JPH0563785B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material.
More specifically, the present invention relates to a silver halide photographic material having a rhodium-containing emulsion layer and a backing layer on the back surface. (Prior Art) It is known to dope silver halide emulsions with rhodium to increase their contrast. It is widely known as a technique for preparing silver halide emulsions because contrast can be increased by controlling the amount of doping within silver halide grains. However, the storage stability of this emulsion is poor, and there are disadvantages in that the emulsion becomes soft and fog increases when stored for a long time or under severe heat conditions. Techniques are known in which fog suppressants are added to emulsions in order to improve stability over time, but these techniques have various drawbacks in photographic performance and cannot be said to be sufficient techniques. In addition, as a technique for improving the stability over time of rhodium-doped silver halide grains,
A method of adding an iron-EDTA complex to No. 22409 is known. Contrast can be maintained during storage and the occurrence of fog can be suppressed, but if the above-mentioned silver halide photographic materials are left in an exposed state, the generated latent image is unstable, so there are problems with storage stability after exposure. However, it has the disadvantage that the photographic performance cannot be made constant. Furthermore, a method of adding a tetrazaindene compound as described in JP-A-54-103018 is known, but although this compound has an effect on storage stability, it is not sufficiently effective.
There is a method of suppressing this by adding a compound having a mercapto group, as in No. 127714, or by using it in combination with the above-mentioned tetrazaindene compound. However, this method has the disadvantage that it is difficult to obtain stable characteristics because fog is suppressed and at the same time a development suppressing effect occurs, and the developability changes greatly depending on the temperature and time of development or the degree of fatigue of the developer. Additionally, in order to improve stability over time, JP-A-52
A method is known in which a compound having a reductive monoxide reaction, such as that disclosed in Japanese Patent No. 11029, or a compound such as hydroquinone or resorcinol, is added to an emulsion. This method involves adding reducing substances or these oxidizing substances to the emulsion, and when added to the emulsion, a reduction-oxidation reaction occurs, resulting in a lack of stability of the emulsion coating solution, which is difficult for stable production. However, it also has the disadvantage of changing the developability of the emulsion. Similarly, methods of adding compounds such as British Patent No. 623,448 and US Pat. No. 2,675,314 are known, but both have the above-mentioned drawbacks and cannot obtain sufficient performance. Further, in JP-A-52-20822 and JP-A-52-21366, a compound having a 1-phenyl-5-pyrazolone ring is contained in the emulsion layer, which is effective in improving storage stability. However, on the other hand, apart from silver halide photographic materials that have the same light-sensitive silver halide emulsion layer on both sides, such as photographic materials for X-rays, silver halide photographic materials for printing plates, etc. Silver halide photographic materials, which have a non-photosensitive anti-halation layer on the back side, can be packaged for 10 to 100 sheets.
Layered in sheets, or several tens to several
It is packaged in rolls 100 meters long, and sometimes shipped in bulk rolls several thousand meters long. In such cases, the emulsion side and back side are stored in contact with each other for a long time under pressure, which has the disadvantage that transfer from the back side occurs and the photographic performance of the emulsion side changes. . In particular, when several types of antihalation dyes are used, photographic properties tend to deteriorate under packaging as described above, so it is preferable to use a mixture of several types of dyes to improve antihalation effects, decolorization properties during processing, and color staining. The means are suppressed. (Objective of the Invention) Therefore, the object of the present invention is to provide a silver halide that is stable for long periods of storage, is stable even under severe storage conditions, has excellent process stability, and has good developability. Our objective is to provide photographic materials. Another object of the present invention is to provide a silver halide photographic material that exhibits good decolorization properties after processing and has little residual color. Furthermore, it is an object of the present invention to provide a stable photosensitive