JPH043861B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an improved photographic processing agent composition storage pack. More specifically, it relates to a container for storing a photographic processing agent composition, which has a long life even when storing a photographic processing liquid that does not require mixing, and which facilitates the disposal of waste liquid. This relates to a liquid storage pack. [Background of the Invention] Many of the photographic processing solutions used when exposing and developing photographic materials have redox properties and are generally susceptible to air oxidation. For example, since developing solutions and color developing solutions are susceptible to air oxidation, sulfites are added as preservatives to reduce the degree of oxidation. In addition, sulfite is added to the fixing solution and bleach-fixing solution to prevent air oxidation from decomposing the fixing agent, sodium thiosulfate, and releasing sulfur, resulting in a serious accident. Furthermore, in the stabilizer for anhydrous washing, the anti-bacterial agent easily deteriorates due to air oxidation, so sulfite is also often added to prevent this. Even if these treatment liquids are prevented from being oxidized in the air using sulfites as described above, they cannot be processed in the conventionally used kit containers such as polyethylene bottles or polyethylene film bags (flexible containers called by trade names such as Shyori Pack). If the liquid is prepared and kept in the used state, it will not withstand storage for more than two weeks and will deteriorate due to oxidation. Therefore, the drug composition should be separated and packaged to prevent oxidation as much as possible, and dissolved water should be added immediately before use. The treatment agent composition was supplied in a pre-mixed kit called a pre-mixed kit, which can be dissolved and used in a short period of time. [Problem to be solved by the invention] Therefore, each photo lab uses a plurality of sachets to
This requires dissolving two processing solutions, which is a tedious task. Generally, each sachet must be completely dissolved before the next sachet can be added, and the patient must wait while stirring for several minutes or even tens of minutes in some cases. , which required a considerable amount of manpower. In particular, as mini-labs and simple automatic processors and processors for copy machine-like dispersion processing become available, complicated kits packaged in many containers can lead to erroneous melting because complete amateurs cannot understand their names or distinctions. Many problems have begun to occur in the market, causing serious problems in photographic performance, and as the work has shifted from professional processing companies to camera store clerks, this problem is becoming more and more obvious. Furthermore, as processing becomes waterless, many automatic developing machines have come on the market that eliminate the need for drain pipes and the overflow of each processing solution is collected in a dedicated waste tank. This is very desirable from a pollution prevention perspective, but when the waste liquid tank is full, it is equipped with a buzzer.Although safety measures have been taken, I accidentally turn off the alarm buzzer and close the waste liquid tank. There have been many cases where people forget to replace the water and the waste fluid overflows, staining the floor and leading to serious accidents. Therefore, in the era of decentralized photo processing, users need a highly amateurish process that eliminates the troublesome and error-prone kit dissolution process that involves complicated packaging, and allows them to work with peace of mind without having to worry about waste liquid management. It can be said that there is a strong demand for a storage pack for photographic processing solutions that is a solution supply system and has a high shelf life of processing solutions. [Object of the Invention] Therefore, the object of the present invention is, firstly, to provide a storage pack for a photographic processing solution which has high storage stability, and secondly, which does not require complicated dissolution work. Thirdly, it is to provide a storage pack for photographic processing liquid that allows a completely failure-free waste liquid recovery system to be constructed. [Means for Solving the Problems] As a result of intensive studies, the present inventors have discovered that, in a flexible pack for storing a photographic processing solution for a silver halide photographic light-sensitive material, the pack is divided into at least two parts vertically partitioned by a diaphragm. It has a tank shape with a compartment, the lower half of which is a supply chamber for photographic processing solution, and the upper half is a waste solution chamber, and at least a membrane forming the photographic processing solution supply chamber. The membrane on the outer surface facing the diaphragm has an oxygen permeation rate of 20ml/m ² /
The photographic processing solution storage pack is made of a flexible synthetic resin film that lasts for 24 hours or less, and is configured so that one side of the diaphragm is covered with the waste solution collected in the waste solution chamber. The inventors discovered that the object (technical problem) can be achieved, leading to the present invention. By the way, Japanese Patent Publication Nos. 55-55942 and 56-131155
