JPS6317453A - Container for processing agent for silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To eliminate the change with the lapse of time of a processing agent for color photography due to oxidation by setting the oxygen permeation speed and vapor permeation speed of a container below a specific value. CONSTITUTION:When a supply liquid cassette 11 is used, a cap 12 is removed from a mouth 11a and a nozzle 13 is inserted to supply supply liquid 16 automatically. The wall of this cassette 11 uses a magnetic which has a <=10cc/m<2>.24 hr.atm oxygen permeation speed and a <=50g/m<2>.24hr (40 deg.C and 90% RH). This container eliminates the change with the lapse of time of the color photographic processing agent due to air oxidation. Further, a processing material (supply liquid) with desired composition is held stably, so liquid adjustment at the time of the addition of the supply liquid is not necessary and the operation efficiency is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a container for a processing agent used in processing photographic materials.

(Prior Art) Generally, photographic processing agents are supplied in the form of powder or concentrated liquid, and when used, they are prepared into a working liquid by dissolving or diluting them in a certain amount of water. In consideration of stability, these photographic processing agents are divided into kits containing one or more parts, and these are dissolved in a certain amount of water before use.

It is diluted and mixed as needed.

Recently, in developing processing apparatuses for photosensitive materials, the above-mentioned kit parts are prepared in a replenishment tank by circulation using a pump or by manual stirring, and are automatically supplied by a replenishment pump. However, there are still drawbacks such as the need for liquid preparation work and poor work efficiency due to the large number of types of parts.

Furthermore, the method of replenishing each part agent and water separately in fixed quantities, which has already been put into practice, as described above, has problems with replenishment accuracy and also has the disadvantage of requiring a large number of pumps due to the large number of parts agents. there were.

Also, JP-A-58-184145, JP-A-61-32
No. 848 and Japanese Unexamined Patent Publication No. 61-38947 disclose a method in which the packaging material for the processing agent is modified, but it still requires a liquid preparation operation and cannot be called a simple method.

On the other hand, in simple processing equipment such as camera processors used for microfilm processing, replenisher fluids packaged in polyethylene containers are frequently used. However, these processing liquid containers are generally not suitable for color processing liquids in terms of stability over time. This is because, especially when this container is used for a color developer, air oxidation of the developing agent is large and it cannot be put to practical use.

In other words, color developers generally contain aromatic primary amine developing agents that couple with couplers to form dyes, but this compound is susceptible to oxidation by carbon atoms in the air or metal ions in the developer. Oxidizes over time and affects photographic properties, for example when kept in a container for at least 2-4 weeks.

Color developing solutions cause clogging of the supply port of the container to the processing equipment due to coloring of the solution and generation of tar, or oxidative deterioration of the color developing agent affects photographic performance.

On the other hand, there is a method of increasing the storage stability of color processing solutions using antioxidants.For example, it is well known that sulfites are used as antioxidants in color developing agents, but sulfites are used in the coupling reaction between the developing agents and couplers. significantly inhibits Therefore, the amount used is limited, and it cannot be used in large amounts as in the case of black and white developer.

Further, hydroxylamines can be used as antioxidants together with sulfites, but the presence of heavy metal ions tends to accelerate the decomposition of hydroxylamines and generate ammonia. Therefore, even when hydroxylamine is used, the stability of color developers is often insufficient.

Furthermore, a method using an alkanolamine described in JP-A-54-3532, U.S. Pat. No. 3,615,50
Method using hydroxyacetone described in No. 3, JP-A-5
Many methods have been proposed, such as the method using an aromatic polyhydroxy compound described in No. 6-32140, but all of them are insufficient in terms of preventing air oxidation of the replenisher, and no practically satisfactory results have been obtained. It has not been done.

On the other hand, many compounds are known as metal ion masking agents (chelating agents) used in developing solutions, but even when used in replenishers, their stability against air oxidation is insufficient, and results that are not satisfactory for practical use are lacking. has not been obtained.

(Problems to be Solved by the Invention) An object of the present invention is to provide a container for a color photographic processing agent that prevents the processing agent from deteriorating over time due to oxidation.

