JPH0562323B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention can be used in photographic technology, particularly in manufacturing technology for photographic light-sensitive materials. The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material having a hydrophilic colloid layer colored with a novel light-absorbing dye and having improved residual color staining after processing. Prior Art In general, silver halide photographic materials (hereinafter referred to as "photosensitive materials") use light absorption filters,
It is well known that for the purpose of preventing halation, preventing irradiation, or adjusting the sensitivity of a photosensitive emulsion, dyes are incorporated into the constituent layers of photosensitive materials in order to absorb light of a specific wavelength. Coloring of hydrophilic colloid layers has been conventionally practiced. Among the constituent layers of the above-mentioned light-sensitive material, the filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and converts incident light reaching the emulsion layer into light having a preferable spectral composition. It plays the role of changing the Regarding the antihalation layer, in order to improve the sharpness of images, an antihalation layer is provided between the light-sensitive emulsion layer and the support, or on the back side of the support, so that the emulsion layer and the support are separated. It improves image sharpness by absorbing harmful reflected light from the interface and the back surface of the support. Furthermore, the sharpness of images is improved by coloring the photosensitive emulsion layer using a dye to absorb harmful reflected light and scattered light to silver halide grains, thereby preventing irradiation. It is also often done. Dyes used for such various purposes need to have good absorption spectrum characteristics depending on the purpose of use, but also to be completely decolorized during the development process and easily eluted from the photosensitive material during the development process. After processing, there is no residual color staining caused by dyes, and there are no other negative effects such as fogging or desensitization on photosensitive emulsions.
In addition, it must not diffuse from the colored layer to other layers, and it must also have excellent stability over time in photosensitive materials or aqueous solutions, and must meet various conditions such as not causing discoloration or fading. Must be. To date, numerous studies have been conducted with the aim of developing dyes that satisfy the above conditions.
For example, US Pat. No. 3,540,887, US Pat. No. 3,544,325, US Pat.
-3623, etc., benzylidene dyes were proposed, British Patent No. 506385 and Japanese Patent Publication No. 39-22069 proposed oxonol dyes, U.S. Patent No. 2493747 proposed merocyanine dyes, and U.S. Patent No. 1845404 proposed styryl dyes. Each is proposed. However, the present situation is that a dye that satisfies the above conditions has not yet been found. Purpose of the Invention Therefore, the purpose of the present invention is to have optimal absorption spectrum characteristics, completely decolorize during development processing,
Dyes that have extremely little residual color staining after processing, are prevented from spreading to other layers, and have excellent stability over time in light-sensitive emulsions or aqueous solutions, as well as silver halide photographic materials containing such dyes. Our goal is to provide the following. Structure of the Invention As a result of various studies, the present inventors have found that the above object can be achieved by a silver halide photographic material containing a compound represented by the following general formula (). General formula () In the formula, R ₁ represents a hydroxy group, an alkoxy group, an amino group or a ureido group, and R ₂ represents an aryl group having at least one sulfo group,
and Yes, X and Y
and may be combined with each other to form a 5- or 6-membered ring. Further, L represents a methine group, and n represents an integer of 1 or 2. The present invention will be explained in more detail below. In the present invention, the dye contained in the photosensitive material can be represented by the above general formula (). In the general formula (), examples of the alkoxy group represented by R ₁ include methoxy, ethoxy, butoxy, 2- Preferred examples of the methoxyethoxy, 2-hydroxyethoxy group and amino group include amino, methylamino, dimethylamino, ethylamino, diethylamino, and anilino, and examples of the ureido group include ureido, methylureido, and ethylureido. Next, the aryl group having at least one sulfo group represented by R ₂ is, for example, an alkyl group,
Hydroxy group, mercapto group, alkoxy group, alkylthio group, alkylsulfonyl group, arylthio group, arylsulfonyl group, carboxyl group, alkoxycarbonyl group, cyano group, nitro group, amino group, acylamino group, sulfonamido group, carbamoyl group and sulfamoyl group It is preferable that the substituent is substituted with a group selected from the following. The preferred aryl group having at least one sulfo group represented by R ₂ above is represented by the following general formula (). General formula () In the formula, M represents a hydrogen atom or a cation,
Z is an alkyl group (e.g. methyl group, ethyl group),
Hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), mercapto group, alkylthio group (e.g. methylthio group, ethylthio group), alkylsulfonyl group (e.g. methanesulfonyl group,
