JPH0453301B2 - - 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 triazole compound 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, processing temperatures have been made higher and processing times have been made shorter than in the past. Increasingly, so-called high-temperature, rapid processing is being carried out, and it can be said that among photographic characteristics, fogging is particularly likely to occur. 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 lower 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) Purpose of the Invention The present invention aims to solve the above problems and provide a means for effectively preventing the occurrence of fogging and dura film inhibition while maintaining the original sensitivity and gradation of the photosensitive material. This is the purpose. (D) Structure of the Invention After extensive study, the present inventors discovered that a triazole compound represented by the following general formula () satisfies the above conditions. General formula () [In the formula, R ₁ is a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group,
Nonyl group, undecyl group, tridecyl group, hexadecyl group, heptadecyl group, benzyl group, cyclohexyl group, α-hydroxyisopropyl group, β
-Hydroxypropionyl group, cyanomethyl group,
2,5-dioxaheptyl group, 2,5,8-trioxadecyl group, 2,5,8,11-tetraoxapentadecyl group, 7-phenooxy-2,5-dioxaheptyl group, 4,7 -dioxanonyl group,
1-methyl-3,6,9,12-tetraoxatridecyl group, etc.), aryl group (e.g., phenyl group,
tolyl group, methoxyphenyl group, 3,6-dioxaoctyloxyphenyl group, hydroxyphenyl group, chlorophenyl group, cyanophenyl group, dibromophenyl group, etc.), heterocyclic groups (e.g. pyridyl group, thienyl group) ), or represents an alkenyl group (e.g., allyl group, butenyl group, etc.),
R ₂ and R ₃ are alkyl groups (e.g., methyl group,
ethyl group, butyl group, hydroxyethyl group, etc.),
It represents an aryl group (eg, phenyl group, etc.) or an alkenyl group (eg, allyl group, etc.). However, R ₂ and R ₃ may be the same or different.
It also includes tautomers of the general formula. ] Representative examples of the compound represented by the general formula () are shown below, but the present invention is not limited thereto. These compounds advantageously used in the present invention are 1,
1,1 produced by heating 1-disubstituted-3-thiocarbonohydrazide and carboxylic acid, or by heating 1,1-disubstituted-3-thiocarbonohydrazide, carboxylic acid ester, and sodium alcoholate in alcohol. -Disubstituted-5-acyl-3-thiocarbonohydrazide can be synthesized by heating in an aqueous alkaline solution. The detailed synthesis method is described below. Synthesis Example Synthesis of Compound 2: 1.34 g (0.01 mol) of 1,1-dimethyl-3-thiocarbonohydrazide and 1.8 g (0.01 x 3 mol) of acetic acid were heated under reflux for 6 hours, then cooled, water was added, and the mixture was precipitated. The crystals were collected, washed with water on a filter, and then recrystallized from water to obtain 0.8 g of white crystals. Melting point is 164.0℃
The temperature was ~165.5℃. Synthesis of compound 17: 1.34 g (0.01 mol) of 1,1-dimethyl-3-thiocarbonohydrazide, 1.37 g (0.01 mol) of nicotinic acid methyl ester, and 0.23 g of sodium metal.
(0.01 mol) dissolved in 10 ml of methanol was mixed with a solution, and after heating under reflux for 6 hours, the distillate was distilled off from the reaction solution under reduced pressure on a water bath. The residue was mixed with 10 ml of 2N sodium carbonate solution, heated on a water bath at 80°C ± 5°C for 1 hour, allowed to cool to room temperature, acidified with acetic acid, collected crystals, washed the filter with water, and washed with aqueous ethanol. Recrystallization yielded 1.3 g of white crystals. The melting point was 212.0°C to 213.0°C. Synthesis of compound 22: 1.96 g (0.01 mol) of 1-methyl-1-phenyl-3-thiocarbonohydrazide and methyl benzoate
1.36g (0.01mol) and 0.23g of metallic sodium
(0.01 mol) dissolved in 10 ml of methanol was mixed with a solution, and the mixture was heated under reflux for 6 hours, and then the distillate was distilled off from the reaction solution under reduced pressure on a water bath. The residue was mixed with 10 ml of 2N sodium carbonate solution and heated on a water bath at 80°C ± 5°C for 1.5 min.
The mixture was heated for an hour, allowed to cool to room temperature, acidified with acetic acid, and the precipitate was collected, washed with water on a filter, washed with a small amount of methanol, and then recrystallized from methanol to obtain 1.2 g of white crystals. The melting point was 182.0°C to 183.0°C. Compounds other than those in the above synthesis examples can also be easily synthesized according to these synthesis examples. In the present invention, the exposed silver halide photographic material is developed with various known developers in the presence of the compound represented by the general formula (). There are various means for making the compound represented by the general formula () present at the time of development. It is desirable to add it to the overcoat or undercoat layer for the emulsion layer, or to the developer or a pre-bath of the developer. The antifoggant of the present invention is 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 latex and add it to the silver halide emulsion or colloidal dispersion using a method as shown in JP-A-53-137131. be. When added to the processing solution, it can be added as is or dissolved in a water-miscible solvent such as DMF, methanol, or ethanol. When added to silver halide photographic materials,
The amount of the antifoggant of the invention is generally from 10 ^-6 to 10 ^-2 mol per mol of silver halide, preferably:
It can be set in the range of 10 ^-5 to 10 ^-2 mol, and when added to the processing liquid, in the range of 10 ^-5 to ^{10 -1} mol/preferably 10 ^-4 to 10 ^-2 mol/. 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 can be carried out as either a development process that forms a silver image (processing including black 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), ascorbic 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-methanesulfonamide 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 release agent,
It may also contain a toning agent, 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 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;
789823) 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) Examples The present invention will be explained in more detail with reference to Examples below. The following two types of compounds were used as comparative compounds. Comparative compound (A) Comparative compound (B) Example 1 Silver iodide 1 mol%, silver bromide 47%, silver chloride 52 mol%
A commonly used surfactant and hardener were added to a chlorobromide photographic paper emulsion consisting of silver halide, and the emulsion was divided into 7 parts. One part was used as a control, and to the remaining part, the compound according to the present invention and the above-mentioned comparative compound were dissolved in methanol and added at a rate of 1.5×10 ^-3 mol per mol of silver halide. All the 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 which was not exposed to light was developed with D-72 developer at 30 DEG C. for 6 minutes and the fog density was measured, and the following results were obtained.

