JP2709653B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which can be handled in an environment which can be called a bright room. .

[0002]

2. Description of the Related Art In the field of print duplication, there is a demand for an improvement in the work efficiency of a photomechanical process in order to cope with the variety and complexity of printed matter. In particular, in the plate collection and reversing processes, work efficiency has been improved by working in a brighter environment.Therefore, handling in an environment that can be substantially called a bright room has been attempted. Development of a silver halide photographic light-sensitive material for plate making and development of an exposure printer have been promoted. The silver halide photographic light-sensitive material for a bright room described in this patent is defined as 4
It is a photographic material in which light having a wavelength of 00 nm or more can be used as safelight light. The silver halide photographic light-sensitive material for bright rooms used in the plate collection and reversing processes is composed of a developed film on which characters or halftone images are formed as a document, and a silver halide photographic light-sensitive material for reversal. This is a photosensitive material used to perform negative image / positive image conversion or positive image / negative image conversion by contact exposure. Halftone images and line drawings, and character images are each used for their halftone dot area and line width, It has the ability to convert negative / positive images according to the width of the character image. It is required to have the ability to adjust the tone of halftone images and the line width of characters and line images. Silver halide photographic light-sensitive materials have been provided. However, in the tone adjustment of a halftone dot image in a light room reversing process using a silver halide photographic light-sensitive material for a light room, if underexposure occurs, the image is developed entirely over the entire surface, and the density of the portion to be blackened is liable to be significantly reduced. Had the drawback.

As a method for achieving a high contrast and an increase in Dmax, a method in which a developing agent is contained in a silver halide photographic light-sensitive material is disclosed in US Pat. No. 4,617,258,
Nos. 9-171947, 59-206828, and JP-A-1-262533, but they do not satisfy all of safelight, storage stability with time, and Dmax performance. In addition, a method in which an impurity (heavy metal) is contained in a silver halide crystal is disclosed in EP 3364.
Nos. 27 and 336689, the storage stability is poor and fogging occurs, and the Dmax performance cannot be stably maintained.

[0004]

Accordingly, an object of the present invention is to provide an excellent silver halide photographic light-sensitive material for a bright room which can be handled in a bright room environment, and which is excellent in that the density is reduced stably during underexposure. An object of the present invention is to provide a silver halide photographic light-sensitive material which gives reversal performance.

[0005]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein each emulsion layer has at least 1.times. A silver halide emulsion containing ^10-6 moles of a nitrosyl or thionitrosyl ligand and a compound containing a transition metal selected from the elements of Groups 5 to 10 of the periodic table; ] ~
This has been attained by a silver halide photographic material characterized by containing the compound (C). General formula [A] Z-SO ₂ -SM General formula [B]

[0006]

Embedded image General formula [C]

[0007]

Embedded image

Wherein Z is an alkyl group (having 1 to 1 carbon atoms)
8) an aryl group (having 6 to 18 carbon atoms) or a heterocyclic group Y: an atom necessary for forming an aromatic ring (having 6 to 18 carbon atoms) or a hetero ring M: a metal atom or an organic cation n: 2 Integer from 10 to 10

The transition metal coordination complex which achieves the object of the present invention is preferably a hexacoordination complex represented by the following general formula. [M (NY) L ₅ ] ^m (where M is a transition metal selected from elements of Groups 5 to 10 of the periodic table of elements, L is a bridging ligand, and one (NY) Y is oxygen or sulfur, m = 0, -1, -2, -3.) Preferred specific examples of L other than nitrosyl and thionitrosyl bridging ligands include halogen. Fluoride ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, acid ligands And aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Particularly preferred specific examples of M are rhodium, ruthenium, rhenium, osmium and iridium.