ethanesulfonyl group), arylthio group (e.g. phenylthio group, tolylthio group), arylsulfonyl group (e.g. benzenesulfonyl group, toluenesulfonyl group), carboxyl group, alkoxycarbonyl group (e.g. ethoxycarbonyl group, methoxycarbonyl group), cyano group, Nitro group, amino group (e.g. amino, methylamino, dimethylamino, anilino), acylamino group (e.g. acetylamino group, benzoylamino group), sulfonamide group (e.g. methanesulfonamide, benzenesulfonamide group), carbamoyl group, ( Examples include carbamoyl, methylcarbamoyl, phenylcarbamoyl), and sulfamoyl groups (eg, sulfamoyl, methylsulfamoyl, phenylsulfamoyl). u represents an integer from 1 to 3, and v represents an integer from 0 to 4. However, 1≦u+v≦5. Specific examples of the group represented by R ₂ above include 3-flufophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-methoxy-4-sulfophenyl group, and 2-hydroxy-4-sulfophenyl group. , 2,6-dimethyl-4-sulfophenyl group,
3-carboxy-2-hydroxy-5-flufophenyl group, 2,5-disulfophenyl group, 3,5
-disulfophenyl group, 3,6-disulfo-α-
Examples include naphthyl group, 8-hydroxy-3,6-disulfo-α-naphthyl group, 5-hydroxy-7-sulfo-β-naphthyl group, and 6,8-disulfo-β-naphthyl group. In the general formula (), the alkyl group represented by X and Y is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and the like. When this alkyl group has a substituent, examples of the substituent include those in which the sum of the values of hydrophobic substituent constants π is greater than −4.70. Examples of these substituted alkyl groups include cyano Alkyl, hydroxyalkyl, halogenoalkyl, carboxyalkyl, alkoxycarbonylalkyl,
(e.g. methoxycarbonylalkyl), acylalkyl (e.g. acetylalkyl), acyloxyalkyl (e.g. acetyloxyalkyl),
alkoxyalkyl (e.g. methoxyalkyl),
phenoxyalkyl, dialkylaminoalkyl (e.g. dimethylaminoalkyl), phenylaminoalkyl, acylaminoalkyl (e.g. acetylaminoalkyl), alkylsulfonylaminoalkyl (e.g. methylsulfonylaminoalkyl), alkylsulfonylalkyl (e.g. methylsulfonylalkyl) ), alkylthioalkyl (eg, methylthioalkyl), aminoalkyl (eg, methylaminoalkyl), aralkyl (eg, benzyl), and the like. Further, X and Y may be different from each other or may be the same. Furthermore, examples of the 5-membered ring or 6-membered ring formed by X and Y bonding to each other include a pyrrolidino group, a piperidino group, a morpholino group, and the like. In the present invention, the substituent of the alkyl group having the substituents represented by X and Y is the sum of the values of the hydrophobic substituent constant π, Σπ
is a substituent greater than -4.70, i.e. X and/or Y are -R-X' and/or -R-Y' (where R represents an alkylene group and each represents a substituent), the substituents X' and Y' are selected such that the sum of the hydrophobic substituent constants π of each of X' and Y', Σπ, is greater than -4.70. The value of this hydrophobic substituent constant π is described on the same page of the above-mentioned publication, and the substituent can be selected based on the description in this table. The methine group represented by L in the general formula () may be substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-butyl group) or an aryl group (eg, phenyl group). The dye according to the present invention represented by the general formula () can be synthesized by condensing an aldehyde compound represented by the following general formula () and a pyrazolone compound represented by the following general formula (). General formula () General formula () In the formula, R ₁ , R ₂ , X, Y and L each represent the same groups and numbers as in the above general formula (). p and q represent an integer of 1 or 2. However, since there is a relationship n=p+q-1 with n in the general formula (), p and q are never 2 at the same time. The above reaction is performed using a basic condensing agent, such as pyridine,
This is carried out by heating a mixture of the above general formulas () and () in the presence of piperidine, triethylamine, etc. The above reaction can be carried out in the presence or absence of the above basic condensing agent using methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane,
It can also be carried out in an inert solvent such as acetic acid or water. The aldehyde compound represented by the above general formula () can be produced by a known method. For example, an aldehyde compound with P=1 in the general formula () can be prepared by using dimethylformamide as a formylating agent and using the reaction of Vilsmeier and Hack (Berichte, Vol. 60, p. 119, 1927) to produce the corresponding substituted aniline. It can be made from. on the other hand,
The aldehyde with P=2 is prepared using N-methylanilinopropane(1)-al(3) and the appropriate aniline,
It can be produced in the same manner as the Vilsmeier reaction, as described in Berichte, Vol. 91, p. 850 (1958). Also Berichte, vol. 61, p. 2074 (1928)
It can also be obtained from the reaction of the corresponding substituted aminobenzaldehyde with paraldehyde as described in . Pyrazolone compounds of the general formula () where q=1 can be prepared by condensing various sulfoarylhydrazines with suitable substituted esters by known methods practiced in dye chemistry. The intermediate represented by q=2 in the general formula () can be obtained by condensation of the product represented by q=1 in the general formula () with a dialkyl ketone, an alkylaryl ketone or an aliphatic aldehyde. The pyrazolone compound represented by the general formula () can be prepared, for example, by the method described in Organic Syntheses, Vol. 28, p. 87 (1948), J.Am.Chem.Soc.
