JPH0456846A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain high maximum density, high sensitivity and high contrast and to reduce black spots by incorporating a hydrazine derivative in an emulsion layer containing one of specified hexadental coordination complexes having at least 4 cyanide ligands or another hydrophilic colloidal layer. CONSTITUTION:The emulsion layer comprises silver halide grains containing at least one of the ruthenium, rhodium, rhenium, osmium, or iridium hexadental coordination complexes and the same or other emulsion layer or the other hydrophilic colloidal layer contains at least one of the hydrazine derivatives. Said complex is added properly at the time of manufacture of the emulsion or in any step before coating with the emulsion, thus sensitivity, contrast, and blackening density to be enhanced and occurrence of black spots to be reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to silver halide photographic materials (particularly negative materials) that are used in the field of photoengraving and are capable of rapidly forming ultra-high contrast images using a highly stable processing solution. (type).

(Prior Art) In order to improve the reproduction of continuous tone images or line images using halftone images in the field of photoengraving,
There is a need for an image forming system that exhibits photographic characteristics of ultra-high contrast (especially gamma of 10 or higher).

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is extremely low (usually 0). Therefore, the Lith developer has the serious disadvantage that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4.224.401 and U.S. Pat.
．． 168,977, 4,166.742, 4.311.781, 4.272,606, 4.221.857, 4.243,739,
There is a method using a hydrazine derivative described in 4,269.929 and the like. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and since it is allowed to add a highly sensitive sulfite to the developer, the stability against air oxidation of the developer is better than that of the lithium developer. A dramatic improvement in comparison.

This new high-contrast negative image system can increase the maximum density by changing the amount of hydrazine derivative added and achieve a remarkable high-contrast contrast.
) may cause undesirable development.
This is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that appears in an unexposed area that should become a non-image in the future.

Black spots occur frequently due to a decrease in sulfite ions, which are generally used as preservatives in developing solutions, and an increase in pH value, and this significantly reduces the commercial value of photolithographic materials. Therefore, there has been a strong desire for an improved black-out system that maintains high maximum density and high contrast sensitivity.

Furthermore, in the field of photolithography, in order to deal with the versatility and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment.

In particular, manuscripts in the line drawing process are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction. On the other hand, for making catalogs and large posters,
Enlarging (stretching) or reducing (shrinking) halftone photographs is widely practiced, and in plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. In reduction, the number of lines per inch is thicker than in the original (thinner dots are photographed. Therefore, an image forming method with wider latitude is required in order to maintain the reproducibility of halftone gradation.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain photographic sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and reproducibility of originals, there is a desire for a system with further improved reproducibility of originals in order to accommodate the diversity of printed matter in recent years.

An example of a silver halide emulsion containing an iron, cobalt hexacoordination complex with cyanide ligands is given in U.S. Pat.
No. 0,390, No. 3.890154, etc. Also, European Patent Application Publication No. 0.242,19
No. 0/A2 contains 1 with 3, 4, 5 or 6 cyanide ligands bonded to each rhodium ion.
Examples of silver halide emulsions formed in the presence of one or more complex compounds of rhodium (Ill) are disclosed. And European Patent Application Publication No. 0.
No. 336.425/AI, No. 0336.426/A1 describes silver halides formed in the presence of hexacoordination complexes of rhenium, ruthenium, osmium or iridium with at least four cyanide ligands. Examples of emulsions are disclosed. However, these do not mention anything about the use in combination with hydrazine derivatives.

Examples of using hydrazine derivatives and iridium in combination are JP-A No. 61-29837, JP-A No. 61-47942, and JP-A No. 61-47942.
It is disclosed in No. 201233 and the like.

An example of using hydrazine derivatives and rhodium in combination is JP-A-6
It is disclosed in No. 0-83028 and the like.

Furthermore, examples of using hydrazine derivatives and ruthenium in combination are disclosed in JP-A No. 2-3032;
The use of hexacoordination complexes containing cyanide ligands is not mentioned. Regarding iron, an example of using a hexacoordination complex containing a cyanide ligand and a hydrazine derivative in combination is described in Japanese Patent Application No. 1-307362.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide a silver halide photographic material and image with high sensitivity, high contrast (for example, T of 10 or more), high blackening density, and few black spots. The object of the present invention is to provide a forming method.