The following are specific examples of the transition metal coordination complex. 1 [Ru (NO) Cl ₅ ] ^-22 [Ru (NO) ₂ Cl ₄ ] ^-13 [Ru (NO) (H ₂ O) Cl ₄ ] ^-14 [Rh (NO) Cl ₅ ] ^-2 5 [Re (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Cr (NO) Cl _5] ^-3 15 [Re (NO) Cl _5] ^-1 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 17 [Ru (NS) I _5] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The above metal complex can be added to silver halide during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ⁻⁶ mol, preferably 10 ^{−6 to} 5 × 10 ⁻⁴ mol, particularly 1 × 10 ⁻⁵ to 1 mol per mol of silver halide. 5
× 10 ^-4 mol. There is no particular limitation on the distribution of the transition metal in the silver halide grains, but it is preferable that the transition metal be present more outside the grains.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is preferably a silver halide comprising 90% by mole or more of silver chloride, and silver chlorobromide containing 0 to 5% by mole of silver bromide or It is silver chloroiodobromide. An increase in the ratio of silver bromide or silver iodide is not preferable because the safelight safety in a bright room deteriorates or γ decreases. The silver halide used in the present invention is preferably a so-called core / shell type silver halide, and particularly preferably a core / shell type silver halide having a higher metal content in share than the core.
When the water-soluble metal complex salt is present in the silver halide grains using a water-soluble metal complex salt, when the water-soluble silver salt and the water-soluble halide solution are simultaneously mixed, a method in which the water-soluble silver salt is added to the water-soluble silver salt or the halide solution is used. preferable. Alternatively, when a silver salt and a halide solution are simultaneously mixed, silver halide grains may be prepared as a third solution by a three-solution simultaneous mixing method. The grain size of the silver halide emulsion of the present invention is preferably 0.20 μm or less. In the present invention, silver halide fine particles are prepared by mixing at a reaction temperature of 50 ° C. or lower, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, under conditions of sufficiently high stirring speed so as to achieve uniform mixing. Good results can be obtained by adjusting the potential to 70 mV or more, preferably 80 mV to 120 mV. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size, and more preferably within ± 20%. The silver halide grains of the present invention preferably have regular crystals such as cubes and octahedrons, and particularly preferably cubes.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. A specific example is U.S. Pat.
8,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a first tin salt, an amine, formamidinesulfinic acid, a silane compound and the like can be used.

The general formula [A] used in the present invention,
[B] and [C] will be described in detail. The alkyl group, aryl group, heterocyclic group, aromatic ring and heterocyclic group represented by Z and Y in the general formulas [A], [B] or [C] may be substituted. As the substituent,
Examples thereof include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carboxyl group. Examples of the hetero ring represented by Z and Y include a thiazole, benzthiazole, imidazole, benzimidazole, oxazole ring and the like. The metal atom represented by M is preferably an alkali metal atom such as a sodium ion or a potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. Preferred groups for Z are alkyl groups having 1 to 12 carbon atoms. General formula [A],
Specific examples of the compound represented by [B] or [C] include the following. Compound example

[0015]

Embedded image

8 nC ₈ H ₁₇ SO ₂ .SNa 9 nC ₁₂ H ₂₅ SO ₂ .SNa 10 nC ₁₆ H ₃₃ SO ₂ .SNa

[0017]

