JPS63121053A - Vessel for supplying and recovering processing liquid for photographic sensitive material - Google Patents

Abstract

PURPOSE:To permit long-term preservation of a processing liquid by specifying the coefft. of oxygen permeability of at least part of a wall directly enclosing at least one of plural chambers to <=20ml/(m<2>.24hrs.1atm). CONSTITUTION:One outside wall 21 is formed of a sheet which has the large coefft. of oxygen permeability and has high resilience. The other outside wall 22 is formed by superposing an outer side sheet 22A which consists of the resilient sheet and an inner side sheet 22B which has the low resilience but has <=20ml/(m<2>.24hrs.1atm) coefft. of oxygen permeability and a high gas barrier property in an independent state. This vessel is constituted by using a gas barrier type sheet to form a partition wall 30 segmenting a supplying chamber 11 and a recovering chamber 12. One side of the chamber 11 is directly enclosed by the gas barrier type sheet forming the wall 30 and the other side is directly enclosed by the gas barrier type sheet forming the sheet 22B; in the end, the entire part thereof is enclosed directly by the gas barrier type sheets. The generation of the early oxidation deterioration of the processing liquid by air is thereby obviated and the stable long-term preservation of the processing liquid is permitted.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to supplying and supplying a flexible photographic material processing solution.
Regarding the collection container, in particular, it is a supply/recovery container that takes up a small space and is convenient for supplying and collecting the photographic material processing solution using one container, and also enables long-term storage of the photographic material processing solution. -Regarding collection containers.

[Background of the invention]

Generally, in the formation of photographs, a process is required in which a photographic light-sensitive material is subjected to processing such as development to form a negative film or a positive film.

For example, in the case of black-and-white photographic materials, a black-and-white negative film or positive film is usually formed through processes such as development, fixing, and water washing, whereas in the case of color photographic materials, usually A color negative or positive film is formed through processes such as color development, bleach-fixing (bleaching and fixing may be carried out separately), and water washing.

Each processing such as development processing and fixing processing is carried out using a processing liquid exclusively for the processing, and as the processing of the photographic light-sensitive material progresses, the processing agent components contained in the processing liquid are gradually consumed. As a result, reaction products unnecessary for treatment increase and accumulate. Therefore, in order to continue processing with uniform processing performance, it is necessary to replenish new processing liquid as appropriate and to drain exhausted processing liquid appropriately to maintain the concentration of processing agent components in the processing liquid at a constant level. . Specifically, in developing processing, for example, as the processing of a photographic light-sensitive material progresses, reaction products such as bromide ions increase in the processing solution, causing the processing solution to become fatigued. As the processing progresses, reaction products such as silver ions increase in the processing solution and the processing solution becomes fatigued. Therefore, new processing solution is replenished into the processing tank as needed, and the exhausted processing solution is removed from the processing tank, for example. The reaction product is discharged by overflowing, thereby diluting and further removing the reaction product, thereby maintaining the concentration of the processing agent component in the processing liquid at a constant level.

On the other hand, water washing is performed to remove residual chemicals that have been impregnated into the photographic material during the previous processing, and usually a certain amount of washing water is poured into a washing tank per certain area of the photographic material. In addition to continuously supplying the water, the washing process is performed while causing tired washing water to overflow from the processing tank.

Effluent that overflows from processing tanks such as developing processing tanks and fixing processing tanks is usually temporarily stored in a recovery tank, and then subjected to biological or chemical treatment to render it harmless by an effluent processing company. , discharged into sewers or rivers, etc. In the washing treatment tank, the amount of washing water required for treatment is large, resulting in a considerable amount of overflowing effluent. Temporary storage in the recovery tank is not enough, and the effluent is usually kept harmless. After treatment, the waste is directly discharged into sewers, rivers, etc.

On the other hand, in response to demands for protecting water resources, saving on water and sewerage costs, and further downsizing automatic developing devices, stabilization processing has been developed in recent years as an alternative to water washing processing. In this stabilization treatment, it is possible to obtain the same effect as water washing treatment with a small amount of stabilizing treatment liquid, and as a result, large-scale equipment for water supply and drainage, such as a boiler, which is indispensable in water washing treatment, can be used. It is no longer necessary to provide hot water supply equipment such as the above, cooling water supply equipment for temperature adjustment, etc., and it has become possible to obtain a compact automatic developing device that is compact, movable, and convenient.

In other words, in the stabilization treatment, a treatment liquid supply tank,
It is possible to perform sufficient processing with simple equipment consisting of a supply pump to supply the processing liquid from this supply tank into the processing tank and a recovery tank to collect the processing liquid that overflows from the processing tank. . Since only a small amount of replenishment of the stabilizing solution is required, a collection tank with a small collection volume can be used. For example, when the collection tank is placed in an automatic developing device, the amount of collection usually corresponds to one day's worth. For example, if the collection tank is placed outside the automatic developing device, it is usually sufficient to have a capacity that matches the
It is said that it is sufficient if the capacity is sufficient to accommodate the weekly amount of collection.

In this way, processing liquid can be refilled easily and in a small space, and as a result, the automatic developing device can be made compact and movable, so it can be used not only in camera stores but also indoors such as offices. It became possible to install and use a developing device, and the scope of use of automatic developing devices was greatly expanded.

However, in recent years, there has been a demand for smaller automatic developing apparatuses, and a means for replenishing the processing liquid is required to be simpler and take up less space. However, in the above-mentioned replenishment means, a supply tank and a recovery tank must be arranged for each processing tank. For example, when processing color photographic materials, a color development processing tank, a bleach-fixing tank, Each treatment tank and stabilization treatment tank requires a supply tank and a recovery tank, for a total of 6 tanks. Even if a common recovery tank is used, overflow from each treatment tank is required. A device with a capacity that can recover the entire processing liquid is required, and as a result, it cannot sufficiently meet the recent demands for miniaturization.

For this reason, a flexible inner container is provided inside a flexible outer container, the processing liquid is filled into the inner container, and the processing liquid is supplied from the inner container, and the thickness gradually increases as the processing liquid is supplied. A technical means (see Japanese Utility Model Application Publication No. 56-94754) has been disclosed in which the processing liquid that overflows into the gap between the outer container and the inner container is recovered.

However, in the above technical means, when the container is constructed using polyethylene, which is widely known as a material for constructing flexible containers, the processing liquid stored in the container deteriorates due to oxidation at an early stage. There is a problem that the processing liquid cannot be stored stably for a long period of time. That is, for example, some processing agent components contained in a color developing solution are easily oxidized by air, and for this reason, preservatives such as sulfites are usually added and mixed into the processing solution. This suppresses oxidation, and also in the fixing solution and bleach-fixing solution.
Since the fixing agent, sodium thiosulfate, is easily decomposed by oxygen in the air and harmful sulfur oxides are released, a preservative such as sulfite is usually added to the processing solution to prevent such sulfur oxidation. Antifungal agents are usually added to the stabilizing treatment solution to prevent sulfurization or to improve the long-term storage stability of images. Since some substances are easily oxidized by air, preservatives such as sulfites are usually added to the processing liquid to suppress oxidation, but in flexible containers made of polyethylene etc. There is a problem in that oxygen easily enters the inside of the container through the wall, and as a result, the processing liquid stored in the container deteriorates due to oxidation in a short period of, for example, about two weeks.

In order to avoid this problem of deterioration due to oxidation,
Processing agent components that are easily oxidized by air are individually packaged in powder form, and this package is supplied to the user along with the container. When the user starts processing, the package is opened and each A so-called kit system is known in which processing agent components are dissolved in a solvent and used.