Volume 66, page 1849 (1944) Method described, J.Am.
Chem.Soc., Vol. 65, p. 52 (1943), J.Am.Chem.Soc., Vol. 64, p. 2136 (1942)
It can be obtained by using the method described in 2010). Typical specific examples of the dyes according to the present invention are described below. Next, a synthesis example will be shown and a detailed explanation will be given of the dye synthesis method according to the present invention. Synthesis Example 1 (Synthesis of Exemplary Dye (1)) In 40 ml of methanol, 3.06 g of 3-ethoxy-
1-(4-sulfophenyl)-2-pyrazoline-5
-on sodium salt and 1.57 g of 4-dimethylaminobenzaldehyde, plus 1.6 g of pyridine.
was added and reacted for 2 hours under heating under reflux. after that,
0.82g anhydrous sodium acetate dissolved in 10ml distilled water
was added and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected by filtration, thoroughly washed with methanol, and then dried to obtain 4.22 g of the above exemplary dye.
The λmax of the aqueous solution of this dye was 477 nm. Synthesis Example 2 (Synthesis of Exemplary Dye (7)) In 40 ml of methanol, 2.56 g of 3-hydroxy-1-(4-sulfophenyl)-2-pyrazoline-
5-one and 1.64 g of 4-dimethylaminobenzaldehyde were added, followed by 1.58 g of pyridine, and the mixture was reacted under heating under reflux for 2.5 hours. Then distilled water 10
1.64 g of anhydrous sodium acetate dissolved in 1 ml was added, and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected by filtration, thoroughly washed with methanol, and then dried to obtain 3.35 g of the above exemplary dye. The λmax of the aqueous solution of this dye was 488 nm. The dye according to the present invention produced as described above is
As shown by the general formula (), the pyrazolone ring has a hydroxy group, an alkoxy group, an amino group, or a ureido group as R ₁ at the 3-position, and 1
has at least one sulfo group as R ₂ in position,
Furthermore, the dye according to the present invention is characterized by having an aryl group which may have a substituent, and therefore the dye according to the present invention has better storage stability in an aqueous solution (acidic aqueous solution) than conventionally known dyes. In addition, the treatment bath has excellent decolorizing properties and very little residual color staining. Moreover, the dye according to the invention is
Since the substituted alkylamino group of the benzylidene group is substituted with a substituent having a hydrophobic substituent constant π value sufficient to prevent the dye diffusivity as described above, diffusion to other layers is small. Therefore, the decrease in sensitivity was also improved. In the light-sensitive material of the present invention, the oxonol dye represented by the above general formula can be contained in the silver halide emulsion and used as an anti-irradiation dye, or it can be contained in the non-photosensitive hydrophilic colloid layer. , filter dye or
It can also be used as an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. Incorporation of the dye according to the present invention into a silver halide emulsion layer or other hydrophilic colloid layer can be easily carried out by a conventional method. In general, a dye or an organic or inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. I can do it. The content of these dyes is
Although it varies depending on the purpose of use, it is generally applied in an amount of 1 to 800 mg per ^square meter of area on the photographic material. Supports in the photosensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate,
For example, there are polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin coated papers, polypropylene synthetic papers, glass plates, metals, etc. These supports are used depending on the intended use of the photosensitive material. , is selected as appropriate. Hydrophilic colloids in the photosensitive material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid;
