JPH0259969B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing silver halide photographic materials using a substituted benzotriazole having a specific structure. 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 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 a compound that satisfies both the maintenance of sensitivity and the prevention of fogging has not yet been found. SUMMARY OF THE INVENTION An 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. The present inventors conducted extensive studies and found that the benzotriazole compound represented by the following general formula () is
It was found that the above conditions were satisfied. General formula () (In the formula, R is an alkyl group (for example, a 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.) or alkenyl group (e.g., allyl group, etc.), and R' represents a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), or ,
represents a halogen atom (e.g., chlorine, bromine, etc.), A represents an alkylene group (e.g., ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, etc.), and n represents an integer from 1 to 8. ). 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 synthetic methods, and have a polyether substituent R(-OA)- _o O- shown in the formula [] | It can be synthesized by diazotization and ring closure of Q|-phenylenediamine. The detailed synthesis method is described below. Synthesis example Synthesis of compound 1: 10.54 g (0035 mol) of 4-(2-n-butoxyethoxy)-Q-phenylenediamine hydrochloride and 2N-
A solution of 2.61 g (0035 x 1.05 mol) of sodium nitrite dissolved in 20 ml of water was added dropwise to 100 ml of hydrochloric acid while stirring vigorously while keeping the internal temperature below 10°C over about 30 minutes. Stir for hours. After further stirring at room temperature for 2 hours, the reaction mixture was extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure on a water bath. The residue was purified by column chromatography (silica gel was used as the column, and a 1:1 mixed solvent of ethyl acetate and n-hexane was used as the solvent) to obtain 4.5 g of the target product as an oil.
PMR (CDCl ₃ ) δ: 0.93 (3H, t, J = 6Hz, C
H ₃ , CH ₂ , CH ₂ CH ₂ O―), 1.13-2.00 (4H, m,
CH ₃ , CH ₂ CH ₂ CH ₂ O―), 3.57 (2H, t, J=7
Hz, CH ₂ CH ₂ - _{CH 2} CH ₂ O -), 3.67-4.30 (4H,
m, -OC H ₂ C H ₂ O-), 6.97 (1H, dd, J=9
Hz, 2Hz, armatic.CH , 6th place), 7.10 (1H, d,
J = 2Hz, aromatic.C H 4th place), 7.75 (1H, d,
J = 9Hz, aromatic.C H 7th), 11.67 (1H, brs,
N H ) Synthesis of compound 4: 4-[2-{2-phenoxyethoxy}ethoxy]-O-phenylenediamine hydrochloride 5.42 g (0015
mol) and 50 ml of 2N-hydrochloric acid, while keeping the internal temperature below 3°C and stirring vigorously, add sodium nitrite.
A solution of 1.10 g (0015 x 1.05 mol) dissolved in 10 ml of water was added dropwise over about 8 minutes, followed by stirring at the same temperature for 1.5 hours. After further stirring at room temperature for 2 hours, the reaction mixture was extracted with ethyl acetate, the extract was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure on a water bath. The residue was thoroughly kneaded with n-hexane, and the precipitate was collected. These crystals were recrystallized from aqueous ethanol to obtain 2.6 g of white crystals. The melting point was 103.0°C to 104.0°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 compound represented by the general formula []. The compound represented by the above general formula [] exhibits much better water affinity than the corresponding compound in which the ether bond is replaced with a methylene bond, so it is extremely suitable for introduction into photosensitive materials and processing solutions. This is advantageous, and since it exhibits strong photographic properties, it has the advantage that the amount used can be reduced. There are various means for making the compound represented by the above formula [] present during development, but it may be present 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, for example. 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 can be dissolved in water or a water-miscible solvent such as DMF, methanol, ethanol, or an alkaline aqueous 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 silver halide emulsion or colloidal dispersion using a method as shown in JP-A-53-137131. It is. 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 according to the invention is generally between 10 ^-6 and 110 ^-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 treatment liquid, in the range of 10 ^-5 to ^{10 -1} mol/l, preferably 10 ^-4 to 10 ^-2 mol/l. 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-and-white photographic processing and diffusion transfer) or a development process that forms a dye image (color photographic process). The developer used when performing 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, phenylenediamines (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, 5-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 developer generally contains other well-known preservatives, alkaline agents, PH buffers,
Contains antifoggants other than the antifoggants used in the present invention, and further includes a dissolving agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc. as necessary. It may also contain 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 linear emulsions, infrared sensitive emulsions, etc.
The emulsion may be a high-speed negative emulsion or a low-speed positive emulsion, and furthermore, the emulsion 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, and rhodium). 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 breakers. Since the processing method of the present invention uses a new anti-fogging agent, 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. Therefore, it can be advantageously applied to developing black-and-white photographic materials, black-and-white print materials, color negative films, color papers, color reversal films, X-ray films, and the like. The present invention will be explained in more detail with reference to Examples below. Example 1 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 6 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. Apply wedge exposure to each sample, 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 5 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. Comparative Compound A [Formula] Comparative Compound B [Formula] Comparative Compound C [Formula] [Table] It can be seen that the exemplified compounds have a large antifogging effect and little desensitization. Example 2 Using Sample 1 of Example 1 (photographic paper containing no antifoggant), an antifoggant was added to the D-72 developer.
The same development process as in Example 1 was carried out using a developer containing 7.5×10 ^-4 mol/l, and the following results were obtained. [Table] It can be seen that favorable results can be obtained even when the compound according to the present invention is added to a developer.

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 benzotriazole compound having the following general formula (). General formula () (In the formula, R represents an alkyl group, an aryl group, or an alkenyl group, R' represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and A
represents an alkylene group, and n represents an integer from 1 to 8. )