However, in such a kit method, when dissolving the processing agent components, it is usually necessary to start dissolving the next processing agent component after the - processing agent component has been completely dissolved. It is usually necessary to wait for several minutes to several tens of minutes while stirring until the dissolution of the processing agent components begins, which requires a considerable amount of time and effort.

In addition, in the case of in-house processing minilab systems installed in camera stores or offices, the operators are usually amateurs who have little or no experience in processing photographic materials, so they are unable to prepare processing solutions. In some cases, it is difficult to distinguish between individually packaged processing agent components, and the processing liquid may be prepared incorrectly, resulting in failure to obtain a processing liquid with appropriate performance.

[Problem that the invention seeks to solve]

Because of these circumstances, it is possible to use an appropriate processing solution prepared by a specialist without the hassle of using a kit method, and in addition, the processing solution can be stored stably for a long period of time without premature oxidation deterioration. There is a desire for a processing liquid container that has a simple structure, low manufacturing cost, takes up little space, and is compact.

Therefore, we considered forming a flexible container using a material such as saran, polyester, or nylon, which has a higher gas barrier performance than polyethylene. Saran, polyester, and nylon have higher gas barrier properties than polyethylene, especially with an oxygen permeability coefficient of about 1.
/100 to 1/1000, and the ability to block oxygen is extremely excellent. However, on the other hand, it is harder than polyethylene, so if the container is subjected to shocks such as vibrations during transportation or storage, FtLts such as cracks are likely to occur in the wrinkled areas of the container. This may cause problems such as leakage and contamination or contamination of the surrounding area.

On the other hand, as shown in FIG. 7, the present inventor constructed one outer wall 21 forming the processing liquid recovery chamber 12 from a sheet with high gas barrier properties such as nylon.
The partition wall 30 that partitions the supply chamber 11 and the supply chamber 11 is made of a highly flexible sheet such as polyethylene, and the other outer wall 22 forming the supply chamber 11 is made of an inner sheet 22B made of a highly flexible sheet and has gas barrier properties. A supply/recovery container has been developed which is composed of multiple sheets in which an outer sheet 22A consisting of a sheet with a high temperature and an outer sheet 22A are stacked independently.

According to such a supply/recovery container, the partition wall 30 and the inner sheet 22B, which are the walls that directly form the supply chamber 11, are both made of highly flexible sheets.
These walls are less susceptible to damage such as cracks, and therefore there is no risk of leakage of the processing liquid.

Moreover, since the wall that indirectly surrounds the supply chamber 11, that is, the - side outer wall 21 and the outer sheet 22A, are both made of sheets with high gas barrier properties, air from outside the container enters the supply chamber 11. It is considered that this prevents the intrusion of the processing liquid and prevents deterioration of the processing liquid due to early oxidation.

However, when we conducted a test in which we filled the supply chamber 11 of such a supply/recovery container with processing liquid and provided it to a user for practical use, we found that the processing liquid disappeared in about two months from the time of filling the processing liquid. It was found that long-term storage was actually difficult due to deterioration due to oxidation.

When we investigated the cause of these problems, we found that the first
In addition, when filling the processing liquid, air enters the inside of the recovery chamber 12, and the inner sheet 22B and the outer sheet 22
Air also enters the gap between A and the supply/recovery container is placed in the distribution process with this air remaining.
This air passes through the partition wall 30 made of a highly flexible sheet such as polyethylene and the inner sheet 22B and reaches the supply chamber 11.Secondly, when the supply/recovery container is placed in the distribution process, It is often transported in a vehicle such as a trunk, so the inner sheet 22B is made of a highly flexible sheet such as polyethylene, and the outer sheet 22 is made of a sheet with high gas barrier properties such as nylon.
This frictional contact creates pinholes in the outer sheet 22A made of a sheet with high gas barrier properties such as nylon, and through these pinholes, outside air flows between the inner sheet 22B and the outer sheet. 22A, and furthermore, this air passes through the inner sheet 22B and reaches the inside of the supply chamber 11, causing early oxidation deterioration of the processing liquid due to air. The present invention has been completed.

[Purpose of the invention]

The present invention has been made based on the above-mentioned circumstances, and its purpose is to prevent deterioration of a photographic material processing solution due to early oxidation so that the processing solution can be stored stably for a long period of time. An object of the present invention is to provide a supply/recovery container for a photographic material processing solution.

Another object of the present invention is to provide a highly safe supply/recovery container for photographic material processing liquid that can sufficiently prevent leakage of the processing liquid to the outside.

[Means for solving problems]

The supply/recovery container for photographic light-sensitive material processing liquid of the present invention has a flexible outer wall and a flexible partition wall that partitions an internal space surrounded by the outer wall into a plurality of chambers. In the supply/recovery container, at least a portion of the wall directly surrounding at least one of the plurality of chambers has an oxygen permeability coefficient of 20 d/(m" 24 hrs 1
at+w) or less.

[Function and effect of the invention]

According to the present invention, at least a portion of the wall directly surrounding at least one of the plurality of chambers has an oxygen permeability coefficient of 20 d/(m
・24hrs ・fatl) or less, by using this chamber as a processing liquid filling chamber, even if air remains in other chambers or gaps adjacent to the chamber, The intrusion of air into the processing liquid filling chamber is considerably suppressed, and as a result, the processing liquid can be stably stored for a long period of time without premature oxidation and deterioration of the processing liquid due to air. In fact, it is possible to store the processing solution stably for more than 6 months.

As described above, according to the supply/recovery container of the present invention, the processing liquid can be stored for a long period of time, so that it is extremely suitable for application to, for example, an automatic developing device in an in-house processing type minilab system.

[Specific structure of the invention]

The present invention will be explained in detail below.

In the present invention, a supply/recovery container is configured by providing a flexible outer wall and a flexible partition wall that divides an internal space surrounded by the outer wall into a plurality of chambers, and at least one of the plurality of chambers is At least part of the wall directly surrounding the two chambers has an oxygen permeability coefficient of 20 d/(so3・24 hr
s・1ate) shall be as follows. Then, the chamber is used as a chamber for filling the processing liquid. The number of the plurality of chambers is
It is not particularly limited, and may be 2 or 3 or more.

In the above, all of the walls directly surrounding the chamber, that is, the processing liquid filling chamber, have an oxygen permeability coefficient of 20tZ/vat.
If the storage time exceeds 24hrs/1atIl), the photographic material processing solution filled in the chamber will be easily oxidized and deteriorated by the air, making it impossible to store it for a long time. It will be difficult.

In addition, in the present invention, the oxygen permeability coefficient is ASTMD-
Defined as a value measured based on the 1434-75M method. The environmental conditions at the time of measurement were a pressure of 1 atm, a temperature of 20°C,
The relative humidity is 65%.

The chamber for filling the processing liquid has a wall that directly or indirectly has gas barrier properties, preferably an oxygen passage coefficient of 20 d/(, m'' ・24 hrs ・1 ate).
Preferably, it is surrounded by the following walls:

The outer walls and partition walls may be formed from a single flexible sheet, or may be formed from a plurality of independent flexible multi-sheets.

Further, the flexible sheet forming the outer wall and the partition wall may have a multilayer structure in which a plurality of thin layers are adhesively laminated.

FIGS. 1 to 6 are explanatory cross-sectional views showing examples of specific configurations of a supply/recovery container for photographic material processing liquid according to the present invention. In each of these examples, there are two chambers.

In these figures, 11 is a processing liquid supply chamber, 12 is a processing liquid recovery chamber, 21 is one outer wall of the container, 22 is the other outer wall of the container, 30 is a partition wall, 41 is a supply port, and 42 is a recovery port. It is.

The outer wall 21 on one side and the outer wall 22 on the other side constitute the outer wall of the entire container, and these outer walls 21 and 22 and the partition wall 3
0, a supply chamber 11 and a recovery chamber 12 are formed, respectively.