Another object of the present invention is to provide a container for a color photographic processing agent which eliminates the need for liquid preparation when adding a replenisher and can significantly improve work efficiency.

(Means for Solving the Problems) The present inventors prepared the above-mentioned conventional color photographic processing agent,
In particular, as a result of intensive research to solve the problems of replenisher preparation, work efficiency, and replenisher stability, we found that the oxygen permeation rate and water vapor permeation rate of the container were set below a certain value. The present invention was completed based on this finding.

That is, in the present invention, the oxygen permeation rate is 10 cc/ln2,
24 hrs, aLs or less, and a water vapor permeation rate of 50 g/g/g, 24 hrs, (40°C, 90% RH) or less A container for a processing agent (hereinafter simply referred to as a processing agent) is provided.

If we focus only on preventing oxidation of the processing agent, this problem can generally be solved by appropriately selecting the thickness of the container.

However, this method cannot be said to be sufficient to solve the problems associated with forming the container or evaporating and concentrating the processing agent.

For example, when polyethylene is used as a container material for a kit for a photographic processing agent that can be used without preparing the solution, it is necessary to sufficiently prevent the processing agent from oxidation and to make it practical. At least 5.0 layers are required to maintain the strength necessary to hold a sufficient amount of processing agent.
A thickness greater than that is required. However, when manufacturing containers, such an increase in thickness imposes restrictions on arbitrary molding (particularly molding into the cassette shape described in the present invention).
In addition, it is difficult to achieve the above objective because it results in a large waste in terms of cost.

Furthermore, when a material such as nylon is used, although the oxygen permeation rate is low, evaporation concentration occurs due to an increase in temperature during storage of the processing agent, and oxidative deterioration significantly increases due to an increase in humidity. It will be done. Therefore, if stored for a long period of time, the processing agent may deteriorate and become unusable.

On the other hand, in the present invention, in order to improve the stability of the processing agent, the material of the container has an oxygen permeation rate of 1 O
In addition to being below cc/m2, 24hrs, atm, the water vapor transmission rate is 50g/m'', 24hrs (
In the present invention, the desired effect cannot be achieved even if either the oxygen permeation rate or the water vapor permeation rate exceeds the above conditions.

The materials having the above oxygen permeation rate and water vapor permeation rate used in the container of the present invention include polypropylene with a thickness of 2.5 mm or more (average thickness (hereinafter the same)), and a thickness of 2.5 mm.
High-density polyethylene with a thickness of O, 1 m or more, polyvinylidene chloride with a thickness of 0.1 m or more, polyethylene terephthalate with a thickness of 0.1 m or more, polyvinyl chloride with a thickness of 0.21 m or more, nylon with a thickness of 0.15 m or more , thickness 0.02m-
The above polyvinyl alcohol/polyethylene copolymers,
Vinylidene chloride/vinyl chloride copolymer with a thickness of 0.05 s or more, acrylonitrile/butadiene copolymer with a thickness of 0.3 or more layers, hydrochloric acid rubber, glass, metals, etc. with a thickness of 0.1 mm or more. It will be done.

In the present invention, two or more of these materials may be used in combination, or may be used in a multilayer structure.

The present invention is characterized in that plastics can also be used, and among these materials, polyvinyl chloride and polyethylene terephthalate are more preferable from the viewpoints of being difficult to crack or deform, ease of R& molding, cost, etc. A container made by laminating and molding the above materials can also be used. In particular, polyethylene with a thickness of 1 mm or more coated with vinylidene chloride with a thickness of 0.01-1 or more, 0.005
Polyethylene coated with polyvinyl alcohol/polyethylene copolymer, thickness 0.02 mm or more; polyethylene coated with polyvinyl alcohol/polyethylene copolymer, thickness 0.15 m5 or more. Polyethylene coated with the above nylon and having a thickness of lam or less is good.