A second object of the present invention is to provide a silver halide photographic material with excellent line image quality, extremely high sensitivity and ultra-high contrast with γ exceeding 10.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. at least one of the hexacoordination complexes of ruthenium, rhodium, rhenium, osmium, or iridium having at least 4 cyanide ligands;
This can be achieved by a silver halide photographic material comprising a silver halide emulsion containing seeds and containing at least one hydrazine derivative in the emulsion layer or other hydrophilic colloid layer.

The silver halide grains in the photographic emulsion used in the present invention may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. It may have crystals or a composite form of these crystal forms.

The average grain size of the silver halide grain crystals in the present invention is preferably 0.7 μm or less, more preferably 0.1 μm or less.
6 Particle size distribution of m to 0.5 μm is preferably monodisperse.

Monodisperse grains herein mean a silver halide emulsion having a grain size distribution with a coefficient of variation defined below of 20% or less, particularly preferably 15% or less.

The silver halide emulsion used in the present invention can be prepared by various methods known in the field of silver halide photographic materials.
iie et Physique Photograp
hique (Pau1Monte1, 1967)
Photograph by G. F. Duffin
ic Emulsion Ches+1str
y (The Focal Press, 1966) V, L, Zelikman et al Ma
King and Coating Photo
graphic emulsion
Cal Press, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, a controlled double jet method, can also be used. Grains can also be formed using so-called silver halide solvents such as ammonia, thioethers, and tetrasubstituted thioureas.

The controlled double jet method and the grain formation method using a silver halide solvent can easily produce a silver halide emulsion with a regular crystal shape and a narrow grain size distribution, and are suitable for producing the emulsion used in the present invention. It is an effective method.

In addition, in order to make the particle size uniform, British patent 1,
No. 535.016, Special Publication No. 4B-36890, No. 52-
As described in No. 16364, there is a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242.445, Japanese Patent Application Laid-open No. 5
It is preferable to use a method of varying the concentration of an aqueous solution as described in Japanese Patent No. 5-158124 to grow rapidly within a range that does not exceed the critical saturation level.

The monodispersed emulsion preferably has a regular crystal shape such as a cube, an octahedron, or a dodecahedron, and a cubic or dodecahedral shape is particularly preferred.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, and may consist of any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, and silver iodochlorobromide. But that's fine.

The silver halide emulsion used in the present invention is characterized by a hexacoordination complex of ruthenium, rhodium, rhenium, osmium, or iridium having at least four cyanide ligands.
It is formed in the presence of at least one species.

Transition metal coordination complexes satisfying the requirements of the present invention contain the above-mentioned transition metals as transition metals, and contain 4.5 or 6 cyanide ligands, and 4 or 5 cyanide ligands. If only a cyanide ligand is present, the remaining ligands can be any suitable conventional bridging ligand. Also, these hexacoordination complexes mostly have an ionic charge. Therefore, it has one or more counterions, forming a charge-neutral compound. The counter ion is of little importance since the complex and its counter ion dissociate upon introduction into an aqueous medium, such as that used, for example, in the production of silver halide grains. Ammonium and alkali metal counterions are particularly suitable for anionic hexacoordination complexes satisfying the requirements of the present invention, since these cations are known to be well suited for silver halide precipitation operations.

In a preferred embodiment, the hexacoordination complex can be represented by formula (A) as follows: (A) CM(CN)a□Ly)l' where M is ruthenium, rhodium, rhenium, osmium. or iridium, L is a bridging ligand, y is 0.1 or 2, and n is -2, 3 or -4
It is.

Representative coordination complexes that satisfy the requirements of the present invention are shown below. However, the present invention is not limited to the following compounds.

(Ru (CN).] (RuBr (CN) s ) (Ru (CN) 5Hzo) (Ru (CN) s (OCN) ) (RuBr 2
(CN) a ) (Rh(CN)b ) -co(RhBr(CN)s ) (Rh (CN) 5HtOE (RhC12(CN)a) (Rhlz(CN)a ) (ReCl (CM) s ) (Rel (CN) 5) (Re(CN)s(SCN)) -'(ReBrz(CN)a]-' (Os(CN)*) (OsBr (CN) s ) (Os (CN) 5LO) -4 COsC1t (CN) *) −' (031! (CN)4 ) ~ 4 (RuCA (CN)s) (Ru I (CN) s ) (Ru (CN) s (SCN) ) (RuCl 2
(CN) 4 ) (Rulz(CN)n ) (RhCβωN), ] (Rhl(CN)s) (Rh (CN) s (SCN) ) (RhBrz(
CN)a) (Re(CN)&) (ReBr(CN)s) -'(Re(CN)sHzo)-' (ReCJ! * (CN) a) (Rely(CN)a) (OsCl (CN) 5) (Osl(CN)s) (Os(CN)s (SCN)) (OsBr2(
CN)n]−' (Ir(CN)i) −” ([r(!! (CN)s) −, (IrBr(
CN)s ) (JrI(CN)s) −, (Ir(
CN)sHzO)(Ir(CN)s(SCN))-, (
IrCjlz(CN)a) (IrBrz(CN)a)
−+ (Irlz(CN)a) −”These hexacoordination complexes have 1O−
It is used alone in an amount corresponding to from @mole to 10-3 mole, or two or more compounds are used in combination.

