JPH02284138A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease desensitization and to effectively prevent fogging by adding a specific fogging preventive agent to the photosensitive material and developing the material. CONSTITUTION:The compd. expressed by formula I is added as the fogging preventive agent to the photosensitive material at the time of development. In the formula I, R<1> and R<2> respectively denote a hydrogen atom, alkoxy group; X denotes a bivalent group contg. an oxygen atom or nitrogen atom and forms a 15- or 21-membered ring. The amt. of the fogging preventive agent to be added is specified generally to 10<6> to 10<-2> mol per 1mol silver halide in the case of adding the same into the silver halide photographic sensitive material and to a 10<-5> to 10<-1>mol/l range in the case of adding the same into a processing liquid. The degradation of the sensitivity and the increase of the fogging are prevented in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a method for processing silver halide photographic materials using an anticapri agent.

(B) 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, so-called high-temperature, rapid processing, which uses higher processing temperatures and shorter processing times than in the past, has become more common.
, it can be said that it is in a state where fogging is likely to occur even among photographic characteristics.

To date, a large number of stabilizers and anti-capri agents have been discovered and patented to prevent or reduce the intensification of fog during storage and the generation of capri during development processing.
Compounds that exhibit a strong anti-capri effect tend to reduce the sensitivity of photosensitive materials, and no compound has yet been found that satisfies both sensitivity retention and fog prevention.

(C) Object of the Invention An object of the present invention is to provide a method for processing silver halide photographic materials with high sensitivity and less fog.

(D) Structure of the Invention As a result of perceptual research, the present inventors discovered that a 5-mercaptotetrazole derivative having a certain haze substitution was developed for the above-mentioned purpose. I found something to accomplish.

That is, the present invention provides 5- represented by the following general formula (I).
Silver halide photographic materials in the presence of mercaptotetrazole derivatives? Develop 4! This processing method is characterized by:

General formula (I) A valent group forms a 15-membered ring or a 21-membered ring.

Typical specific examples of the anti-capri agent of the present invention are shown below.

In the general formula (I), R''I R2 may be the same or different and each represents a hydrogen atom or an alkoxy group, and X contains an oxygen atom or a nitrogen atom. It can be easily produced by a conventional method using an aniline derivative obtained by nitrating and then reducing benzo crown ether, which is the core.
thesis) 680 (1986).

Tetrahedron Letters (Tetrahedron L)
ett, ) 1 2705 (1985), Chemical Communication (Chem, commun) 268 (
1986) Journal of Holmer Science (J
, Po-Po-1y Sci, A-1dan 817 (1
971), Journal of American Chemical Science (J-Amer, Chm, Soc,) 95.
3842 (1973) Chemical 0 Community 3 Cage w
y (Chem, commun) 414 (1975)
, 639 (1976), 640 (1976).

Synthesis examples of representative compounds of the present invention are shown below.

Synthesis Example (Synthesis of Exemplified Compound 1) Pen/-15-crown-5 in chloroform 350fn
After stirring at room temperature, 85 dft of HNOs (1.42 in d) was added dropwise over 35 minutes, and the mixture was further stirred at room temperature for 6 hours.

Chloroform was added to the reaction solution, washed with water, washed with an aqueous potassium carbonate solution, washed thoroughly with water, dried over anhydrous sodium sulfate, and chloroform was distilled off under reduced pressure to give 27.4 g of the crude 4-nitro compound (mp 84-87°C). ) was obtained as a pale yellow solid.

10 g of iron powder was dispersed in dioxane 100-, and acetic acid 2- and water 10- were added, and while stirring at an internal temperature of 85° to 95°C, the nitro compound 10ge was dissolved in dioxane 100- and added dropwise. After the dropwise addition, the mixture was further stirred for 30 minutes at the same temperature, and the insoluble materials were removed through f and the dioxanke was distilled off under reduced pressure to obtain the crude amine compound 1.
0 g was obtained as an oil. Ami 7 bodies 10 g
k2N hydrochloric acid 1 hydrochloric acid 100 solution jK solution thiophosgene 2.85
dt'' was added and stirred at room temperature for 5 hours.Original crystals were taken, washed with water, and dried to give 6.9gt of thioisocyanate.
Obtained as a white solid.

Add 70rnte of water to 6.9g of thioisocyanate,
It was added to 52.70 g of NaN and heated under reflux for 4 hours.

Insoluble materials were filtered off during heating, and the P solution was allowed to cool and then made acidic with concentrated hydrochloric acid.

The precipitated crystals were collected, washed with water, dried, and then recrystallized from ethanol.

Yield ii: 1.45g mp 183-185゜”Hnmr(DMSO)r, 9.54(IH, 5-8H
) 7.56 (IH, d, J=2Hz 2nd place) 6.9
3 (IH, d, J = 9Hz 6th place) 6.65 (IH, d
d, J=9Hz 2Hz 5th place) 4.06 (4H,
s ) 3.79 (4H, s ) 3.64 (8a s)
13Cnmr(DMSO)e, 180.1 (Tetrazole 2nd position) 148.2.145.8.132.3.1
16.1.114.0゜110.3 (benzene nucleus)
70.2.69.5.66.6.

66.2 (more than methylene carbon) In the processing method of the present invention, the exposed Rogge/Silver Cide photographic light-sensitive material is developed with various developing solutions in the presence of the anti-capri agent of the present invention.