The shape of the container of the present invention is not particularly limited, and may be a bottle type with a sufficiently airtight cap, a flexible plastic bag with a sufficiently sealed opening, or a foldable plastic container. The form is adopted. As for the airtightness of the cap, it is preferable to use a method such as attaching a sheet of an inert elastic material to the inside of the cap and press-fitting it. As the sheet, the above-mentioned materials, raw rubber, neorene rubber, etc. can be used. As the cap material, the above-mentioned materials, ebonite, etc. can be used.

Furthermore, it is more effective to heat-seal a polyethylene film laminated with aluminum foil or the like to the mouth of the bottle and place the aforementioned cap on top of it.

In the present invention, the processing agent may include a photographic processing solution or its replenisher. The processing agent may be any color processing solution and is not particularly limited, but is preferably a color developer, a bleach-fix solution, a fixer, a first developer for various color reversal treatments, a reversal solution, or a conditioner solution, and particularly preferred. is a color developer.

Further, the processing agent referred to in the present invention is preferably a so-called replenisher, but it may be divided into two or more parts so that it automatically becomes a replenisher before finally entering the processing tank. In the present invention, the term "solution preparation" refers to mixing and/or stirring the processing agent and water or the processing agent divided into two or more parts by hand.

When storing the treatment agent (replenisher) in the container of the present invention, the water used for preparing the treatment agent must be free from the effects of heavy metals, calcium,
Deionized water or distilled water is preferred to prevent precipitation caused by magnesium. Deionized water is wood that has been passed through an ion exchange resin to remove metals.

The container of the present invention can preferably be used as a cassette for an automatic processor.

A cassette is a type of container that can be used by directly installing a processing agent container into the processing equipment. Therefore, in this case, the processing equipment does not have a replenishment tank or a liquid preparation tank like in the past. Good too.

Air oxidation of the processing agent generally becomes a problem when it is stored before use, but even during processing, when the processing agent is kept in the container for a long time, prevention of air oxidation is necessary.

Therefore, in the case of such a container, an oxygen absorber is used in the air intake port of the container to facilitate the outflow of the processing agent, or a flexible material or material is placed inside the container to prevent oxidation.
It is preferable to use floating balls, floats, etc.

Oxygen absorbers include, for example, reducing iron powder, ascorbic acid aqueous solution, sodium sulfite aqueous solution, alkali pyrogallol solution, sodium dithionite aqueous solution, chromium chloride (
n) There are aqueous solutions, ammonia aqueous solutions, etc. As for a specific method of using the oxygen absorbent, if it is an aqueous solution, it may be used as a filter by impregnating it with water, such as in fibers with good water absorption properties. Further, as the float, there are methods such as fixing a float made of polypropylene or the like or a flat plate of polyvinyl chloride or the like inside the container so that it acts as a float when the container is set.

In addition, one method for preventing oxidation of the processing agent during processing is to collect the processing waste liquid into the processing agent discharge space of the container to prevent oxidation.

Other oxidation prevention measures include removing the air from the container and filling it with an inert gas such as nitrogen, but these are particularly effective for storing the processing agent before use.

Next, the container for the final IJI will be explained according to the illustrated embodiment using a replenisher cassette as an example, but the present invention is not limited thereto.

In FIG. 1, 11 is a replenisher cassette of the present invention, 1
2 is the cap, 13 is the nozzle, 14 is the air intake 0.15
1 is a main body of a processing machine for photographic light-sensitive materials, and 16 is a replenisher.

When using the replenisher cassette, open the opening 1 as shown in the figure.
The cap 12 is removed from 1a, and the nozzle 13 is inserted to automatically replenish the replenisher 16.

At this time, it is preferable that the air intake port 14 of the replenisher cassette 11 is such that air enters through the oxygen absorbent 14a as shown in the figure. There may also be a separate opening for air intake.

In FIG. 2, the replenisher cassette is turned upside down to supply replenisher. The replenisher cassette 21 with the cap removed is turned upside down, and the receiver is set on the tray 22. This receiver has a protrusion 23 on the plate, and the opening 21 of the cassette 21
When a is set on the tray 22, the protrusion 23 pushes up the spout 24 and opens it, allowing the liquid to flow out. The outflow replenisher 25 passes through the pipe 26 and is automatically replenished into the processing machine main body 27.

