JPH0488336A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to reduce fog by developing the photographic sensitive material in the presence of a specified 2-mercaptobenzothiazole derivative. CONSTITUTION:The silver halide photographic sensitive material is developed in the presence of the 2-mercaptobenzothiazole derivative represented by formula I in which each of R<1> and R<2> independently H or alkoxy; X is a divalent group having O or N, and forming a 15- or 21-membered ring on the whole together with the combined other atomic group. The antifoggant of the formula I is added at the time of development, preferably, into a silver halide emulsion layer, or a colloidal layer common in water permeability with the emulsion layer, for example, added to the overcoat or undercoat layer of the emulsion layer, or into a developing solution or the bath preceding to the developing solution, thus permitting sensitivity to be enhanced and fog to be effectively prevented.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for processing silver halide photographic materials using an antifoggant.

[Prior art and its problems]

Silver halide photographic materials change over time during storage.
It is well known that photographic characteristics such as sensitivity, fog, and color tone change. In addition, in recent years, due to the desire to shorten access time, processing temperatures have been increased and processing times have been shortened compared to conventional methods.
Increasingly, so-called high-temperature, rapid processing is being carried out.
Among photographic characteristics, it can be said that 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. Compounds that exhibit antifogging effects tend to reduce the sensitivity of photosensitive materials, and a compound that satisfies both sensitivity retention and fog prevention has not yet been found.

[Purpose of the invention]

An object of the present invention is to provide a method for processing a silver halide photographic material with high sensitivity and low fog.

[Structure of the invention]

As a result of extensive research, the present inventors have discovered that 2-mercaptobenzothiazole derivatives having certain substituents achieve the above object. That is, the present invention provides 2- represented by the following general formula (I).
This processing method is characterized by developing a silver halide photographic material in the presence of a mercaptobenzothiazole derivative. General formula (I) represents a koxy group, and X contains an oxygen atom or a nitrogen atom 2
It is a valent group and forms a 15-membered ring or a 21-membered ring as a whole. Typical specific examples of the antifoggant of the present invention are shown below. K'' In the general formula (I), R' and R'' may be the same or different, and each is a hydrogen atom or AlCB. The compounds of the present invention are synthesized by brominating benzo crown ether, which is the mother nucleus, and then nitrating the resulting nitrobenzene derivative. After nucleophilic substitution of the halogen, the nitro group is reduced with H2S, and then CS2 is This was achieved by reacting. The benzocrowne ether which is the mother nucleus is, for example, Synthesis 6811 (1986),
Tetahedron Letters
eH, ) 262705 (1985). Chemical communication (Chew, commo)
n) 26g (1986) Journal of Polymer Science (J, Po17met Sci, ^-
19817 (197+), Journal of American Chemical. Bi Society (J, Ameτ, Chm,
5 (IC,) 95.3842 (1973) Chemical
Communication (Chem, commun> 4
14 (1975), 639 (1976), 64
0 (1976). Synthesis examples of representative compounds of the present invention are shown below. Synthesis Example (Synthesis of Exemplified Compound 1) 56.7 g of benzo-15-crown was dissolved in chloroform 4
84.90 g of NB was added thereto, and the mixture was heated under reflux for 5 hours. After cooling, chloroform was added to the reaction solution, and the chloroform layer was distilled off under reduced pressure from the water washing solution to obtain the crude bromine compound 9.
．． 2 g were obtained as a waxy solid. Add this to 30m of acetic acid
1, and at an internal temperature of 10-15℃, add nitric acid (d=1.
8) 5. A mixture of 7 ml and 10 ml of acetic acid was added dropwise. (Required time: 30 minutes) After further stirring at room temperature for 1 hour, the reaction mixture was poured into water and CHCj! Extracted with 3. CH
The Cl s layer was washed with an aqueous NaHCO3 solution, then with water, dried over anhydrous sodium sulfate, and then distilled off under reduced pressure to obtain 7.8 g of a crude nitro compound. (yellow solid) 7.8 g of crude nitro compound was dissolved in 120 ml of EIO,
While heating under reflux, a suspension of Na5H7,8 in EtOt (10 ml) was added dropwise. (Required time: 20 minutes)
Furthermore, after refluxing for 1 hour, the mixture was allowed to cool, and H and S were passed through it at room temperature for 1 hour. C52201DI was added and the mixture was further heated under reflux for 2 hours. After cooling, EIOH was distilled off under reduced pressure, and the residue was extracted with 20% KOH. Insoluble materials were filtered, the filtrate was acidified with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, dried, and recrystallized from MeoH to give pale yellow crystals. m p 226-228° Yield 2.5 g PMR (DM
SO) δ7.19 (IH,S)'l 06 (IH
, S) 3.80-3.98 (4H. m) 2.44-2゜68 (12H, m) CMR (DMS
O/Na0H) δ, 183.93 (2nd place) 150.03
．． 146.32.143゜62.128.76.105
．． 27.103.20.68.87.68.54.68
．． 47.68°47.68.17.68. 09 In the processing method of the present invention, the exposed silver halide photographic material is subjected to various developing solutions in the presence of the antifoggant of the present invention. 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 in a water-permeable relationship with the emulsion layer, for example, in the emulsion layer. Add it to the top coat or undercoat layer, or
Alternatively, it is desirable to add it 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 M, F, methanol, ethanol, or an alkaline aqueous solution, and added to the silver halide emulsion or colloidal dispersion before coating. By adding and mixing, it can be added to the silver halide emulsion or colloidal dispersion. Furthermore, it is also possible to disperse the antifoggant of the present invention in 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. Also, when adding it to the processing solution, either add it as is or
It can be added after being dissolved in a water-miscible solvent such as D, M-Fl, methanol or ethanol. When added to a silver halide photographic light-sensitive material, the amount of the antifoggant of the present invention is generally 10-6 to 10-2 mol, preferably 10-5 to 1 mol, per 1 mol of silver halide.
0-2 mol range, 10-5 when added to processing solution
~10-1 mol/l, preferably 10-4 to 10-2 mol/l! It can be set within the range. 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. and diffusion transfer) or development processing to form a dye image (color photographic processing). The developer used in black-and-white photographic processing can contain a known developing agent. As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone)
, aminophenols (e.g., N-methyl-P-aminophenol), hydroxylamyls (e.g., N
, N-diethylhydroxylamine), ascorbic acid and 1 described in U.S. Pat. No. 4,067.872.
．． A heterocyclic compound such as a 2.3.4-tetrahydroquinoline ring and an intrene ring fused together 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-β-hydroxyethylaniline, 3-methyl-4-amino-methyl-
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. can be used alone or in combination. The developer generally contains other known preservatives,
Contains an alkaline agent, a pH buffering agent, an antifoggant other than the antifoggant used in the present invention, and, if necessary, a silver halide solubilizer, a color toner, a development accelerator, a surfactant,
It may also contain antifoaming agents, water softeners, hardening agents, viscosity imparting agents, 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 unsensitized emulsions, X-ray emulsions, and infrared-sensitive emulsions, and they may be high-speed negative emulsions or low-speed positive emulsions. Furthermore, the emulsions may be of the orthochrome or banchrome 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.). The silver halide can be dispersed in common hydrophilic colloids such as gelatin, casein, polyvinyl alcohol, carboxymethylcellulose, etc., gelatin being preferred. Silver halide emulsions can also be chemically sensitized by ripening in the presence of small amounts of sulfur-containing compounds (eg, aryl thiocyanates, allylthioureas, sodium thiosulfate, etc.). The emulsion or reducing agent (e.g. French Patent No. 1.1)
No. 46,955, U.S. Patent No. 2°487.850
tin compounds as described in British Patent No. 789,823;
(such as aminomethane sulfinic acid compounds) and small amounts of noble metals (such as gold, platinum, palladium, iridium, ruthenium, and rhodium). Other additives, such as development accelerators, sensitizers, antioxidants,
Hardeners, surfactants, brighteners, color image-forming couplers, DI
Various additives known in the photographic art, such as R couplers, can also be added to the silver halide emulsion layer or other water permeable colloid layer. Furthermore, the antifoggants of the present invention can be used in combination with other antifoggants or antifoggant precursors.

