JPH0469771B2 - - 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 is increasingly being carried out, and it can be said that among photographic characteristics, fogging is particularly likely to occur. To date, a large number of stabilizers and antifoggants have been discovered and patents have been applied for in order to prevent or reduce the increase in fog during storage and the occurrence of fog during development. The more a compound exhibits a fog-preventing effect, the more it tends to reduce the sensitivity and gradation of a photosensitive material, and a compound that satisfies both the maintenance of sensitivity and gradation and the prevention of fog 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 and gradation of a photosensitive material. The present inventors conducted extensive studies and found that the benzotriazole compound represented by the following general formula (I) is
It was found that the above conditions were satisfied. General formula (I) [In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms, alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.),
Halogen atoms (e.g. chloro, brome, etc.), R
(-O-A)- _o O-B-CONH-, R(-O-A)- _o O
-B- _SO2NH- , R(-O-A)- _o O-B-
NHCO- or R(-O-A)- _o O-B-NHSO ₂ -
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.), an aryl group (e.g., phenyl group, tolyl group, etc.) or alkenyl group (e.g.
A and B represent an alkylene group (e.g., methylene group, ethylene group, methylmethylene group, ethylmethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, etc.), and n represents an integer from 1 to 8. However, one of R ₁ , R ₂ , R ₃ , R ₄ is R(-O
-A)- _o O-B-CONH-, R(-OA)- _o O-B-
_SO2NH- , R(-O-A) _-o OB-NHCO- or R(-O-A) _-o OB- _NHSO2- . ] Representative examples of the compound represented by the general formula (I) 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, including diazotization and ring closure of acylamide-O-phenylenediamine or sulfonamide-O-phenylenediamine compounds. It can be synthesized by
The detailed synthesis method is described below. Synthesis Example Synthesis of Compound 5: 4-(3,6,9,12-tetraoxatetradecanamide)-O-phenylenediamine 9.78g
(0.0286 mol), dioxane 70ml and 2N hydrochloric acid 100ml
While stirring, a solution prepared by dissolving 2.0 g (0.0286 mol) of sodium nitrite in 10 ml of water was added dropwise over about 10 minutes while keeping the internal temperature below 3° C., followed by stirring at the same temperature for 1 hour. After further stirring at room temperature for 5 hours, 23 g of sodium acetate was added and concentrated under reduced pressure on a water bath. After adding water to the concentrated solution, it was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure on a water bath. Ethyl acetate was distilled off. Ethyl acetate was added to the residue, kneaded well under ice cooling, and the precipitated crystals were collected and recrystallized from ethyl acetate to obtain 5.3 g of white crystals. Melting point is 110.5° ~
The temperature was 111.5℃. 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 [I]. The compound represented by the above general formula [I] 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 ways to make the compound represented by the above general formula [I] 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 in 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 DMP, methanol, ethanol, or an aqueous alkali 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 processing solution, it can be added as is or dissolved in a water-miscible solvent such as DMP, 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-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), 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-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.), aminophenols, etc. are used alone or in combination. be able to. The developer generally contains other known preservatives, alkaline agents, PH buffers, antifoggants other than the antifoggants used in the present invention, and, if necessary, solubilizers, color toning agents, etc. 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. Processing after black and white development or color development is as follows:
A commonly used composition having a known composition can be used. 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 as described in French Patent No. 1,146,955, US Pat. No. 2,487,850, British Patent No.
789823) and small amounts of noble metals (e.g. gold, palladium, iridium,
and 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 breakers. 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. The present invention will be explained in more detail with reference to Examples below. The following four types of compounds were used as comparative compounds. Example 1 A commonly used surfactant and hardener were added to a chlorobromide photographic paper emulsion consisting of silver halide containing 1 mol% of silver iodide, 47 mol% of silver bromide, and 52 mol% of silver chloride to form an emulsion. Divided into 6 parts. One part was used as a control, and to the remaining part, the compound according to the present invention and the following comparative compound were dissolved in methanol and added at a ratio of 1.5 x 10 ^-3 mol per mol of silver halide. All emulsions were sampled by coating them on a polyethylene coated paper support at a silver content of 1.5 g/m ² . Wedge exposure was applied to each sample, and D-72
Sensitometry was performed after developing with a developer for 90 seconds at 20°C. A sample which 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.

[Table] It can be seen that the exemplified compounds have a large antifogging effect and almost no desensitization. Example 2 Using Sample 1 of Example 1 (photographic paper containing no antifoggant), 2.5% of the antifoggant was added to the D-72 developer.
The same development process as in Example 1 was carried out using a developer containing ×10 ^-4 mol/ml, 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. Example 3 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 0.3μ prepared by the double jet method was used. The results were obtained. (However, regarding fog resistance, the film was developed at 30°C for 6 minutes and the fog density was measured.)

[Table] It can be seen that the exemplified compounds have a large antifogging effect and low desensitization. Example 4 Using sample 1 of Example 3 (photographic paper containing no antifoggant), the antifogging effect was added to the D-72 developer.
The same development process as in Example 3 was carried out using a developer containing 2.5×10 ^-4 mole/additional solution, and the following results were obtained.

[Table] It can be seen that the exemplified compounds have a large antifogging effect and low desensitization.

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 represented by the following general formula (I). General formula (I) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ are hydrogen atoms, alkyl groups, alkoxy groups, halogen atoms, R(-O-
A)- _o O-B-CONH-, R(-O-A)- _o O-B-
_SO2NH- , R(-O-A) _-o O-B-NHCO- or R(-O-A) _-o O-B- _NHSO2- , R
represents an alkyl group, an aryl group or an alkenyl group, A and B represent an alkylene group, and n represents an integer from 1 to 8. However, R ₁ , R ₂ ,
One of R ₃ and R ₄ is R(-O-A)- _o O-B-
CONH-, R(-O-A)- _o O-B-SO ₂ NH-,
R(-O-A)- _o O-B-NHCO- or R(-O-A
)-o _O -B- _NHSO2- . )