JPH0456966B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a method for processing silver halide photographic materials using a substituted mercaptotetrazole having a specific structure. (B) Prior art and its problems It is well known that silver halide photographic materials change over time during storage, resulting in changes in photographic properties such as sensitivity, fog, and color tone. In addition, in recent years, due to the desire to shorten access time, so-called high-temperature, rapid processing, in which processing temperatures are higher and processing times are shorter than in the past, has become more common. It can be said that the situation is easy. To date, many stabilizers and antifoggants have been discovered and patented in order to prevent or reduce the increase in fog during storage and the occurrence of fog during development. The more a compound exhibits an antifogging effect, the more it tends to reduce the sensitivity of a photosensitive material and reduce the gradation, and a compound that satisfies both the maintenance of sensitivity and gradation and the prevention of fog has not yet been found. (C) Object of the Invention The object of the present invention is to solve the above problems and provide a means for effectively preventing fog while maintaining the original sensitivity of a photosensitive material. (D) Structure of the invention After intensive study, the inventors found that 1-phenyl-
It has been found that a 5-mercaptotetrazole compound having at least one of the following general formulas (a) to (c) in the phenyl nucleus satisfies the above conditions. General formula (a) R-(OA) _o -O-B-CONH- General formula (b) R-(OA) _o -O-B-SO ₂ NH- General formula (c) R-(OA) _o - O- [In formulas (a) to (c), A and B represent an alkylene group (e.g., ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, etc.), and R represents an alkyl group (e.g., methyl group). , ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, dodecyl group, etc.), aryl group (e.g. phenyl group, tolyl group, etc.), alkenyl group (e.g. allyl group, etc.) ), and n represents an integer from 1 to 8. ] Among the above 1-phenyl-5-mercaptotetrazoles, preferred are those represented by the following general formula (). General formula () [In formula (), R ₁ to _{R 5} are hydrogen atoms, halogen atoms (e.g., chloro, bromine, etc.), alkyl groups (e.g., methyl, ethyl, etc.), alkoxy groups (e.g., methoxy), and the above general formula (a). ) to (c). However, at least one of R ₁ to _{R 5} has the general formula (a) to
It shall include the substituent represented by (c). Representative examples of compounds represented by the general formula () are shown below, but the present invention is not limited thereto. These compounds advantageously used in the present invention can be synthesized by various known synthesis methods, but compounds having general formulas (a) and (b) as substituents are 1-
A compound synthesized by acylation or sulfonylation of (aminobenzene)-5-mercaptotetrazole or a derivative thereof and having general formula (c) as a substituent is R(-OA) shown in formula (c) _. It was obtained by reacting phenyl isothiocyanate having a polyether substituent group -O- with sodium azide to cause ring closure. Synthesis Example Synthesis of Compound 4: 1.15 g of 1-(4-aminobenzene)-5-mercaptotetrazole was suspended in 6 ml of dioxane, and 0.48 ml of pyridine was added. Further, 1.04 g of 2-ethoxy-ethoxyacetyl chloride dissolved in 9 ml of dioxane was added dropwise at room temperature while stirring. Stirring was continued for 3 hours at the same temperature. Then, add the reaction solution to 60ml of chloroform, and add 60ml of water.
Extracted in ml. The same operation was repeated twice.
The chloroform layer was separated and dried over sodium sulfate. Subsequently, sodium sulfate was filtered, and the solvent was distilled off under reduced pressure on the water solution. This residue was recrystallized from ethanol. Yield 1.3g Melting point 166.4-166.8
°C Synthesis of compound 10: 1.55 g of 4-(3,6,dioxa-n-decyloxy)benzene isothiocyanate was added to dioxane 10
ml of sodium azide dissolved in 10 ml of water was added at room temperature. After heating under reflux for another 6.5 hours and cooling,
The solvent was concentrated under reduced pressure on the aqueous solution, 1N sodium hydroxide and water were added to the residual liquid, and activated carbon was added and filtered. The liquid was extracted with benzene, and the aqueous layer was acidified with 6N hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and then dried over sodium sulfate. After removing the sodium sulfate, the solvent was distilled off to obtain 0.9 g of the desired product. Melting point: 57.0°C to 63.0°C Compounds other than those in the above synthesis examples can also be easily synthesized according to these synthesis examples. In the processing method of the present invention, the exposed silver halide photographic light-sensitive material is developed with various known developers in the presence of the above-mentioned antifoggant of the present invention. The above antifoggant of the present invention exhibits much better water affinity than the corresponding compound in which the ether bond is replaced with a methylene bond, so it is extremely advantageous when introduced into photosensitive materials and processing solutions. It also has the advantage that the amount used can be reduced. There are various means for making the antifoggant of the present invention present during development, but in the silver halide emulsion layer of a photographic light-sensitive material, or in a colloid layer having a water-permeable relationship with the emulsion layer, such as an overcoat for the emulsion layer. Alternatively, it is desirable to add it to the undercoat layer, or to the developer or a pre-bath of the developer. The antifoggant of the present invention can be dissolved in water or a water-miscible solvent such as DMF, methanol, ethanol, or an aqueous alkaline solution, and added to and mixed with the silver halide emulsion or colloidal dispersion before coating. Accordingly, it can be added to the silver halide emulsion or the colloidal dispersion. Furthermore, it is also possible to disperse the antifoggant of the present invention in a latex and add it to the above silver halide emulsion or the above colloidal dispersion using a method as shown in JP-A-53-137131. It is. When added to the treatment liquid, it can be added as is or dissolved in a water-miscible solvent such as D.MF., methanol or ethanol. When added to silver halide photographic materials,