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14 1-cystine-disulfoxide 15 C ₂ H ₅ .SO ₂ .SNa 16 C ₄ H ₉ .SO ₂ .SNa The compound contained in the general formula [A], [B] or [C] is generally Can be synthesized by well-known methods. For example, it can be synthesized by reacting the corresponding sulfonyl fluoride with sodium sulfide or reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can be easily obtained as commercial products. The amount of the compound represented by the general formula [A], [B] or [C] in the present invention is 1 × 10 ⁻⁵ per mol of silver halide.
１1 × 10 ^-3 mol, particularly preferably 5 × 10 ^{-5 -1} × 10 ^-3 mol. The location where these compounds are added is preferably in the emulsion layer, and the time of addition is at the time of grain formation, chemical ripening, or immediately before coating. Particularly preferred is immediately before coating. The light-sensitive material prepared by using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener.
For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis- [β
-(Vinylsulfonyl) propionamide]), active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts ((1
-Morpholi) carbonyl-3-pyridinio) methanesulfonate and the like, and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium and 2-naphthalenesulfonate) can be used alone or in combination. Above all, JP-A-53-41220,
53-57257, 59-162546, 60-
Preferred are the active vinyl compounds described in 80846 and the active halides described in U.S. Pat. No. 3,325,287.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention, a coating aid, antistatic, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (for example, development acceleration For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. In order to prevent charging, Japanese Patent Application Laid-Open No. Sho 60-80849
It is preferable to use the fluorinated surfactant described in the above item.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate for the purpose of preventing adhesion to the photographic emulsion layer or other hydrophilic colloid layers. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
A polymer having a monomer component of acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like alone or in combination, or a combination of these with acrylic acid, methacrylic acid, or the like can be used. Gelatin is advantageously used as a condensing agent or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole can be used. As gelatin, coal-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. Cellulose triacetate as a support of the light-sensitive material of the present invention,
Cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, and the like can be used.

