JPH07159940A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress silver stain in the development of a silver halide photosensitive material without adversely affecting other photographic performance. CONSTITUTION:At least one kind of compd. represented by the general formula is incorporated into a developing soln. for a silver halide photosensitive material. In the formula, R is <=2C alkyl or optionally substd. phenyl and M is an alkali metallic atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material, and more particularly to a developer used therein.

[0002]

2. Description of the Related Art Generally, it is well known that a developer used for developing a silver halide photographic light-sensitive material contains a sulfite for the purpose of enhancing the storage stability of the developer. In some cases, a developing solution containing a compound having a strong dissolving action for silver halide such as thiosulfate such as a developing solution for silver salt diffusion transfer or a one-bath developing / fixing solution is also used. When a light-sensitive material is treated with a developing solution containing a compound having a dissolving effect on silver halide such as sulfite or thiosulfate, a large amount of silver complex is easily reduced and accumulated as silver sludge. Especially when continuously processing the photosensitive material using an automatic processor, not only the silver sludge floats but also adheres to the rollers and belts, causing light reflection on the photosensitive material called silver stain on the roller streaks. As a result, yellow or brown stains are generated due to the precipitated silver. 2-Mercapto-1,3,4 as an agent to prevent silver sludge and liquid stains
-Thiadiazoles (British Patent No. 940169), 2
-Mercapto-1,3,4-oxadiazoles or 1
-Phenyl-5-mercaptotetrazole (US Patent No.
3,173,789), D, L-6,8-dithiooctanoic acid (US Pat. No. 3,318,701), o-mercaptobenzoic acid (GB 1144481), aliphatic mercaptocarboxylic acid (US patent). No. 3,628,955), L
-Thiazolidine-4-carboxylic acid (J. Photogr. Sci., 13,
233 (1965)), a disulfide compound (JP-A-52-36029)
Publication), 2-benzoxazole thiol, 2-benzimidazole thiol (Photogr. Sci. Eng., 20, 220 (19
76)), acetylene glycols (JP-A-55-95947), 2-mercaptobenzothiazole-5-sulfonic acid (JP-A-56-72441), and the like. However, when these compounds are used as an anti-sludge agent in a developing solution having a dissolving action for silver halide, particularly in a developing solution containing a high concentration of sulfite (for example, 0.2 mol / liter or more), they are susceptible to air oxidation. Loss of sludge prevention effect, weak sludge prevention effect requires the use of a large amount, adversely affects photographic characteristics such as sensitization, softening, and development inhibition, and is expensive.
There is a problem that it is difficult to say that it is sufficiently satisfactory because it has an unpleasant odor.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to sensitize a developing solution having a dissolving action for silver halide, particularly a stable developing solution containing a high concentration of sulfite, by using an automatic processor. To provide a developer capable of preventing a liquid stain due to silver sludge and a stain on a roller or a belt of an automatic processor when a material is processed and obtaining a photographic image with excellent finish quality without silver stain, yellow fog, etc. It is in. Still another object of the present invention is to provide a method for processing a silver halide black-and-white photographic light-sensitive material with a developer which prevents the generation of silver sludge without the above-mentioned problems.

[0004]

The above objects of the present invention have been achieved by incorporating at least one compound represented by the following general formula into a developer for silver halide photographic light-sensitive materials.

[0005]

[Chemical 2]

[Wherein R is an alkyl group having 2 or less carbon atoms,
A substituted or unsubstituted phenyl group, M is an alkali metal atom. ] Specific examples of the compound represented by the general formula are described below.

[0007]

[Chemical 3]

The above-mentioned dithiocarbamate compound can be produced by reacting the corresponding acylhydrazine, carbon disulfide and alkali hydroxide in absolute ethanol according to the following documents. [Reference: J. Chem. Soc. 1952, page 4812 or J. Pr Chem. 93, page 49 (1916)] The preferred concentration of the compound of the present invention in a developer (use solution) is Liquid used) It is about 0.005 to about 5 g, and more preferably about 0.01 g to about 2 g per liter.