The amount of the antifoggant of the present invention is generally in the range of 10 ^-6 to 10 ^-2 mol, preferably 10 ^-5 to 10 ^-2 mol, when added to the processing solution, per 1 mol of silver halide. is 10 ^-5 to 10 ^-1 mol/preferably 10 ^-4 to 10 ^-2
It can be set within the range of mol/mole. In the processing method of the present invention, known processing solutions and processing methods can be used except for the presence of the antifoggant of the present invention, but depending on the purpose,
It is possible to carry out either a development process that forms a silver image (processing including black-and-white photographic processing and diffusion transfer) or a development process that forms a dye image (color photographic process). The developer used in black-and-white photographic processing can contain a known developing agent. As developing agents, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-
phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-P-aminophenol), hydroxylamines (e.g. N,N-
diethylhydroxylamine), asyurbic acid and 1,2, as described in U.S. Pat. No. 4,067,872.
Heterocyclic compounds in which a 3,4,-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developer used in color photographic processing can contain a known developing agent. As a developing agent, phenylene diamines (for example, 4-amino-N,N-diethylaniline, 3-methyl-4
-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.), aminophenols, etc., alone or in combination. Can be used. The developing solution generally contains a known preservative, an alkaline agent, a PH buffer, an antifoggant other than the antifoggant used in the present invention, and, if necessary, a solubilizing agent, a color toning agent, It may also contain a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The processing method of the present invention can be applied to various known silver halide photographic materials. Silver halide emulsions to which the present invention can be applied include, for example, spectrally sensitized and non-sensitized emulsions;
There are X-ray emulsions, infrared-sensitive emulsions, etc., and these may be high-sensitivity negative emulsions or low-sensitivity positive emulsions, and furthermore, the emulsions may be of the orthochrome type or the panchrome type. Various silver salts can be used as the photosensitive silver salt. Examples include silver bromide, silver iodide, silver chloride, or mixed silver halides (silver chlorobromide, silver iodobromide, etc.). Silver halide can be used in common hydrophilic colloids such as gelatin, casein, polyvinyl alcohol,
It can be dispersed in carboxymethylcellulose, etc.
Gelatin is advantageous. Silver halide emulsions can be sensitized both chemically and optically by ripening in the presence of small amounts of sulfur-containing compounds (e.g. aryl thiocyanate, allyl thiourea, sodium thiosulfate, etc.). can be sensitized to The emulsion may also contain reducing agents such as tin compounds such as those described in French Patent No. 1,146,955, US Pat. No. 2,487,850;
789,823) and small amounts of noble metals (eg, gold, platinum, palladium, iridium, ruthenium, rhodium, etc.). They can also be optically sensitized by cyanine and merocyanine dyes. Other additives, such as development accelerators, sensitizers, antioxidants, hardeners, surfactants, brighteners, color image-forming couplers, DIR couplers, and various other additives known in the photographic field may also contain halogens. It can be added to silveride emulsion layers or other water permeable colloid layers. Furthermore, the antifoggants of the present invention can be used in combination with other antifoggants or antifoggant precursors. Since the processing method of the present invention uses a new antifoggant, it is possible to reduce the decrease in sensitivity and significantly suppress the occurrence of fog, and the effect is also reduced for photosensitive materials stored under high temperature and high humidity. Since there is no oxidation, it can be advantageously applied to the development of black and white photographic materials, black and white print materials, color negative films, color papers, color reversal films, X-ray films, etc. (E) Example Silver iodide 1 mol% Silver bromide 47 mol% Silver chloride 52 mol%
A commonly used surfactant and hardener were added to a chlorobromide emulsion for photographic paper consisting of silver halide, and the emulsion was divided into 9 parts. One part was kept as a control, and the remaining part was prepared by dissolving the compound according to the present invention and the following comparative compound in methanol, and adding 1.5 x 10 ^-3 per mole of silver halide.
It was added in molar proportions. All emulsions were coated on a paper support coated with polyethylene to give a silver content of 1.5 g/m ² and used as samples. Wedge exposure was applied to each sample, and D-72
The film was developed with a developer for 90 seconds at 20°C, and sensitometry was performed. A sample that was not exposed to light was developed with D-72 developer for 10 minutes at 30°C, and the fog density was measured, and the following results were obtained. The following three compounds were used as comparative compounds.

[Table] (F) Effects of the Invention As is clear from the results of the above examples, the compounds according to the present invention have a large antifogging effect and low desensitization. Furthermore, the compound according to the present invention hardly causes any change in gradation when used.

Claims (1)

[Scope of Claims] 1. A 1-phenyl-5-mercaptotetrazole compound, which has the following general formulas (a) to (c) in the phenyl nucleus.
1. A method for processing a silver halide photographic material, which comprises developing the silver halide photographic material in the presence of a compound having at least one of the following. General formula (a) R-(OA)n-O-B-CONH- General formula (b) R-(OA) _o -O-B-SO ₂ -NH- General formula (c) R-(OA) _o -O- (In the formulas (a) to (c), A and B represent an alkylene group, R represents an alkyl group, aryl group, or alkenyl group, and n represents an integer from 1 to 8.)