3(a) and 3(b) show a closed type cassette with an air intake port 36, and FIG. 3(a) shows a cassette with an oxygen absorbent 36a provided in the air intake port 36. FIG. 3(b) shows a cassette 31 in which a flexible wall 37 with low oxygen permeability is provided inside the cassette 31. In the figure, 32 is a tray for the opening 31a of the cassette, 33 is a protrusion, and 34 is a stopper.The mechanism for the replenisher 35 to flow out is the same as in Figure 2.0 In the figure, 38 is a replenisher outflow pipe. , 39 is a processing machine main body.

Next, FIGS. 4(a) and 4(b) show a floating ball 47 instead of the flexible wall 37 in FIG. It uses floating material such as Ubuta 48. In the figure, 41 is a cassette, 42 is a plate for the mouth 41a of the cassette, 43 is a protrusion, and 44 is a stopper, and the rest of these parts are the same as in FIG. 2.

In FIG. 4, by opening the air intake port 49 and supplying liquid, the floating balls 47 or floats 48 become free, and the replenishing liquid 45 flows out from the pipe 46 into the main body of the processing machine.

Next, FIGS. 5 to 7 show the case where the cassette of the present invention is also used as a treatment waste liquid collection container.

Figure 5(a) shows the replenisher cassette before collecting waste liquid, and Figure 5(b) shows the replenisher cassette while collecting waste liquid. 2nd ~
This is the same as in Figure 4. In the figure, 51 is the cassette of the present invention, 52 is a flexible film bag (polyethylene, vopropylene, etc.), 53 is a cap, 54 is a replenisher, 55 is a waste liquid nozzle, 56 is a waste liquid, and 57 is an opening of the cassette 51. 58 is a plate for the processing machine body,
59 is a protrusion. In this embodiment, a flexible film bag 52 serves as a partition between the replenisher (processing liquid) chamber and the drain chamber.

Figures 6 (a) and (b), like Figures 5 (a) and (b), show the replenisher cassette before waste liquid collection, and the replenisher cassette while the replenisher is flowing out and waste liquid is being collected, respectively. It is.

In the figure, 61 is a cassette of the present invention, and 62 is a bag made of a flexible material, which is folded.

63 is a cap, 64 is a replenisher, and 65 is a waste liquid.

66 is a waste liquid nozzle, and 67 is a replenishment liquid nozzle.

68 is a partition wall between the replenisher and waste fluid. In the case of the cassette shown in this figure, the cap 63 of the cassette 61 is removed, and the replenisher nozzle 67 and the waste liquid nozzle 66 are attached. The waste liquid is sent into the bag 62 from the bag 62.

Figure 7 shows three types of processing liquid containers (A) with structures similar to those in Figure 6.
, (B), and (C) are put together in one cardboard box (D), the perforation (F) of the cap part is pushed open, the cap is removed, and the nozzle is inserted. Figure 7(a)
7(b) is a side view before use, and FIG. 7(c) is a side view during use. In the figure, 71 is the cassette of the present invention, 72 is a flexible bag, 73.74 is a cap, 75 is a processing liquid, 76 is a waste liquid, 77 is a waste liquid nozzle, 7
8 is a replenisher nozzle. Note that 79 is a sealing rubber cap attached to the lower 1a. The method of using this processing liquid container is the same as in Example 6.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereby.

Example 1 The cassette type containers shown in FIG. 2 were made using the materials shown in Table 1. The following processing solution (9, color developer replenisher) was placed in these containers, and after the containers were kept at room temperature for 10 months, the amount of color developing agent (1) was measured. The results are shown in Table 1.

Each container volume is approximately 4 fL.

Treatment liquid〉 Water 800m
Jl Diethylenetriaminepentaacetic acid 3.0g Sodium sulfite 4.4g Potassium carbonate
32.0g potassium bromide
0.7g hydroxylamine sulfate
2.6g 4-(N-ethyl-N,β-hydroxyethylamino)-2-methylaniline sulfate, add 0g water
1.0nP)1
10.20 As is clear from Table 1, polyethylene (container 1) or polypropylene (container 2) having a practical thickness has a large oxidation of the color developing agent.

