JPH05313277A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material to be handled under light having high contrast and superior processability and superior storage stability. CONSTITUTION:The silver halide photographic sensitive material has a silver halide emulsion layer containing a silver halide emulsion composed of a transition metal selected from group V-VIII elements of the periodic table and nitrosil or thionitrosil ligands in the amount of 1X10<-6>mol per 1mol of silver halide, and contains a compound represented by formula I in which each of R1-R3 is H or a substituent, and X<-> is an anion.

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, particularly a silver halide photographic light-sensitive material used in a photomechanical process, more specifically, a super-high-contrast negative suitable for a light room light-sensitive material. Type photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, a silver halide photosensitive material has been used to
It is known that very high contrast photographic images can be formed. For example, the silver halide grains are fine grains having an average grain size of about 0.5 μm or less, a narrow grain size distribution, uniform grain shapes, and a high silver chloride content of, for example, 50 mol% or more. By processing a silver halide light-sensitive material having an emulsion layer composed of silver chlorobromide or silver chloroiodobromide emulsion with an alkaline developing solution having a low sulfite ion concentration and containing only hydroquinone as a developing agent, a high-contrast screen is obtained. A method of obtaining a dot image or a line drawing is known. This type of hydroquinone light-sensitive material is known as a lith type silver halide photographic light-sensitive material. This lith-type silver halide photographic light-sensitive material is said to be incompatible with the lith-type developer. For this lith-type developer, see JA C Yule; J. Franklin Instrtute, Journal of the Franklin Institute,
Vol. 239, p. 221 (1945), it is essentially a developer containing only hydroquinone as a developing agent and having a low sulfite ion concentration which serves as an antioxidant for the developing agent. is there. Such a developing solution is poor in preservability and is susceptible to autoxidation. Since the merits of improving the preservability of the lith type developer are extremely large,
Although great efforts have been made for that purpose, it is quite insufficient as compared with the continuous tone developing solutions, methol hydroquinone developing solution and phenidone hydroquinone developing solution. So Phenidone with high sulfite ion concentration
As a method of forming a high-contrast image comparable to lith development using a hydroquinone type developer, Japanese Patent Publication No. 59-1782.
5, No. 59-17819, No. 59-17821,
No. 59-17822 and the like disclose a silver halide photographic light-sensitive material containing a tetrazolium compound.
Further, in the field of print reproduction, it is desired to improve the work efficiency of the photoengraving process in order to deal with the variety and complexity of printed matter. In particular, when performing plate collection, reversing, and process work, it has been attempted to improve work efficiency by performing work in a brighter environment. Therefore, handle in an environment that can be called a bright room. The development of a silver halide photographic light-sensitive material for plate making and a development of an exposure printer have been promoted. As a method for reducing the sensitivity in the light-sensitive material for bright room, a light-sensitive material containing a tetrazolium compound using a heavy metal (rhodium salt) is disclosed in, for example, JP-A-61-23.
145, 63-95437, JP-A-3-2745.
No. 42 and No. 3-276152. However, in the above-mentioned technique, since the tetrazolium compound having an oxidizing property is contained in the light-sensitive material, there is a drawback that the sensitivity is changed and the contrast is lowered under the conditions of long-term storage or high temperature and high humidity. ing.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a bright room light-sensitive material which has a high contrast and is excellent in processing and storage stability.

[0004]

The above 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 is nitrosyl or thionitrosyl coordination. A silver halide emulsion containing at least 1 × 10 ⁻⁶ mol of a compound containing a transition metal selected from the group V to VIII elements of the periodic table per mol of silver, and having the following general formula (I ), A silver halide photographic light-sensitive material characterized by containing a compound of General formula (I)

[0005]

[Chemical 2]

In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion.

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

Specific examples of the transition metal coordination complex are shown below. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) ₂ (H ₂ O) Cl ₄ ] ^-1 4 [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 ] ^-1

The above metal complex can be added to the silver halide during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ^-7 mol, preferably 10 ^{-6 to} 5 × 10 ^-4 mol, and particularly 5 × 10 ^-6 to 1 mol per mol of silver halide. 2 x 10 ^-4
It is a mole. Moreover, you may use together the said transition metal. The distribution of the transition metal in the silver halide grain is not particularly limited, but it is preferable that the transition metal is more present outside the grain. The silver halide emulsion of the present invention is preferably silver chlorobromide or silver chloroiodobromide containing 70 mol% or more of silver chloride. A high silver chloride emulsion is preferred because an increase in the ratio of silver bromide or silver iodide deteriorates the safety of safelight in a bright room. In the present invention, silver halide grains are prepared by mixing at a reaction temperature of 50 ° C. or lower under a condition with a sufficiently high stirring speed so as to uniformly mix the Ag potential of 70 mV or more, preferably 80 mV or more.
Good results can be obtained by preparing at 120 mV.
The particle size distribution is basically not limited, but monodispersion is preferable. The term "monodispersion" as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size, and more preferably within ± 20%. The particle size is preferably 0.20 μm or less.

