additives such as pH buffering agents such as ammonium nitrate, metal corrosion inhibitors such as ammonium sulfate, optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, and methanol can be included.

The fixer contains aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-13-diphosphonic acid, ethylenediamine-N, N, N', N' It is preferable to contain tetraphosphonic acid, nitrilo-N,N,N-)limethylenephosphonic acid).

The pH of the bleach-fix solution is set in the range of 3 to 8, but the preferred pH is from the viewpoint of promoting desilvering, improving color restoration, and preventing staining.
is 4.5 to 7.5, particularly preferably 5.5 to 6.
It is 5. The pH of the bleaching solution is set in the range of 2.5 to 6.5, preferably 2.5 to 4.0.

In the case of color paper, the replenishment amount of the bleaching solution, bleach-fixing solution, and fixing solution is preferably 30 to 300 tni/nT, more preferably 40 to 200 d/n'r, particularly preferably 50 to 150 m1/nT. , in the case of color negative film, preferably 60 to 800 d/n? , more preferably 80 to 600 Id/I, particularly preferably 100
~300d/i.

The temperature of bleach-fixing and bleaching is 25 to 45°C, but from the viewpoint of speed and preservation, the temperature is 30 to 40°C.
C is preferred, and 33 to 38°C is particularly preferred.

The photographic materials according to the present invention include ordinary black-and-white silver halide photographic materials (for example, black-and-white photographic materials,
black and white photosensitive materials for X-ray, black and white photosensitive materials for printing, etc.)
, ordinary multilayer color photosensitive materials (such as color negative film, color reversal film, color positive film, color negative film for movies, color paper reversal color paper, direct positive color paper, etc.), photosensitive materials for laser scanners, infrared light Examples include photosensitive materials for use. In particular, photosensitive materials for color paper are preferably used.

The type and manufacturing method of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material according to the present invention,
Binders, chemical sensitization, antifoggants, stabilizers, hardeners,
There are no particular restrictions on antistatic agents, couplers, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral enhancers, dyes, ultraviolet absorbers, supports, etc.
Product Licensing Magazine
g), vol. 92, pp. 107-110 (1971, 12
) and Research Disclosure magazine (Resea)
rch Disclosure), vol. 176, 22-
p. 31 (December 1978), vol. 238, 144-46
(1984) can be referred to.

The magenta coupler used in the present invention is preferably a 2-equivalent magenta coupler, particularly preferably a pyrazoloazole type magenta coupler. These magenta couplers include JP-A-62-89964 and JP-A-62-89964;
Examples include those described in No. 250447 and No. 63-141054.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material used in the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g.,
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The silver halide emulsion of the photographic light-sensitive material used in the present invention may be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc., but the color developing solution should be kept low in replenishment. In the above, it is preferable that the development inhibiting effect of halogen released from the light-sensitive material during development is small.From this point of view, the photographic light-sensitive material used in the present invention has a silver halide emulsion of 8.
A high silver chloride emulsion containing 0 mol % or more of silver chloride has a small number of layers (preferably one layer), and a high silver chloride emulsion containing 95 mol % or more, particularly 98 mol % or more is preferable. It is particularly preferred that each photosensitive emulsion layer is a high silver chloride emulsion.

Other silver halide emulsions used in the photographic material used in the present invention include those described in JP-A-63-85627, page 12, upper right column, line 10 to page 13, lower left, line a6. be able to.

In addition, the sensitizing dyes, coupler antifading agents, ultraviolet absorbers, filter dyes, anti-irradiation dyes, brighteners, and gelatin used in the photographic material used in the present invention include the aforementioned JP-A-63- The same ones as described in No. 85627, page 13, lower left column, line 7 to page 24, lower right column, line 4, can be used.

(Example) Next, the present invention will be described in detail based on an example.

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating liquid is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler, and the preparation method for each is shown below.

Preparation of coupler emulsion: 27.2 g of ethyl acetate to 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1)
cc and solvent (Solv-1) 7.7 cc were added and dissolved, and this solution was mixed with 185 c of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in c.

Thereafter, emulsions for magenta, cyan, and intermediate layers were prepared in the same manner. The compounds used in each emulsion are shown below.

