JPH07111557B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and in particular, it contains a benzimidazole compound having a heterocyclic group at the 2-position and is stored over time. The present invention relates to a silver halide photographic light-sensitive material in which fogging is prevented.

(Prior Art) A photosensitive silver halide photographic light-sensitive material tends to generate fog due to generation of nuclei that induce development even if it is not exposed to light.
In particular, the occurrence of fog during storage with time often causes a decrease in sensitivity or deterioration of gradation.

Many compounds have been proposed in the past for the purpose of improving such a phenomenon, for example, 4-hydroxy-6-methyl-
1,3,3a, 7-tetraazaindene or 1-phenyl-
Heterocyclic compounds having a mercapto group such as 5-mercaptotetrazole are widely known.

(Problems to be Solved by the Invention) However, these compounds are not always sufficient in suppressing fog during storage of a light-sensitive material, and when used in a large amount in anticipation of an effect, sensitivity is lowered and gradation is softened. Will result.

Further, when a large amount of this type of stabilizer is used, the spectral sensitivity is reduced due to the desorption of the sensitizing dye, and further, as a result of diffusion into the adjacent photosensitive layer, a fatal defect such as an undesirable change is caused. May suffer.

Thus, there has been a strong demand for the development of an antifoggant capable of withstanding the long-term storage of silver halide photographic light-sensitive materials without adversely affecting other photographic performances.

(Object of the Invention) The present invention has been achieved in view of the above-mentioned circumstances, and the first object thereof is stable during storage of a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) with time. Another object of the present invention is to provide a light-sensitive material containing an antifoggant or stabilizer capable of maintaining photographic characteristics.

A second object of the present invention is to provide a light-sensitive material containing an antifoggant, which can obtain a fog-inhibiting property with less desensitization even when used in a large amount in a light-sensitive material, and which does not impair the spectral sensitivity. is there.

(Means for Solving the Problems) The above-mentioned object is achieved by a light-sensitive material containing at least one compound represented by the following general formula [I].

General formula [I] In the formula, R _{1 to} R _{4 each} independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a carboxyl group, a sulfo group, a carbamoyl group or a sulfamoyl group.

In the substituents R ₁ to R ₄ , R ₁ and R ₂ , R ₂ and R ₃ , and R ₃ and R ₄ may be linked to each other to form a 5- or 6-membered ring.
Q represents an atomic group necessary for forming a 5- or 6-membered ring.

Q includes, for example, an imidazole ring, a pyrazole ring, a triazole ring, a thiazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyrimidine ring, and a triazine ring, and these rings have a substitutable substituent (for example, R ₁ described above).
To a substituent represented by R ₄ ).

Next, specific examples of the compound used in the present invention will be listed.
The scope of the invention is not limited to these examples.

Regarding the synthetic method of the compound of the present invention, the general formula [II] is generally used.
It can be obtained by the reaction of the 2-chlorobenzimidazole compound represented by and the corresponding azole [III].

In addition, 2- (1-pyrazolyl) benzimidazoles can be easily synthesized by a reaction between 2-hydrazinobenzimidazole described in Belgian Patent No. 656,016 and 1,1,3,3-tetraalkoxypropane. it can.

The specific method for synthesizing the compound of the present invention will be described below.

Synthesis example 1 In a round bottom flask equipped with a stirrer and a thermometer, 2,5-dichlorobenzimidazole 3.7g (0.02mol) and imidazole
Add 3.4 g (0.05 mol) without solvent and add 13
The mixture was heated and melted at 0 to 140 ° C and reacted for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, to which 100 ml of water was added,
Add 100 ml of ethyl acetate to extract the desired product, and extract this extract.
After being washed twice with 0.5N hydrochloric acid water, further washed with water, and dried over anhydrous sodium sulfate, ethyl acetate was distilled off to obtain the desired product, 2- (imidazol-1-yl) -5-chlorobenzimidazole as a solid ( 4 g: 90% yield). When it was recrystallized from toluene, it showed mp. 238 to 240 ° C.

Synthesis example 2 To a round-bottomed flask equipped with a stirrer and a thermometer, 3.1 g (0.02 mol) of 2-chlorobenzimidazole and 3.5 g (0.05 mol) of 1,2,4-triazole were added without using a solvent, and this was added to 130- It was heated and melted at 140 ° C. and reacted for 1 hour. After cooling the reaction mixture to room temperature, 100 ml of water and ethyl acetate 1
The desired product was extracted by adding 00 ml, and the extract was washed twice with 0.5 N hydrochloric acid water, further washed with water, and dried over anhydrous sodium sulfate, and ethyl acetate was distilled off to obtain the desired product, 2- (1,2 , 4-
Triazo-1-yl) benzimidazole solid (3.0 g:
Yield 80%). It was recrystallized from toluene and had an mp of 210 to 211 ° C.