Next, the compound of the general formula (I) used in the present invention will be explained in detail. In the general formula (I), preferred examples of the substituent represented by R ¹ or R ² include an alkyl group (eg, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino Group, acylamino group (eg acetylamino), hydroxyl group, alkoxy group (eg methoxy, ethoxy, propoxy, butoxy, pentoxy etc.), acyloxy group (eg acetyloxy), halogen atom (eg fluorine,
Chlorine, bromine, etc.), carbamoyl group, acylthio group (eg acetylthio), alkoxycarbonyl group (eg ethoxycarbonyl), carboxyl group, acyl group (eg acetyl), cyano group, nitro group, mercapto group, sulfoxy group, aminosulfoxy Examples include groups such as groups. Examples of the anion represented by X ⁻ include halogen ions such as chloride ion, bromide ion and iodide ion, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid, and organic acids such as sulfonic acid and carboxylic acid. Acid roots and anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion, and higher alkyl sulfates such as lauryl sulfate anion. Ester anions, borate anions such as tetraphenylpolone, di-2-ethylhexyl sulfosuccinate anions such as dialkyl sulfosuccinate anions, cetyl polyethenoxysulfate anions such as polyether alcohol sulfate anions, and stearic acid anions. Higher aliphatic anions on such, can be cited, such as those with a acid radical in a polymer such as polo acrylic acid anion. Hereinafter, specific examples of the compound represented by the general formula [I] used in the present invention will be listed, but the compound of the present invention is not limited thereto.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

The tetrazolium compound used in the present invention can be easily synthesized, for example, according to the method described in Chemical Reviews, Vol. 55, pages 335 to 483. The tetrazolium compound represented by the general formula [I] of the present invention is used in an amount of about 1 mg to 10 g, preferably 10 mg to 2 g, per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferably used.

A water-soluble dye or a dye dispersed in a solid state may be used as a filter dye in a hydrophilic colloid layer or an emulsion layer of a light-sensitive material produced by using the present invention or for various purposes such as prevention of irradiation. Good.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, 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], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts ((1
-Morpholinyl) carbonyl-3-pyridinio) methanesulfonate etc.) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate etc.) can be used alone or in combination. Among them, JP-A-53-41220,
53-57257, 59-162546, 60-
The active vinyl compounds described in 80846 and the active halides described in US Pat. No. 3,325,287 are preferred.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Hardening, and sensitization), various surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (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 silicones), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy salts, sulfo salts, phospho salts, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic primary surfactants. 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 can be used. Further, in order to prevent electrification, JP-A-60-80849 is used.
It is preferable to use the fluorine-containing surfactants described in Japanese Patent No.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethylmethacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
Acrylics, alkoxyacryl (meth) acrylates, glycidyl (meth) acrylates or the like may be used alone or in combination, or a polymer having a combination of these with acrylic acid, methacrylic acid or the like as a monomer component may be used. As the condensing agent or protective colloid for the photographic emulsion, it is advantageous to use gelatin, 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 hydroxyethyl cellulose, carboxymethyl cellulose 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 synthetic hydrophilic molecular substances such as a single or copolymer such as polyvinylpyrazole can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. As the support of the photosensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, potastyrene, polyethylene terephthalate paper, baryta coated paper,
Polyolefin coated paper or the like can be used.