material that is less susceptible to changes in conditions due to development temperature and processing time. (Structure of the Invention) The silver halide photographic light-sensitive material of the present invention has at least one emulsion layer containing a photosensitive silver halide containing 60 mol% or more of silver chloride and a hydrophilic colloid on one surface of a support. and containing rhodium in the silver halide grains, the silver halide photographic material has at least one non-photosensitive hydrophilic colloid layer on the other surface of the support, and the hydrophilic colloid The layer is characterized by containing a dye having an acidic group represented by the following general formulas []-(a), []-(b) and []-(c) and a polyhydroxybenzene compound. be done. The acidic group referred to in the present invention refers to acidic groups such as sulfonic acid and carboxylic acid, or their sodium, potassium, and ammonium salts, but preferably sulfonic acid groups or their sodium, potassium, and
It is an ammonium salt. The amount of the acidic group-containing dye used in the present invention varies depending on the type of silver halide photographic material and the purpose of use, but it is preferably 1 to 30 parts by weight per 100 parts by weight of the generally used hydrophilic colloid. The acidic group-containing dye of the present invention may be dissolved in alcohol such as methanol or ethanol in addition to water and added to a hydrophilic colloid layer such as gelatin, or it may be solidified directly into a hydrophilic colloid solution. It may be added as is and then dispersed and dissolved. Alternatively, it may be added as a solution dissolved together with a coating aid. The dyes having acidic groups according to the present invention are represented by the following general formulas []-(a), []-(b) and []-(c). General formula []-(a) In the formula, R ₁ is −OX or

[Formula] X and Y are hydrogen atoms, alkyl groups, cyanoalkyl groups, carboxyalkyl groups, sulfoalkyl groups, hydroxyalkyl groups,
It represents a halogenated alkyl group or an optionally substituted alkyl group, and R ₂ and R ₃ represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the above-mentioned -OX group. Q represents a phenyl group substituted with at least one halogen atom, carboxy group, sulfo group, or sulfoalkyl group, or a sulfoalkyl, sulfoalkoxyalkyl, or sulfoalkylthioalkyl group, and L may be substituted. Represents a methine group. R ₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group, or an acyl-substituted or unsubstituted amino group;
At least one of R ₁ , R ₂ , R ₃ and R ₄ contains a sulfonic acid group or a carboxylic acid group. m is an integer 0, 1
or 2, and n represents an integer 0 or 1, respectively. General formula []-(b) In the formula, R ₅ , R ₆ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms,
represents a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group, R ₇ represents an alkyl group or a carboxyl group, R ₅ , R ₆ ,
At least one of R ₇ , R ₈ , R ₉ and R ₁₀ contains a sulfonic acid group or a carboxylic acid group. General formula []-(c) In the formula, R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R ₁₃ and R ₁₄ represent an alkyl group or a sulfonic acid group substituted with a sulfonic acid group or a carboxyl group, or It represents an aryl group substituted with a carboxyl group or a sulfonic acid group, and L represents a substituted or unsubstituted methine chain. M represents sodium, potassium or hydrogen atom; m represents 0 or 1; Next, typical examples of the dyes according to the present invention will be shown, but the present invention is not limited thereto.

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[Table] The polyhydroxybenzene compounds related to the present invention are compounds based on a structure having at least two hydroxyl groups on the benzene ring, and the portions other than the hydroxyl group are substituted with other arbitrary substituents, such as halogen atoms. , an alkyl group, a substituted alkyl group, an alkoxy group, a sulfonic acid group, a carboxy group, or the like. The amount of the polyhydroxybenzene compound used in the present invention varies depending on the type of silver halide photographic material and the purpose of use, but it is preferably from 0.1 to 30 parts by weight per 100 parts by weight of the generally used hydrophilic colloid. These compounds may be added in the same manner as for dyes having acidic groups. In addition, when it is composed of two or more non-photosensitive layers, a polyhydroxybenzene-based compound may be added to the hydrophilic colloid layer adjacent to the hydrophilic colloid layer containing a dye having an acidic group. It may be added to the colloid layer. Next, typical examples will be given, but the present invention is not limited thereto.