Specifically, for example, one outer wall 21 in the shape of a rectangular sheet,
The other outer wall 22 in the form of a rectangular sheet are superimposed and fixed, for example, by adhesive, at their outer edges, with the outer edge of the partition wall 30 in the form of a rectangular sheet being interposed therebetween, whereby the outer walls 21 and 22 The internal space surrounded by is divided from the outside, and the internal space is
It is divided into a supply chamber 11 and a recovery chamber 12.

In the example shown in FIG. 1, one outer wall 21 is made of a highly flexible sheet with a large oxygen permeability coefficient (hereinafter also referred to as "flexible sheet"), and the other outer wall 22 is made of a flexible sheet. A side sheet 22A, and an inner sheet made of a sheet with low flexibility but high gas barrier properties (hereinafter also referred to as "gas barrier sheet") with an oxygen permeability coefficient of 20 d/(m''・24 hrs・1 atm) or less) 22B are independently stacked on top of each other, and the supply chamber 1
The partition wall 30 that partitions the recovery chamber 1 and the collection chamber 12 is formed of a gas barrier sheet. Supply chamber 1 in this example
1 is a configuration in which the good example is directly surrounded by the gas barrier sheet forming the partition wall 30, the other side is directly surrounded by the gas barrier sheet forming the inner side seam 22B, and the whole is directly surrounded by the gas barrier sheet. It becomes.

The example shown in FIG. 2 has the same structure as the example shown in FIG. 1, except that the outer seam 22A of the other outer wall 22 is formed of a gas barrier sheet, and the inner seam 22B is formed of a flexible sheet. This is an example.

The supply chamber 11 in this example has a configuration in which one side is directly surrounded by a gas barrier sheet forming the partition wall 30, and the other side is indirectly surrounded by a gas barrier sheet forming the outer sheet 22A.

The example shown in FIG. 3 is constructed in the same manner as the example shown in FIG. 1, except that one outer wall 21 is formed of a gas barrier sheet and the partition wall 30 is formed of a flexible sheet. The supply chamber 11 in this example has a configuration in which one side is indirectly surrounded by a gas barrier sheet forming one outer wall 21, and the other side is directly surrounded by a gas barrier sheet forming an inner sheet 22B.

The example shown in FIG. 4 is constructed in the same manner as the example shown in FIG. 2, except that one outer wall 21 is formed of a gas barrier sheet. The supply chamber 11 in this example is directly surrounded by a gas barrier sheet forming the partition wall 30 on one side,
The other side is indirectly surrounded by a gas barrier sheet forming the outer sheet 22A.

The example shown in FIG. 5 is an example in which one outer wall 21, the partition wall 30, and the other outer wall 22 are all formed of gas barrier sheets. The supply chamber 11 in this example has a partition wall 30 on one side.
The outer wall 22 is directly surrounded by a gas barrier sheet forming the outer wall 22, and the other side is directly surrounded by a gas barrier sheet forming the other outer wall 22.

In the example shown in FIG. 6, one of the outer walls 21 in the example shown in FIG. 1 is formed by independently overlapping an outer sheet 21A made of a flexible sheet and an inner sheet 21B made of a gas barrier sheet. This is an example configured in the same manner except for the above. The supply chamber 11 in this example has a configuration in which one side is directly surrounded by a gas barrier sheet forming the partition wall 30, and the other side is indirectly surrounded by a gas barrier sheet forming the external sheet 22A of the other outer wall 22. ing.

In the examples shown in FIGS. 1 and 6, the inner sheet 22B constituting the other outer wall 22 is formed of a gas barrier sheet.
Because it comes into direct contact with the processing liquid filled in the supply chamber 11 and becomes taut with the processing liquid, when the supply/recovery container is filled with processing liquid and placed in the distribution process, the details will be described later. As can be understood from the description of the experimental example, even if there is frictional contact between the inner sheet 22B and the outer sheet 22, pinholes are less likely to occur in the inner sheet 22B. Therefore, the supply chamber 11 is directly surrounded by the inner sheet 22B and the partition wall 30, both of which are made of gas barrier sheets, and it is possible to prevent the processing liquid from deteriorating due to early oxidation.

In the examples shown in FIGS. 2 and 4, in the other outer wall 22, the outer sheet 22A is formed of a gas barrier sheet, and the inner sheet 22B is formed of a flexible sheet, so that the processing liquid is filled and supplied.
When the collection container is placed in the distribution process, pinholes are created in the outer sheet 22A due to frictional contact between the outer sheet 22A and the inner sheet 22B, and air enters the gap space through the pinholes. There is a possibility that
Since the partition wall 30, which is one wall directly surrounding the supply chamber 11, is formed of a gas barrier sheet, the air remaining in the recovery chamber 12 is reliably prevented from entering the supply chamber 11. As will be understood in detail from the explanation of experimental examples to be described later, it is possible to stably store the processing liquid filled in the supply chamber 11 for a practically sufficient period of time.

In the example shown in FIG. 3, the inner sheet 22B constituting the other outer wall 22 is formed of a gas barrier sheet, but as in the example of FIG. 1, the inner sheet 22B and the outer sheet Even if there is frictional contact with the inner sheet 22A, pinholes are less likely to occur in the inner sheet 22B. Therefore, the inner sheet 22B, which is one wall directly surrounding the supply chamber 11, reliably prevents air that has entered the gap between the outer sheet 22A and the inner sheet 22B from entering the supply chamber 11. As a result, the processing liquid filled in the supply chamber 11 can be stably stored for a practically sufficient period of time, as will be understood in detail from the explanation of experimental examples to be described later.

In the example shown in FIG. 5, the other outer wall 22 is formed of one gas barrier sheet, and the outer wall 22 comes into direct contact with the processing liquid filled in the supply chamber 11. Therefore, when the processing liquid is filled and the supply/recovery container is placed in the distribution process, the outer wall 22 has a pin, as will be understood in detail from the explanation of the experimental example described later. Holes are less likely to occur. Therefore, the supply chamber 11 is directly surrounded by the outer wall 22 and the partition wall 30, both of which are made of gas barrier sheets, and it is possible to prevent the processing liquid from deteriorating due to early oxidation.

The gas barrier sheet used in the present invention may have a single layer structure or a multilayer structure in which a plurality of thin layers are bonded and laminated.The thickness of the gas barrier sheet varies depending on the constituent materials. -Although it cannot be generally defined, it is preferably approximately 1 to 400 trm, particularly preferably 5 to 200n, and most preferably 10 to 120n.
It is n.

Examples of such gas barrier sheets having a one-layer structure include saran-coated nylon, polyethylene terephthalate sheets with a thickness of 5I or more, acrylonitrile-butadiene copolymer sheets with a thickness of 10N or more, and hydrochloric acid rubber with a thickness of 5N or more. Among these, Saran-coated nylon and polyethylene terephthalate sheets are particularly preferred because they have excellent alkali resistance and acid resistance.