The developing agent used in the developing solution used in the present invention is not particularly limited, but it is preferable to contain dihydroxybenzenes from the viewpoint that good halftone dot quality can be easily obtained, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Examples of the dihydroxybenzene developing agent used in the present invention include 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 preferable. 1-phenyl-used in the present invention
As a developing agent for 3-pyrazolidone or its derivative, 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- There is pyrazolidone. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N
-(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 preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. In addition, dihydroxybenzenes and 1-phenyl-3-
When using a combination of pyrazolidones or p-amino-phenols, the former is 0.05 mol / liter or more.
It is preferable to use 0.5 mol / liter and the latter in an amount of 0.06 mol / liter or less. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.3 mol / sulfite
It is preferably at least liter, particularly at least 0.4 mol / liter. The upper limit is 2.5 mol / liter, especially 1.2.
It is preferable to be up to. Alkali agents used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, and potassium silicate. Contains a buffer. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, bimethylformamide, methyl Organic solvents such as cellosolve, bexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5
Mercapto-based compounds such as sodium sulfonate, 5-
An indazole compound such as nitroindazole, an antifoggant such as a benztriazole compound such as 5-methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, a water softener, a hardener Film agent,
May be included. Particularly, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-48-35493 are preferable from the viewpoint of promoting development or increasing sensitivity. In the developer used in the present invention, a compound described in JP-A-56-24347 is used as a silver stain preventing agent, and a development unevenness preventing agent is used (JP-A-62-212,6).
No. 51), and as a dissolution aid, JP-A-61-161
The compounds described in 267759 can be used.
In the developer used in the present invention, a buffer agent is used as disclosed in Japanese Patent Laid-Open No.
Boric acid described in JP-A-2-186259, JP-A-60-93
The sugars described in 433 (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and preferably Boric acid is used. Development temperature and time is about 20 ° C to 5
It is preferably 10 seconds to 1 minute at 0 ° C.

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 salts thereof), if necessary, in addition to the fixing agent, and preferably. , PH 3.8 or higher, and 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 used can be appropriately changed, and is generally about 0.1
It is about 5 mol / liter. The water-soluble aluminum salt that 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 kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 mol / liter to 0.03 mol / liter.
The liter is particularly effective. Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. The fixer may further contain a preservative (eg, sulfite, bisulfite), if desired.
pH buffer (eg, acetic acid, boric acid), pH adjuster (eg,
Ammonia, sulfuric acid), an image preservation improving agent (for example, potassium iodide), and a chelating agent can be included. Since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, and are preferably about 20 ° C. to about 50 ° C. and 10 seconds to 1 minute. In addition, for washing water,
Antifungal agents (for example, compounds described in Horiguchi, "Bacterial and Antifungal Chemistry", JP-A No. 62-115154), water washing accelerators (sulfites, etc.), chelating agents and the like may be contained. ..

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and the temperature is about 20 ° C.
10 seconds to 3 minutes at about 50 ° C is preferred. About 40 ℃
It is carried out at about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 3 seconds. For a roller-conveying type automatic developing machine, U.S. Pat. No. 302
No. 5779, No. 3545971, and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of developing, fixing, washing and drying, and the method of the present invention also includes other steps (for example, stopping step).
However, it is most preferable to follow these four steps. Here, in the water washing step, a water saving treatment can be performed by using a countercurrent water washing method of two or three stages. 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 developing solution used in the present invention is disclosed in JP-A-62-9193.
The replenishment system described in No. 9 can be preferably used. The silver halide photographic light-sensitive material of the present invention has a high Dma.
Since x is given, when the reduction processing is performed after the image formation, the high density is maintained even if the halftone dot area is reduced. There is no particular limitation on the reducing liquid used in the present invention. For example, Mies, “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), etc., as well as JP-A Nos. 50-27543, 52-68429 and 55.
-17123, 55-79444, 57-10.
No. 140, No. 57-142639, JP-A No. 61-61.
Those described in No. 155 and the like can be used. That is, as an oxidant, permanganate, persulfate, ferric salt, cupric salt, cerium salt, red blood salt, dichromate, etc. may be used alone or in combination, and if necessary. An inorganic salt such as sulfuric acid, a reducing solution containing alcohols, or an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetic acid salt, and a halogen such as thiosulfate, rhodan salt, thiourea or their derivatives. 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 ethylenediaminetetraacetic acid salt, potassium permanganate, ammonium persulfate reducer (Kodak R
-5), and a ceric salt reducing solution. The condition for the reduction treatment is generally 10 ° C to 40 ° C, particularly 15 ° C to 30 ° C.
It is preferable that the heating can be completed at a temperature of several seconds to several tens of minutes, and especially within several minutes. By using the plate-making photosensitive material of the present invention, 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 through the non-photosensitive top layer containing the compound of the invention.
Specifically, there are various methods, such as immersing the plate-making sensitizer in a reducing solution and stirring the solution, or applying the reducing solution to the surface of the plate-making sensitizing agent with a brush, roller, etc. Methods are available.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these.