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[Table] Silver halide emulsions containing 60 mol% or more of silver chloride, such as silver chlorobromide, silver chloroiodobromide, and silver chloride, are used as the silver halochlorides related to the present invention. Silver halide has an average grain size of 0.05~
1.5μ preferably 0.1~0.8μ, more preferably 0.15~
0.5μ, at least 75% of the total particle number preferably 80
% or more of the most preferred average particle size of 0.6
Silver chlorobromide or silver chloride containing at least 90 mol % silver chloride containing silver halide grains having a grain size of ~1.4 times, preferably 0.7 to 1.3 times, and preferably having the above grain size and grain size distribution conditions. Silver chloroiodobromide is used. The silver halide having the above-mentioned average grain size and grain size distribution used in the present invention can be obtained by any known method, such as U.S. Pat.
No. 3317322, No. 2222264, No. 3320069,
No. 3206313, or “J.Phot.Sci.” No.
Volume 12, No. 5 (September and October issues), 1964, 242-251
It can be prepared by the method described on page etc. It is also possible to use a mixture of silver halides prepared by methods different from these methods. According to a preferred embodiment of the invention, the silver halide according to the invention is 0.1 to 0.8μ, more preferably
Silver chloroiodobromide or silver chlorobromide has an average grain size of 0.25 to 0.5μ, and 80% or more of all grains have a grain size of 0.7 to 1.3 times the average grain size. In either case, silver chloride should be contained in an amount of 90 mol % or more, preferably 95 mol % or more. When the silver chloride content is less than 90 mol %, the sensitivity becomes high, the tone becomes soft, and the density decreases, making it impossible to achieve the object of the present invention. Examples of water-soluble rhodium salts used in the present invention include rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferably a complex compound of rhodium trichloride and a halogen. Addition amount is per mole of silver halide
The amount is 10 ^-3 to 10 ^-5 mol, more preferably 10 ^-3 to 10 ^-4 mol. The silver halide emulsion used in the present invention can be sensitized with various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.) , reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate , various noble metal sensitizers represented by sodium chloroparadite, etc. can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat.
No. 1189380, West German Publication No. 2058626, West German Publication No.
No. 2118411, Special Publication No. 43-4133, U.S. Patent No. 3342596
No., Special Publication No. 47-4417, West German Application Publication No. 2149789
Compounds described in Japanese Patent Publication No. 39-2825 and Japanese Patent Publication No. 49-13566, preferably for example 5,
6-trimethylene-7-hydroxy-s-triazolo(1,5-a)pyrimidine, 5,6-tetramethylene-7-hydroxy-s-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy -s-triazolo(1,5-a)pyrimidine, 7-hydroxy-s-triazolo(1,5-a)
-a) Pyrimidine, 5-methyl-6-bromo-7
-Hydroxy-s-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1
-Phenyl-5-mercaptotetrazole, 2-
It can be stabilized using mercaptobenzthiazole), benztriazoles (5-bromobenztriazole, 4-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), and the like. In addition, the silver halide emulsion used in the present invention includes, for example,
A latent image stabilizer such as a sulfur-containing amino acid compound described in 2217153, 2217895, etc. can also be used. The hydrophilic colloid used in the present invention is gelatin, but examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide,
Polyvinyl alcohol, hydrolyzed polyvinyl acetate, e.g. British Patent No. 523661, West German Publication No. 2255711, German Publication No. 2046682, U.S. Pat.
Water-soluble polymers such as those described in US Pat. No. 3,341,332, gelatin derivatives, such as US Pat.
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in US Patent No. 2525753, etc., or US Patent No. 2548520,
Examples include gelatin graft polymerized with polymerizable monomers having ethylene groups, such as styrene acrylate, acrylic ester, and methacrylic ester, as described in No. 2831767, etc., and these hydrophilic The colloids can also be applied to hydrophilic colloid layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, etc. The light-sensitive material of the present invention is coated on a suitable photographic support, and the support used in the present invention includes:
Typical examples include Paraita paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. Each of these supports is appropriately selected depending on the intended use of the photosensitive material. The light-sensitive material of the present invention is typically formed by coating on a support at least one hydrophilic colloid layer containing the silver halide of the present invention. A protective layer having a suitable thickness, preferably 0.1 to 10μ, particularly preferably
Preferably, a protective gelatin layer of 0.8 to 2 μm is applied. In the hydrophilic colloid layer including the emulsion layer used in the present invention, various photographic additives such as hardeners, surfactants, image stabilizers, ultraviolet absorbers,
Anti-staining agents, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc., can be used without impairing the effects of the present invention. Can be used within the range. For example, as a thickener or plasticizer, U.S. Pat.
