JPH06130586A - Processing method for silver halide black-and-white photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a processing method for a silver halide black-and-white photographic sensitive material by which the sticking of a stain and defective fixation due to the sticking are not caused even in the case of processing at a low pH. CONSTITUTION:A silver halide black-and-white photographic sensitive material is processed with a fixing soln. of <=pH4.5 contg. a fluorine-free betaine type surfactant. The sticking of a stain in a fixing tank and defective fixation due to the sticking are not caused and rapid processing at a high temp. can be carried out with an automatic processing machine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a black-and-white photographic light-sensitive material in which stains and improper fixing are less likely to occur during processing.

[0002]

BACKGROUND OF THE INVENTION Black-and-white silver halide photographic light-sensitive materials are widely used in the plate making field, medical field and the like. In recent years, technological advances in these fields have been remarkable, and accordingly, photographic light-sensitive materials have also been required to have a high level of quality. For example, not only is it necessary to have appropriate photographic characteristics for faithfully reproducing images, but there is an increasing demand for rapid processing stability that can obtain constant results in the shortest possible processing time. Is coming.

In most cases, an automatic processor is used for the development processing of photographic materials, and in order to meet the demand for rapid processing mentioned above, the processing temperature has been increasing. When the processing temperature rises, the amount of gelatin and other chemicals eluted from the photosensitive material into the processing solution increases, and the concentration of the processing solution evaporates further, resulting in the development, fixing, and washing tanks and transportation. Roller stains tend to adhere, and the influence of the stains on the photosensitive material on quality has become a problem.

Since the contamination of the light-sensitive material in the developing tank causes unevenness of development and causes a serious quality problem, many improvements have been noted and proposed. However, the contamination during the fixing process has not been so much until now. It hasn't been a problem.

In the automatic processor processing, the light-sensitive material is generally passed directly through the fixing solution without passing through the stop solution after development, so that the pH is raised by the introduction of the developing solution and the fixing ability is lowered or the developing ability is lowered. There may be unevenness. In order to prevent this, so-called acidic fixers are used, but with the speeding up of processing, it has become necessary to lower the pH thereof. However, it has been found that when high-temperature rapid processing is performed using a fixing solution having a pH of 4.5 or less, stains in the fixing tank and fixing failure due to the stains are likely to occur, and a solution to the problem is desired.

[0006]

The object of the present invention is to provide a low p
Another object of the present invention is to provide a method of processing a silver halide black-and-white photographic light-sensitive material which does not cause stains or defective fixing due to the treatment with H. Another object of the present invention is to provide a photographic processing solution suitable for use in the above method.

[0007]

The above objects of the present invention are as follows.
In a processing method for at least developing and fixing a silver halide black and white photographic light-sensitive material, the processing method is characterized in that the fixing solution has a pH of 4.5 or less and contains a non-fluorine betaine type surfactant. Achieved

The present invention will be described in more detail below. Examples of the non-fluorinated betaine-type surfactant used in the present invention and anionic surfactant of the comparative product are shown below,
Of course, it is not limited to these examples.

[0009]

[Chemical 1]

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[0023]

[Chemical 15]

The amount of these betaine-type surfactants added to the fixing solution is ^10-6 mol / L or more, preferably ^10-5 mol / L or more, and of course the solubility is desirable.

The pH of the fixing solution of the present invention is 4.5 or less, but if it is too low, the storage stability is deteriorated due to decomposition of hypo, etc., so pH of 3.9 or more is desirable.

The fixing solution of the present invention is not limited except that it has a pH of 4.5 or less and contains a non-fluorine type betaine type surfactant, and may have a publicly known and publicly used composition. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, and fixing agents such as thiourea, as well as hard films such as aluminum chloride, aluminum sulfate and potassium alum. Agents, preservatives such as sodium sulfite and sodium bisulfite, organic acids such as acetic acid, citric acid, tartaric acid, malic acid and succinic acid, chelating agents and the like.

The processing method of the present invention includes at least the steps of development, fixing and washing with water or stabilization. The developing agent used in the developer used in the developing step of the present invention is not particularly limited, but preferably contains dihydroxybenzenes, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or dihydroxybenzenes. In some cases, a combination of and p-aminophenols is used. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
There are 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, and hydroquinone is particularly preferable.

Further, as a developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Examples include tolyl-4,4-dimethyl-3-pyrazolidone. Further, as p-aminophenol-based developing agents, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2
-Methyl-p-aminophenol, p-benzylaminophenol and the like.