[0021]

【Example】

Example 1 Preparation of Silver Halide Emulsion An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 4 × 10 ⁻⁵ mol of transition metal complex per mol of silver were simultaneously added to an aqueous solution of gelatin kept at a certain temperature for 3.5 minutes, 1 minute later,
An aqueous silver nitrate solution and an aqueous sodium chloride solution containing 1.2 × 10 ⁻⁴ mol of transition metal complex per mol of silver were simultaneously added in 7 minutes to prepare silver chloride particles. Then, it was desalted by flocculation using a formalin condensate of naphthalenesulfonic acid by a conventional method. Table 1 shows the outline of each emulsion such as the compound name of the transition metal complex and the addition amount.

[0022]

[Table 1]

Preparation of Coating Sample 5,6-Cyclopentane-4-hydroxy- was added to the above emulsion.
24 mg / m ^{2 of} 1,3,3a, 7-tetrazaindene, ethyl acrylate latex (average particle size 0.05 μm)
The 770 mg / m ^2, the following compounds 3 mg / m ^2, Compound I-2 of the present invention 1 g / Ag mole,

[0024]

[Chemical 5]

126 mg / m ² of 2-bis (vinylsulfonylacetamide) ethane was added as a hardener and coated on a polyester support so as to give 3.0 g / m ² of silver. The gelatin was 1.5 g / m ² . On top of this, as a lower layer of a protective layer, gelatin 0.8 g / m ² , polyacid 8 mg / m ² , C ₂ H ₅ SO ₂ SNa
The 6 mg / m ^2, coated with acrylate latex (average particle size 0.05μm) 230mg / m ^2, further gelatin 0.7 g / m ² as a protective layer upper layer thereon, 40 below dyes
It was applied in the state of mg / m ² solid dispersion. At this time, a matting agent (silicon dioxide, average particle size 3.5 μm) 55 mg / m ² , methanol silica (average particle size 0.02 μm) 135 mg / m ²
m ² , sodium dodecylbenzenesulfonate 25 mg / m ² as a coating aid, poly (degree of polymerization 5) oxyethylene nonylphenyl ether sulfate ester sodium salt 20 mg
/ M ² , N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3 mg / m ² were simultaneously applied to prepare a sample.

[0026]

[Chemical 6]

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-sulfosuccinate 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-sulfosuccinate sodium 20 mg / m ² sodium dodecylbenzenesulfonate 67 mg / m ²

[0028]

[Chemical 7]

[0029]

[Chemical 8]

Ethyl acrylate latex (average particle size: 0.05 μm) 260 mg / m ² 1,3-divinylsulfonyl-2-propanol 149 mg / m ²

Photographic properties The sample thus obtained was exposed through a light wedge to a P-627FM printer (mercury) manufactured by Dainippon Screen Co., Ltd., and a developing solution of the following formulation and an automatic developing machine having a developing tank capacity of 20 liters were used. Development at 28 ° C for 30 seconds, fixing,
Washed with water and dried. For these samples, in order to examine the changes immediately after application and with the passage of time, the samples were conditioned at 25 ° C. and 60% RH, sealed in a photographic barrier packaging material, and heat-treated at 40 ° C. for 20 days for testing. .. The evaluation items are as follows.

[0032]

[Table 2]

1) Dmax; a film having a halftone image formed thereon (halftone original) is fixed with an adhesive tape on the laminating base, and the protective layer of each film sample and the halftone original are emulsion surface-to-emulsion. The maximum blackening densities were measured by Macbeth when the films were exposed to each other so as to overlap each other and exposed so that the dot area of 50% became the dot area of 50% on the film sample. 2) Gradation: (1.5-0.1) / {log (exposure amount giving density 1.5) -log (exposure amount giving density 0.1)} The results are shown in Table 2. As is apparent from the table, it is understood that the sample of the present invention is a silver halide light-sensitive material having a small change with time, a high Dmax and a hard gradation.

[0034]

[Table 3]

[0035]

INDUSTRIAL APPLICABILITY The deterioration of photographic performance due to long-term storage of a light-sensitive material for a bright room in which the sensitivity is reduced by a rhodium salt containing no NO or NS ligand and the contrast is increased by a tetrazolium compound is caused by the NO or NS ligand. Group 5 containing
It is significantly improved by using the Group 8 transition metal complex.

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[Procedure amendment]

[Submission date] May 13, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

[0032]

[Table 2]

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
Each emulsion layer contains at least 1 compound per mole of silver containing a nitrosyl or thionitrosyl ligand and a transition metal selected from elements of Groups V to VIII of the Periodic Table.
A silver halide photographic light-sensitive material represented by the general formula (I), which comprises a silver halide emulsion having a content of × 10 ^-6 mol and contains a compound represented by the following general formula (I). In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion.