JPH061357B2 - Fixer storage method with improved storage stability - Google Patents

Description

The present invention relates to a method for storing a fixing solution for a silver halide photographic light-sensitive material, and more particularly to a fixing method used in a developing process for obtaining a high-contrast image useful in the field of photoengraving. The present invention relates to a method for storing a liquid.

[Conventional technology]

In the field of photoengraving, a fixer for rapid access (black-and-white fixer) has been widely used in recent years.

The fixer for rapid access contains thiosulfate as a fixer and sulfite as a preservative so that it can be fixed quickly, and also neutralizes a high-pH developer and prevents the development reaction. It is necessary to stop and therefore the pH
It contains an organic salt or an inorganic salt that makes the acid acidic.

It is known that the fixer is oxidized during long-term storage, even though it contains a relatively high concentration of sulfite.

The fixing solution is usually left in a warehouse or outdoors under adverse conditions compared to silver halide photographic light-sensitive materials.
It is desired to be stable even under such adverse conditions.

The fixer for rapid access is not only a type that can be used as it is, but also a concentrated type that is used after being concentrated as much as possible for convenience of transportation and cost. In this case, the concentration decreases as the amount of ammonium thiosulfate or sulfite increases, so it is necessary to prepare the sulfite concentration as low as possible. With such a method, the preservability is insufficient, and another good method is required.

Focusing on the oxygen permeability of the packaging material, it is conceivable that the packaging material may be sealed with a treatment liquid storage packaging material having low oxygen permeability or air permeability.

However, we have found that pursuing oxygen permeability cannot be regarded as a preferable method for storing a photographic fixing solution. That is, when these synthetic organic polymer materials are used as storage packaging materials and the fixer is stored under high temperature and high humidity, the storage stability is never improved.
It is considered that this is because oxygen easily permeates under high humidity, and the storage stability is deteriorated due to factors such as a fixing agent and other compounds. That is why a packaging material suitable for the fixer is desired.

[Object of the Invention]

An object of the present invention is to provide a method for stably storing a fixing solution containing a fixing agent, a preservative, and an organic salt and / or an inorganic salt having a pH of 6 or less.

[Structure of Invention]

The object of the present invention is (a) fixing agent, (b) 0.6 mol of sulfite /
In the following method, and (c) a method for preserving a fixing solution in which a fixing solution containing at least an organic salt and / or an inorganic salt for adjusting the pH of the fixing solution to 6 or less is stored in a container made of an organic polymer packaging material, The packaging material consists of at least 3 layers,
The organic polymer in the layer in contact with the fixer is represented by the following general formula [a], and the organic polymer in the inner layer is represented by the following general formula [b] or [c]. Achieved by the preservation method. Furthermore, when the organic polymer of the outermost layer among the above-mentioned at least three layers is represented by the following general formula [a], the object of the present invention is achieved to a higher degree.

General formula [a] In the formula, X and Y each represent a hydrogen atom, a halogen atom or an alkyl group, and n represents an integer of 100 or more.

General formula [b] In the formula, p and q each represent an integer of 1 to 12, and m is 100.
Represents the above integers.

General formula [c] In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more.

In the general formula [a], the alkyl group represented by X and Y may be linear or branched, and preferably has 1 to 5 carbon atoms,
It may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, and n is preferably 10,000 or less.

In the general formula [b], m is preferably 10000 or less,
In general formula [c], l is preferably 10000 or less.

The following can be mentioned as specific examples of the compound represented by the general formula [a].

The following can be mentioned as specific examples of the compound represented by the general formula [b].

The following can be mentioned as specific examples of the compound represented by the general formula [c].

The organic polymer represented by the above general formula [a], [b] or [c] in the present invention can be easily synthesized from a monomer by homopolymerization, copolymerization or polycondensation. The degree of polymerization may be arbitrary, but it is preferably 100 or more and 100,000 or less. In addition,
Although the terminal groups are not shown in these general formulas, those which are usually generated in such a polymerization reaction are included.