The compound of the present invention can be used in a layer containing or not containing silver halide, but it is preferably used in a ratio of 10 ^-5 mol to 10 ^-2 mol per mol of silver halide, particularly 10 ^-4 mol. It is preferably used in a ratio of mol to 10 ^-3 mol.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. For example, in the case of performing rapid processing or low replenishment processing of color paper, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the silver chloride content is 80 to 100. The case of mol% is particularly preferable. In addition, high sensitivity is required, and at the time of manufacturing,
When it is necessary to suppress fog during storage and / or processing to a particularly low level, a silver chlorobromide emulsion or a brominated grain emulsion containing silver bromide in an amount of 50 mol% or more (3 mol% or less of silver iodide May be contained), and more preferably 70 mol% or more. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photographing, and the silver iodide content is preferably 3 to 15%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more,
Emulsions which account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention can be obtained by Research Disclosure, Volume 170, No. 17643.
It can be prepared using the method described in Sections (I, II, III) (December 1978).

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure Volume 176, No. 17643 (December 1978) and Volume 187, N.
No. 18716 (November 1979), and the corresponding places are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Examples of the photographic light-sensitive material used include various color and black-and-white light-sensitive materials.

For example, a color negative film for photography (general use, movie etc.), a color reversal film (for slide, movie etc. and sometimes not containing a coupler), color photographic paper, color positive film (movie etc.), Color reversal printing paper, photothermographic material (for details, see US Pat.
626, JP-A-60-133449, JP-A-59-218443, JP-A-61-
No. 238056), color light-sensitive materials using the silver dye bleaching method, photographic light-sensitive materials for plate making (lith film, scanner film, etc.), X-ray photographic light-sensitive materials (direct / indirect medical,
(Industrial etc.), black and white negative film for photography, black and white photographic paper, micro photosensitive material (for COM, micro film etc.), color diffusion transfer photosensitive material (DTR), silver salt diffusion transfer photosensitive material, printout photosensitive material, etc. Can be mentioned.

When applied to color light-sensitive materials, various couplers can be used.

Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are Research Disclosure (RD) No. 17643 (1978).
December) VII-D and the patent cited in the same No. 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9 are used.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-55-10739, U.S. Pat.No. 4,401,752, No. 4,326,0
No. 24, Research Dice Closure No. 18053 (April 1979)
Mon), British Patent No. 1,425,020, West German Published Application No. 2,219,9
No. 17, No. 2,261,361, No. 2,329,587 and No. 2,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A No. 433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure No. 24220 (June 1984) and Research Disclosure No. 2
The pyrazolopyrazoles described in 4230 (June 1984) can be mentioned. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferable.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and 2,5-diacylamino-substituted phenol couplers described in JP-A-59-166956 and U.S. Patents. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, a phenol-type coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the 5-type coupler described in JP-A-61-179438.
Examples include amide-1-naphthol couplers.

The graininess can be improved by using a coupler in which the color forming dye has excessive diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the process of the latex dispersion method, the effect, specific examples of the latex for impregnation, U.S. Pat. No. 4,199,
363, West German Patent Application (OLS) Nos. 2,541,274 and
It is described in No. 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a rigid support such as a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or glass. . The support and the coating method are described in detail in Research Dice Closure, Volume 176, No. 17643, XV page (P.27), XVII section (P.28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

There is no particular limitation on the developing method of the silver halide photographic light-sensitive material, and for example, Research Disclosure, No. 17
Any of known methods and known processing solutions as described in Volume 6, pages 28 to 30 can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. Treatment temperatures are usually chosen between 18 ° C and 50 ° C, but may be below 18 ° C or above 50 ° C.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (for example, “Journal of the Society of
Motion Picture and Teleuision Engineers ", Vol. 61 (1953), pp. 667-701); developed with a developer containing a black-and-white developing agent to produce a negative silver image, and then at least once. Color reversal method in which a positive dye image is obtained by subjecting it to various exposures or other suitable fog treatments followed by color development; a photographic emulsion layer containing the dye is developed after exposure to form a silver image, which is used as a bleach catalyst For example, a silver dye bleaching method for bleaching a dye is used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 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
-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

LFA Mason Photographic Processing Chemist
ry (Focal Press, 1966), pages 226-229, US patent
Those described in 2,193,015, 2,592,364 and JP-A-48-64933 may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competing couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, ferricyanide, dichromate, iron (III)
Or an organic complex salt of cobalt (III) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixer, those 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 a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of tiers), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is shown in the Journal of the Society of Motion Picture and Television Engineers (Journal).
of the Society of Motion Picture and Television En
gineers) Vol. 64, pp. 248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2-6, particularly preferably 2-4.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p)
-Aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc.,
Further, if necessary, a solubilizing agent, a color toning agent, a development accelerator, a surfactant, a defoaming agent, a water softening agent, a film hardening agent, a viscosity imparting agent and the like may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under a low sulfite ion concentration. Is contagiously developed (details are described in Mason's "Photographic Processing Chemistry" (1966), pages 163-165).