In addition, the oxygen permeation rate is 1oTrl/rrf・24hrs
・Even if a material exceeding aLm is used (container 3.
4.5) Oxidation prevention of the color developing agent is insufficient.

On the other hand, it can be seen that according to the containers 6 to 11 of the present invention, a stable processing liquid can be supplied within 1 minute even if the thickness is large.

Example 2 A container was made in the same manner as in Example 1, and the following processing solution (9, color developer replenisher) was added and stored at 40"C for 3 months, followed by color development a.
The remaining amount of 'ti was measured. The results are shown in Table 2.

From Table 2, it is clear from IJJ that when materials related to undeveloped 11 are used, there is less deterioration of the color developing agent and good 11f.
It is. Regarding nylon, it can be seen that when stored at 40°C, the water vapor transmission rate increases, so the e17M of the treatment liquid is large.

(Treatment liquid prescription) Water 800m
Diethylenetriaminepentaacetic acid 0.9g 1-Hydroxyethylidene-1,1'-diphosphonic acid 1.0g Benzyl alcohol 18m Diethylene glycol
10m sodium sulfite
2.5g Hydroxylamine sulfate 3.5g Potassium carbonate 30g N-ethyl-N-(βmethanesulfonamidoethyl) 3-methyl 4-aminoaniline sulfate 7.5g Optical brightener (
4) Add 1.5 g of water and adjust the pH to 10.65 with potassium hydroxide.Example 3 Prepare a container in the same manner as in Example 1, and add a color negative film processing agent manufactured by Fuji Photo Film Co., Ltd. Kit (Product name: rC
N-1-6N1-RJ) was prepared as specified, and each prepared container was filled with the resulting treatment solution. It was packed in a cardboard box in the same manner as the unused kit rCN-16N1-RJ and kept at room temperature for 10 months.

First, an automatic developing machine that can use the cassette method described in the present invention and has a liquid preparation tank is prepared, and the processing agent after the L period of time and the unused rCN-16N1-RJ kit are packed. The time taken to reach a processable island was measured and compared.

Next, the following processing solution (mother liquor) is placed in the automatic developing machine, and after the aging process, two types of processing agents (replenisher solution) whose containers are made of polyethylene and polyvinyl chloride are shown in Table 3. using i! Ibc treatment (hereinafter referred to as running treatment) was performed. Running was continued until the processing solution reached an almost equilibrium state, and the photographic performance of each was compared after the running equilibrium. The above results are shown in Table 4. However, the running conditions are as shown in Table 3.

Replenishment amount of photosensitive material 35IIl1 width/1m length -1-
In the following steps, the first stage of stabilization was performed using a three-stage countercurrent method in which the liquid flowed in the order of ■→■→■.

The composition of the treatment liquid used in each step is as follows.

2 (Color developer) (Mother liquor) 1 Potassium acid 30g Sodium bicarbonate 2.5g Potassium sulfite
5g sodium bromide
1.3g potassium iodide
2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Diethylenetriaminepentarate Thorium acetate 2.5 g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 5.0 g Add wood 1
Assume that pH=1O,06.

(Auxiliary liquid) (A) Liquid kept in the aforementioned polyethylene container for 10 months.

(B) In the aforementioned polyliquefied vinyl container Liquid kept for 10 months.

(??? White liquor) <Mother liquor><Replenisher> Ethylenediaminetetraacetic acid ferric ammonium salt 100g 110g Ethylenediaminetetraacetic acid disodium salt Log l1g Aqueous ammonia 7mi 5rr9゜Ammonium stoneate 10.0g 12.0g Ammonium bromide 150g Add 170g water
11 1 sentence pH 6,05,8 (Fixer) (Mother liquor) <Replenisher> Ethylenediaminetetraacetic acid di-sodium trilum Ii!1.og 1.2g Sodium sulfite 4.0g 5.0g Sodium bisulfite 4.6g 5.8g Thio Unum sulfate aqueous solution (70%) 175 ml 200
m Add standing tree l intersection 1 sentence p
H6,66,6 (Stable solution) <Mother solution> (Replenisher solution) Formalin (: 17$ w/v) 0.5mM O,7
ml Polyoxyethylene-p-monononylphenyl ether (uniform degree of polymerization 10) 0.3g Add 0.5g of wood to make one sentence.