There are various means for making the anti-capri agent of the present invention present during development, but it can be present in the Rogge/silver oxide emulsion layer of a photographic light-sensitive material, or in a colloid layer that has a water-permeable relationship with the emulsion layer, for example. It is preferable to add it to the upper stopper 9 or lower stopper 9 for the emulsion layer, or to the developer or a pre-bath of the developer.

The anti-capri agent of the present invention is dissolved in water or a water-miscible solvent such as M, F, methanol, ethanol or an aqueous alkaline solution, and added to the silver halide emulsion or colloidal dispersion before coating. By adding and mixing,
It can be added to the above silver norogenide emulsion or the above colloidal dispersion.

Furthermore, the anti-capri agent of the present invention is dispersed in latex and added to the above-mentioned 710 silver gemide emulsion or the above-mentioned colloidal dispersion using a method as shown in JP-A-53-137131. It is also possible.

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, F, methanol or ethanol.

When added to a silver halide photographic light-sensitive material, the amount of the anti-capri agent 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
It can be set in the range of 10-1 mol/l, preferably 101-10-2 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 anti-capri agent of the present invention. processing (including processing and diffusion transfer) or development processing (color photographic processing) to form a dye image.

The developer used in black-and-white photographic processing can contain a known developing agent. Examples of developing agents include dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-7enyl-3-pyrazolidone), aminephenols (e.g., N-methyl-P-
aminophenol), hydroxylamines (e.g., t,N,N-diethylhydroxylamine), ascorbic acid, and the t,2,3.4-tetrahydroquinoline ring described in U.S. Pat. No. 4,067,872. Heterocyclic compounds such as a fused compound and an intrene ring 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-NIN-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'#), amine phenols, etc. alone or in combination. It can be used as The developing solution generally contains a known preservative, an alkaline agent, a PH buffer, an anti-capri agent other than the anti-capri agent used in the present invention, and, if necessary, a silver halide solubilizer and a coloring agent. It may also contain preparations, development accelerators, surfactants, antifoaming agents, water softeners, hardeners, viscosity-imparting agents, and the like.

As the fixer, any of the commonly used compositions 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, X&! There are emulsions, infrared-sensitive emulsions, etc., and they may be high-speed negative emulsions or low-sensitivity positive emulsions, and 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 halide (silver chlorobromide, silver iodobromide, etc.).

The silver halide can be dispersed in common hydrophilic colloids such as gelatin, casein, polyvinyl alcohol, carboxymethylcellulose, etc., with gelatin being preferred.

Silver halide emulsions can also be chemically sensitized by ripening in the presence of small amounts of sulfur-containing compounds (e.g. aryl thiocyanate, allyl thiourea, sodium thiosulfate, etc.). .

The emulsion or reducing agent (for example, 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;
The sensitization can also be carried out with aminomethane sulfinic acid compounds, etc.) and small amounts of metals (eg, gold, platinum, palladium, iridium, ruthenium, rhodium, etc.).

Other additives, such as development accelerators, sensitizers, antioxidants,
Hardener, surfactant, brightener, color image-forming caglar, 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 anticapri agents of the present invention can be used in combination with other anticapri agents or anticapri breaker.

(E) Examples The present invention will be explained in more detail with reference to Examples below.

Example 1 A commonly used surfactant and a hardening agent were added to a chlorobromide photographic paper emulsion containing 1 mol of silver iodide, 47 mol of silver bromide, and 52 mol of silver chloride to form an emulsion of 6 mol.
Divided into sections.

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 94 x 10-3 mol per mol of silver halide saponide. All the emulsions were coated on a paper support coated with polyethylene to give a silver f1.5ν♀ to prepare a sample.

The sample was then subjected to wedge exposure, developed with a D-72 developer at 20° C. for 90 seconds, and subjected to sensitometry.

Sample iD-72 developer without additional exposure at 30℃5
After developing the film, the capri density was measured and the following results were obtained.

The following two types of compounds were used as comparative compounds.

Example 2 Sample 1 of Example 1 (photographic paper containing no anti-capri agent) was used, and the same procedure as in Example 1 was carried out using a developer containing D-72 developer with antifogging agent added at 2 x 10 = mono L/l. After processing, the following results were obtained.

Give a 10 second wedge exposure and heat at 30'C with PQ developer.
The film was developed for 60 seconds and sensitometry was performed.

The anti-capri agent is 52X10-3 per mole of silver halide.
They were added in molar proportions and the following results were obtained.

Example 3 After chemically sensitizing a cubic silver chloride emulsion with an average grain size of 0.3 μm, the following sensitizing dye ? per mole of silver halide, 5X1
0-' mol added, surfactant and 2,4-dichloro-
5 g of silver jk on a polyester film support by adding 6-hydroxy-1,3,5-triazine (Na salt)
/rr? It was applied as a sample and used as a sample.

(F) Effects of the Invention The anti-capri agent of the present invention has little desensitization and can effectively prevent capri. 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)

[Scope of Claims] 1. A processing method for developing a silver halide photographic light-sensitive material, which is characterized in that the processing is carried out in the presence of a 5-mercaptotetrazole 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 represent a hydrogen atom and an alkoxy group, respectively, and X is a divalent group containing an oxygen atom or a nitrogen atom. , forming a 15- or 21-membered ring)