Examples include synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose derivatives such as carboxymethyl cellulose, and these can be used alone or in combination. The silver halide emulsion in the light-sensitive material of the present invention may be any of the silver halide emulsions normally used for silver halide emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Includes: The silver halide emulsion used in the light-sensitive material of the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, the method described in Japanese Patent Publication No. 46-7772 or the method described in U.S. Pat. A method for producing a so-called compound emulsion, such as forming an emulsion of silver salt grains and then converting at least a portion of the grains into silver bromide salt or silver iodobromide salt, or fine grains having an average grain size of 0.1μ or less It can be produced by any production method such as the production method of Lippmann emulsion made of silver halide. This silver halide emulsion is
Chemical sensitizers, such as thiosulfates, allylthiocarbamide, thiourea, allyl isothiocyanate, sulfur sensitizers such as cystine, active or inactive selenium sensitizers, potassium chloroaurate, auricul trichloride , gold compounds such as potassium auricular thiocyanate, 2-aurothiabenzthiazole methyl chloride, palladium compounds such as ammonium chloroparadate, sodium chloropalladite, etc., platinum compounds such as potassium chloroplatinate,
Sensitization can be performed using noble metal sensitizers such as ruthenium compounds or combinations of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. In addition, a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be contained. The silver halide emulsion used in the light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. Sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Various dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, and streptocyanin dyes can be used, and one type of sensitizing dye or a combination of two or more types of each can be used. In the light-sensitive material of the present invention, glycerin, 1,5
- dihydroxyalkanes such as pentanediol,
It can contain wetting agents such as esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. aldehyde compound, N,
N-methylol compounds such as N'-dimethylol urea, mucohalogenic acid, divinylsulfonic acid, 2,
Active halogen compounds such as 4-dichloro-6-hydroxy-S-triazine, hardening agents such as dioxane derivatives, divinyl ketones, isocyanates, carbodiimides, saponins, polyalkylene glycols, polyalkylene glycol ethers,
Surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates, as well as photographic additives such as fluorescent brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers. It can be included. In the light-sensitive material of the present invention, the emulsion layer may contain a color coupler, and the coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for masking or a coupler that releases a development inhibitor. It's okay. As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenolic or naphthol-based compounds are usually advantageously used. Furthermore, the photosensitive material of the present invention can have any layer structure that can be used in conventional photosensitive materials. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 2.0×10 ^-5 mol/of exemplary dye (1) according to the present invention
0.5 ml of glacial acetic acid was added to 100 ml of the aqueous solution and stirred to prepare a solution for measuring decomposition rate (PH 2.8 to 2.9). Using a spectrophotometer, the decrease in absorbance at the maximum absorption wavelength of this solution was measured over time (every 10 minutes for 1 hour) to determine the initial decomposition rate. In the same way, exemplified dyes (8), (13), (19), and (21) and the following comparative dyes (A), (B), (C), (D), and (E) were also measured. Summer. The results obtained are shown in Table 1 below. Comparative dye (A) Comparative dye (B) Comparative dye (C) Comparative dye (D) Comparative dye (E)

[Table] As is clear from Table 1, the dyes according to the present invention, like comparative dyes (A) to (D), have three pyrazolone rings.
Compared to dyes having a group other than a hydroxy group, alkoxy group, amino group or ureido group in the position,
It can be seen that the stability in acidic aqueous solutions is significantly improved. In addition, when the 1st position of the pyrazolone ring is substituted with an alkyl group like comparative dye (E),
It was also understood that having an alkoxy group at the 3-position does not improve the storage stability as described above. Example 2 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
To this was added 5 ml of an aqueous solution containing 2.0 x 10 ^-4 mol each of exemplary dyes (6), (11) and (16) according to the present invention, and further 1.25 ml of a 10% saponin aqueous solution and 1.
