JPH0548895B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material for obtaining a silver image, and more particularly to a silver halide photographic material that prevents deterioration of a silver image formed on a water-impermeable support over time. It is. In the field of silver halide photographic materials, silver images are more durable than so-called color images (dye images) and are therefore suitable for recording information that needs to be preserved for a long period of time. However, it has been found that such silver images also tend to deteriorate over time, and this tendency is particularly great when water-impermeable supports such as plastic films are used. Water-impermeable supports such as plastic films are
In general, it is stronger than water-permeable supports such as paper or cloth, so it is suitable for long-term storage, but on the other hand, it has the dilemma of increasing the tendency of silver images to deteriorate as described above. (Deterioration of silver images on such water-impermeable supports is described in Photographic Science and
Engineering magazine Vol. 7, pages 253-261 (1963)
and UK Patent (Publication) No. 2019024A). Regarding the prevention of such deterioration of silver images, a method using mercaptobenzimidazole compounds, mercaptotetrazaindene compounds, etc. is described in JP-A-57-14836. However, the compounds described in the above-mentioned publication had problems in that they significantly lowered the sensitivity and were unable to prevent significant blackening of images due to sub-exposure. Here, sub-exposure (post-exposure)
Darkening of images is caused by, for example, the filter fading in a dark room between image exposure and development (for example, when used for a long period of one year or more) due to safelight exposure. Then,
This is a phenomenon in which the entire photosensitive material appears dark after development, resulting in a decrease in the contrast of the image, and the overall appearance is poor. If such a phenomenon occurs, the value as a photographic material will be significantly reduced. It is an object of the present invention to prevent the deterioration of silver images over time that occurs when water-impermeable supports are used. Another object of the present invention is to provide a silver halide photographic material containing an antifoggant that causes less blackening of images due to sub-exposure. The above-mentioned object of the present invention is to provide a silver halide photographic material for obtaining a silver image having at least one silver halide emulsion layer on a water-impermeable support. This could be achieved by containing the compound represented by the formula (2) and the compound represented by the general formula (). General formula () In the formula, M represents a hydrogen atom, NH ₄ or an alkali metal, R represents a hydrogen atom, an alkyl group or an aryl group, and Z represents a group necessary to form a 5-membered heterocycle which may have a substituent. Represents an atomic group or an atomic group necessary to form a 5-membered heterocycle fused with a benzene ring. General formula () In the formula, X is a sulfur atom, an oxygen atom, a selenium atom,
N-R ₁₄ group (R ₁₄ represents an alkyl group, aralkyl group or aryl group) or -CH=CH- group, R ₁₁ and R ₁₂ are hydrogen atoms,
Represents an alkyl group, an aryl group, or an alkoxycarbonyl group, R ₁₁ and R ₁₂ may be bonded to each other to form a ring having 5 to 6 carbon atoms, and R ₁₃ represents an alkyl group, an aralkyl group, or an aryl group. represent The phenomenon of blackening of images due to sub-exposure of photographic light-sensitive materials containing the compound represented by the general formula () cannot be prevented simply by adding benzotriazoles and tetrazoles, which are generally well known, and on the contrary, it becomes even worse. However, by including the compound represented by the above-mentioned general formula (), it was possible to significantly suppress the above-mentioned image blackening phenomenon without impairing the stability of the image silver over time. . Next, general formula () will be explained in detail. The alkyl group represented by R preferably has 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, hexyl, octyl), and the aryl group preferably has 6 to 10 carbon atoms (for example, phenyl group, naphthyl group). Z is an atomic group necessary to form a 5-membered heterocycle which may have a substituent or 5 fused with a benzene ring
Represents a group of atoms necessary to form a member heterocycle.