The development processing of the present invention is carried out by a conventional black and white photographic developing agent such as hydroquinone, alkylhydroquinone (eg t-butylhydroquinone, methylhydroquinone, dimethylhydroquinone), catechol, chlorohydroquinone, dichlorohydroquinone, alkoxyhydroquinone (eg methoxy or Ethoxyhydroquinone), aminophenol developing agent (eg N-methyl-p-aminophenol, 2,4-diaminophenol, N-methyl-p-aminophenol sulphate), acacorbic acid developing agent, pyrazolones (eg 4-aminopyrazolone) ), 3-pyrazolidone developing agent (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone) Down, 1-phenyl-4
Methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-
Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl)-
3-pyrazolidone, 3-acetoxy-1-phenyl-3
-Pyrazolidone) or the like is preferably used alone or in combination. Particularly, a combination of hydroquinone and 3-pyrazolidones or hydroquinone and aminophenols is useful for high-temperature and rapid treatment. However, it may be a so-called activator type developer which does not substantially contain a developing agent.

The developing solution containing the general formula used in the present invention exhibits a particularly remarkable sludge preventing effect when it contains a large amount of sulfite ions. At this time, specifically, 0.1 mol or more per liter of the developer, preferably,
It contains 0.2 to 1.0 mol of sulfite ion.
Specific examples of sulfites that give sulfite ions include alkali metal sulfites such as sodium sulfite, potassium sulfite, and potassium metabisulfite. The silver sludge generated in the developing solution is particularly likely to be deposited on the roller or belt in the developing solution, and the silver sludge attached to the roller or belt is likely to contaminate the photosensitive material.
Therefore, the present invention is particularly useful when processed by an automatic processor. As such an automatic developing machine, for example, a facing roller system (for example, Pakorol Super G24-2 manufactured by PAKO,
Fuji Photo Film Co. G-14LFG-24SQ, RN, etc., staggered roller system (eg Eastman Kodak Kodalith Processo)
r, M6 Processor, FUJI PHOTO FILM CO., LTD RU), belt transfer method (eg Log-E-tronics LD-241D etc.) and others (dupont Cronalith 24L etc.).

If necessary, the developer may contain a buffering agent (eg, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium) Salt), a development accelerator, a surfactant, a hardener and the like.

The developer further includes an antifoggant (eg, benzotriazole such as 5-nitroindazole, 5-nitro-benzimidazole, 5-methyl-benzotriazole, 5-nitrobenzotriazole, benzothiazole, 1-phenyl). Tetrazole such as -5-mercaptotetrazole, thiazole or British Patent No.
No. 1,269,268) and a chelating agent (eg, ethylenediaminetetraacetic acid, alkali metal salts thereof, polyphosphate salts, nitriloacetate salts). The pH of the developer is chosen to be sufficient to provide the desired density and contrast, but is preferably in the range of about 8-13. The developer treatment temperature and time are interrelated and determined in relation to the total treatment time, generally about 20-40 ° C for 10 seconds to 3 minutes, but about 25 ° C for high temperature rapid processing. The temperature is ~ 45 ° C.

In the present invention, such a component of the developing solution may contain components necessary for use, and the form before treatment before use as a use liquid may be, for example, a mixture of solid components or a concentrate. , A solution, an emulsion or a suspension. For example, the components of the developing solution may be divided into several parts to have the same or different forms, or may be in the form of a powder or liquid preparation liquid prepared in advance. If necessary, the prepared liquid can be dissolved in water or diluted with water to prepare a use liquid. On the other hand, the fixing solution is a solution containing thiosulfate and a water-soluble aluminum compound, preferably
It has a pH of about 3.8 to 5.5 (20 ° C). In the method of the present invention, a stopping step may be provided after the development, but the stopping step is generally omitted in a roller-conveying type automatic developing machine. Therefore, the developing solution is brought into the fixing solution, and the pH of the fixing solution rises. For that reason, the pH of the fixer is about 3.8-
It is desirable to adjust to 5.0 (20 ℃). The fixing agent is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to 5 mol / liter. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

According to the method of the present invention, the developed and fixed photographic material is washed and dried. Wash with water at about 5-50 ° C
10 seconds to 3 minutes is preferable. Drying is performed at about 30-180 ℃,
About 5 seconds to 3 minutes and 30 seconds may be sufficient. The light-sensitive material processed by the method of the present invention may be of any use, but is preferably a black and white light-sensitive material, that is, an X-ray light-sensitive material,
It is applied to micro sensitive materials, sensitive materials for ANRIS, photographic sensitive materials, and black and white sensitive materials for general amateurs. The silver halide of the photosensitive layer includes silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and the like. The light-sensitive material used in the present invention may be either a negative type or a direct positive type.