No. 58-52065 and Japanese Utility Model Application No. 56-94754 disclose techniques in which one pack is divided into two parts by a diaphragm. According to these techniques, the processing solution supply pack and the waste solution storage pack can be provided in one pack, which certainly reduces space, but it is not possible to maintain the storage stability of the photographic processing solution. Further, Japanese Utility Model Publication No. 51-27809 discloses a technique for collecting waste liquid into a space between the inner pack and a liquid-tight outer container that is created by supplying the processing liquid in the inner pack. However, this technique has the disadvantage that since the outer container is rigid and liquid-tight, the space tends to be in a negative pressure state when the processing liquid is supplied, and the processing liquid cannot be supplied smoothly. In addition, since the outer container is rigid, compared to a case where the entire container is made of flexible material,
It has the disadvantage that it requires a large space during manufacturing and before storing the processing liquid. [Specific Configuration of the Invention] Hereinafter, an example of a specific configuration of the present invention will be described based on the accompanying drawings. 1 and 2 are cross-sectional views showing one embodiment of the present invention, and FIG. 1 shows a state in which photographic processing liquid is stored in the supply chamber and before waste liquid is stored in the waste liquid chamber. , FIG. 2 shows a state in which waste liquid is collected in the waste liquid chamber. 1 and 2, reference numeral 1 denotes a storage pack, and the storage pack 1 is a flexible bag made of resin. It is divided into upper and lower parts of 2.
The upper half is the waste liquid chamber 3, and the lower half is the supply chamber 2. Reference numeral 4 designates an opening provided in the supply chamber 2 for photographic processing liquid, and 5 designates an opening provided in the waste liquid chamber 3.
Note that in this specification, "separated vertically" does not mean absolute upper and lower, but also includes cases where it is divided in other directions, such as left and right, as long as it is divided via the diaphragm 1A. For example, in the storage pack 1 shown in FIG. 3, a waste liquid chamber 3 is provided in the right half, and a supply chamber 2 and another supply chamber 2' are provided in the left half. The details of the structure of the embodiment shown in FIGS. 1 and 2 are as follows. That is, from the manufacturing example, first, along the edge of the rectangular flexible film F1 having the through holes for the openings 4 and the openings 5, the edge of the rectangular flexible film F2 forming the diaphragm 1A is drawn. Seal S. At this time, a liquid-absorbing and swelling substance 6 is interposed as necessary. The rectangular flexible film F2 has an opening 4,
The opening 4 is sealed S while passing through the through hole of the rectangular flexible film F1. As a result of the above, a waste liquid chamber 3 is formed in which a liquid-absorbing and expanding substance 6 is provided as required. Next, the flexible film F3, which is a film on the outer surface facing the diaphragm 1A, is attached to the seal S.
to form a supply chamber 2. The flexible film F
3 has an oxygen permeation rate of 20ml/m ² /24Hr or less. In addition, it is preferable that the openings 4 and 5 are threaded to attach a lid. In the present invention, the photographic waste liquid stored in the waste liquid chamber 3 includes, for example, a black and white developer with a specific gravity of 1.01 or more, a color developer, a fixer, a bleach-fixer, a bleach, a stabilizer,
A photographic processing solution such as a stop solution, an image stabilizing solution, a rinsing solution, and an alternative stabilizing solution for washing, which is a solution used after processing photographic materials.
The liquid may be a seed or a mixture of two or more, but if necessary, it may be a waste liquid for reuse. On the other hand, the photographic processing liquids stored in the supply chamber 2 are the various photographic processing liquids themselves. Among these photographic processing liquids, the photographic processing liquids particularly preferably used in the present invention are black and white developer, color developer, fixer, bleach-fixer, bleaching liquid, and water washing substitute stabilizing liquid. It is preferable to apply it to a processing solution containing easily oxidized sulfite, a preservative such as hydroxyamine, a developing agent, a thiosulfate, an anti-bacterial agent, etc., and it is especially suitable to apply it to a processing solution containing sulfite. preferable. The photographic processing liquid used in the present invention may be a processing liquid for directly processing a photosensitive material. It may be a part agent in which part or all of the replenisher solution used for replenishment and the composition used for preparing these processing solutions are concentrated. In the present invention, the membrane forming the supply chamber 2 and the membrane on the outer surface facing the diaphragm 1A has an oxygen permeation rate of 20
ml/m ² /24Hr or less flexible synthetic resin film is used, and the amount of oxygen permeation can be measured by a conventionally known method. Measurements are shown in % relative humidity. Next, the amount of oxygen permeation used in the present invention is 20ml/