The 5-membered heterocycle is preferably an imidazole ring, a triazole ring, a tetrazole ring, etc., and the substituent for the heterocycle is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a hexyl group, octyl group, etc.) and an aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group). The 5-membered heterocycle fused to the benzene ring is preferably a benzimidazole group. In the compound represented by the general formula (), at least one carbon atom in the formula must be bonded to a water-soluble group. Here, the water-soluble group is a group that can impart sufficient ability to make the compound water-soluble, and is preferably a carboxy group or a salt thereof, a carbamoyl group (-CONH ₂ ), a hydroxy group, a sulfo group, or a group thereof. It refers to a salt, an amino group ( _-NH2 ), or a lower alkoxy group (preferably one having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group). Among these, a carboxy group or a salt thereof, and a sulfo group or a salt thereof are particularly preferred. Among the compounds represented by the general formula (), the following general formula (a), general formula (b), or general formula (
Compounds represented by c) are preferred. General formula (a) In the formula, _R2 is an alkyl group substituted with the water-soluble group described above (preferably one having 1 to 8 carbon atoms) or an aryl group substituted with the water-soluble group described above (preferably one having 6 to 10 carbon atoms). represents. As the water-soluble group, a carboxy group or a salt thereof, a carbamoyl group, a hydroxy group, a sulfo group or a salt thereof, or an amino group are preferable, and a carboxy group or a salt thereof, a sulfo group or a salt thereof are particularly preferable. General formula (b) In the formula, R ₃ and R ₄ each represent a hydrogen atom, a halogen atom, or the above-mentioned water-soluble group. However, R ₃ and R ₄
At least one of them is a water-soluble group. Water-soluble groups include carboxy groups or salts thereof, carbamoyl groups, hydroxy groups, sulfo groups or salts thereof,
Examples include amino groups and lower alkoxy groups, and among these, carboxy groups or salts thereof, and sulfo groups or salts thereof are particularly preferred. General formula (c) In the formula, R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₇ represents a phenyl group having at least one carboxyl group, and M represents hydrogen Represents an atom, NH ₄ or an alkali metal (Na, K, etc.). The alkyl group represented by R ₅ or R ₆ may be substituted with a halogen atom (chlorine atom, bromine atom, etc.), an alkoxy group, a hydroxyl group, etc., such as a methyl group, an ethyl group, a methoxyethyl group, Examples include ethoxyethyl group, chloroethyl group, and benzyl group. The number of carbon atoms is preferably 1 to 14. The aryl group represented by R ₅ or R ₆ is a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group, an alkoxy group, an alkylsulfol group, an arylsulfonyl group, a sulfamoyl group, an alkylsulfonamide group, an arylsulfonamide group. , carbamoyl group, carbonamide group, etc. The number of carbon atoms is preferably 6 to 14. The heterocyclic group represented by R ₅ or R ₆ is
Substituted or unsubstituted ones containing at least one of 5- to 7-membered nitrogen atoms, oxygen atoms, and sulfur atoms are preferred. The number of carboxyl groups substituted with the phenyl group represented by R ₇ is preferably 1 to 2. The phenyl group represented by R ₇ may be further substituted with the following substituents. That is,
Halogen atoms (chlorine, bromine, etc.), alkyl groups (methyl, ethyl, etc.), alkoxy groups (methoxy, ethoxy, etc.), alkylsulfonyl groups, arylsulfonyl groups, sulfamoyl groups, alkylsulfonamide groups, aryl It may be substituted with a sulfonamide group, a carbamoyl group, a carbonamide group, etc. These substituents preferably have 14 or less carbon atoms. Among general formulas (a), (b), and (c), the compound represented by general formula (c) is particularly preferred. Preferred examples of the compounds of the present invention represented by the general formula () are shown below, but the scope of the present invention is not limited thereby. -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 −12 −13 −14 −15 −16 −17 −18 −19 −20 −21 −22 −23 −24 −25 −26 −27 −28 −29 These compounds represented by the general formula () are known, and for example, US Patent No. 2585388,
No. 2541924, Special Publication No. 21842 (1977), No. 21842 (No. 21842)
Publications No. 50169; British Patent No. 1275701;
DABerges et al, “Journal of Heterocyclic
Chemistry”, Vol. 15, p. 981 (1978); “The
“Chemistry of Heterocyclic Compounds”
Imidazole and Derivatives part ，336～
339 and Chemical Abstracts 58 , No. 7921 (1963), 384; E. Hoggarth, “Journal of
Chemical Society” 1949, pp. 1160-1167;
This can be easily achieved by the method described in, etc., and a method analogous thereto. The compound represented by the general formula () is added to the silver halide agent layer or a layer adjacent thereto. The addition period is preferably before the coating of each layer, but it is also possible to impregnate the coated layer with a solution of the compound after coating. The compound represented by the general formula () is preferably used in an amount of 1×10 ^-4 to 1×10 ^-2 per mole of coated silver.