% formalin solution was added, and water was added to bring the total volume to 50 ml. This dye solution was applied onto an acetyl cellulose film support and dried to obtain samples [1], [2], and [3]. Comparative samples [4] and [5] were also prepared in the same manner using the following comparative dyes (F) and (G) instead of the dye according to the present invention. Comparative dye (F) Comparative dye (G) Each of these samples was added to a developer with the following composition at 25°C.
After soaking for 20 minutes, washing with water for 20 seconds, and drying. (Composition of developer) Metol 3.0g Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 80.0g Potassium bromide 2.0g Add water to make 1. The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 2 below. Decolorization rate = E ₁ - E ₂ / E ₁ × 100 (%) (E ₁ is the absorbance before immersion in the developer, and E ₂ is the absorbance after immersion in the developer.)

[Table] As is clear from Table 2, it was found that the dyes according to the present invention exhibited superior decolorizing properties compared to the comparative dyes. In addition, in the samples containing the comparative dyes (F and G), the processing solution was slightly colored and contaminated by the eluted dye, but such coloring and staining was not observed at all with the dye according to the present invention. Example 3 A silver chloroiodobromide gelatin emulsion containing 80 mol % of silver chloride, 19.5 mol % of silver bromide and 0.5 mol % of silver iodide and having an average grain size of 0.32 μm was prepared. 2,4-dichloro-6-hydroxy-1, 2,4-dichloro-6-hydroxy-1,
3,5-triazine sodium salt (1% aqueous solution)
After adding 35 ml and 50 ml of saponin (10% aqueous solution), it was coated on a subbed-treated polyethylene terephthalate film support so that 50 mg of silver was contained per 100 cm ² and dried. Further, on this emulsion layer, a protective layer containing the exemplary dye (2) according to the present invention and having the following composition was applied to a dry film thickness of 2 μm.
It was applied so that the thickness was m. (Same as sample 6) (Protective layer composition) Gelatin 40g Water 850ml Exemplary dye (2) according to the present invention (2% aqueous solution)
100ml 2,4-dichloro-6-hydroxy-1,3,
5-triazine sodium salt (1% aqueous solution)
20ml Saponin (10% aqueous solution) 30ml Similarly, instead of the exemplary dye (2) according to the present invention, exemplary dyes (9) and (16) according to the present invention and the comparative dye (F) used in Example 2 and Create samples containing (G), respectively, and sample 7,
8, 9 and 10. Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using developer and fixer solutions having the following compositions. Development was carried out at 20°C for 15 minutes, fixing was carried out at 20°C for 2 minutes, water washing was carried out at 20°C for 5 minutes, and then dried. (Developer composition) Hydroquinone 15g Formaldehyde sodium bisulfite adduct
55g Anhydrous sodium sulfite 3g Sodium carbonate (monohydrate) 80g Boric acid 5g Potassium bromide 2.5g Disodium ethylenediaminetetraacetate 2g Add water to 1000ml (Fixer composition) Sodium thiosulfate 160g Anhydrous sodium sulfite 14g Glacial acetic acid 12ml Borax Add 12 g of potash alum and 5 g of water to 1000 ml. Ten sheets of each developed sample were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 3 below.

[Table] In the samples using comparative dyes, colored stains were observed in the samples, but with the dyes according to the present invention, there was no colored staining due to excellent run-off and decoloring properties. Example 4 A silver chlorobromide gelatin emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having grains having an average particle size of 0.3 μm was prepared. After adding 20 ml of formalin (1% aqueous solution) and 50 ml of saponin (10% aqueous solution) per 1 kg of this gelatin emulsion (containing 48 g of silver and 75 g of gelatin), it was coated on a subbed-treated polyethylene terephthalate film support, and then A protective layer having the following composition was coated on this emulsion layer. (Protective layer composition) Gelatin 40g Water 960ml Formalin (1% aqueous solution) 12ml Saponin (10% aqueous solution) 30ml Next, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye with the following composition was applied. The coating was applied so that the dry film thickness was 3 μm. (Sample 11
) (Gelatin layer composition) Gelatin 50g Water 835ml Exemplary dye (2) according to the present invention (2% aqueous solution)
100ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml Similarly, in place of the exemplary dye (2) according to the present invention, exemplary dye (28) according to the present invention and the following comparative dye [H] were added. Sample (12)
and (13). Comparative dye [H] Development was performed in the same manner as in Example 3, and 10 sheets of each sample were stacked one on top of the other to evaluate color staining. The results obtained are shown in Table 4 below.