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example-1 A silver iodobromide emulsion (average silver halide grain size 0.8 µm) containing 6 mol% of silver iodide was chemically ripened to the maximum sensitivity by a gold and sulfur sensitization method to obtain a highly sensitive silver iodobromide. An emulsion was obtained.

Then, the emulsion was divided into equal parts and the compound of the present invention and the comparative compound were added as shown in Table 1 below to prepare 1-oxy-
An appropriate amount of 3,5-dichloro-s-triazine sodium salt and saponin as a coating aid were added. Samples 1 to 11 were obtained by coating these emulsions on a polyester support which had already been subbed so as to have a dry film thickness of 5 µm and drying.

One set of the obtained samples was left at room temperature for 4 days, and the other two sets were left under high temperature and low humidity and high temperature and high humidity (Table 1) for 4 days, respectively, and then these three sets were optically analyzed by an ordinary method. Expose through a wedge, develop with Kodak D-72 developer for 4 minutes at 20 ° C,
After fixing, washing with water and drying, the photographic properties (sensitivity and fog) were measured by the usual methods, and the results shown in Table 1 were obtained.

The sensitivities in the table are expressed as relative sensitivities, using the logarithm of the exposure amount required to obtain an optical density of fog value +0.2, relative to the comparative sample being 100, and the fog value is the value obtained by subtracting the base density. .

As is clear from Table 1, the compound according to the present invention suppresses the generation of fog and has a smaller decrease in sensitivity than the comparative compound even when the compound is left under severe storage conditions.

The following compounds were used as comparative compounds in Table 1.

Comparative compound [A] Comparative compound [B] Comparative compound [C] Example-2 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the layer constitution shown in Table 2 was prepared.

The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer Yellow coupler (a) 19.1 g and color image stabilizer (b) 4.4
To g, 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g of Ag / Kg) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 5.0 × 10 ⁻⁴ mol. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted so that the composition shown in Table 2 was obtained to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion. Blue-sensitive emulsion layer (5.0 × 10 ^-4 mol added per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-4 mol added per mol of silver halide) Red-sensitive emulsion layer (1.0 × 10 ⁻⁴ mol added per mol of silver halide) For the red-sensitive emulsion layer, the following compounds were added to silver halide 1
2.6 × 10 ⁻³ mol was added per mol.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green sensitive emulsion layer Red-sensitive emulsion layer Structural formulas of compounds such as couplers used in this example are as follows.

After adding a sensitizing dye to each of the third and fifth layers, which are the silver halide emulsion layers, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added to 150 × 10 ^-4 mol per mol of silver halide and 1-phenyl-5-mercaptotetrazole was added to 1 mol of silver halide.
Stabilized by adding 1.5 × 10 ⁻⁴ mol per mol.

Before adding the yellow coupler (a) to the following first layer (blue-sensitive layer), the comparative compound and the compound of the present invention were added as shown in Table 2 below and then adjusted and coated.

The obtained multilayer color light-sensitive material was subjected to a high temperature and high humidity treatment for a storability test in the same manner as in Example 1, and then subjected to ordinary wedge exposure, and then subjected to the following color treatment. Processing process Temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Rinse 1 35 ℃ 20 seconds Rinse 2 35 ℃ 20 seconds Rinse 3 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Rinse 3 to rinse 1 tank It was washed with countercurrent water. The treatment liquids used are as follows.

Color developer Hydroxylamine 0.04 mol Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 0.2 g Potassium carbonate 30 g EDTA ・ 2Na 1 g Sodium chloride 1.5 g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl ] -p- phenylenediamine sulfate 5.0g brightener (4,4'-diaminostilbene type) was added to 3.0g water 1000 ml pH 10.05 bleach-fixing solution _{EDTAFe (III) NH 4 · 2H} 2 O 60g EDTA · 2Na・ 2H ₂ O 4g Ammonium thiosulfate (70%) 120ml Sodium sulfite 16g Glacial acetic acid 7g Water added 1000ml pH 5.5 Rinse solution Formalin (37%) 0.1ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 1.6 ml Bismuth chloride 0.35 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g EDTA / 4H ₂ O 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 50 mg 1000 ml after addition of water Table 3 shows the results of the storage test on the blue-sensitive layer. From these results, the compound according to the present invention does not deteriorate the photographic characteristics with the passage of time and has a less desensitizing effect on fog prevention. It can be seen that

(Effects of the Invention) As is apparent from the above examples, according to the present invention, a silver halide photographic light-sensitive material can be obtained which does not cause fog or decrease in sensitivity even under severe storage conditions. ,
A preferable photosensitive material can be provided.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [I]. In the formula, R _{1 to} R _{4 each} independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a carboxyl group, a sulfo group, a carbamoyl group or a sulfamoyl group.
In the substituents R ₁ to R ₄ , R ₁ and R ₂ , R ₂ and R ₃ , and R ₃ and R ₄ may be linked to each other to form a 5- or 6-membered ring.
Q represents an atomic group necessary for forming a 5- or 6-membered ring.