No. 15462, Belgian Patent No. 762833, US Patent
3767410, Belgian Patent No. 558143, etc., such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone,
Various hardeners such as isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, and acyloyl-based hardeners can be used in the hydrophilic colloid layer including the emulsion layer of the light-sensitive material used in the present invention. Examples of the developer that can be included in the developer used for developing the photosensitive material of the present invention include the following. Typical HO-(CH=CH) _o -OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5
-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4 -Phenyl-
Catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4(2'-hydroxybenzoyl)pyrogallol, sodium ascorbate and the like. HO-(CH=CH) _o -NH Typical ortho- and para-aminophenols or aminopyrazolones are typical _2- type developers, including 4-aminophenol, 2-amino-6-phenylphenol, and 2-aminophenol.
amino-4-chloro-6-phenylphenol,
4-Amino-2-phenylphenol, 3,4-
Diaminophenol, 3-methyl-4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-amino Phenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc. Examples of the HN-(C=C)-NH developer include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, and N-(4-amino-diethylaniline). 3-methylphenyl)-
Morpholine, p-phenylenediamine, 4-amino-N,N-dimethyl-3-hydroxyaniline, N,N,N',N'-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N-
(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β-methoxyethyl)-3-methyl -aniline, 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)-aniline,
4-Amino-N-butyl-N-γ-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl, 1,2,3,4-
Tetrahydroquinoline etc. Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone (phenidone), 1-phenyl-4-amino-5-pyrazolone, 1-(p
-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5
-pyrazolone, 4,4'-dimethyl-1-phenyl-pyrazolidone (dimezone), 5-aminouracil, etc. Other books include The Theory of the Photographic Process, 4th edition, by TH James.
Fourth Edition, pp. 291-334 and Journal of the American Chemical Society.
73, p. 3100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, and it is preferable to use hydroquinone in an amount of 5 to 50 g/, and phenidone or dimezone in an amount of 0.05 to 5 g/. Further, even if a sulfite such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developer used in the present invention, the effect of the present invention is not impaired, which is one of the features of the present invention. It can be mentioned as. Suitable sulfite concentration is 0.06 to 1 gram ion/g. Furthermore, hydroxylamine or hydrazide compounds may be used as a preservative. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as brompotali, metal ion promoters such as ethylenediaminetetraacetic acid, methanol, ethanol, etc. , benzyl alcohol, development accelerator such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponin, surfactant such as saccharide or alkyl ester of the above compound, hardening agent such as glutaraldehyde, formalin, glyoxal, sulfuric acid. It is optional to add an ionic strength adjusting agent such as sodium.
Although the PH value can be set arbitrarily between 9 and 12, it is preferably used within the range of PH 10 to 11 from the viewpoint of durability and photographic properties. The developer may optionally contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, etc., and triethanolamine is preferred. The preferred amount of these alkanolamines used is 20 to 500 g per developer, particularly preferably 60 to 300 g per developer. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, etc.
Diethylene glycol is preferred. The preferred amount of these glycols used is 20 to 500 g per developer, especially 60 g per developer.
~300g is preferred. The above alkanolamines and glycols may be used alone or in combination of two or more. Preferred compounds used in the image forming method of the present invention are 5-nitroindazole, 6-nitroindazole, and
These include nitroindazole, 5-methylbenzotriazole, 6-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole, and the like. The preferred amount of these development inhibitors used is 10 ^-1 to ^{10 -5} mol per developer,
Particularly preferred is 10 ^-2 to 10 ^-4 mol per developer. Further, it is preferable that the above-mentioned development inhibitor is dissolved in alkanolamine and glycol before being added to the developer. The photosensitive material of the present invention can be processed under various conditions. Regarding the processing temperature, for example, the development temperature is preferably 50°C or less, particularly preferably around 30°C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which gives good results. There are many. In addition, it is optional to adopt processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, steps such as pre-hardening and neutralization.
