JPH0553258A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic processing agent which obviates the splashing of powder at the time of handling the photographic processing agent, drastically decreases the amt. of the powder remaining in a waste packaging material and has excellent environmental adaptability and the image preservable property after processing. CONSTITUTION:Fixing processing is executed in the presence of the compd. expressed by formula I in the photographic processing method for developing a silver halide photographic sensitive material and fixing this material by using a fixer obtd. by incorporating water-soluble wax as a binder at >=5wt.% of the total weight of the constituting components for a photographic fixing agent, granulating or tabletting this fixing agent and dissolving the fixing agent. In the formula I: R-SX [where R denotes a univalent org. group, 1 to 12C alkyl group phenyl group or org. heterocycle. These org. groups may be substd. X denotes a hydrogen atom, alkaline metal, ammonium.].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new processing method for silver halide photographic light-sensitive materials.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a processing agent for a photographic light-sensitive material, a liquid agent or a powder agent is used. In the case of a liquid agent, it is used as it is or after mixing with water at an arbitrary ratio. or,
In the case of powder, it is used after dissolving it in water.

However, in the case of a liquid agent, although the dissolution method is simple, it contains water in advance, and therefore has a large volume and weight, which poses safety problems such as transportation cost and liquid leakage. In addition, when handling a large amount, the weight is a burden on the user. On the other hand, in the case of a powder agent, although it is significantly superior in compactness to a liquid agent, the powder is scattered during the preparation of the solution, which is a problem in the working environment.

Further, both the liquid agent and the powder agent remain liquid or powder in the packaging material after preparation, which poses a problem as environmental pollution at the time of disposal.

As a method for solving these problems, a method of granulating or tableting a treating agent has been studied in the art.

As a general method for granulating or producing tablets, starch, polyvinyl alcohol, cellulose, etc. are used in order to maintain the strength of the granules or tablets. Are uniformly mixed, and then granulated by a method such as an extrusion granulation method or a mixing stirring granulation method, or pressure-molded to form tablets.

After that, residual water is removed through a drying process to obtain a final product.

Water, starch, cellulose and the like are known as binders, but when they are used, the strength of granules is weak and a large amount of powder is produced during transportation, and they have the same disadvantages as simple powder treating agents. Further, as the processing amount of the photosensitive material increases, starch and cellulose accumulate in the automatic developing machine and stain the rollers and the photosensitive material being processed.

The waxy water-soluble polymer is very effective as a binder because the strength of the granules is high and the above-mentioned contamination does not occur. However, if the content of 5% by weight or more is contained in order to maintain the strength of the granules, the processed silver image of Storability deteriorates significantly. When a processed light-sensitive material is stored for a long period of time, it is a phenomenon in which a silver image is discolored from black to dark brown, which significantly lowers the commercial value.

[0010]

To solve the above problems, the object of the present invention is to prevent the powder from scattering during handling of the photographic processing agent, and to significantly reduce the amount of powder remaining in the waste packaging material, which is excellent in environmental suitability.
Moreover, it is to provide a photographic processing agent having excellent image storability after processing.

[0011]

The above object of the present invention is to develop a silver halide photographic light-sensitive material and to contain a waxy water-soluble polymer as a binder in an amount of 5% by weight or more based on the total amount of the constituent components of a photographic fixing agent. In a photographic processing method of fixing using a fixing solution obtained by dissolving a fixing agent formed into a tablet or a tablet, the fixing treatment is carried out in the presence of a compound represented by the following general formula [I]. It is achieved by the characteristic method of processing a silver halide photographic light-sensitive material.

General formula [I] R-SX [In the formula, R represents a monovalent organic group and represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or an organic heterocycle. These organic groups may be substituted. X is a hydrogen atom,
Represents an alkali metal and ammonium. The present invention will be specifically described below.

First, specific examples of the compound represented by the general formula [I] are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

Examples of the water-soluble or alkali-soluble waxy polymer used in the present invention include polyalkylene glycol such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether. It can be used by selecting from alkyl ethers, polyoxyethylene alkylphenol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, or water-soluble binders described in Japanese Patent Application No. 2-203165.

The amount of the soluble polymer used in the present invention depends on the properties of the soluble polymer to be used and the solubility and strength of the required granules or tablets (hereinafter referred to as granules). 1 to 50 relative to the total amount of processing agent components
%, Preferably 5 to 30% by weight is used.

The granulation method used in the present invention includes rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method,
A stirring granulation method, a spray drying method, a dissolution solidification method and the like can be used, but an extrusion granulation method and a compression granulation method are particularly preferable.

The particle size and shape of the granulated product suitable for the present invention vary depending on the desired characteristics, but generally the solubility desired for the photographic processing agent and the amount of powder remaining in the waste packaging material after the preparation are adjusted. Alternatively, considering the resistance to breakage of the granulated product due to vibration during transportation, in the case of granules, the particle size is preferably about 0.1 mm to 10 mm, preferably about 0.5 to 5 mm, and the shape is cylindrical.
It is spherical, cubic, rectangular parallelepiped, or the like, and more preferably spherical or cylindrical.

Similarly, in the case of tablets, the diameter is preferably about 5 mm to 5 cm, although it depends on the desired characteristics. When it is desired to improve the solubility, a flat tablet having a reduced tablet thickness, a flat tablet having a further reduced central portion thickness, and a hollow donut tablet are also useful. On the contrary, the diameter may be further increased for the purpose of slow dissolution, and can be adjusted arbitrarily.

The surface condition (smoothness, porosity, etc.) may be changed to control the solubility.