The silver halide photographic light-sensitive material applicable to the method of the present invention comprises a support and at least one silver halide emulsion layer coated thereon. The silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer) and the like can be provided if necessary. The silver halide emulsion is a dispersion of silver halide in a hydrophilic colloid (eg, gelatin, modified gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone or a mixture thereof). Is. The silver halide emulsion is generally prepared by mixing a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt with water by a method well known in the art (for example, single jet method, double jet method, control double jet method, etc.). And in the presence of a hydrophilic colloid, followed by physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization.

The silver halide emulsion contains a spectral sensitizer (for example, a cyanine dye, a merocyanine dye, or a mixture thereof) and a stabilizer (for example, during the production process or immediately before coating).
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene), sensitizers (for example, compounds described in US Pat. No. 3,619,198), antifoggants (for example, benzotriazole, 5 -Nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole), hardeners (eg formalin, glyoxal, mucochloric acid, 2-
Hydroxy-4,6-dichloro-s-triazine), coating aids (for example, saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide)
Etc. can be added. The silver halide emulsion produced in this manner is used for Paraita paper, resin coated paper,
A support such as a cellulose acetate film or a polyethylene terephthalate film is coated and dried by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method or the like.

[0017]

The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. The following developers (A) to (C) were prepared. <Development concentrate> Pure water 640 ml Potassium sulfite 259 g Ethylenediaminetetraacetic acid tetrasodium salt 4.8 g Potassium hydroxide 34.2 g Hydroquinone 80 g Potassium carbonate (anhydrous) 57.7 g 4,4-Dimethyl-1-phenyl-3-pyrazolidone 1.6 g Methylcellosolve 38.7 ml 1-phenyl-5-mercapto-1,2,3,4-tetrazole 0.2 g potassium bromide 10 g Pure water is added to bring the total volume to 1 liter. The pH at this time is
11.40. The developer is prepared by diluting the above concentrate as follows.
(A). Development concentrate 500 ml + pure water 1500 ml = developer (A) developer (B); developer (A) 300 m of Compound Example 1 in 1 liter
g added developer solution (C); developer solution (A) 300m of compound example 2 in 1 liter
Next, using various developing solutions (A) to (C), the roller transport automatic developing machine Gevaset 437N machine (Agfer Gewert
30 seconds development time,
HLF-100 (Oriental Photo Industry Co., Ltd.)
Manufactured). The replenishment amount was 40 ml / 10 inches × 12 inches (quarter size) of the developing solution, 60 ml / 10 inches × 12 inches (quarter size) of the fixing solution, and 3.5 liters / min of washing water. As the fixing solution, GF-500 (manufactured by Oriental Photography Co., Ltd.) was used. To check the photographic properties of this light-sensitive material, a sensitometer was used to perform stepwise exposure with an optical wedge. The automatic processor is operated for 6 days a week, and half-exposed four-cut size (10
50 inches (12 inches) were processed. The above running experiment was continued for 2 weeks. The total number of processed sheets was 600. Table 1 shows the results of photographic properties and silver stains obtained by running experiments. The sensitivity was obtained as the relative value of the reciprocal of the exposure amount required to obtain the blackening degree +3.52 and the comparison sensitivity was set to 100. Fog value was measured as the net increase in density corrected for base density. Average gradation is D on the characteristic curve
The section between 90% of M and the fog value +0.1 was regarded as a straight line and expressed as the slope. DM represents maximum concentration.

[0018]

[Table 1]

As shown in Table 1, the developer containing the compound used in the present invention has good silver sludge prevention performance and does not adversely affect photographic performance.

[0020]

INDUSTRIAL APPLICABILITY According to the present invention, silver sludge generated in a developer containing a silver halide solvent such as sulfite can be effectively prevented by using at least one compound represented by the general formula, And it does not adversely affect the photographic performance.

Claims (1)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula. [Chemical 1] [Wherein R represents an alkyl group having 2 or less carbon atoms, a substituted or unsubstituted phenyl group, and M represents an alkali metal atom. ]