Examples of multilayer structures include 3N sheets of polyethylene terephthalate/polyvinyl alcohol/ethylene copolymer/polyethylene, stretched polypropylene/
Three-layer sheet of polyvinyl alcohol/ethylene copolymer/polyethylene, three-layer sheet of unoriented polypropylene/polyvinyl alcohol/ethylene copolymer/polyethylene, three-layer sheet of nylon/aluminum foil/polyethylene, polyethylene terephthalate/aluminum foil/
3-layer sheet of polyethylene, 4-layer sheet of cellophane/polyethylene/aluminum foil/polyethylene, 3-layer sheet of aluminum foil/Gi/polyethylene, 4-layer sheet of polyethylene terephthalate/polyethylene/aluminum foil/polyethylene, 4-layer sheet of nylon/polyethylene/aluminum foil / 4-layer polyethylene sheet, paper / polyethylene / aluminum foil / 4N sheet of polyethylene,
4-layer sheet of polyethylene terephthalate/aluminum foil/polyethylene terephthalate/polypropylene,
4-layer sheet of polyethylene terephthalate/aluminum foil/polyethylene terephthalate/high-density polyethylene, 4N sheet of polyethylene terephthalate/aluminum foil/polyethylene/low-density polyethylene, 2-layer sheet of polyvinyl alcohol/ethylene copolymer/polypropylene, polyethylene terephthalate/aluminum A three-layer sheet of foil/polypropylene, a three-layer sheet of M/aluminum M/polyethylene, particularly preferably a four-layer sheet of polyethylene/polyvinylidene chloride-coated nylon/polyethylene/ethyl vinyl acetate/polyethylene condensate, polyethylene/polyvinylidene chloride Three-layer sheet of coated nylon/polyethylene, five-layer sheet of ethyl vinyl acetate/polyethylene condensate/polyethylene/aluminum-deposited nylon/polyethylene/ethyl vinyl acetate/polyethylene condensate,
Aluminum deposited nylon/nylon/polyethylene/
4-layer sheet of ethyl vinyl acetate/polyethylene condensate, 3-layer sheet of oriented polypropylene/polyvinylidene chloride-coated nylon/polyethylene, 3-layer sheet of polyethylene/polyvinylidene chloride-coated nylon/polyethylene, oriented polypropylene/polyvinyl alcohol/ethylene copolymer Combined/(3-layer sheet of In degree polyethylene, 3-layer sheet of oriented polypropylene/polyvinyl alcohol/ethylene copolymer/unoriented polypropylene, 3-layer sheet of polyethylene terephthalate/polyvinyl alcohol/ethylene copolymer/low-density polyethylene, oriented Examples include a three-layer sheet of nylon/polyvinyl alcohol/ethylene copolymer/low density polyethylene, and a 3M sheet of unstretched nylon/polyvinyl alcohol/ethylene copolymer/low density polyethylene.

The flexible sheet used in the present invention is not particularly limited as long as it has high flexibility, but it usually has an oxygen permeability coefficient of more than 20 d/(m" 24 hrs 1 atw+). This flexible sheet The flexible sheet may have, for example, a single-layer structure or a multi-layer structure in which a plurality of thin layers are adhesively laminated.The thickness of such a flexible sheet varies depending on the constituent material and is generally defined However, it is preferably approximately 1 to 400 tts, particularly preferably 5 to 200 n, and most preferably 10 to 120 tts.
μ.

Examples of such flexible sheets having a one-layer structure include low-density polyethylene sheets, ethylene/vinyl acetate copolymer sheets, and polypropylene sheets.

Examples of multilayered sheets include nylon/polyethylene laminate sheets, nylon/vinyl acetate/ethylene copolymer laminate sheets, ethylene vinyl alcohol copolymer/polyethylene laminate sheets, and the like.

The supply/recovery container configured as described above has a supply pipe (not shown) and a collection pipe (not shown) provided in the processing tank of the automatic developing bag W (not shown), respectively. A supply pump (not shown) or the like normally provided on the supply pipe sucks the processing liquid in the supply chamber 11 and supplies it to the processing tank via the supply pipe. On the other hand, the exhausted processing liquid overflowing from the processing tank due to the supply of the processing liquid is introduced into the recovery chamber 12 by gravity, for example, by allowing it to fall naturally through the recovery pipe. The internal volume of the supply chamber 11 becomes smaller as the supply of processing liquid progresses due to the suction force of the supply pump, etc., so the internal volume of the recovery chamber 12 is allowed to increase, and as a result, the exhausted processing liquid can be removed. I can fully accept it.

- Although representative examples of specific configurations of the present invention have been illustrated and explained above, the present invention is not limited to the above representative examples, and various other configurations can be adopted.

(1) The number of supply chambers or collection chambers is not particularly limited,
A configuration in which a plurality of chambers are provided may be used. In this case, a supply port is provided corresponding to each supply chamber, and a recovery port is provided corresponding to each collection chamber. The plurality of supply chambers may store different types of processing liquids or the same processing liquid, and the plurality of recovery chambers may contain different types of processing liquids. Alternatively, the same processing solution may be collected.

(2) A liquid-absorbing and swelling material may be present in the recovery chamber in order to improve the recovery performance of the processing liquid. Various materials can be used without particular limitation as long as they have the property of expanding in volume. When this liquid-absorbing and expanding substance is present in the recovery chamber, the internal volume of the recovery chamber is accelerated to increase during recovery of the processing liquid, making recovery of the processing liquid even easier.

In the present invention, the processing solution for the photographic light-sensitive material stored in the supply chamber is selected in accordance with each processing tank of the automatic developing device, and specifically, the processing solution for black and white, the color development processing solution for color, Fixing processing liquid, bleaching processing liquid, bleach-fixing processing liquid,
Various processing liquids can be mentioned, such as a stabilization processing liquid, a stop processing liquid, an image stabilization processing liquid, and a rinsing processing liquid. These processing liquids may be used in combination as necessary. Furthermore, some of these processing liquids can be used repeatedly several times, and in that case, the collected processing liquid may be reused.

Among these processing liquids, processing liquids that can be particularly preferably used include a black and white developing liquid, a color developing liquid, a fixing liquid, a bleaching liquid, a bleach-fixing liquid, a stabilizing liquid, and the like. . These processing solutions contain preservatives such as sulfites, developing agents, thiosulfates, antifungal agents, and the like, as necessary.

In the black-and-white developing solution, at least one kind of black-and-white developing agent is used, and examples of the black-and-white developing agent include hydroquinones, 1-phenol-3-pyrazolidones, para-aminophenols, and the like. .

Hydroquinones include, for example, "The Theory of the Photographic Process" (rThe
Theory of The Photography
c Process JT, H. James (1977
Compounds described in pages 300 to 311 of 2003) can be used.

Specifically, for example, hydroquinone, methylhydroquinone, 2.3-dimethylhydroquinone, 2.5-dimethylhydroquinone, 2.3.5-)dimethylhydroquinone, tetramethylhydroquinone, 2,6-dimethylhydroquinone, methoxyhydroquinone, 2. .5-
Dimethoxyhydroquinone, 2-chlorohydroquinone, 2.3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2゜6-dichlorohydroquinone, aminohydroquinone, bromohydroquinone, hydroxyhydroquinone, butylhydroquinone, phenylhydroquinone, 2-methyl- 3-chlorohydroquinone, hydroquinone monosulfonic acid, etc. can be used. The proportion of these hydroquinones used is generally preferably 0.1 to 200 g, more preferably 1 to 100 g, particularly preferably 2 to 50 g, based on IIV of the treatment liquid.

Examples of 1-phenyl-3-pyrazolidones include 1
-Phenyl-3-virapritone, British Patent No. 943,9
No. 28, No. 1,093,281, U.S. Patent No. 2.2
No. 89,367, No. 3,241,967, No. 3,
Compounds having substituents at the 2-position, 4-position and/or 5-position of the 3-pyrazolidone ring as described in the specifications of No. 453,109, such as 4-hydroxymethyl-
4-Methyl-1-phenyl-3-pyrazolidone, 4.4
-'; Hydroxymethyl-1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone,
4.4-dimethyl-1-phenyl-3-pyrazolidone,
2-morpholinomethyl-1-phenyl-3-pyrazolidone, 2-(1,2,3-tetrahydroquinolylmethyl)-1-phenyl-3-pyrazolidone, 2-piperadimethyl-1-7enyl-3-pyrazolidone, 2 -Hydroxymethyl-1-phenyl-3-pyrazolidone, 2-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-2-hydroxymethyl-1
-Phenyl-3-pyrazolidone, 4-chloromethyl-2
-Hydroxymethyl-4-methyl-1-phenyl-3-
Pyrazolidone, l-morpholinomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 2-(methyl-β-hydroxyethyl)aminomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 2 -(di-β
-hydroxyethyl)aminomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 5-methyl-1-
Phenyl-3-pyrazolidone and the like can be used. Among these, l-phenyl-3-pyrazolidone and a compound having a substituent at the 4-position of the 3-pyrazolidone ring can be particularly preferably used.