The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes from the viewpoint that good halftone dot quality can be easily obtained. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferred. 1-phenyl- used in the present invention
The developing agent for 3-pyrazolidone or a derivative thereof is 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3- And pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol and N-methylphenol.
-(Β-hydroxyethyl) -p-aminophenol,
There are N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is usually 0.05 mol / l or more.
It is preferably used in an amount of 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenol is used, the former is 0.05 mol / l-0.5 mol / l and the latter is 0.06 mol / l. It is preferably used in an amount of not more than / l.
As a sulfite preservative used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde sodium bisulfite. The sulfite is preferably at least 0.3 mol / l, particularly preferably at least 0.4 mol / l. The upper limit is up to 2.5 mol / l, especially 1.
It is preferably up to 2. Examples of the alkaline agent used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium silicate, and potassium silicate. Contains a buffer. Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5
-Mercapto compounds such as sodium sulfonate, 5
-An indazole compound such as nitroindazole;
It may contain an antifoggant such as a benztriazole-based compound such as methylbenztriazole, and may further contain, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardener, and the like. In particular, JP-A-56-10624
The amino compound described in No. 4 and the imidazole compound described in JP-B-48-35493 are preferred in terms of accelerating development or increasing sensitivity. The developer used in the present invention includes a compound described in JP-A-56-24347 as a silver stain preventive agent, and a compound described in JP-A-62-21 as an uneven development inhibitor.
No. 2,651) and compounds described in JP-A-61-267759 can be used as dissolution aids. In the developer used in the present invention, boric acid described in JP-A No. 62-186259 and buffer
-93433 saccharides (e.g., saccharose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalilic acid), tertiary phosphates (e.g., sodium salts, potassium salts), and the like are preferably used. Is boric acid.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or a salt thereof), if necessary, in addition to the fixing agent. , PH 3.8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to
It is about 5 mol / l. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of fixing solution, and particularly effective is 0.01 mol / l to 0.03 mol / l. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.
Examples of citric acid or a derivative thereof effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. The fixing solution may further contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), a pH adjuster (eg, ammonia, sulfuric acid), an image preserving agent (eg, Potassium iodide) and a chelating agent. Here, the pH buffer is 10 to 40 g / l, more preferably 18 to 25 g, because the pH of the developer is high.
Use about g / l. The fixing temperature and time are the same as in the case of development, and are preferably from about 20 ° C. to about 50 ° C. for 10 seconds to 1 minute. Further, the washing water may contain a fungicide (for example, a compound described in Horiguchi's "Bacterial Prevention and Prevention Chemistry", JP-A-62-115154), a washing accelerator (such as a sulfite), a chelating agent, and the like. May be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. The water washing is performed in order to almost completely remove the silver salt dissolved by the fixing.
Preferred is about 50 ° C. for 10 seconds to 3 minutes. Drying is about 40 ° C ~
The drying is performed at about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but it is usually about 5 seconds to 3 minutes 3 seconds. U.S. Pat. No. 302 discloses a roller transport type automatic developing machine.
Nos. 5,779, 354,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention also includes other steps (for example, a stop step).
Is not excluded, but it is most preferable to follow these four steps. Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method. The developer used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147.
The developer used in the present invention is described in JP-A-62-9193.
The replenishment system described in No. 9 can be preferably used. The silver halide photographic material of the present invention has a high Dma.
Since x is given, when the image is subjected to a reduction process after image formation, a high density is maintained even if the dot area is reduced. There are no particular restrictions on the reducer used in the present invention. For example, Meesz, The Theory of the Photographic Pro
cess ", pp. 738-744 (1954, Macmilla
n), Tetsuo Yano, Photo Processing Theory and Practice, 166-1
69 pages (1978, Kyoritsu Shuppan), and JP-A-50-27543, JP-A-52-68429, and JP-A-55-68429
Nos. -17123, 55-79444, and 57-10
No. 140, No. 57-142639, JP-A-61-61
No. 155 or the like can be used. That is, as an oxidizing agent, permanganate, persulfate, ferric salt, cupric salt, ceric salt, red blood salt, dichromate, or the like alone or in combination, and further if necessary A reducing solution containing an inorganic acid such as sulfuric acid or an alcohol, or an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetate, and a halogen such as thiosulfate, rodane salt, thiourea or a derivative thereof. A reducing solution containing a silver halide solvent and, if necessary, an inorganic acid such as sulfuric acid is used. Typical examples of the reducer used in the present invention include so-called Farmer reducer, ferric ethylenediaminetetraacetate, potassium permanganate, and ammonium persulfate reducer (Kodak R).
-5), cerium salt reducer. The conditions of the reduction treatment are generally 10 ° C to 40 ° C, particularly 15 ° C to 30 ° C.
It is preferable that the process can be completed at a temperature of several seconds to several tens of minutes, especially within a few minutes. If the photosensitive material for plate making of the present invention is used, a sufficiently wide reduction range can be obtained within the range of these conditions. The reducer acts on the silver image formed in the emulsion layer via the non-photosensitive upper layer containing the compound of the present invention. Specifically, there are various methods, for example, immersing the plate-making sensitizer in the reducer, stirring the liquid, or applying the reducer to the surface of the plate-form sensitizer with a brush, a roller, or the like. Method is available.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, a developer having the following formulation was used. -Potassium sulfite 67 g-Ethylenediamine-4-acetic acid-2-sodium 3.0 g-Hydroquinone 23 g-4-hydroxymethyl-4-methyl-1-phenyl 0.4 g -3-pyrazolidone-2-mercaptobenzimidazole-5-sulfone 0.3 g sodium acid ・ potassium hydroxide 11 g ・ 5-methylbenzotriazole 0.1 g ・ sodium carbonate 11 g ・ potassium bromide 3.0 g Add water to make 1 liter. (Adjusted to pH 10.7)

[0026]