(EXY) Yellow coupler (ExMl) Magenta coupler @11+ 7LLノ (ExCl) Cyan coupler (Cpd-2) Color mixture inhibitor 1 (EXC2) Z Cyan coupler υ■ (Cpd-3) Color image stabilizer (ExC3) Z Cyan coupler (Cpd-4) Color image stabilizer (Cpd 1) 1 Color image stabilizer (Cpd-5) Color mixture prevention agent Same as Cpd-2, except that R-CeLt(t) (Cpd
-6) Color image stabilizer (Solv-1) solvent Cpd-6a: Cpd-6b: Cpd-6c=
5:8:9 mixture (weight ratio) (Solv-2) Solvent 0=P −+o Cs1l+t(iso))i(So
lv-3) Solvent 0=PiOCJ+q(iso))s (Sol Sea 4) Solvent (Cpd-7) Polymer ncHz-C1l)-T- Average molecular weight 80,000 CONHCaHq(t) (UV-1) Ultraviolet absorber Cpd-6a: Cpd-6b: Cpd-6c=
A mixture of 2:9:8 (weight ratio) The following dyes were added to the emulsion layer to prevent irradiation.

Red-sensitive layer: Dye-R shown below, where n=2 ye-R Green layer: Same as Dye-R above, but n=1°For the red-sensitive emulsion layer, the following compound was halogenated. ! 1
2.6×10 −1 moles were added per mole.

Next, the emulsion used in this example will be shown.

Blue-sensitive emulsion: average grain size 1.1-1 coefficient of variation (standard deviation divided by average grain size - s/d)
)0.10 monodisperse cubic silver chloride emulsion (KilrCZ6
．． 1.3-dimethylimidacillin-2thione) was prepared, and 26 cc of a 0.6% solution of blue spectral sensitizing dye (S-1) was added to this emulsion 1.
A silver bromide fine grain emulsion of 0.5m was added at a ratio of 0.5 mol% to the host silver chloride emulsion, and after ripening, sodium thiosulfate was added to optimally chemically sensitize the emulsion, and a stabilizer (Stb
-1) was prepared by adding 10-4 mol and 1 mol of Ag.

Green-sensitive emulsion: Ir11J and 1.
Silver chloride grains containing 3-dimethylimidacylin-2-thione were prepared, sensitizing dye (S-2) (4×10-' mol 1 mol Ag) and KBr were added, and after ripening, sodium thiosulfate was added. Optimal chemical sensitization and stabilization (
Stb-1) by adding 5XlO-' mol 1 mol Ag,
Average particle size 0.48t! A monodisperse cubic silver chloride emulsion with m and a coefficient of variation of 0.10 was prepared.

Red-sensitive emulsion: Prepared in the same manner as the green-sensitive emulsion.

However, sensitizing dye (S-3) is used instead of sensitizing dye (S-2).
) was used in an amount of 1.5×10 −′ mol 1 mol Ag.

The compounds used are shown below.

(Stb-1) Stabilizer (S-1) 503° to sensitizing dye S03 (S-2) Sensitizing dye (S-3) Sensitizing dye (layer structure) The composition of each layer in the sample is shown below. The numbers are the amount of coating (
g/%). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti(h) and a bluish dye (ulmarine blue)]) Layer - (Blue Sensitivity N) Silver halide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35
Second layer (color mixture prevention layer) Gelatin 0.99 color mixture prevention agent (Cpd-2) Third layer (green sensitive layer) Silver halide emulsion gelatin magenta coupler ([!xMl) Color image stabilizer (Cpd-3) Color Image stabilizer (Cpd-4) Container (Solv-2) 4th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) 1st container (Solv-3) Five seven! (Red-sensitive layer) Silver halide emulsion gelatin cyan coupler (1 of ExCl, ExC2, ExC3:
2:2 mixture (molar ratio)) Color image stabilizer (Cpd-6) Polymer (Cpd-7) 0.08 0.36 1.24 0.31 0.25 0.12 0.42 1.58 0. 62 0.05 0.24 0.23 1.34 0.34 0.17 0.40 Solvent (Solv-4) 0.
23 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.21 Solvent (SOIV-3) 0.08
Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Hardening agent for each layer is ■-oxy-3.5-dichloro-5-
) using riazine sodium salt.

82.5 mm 1 liter of color photographic paper made as above
After cutting into pieces, standard exposure was applied using an automatic printer, and running processing was performed using the following processing steps and processing solution.

The running process was carried out using a processor that circulated and controlled the temperature for 10 hours per day. 90 m of color photographic paper was processed per day for 30 days.

Table-1 Treatment process The treatment liquid formulation used is as follows.