It is preferably used in a range of 10-' mol to 10-4 mol.

These hexacoordination complexes can be added as appropriate during the production of the silver halide emulsion and at each stage before coating the emulsion. When producing silver halide grains,
It may be added during grain formation or physical ripening, or further during chemical ripening of the silver halide emulsion. In particular, it is preferably incorporated into silver halide grains.

In order to add the above-mentioned complex at the time of grain formation, it is preferable to add it to the water-soluble silver salt or the halide solution when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution. Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be prepared by a three-liquid time mixing method as a third solution, or a required amount of the above complex aqueous solution may be added during grain formation. It may be put into a reaction vessel.

The silver halide emulsion of the present invention is preferably prepared in the presence of "another iridium salt or a complex thereof" in addition to the hexacoordination complex having a cyanide ligand. The presence of "other iridium salts or complexes thereof" is preferable because the obtained line drawing image becomes more excellent.

The amount of such iridium salt or its complex used is preferably 1 o-' to 10-' mol per 1 mol of silver.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process, particularly during grain formation.

The "iridium salt other than a hexacoordination complex having at least four cyanide ligands" used here is a water-soluble iridium salt or an iridium complex salt.

Preferred are trivalent or tetravalent iridium halides, trivalent or tetravalent hexachloroiridates, hexabromoiridates, and hexaiodoiridates. Especially iridium trichloride, iridium tetrachloride,
Potassium hexachloroiridate (I[[), potassium hexachloroiridate (rV), ammonium hexachloroiridate (I[I)], and the like are preferred.

A cadmium salt, sulfite, lead salt, or thallium salt may be present in the silver halide emulsion used in the present invention during the formation or physical ripening of silver halide grains.

The emulsion of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method for chemical enhancement, known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used, and these may be used alone or in combination. A preferred chemical enhancement method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg during chemical sensitization is preferably 8.3 or less, more preferably in the range of 7.3 to 8.0.

Furthermore, Mo1sar, Klein Gelatin
e, Proc, Syp.

2nd, 301-309 (1970) et al., which uses polyvinylpyrrolidone and thiosulfate in combination, also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold plates, such as platinum, palladium, and iridium.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The silver halide emulsion in the light-sensitive material used in the present invention is
One type may be used alone, or two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions) may be used in combination.

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodisperse emulsions with different average particle sizes as disclosed in No. 3734 and No. 62-90646 from the viewpoint of increasing the maximum density (Dsax).
The small size monodisperse emulsion is preferably chemically sensitized, and the most preferred method of chemical sensitization is sulfur sensitization.The large size monodisperse emulsion does not need to be chemically sensitized, but it You can leave it there. Large-sized monodisperse particles generally tend to generate black spots, so it is especially preferable not to perform chemical sensitization, or when chemically sensitizing, to apply the chemical sensitization shallowly to the extent that black spots do not occur.Here, "shallow application" means Compared to chemical sensitization of small-sized particles, the chemical sensitization time is shorter,
This is done by lowering the temperature or reducing the amount of chemical sensitizer added. There is no particular limit to the sensitivity difference between large-sized monodispersed emulsions and small-sized monodispersed emulsions, but △jogE is 0.
It is preferably from 1 to 1.1, more preferably from 0.2 to 0.7, and is preferably higher for large-sized monodisperse emulsions.

Here, the sensitivity of each emulsion is obtained when it is coated on a support containing a hydrazine derivative and processed using a developer with a pH of 10.5 to 12.3 containing 0.15 mol/1 or more of sulfite ions. It is something.

More specifically, the evaluation method described in Example 1 was followed.

The average grain size of the small monodisperse grains is 90% or less, preferably 80% or less, of the average grain size of the large monodisperse silver halide grains.