As para-aminophenols, for example, [The Theory or the Photographic Ink Process J (
rThe Theory of The Photog
Compounds described in pages 311 to 315 of "RaphicProcess Jτ, H. Jasea (1977)" can be used. Specifically, for example, para-aminophenol, N-methyl-para-aminophenol, p-β-hydroxyaminophenol, p-α
-aminoethylaminophenol, p-sulf7methylaminophenol, p-hydroxyphenylglycine,
4-amino-2-chlorophenol, 4-amino-3-
Chlorophenol, 4-aminophenonyl-2-sulfonate, 4-7 minophenol-3-sulfonate,
N-methyl-N-(β-sulfoamidoethyl)-p-
Aminophenol, N-benzyl-p-aminophenol, N-methyl-p-aminophenol-2-sulfonic acid, 2,6-dichloro-p-aminophenol, 3-methyl-p-aminophenol, etc. can be used. .

The usage ratio of the above 1-phenyl-3-pyrazolidones and/or para-aminophenols is usually preferably 0.01 to 100 g, more preferably 0.05 to 50 g, based on H of the treatment liquid, Particularly preferably 0
．． It is 1 to 10 g.

In addition to the hydroquinones, 1-phenyl-3-pyrazolidones, and para-aminophenols, various additives can be added to the black and white developing solution as necessary. Such additives include, for example, buffering agents such as carbonates, boric acid, borates, phosphates, alkanolamines, and silicates; alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate; alkali metal sulfites; Preservatives such as alkali metal bisulfites, bisulfite adducts of aldehydes or ketone compounds; alkali metal thiocyanates, polyalkylene oxide compounds, sodium thiosulfate, ammonium, phosphonium, sulfonium-type onium compounds or polyionium compounds, especially Kaisho 5
Development accelerators such as thioether compounds as described in Publication No. 7-63530; antifoggants such as alkali metal halides, benzotriazole, benzothiazole, cheatrazole, thiazole; phosphates such as polyphosphates, nitrile Triacetic acid, 1,3-diaminopropanol tetranoic acid, diethylenetriaminepentaacetic acid, 7-minobolycarboxylic acids such as hydroxyethyliminodiacetic acid, oxycarboxylic acids such as citric acid and gluconic acid, ■-Hydroxyethylidene-1.1 -Chelating agents such as organic acids such as diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid), polyhydroxy compounds such as 1,2-dihydroxybenzene-3,5-disulfonic acid; ethylene glycol, diethylene glycol, polyethylene Thickening agents such as glycols or esters thereof; etc. can be mentioned.

The pit of the black and white developing solution is usually 865 to 11.5.
is preferable, particularly preferably 9.0 to 11.0.

Further, the treatment temperature is usually preferably 10 to 60°C, particularly preferably 20 to 50°C.

Various color developing agents are used in the color developing solution. As such a color developing agent, for example, an aromatic primary amine color developing agent, and various other compounds widely used in various color photographic processes can be used. These compounds are generally used in salt form, such as hydrochloride or sulfate, to make them more stable than in the free state. The proportion of these compounds to be used is generally preferably about 0.1 to 30 g, particularly preferably about 1 to 15 g, per 17 g of the treatment liquid.

Particularly useful aromatic primary amine color developing agents are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent.

Specifically, for example, N,N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-N-pro and luparaphenylenediamine sulfate, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino -5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-
β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-
Amino-3-methyl-N, N-diethylaniline sulfate, 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3- (β-methanesulfonamidoethyl)-4-aminoaniline sulfate and the like can be mentioned.

Particularly effective color developing agents are phenylenediamine-based ones having at least one water-soluble group (m-aqueous group) in the amino group. Such water-soluble groups include:
For example, the following can be mentioned.

0 water-soluble group -(CHI), l-C1,011 (CHi)-NHSOt (CHz)--CHi(C
Ilt)--0(CHt)-CHi(CHtCHtO)
-C-Ht-, + C0OH 5Osll (where m and n are integers of 0 or more), typical paraphenylenediamine color developing agents having such a water-soluble group include: For example, those represented by the following formula can be mentioned.

Hs Ct Ct HaN HS Oz CHs
Ht Hs Ct Ct Ha OCHsHz N) 1 Snow Ht Nl (Wings HCHx C00H Ht th HsCz (CHzCHtO)zctHsti
Particularly useful color developing agents include (C11-RCHzOH) as a substituent on the amino group.

(CHz)-NH30t (CHz), ICH*,
(C1lt)-0-(C1l, l-CH3, -(CH
tCIltO)1. C, H! ,. 1, and specific examples include the formula ill, (2)
, (3), (4), (6) and (7). Note that m and n are integers of 0 or more,
Preferably it is an integer between θ and 5.

Particularly preferred among these compounds are those represented by the formula (
1), (3) and (4),
Among these, compounds represented by formulas (1) and (3) can be particularly preferably used.

In addition to the above-mentioned color developing agent, various additives can be added to the color developing solution as necessary. Such additives include preservatives, alkaline agents, buffering agents, and the like.

Preservatives include, for example, alkali metal sulfites, alkali metal bisulfites, bisulfite adducts of aldehyde or ketone compounds, water-soluble salts of hydroxylamine, sulfates, hydrochlorides, phosphates, etc. . Examples of alkaline agents and buffering agents include sodium hydroxide, silicate, sodium carbonate, potassium metaborate, boric acid,
Examples include phosphates, and these can be used alone or in combination. More lA11!
Due to the above requirements or for the purpose of increasing ionic strength, disodium hydrogen phosphate, sodium bicarbonate, etc. can also be used.

Further, if necessary, it is also possible to use an antifoggant made of an inorganic substance or an organic substance. Typical compounds that can be used as antifoggants include, for example, inorganic halide compounds such as potassium bromide and potassium iodide; 6-nitrobenzimidazole described in U.S. Pat. No. 2,496,940; ; U.S. Pat. No. 2,497.917 and U.S. Pat. No. 2,656,271
5-nitrobenzimidazole; O-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole;
Examples include heterocyclic compounds described in Japanese Patent No. 1675.

In addition to these various components, Japanese Patent Publication No. 46-19039, Japanese Patent Publication No. 45-6149, and U.S. Patent No. 3,295
．． The development inhibitors and development accelerators described in the specification of No. 976 can also be added to the color development treatment solution, if necessary. Among these development accelerators are those described in U.S. Pat. No. 2,648,604;
Various pyridium compounds, other coloronic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, and U.S. Pat. .99
Specification No. 0, Specification No. 2.531.832, No. 2
．． Nonionic compounds such as polyethylene glycol or its derivatives, polythioethers, etc., described in Japanese Patent Publication No. 950,970, No. 2,577, 127, and Japanese Patent Publication No. 1987-9504, polythioethers, etc.
Organic solvents or organic amines, ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. described in Japanese Patent No. 9 are included. In addition, benzyl alcohol, phenethyl alcohol, and others described in U.S. Patent No. 2,304,925,
Acetylene glycol, methyl ethyl ketone, cyclohexane, thioethers, pyridine, ammonia, hydrazine, amines and the like can also be effectively used as development accelerators. In addition, if necessary, ethylene glycol,
Methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others
Compounds described in Japanese Patent Nos. 7-33378 and 44-9509 can be used as organic solvents for increasing the solubility of the developing agent.