Color negative film for running processing> A color negative film HR-Zoo manufactured by Tomishichi Photo Film Co., Ltd. that was imagewise exposed was used.

Color negative film for evaluating photographic characteristics and evaluation items> Color negative film HR-100 with color temperature 4800
Exposures of lOlooC were changed using a standard wedge at 10°C. After the start of running and equilibration, the above color negative film for evaluation was processed and the photographic properties obtained by running with each replenishment M (A) and (B) were evaluated as minimum density, sensitivity, and yellow.

The uniform gradation of the coloring layers of magenta and cyan was investigated. However, for the upward gradation, the coloring point () corresponds to the logarithmic intersection of the point (a) that gives a density of 0.2 plus the minimum density and the exposure amount (Ea) corresponding to that point, minus 1.5 from ogEa. b) refers to the slope of the straight line connecting (hereinafter G-1, 5
) Also, the sensitivity is the value of flogEa above. The minimum density is the absolute value of sensitometry 1 of HR-100 sensitive material.

The results of 1- below are shown in Table 4.

As is clear from Table 4, first, the replenisher is prepared from the processing agent using the conventional kit, and it takes about 100 minutes to reach the usable state.
It can be seen that while it used to take 3 minutes, the process can be completed within 1 minute with the cassette type container of IJ1, which significantly shortens the time. Furthermore, since this is the case only for color development processing solutions, if a similar comparison is made for bleaching, fixing and stabilizing solutions, the overall time reduction will be about 20 to 30 minutes. Furthermore, photographic properties change over time, especially in this developer containing amines, each coloring layer has a G
-1,5 becomes large. Moreover, the minimum concentration also increases. In contrast, according to the present invention, it can be seen that photographic properties are not affected by aging.

Example 4 A treatment liquid was prepared in the same manner as in Example 1, and containers made of the materials shown in Table 5 were created. In addition, containers made of each material have the characteristics shown in Table 5, that is, the shape (A) shown in Figure 3 above, the shape (B) shown in Figure 4, or the shape shown in Figure 5a. It has a shape (C). The oxygen permeation rate and water vapor permeation rate of the polyethylene, polyvinyl chloride, or polyethylene terephthalate film used here are as follows.

Oxygen permeation rate Water vapor permeation rate cc/g/24hrs-aLs g/m' -24h
rs (40°C90$R11) Polyethylene (Ismaro thickness) 250
0.3 Polypropylene (1mi thickness) 130 0.2
Polyvinyl chloride (0,5ms thickness > 4
1.0 Polyethylene terephthalate (0,5@II thickness > 2 2.
0 Fill these containers with the processing solution prepared above.

After storage for 10 months, the residual rate of the main drug in each treatment solution was measured.

Furthermore, after draining the treatment solution at a rate of 200 mjL/day and holding it for 2 weeks, the residual rate of the main drug (immediately after the preparation solution) was similarly measured and calculated for the remaining solution in the container. Note that the above shape (C
The treated waste liquid collected in ) is stored in the container N01 of Example 3.
200 m of treated waste liquid obtained from the running treatment in step 4.
It was made to flow in from the waste liquid nozzle at a rate of jL/day. Also, for comparison, the air intake port is left open without any modification.
) containers were also prepared.

The results are shown in Table 5.

As is clear from Table 5, after storage for 10 months, polyethylene and polypropylene containers 1 to 8 had a concentration of 10 to 15%.
It can be seen that the color developing agent in the image has deteriorated due to oxidation. In contrast, according to the present invention, the deterioration is only 0 to 2%, and at this point, the shapes (A), (B), (C), and (D)
It can be seen that there is almost no difference in the degree of oxidative deterioration between the two.

After aging for another two weeks, the open type (D) deteriorates in any container, but undeveloped IJ
According to +, contact with oxygen in the air is mostly limited to the oil surface, which indicates that the degree of contact with oxygen in the air is smaller than in the comparative example. In addition, regarding forms (A), (B), and (C), the comparative example still progresses in deterioration of the drug by 1.
It can be seen that according to the present invention, there is almost no deterioration.

Example 5 Containers made of the materials shown in Table 6 were prepared in the same manner as in Example 1, each filled with the treatment liquid shown below, and stored at room temperature for 10 months. (shown in alphabetical and lowercase letters). The results are shown in Table 6.

<Processing liquid> (A) Fixer ethylenediaminetetraacetic acid monosodium salt 1.2 g (a) Sodium sulfite 5.0 g Sodium bisulfite
5.8g (b) Ammonium thiowtate aqueous solution (70ml Add 200m water and see P8
6.6 (B) Bleach-fix solution (b) Thio II & ammonium aqueous solution (70 liters 300 mJL) (a) Sodium sulfite 36 g Ethylenecyaminetetraacetic acid (II) ammonium 110g Ethylenediaminetetraacetic acid 10g Add water
IJIpi-i
a, 30 (C) Reversal color film, first developer water 700 m Nitrilo-N, N, N- Pentasodium trimethylenephosphonate 2.0 g Sodium fEiv 30 g Potassium hydroquinone monosulfonate 20 g Potassium carbonate 33 g (a ) l-phenyl-
4-Methyl-4-hydroxymethyl-3-pyrazolidone 2.0g Potassium bromide 1.4g Potassium thiocyanate
Add 1.2g water and IJI PH
=9.6 As is clear from Table 6, according to the present invention, the deterioration of sodium sulfite in the bleach-fix solution, which tends to cause deterioration, can be extremely effectively suppressed. It can be seen that the deterioration of the auxiliary developing agent is at a level that does not pose any problem according to the present invention.

(Effects of the Invention) The container of Endan II can prevent color photographic processing agents from deteriorating over time due to air oxidation. Furthermore, since the processing agent (replenisher) having a desired composition can be stably held, there is no need to prepare the solution when adding the replenisher.

It can significantly improve work efficiency.

In particular, the container of the present invention not only prevents oxidation and stabilizes the composition of the color developing agent in the processing agent during storage, but also prevents deterioration over time during processing and during long retention periods in the processing agent container. Since it can prevent this, it can be suitably used as a replenisher cassette. Further, according to the container of the present invention, there is no need to provide a separate tank space for waste liquid, and the treated waste liquid can be collected into the treatment agent discharge space of the container, and at the same time, the treatment agent can be prevented from oxidation, which is an excellent effect. .

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views showing an embodiment of the container of the present invention, and FIGS. 3(a) and 3(b) are cross-sectional views of an embodiment of the container of the present invention with a closed mouth. Figures 4(a) and (b) are cross-sectional views of examples of floating ball type or floating type containers of the present invention, Figures 5(a) and (b), and @Figure 6(a). , (b
) is a sectional view illustrating the usage state of an embodiment in which the container of the present invention is also used for waste liquid collection, and FIG. 7(a) is a perspective view showing a state in which three containers of the present invention are assembled into a set. , FIGS. 7(b) and 7(c) are side views illustrating the state of use. Explanation of symbols 11... Replenisher cassette 12... Cap 13... Nozzle 14... Air intake port 14 a --- Oxygen absorber 15... Processing machine main body 16... Replenisher patent application Person Fuji Photo Film Co., Ltd. Agent Patent Attorney Ii 1) Satoshi)-11 Figure 1
Figure 2 (a) (b) Figure 4 (a) (b) Figure 5 (a) (b) Figure 6
Figure (a) (b) 7th
Diagrams (a) (b) (e) - "-wa°dne city II mo ri (spontaneous) 19861
October 31 [1 Mr. Kuro III IJll, Commissioner of the Patent Office, Mr.
1°C Indication Patent Application No. 159540 filed in 1985 2 Name of the invention Container for processing agent for silver halide color photographic light-sensitive materials 3 Person making the correction/Relationship with the case Patent applicant address Minamiashigara City, Kanagawa Prefecture Nakanuma 210 address name (52
0) Fuji Photo Film Co., Ltd. Representative: Sho Ohnishi 4, Agent address: 7th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105 Telephone: Tokyo (03) 591-7387 Name (7643) Patent attorney Mei 1) Toshi 35, with II of amendment order Voluntary motion 6, subject of amendment "Claims" and "
Column 7 of ``Detailed Description of the Invention'', Contents of Amendment (1) 1 Hosokichi's ``Scope of Claims'' column will be amended as shown in the attached sheet. (2) r l Occ/rn on page 7, line 11 of the city
', Correct J to r10cc/rre・J. (3) r50g/rrr', J on line 13 of the same page in the same book
Correct it to r50g/rn'. (4) "Ammonia" on page 13, line 12 of the same book will be corrected to "copper (I) ammonia." (5) "Otemo" on page 19, line 18 of the same book has been corrected to "Oteha". (6) Container No., 1 in Table 4, page 32 of the same book (comparative example)
The time required for setting as a replenisher is 13 seconds.
Correct to 1B. (7) "(■) Ammonium" in the second line of page 38 of the same book will be corrected to "ferric ammonium." are corrected to "68" and "70" respectively. (E) “Claims (+) Oxygen permeation rate is 10 cc/rr? -24hr
S-ATM or higher, and a water vapor transmission rate of 50g
/m"・24 hrs (40°C, 90% RH) or less. A container for a processing agent for a silver halide color photographic light-sensitive material, characterized in that the container wall is made of a material having a temperature of 24 hrs (40° C., 90% RH) or less. (2) A processing agent to be filled. (3) The container according to claim 1, wherein the processing agent is a processing agent for color development. Container. (4) The container according to claim 1, wherein the processing agent is a fixing treatment agent. (5) The container according to claim 1, wherein the processing agent is a bleach-fixing treatment agent. (6) The container according to claim 1, wherein the processing agent is a first developing processing agent for a 1-inversion color photograph. (7) The container according to claim 1, which is a cassette for an automatic developing machine.
'Jl listed container. (8) The container according to claim 1, wherein the processing waste liquid can be collected and stored in the space of the processing agent discharged from the container. (9) The container according to claim 7, wherein the container is configured to prevent oxygen in the air sucked into the container from coming into contact with the processing agent inside the container when the processing agent inside is sent out. (lO) The container according to claim 9, wherein an oxygen absorbent is provided in the air intake part of the container to prevent contact between oxygen in the air and the processing agent in the container. (11) The container according to claim 9, characterized in that a floating material is provided on the top surface of the processing agent in the container to prevent contact between oxygen in the air and the processing agent inside the container.

Claims (11)

[Claims] (1) Oxygen permeation rate is 10cc/m^2, 24hrs.
ATM or less, and the water vapor transmission rate is 50 g/m
^2. A container for a processing agent for a silver halide color photographic light-sensitive material, characterized in that the container wall is made of a material having a temperature of 24 hrs (40° C., 90% RH) or less. (2) The container according to claim 1, wherein the processing agent to be filled has a composition that can be used for color photographic processing without being prepared. (3) The container according to claim 1, wherein the processing agent is a color development processing agent. (4) The container according to claim 1, wherein the processing agent is a fixing processing agent. (5) The container according to claim 1, wherein the processing agent is a bleach-fixing processing agent. (6) The container according to claim 1, wherein the processing agent is a first developing processing agent for reversal color photography. (7) Claim 1, which is a cassette for an automatic processor
Containers listed in section. (8) The container according to claim 1, wherein the processing waste liquid can be collected and stored in the space of the processing agent discharged from the container. (9) The container according to claim 7, wherein the container is configured to prevent oxygen in the air sucked into the container from coming into contact with the processing agent inside the container when the processing agent inside is sent out. (10) The container according to claim 9, wherein an oxygen absorbent is provided in the air intake portion of the container to prevent contact between oxygen in the air and the processing agent in the container. (11) The container according to claim 9, characterized in that a floating material is provided on the upper surface of the processing agent inside the container to prevent contact between oxygen in the air and the processing agent inside the container.