A flexible synthetic resin film of m ² /24Hr or less will be explained. The flexible synthetic resin film of the present invention having an oxygen permeability of 20 ml/m ² /24 Hr or less may be a single layer (polymer) resin film or a laminated (polymer) resin film of two or more layers. Good too. Examples of one-layer polymer resin films that meet the conditions of the present invention include (1) polyethylene terephthalate (PET) with a thickness of 0.1 mm or more, (2) acrylonitrile butadiene copolymer with a thickness of 0.3 mm or more, (3) ) Hydrochloric acid rubber having a thickness of 0.1 mm or more, among others, polyethylene terephthalate is excellent in alkali resistance and acid resistance, so it can be suitably used in the present invention. Next, laminated polymer resin films that meet the conditions of the present invention include (4) PET/polyvinyl alcohol/ethylene copolymer (EVAL)/polyethylene (PE), (5) oriented polypropylene (OPP)/ EVAL/PE, (6) Unoriented polypropylene (CPP)/EVAL/PE,
(7) Nylon (N)/Aluminum foil (Al)/PE, (8)
PET/Al/PE, (9) Cellophane/PE/Al/PE,
(10)Al/Paper/PE, (11)PET/PE/Al/PE, (12)N/
PE/Al/PE, (13) Paper/PE/Al/PE, (14)
PET/Al/PET/Polypropylene (PP), (15)
PET/Al/PET/High Density Polyethylene (HDPE), (16) PET/Al/PE/Low Density Polyethylene (LDPE), (17) EVAL/PP, (18)
PEL/Al/PP, (19) Paper/Al/PE, (20) PE/
PVDC coated nylon/PE/ethyl vinyl acetate polyethylene condensate (EVA), (21)
PE/PVDC coat N/PE, (22) EVA/PE/aluminum vapor deposited nylon/PE//EVA, (23) aluminum vapor deposited nylon/N/PE/EVA, (24) OPP/
PVDC coat N/PE, (25) PE/PVDC coat N/PE, (26) OPP/EVAL/LDPE, (27)
OPP/EVAL/CPP, (28) PET/EVAL/
LDPE, (29)ON (stretched nylon)/EVAL/
There are LDPE, (30) CN (unstretched nylon)/EVAL/LDPE, etc., among which the above (20) to (30)
is preferably used. The thickness of these films varies depending on the type, but films with a thickness of preferably 0.5 μm to 500 μm, particularly preferably 1 μm to 200 μm are suitably used. A supply chamber 2 shown in FIG. 1 is filled with a photographic processing solution. From this state, the processing liquid is supplied through the opening 4 to an automatic developing machine (not shown). The waste liquid from the automatic developing machine is sent into the waste liquid chamber 3 through the opening 5. At this time, the waste liquid is in the waste liquid chamber 3.
As the photoprocessing solution is absorbed into the supply chamber 2, one side of the diaphragm 1A is wetted or soaked to eliminate air permeation, thereby preventing oxidation of the photographic processing solution in the supply chamber 2 and eliminating storage deterioration. At this time, since the liquid in the supply chamber 2 is decreasing, the state gradually approaches the state shown in FIG. 2. Although one embodiment of the present invention has been described above, the embodiments of the present invention are not limited thereto. For example, the storage tank 1 is not limited to the illustrated form;
Any other form may be used as long as it is divided into two or more parts, and specifically, the form shown in FIG. 3 may be used. That is, the same reference numerals in the figure as in FIGS. 1 and 2 indicate corresponding member names. The embodiment shown in FIG. 3 is an example in which another supply chamber 2' is provided, which has its own opening 4'. In this case, another flexible film F4 may be used during manufacturing. Note that the opening 4' can also be made to protrude toward the opening 5 in the same way as the opening 4. It is preferable to provide the liquid-absorbing and expanding substance 6, for example, it may be placed on the diaphragm 1A, it may be fixed to the diaphragm 1A, or it may be fixed to the inner wall (F1) of the storage tank 1. It's okay. The diaphragm 1A is preferably stretchable (by expansion of the liquid-absorbing and swelling material 6), such as a stretchable or flexible synthetic resin sheet or film (including a laminated one) or a rubber sheet. (Natural rubber or synthetic rubber may be used, but a chemical-resistant rubber) and one having an oxygen permeation rate within the range of the present invention is particularly preferably used. Further, the diaphragm 1A is preferably composed of at least two layers of flexible synthetic resin film, and in this case, at least one layer excluding the outermost layer is
Eval, aluminum foil, or aluminum vapor-deposited synthetic resin film is preferable. In addition, it is preferable to use the flexible synthetic resin film according to the present invention for the membrane constituting the waste liquid chamber 3 as well. [Examples] The present invention will be illustrated below with reference to Examples. Example 1 A color developer replenisher with the following formulation was prepared, and two storage packs of 5 sizes of 6 types of different synthetic resins were prepared in the form shown in Figure 1, and one storage pack was filled with processing liquid. I put 4 colors of color developer replenisher prepared according to the following recipe in the supply chamber and 1 color developer waste solution in the waste solution chamber, but in the other storage pack, I only put 5 colors of color developer replenisher in the processing solution supply chamber.
Color developer replenisher was not put into the waste liquid chamber. Next, these storage packs were stored in a thermostat at 50°C for two weeks, and the rate of decrease in sulfite ions in the color developer replenisher was measured. The layer structure and oxygen permeation rate of the diaphragm and the membrane (F3) that forms the processing liquid supply chamber facing the diaphragm are shown in Table 1.
It was shown to. The diaphragm has a thickness of 50 μm and an oxygen permeation rate of 2700
LDPE of ml/m ² /24 Hr was used. The results are shown in Table 1. [Color developer replenisher] Benzyl alcohol 18ml Diethylene glycol 10ml Fluorescent brightener (Tinopanol SFP manufactured by Ciba-Geigi) 2g Hydroxylamine sulfate 4g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 7.0g Potassium carbonate 25g Potassium sulfite (50% aqueous solution) 6ml Potassium hydroxide 2.3g Adjust to 1 with water.