If necessary, various chelating agents can be added to the color development processing solution as water softeners or heavy metal sequestering agents. Such chelating agents include phosphates such as polyphosphates, aminopolycarboxylic acids such as nitrilotriacetic acid, l,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, citric acid, and gluconic acid. oxycarboxylic acids such as
1-Hydroxyethylidene-1,! - diphosphonic acid, aminopolyphosphonic acid such as aminotri(methylenephosphonic acid), 1,2-dihydroxybenzene-3
, 5-disulfonic acid, and other polyhydroxy compounds.

If necessary, an auxiliary developer may be added to the color development processing solution. Such auxiliary developers include, for example, N~methyl-p-aminophenol sulfate (methol), phenidone, N,N-diethyl-
Examples include p-aminophenol hydrochloride, N,N,N,N-tetramethyl-p-phenylenediamine hydrochloride, etc., and the usage ratio is usually 0 to 11 of the treatment liquid.
．． 01 to 1.0 g is preferable, and if necessary, a competitive coupler such as citradinic acid and N as a fogging agent.

N, N-) Tin chelate compounds such as tin rimethylenephosphonate and tin citrate, borohydride compounds such as tart-butylamine borane, colored couplers, development-inhibited release couplers (so-called DIR couplers),
Alternatively, a development inhibitor-releasing compound or the like can also be used.

The color developing agent for color is generally preferably used within the pH range of 8 to 14, more preferably within the pH range of 9.
, 5 to 14, particularly preferably pH 11.5 to 13.
．． It is 5. Further, the treatment temperature is preferably 10 to 60°C,
Particularly preferred is 20 to 50°C.

In the stabilizing treatment liquid, a chelating agent having a chelate stability constant of 8 or more with respect to iron ions can be preferably used.

In addition, "chelate stability constant" is "stability constant of metallion complex J (
rsLability Con5tants of M
etallonComplexesJ +The
Chemical 5occlety, London (
1964).

Written by L, G, 5illen ・^, E, Martell)
, [Organic Sexestering Agent J
(rorganicSequestering Ag
entsJ Jiley (1959), Chabe, S.
It means a constant generally known by A, E. Martell), etc.

Examples of such chelating agents having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe'').

Specific examples of chelating agents having a chelate stability constant of 8 or more for ferric ions include, for example, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, Ethylenediamine diacetic acid, ethylenediamine nipropionic acid,
Iminoniacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid,
trans-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid,
! -Hydroxyethylidene-1,1-diphosphonic acid, 1
．． 1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2゜4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid , sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, etc., and particularly preferred ones include diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid. etc. can be mentioned. Among these, 1-hydroxyethylidene-1,
1-diphosphonic acid can be most preferably used.

The proportion of these chelating agents used is generally preferably 0.01 to 50 g, particularly preferably 0.05 to 20 g, per 11 g of the treatment liquid.

An ammonium compound can be further added to the stabilization treatment liquid as necessary. Such ammonium compounds are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, and phosphorous acid. Ammonium, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, adipic acid Ammonium, ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate,
Ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, oxalic acid ammonium, ammonium phthalate, ammonium picrate,
Examples include ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, and 2,4,6-dolinitrophenol ammonium. Among these ammonium compounds, ammonium thiosulfate can be particularly preferably used.

The usage ratio of these ammonium compounds depends on the In of the treatment solution.
Generally, the amount is preferably 1.0×10 −′ mol or more, more preferably 0.001 to 5.0 mol, particularly preferably 0.002 to 1.0 mol.

Further, it is desirable to add sulfite to the stabilizing treatment liquid from the viewpoint of preventing the generation of bacteria.

As such a sulfite, any organic or inorganic substance can be used as long as it releases sulfite ions, and among these, inorganic salts are preferably used. Preferred sulfites include, for example, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, hydrosulfide, and cartaraldehyde bisulfite. Sodium bisulfite, sodium cono-lamb acid aldehyde bisbisulfite, and the like can be mentioned.

The ratio of these sulfites used is 11 to 11 in the treatment liquid.
Usually, it is preferably 1.0×1 G-'-1 or more, and particularly preferably 5×10-' to 1, OXl0-' mol.

An antifungal agent can be further added to the stabilizing treatment liquid, if necessary. By adding a fungicide, sulfurization prevention and image storage stability can be improved. Examples of such antifungal agents include isothiazoline-based, benzimidazole-based, benzisothiazoline-based, thiabendazole-based, phenol-based, halogen-substituted compounds, mercapto-based compounds, benzoic acid or derivatives thereof, and the like. Among these, isothiazoline series, benzisothiazoline series, thiabendazole series, phenol series, benzoic acid, etc. can be preferably used, and isothiazoline series, benzisothiazoline series, and thiabendazole series can be particularly preferably used. Specific compounds that can be used as such antifungal agents include, for example, the following.

[Exemplary compounds of antifungal agents]

(1) 2-Methyl-4-isothiazolin-3-one (2) 5-chloro-2-methyl-4-isothiazolin-
3-one (3) 2-methyl-5-phenyl-4-isothiazolin-3-one (4) 4-bromo 5-chloro-2-methyl-4-isothiazolin-3-one (5) 2-hydroxymethyl- 4-isothiazoline-3
-one (6) 2-(2-ethoxyethyl)-4-isothiazolin-3-one (7) 2-(methyl-carbamoyl)-4-isothiazolin-3-one (8) 5-bromomethyl-2-(N -dichlorophenyl-carbamoyl)-4-isothiazolin-3-one (9) 5-chloro-2-(2-phenylethyl)-4-
Isothiazolin-3-one (10) 4-Methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one (11) 1.2-benzisothiazolin-3-one (
12) 2-(2-bromoethyl)-1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-benzisothiazolin-3-one (14) 2-ethyl-5-nitro1. 2-benzisothiazolin-3-one (15) 2-benzyl-1,2-benzisothiazolin-3-one (16) 5-Li:10-1,2-benzisothiazolin-3-one (17) Hydroxy Benzoic acid (18) Thiabendazole
7, 172, 2.767.173, 2.7
No. 67.174, No. 2,870.015, British Patent No. 848.130, French Patent No. 1.555.4
The various specifications of No. 16 describe its synthesis method and examples of its application to other fields. In addition, commercially available products include, for example, "Topside 300 J", "Topside 600" (manufactured by Permakem Asia Co., Ltd.), [Fineside J-700J (manufactured by Tokyo Fine Chemical Co., Ltd.),
There are products such as rProxsl GXLJ (manufactured by 1.G, 1.), and these can also be used. The usage ratio of these antifungal agents is usually 0.01 to 0.01 to Iz of the treatment solution.
50g is preferred, particularly preferably 0.05-20g.

The pH of the stabilizing treatment liquid is usually preferably 3.0 to 9.5, particularly 3.0 to 9.5 from the viewpoint of effectively preventing precipitation.
It is preferable that it is 5-9.0.

Various additives can be further added to the stabilizing treatment liquid as necessary. Such additives include, for example, organic acid salts such as citric acid, acetic acid, succinic acid, Sierra acid, and benzoic acid; pH buffering agents such as phosphoric acid, borate, hydrochloric acid, and sulfuric acid; or surfactants; and preservatives. agent; for example, Bi, , M
Examples include metal salts such as g%Zns, NtSlit%5nsTis, and Zr. These additives may be used alone or in combination, and their usage ratios are not particularly limited. It is preferable to set this value in consideration of ensuring the above-mentioned conditions and effectively preventing the occurrence of precipitation.