The average grain size of the silver halide emulsion grains is preferably 0.02μ to 1.0μ, more preferably 0.1μ to 0.5μ.
It is preferable that the average particle size of large size and small size monodisperse particles is included in this range.

In the present invention, when two or more emulsions of different sizes are used, the coating silver amount of the small-sized monodisperse emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total coating silver amount. %.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When introduced in separate layers, it is preferred that the large emulsion be in the upper layer and the small emulsion in the lower layer.

Further, the emulsion used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 61-219948.
No. 61-219949, No. 62240951,
As shown in No. 63-40137 and No. 6340139, it is preferable to use a silver halide emulsion treated with a porous adsorbent or an ion exchange resin during the manufacturing process, especially a porous adsorbent. It is preferable to use a silver halide emulsion treated with.

The hydrazine derivative used in the present invention has the following formula (
Compounds represented by 1) are preferred.

General formula (I) A+Az In the formula, R1 represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hcarbonyl group, or an iminomethylene group. A and A both represent a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. .

In the general formula (I), the aliphatic group represented by R preferably has 1 to 3 carbon atoms, particularly 1 to 3 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R1 in general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be fused with an aryl group.

R is preferably an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkyne group, an aryl group, a substituted amine group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group, R2-NHCN-C- group, etc. Preferred substituents include an alkyl group (preferably a carbon number of 1 to 20
), an aralkyl group (preferably one having 7 to 30 carbon atoms), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably one substituted with an alkyl group having 1 to 20 carbon atoms) amine group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), Examples include a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms).

The alkyl group represented by R2 in general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). .

When G is a -C- group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), oryl group (e.g., phenyl group, 3゜5-dichlorophenyl group, 0-methanesulfone group) amidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R2 may be substituted, and the substituents listed for R can be used as substituents.

G in general formula (I) is most preferably a 10-group.

Also, R2 splits the G, -R2 part from the remaining molecule,
It may be one that causes a cyclization reaction to produce a cyclic structure containing the atom of the -G1-Rt moiety; examples thereof include those described in JP-A No. 63-29751. .

Hydrogen atoms are most preferred as A1 and A2.

- R1 or R2 in formula (I) may have incorporated therein a ballast group or a polymer commonly used in immobile photographic additives such as couplers. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A No. 1-100530.

R1 or R2 in general formula (I) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group, and the like in U.S. Pat.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜231, 59-201,045, 59
-201.046, 59-201,047, 5
9-201,048, 59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

-Formula (1) Specific examples of compounds represented by are shown below. Shown below.

However, the present invention is not limited to the following compounds.

■-12 ■-13 ■-10 ■-14 ■-15 ■-24 ■-18 ■-20 ■-25 ■-26 In addition to the above-mentioned hydrazine derivatives, RESEARCHDISCLO3URE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
5.108, 4,459,347, 4,560
, No. 638, No. 4.478.928, British Patent No. 2,0
11,391B, JP-A-60-179734, JP-A No. 62
-270,948, 63-29,751, 61
-170゜733, 61-270,744, 6
No. 2-948, EP 217.310, or US 4
゜686.167, JP 62-178,246,
No. 63-32,538, No. 63-104゜047,
No. 63-121,838, No. 63-129.337, No. 63-223,744, No. 63-234,244
No. 63-234,245, No. 63-234,24
No. 6, No. 63-294.552, No. 63-306.4
No. 38, JP-A-1-100,530, JP-A No. 1-105,
No. 941, No. 1-105,943, JP-A-64-10
．． No. 233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1983-
No. 105,682, No. 63-114.118, No. 63
-110,051, 63-114.119, 6
No. 3-116,239, No. 63-147,339, No. 63-179,760, No. 63-229,163,
Patent Application No. 1-18.377, No. 1-18,378, No. 1-18.379, No. 1-15,755, No. 1-1
No. 6.814, No. 1-40,792, No. 1-42.6
No. 15, No. 1-42,616, No. 1-123.693
No. 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention is from lXl0-@mol to 5XlO per mole of silver halide.
-2 mol is preferred, and a particularly preferred addition amount is in the range of 1x10-' mol to 2xlo-1 mol.

The hydrazine derivative of the present invention may be used alone, or two
More than one type may be used in combination.

In the present invention, it is preferable to use a compound that releases a development inhibitor when oxidized to further improve the quality of the resulting image.