[Table] As is clear from the results in Table 1, when the oxygen permeation rate of F3 is less than 20ml/m ² /24Hr and there is waste liquid in the waste liquid chamber, the reduction rate of sulfite ions in the color developer is extremely high. In particular, it can be seen that the rate of decrease in oxygen permeation through the diaphragm is lower than that at 20ml/m ² /24Hr. Example 2 An experiment was conducted in the same manner as in Example 1, but instead of the color developing replenisher, a bleach-fixing replenisher with the following formulation was used, and the sample was stored in a thermostat at 50°C for one week to reduce sulfite ions. The rate was measured. [Bleach-fix replenisher] Ethylenediaminetetraacetate iron ammonium
75g Ammonium sulfite 10g Ammonium thiosulfate 110g Aqueous ammonia (28%) 10ml Finished to 1 with water and adjusted to PH6.5 with acetic acid and aqueous ammonia. The results are shown in Table 2. In addition, sample No. 13 in Table 2 ~
24 corresponds to sample Nos. 1 to 12 shown in Table 1 of Example 1.

【table】

[Table] As is clear from Table 2, the bleach-fixing replenisher exhibits the same tendency as the color developing replenisher. Example 3 The coloring used in Example 1 was applied to the processing liquid supply chamber of a storage pack similar to that used in Example 1, but with the membrane (F3) and membrane (F1) changed as shown in Table 3. 5. Fill with developer replenisher, connect the opening of the processing solution supply chamber to the bellows pump of the automatic processor for color paper, connect the piping so that the color developer replenisher is replenished to the color developer tank, and open the waste solution chamber opening. was connected to the overflow pipe from the color developing tank so that the color developing waste liquid chamber flows into the waste liquid chamber. 1
Adjust the amount of color paper processed so that approximately 200ml of color developer replenisher is refilled into the color developer tank per day.
After running for 24 hours, the sulfite ions in the color developer replenisher in the processing solution supply chamber of the storage pack were measured to determine the rate of decrease in sulfite ions. The results are shown in Table 3.

[Table] As is clear from Table 3, membrane (F3) and membrane (F1)
It can be seen that when a storage pack with an oxygen permeation rate of 20ml/m ² /24Hr or less is used, the reduction rate of sulfite ions is extremely low. [Effects of the Invention] Since the present invention has the above configuration, it provides a storage pack for a photographic processing solution that has high storage stability, eliminates the need for complicated dissolution work, and allows a completely failure-free waste solution recovery system to be constructed. can do.

[Brief explanation of drawings]

1 and 2 are cross-sectional views showing one embodiment of the present invention, and FIG. 1 shows a state in which photographic processing liquid is stored in the supply chamber and before waste liquid is stored in the waste liquid chamber. , FIG. 2 shows a state in which waste liquid is collected in the waste liquid chamber. FIG. 3 is a sectional view showing another embodiment of the present invention. 1: Storage tank, 1A: Diaphragm, 2: Supply chamber,
3: Waste liquid chamber, 4: Opening, 5: Opening, F1 to F
4: Flexible synthetic resin film or sheet.

Claims (1)

[Claims] 1. A flexible pack for storing a photographic processing solution for a silver halide photographic light-sensitive material. In addition to being a supply chamber for photographic processing liquid, the upper half is a waste liquid chamber,
At least the membrane forming the photographic processing solution supply chamber and the membrane on the outer surface facing the diaphragm is made of a flexible synthetic resin film with an oxygen permeation rate of 20 ml/m ² /24 Hr or less, and 1. A storage pack for photographic processing liquid, characterized in that one side of the diaphragm is covered with waste liquid collected in a chamber.