A bleaching agent is used in the bleaching solution or bleach-fixing solution. As such a bleaching agent, known ones can be used, including, but not limited to, red blood salt and iron chloride described in British Patent No. 736,881 and Japanese Patent Publication No. 56-44424. For example, persulfuric acid described in German Patent No. 2.141,199; For example, Japanese Patent Publication No. 11617/1982, Japanese Patent Publication No. 58-11
Hydrogen peroxide described in Japanese Patent No. 618; ferric complex salts of organic acids such as ferric salts of ethylenediaminetetraacetic acid; and the like can be used.

Among these bleaching agents, the following ferric complex salts of organic acids can be preferably used.

(Exemplary compounds of organic acids) (1) Diethylenetriaminepentaacetic acid (2) Diethylenetriaminepentamethylenphosphonic acid (3) Cyclohexanediaminetetraacetic acid (4) Ethylenediaminetetraacetic acid (5) Methyliminodiacetic acid (6) Propyliminodiacetic acid (7) Butyliminodiacetic acid Acetic acid (8) Cyclohexanediaminetetramethylenephosphonic acid (9) Triethylenetetraminehexaacetic acid (10) ) Liethylenetetraminehexamethylenephosphonic acid (11) Glycol ether di7minetetraacetic acid (12) Glycol ether diamine tetramethylene phosphonic acid (13) ) 1.2-diaminopropanetetraacetic acid (14)
1.2-Diaminopropane tetramethylenephosphonic acid (15) 1.3-Diaminopropan-2-ol tetraacetic acid (16) 1.3-Diaminopropane-2-ol tetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxyphenyl Acetic acid (18) Ethylenediamine diorthohydroxyphenylmethylenephosphonic acid (19) Ethylenediamine tetramethylenephosphonic acid (20
) N-Hydroxyethyliminodiacetic acid The ferric complex salt of an organic acid used as a bleaching agent is a free acid (hydrogen salt).
, alkali metal salts such as sodium salts, potassium salts, and lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine salts, but preferably potassium salts, sodium salts, and ammonium salts. These 2nd J & complex salts of organic acids may be used alone or in combination of two or more, and the ratio of use is not particularly limited, but it depends on the amount of silver in the photographic material to be processed and It is determined as appropriate depending on the composition of silver halide. Since these ferric complex salts of organic acids generally have high oxidizing power, they can be used at lower concentrations than other aminopolycarboxylic acid salts. Specifically, it is usually preferable to use it in a proportion of 0.01 mol or more, particularly 0.05 to 0.
It is preferable to use it in a proportion of 6 moles.

When filling a bleaching solution or a bleach-fixing solution into the supply/recovery container according to the present invention, it is preferable to keep the bleach content high. Appropriate processing can be efficiently performed while reducing the amount of replenishment of the bleaching solution or bleach-fixing solution from inside the container.

The pH of the bleaching solution and bleach-fixing solution is usually 0.
It is preferably 2 to 9.5, more preferably 4 to 9, particularly preferably 5.5 to 8.5. Further, the treatment temperature is preferably 80°C or lower, more preferably 55°C or lower, particularly preferably 45°C or lower, and it is preferable to use the treatment liquid while suppressing evaporation.

Various additives can be further added to the bleaching solution or the bleach-fixing solution, if necessary. As such additives, alkali halides or ammonium halides can be preferably used, and specifically, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide,
Ammonium iodide and the like can be used. Other additives include borates, oxalates, acetates,
pH buffering agents such as carbonates and phosphates; solubilizing agents such as triethanolamine; acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids,
Those commonly used as additives in bleaching solutions or bleach-fixing solutions, such as polycarboxylic acids, alkylamines, and polyethylene oxides, can be used.

In addition, the bleach-fixing solution may be a bleach-fixing solution containing a small amount of a halogen compound such as potassium bromide, or conversely, a bleach-fixing solution containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a fixing solution, as well as a special bleach-fixing solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide. In addition to potassium bromide, such halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide,
Potassium iodide, sodium iodide, ammonium iodide, etc. can also be used.

As the silver halide fixing agent used in the bleach-fixing processing solution, compounds that react with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processing, can be used. Specifically, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate, thioureas, thioethers, high concentrations of bromides, iodides, and the like can be mentioned. These fixing agents are used to the extent that they can be dissolved in the bleach-fixing processing solution, and specifically, they are
Generally, the amount is preferably 5 g or more, more preferably 50 g or more, and particularly preferably 70 g or more.

As additives in the bleach-fixing solution, boric acid, borax, sodium hydroxide,
pHTL buffer agents made of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be used alone or in combination of two or more. . Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can also be used. Preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes or ketone compounds; acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids , organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids; stabilizers such as nitro alcohols and nitrates; solubilizers such as alkanolamines; stain inhibitors such as organic amines; other additives; methanol, dimethylformamide, Organic solvents such as dimethyl sulfoxide can be used as appropriate.

Examples of the fixing agent used in the fixing solution include thiosulfate as described in JP-A-57-185435; for example, British Patent No. 565.135;
Thiocyanates described in JP-A No. 4-137143; halides described in JP-A-52-130639; for example, Belgian Patent No. 626.
Thioethers as described in GB No. 970; for example, thiourea as described in British Patent No. 1.189.416; and the like can be used. As additives in the fixing solution, boric acid, borax, sodium hydroxide, potassium hydroxide,
pH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be used alone or in combination of two or more. Furthermore,
Various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be used. Also hydroxyamine, hydrazine,
Preservatives such as sulfites, isomeric bisulfites, bisulfite adducts of aldehydes or ketone compounds; acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids,
Organic chelating agents such as oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids and aminopolycarboxylic acids; Stabilizers such as nitro alcohols and nitrates; Solubilizers such as alkanolamines; Anti-stinting agents such as organic amines; Other additives ; Organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be used as appropriate.

[Experiment example]

Hereinafter, a specific example of an experiment conducted by actually producing a supply/recovery container will be described.

-a'' (1) Supply/Recovery Container 1 (For the Present Invention) A supply/recovery container according to the present invention having a supply chamber capacity of 51 was manufactured based on the configuration shown in FIG.

This is referred to as the "supply/recovery container 1", and the specific configuration of each part is as follows.

One side outer wall 21> A flexible sheet made of polyethylene with a thickness of 50 nm <Corner wall 30> A gas barrier sheet made of saran coated nylon with a thickness of 110 nm (oxygen permeability coefficient: 13 dl (I11!・24)
hrs 01at+m) Other outer wall 22> Inner sheet 22B: Gas barrier sheet made of saran coated nylon with a thickness of 110 nm (oxygen permeability coefficient:
13a7/(m” ・24hrs ・1ate) External sheet 22A: Flexible sheet made of polyethylene with a thickness of 50 nm (2) Supply/recovery container 2 (for the present invention) Based on the configuration shown in FIG. A supply/recovery container according to the present invention having a chamber capacity of 51 was fabricated.

This is referred to as the "supply/recovery container 2", and the specific configuration of each part is as follows.

One outer wall 21 > A flexible sheet made of polyethylene with a thickness of 50 nm / Partition wall 30 > A gas barrier sheet made of saran coated nylon with a thickness of 110 fm (oxygen permeability coefficient: 13 af/(m"・2)
4hrs +1ats+) <Other outer wall 22> Inner sheet 22B: Flexible sheet made of polyethylene with a thickness of 70 nm External sheet 22A: Gas barrier sheet made of Saran coated nylon with a thickness of 110 μm (Oxygen permeability coefficient port 3
d/(m” ・24hrs ・1ate) (3) Supply ・
Collection Container 3 (For the Present Invention) A supply/recovery container according to the present invention having a supply chamber capacity of 51 was produced based on the configuration shown in FIG.