The redox compound preferably used in the present invention and capable of releasing a development inhibitor upon oxidation will be described.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminephenols, pyrazolidones, hydrazines, hydroxylamines, and reductones, and more preferably hydrazines.

The hydrazines used as the redox compound capable of releasing a development inhibitor upon oxidation of the present invention preferably have the following general formula (R-1), general formula (R-2), and general formula (R-3). It is expressed as A compound represented by general formula (R-1) is particularly preferred.

General formula (R-1) General formula (R-2) -G.

-G -N- N-CHzCH-(Time).

PUG A, A.

General formula (R-3) Synonymous with AI or -CH,CH云Time), -P
UG In these formulas, R8 represents an aliphatic group or an aromatic group,
G2-R2 group, -〇- group, -So- group, -8○2- group or -P- group. G2 is just a knot G2
R1 represents a compound, -O--S- or -N-, and R2 represents a hydrogen atom or R1.

A1 and A2 represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In general formula (R-1), at least one of A1 and A2 is a hydrogen atom. A represents.

A4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group, -G, or G2-R1.

Time represents a divalent linking group, and t represents O or 1. PUG stands for development inhibitor.

General formulas (R-1), (R-2), and (R-3) will be explained in more detail.

In general formulas (R-1), (R-2), (R-3),
The aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

This alkyl group may have a substituent.

In general formulas (R-1), (R-2), (R-3),
The aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

For example, among the benzene ring, naphthalene ring, pyridine ring, quinoline ring, isoquinoline ring, etc., those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide groups, sulfonamide groups, carboxyl groups, phosphoric acid amide groups, etc. Preferred substituents include linear, branched or cyclic alkyl groups (preferably those having 1 to 2 carbon atoms) and aralkyl groups (preferably has 7 to 30 carbon atoms), alkoxy group (preferably has 1 to 30 carbon atoms), substituted amino group (preferably has 1 to 30 carbon atoms)
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, a ureido group (preferably one having 1 to 40 carbon atoms,
Phosphoric acid amide group (preferably -0- group, -
The SO,- group is preferred, and the -C- group is most preferred.

A, A2 is preferably a hydrogen atom;

is a hydrogen atom, -CH2-CH-eT im e+
-rPUGA.

is preferred.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group and may have a timing adjustment function.

The divalent linking group represented by Time represents a group that releases PUG from the Time-PUG released from the oxidized product of the redox mother nucleus through a reaction of one or more steps.

As the divalent linking group represented by Time, for example, U.S. Pat.
No. 135), etc., which release PUG through an intramolecular ring-closing reaction of p-nitrophenoxy derivatives; U.S. Pat. Those that release PUG by an intramolecular ring-closing reaction after ring cleavage as described in US Pat. No. 4,330,617, US Pat.
No. 4,483,919, JP 59-121.328
U.S. Patent No. 4,40, which releases PUG with the formation of an acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analog described in No.
No. 9,323, No. 4,421,845, Research Disclosure Magazine Nα21,228 (1981
(February), U.S. Patent No. 4,416,977 (Japanese Unexamined Patent Publication No. 1983)
-135.944), JP-A No. 58-209.736, JP-A No. 58-209,738, etc., quinomonomethane is produced by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group. , or an analog thereof to release PUG; U.S. Patent System 4,420,
No. 554 (Japanese Patent Publication No. 57-136,640), Japanese Patent Application Publication No. 5
No. 7-135゜945, No. 57-188,035, No. 58-98.728, and No. 58-209,737, etc., by electron transfer of the moiety having an enamine structure of the nitrogen-containing heterocycle. Release of PUG from the γ-position; intramolecular ring-closing reaction of an oxy group generated by electron transfer to the carbonyl group conjugated with the nitrogen atom of the nitrogen-containing heterocycle described in JP-A No. 57-56,837 Those that release PUG by: U.S. Patent No. 4,146,396 (JP-A-52-90932), JP-A-59-93,442, JP-A-59-75475, JP-A-60-24914
No. 8, JP-A-60-249149, which releases PUG with the production of aldehydes; JP-A-51
-146,828, 57-179.842, 5
9-104,641 which depressurizes PUG with decarboxylation of carboxyl groups; -〇-C○○CR,R
, -PUG (R, , R, represents a -valent group) structure, and releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7,429 Examples include those that release PUG with the production of incyanate as described in US Patent No. 4,438,193, etc.; can.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
It is also described in detail in No. 98,803.