These can also be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development. (Example) Hereinafter, the present invention will be described in more detail with reference to Examples. The technical scope of the present invention is not limited in any way by the following examples, and various embodiments are possible. Example 1 To an aqueous solution obtained by dissolving 70 g of gelatin and 4 g of saponin in 700 c.c. of water, a 0.15% aqueous solution of the dye having an acidic group listed in the following Table 1 was added.
300 c.c., and further added 2 copolymers of butyl acrylate and vinyl acetate as a binder property improver.
g, 0.3g of styrene-maleic acid copolymer was added as a thickener and the pH was adjusted to a viscosity of 10 centipoise.
The total amount was adjusted to 5.3 with citric acid, and water was added to adjust the total amount to 1.75 (A
liquid). Separately, 60g of gelatin in 600c.c. of water and 2g of polymethyl methacrylate with an average particle size of 3μ as a matting agent.
A solution prepared by adding 0.5 g of di-ethylhexyl sulfosuccinate sodium salt as a spreading agent, and further adding an ethyleneimine hardener (methine chain 6), mucochloric acid, and glyoxal as a hardening agent (liquid B) 1 I got it. Multilayer coating was carried out on a subbed polyethylene terephthalate support so that the B solution was simultaneously superimposed on the A solution. The amount of gelatin applied is 2g/layer containing the pigment.
m ² , and the protective layer was coated at 1 g/m ² . Furthermore, a solution having the same composition as Solution A was separately prepared, and 10 g of the polyhydroxybenzene compound listed in Table 1 below was added thereto and applied. These two types of colloidal solutions were coated on polyethylene terephthalate and dried to obtain a non-photosensitive hydrophilic colloid layer.The back surface on the opposite side contained 80 mol% of silver chloride and 0.3 mol% of silver iodide. silver 1
After grain formation, cubic silver chloroiodobromide doped with 2×10 ^-7 mol of rhodium atoms and having an average grain size of 0.23 μm was washed with demineralized water, then subjected to conventional sulfur-gold sensitization, and 2-methyl was added as a stabilizer. -4-hydroxy-
An emulsion with a pH of 5.5 was prepared by adding 1,3,3a,7-tetraazaindene, styrene maleic acid as a thickener, and the following compound as a sensitizing dye. For emulsion coating, a gelatin protective film containing silica with an average particle size of 4.3 μm and a viscosity of 7 centipoise and a pH of 6.0 was separately prepared, coated on the emulsion layer simultaneously, and dried. During coating, formalin was added as a hardening agent to the emulsion layer, and an ethyleneimine (methine chain 6) hardening agent was added to the protective film. The above two types of samples were measured at a temperature of 23°C + 2°C and a humidity of 55%.
After being exposed to a +5% atmosphere for 24 hours, it was cut into piece-sized pieces, stacked into 100 pieces, and sealed in a film packaging bag. This sample was left in a heating box at 50° C. for 4 weeks, and was used as a thermal variable test sample. A sample was taken out from the center of the heavy sample using a developing solution with the following formulation, developed at 40°C for 20 seconds, fixed, washed with water, and dried. sensitizing dye Developer potassium sulfite 50% solution 100g Dimaison 0.3g Hydroquinone 15g Potassium carbonate 30g Potassium bromide 3g 1-phenyl-5-mercaptotetrazole
0.06g 5-Nitroindazole 0.06g Diethylene glycol 100g Add water to make 1 Silver halide composition The presence or absence of rhodium pigments and the presence or absence of polyhydroxybenzene compounds are shown in the table below.
A sample prepared with the following contents was added. The amount added is 2 x 10 ^-7 mol/1 mol silver for rhodium, and 0.45 each for pigments.
10g of the polyhydroxybenzene compound was added to each solution of composition A.