The thickness of each of the above single layers constituting the organic polymer packaging material of the present invention is preferably in the range of 10 to 200 μm, and the total laminated film thickness is more preferably in the range of 30 to 600 μm. More preferably, each single layer has a thickness of 20-100 μm,
The total laminated film thickness is in the range of 60 to 300 μm.

The thickness of each of the above single films constituting the organic polymer packaging material of the present invention is 10 μm or less because the storage stability of the fixer is poor as a container for enclosing the fixer in the range of 10 to 20 μm.
It is preferable that the thickness is m or more, and if the thickness is 200 μm or more, the flexibility of the packaging material is poor and it does not deform according to the amount of the fixing solution inside, so that air easily accumulates in the dead space under the lid. Therefore, the storability of the fixer becomes poor.

The laminated organic polymer packaging material of the present invention has the general formula
The compound represented by [a] is preferably 10 to 200 μm on the thin film, preferably 10 to 200 μm of the general formula [b] or [c].
To obtain a thin film of the compound represented by (1) as it is or by laminating it with overheat contact or an adhesive (so-called lamination), or by further laminating or laminating a thin film of the compound of the general formula [a] on it. You can

The container made of the packaging material of the present invention may be made of a single layer of the packaging material, and is further covered with the packaging material in a single layer or a double layer, that is, a container made of a double layer or a triple layer of the packaging material. However, the effect of the present invention can be further enhanced according to the double or triple mode.

In the packaging material of the present invention, the material forming the outermost layer can be arbitrarily selected, but as described above, the organic polymer of the layer is preferably selected from the compounds represented by the general formula [a]. That is.

In a preferred embodiment of the present invention, the packaging material has a layer structure of 3 layers or 4 layers, and the organic polymer of the innermost layer and the outermost layer of these layers is represented by the general formula [a]. And an organic polymer of at least one layer other than these two layers is represented by the general formula [b] or [c].

The fixing agent contained in the fixing solution to which the method of the present invention is applied is
It is a thiosulfate salt that is usually used as a fixing agent such as ammonium thiosulfate, sodium thiosulfate, and potassium thiosulfate. There is no limitation on the concentration of the fixing agent, and at least the present invention is effective in the range of 0.1 to 5 mol / generally used.

Examples of the sulfite salt contained in the fixing solution to which the method of the present invention is applied include sodium sulfite, potassium sulfite, ammonium sulfite and the like which are commonly used in fixing solutions. The effect of the present invention is remarkable when the concentration of the sulfite in the fixing solution is 0.6 mol / or less in a concentrated storage formulation which is usually called a part A solution in a commercial product. The concentration is preferably 0.3 mol / or more from the viewpoint of storage stability of the liquid.

The organic salts and inorganic salts used for adjusting the pH of the fixer to which the method of the present invention is applied to 6 or less are known to have a pH value higher than that of known fixers.
Those used as buffers (for example, acetic acid, boric acid, dibasic acid and salts thereof) and pH adjusters (for example, sulfuric acid) are included. The total amount of acetic acid, boric acid and citrate as the pH buffer is in the range of 10 to 50 g /, preferably 15 to 30 g /. The pH of the fixing solution is preferably 3 or more, more preferably 4 or more, because the storage stability of the solution will be deteriorated if it is lowered too much.

As the dibasic acid, tartaric acid or a derivative thereof, citric acid or a salt thereof can be used alone or in combination of two or more kinds. These compounds per fixer
The present invention is effective at least for a fixing solution containing 0.005 mol or more, especially 0.01 mol / -0.03 mol /.

Specific examples thereof include tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, and manmonium tartrate.

Examples of citric acid or salts thereof include citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixing solution to which the present invention is applied may further contain a hardening agent such as a water-soluble aluminum salt (eg, aluminum chloride, aluminum sulfate, potassium alum, etc.). In order to stabilize the aqueous aluminum salt, acetic acid or the above dibasic acid is preferably used as the organic salt and the inorganic salt in the present invention.

