JPH0588304A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce desensitization and to effectively prevent occurrence of fog by making development in the presence of a specified compound. CONSTITUTION:The silver halide photographic sensitive material is developed in the presence of the compound of formula I in which R is alkylene, such as ethylene, propylene, or butylene: M is H, a metal cation or organic ammonium salt; and n is 1-4. This compound is an antifoggant, and it is added to the silver halide photographic material in an amount of, generally, 10<-6>-10<-2>mol, preferably, 10<-5>-10<-2>mol, and it is added into a developing solution in an amount of 10<-5>-10<-1>mol, preferably, 10 <-4>-10<-2>mol, thus permitting desensitization to be reduced and occurrence of fog to be effectively prevented.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material using an antifoggant.

[0002]

2. Description of the Related Art It is well known that silver halide photographic light-sensitive materials change their photographic characteristics such as sensitivity, fog and color tone with the passage of time during storage. Further, in recent years, due to a demand for shortening access time, so-called high temperature and rapid processing, in which the processing temperature is higher and the processing time is shorter than before, is often performed, and fog is particularly likely to occur among photographic characteristics. It can be said that it is under condition. To date, a large number of stabilizers and antifoggants have been found to prevent or reduce the increase of fog during storage and the occurrence of fog during development.
A compound having a stronger antifoggant effect tends to lower the sensitivity of the light-sensitive material, and a compound satisfying both retention of sensitivity and prevention of fog has not yet been found.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having high sensitivity and less fog.

[0004]

The present invention has been accomplished by a processing method characterized in that a silver halide photographic light-sensitive material is developed in the presence of a compound of the formula (2).

[0005]

[Chemical 2]

In the formula, R represents an alkylene group (for example, ethylene, propylene, tetramethylene), M is a hydrogen atom, a metal cation or an organic ammonium salt, and n
Represents 1 to 4.

Representative specific examples of the compound of Chemical formula 2 used in the present invention are shown below.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

[0013]

[Chemical 8]

The synthesis of the thioethers according to the invention was basically carried out by alkylation of the corresponding thiols. Alkylating agents include, for example, Journal of Organic
Chemistry (JOC) 26 , 4987 (196)
It can be easily synthesized by the method 1). The details of the synthesis method will be described below using synthesis examples.

Synthesis Example 1 (Synthesis of Compound of Chemical Formula 3) 2,5-dimercapto-1,
3,4-thiadiazole 1.5 g ethyl alcohol 3
Dissolve in 0 ml, add 1.1 g of triethylamine, followed by 2-chloro-2. 1.4 g of hydroxydiethyl sulfide are added. After 3 hours under reflux, the reaction mixture was poured into water, extracted with ethyl acetate, the ethyl acetate layer was washed with water and dried over anhydrous sodium sulfate. After evaporation under reduced pressure, the residue was subjected to column chromatography (chloroform / methanol = 3 /
Separated in 1). Recrystallization from a mixed solvent of ethyl acetate / n-hexane gave a white powder. mp83-84.5 ° C
Yield 2.11 g PMR (DMSO) δ14.4 (1
H), 3.85 (2H), 3.35 (2H), 2.86.
(2H), 2.64 (2H) CMR (DMSO) δ18
7.0, 157.0, 60.9, 33.9, 33.4
31.0

In the processing method of the present invention, the exposed silver halide photographic light-sensitive material is subjected to various developers in the presence of the antifoggant of the present invention. There are various means for allowing the antifoggant of the present invention to be present at the time of development, but in a silver halide emulsion layer of a photographic light-sensitive material or a colloid layer having a water-permeable relationship with the emulsion layer, for example, of the emulsion layer. It is desirable to add it to the overcoat or undercoat layer for the purpose, or to add it in the developing solution or in the pre-bath of the developing solution. The antifoggant of the present invention is described in D. M. F. It can be added to the above silver halide emulsion or the above colloidal dispersion by dissolving it in methanol, ethanol, or an aqueous alkali solution and adding it to the above silver halide emulsion or the above colloidal dispersion before mixing. Furthermore, JP-A-53-137131
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 by using the method described in the specification. When it is added to the treatment liquid, it may be added as it is or a water-miscible solvent such as D.I. M. F. , Dissolved in methanol, ethanol or the like and added.

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 mol, based on 1 mol of silver halide.
^-5 to 10 ^-2 mol range, 10 when added to the processing solution
^-5 to 10 ^-1 mol / l, preferably 10 ^-4 to 10 ^-2 / l can be set. The processing method of the present invention can use known processing solutions and processing methods except for the presence of the antifoggant of the present invention, but depending on the purpose, a development processing for forming a silver image (black and white photography And a process including diffusion transfer) or a developing process for forming a dye image (color photographic process).