The amount used is preferably 2×10 ⁻⁴ to 8×10 ⁻³ mol. Next, general formula () will be explained in detail. R ₁₁ and R ₁₂ in the general formula () may be the same or different, and may be a hydrogen atom, an unsubstituted or alkyl group having 1 to 6 carbon atoms substituted with a hydroxyl group, a halogen atom, etc., such as a methyl group, an ethyl group, Butyl group, hydroxyethyl group, 2-chloroethyl group, etc.; unsubstituted or alkyl group, hydroxyl group,
Aryl groups substituted with halogen atoms, such as phenyl groups, 4-methylphenyl groups, 4-hydroxyphenyl groups, 3-chlorophenyl groups, etc.; alkoxycarbonyl groups, such as ethoxycarbonyl groups; bonded to each other with 5 carbon atoms A group necessary to form an unsaturated ring of ~6, such as a trimethylene group, a tetramethylene group, etc.; or a group that is bonded to each other to form an unsubstituted or alkyl group (e.g., methyl group, ethyl group, etc.), an aryl group (e.g., phenyl group, etc.), alkoxyl group (e.g. methoxy group, ethoxy group, etc.),
Represents a group necessary to form a benzene ring substituted with a halogen atom (eg, chlorine atom, bromine atom, etc.). R ₁₃ and R ₁₄ may be the same or different, and are unsubstituted or alkyl groups having 1 to 10 carbon atoms substituted with hydroxyl group, alkoxy group, halogen atom, etc. (e.g. methyl group, ethyl group, 4- chlorobutyl group, methoxyethyl group, n-decyl group, etc.), unsubstituted or halogen atom, alkyl group,
Aralkyl groups substituted with alkoxy groups (e.g. benzyl group, phenethyl group, p-chlorobenzyl group, m-methylbenzyl group, p-methoxybenzyl group, etc.), unsubstituted or halogen atoms, alkyl groups, alkoxy groups, Aryl groups substituted with nitro groups, amino groups, acylamino groups, carboxyl groups, alkoxycarbonyl groups, etc. (e.g. phenyl groups, naphthyl groups, o-chlorophenyl groups, p-methylphenyl groups, p-methoxyphenyl groups, p-
nitrophenyl group, p-methoxycarbonylphenyl group, p-ethylaminophenyl group, m-acetylaminophenyl group, etc.), and X represents a sulfur atom, an oxygen atom, a selenium atom or N- _R14 . Preferred examples of the compounds of the present invention represented by the general formula () are shown below, but the scope of the present invention is not limited thereby. -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 −12 −13 −14 −15 −16 −17 −18 −19 -20 −21 −22 −23 −24 −25 −26 −27 −28 −29 The compound represented by the general formula () can be synthesized by a conventionally well-known method. For example, Japanese Patent Publication No. 48-34169, No. 49-23368
It is stated in the issue bulletin etc. The compound represented by the general formula () is added to the silver halide emulsion layer or a layer adjacent thereto. The addition period is preferably before the coating of each layer, but it is also possible to impregnate the coated layer with a solution of the compound after coating. The compound represented by the general formula () is preferably used in an amount of 1×10 ^-4 to 1×10 ^-2 per mole of coated silver.
The amount used is preferably 2×10 ⁻⁴ to 8×10 ⁻³ mol. Further, it is particularly preferable that the compound represented by the general formula () and the compound represented by the general formula () are contained in the same emulsion layer. In the present invention, a water-impermeable support refers to a support through which water does not permeate at all or only to a very small extent. Examples of such supports include transparent plastic films such as cellulose triacetate and polyethylene terephthalate, whitened plastic films prepared by coating these plastic films with a white pigment such as titanium white dispersed in a binder such as gelatin, or polyethylene. There are paper supports laminated on both sides with hydrophobic polymers. These supports used in the present invention may be subjected to surface activation treatments such as chemical treatment, electric discharge treatment, and ultraviolet treatment, as necessary, and may also be subjected to undercoating instead of or in addition to this surface activation treatment. A layer may also be applied. The silver halide in the silver halide photosensitive material used in the present invention is composed of silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver iodochlorobromide, and the silver halide grains are The average particle size is not particularly limited, but it is preferably not larger than 4μ. As the silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized. For chemical sensitization, please refer to the above-mentioned book by Glafkides or Zelikman et al. or Die Grundlagen der edited by H. Frieser.