【Example】

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 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 4.times.10@-3 mole per mole of silver halide. All emulsions were placed on a polyethylene coated paper support with a silver content of 1.
A sample was coated at a concentration of 5 g/m. Each sample was exposed to wedge light, developed with a D-72 developer at 20° C. for 90 seconds, and subjected to sensitometry. Samples that were not exposed to light were heated to 30°C using D-72 developer.
After developing for 5 minutes, the fog density was measured and the following results were obtained. The following two types of compounds were used as comparative compounds. Comparative Compound A Comparative Compound B Example 2 Using the sample of Example 1 (photographic paper containing no antifoggant), an example was carried out using a developer in which 2XIO-'' mol/I of an antifoggant was added to D-72 developer. 1 and the same sensitizing dye (CI(2), SOa H 2 O was given a wedge exposure for 2 seconds, and was incubated at 30°C with a PQ developer.
The film was developed for 0 seconds and sensitometry was performed. The antifoggant is 2 x Example 3 average particle size 0. After chemically sensitizing a 3 μm cubic chloride emulsion, the following sensitizing dyes were added at 5×1 per mole of silver halide.
0-' mole added, surfactant and 2°4-dichloro-
6-Hydroxy-1,3,5-triazine (Na salt) was added to deposit a silver amount of 5 g/n (
It was applied as a sample and used as a sample. [Effects of the Invention] The antifoggant of the present invention has little desensitization and can effectively prevent fogging. The compounds of the present invention are also useful as additives in silver salt diffusion transfer methods, and also exhibit effects such as color tone improvement.

Claims (1)

[Claims] (1) A processing method for developing a silver halide photographic light-sensitive material, which is characterized in that it is carried out in the presence of a 2-mercaptobenzothiazole derivative represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 may be the same or different and represent a hydrogen atom or an alkoxy group, respectively, and A divalent group containing atoms, with a total of 1
(forms a 5-membered ring or a 21-membered ring)