EXAMPLES Example 1 Preparation of Emulsion An aqueous solution of silver nitrate and silver 1 were added to an aqueous solution of gelatin maintained at 40 degrees.
As shown in the table per mole, an aqueous sodium chloride solution containing 5 × 10 ⁻⁵ of a metal was added simultaneously over 3 minutes and a half, and the potential during that time was controlled to 95 mV to prepare 0.11 μm of core particles. Then, silver nitrate aqueous solution and silver 1
A silver chloride cubic grain having an average grain size of 0.14 μm was prepared by simultaneously adding an aqueous solution of sodium chloride containing 1.5 × 10 ^{−4 of} metal per mole for 7 minutes as shown in the table and controlling the potential during the addition to 95 mV. did. Preparation of Coated Sample 1-phenyl-5-mercaptotetrazole was added to the above emulsion at 2.5 mg / m ² , ethyl acrylate latex (average particle size: 0.05 μm) at 770 mg / m ² , and as shown in Table 1, a comparative compound or The compound of the present invention was added, and 126 mg / m ² of 2-bis (vinylsulfonylacetamido) ethane was added as a hardener, and the mixture was coated on a polyester support so that silver became 3.0 g / m ² . Gelatin was 1.5 g / m ^{2. On} top of this, 0.8 g / m ² of gelatin, 8 mg / m ^{2 of} lipoic acid, ethyl acrylate latex (average particle size 0.05 μm)
30 mg / ² was applied, and further, gelatin 0.7 g / m ² and the following dye (I) were applied in a solid dispersion state as an upper layer of a protective layer. At this time, a matting agent (silicon dioxide,
Average particle diameter 3.5μm) 55mg / ^{m 2,} methanol silica (average particle size 0.02μm) 135mg / ^{m 2,} sodium-dodecyl benzene sulfonate 25m as a coating aid
g / ² , poly (degree of polymerization 5) oxyethylene nonyl phenyl ether sulfate sodium salt 20 mg /
m ² and N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² were simultaneously applied to prepare a sample. Dye (I)

[0027]

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The base used in this example has a back layer and a back protective layer having the following compositions. (The swelling ratio on the back side is 110%.) (Back layer) Gelatin 170 mg / m ² Sodium dodecylbenzenesulfonate 32 mg / m ² Dihexyl-α-sulfosacnate sodium 35 mg / m ² SnO ₂ / Sb (9 / 1 weight ratio, average particle size 0.25 μm) 318 mg / m ² (back protective layer) gelatin 2.7 g silicon dioxide matting agent (average particle size 3.5 μm) 26 mg / m ² dihexyl-α-sulfosacnate sodium 20 mg / m ² sodium dodecylbenzenesulfonate 67 mg / m ²

[0029]

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[0030]

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Ethyl acrylate latex (average particle size 0.05 μ
m) 260 mg / m²  1,3-divinylsulfonyl-2-propanol
 149 mg / m²  Photographic performance The sample obtained in this way was passed through a light wedge to
Exposure with P-627FM printer (mercury)
And a developer LD-835 manufactured by Fuji Photo Film Co., Ltd.
Development processing at 38 ° C for 20 seconds using the current model FG800RA
After fixing, washing and drying. For these samples,
Items were evaluated. 1) r; (1.5-0.1) /-｛log (concentration 0.1
-Log (exposure to give a density of 1.5)
2) Dmax, Dmax (-1%);
Glue a film with a dot image on it (dot document)
What was fixed with tape was the protective layer of each film sample and
Halftone originals are placed so that they overlap face to face, and 50% halftone dots
The area is 50% and 49% halftone dot area on the film sample.
Dmax, the maximum blackening density when exposure is given
Dmax (-1%). 3) Storage property over time (@fog);
After 5 days under the condition of
Dmin was evaluated as an increase in Fresh performance.
As is clear from Table 1, the sample of the present invention has no fog and
Excellent gradation and high Dmaxa
Return performance.

[0032]

[Table 1]

[0033]

According to the present invention, a light-sensitive material handled in a bright room by using a compound represented by the general formula [A], [B] or [C] in a silver halide emulsion containing a transition metal coordination complex. Was able to prevent a decrease in the maximum blackening density at the time of underexposure.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
Halogenation wherein each emulsion layer contains at least 1 × 10 ^-6 moles of nitrosyl or thionitrosyl ligand per mole of silver and a compound containing a transition metal selected from elements of groups 5 to 10 of the periodic table. A silver halide photographic light-sensitive material comprising a silver emulsion and containing compounds represented by the following general formulas [A] to [C]. General formula [A] Z-SO ₂ -SM General formula [B] General formula [C] Here, Z: an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group Y: an atom necessary for forming an aromatic ring (6 to 18 carbon atoms) or a hetero ring M: metal atom or organic cation n: integer of 2 to 10