Photographischen Prozesse mit
Silberhalogenden, (Akademische
Verlagsgesellschaft, 1968) can be used. That is, sulfur sensitization using compounds such as thiosulfates, thioureas, thiazoles, and rhodanines, and activated gelatin, and using stannous salts, amines, hydrazines, formamidine sulfinic acid, silane compounds, etc. It can be used alone or in combination with a reduction sensitization method, a noble metal sensitization method using complex salts of metals of the periodic table group such as platinum, iridium, palladium, etc. in addition to gold complex salts. In addition, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins,
It may also contain quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example US Patent 240532
No. 2423549, No. 2716062, No. 3617280,
Those described in No. 3772021, No. 3808003, etc. can be used. Although it is advantageous in the present invention to use gelatin as the binder or protective colloid in the photographic emulsion, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization). Various known surfactants may be included for various purposes. For example, saponins, glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers; triterpenoid saponins, alkyl carbons. acid salts, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N
- Anionic surfactants such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers;
Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine imides, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Note that in the present invention, no polyalkylene oxide-based surfactant is used. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving the degree of stability. For example alkyl(meth)acrylate, alkoxyalkyl(meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination;
Or these and acrylic acid, methacrylic acid,
A polymer containing a combination of α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol,
methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.),
Isoxazoles, dialdehyde starch, 2-
Chloro-6-hydroxytriazylated gelatin and the like can be used alone or in combination. The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include
Included are cyanine dyes, merocyanine dyes, complex cyan dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful pigments are those belonging to the merocyanine pigments and complex merocyanine pigments. It is a pigment belonging to these pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. The photosensitive material of the present invention includes water-soluble dyes (oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, etc.) used as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation. May contain. The silver halide photographic light-sensitive material of the present invention contains only the compound represented by the general formula () as a mercapto-based antifoggant; however, known antifoggants or stabilizers other than mercapto-based compounds may be used. may be used together. Antifoggants or stabilizers that can be used in combination include benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles,
Benztriazoles, nitrobenztriazoles, benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, azaindenes [e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,
3, 3a, 7) tetraazaindenes). Exposure to obtain a photographic image in the present invention may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, and the like. Exposure time is 1/1000 second to 1, which is normally used in cameras.
Of course, exposure times shorter than 1/1000 seconds can be used, such as exposure times of 1/10 ⁴ to 1/10 ⁶ seconds using xenon flash lamps or cathode ray tubes.
Exposures longer than 1 second can also be used. For the photographic processing of the light-sensitive material of the present invention, any known development processing method for forming a silver image can be used. A known treatment liquid can be used. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. Developers used in black-and-white photographic processing can include known developing agents.
Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-virazolidone), aminophenols (e.g. N-methyl-P-aminophenol), 1-phenyl-3-pyrazoline. Ascorbic acid, and heterocyclic compounds such as those described in US Pat. No. 4,067,872 in which a 1,2,3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, PH buffering agents, antifoggants, etc.
In addition, solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardening agents,
It may also contain a viscosity-imparting agent. The photosensitive material of the present invention usually contains 0.15 sulfite ions as a preservative.
Processed with a developer containing mol/or more. 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. Since the silver halide photographic light-sensitive material of the present invention uses a compound represented by the general formula () and a compound represented by the general formula (), even though a water-impermeable support is used. Regardless, the silver images formed through normal black-and-white photographic processing are highly stable and do not deteriorate over time, and there is significantly less blackening of the images during sub-exposure, and fog is sufficiently suppressed. Because it has advantages,
It has extremely high quality as a microfilm and black and white photographic paper. The present invention will be explained in more detail with reference to Examples below. Example 1 Grains were precipitated by a double jet method, physically ripened and desalted by a conventional method, and then added to an acidic silver chlorobromide emulsion (silver bromide 50 mol %) which was sulfur-sensitized.
- dichloro-6-hydroxy-1,3,5-triazine sodium salt (hardener) and sodium dodecylbenzene sulfonate (coating aid) are added, and then the compounds listed in Table 1 are added; Samples 1 to 14 were prepared by coating the coating solution onto a paper support laminated on both sides with polyethylene so that the amount of coated silver was 16 mg/dm ² . The photographic properties of each of these samples 1 to 14 were measured as described below. The results are shown in Table 1. (A) Measurement of fog characteristics After placing samples 1 to 14 in a dark box at 50℃ and 80%RH for 3 days, each sample was
DP-Papinal C developer (Fuji Photo Film Co., Ltd.)