[Table] It can be seen that the exemplified compounds have a large antifogging effect and low desensitization. Example 2 The following procedure was carried out in the same manner as in Example 1, except that instead of the silver chlorobromide emulsion in Example 1, a pure silver bromide emulsion consisting of cubic grains with an average grain size of 0.3 μm prepared by the double jet method was used. The results were obtained. (However, regarding fog resistance, the film was developed at 30°C for 10 minutes and the fog density was measured.)

[Table] Preferable results can be obtained even when the compound according to the present invention is added to a pure silver bromide emulsion. Example 3 After sufficiently swelling 180 g of gelatin in 1200 ml of water, the temperature was raised to 60°C and dissolved. This gelatin solution and 40 ml of a 5% saponin aqueous solution as a coating aid.
After adding , add 11g of the following hardener. Add water to make a total volume of 1500g. Each of the exemplary compound of the present invention and comparative compound (A) 1
% methanol solution was added to each of the above solutions (50 ml), and water was added to each to make a total volume of 100 ml.
Each of these coating solutions was applied onto photographic polyethylene resin laminated paper, dried, and heat treated at 50° C. for 2 days to prepare test samples. This sample was immersed in water for a certain period of time, and then a swollen sample was used to perform a scratch resistance test using a ball point needle, and the minimum weight that would cause a scratch on the surface of the swollen gelatin film was measured. Hardener used The results obtained are shown in the table below.

【table】

[Table] It can be seen that the exemplified compounds have no or little dura inhibition effect. (F) Effects of the Invention According to the present invention, the occurrence of fog can be prevented and reduced with less adverse effects on sensitivity, gradation, hardness, etc.

Claims (1)

[Scope of Claims] 1. A method for processing a silver halide photographic material, which comprises developing the silver halide photographic material in the presence of a triazole compound having the following general formula (). General formula () (In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or an alkenyl group,
R ₂ and R ₃ represent an alkyl group, an aryl group, or an alkenyl group. However, R ₂ and R ₃ may be the same or different. (including tautomers of the general formula).