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[Table] Regarding the residual color of the sample, five developed samples with unexposed areas were piled up and a grade was set, with 5 representing virtually no residual color and 1 representing residual color that was not practical. However, the contrast is a gamma value between density 0.2 and 1.5. Processing stability showed a change in sensitivity based on the difference in the logarithm of the exposure amount at a density of 3.0 when processed at processing temperatures of 35 and 45. The results obtained are shown in the table below.

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[Table] (Note) * Sample of the present invention As is clear from Table 2, the sample of the present invention has high contrast and low fog, regardless of the presence or absence of diameter, and has excellent processing stability and residual color. Excellent in sex. It is natural that the residual color of Comparative Samples 1 and 9 is grade 5 because the pigment that should remain is not contained. Example 2 A hydrophilic colloid layer on the back side was coated in multiple layers in the same manner as in Example 1, but the protective layer on the back side was coated in multiple layers with and without hydroquinone at 10 wt% of gelatin. A core containing 80 mol% of silver chloride with an average grain size of 0.25μ was on the front side of these two types of samples.
Shell-shaped particles were prepared. The silver halide composition of the core part contains 60 mol% of silver bromide, and the shell part contains 4 x 10 ^-7 mol of rhodium/1 mol of silver and 2 mol% of silver bromide.
Silver chlorobromide containing mol % was prepared by simultaneous mixing method. After physical ripening of these particles, the surface is reduced to 0.3 mol%.
It was coated with silver iodide using the iodine coating method.
The obtained silver chloriodide was demineralized, washed with water, and then treated with ordinary sulfur.
Gold sensitization was carried out, 4-hydroxy-6-methyl-1,3,3a,7tetraazaindene was added as a stabilizer, and a compound with the following structure was further added as a sensitizing dye, but the other procedures were the same as in Example 1. It was created and developed. sensitizing dye Sample No. 21 did not contain hydroquinone in the protective layer on the back side, and Sample No. 22 contained it. Display the results -
Shown in 3.

[Table] (Effects of the Invention) According to the present invention, a silver halide photographic material can be obtained which exhibits stability over time in terms of contrast and fog, as well as excellent processing stability and color retention.

Claims (1)

[Scope of Claims] 1. Silver halide grains having on one surface of a support at least one emulsion layer containing a photosensitive silver halochloride containing 60 mol% or more of silver chloride and a hydrophilic colloid. A silver halide photographic light-sensitive material containing rhodium has at least one non-photosensitive hydrophilic colloid layer on the other side of the support, and polyhydroxybenzene is contained in the hydrophilic colloid layer. 1. A silver halide photographic light-sensitive material characterized by containing a dye represented by the following general formulas []-(a), []-(b) and []-(c). General formula []-(a) In the formula, R ₁ is -OX or an atomic group represented by [Formula], and X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group,
It represents a halogenated alkyl group or an optionally substituted alkyl group, and R ₂ and R ₃ represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the above-mentioned -OX group. Q represents a phenyl group substituted with at least one halogen atom, carboxy group, sulfo group, or sulfoalkyl group, or a sulfoalkyl, sulfoalkoxyalkyl, or sulfoalkylthioalkyl group, and L may be substituted. Represents a methine group. R ₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group, or an acyl-substituted or unsubstituted amino group;
At least one of R ₁ , R ₂ , R ₃ and R ₄ contains a sulfonic acid group or a carboxylic acid group. m is an integer 0, 1
or 2, and n represents an integer 0 or 1, respectively. General formula []-(b) In the formula, R ₅ , R ₆ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms,
represents a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group, R ₇ represents an alkyl group or a carboxyl group, R ₅ , R ₆ ,
At least one of R ₇ , R ₈ , R ₉ and R ₁₀ contains a sulfonic acid group or a carboxylic acid group. General formula []-(c) In the formula, R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R ₁₃ and R ₁₄ represent an alkyl group or a sulfonic acid group substituted with a sulfonic acid group or a carboxyl group, or It represents an aryl group substituted with a carboxyl group or a sulfonic acid group, and L represents a substituted or unsubstituted methine chain. M represents sodium, potassium or hydrogen atom; m represents 0 or 1;