<Color developer>Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, triethanolamine, sodium chloride, potassium bromide, diethylhydroxylamine, optical brightener (4,4'-diaminos 4 .0g 3.0g 4.0g 3.5g 0.01g 5.0g 10.0g 8.0g (Tilbene type) 1.0g 1.5g
Potassium carbonate 26.5 g 28.
0 gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5 g 1
Add 0.0 g potassium hydroxide pfllo, 0
5 Add water to pH 10,20
1ffi, 1ffi Bleach-fix solution〉 U Ammonium thiosulfate) (700g/i) Add ammonium sulfite ethylenediaminetetraacetic acid ferric ammonium dihydrate ethylenediaminetetraacetic acid disodium dihydrate ammonium bromide glacial acetic acid and add water and 0OId 0g 5g g 5g pos, s II!.

00d 5g 10g g 0g pH 4,3 2 (washing solution) (common to mother liquor and replenisher solution) Calcium 27+g/l, Magnesium 4.2■/2,
101 g/j of chlorinated sodium isocyanurate in tap water with a pH of 7.3 and a conductivity of 183 μs/cm! was added.

The above running process is performed by running N11l (comparative example:
(without reverse osmosis membrane treatment).

Furthermore, a reverse osmosis membrane treatment device was installed as follows, and running treatment was performed in the same manner as above.

-Nning N2: According to the method shown in Fig. 5 of JP-A-58-105150,
The washing liquid in the first washing tank was force-fed to the reverse osmosis membrane treatment device, the permeated water was supplied to the second washing tank, and the concentrated liquid was returned to the first washing tank (see Figure 3). In addition, the recovery rate at the initial stage of running (R-f
/f+c) was set to 0.10 by adjusting valves 14-16.

A reverse osmosis membrane treatment device was installed as shown in FIG. 1 of the present invention. However, the recovery rate at the initial stage of running is 14 to 1.
6, it was set to 0.47.

-Nnin~6 A reverse osmosis membrane treatment apparatus was installed as shown in FIG. 1 of the present invention. However, the recovery rate at the initial stage of running is 14 to 1.
0.30.0.20.0.10 respectively by adjusting 6.
And so.

Reverse osmosis membrane treatment is reverse osmosis membrane DR manufactured by Daicel Chemical Industries.
The A-80-5W-03 type spiral module (effective membrane area 1.1%) was housed in the company's pressure-resistant Vencel PSV-03, and a liquid delivery pressure of 4 kg was applied using a magnetic gear pump.
/cii.

After 30 days of running, in each of the running stages 1 to 6, the yellow stain prevention effect, the change in the amount of water permeating the reverse osmosis membrane at the start and end of the run, and its recovery rate, which are the objectives of the present invention, were evaluated. I looked into it.

Changes in yellow stain were determined by measuring the difference in yellow reflection density of the white background area (unexposed area) of the processed color photographic paper at the start and end of each run (at the end of the 30-day run).

(Density difference=density at end-density at start) The yellow stain was measured by measuring the reflection density of the unexposed area against blue light using an X-Rite 310 Photograph Ink Densitometer.

The amount of water permeated through the reverse osmosis membrane was expressed as the amount of water permeated per minute per reverse osmosis membrane (unit: IIi/ll1in-rrT) at the start and end of each run.

The recovery rate (R) is the total amount of liquid treated with the reverse osmosis membrane (f+c
) to the amount of liquid (f) collected as fresh liquid. (Here, C is the amount of concentrated liquid.) The results are listed in Table 2.

Example 2 Using the color photographic paper described in Example 1, the same running process as in Example 1 was performed, except that the washing process, bleach-fix solution, reverse osmosis membrane, and its installation method were changed as follows. .

The washing process is a 4-stage countercurrent washing process, and the processing time for each tank is 15 minutes.
seconds (total of 60 seconds for four stages), and the amount of replenishment to the fourth washing tank was reduced to 60 seconds.

The bleach-fix solution used in Example 1 was prepared by adding 20 g of sodium benzenesulfinate to the mother liquor and 40 g to the replenisher solution.

For the reverse osmosis membrane, a SUM-206 type spiral module (effective area 1.2%) manufactured by Toshi ■ was used, and the liquid delivery pressure was 4.
It was treated at 5 kg/cd.

The installation method for the reverse osmosis membrane treatment equipment was as follows.

1st inning, 2nd No reverse osmosis treatment.

I set up 2 units. In addition, the recovery rate at the beginning of the run is valve 1.
It was set to 0.10 by adjusting from 4 to 16.