The developing agent is usually preferably used in an amount of 0.05 mol to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p
When the combination with -amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.0 mol / l.
It is preferably used in an amount of 6 mol / l or less.

Examples of sulfites used as preservatives in the developer used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. can give. The concentration of sulfite is preferably 0.4 mol / l or more, more preferably 0.5 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

As the alkaline agent used for setting the pH of the developer, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate,
A pH adjuster or buffer such as potassium triphosphate can be included. In addition to the above components, as additives used in the developer, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide , Organic solvents such as methyl cellosolve, hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and indazoles such as 5-nitroindazole Examples include antifoggants such as benzotriazole-based compounds such as 5-based compounds and 5-methylbenzotriazole. Further, if necessary, a toning agent, a surfactant, a defoaming agent, a water softener, a hardener, etc. may be added.

The silver halide black and white photographic light-sensitive material used in the processing method of the present invention is polyethylene terephthalate,
Film such as triacetate, or baryta paper,
It is preferable that at least one silver halide emulsion layer is further provided on a support such as a polyolefin-coated paper, an opaque film or a film provided with a white pigment layer, and further a protective layer, an undercoat layer, a backing layer and the like are provided. The silver halide in the silver halide photosensitive emulsion layer coated on the support may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and the like. Good. The silver halide black-and-white photographic light-sensitive material processed according to the present invention may be either a negative type or a direct positive type.

[0033]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the embodiments of the present invention are not limited thereto.

Example 1 A developing solution and a fixing solution having the following compositions were prepared. (Developer A) Hydroquinone 24 g 1-phenyl-3-pyrazolidone 0.75 g anhydrous sodium sulfite 60 g sodium metaborate 33 g sodium hydroxide 19 g potassium bromide 1 g 6-nitrobenzimidazole 0.5 g Water is added to make 1000 ml.

(Fixer A) (Fixer B) Water (50 ° C.) 700 ml 700 ml Ammonium thiosulfate 200 ml 200 ml Anhydrous sodium sulfite 15 ml 15 ml 20% acetic acid 48 ml 48 ml Potassium sodium tartrate 40 g 40 g Sodium acetate anhydrous 12 g 12 g Potassium alum 15 ml 15 ml 12N ． Sulfuric acid 3.6g 7.2g Add water 1000ml 1000ml

When the developer A and the fixers A and B were mixed and the pH of the fixer was measured, the fixer A was about 4.8.
Further, the fixing solution B was about 4.3. The developing solution A and the fixing solution A or B were put into an automatic developing machine to prepare for development processing. The processing conditions are 38 ° C for 20 seconds in the developing tank and 3 in the fixing tank.
It was set to 5 ° C. for 20 seconds.

First, a commercially available film for a scanner having a polyethylene terephthalate film as a support was continuously treated in an unexposed state in a dark room at a rate of 1 liter / L, and after that, the film was passed through the above film again after being idled for 10 minutes. The presence or absence of improper fixing due to dirt on the surface or adhesion of dirt was examined. An additional 2 liters / L was passed through the paper, and after 10 minutes of idle operation again, the film was examined for dirt. This experiment
The fixing liquids A and B were used, and the fixing liquid B was added with a fluorine-based surfactant.

The results are summarized in Table 1. The degree of fixing failure due to dirt and the adhesion of dirt was evaluated by a numerical value from 1 to 5. The number 1 indicates that these stains are not generated at all, and the number 5 indicates that an extremely large amount of stains or improper fixing has occurred on the entire surface. The practically acceptable level is up to 3.

[0039]

[Table 1]

As described above, it can be seen that the non-fluorine-containing betaine-type surfactant of the present invention can effectively prevent the adhesion of dirt in the fixing tank and the fixing failure due to the dirt.

[0041]

EFFECT OF THE INVENTION By treating with the fixing solution of the present invention having a pH of 4.5 or less and containing a non-fluorine-containing betaine-type surfactant, stains in the fixing tank are not adhered, and fixing defects due to stains do not occur. , High temperature rapid processing is possible with an automatic processor.

Claims (1)

[Claims] 1. A method of processing at least developing and fixing a silver halide black and white photographic light-sensitive material, wherein the pH of the fixing solution is
Is 4.5 or less and contains a non-fluorine-containing betaine-type surfactant.