It is also possible to take a plurality of shapes in order to give different solubilities to a plurality of granules or to adjust the solubilities of materials having different solubilities. Further, it may be a multi-layer granulated product having different compositions on the surface and inside.

[0028]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

<Preparation of photographic light-sensitive material for evaluation> (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 per mol of silver.
Mol added. The obtained emulsion was an emulsion composed of cubic monodisperse grains (average coefficient of variation: 0.20 μm, variation coefficient: 9%). The modified gelatin of JP-A-2-280139 G-8 was added, washed with water and desalted. The pAg at 40 ° C. after desalting was 8.0. Subsequently, a 0.1 mol% aqueous solution of potassium iodide per mol of silver was added to this emulsion to convert the grain surface,
Thereafter, 15 ml of a 1% aqueous solution of the mixture of the compounds [A], [B] and [C] was added to obtain an emulsion A.

[0030]

[Chemical 8]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. Applies a backing layer according to the following formulation (3) so that the amount of gelatin is 2.4 g / m ² , and further a backing protective layer of the following formulation (4) so that the amount of gelatin is 1 g / m ² . Sample No. 1 to 18
Got

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ²

[0033]

[Chemical 9]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² 1-Phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: saponin 0.1g / m ²

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical formula 12]

Gelatin 2.4 g /
m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Average particle size 5.0 μm Monodisperse polymethylmethacrylate 50mg / m
² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² : H-1 35 mg / m ^{2 The} obtained sample was exposed to 3200K tungsten light for 5 seconds with a step wedge in close contact. After that, processing was carried out under the following conditions with an automatic processor GR-26SR for rapid processing manufactured by Konica Corp., in which a developing solution and a fixing solution having the compositions shown below were added.

Developer Formulation Ethylenediaminetetraacetic acid sodium salt 1 g Sodium sulfite 60 g Boric acid 40 g Hydroquinone 35 g Sodium hydroxide 8 g Sodium bromide 3 g 5-Methylbenzotriazole 0.2 g 2-Mercaptobenzothiazole 0.1 g 2-Mercaptobenzothiazole-5- Sulfonic acid 0.2g 1-Phenyl-4,4-dimethyl-3-pyrazolidone 0.2g Add water and adjust pH with sodium hydroxide 1l 10.8 Fixing solution formulation <Preparation of fixing agent for evaluation> Fixing agent formulation (use solution 1l For) 1. Polyethylene glycol (Molecular weight 1540) See Table 1 2. Sodium sulfite 5.0g 3. Boric acid 13.0 g 4. Ammonium thiosulfate 135.0 g 5. Citric acid 80.9 g 6. Compounds of General Formula [I] See Table 1 The fixing agents shown in Table 1 were prepared based on the above fixing agent formulations.

The preparation method is as follows. Compound 6 was added to and dissolved in a mixture obtained by heating and dissolved, and added to the powders of Compounds 2 to 5 previously kneaded, and further thoroughly kneaded, followed by granulation using an extrusion type granulator. Grained. The treating agent at that time was prepared so as to have a granular shape of 1 mm and a length of 2 mm.

[Granularity or tablet strength test] 100 g of each of the obtained samples was weighed and placed in a plastic box of 5 × 5 × 15 cm, sealed, and then 5 cm at a cycle of 100 times / 1 minute.
Shaking above and below was applied for 5 minutes. Then, the sample was emptied from the box, and the amount of powder remaining in the box was visually evaluated.
Those having almost no remaining amount were evaluated as A rank, those adhered to almost the entire surface of the box as E rank, and those in the middle were evaluated as B, C, D ranks.

[Evaluation of image storability]
An optical wedge was used to expose for 1 second with tungsten light, and the developing solution and the fixing solution shown in the above and Table 1 were used to develop 38 ° C, 20 seconds, fix 35 ° C, 20 seconds, and wash with water 30 ℃,
Two sheets were processed under the conditions of 15 seconds, drying at 50 ° C., and 15 seconds.

One of the obtained samples was left to stand naturally, and the other one was heat-treated at 40 ° C. for 7 days.

For each sample, the degree of blackening was visually evaluated.
The rank and the color having extremely strong discoloration were evaluated as the E rank, and the intermediate ones were evaluated as the B, C and D ranks.

The results obtained are shown in Table 1.

[0046]

[Table 1]

Regarding the discoloration of the blackened portion of the sample, a remarkable difference was found particularly in the halftone portion (the portion which is not the maximum density) subjected to wedge exposure.

As shown in the results, only the treatment conditions according to the constitution of the present invention showed almost no discoloration of the blackened portion, and the amount of residual powder in the packaging material was remarkably small, showing good results.

[0049]

EFFECTS OF THE INVENTION According to the present invention, the powder is not scattered during handling of the photographic processing agent, the amount of the powder remaining in the waste packaging material is extremely small, the environmental suitability is excellent, and the image storability after the processing is excellent. A photographic processing agent could be provided.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material is developed, and a wax-like water-soluble polymer is contained as a binder in an amount of 5% by weight or more based on the total amount of the constituent components of a photographic fixing agent. In a photographic processing method of fixing using a fixing solution obtained by dissolving an agent, the fixing processing is carried out in the presence of a compound represented by the following general formula [I]. Method of processing photosensitive material. General formula [I] R-SX [In formula, R is a monovalent organic group and represents a C1-C12 alkyl group, a phenyl group, or an organic heterocycle. These organic groups may be substituted. X is a hydrogen atom,
Represents an alkali metal and ammonium. ]