This is referred to as the "supply/recovery container 3", and the specific configuration of each part is as follows.

One side outer wall 21> Gas barrier sheet made of saran coated nylon with a thickness of 100n (Oxygen permeability coefficient: 15d/(■2.24k
hrs 1late) Partition wall 30> Flexible sheet made of polyethylene with a thickness of 60 nm Other outer wall 22> Inner sheet 22B: Gas barrier sheet made of saran coated nylon with a thickness of 100 nm (oxygen permeability coefficient: 1
5d/(s”・24hrs-1ate) External sea)
22A: Thickness 60. Flexible sheet made of polyethylene (4) Supply/recovery container 4 (for the present invention) Based on the configuration shown in FIG. 4, a supply/recovery container according to the present invention having a supply chamber capacity of 51 was fabricated. .

This is referred to as the "supply/recovery container 4", and the specific configuration of each part is as follows.

<One outer wall 21> Gas barrier sheet made of saran coated nylon with a thickness of 115 nm (oxygen permeability coefficient: 12 d/(w"・24
<Partition wall 30> Gas barrier sheet made of saran coated nylon with a thickness of 100 nm (oxygen permeability coefficient = 15-bar 8.24 hrs)
Other outer wall 22> Inner sheet 22B = Flexible sheet made of polyethylene with a thickness of 50 nm External sheet 22A: Gas barrier sheet made of saran coated nylon with a thickness of 115 nm (Oxygen permeability coefficient: 1
2-bam”・24hrs・1ate) (5) Supply・
Collection container 5 (for the present invention) A supply/recovery container according to the present invention having a supply chamber capacity of 51 was produced based on the configuration shown in FIG.

This is referred to as the "supply/recovery container 5", and the specific configuration of each part is as follows.

One side outer wall 21
4hrs 61atm) Partition wall 30> Gas barrier sheet made of saran coated nylon with a thickness of 110n (Oxygen permeability coefficient: 13-bar ■: ・24hr
1-1ate) Other outer wall 22> Gas barrier sheet made of saran-coated nylon with a thickness of 110 nm (oxygen permeability coefficient: 13 dl (vs”・2
(6) Supply/Recovery Container 6 (For the Present Invention) A supply/recovery container according to the present invention having a supply chamber capacity of 51 was manufactured based on the configuration shown in FIG.

This is referred to as the "supply/recovery container 6", and the specific configuration of each part is as follows.

One outer wall 21> External sheet 21A: Flexible sheet made of polyethylene with a thickness of 60 Inner sheet 21B: Gas barrier sheet made of Saran coated nylon with a thickness of 110 In (oxygen permeability coefficient j
13d/axis"・24hrs・latm) bulkhead 30
〉 Gas barrier sheet made of saran coated nylon with a thickness of 115n (Oxygen permeability coefficient: 12d/(l:・24h
rs・1ate) <Other outer wall 22> Inner sheet 22B: Gas barrier sheet made of saran coated nylon with a thickness of 115 m (oxygen permeability coefficient =
12d/(Maro"・24hrs-1ate) External sheet 22A? Flexible sheet made of polyethylene with a thickness of 60n (7) Supply/recovery container 6 (for comparison) Based on the configuration shown in FIG. A supply/recovery container for comparison with a capacity of 5! was prepared.This is referred to as "supply/recovery container 7", and the specific configuration of each part is as follows.

One side outer wall 21> Thickness 110. Gas barrier sheet made of saran coated nylon (oxygen permeability coefficient: 13dba sz, 24hr
s-fats) Partition wall 30 > Flexible sheet made of polyethylene with a thickness of 60 nm Other outer wall 22 > Inner sheet 22B: Flexible sheet made of polyethylene with a thickness of 60 nm, External sheet 22A: Saran sheet with a thickness of 110 nm Gas barrier sheet made of coated nylon (oxygen permeability @
= 13d/(m”・24hrs・1a
te) <Experimental Example 1> Each of the supply chambers of the supply/collection containers 1 to 7 was filled with 4.51 parts of a color developing treatment solution having the composition below, and each supply port and collection port were airtightly closed. A package for the treatment liquid was formed.

After subjecting these packages to a practical distribution process and transporting them by truck, each package was placed in a laboratory room adjusted to a temperature of 60°C, a relative humidity of 60%, and a pressure of 1 atm. A test was conducted in which the treatment liquid was left for a long period of time, and the sulfite ion concentration in the treatment liquid after a certain period of time was investigated. The results are shown in Table 1 below.

This sulfite ion has the property of being easily oxidized.
By examining its concentration, the degree of oxidative deterioration can be determined.

The concentration of sulfite ions was measured by taking a certain amount of the sample of the treatment liquid and titrating it with an iodine standard solution (1/20 normal).

° Amount of 0 Benzyl alcohol 18-〇 Diethylene glycol 1 〇-〇 Fluorescent brightener [Chippanol 5FP4 2 g (manufactured by Ciba Geigy) 0 Hydroxylamine sulfate 4 g 0 3-Methyl-4-amino-N-ethyl 7L/-N-( β-methanesulfonamidoethyl)-aniline sulfate 7.0gopotassium carbonate
25 go! 1! Potassium sulfate (50
% aqueous solution) 6-〇Potassium hydroxide 6M
2.3 go water total l
! A color developing treatment solution was obtained by mixing and dissolving the above substances in amounts such that

Table 1 As can be understood from the results in Table 1, supply/recovery containers 1 to 6 according to the present invention sufficiently prevent air from entering the supply chamber, thereby stabilizing the processing liquid for a long period of time. can be saved in

On the other hand, according to the comparative supply/recovery container 7, deterioration due to oxidation of the processing liquid occurred early, making it difficult to store it for a long period of time. When the sheets constituting each part of the supply/recovery container 7 were examined in detail, it was found that the outer sheet 22A forming one outer wall 22 had a large number of pinholes. This pinhole is formed in the outer sheet 22A when the supply/recovery container 7 is subjected to the distribution process.
It is presumed that this occurred due to frictional contact between the inner sheet 22B and the inner sheet 22B.

[Brief explanation of the drawing]

FIGS. 1 to 6 are explanatory cross-sectional views showing specific examples of the configuration of the supply/recovery container according to the present invention, and FIG. 7 is an explanatory sectional view showing a specific example of the configuration of the supply/recovery container for comparison. FIG. 11... Supply room 12... Collection room 21.
...One outer wall 22...The other outer wall 21A.
...External sheet 21B...Internal sheet 22A
...Outer side sheet 22B...Inner side sheet 30
... Bulkhead 41 ... Supply port 42 ...
Recovered Mouth Tsune 1 Figure Kaya 4 Figure Capital 6 Prisoners

Claims (1)

[Scope of Claims] 1) A supply/recovery container for a photographic material processing solution having a flexible outer wall and a flexible partition wall that divides an internal space surrounded by the outer wall into a plurality of chambers, comprising: At least a portion of the wall directly surrounding at least one of the plurality of chambers has an oxygen permeability coefficient of 20ml/(m^2・24
1. A supply/recovery container for a photographic material processing solution, characterized in that the amount is less than 1 ATM). 2) The supply/recovery container for photographic material processing liquid according to claim 1, wherein the outer wall and the partition wall are formed of flexible sheets. 3) The supply/recovery container for photographic material processing liquid according to claim 2, wherein the flexible sheet forming the outer wall and the partition wall has a multilayer structure. 4) A supply/recovery container for photographic material processing liquid according to claim 2 or 3, wherein the outer wall and the partition wall are formed of a plurality of independent flexible multilayer sheets.