After developing for 1 minute at 30°C, stopping, fixing, and washing with water, the fog density of each sample was measured. (B) Measurement of relative sensitivity Samples 1 to 14 were exposed to light through a continuous wedge using a sensitometer using a tungsten bulb, and then each sample was developed for 1 minute at 20°C using the same developer as in (A). Then, the relative sensitivity was measured after stopping, fixing, and washing with water. (C) Measurement of aging characteristics of silver images Samples 1 to 14 were exposed through a step wedge, developed using the same developer as in (A) for 24 seconds at 32°C using an automatic developing machine, fixed, washed with water, and dried. I went. Each treated sample was left in a cabinet in a nitrogen dioxide gas (3000 ppm) atmosphere for 20 minutes as described in UK Patent (Publication) No. 2019024A, and then left outdoors (under sunlight) for 2 days. After standing, the degree of deterioration of the silver image that occurred in the image area was observed and evaluated as follows. 〇: No deterioration of the silver image at all △: Some deterioration of the silver image (practical limit) ×: Significant deterioration of the silver image (D) Measurement of the degree of blackening of the image by sub-exposure Samples 1 to 14 After exposure through a continuous wedge with a sensitometer using a tungsten bulb, a normal Safelight Filter ND-2A (manufactured by Fuji Photo Film Co., Ltd.) or a faded (decreased color density) Safelight Filter ND was used. 20 minutes using the same developer as in (A) under a safelight with -2A.
It was developed for 3 minutes at ℃, fixed, washed with water, and the sensitivity was determined. At this time, the sensitivity was expressed as the exposure amount E when giving an optical density of 1.0, and the sensitivity difference ΔlogE when two types of filters were used was determined for each sample and is shown in Table 1.

[Table] Here, the following compounds were used as compounds a, b, c, and d. compound a compound b compound c compound d As shown in Table 1, the blackening of the image due to sub-exposure caused by the addition of the compound represented by the general formula () is reduced by the addition of the compound represented by the general formula (). Relative sensitivity can be significantly suppressed without significant loss,
Moreover, images with stable image silver after processing could be obtained (Samples Nos. 6-9, 11-13, 15-18, 20, 22
~23, 25-26, 28-30). On the other hand, Samples Nos. 3 to 5 using Compounds b to d exhibited even greater blackening of the image due to sub-exposure, and were therefore unsuitable for practical use as photographic materials. Example 2 A 2,4- dichloro-6-hydroxy-1,3,5
- add triazine sodium salt (hardener) and sodium dodecylbenzenesulfonate (coating aid), and also compound -9 at 2 x 10 ^-3 mol/mol Ag and compound -9 at 2 x 10 ^-3 mol/mol Ag. -1 was added thereto, and these coating solutions were then applied to the supporting specimens shown in Table 1 so that the amount of silver coated was 20 mg/dm ² to prepare samples. When the obtained sample was evaluated in the same manner as in Example 1, the stability of the image silver was good, and the blackening of the image due to sub-exposure could be significantly suppressed by the addition of Compound-1.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material for obtaining a silver image having at least one silver halide emulsion layer on a water-impermeable support, in the emulsion layer or its adjacent layer. A silver halide photographic material comprising a compound represented by the following general formula () and a compound represented by the general formula (). General formula () In the formula, M represents a hydrogen atom, NH ₄ or an alkali metal, R represents a hydrogen atom, an alkyl group or an aryl group, and Z represents a group necessary to form a 5-membered heterocycle which may have a substituent. Represents an atomic group or an atomic group necessary to form a 5-membered heterocycle fused with a benzene ring. General formula () In the formula, X is a sulfur atom, an oxygen atom, a selenium atom,
N-R ₁₄ group (R ₁₄ represents an alkyl group, aralkyl group or aryl group) or -CH=CH- group, R ₁₁ and R ₁₂ are hydrogen atoms,
Represents an alkyl group, an aryl group, or an alkoxycarbonyl group, R ₁₁ and R ₁₂ may be bonded to each other to form a ring having 5 to 6 carbon atoms, and R ₁₃ represents an alkyl group, an aralkyl group, or an aryl group. represent