The developing solution used for performing the black and white photographic processing may contain a known developing agent. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-).
Pyrazolidone), aminophenols, (for example, N-
Methyl-P-aminophenol), hydroxylamines (eg, N, N-diethylhydroxylamine),
Ascorbic acid and a heterocyclic compound such as a 1,2,3,4-tetrahydroquinoline ring and an indrene ring described in U.S. Pat. No. 4,067,872 may be used alone or in a condensed form. it can. The developing solution used for color photographic processing may contain a known developing agent. Examples of the developing agent include phenylenediamines (eg, 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-methoxyethyl Aniline etc.), aminophenols etc. can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants other than the antifoggants used in the present invention, and if necessary, a silver halide dissolving agent, A color tone agent, a development accelerator, a surfactant, an antifoaming agent, a film hardening agent, a viscosity imparting agent and the like may be contained.

As the fixing liquid, those having a generally used composition can be used. Thiosulfate as a fixing agent,
In addition to thiocyanate, an organic sulfur compound known to have an effect as a fixing agent 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 light-sensitive materials. Examples of silver halide emulsions to which the present invention can be applied include spectrally sensitized and non-sensitized emulsions, X-ray emulsions and infrared-sensitive emulsions, and they may be high-speed negative emulsions or low-speed positive emulsions. Furthermore, the emulsion may be of orthochrome type or panchrome type. As the photosensitive silver salt, various silver salts can be used. For example, silver bromide, silver iodide, silver chloride, or mixed silver halides (silver chlorobromide, silver iodobromide, etc.) are available. The silver halide can be dispersed in common hydrophilic colloids such as gelatin, casein, polyvinyl alcohol, carboxymethylcellulose and the like, but gelatin is preferred. The silver halide emulsion can also be chemically sensitized and can be chemically sensitized by ripening it in the presence of a small amount of a sulfur-containing compound (eg, aryl thiocyanate, allyl thiourea, sodium thiosulfate, etc.). I can feel it. The emulsion or a reducing agent (for example, tin compounds as described in French Patent No. 1,146,955 and US Pat. No. 2,487,850; British Patent No. 789,823). Can also be sensitized with small amounts of noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium) and imino-aminomethanesulfinic acid compounds as described in the text.

Other additives such as development accelerators, sensitizers,
Various additives known in the photographic field, such as antioxidants, hardeners, surfactants, brighteners, color image-forming couplers, DIR couplers, etc., are also included in silver halide emulsion layers or other water-permeable colloid layers. Can be added to. Further, the antifoggant of the present invention,
It can be used in combination with other antifoggants or antifoggant precursors.

[0022]

The present invention will be described in more detail with reference to the following examples.

Example 1 1 mol% silver iodide, 47 mol% silver bromide, 52 mol% silver chloride
To a chlorobromide photographic paper emulsion consisting of the above silver halide, a commonly used surfactant and hardener were added, and the emulsion was divided into 6 parts. One part was used as a control, and to the rest, the compound of the present invention and the following comparative compound were dissolved in methanol and added at a ratio of 4 × 10 ⁻³ mol per mol of silver halide. All emulsions were coated on a polyethylene-coated paper support so that the amount of silver was 1.5 g / m ² and used as samples. Each sample was subjected to wedge exposure, developed with a D-72 developer at 20 ° C. for 90 seconds, and subjected to sensitometry. Separately, a sample that was not exposed to light was used as a D-72 developer at 30 ° C.
Minute development was performed and the fog density was measured, and the results shown in Table 1 below were obtained. The compound of Chemical formula 9 was used as a comparative compound.

[0024]

[Chemical 9]

[0025]

[Table 1]

Example 2 Using the sample of Example 1 (photographic paper containing no antifoggant), 2 × 10 ^-3 mol / min of antifoggant was added to the D-72 developer.
The same developing treatment as in Example 1 was carried out with the developer added to obtain the results shown in Table 2 below.

[0027]

[Table 2]

Example 3 A cubic chlorinated emulsion having an average grain size of 0.3 μm was chemically sensitized, and then the sensitizing dye of Chemical formula 10 was used at 5 × per mol of silver halide.
10 ^-5 mol was added, and surfactant and 2,4-dichloro-
6-Hydroxy-1,3,5-triazine (Na salt) was added and the amount of silver was 5 g / m ² on the polyester film support.
It was applied so as to obtain a sample. Wedge exposure for 10 ^-5 seconds was given, and development was carried out at 30 ° C. for 60 seconds with a PQ developer, and sensitometry was performed. The antifoggant was added at a ratio of 2 × 10 ⁻³ mol per mol of silver halide, and the results shown in Table 3 below were obtained.

[0029]

[Chemical 10]

[0030]

[Table 3]

[0031]

The antifoggant of the present invention has little desensitization and can effectively prevent fog. The compound of the present invention is also useful as an additive in the silver salt diffusion transfer method, and exhibits effects such as color tone improvement.

Claims (1)

[Claims] 1. A development processing method for a silver halide photographic light-sensitive material, which comprises developing in the presence of a compound represented by the following formula. [Chemical 1] In the formula, R represents an alkylene group, M represents a hydrogen atom, a metal cation or an organic ammonium salt, and n represents 1 to 4.