- Cleaning Nα3': A reverse osmosis membrane treatment device was installed as shown in FIG. 2 of the present invention. However, the recovery rate at the initial stage of running is 14 to 1.
It was set to 0.40 by adjustment in step 6.

A reverse osmosis membrane treatment device was installed as shown in FIG. 2 of the present invention. However, the recovery rate at the initial stage of running is 14 to 1.
6, the values were set to 0.20 and 0.10, respectively.

The results are shown in Table-3.

As shown in FIG. 4 of the present invention, reverse osmosis membrane treatment device Example 3 In Example 1, the color photographic paper was
Fuji Color Paper Super F A (117ml
Example 1 except that diethylhydroxylamine in the color developer was changed to hydrazinoniacetic acid.
A running process almost the same as the running process Nα6 was performed.

That is, the color paper (117M width) was exposed to standard light using an automatic printer and subjected to running processing. The running process was carried out for 18 weeks (running for 5 days per test) using a processor that controlled circulation temperature for 10 hours per day, and processed 60 m of the 117 mm wide color paper per day.

Incidentally, the recovery rate (R=f/f+c) at the initial stage of the running was set to 0.10 by adjusting the valves 14 to 16, as in the case of running process No. 6. Furthermore, the flow rate of the reverse osmosis membrane permeate at the start of running was 180 iffi/sin.

The reverse osmosis membrane permeate flow rate after 18 weeks of running treatment was 14
It was maintained at 0 affi/win, and the change in yellow stain was within 0.015 of the increase at the start of running, indicating good results.

Example 4 A running treatment was carried out in the same manner as in Running N1124-25 (invention) of Example 2, except that the washing liquid was changed to a stabilizing liquid having the composition shown below.

k-fixation: (common to mother liquor and replenisher solution) 1-hydroxyethylidene-1,1-diphosphonic acid 1.4g nitrilo-N,N,N-)rimethylenephosphonic acid 3.0g 5-chloro-2-methyl-4- Isothiazolin-3-one 0.3g Ammonium chloride 0.3g Optical brightener (
4,4°-diaminostilbene system) 0.1g ammonia water and hydrochloric acid pH 6,7 Add water 11 Reverse osmosis membrane permeate 2
Although the amount of IT decreased by about 20% compared to the results shown in Table 3 both at the start of running and at the end of 30 days of running, the effects of the present invention were similarly exhibited.

(Effects of the invention) In the treatment method of the present invention, even if the washing liquid and/or stabilizing liquid is continuously treated with a reverse osmosis membrane for a long period of time in a multi-stage countercurrent system, there is no decrease in the permeate flow rate or clogging of the membrane. It was possible to stably obtain excellent photographic images in which the occurrence of yellow stain after processing was prevented.

[Brief explanation of the drawing]

1 and 2 are schematic diagrams of an automatic development apparatus incorporating a reverse osmosis membrane according to the present invention. That is, the reverse osmosis membrane is installed in the tank just before the final bath. 3 and 4 are schematic diagrams for comparison. That is, FIG. 3 is a schematic diagram of an automatic developing apparatus in which a reverse osmosis membrane is incorporated in the first washing tank of a three-tank washing bath according to the description in JP-A-58-105150, and FIG. 4 is a four-tank arrangement. FIG. 2 is a schematic diagram of an automatic developing device in which a reverse osmosis membrane is incorporated in the second washing tank of the washing bath. In FIGS. 1 to 4, the meanings of symbols in the figures are described below. 1: Color developer tank L 2: Bleach-fix tank L2 3: First washing tank W 4: Second washing tank W2 5: Third washing tank W3 6: Fourth washing tank W4 7: Liquid feed pump P 8: Reverse osmosis Pressure-resistant device R with built-in membrane. 9: Concentrated liquid C 10: Permeated water f 11: Replenishment fresh water 12: Countercurrent washing piping K 13 Nitrogen flow water 0F 14-16: Valve diagram

Claims (1)

[Claims] A method for processing a photosensitive material in which a silver halide photographic light-sensitive material is processed in a bath having fixing ability, and then subjected to water washing and/or stabilization processing in a multistage countercurrent method, wherein the multistage countercurrent method is a multistage countercurrent processing using three or more tanks. This method takes the washing liquid or stabilizing liquid from the tank immediately before the final tank, and processes it with a reverse osmosis membrane at a liquid feeding pressure of 10 kg/cm^2 or less and a recovery rate of permeate flow rate of 0.30 or less relative to the liquid feeding flow rate. A method for processing silver halide photographic materials, characterized by returning the liquid to a final bath.