[Table] As shown in the above table, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes according to the present invention. Furthermore, it has been found that the dye according to the present invention can provide a photographic material having an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on the photographic emulsion. Example 5 On a polyethylene terephthalate support, the first
A gelatin solution containing a dye and having the composition shown below was applied as a layer to a dry film thickness of 2 μm. (Gelatin liquid composition)

[Table] Next, a silver iodobromide gelatin emulsion consisting of 96 mol% silver bromide and 4 mol% silver iodide with an average grain size of 0.8 μm was added with 2,4-dichloro-6 per kg of gelatin emulsion. -20 ml of hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) and 20 ml of sodium dodecylbenzenesulfonate (1% aqueous solution) were added, and a second layer was applied so that the dry film thickness was 5 μm. . Furthermore, a gelatin solution having the composition shown below was coated as a protective layer on this emulsion layer to a dry film thickness of 2 μm to prepare sample (14). (Gelatin liquid composition) Gelatin 20g Water 940ml 2,4-dichloro-6-hydroxy-1,3,
5-triazidine sodium salt (1% aqueous solution)
10ml Sodium dodecylbenzenesulfonate (1%
Aqueous solution) 50ml In the same manner, instead of the exemplary dye (6) according to the present invention in the first layer, the exemplary dye (8) and (16)
Samples were prepared using the following comparative dyes (), (J) and (K). At the same time, a sample containing no dye was also prepared in the same manner. These samples were sequentially divided into samples (15), (16), (17), (18), and (19).
)
and (20). Comparative dye [I] Comparative dye [J] Comparative dye [K] Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using the developer and fixer used in Example 2 having the following composition. Development was carried out at 25°C for 2 minutes, fixation was carried out at 25°C for 2 minutes, water washing was carried out at 25°C for 5 minutes, and then dried. (Composition of developer) Phenidone 0.5g Anhydrous sodium sulfite 50g Hydroquinone 12g Anhydrous sodium carbonate 60g Potassium bromide 2g Benzotriazole 0.2g Add water to 1000ml After processing, perform sensitometry to determine the photographic characteristic curve, and determine the dye. The relative sensitivity was determined by setting the sensitivity of the sample (20) that did not contain the sample as 100. The results obtained are shown in Table 5.

[Table] Samples containing the dye according to the present invention show less decrease in sensitivity than samples containing the comparative dye, that is, the dye according to the present invention diffuses less from the mordanted layer to other layers. I understand. On the other hand, as in comparative dyes (I) to (K), the hydrophobic substituent constant π of the substituent of the substituted alkyl group of the substituted alkylaminobenzylidene group at the 4-position of the pyrazolone ring
The value of is smaller than -4.70 (Samples (I), (J)
and (K), it was found that when the π value of SO ^- ₃ is -4.76), the sensitivity of samples containing these is greatly reduced. Effects of the Invention In the photosensitive material containing the dye according to the present invention as represented by the general formula (), the storage stability of the dye in an acidic aqueous solution is significantly improved.
Moreover, since it has excellent run-off properties and decolorization properties in the processing bath, there is no risk of residual color contamination. Moreover, since diffusion from the mordanted layer is also prevented, a decrease in sensitivity does not occur.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing a compound represented by the following general formula (). General formula () [In the formula, R ₁ is a hydroxy group, an alkoxy group,
represents an amino group or a ureido group, R ₂ represents an aryl group having at least one sulfo group, X and Y each represent a hydrogen atom or an alkyl group, and when the alkyl group has a substituent, , is a substituent for which the sum of the values of hydrophobic substituent constant π of this substituent Σπ is larger than −4.70, and X
and Y may be combined with each other to form a 5-membered ring or a 6-membered ring. Further, L represents a methine group, and n represents an integer of 1 or 2. ) 2 The aryl group having at least one sulfo group represented by R ₂ above is an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylthio group,
Claims characterized in that the compound is substituted with a group selected from an arylsulfonyl group, a carboxyl group, an alkoxycarbonyl group, a cyano group, a nitro group, an amino group, an acylamino group, a sulfonamido group, a carbamoyl group, and a sulfamoyl group. A silver halide photographic material according to Scope 1.