PUG is (Time)−+ PUG or P
UG represents a group having a development inhibiting effect.

The development inhibitor represented by PUG or (Time)-t PUG is a known development inhibitor that has a heteroatom and is bonded via the heteroatom, and these are described, for example, by C.E.C. C.

1: The Theory of the Photographic Process, by K. Mess and T. H. James.
orYof Photographic Proc
3rd edition, 1966 Macmillan (Ma
cmi (1)an) Publishing, pp. 344-346.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R1, and these groups may be further substituted.

Preferred substituents include a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

- In formulas (R-1), (R-2), and (R-3), R1 or (Time+-TPUG is
Among them are ballast groups commonly used in immobile photographic additives such as couplers, and general formulas (R-1) and (R-2).
, (R-3) may be incorporated with a group that promotes adsorption of the compound represented by (R-3) onto silver halide.

The ballast group has the general formula (R-1), (R-2), (R-3
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacylin-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1,2.4-) liazoline-3-thione, 1,3. '4-oxazoline-2-thione, benzimidacillin-2-thion, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriane, ■, 3-imidacillin-2,000 odione, cyclic thioamide group, linear thioamide group, aliphatic mercapto group, aromatic mercapto group, peterocyclic mercapto group (in the case of a -3H group or a nitrogen atom next to a bonded carbon atom, it is synonymous with a cyclic thioamide group that has a tautomeric relationship with this group) (Specific examples of this group are the same as those listed above.) Groups having a disulfide bond, henctriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole , 5- or 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur, and carbon such as oxazoline, thiadiazole, oxathiazole, triazine, and azaindene, and heterocyclic quaternary groups such as benzimidazolinium. Examples include salt.

These may be further substituted with a suitable substituent.

Examples of the substituent include those mentioned above as the substituent for R1.

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited thereto.

■ Test A/ In addition to the above-mentioned redox compounds used in the present invention, for example, Japanese Patent Application Laid-Open No. 61-213゜847,
No. 2-260,153, Patent Application No. 1-102,393,
Those described in No. 1-102,394, No. 1-102,395, and No. 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A-61-213,847 and JP-A-62-260,15.
No. 3, U.S. Patent No. 4,684,604, Patent Application No. 1983-
98,803, U.S. Patent No. 3,379,529, U.S. Patent No. 3,620,746, U.S. Patent No. 4,377.634, U.S. Pat.
．． 332. No. 878, JP-A-49-129,536
No. 56-153,336, No. 56-153,34
It is written in No. 2, etc.

The redox compound of the present invention is preferably 1X10-' to 5X10-2 mol per mole of silver halide, more preferably 1
It is used within the range of Xl0-' to lX10-' moles.

The redox compounds of the present invention can be used in suitable water-miscible organic solvents, such as alcohols (methanol, ethanol, propatool, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl celluloxide. It can be used by dissolving it in.

In addition, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, chryceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. A dispersion can also be prepared and used.

Alternatively, by a method known as solid dispersion method,
The powder of the redox compound can also be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave.

The layer containing the redox compound of the present invention may contain silver halide emulsion grains and/or a hydrazine derivative, or may be another lignophilic colloid layer.

Examples of containing a hydrazine derivative in the photosensitive emulsion layer and containing the redox compound of the present invention in other hydrophilic colloid layers include Japanese Patent Application No. 1-108215 and Japanese Patent Application No. 1-24.
There are issues such as No. 0967.

At this time, the layer containing the redox compound of the present invention may be either an upper layer or a lower layer of the light-sensitive emulsion layer containing the hydrazine nucleating agent. It may also contain silver emulsion particles. An intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the layer containing the redox compound of the present invention and the photosensitive emulsion layer containing the hydrazine nucleating agent.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

The photosensitive material used in the present invention may contain aggravating dyes (for example, cyanine dyes, merocyanine dyes, etc.) described in JP-A No. 55-52050, pages 45 to 53, for the purpose of increasing sensitivity.

These enhancing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of hyperchromatic enhancement.

Along with aggravating pigments, these are pigments that do not themselves have a spectral sensitizing effect or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful enhancing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure+ (Il
search disclosure) I 76
t” 17643 (published December 1978), page 23, item 5.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing capri or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Among these, preferred are benzotriazoles (e.g., 5-methyl-penzotriazole) and nitrointazoles (e.g., 5-nitroindazole); these compounds may also be included in the treatment liquid. Furthermore, a compound which releases an inhibitor during development as described in JP-A No. 62-30243 may be included for the purpose of stabilizing or preventing black spots.