〔Example〕

Preparation of Test Film A silver halide photographic light-sensitive material was prepared according to Comparative Example 3 of JP-B-59-50976.

Preparation of Developer A composition A and composition B were prepared according to the following formulation.

Developer formulation (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-phenyl- 5-Mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the used solution 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25ml Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was finished to 1 and used.

Preparation of Fixing Solution Concentrated fixing solutions A and B were prepared according to the following prescription.

Fixer formulation (concentrated fixer A) Ammonium thiosulfate (72.5% W / V aqueous solution) 250 ml Sodium sulfite 17 g Sodium acetate trihydrate 7.0 g Boric acid 7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / V aqueous solution) 14ml pH 5.0 (Concentrated fixer B) Pure water (ion exchanged water) 17ml Sulfuric acid (50% W / W aqueous solution) 5.0g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / W aqueous solution) 26.5g Fixing When the solution was used, the concentrated fixing solution A and the concentrated fixing solution B were dissolved in this order in 500 ml of water, and the solution was finished to 1 for use. The pH of this fixer was about 4.3.

Preparation of fixer storage container Layer composition and film thickness capacity as shown in Table 1 below
Ten organic polymer packaging materials were made.

10 of the above concentrated fixing solution A (parts fixing solution) is sealed in the above container and stored at high temperature and high humidity {after being left in a thermo tester at 70 ° C and relative humidity of 90% for 12 hours, then at room temperature and normal humidity for 12 hours (twenty five
C., relative humidity 60%), and the history of temperature and humidity was repeatedly stored for 2 weeks}, and then a working solution was prepared using the solution.

To measure the fixing ability, the test film (5 cm
X5 cm) was treated with the above-mentioned developing solution as a developing solution and the above-mentioned working solution as a fixing solution under the following processing conditions in an automatic developing machine, and the degree of fixing (fixing erasability) was visually evaluated and evaluated. . The case where the fixing was the best was set to “5”, and the ranks “4”, “3”, “2”, and “1” were sequentially ranked.

 The processing conditions were set as follows: development 33 ° C. 20 seconds, fixing 30 ° C. 20 seconds, water washing 25 ° C. 20 seconds, drying 50 ° C. 20 seconds.

The results are shown in Table-2.

As is clear from Table 2, the use of the fixing solution packaging material according to the present invention improves the deterioration of fixing erasability when stored under high temperature and high humidity.

In addition, as a result of observing the liquid in the storage container, No.1 to No.5
For No. 6 to No., the decomposition products did not break out at all.
In No. 8, it was observed that a yellow decomposition product was protruding.

〔The invention's effect〕

According to the present invention, in a method of storing a fixing solution in a container composed of an organic polymer packaging material, a fixing agent, 0.6 mol of sulfite, and an organic salt and / or an inorganic salt which makes the pH of the fixing solution 6 or less. The storage stability of the fixer containing at least a salt is improved.

Claims (1)

[Claims] 1. A container made of an organic polymer packaging material containing a fixing agent, a sulfite of 0.6 mol / mol or less, and at least an organic salt and / or an inorganic salt for adjusting the pH of the fixing liquid to 6 or less. In the method of storing the developer to be stored,
The packaging material is composed of at least three layers, the organic polymer in the layer in contact with the fixing solution is represented by the following general formula [a], and the organic polymer in the inner layer is represented by the following general formula [b] or [c]. A method for storing a fixing solution, which is characterized by being performed. General formula [a] [In the formula, X and Y each represent a hydrogen atom, a halogen atom or an alkyl group, and n represents an integer of 100 or more. ] General formula [b] [In the formula, p and q each represent an integer of 1 to 12, and m is 10
Represents an integer of 0 or more. ] General formula [c] [In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more. [Claim 2] The method for preserving a fixing solution according to claim 1, wherein the at least three outermost organic polymers are represented by the general formula [a].