The photographic material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, active vinyl compounds (13,5-triacryloyl-hexahydro-S triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-) (such as riazine), mucohalogen acids (such as mucochloric acid), etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 5B-9412.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
hydroquinone).

Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620.746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
29,536, JP 54-67.419, JP 56-153.336, JP 56-153,342
No., JP-A-59278.853, JP-A No. 59-90435
No. 59-90436, No. 59-138808, and the like.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. 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 lil-soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)acrylates,
Alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination,
Alternatively, a polymer containing a combination of these acrylic acid, methacrylic acid, etc. as a monomer component can be used.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acrylic acid. Polymers or copolymers having acid monomers such as , maleic acid, phthalic acid as repeating units may be mentioned.

Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

In order to obtain photographic characteristics with high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 as described in U.S. Pat. No. 2,419,975. It is not necessary to use a stable developer, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
By using a developer having a pH of 10.5 to 12.3, particularly 11.0 to 12.0, a sufficiently high contrast negative image can be obtained.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3-pyrazolidone are preferred since it is easy to obtain good halftone quality. or a combination of dihydroxybenzenes and P-aminophenols may be used.

Hydroquinone is particularly preferred as the dihydroxybenzene developing agent used in the present invention.

Examples of developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-4-pyrazolidone.

As the P-aminophenol developing agent used in the present invention, N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/l to 0.8 mol/l, and a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is also preferred. When using the former, set it to 0.
05 morph 2-0゜5 mol/l, the latter 0.06 mol/l
It is preferable to use it in an amount of 1 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.15 mol/2 or more, particularly 0.5 mol/1 or more, and the upper limit is preferably up to 2.5 mol/2.

Alkaline salts used for pH setting include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
The pH of the developer, including the Hmm agent and buffering agent, is 10.5 to 1.
It is set between 2.3.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , hexylene glycol, ethanol, methanol, and other solvents with tR = 1-phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, anti-capri agents such as penttriazole compounds such as 5-methylbenztriazole, or black It may also contain a black pepper inhibitor, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a film hardening agent, and JP-A-56-1
06244 and the amino compounds described in JP-A-1-29418.

The developing solution of the present invention contains a silver stain preventive agent.
, No. 347 can be used. Patent application 1986-109.74 as a solubilizing agent added to the developer.
Compounds described in No. 3 can be used. Furthermore, as a pHM buffer for use in developing solutions, JP-A-60-93,433
It is possible to use the compounds described in JP-A-62-186259.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light bread, etc.) as a hardening agent, and the amount of water-soluble aluminum salt is usually 0.4 to 2.
0g-Aj! /j! It is. Furthermore, a trivalent iron compound can be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The processing temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 43°C.

Since the silver halide photographic light-sensitive material of the present invention provides a high Dmax, it maintains a high density even if the halftone dot area is reduced when subjected to power reduction treatment after image formation.

(Example) In the example, developers A, B, and C having the following formulations were used.

Developer solution A At this time, add potassium hydroxide, PH-11゜ Match.

Developer B in developer At the time, add potassium hydroxide, Match.

pH proverb 11° At this time, add potassium hydroxide, PH-11゜ Match.

In addition, the evaluation in each Example was performed by the following test method.

Test method 1, evaluation of image quality +1.1 Creation of manuscript Monochrome scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special photosensitive material 5F-100, a transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed in stages were created. At this time, the number of screen lines was 150 lines/inch.

(2) Photography by Dainippon Screen ■ The original was placed in a plate-making camera C-440 so that the magnification was 1:1, and then the evaluation sample was exposed to light by irradiating it with a Xe lamp.

At this time, exposure was performed so that 95% of the step wedge of the original was exposed to 5%.

(3) Tone reproducibility of the shadow area of the sample with a dot side halftone percentage of 10% by adjusting the exposure time as described in Evaluation (2) (
Relative evaluation was performed on a five-level scale, with 5 being good and 1 being bad in terms of halftone dot collapse resistance.

The obtained sample was exposed to light using a xenon light source, and a developer and a fixer of developer formulation A, GR-F 1 manufactured by Fuji Photo Film Co., Ltd., and an automatic processor FC-71 were used.
Using 0F, development was carried out at 34° C. for 30 seconds, and the eye stretching performance and copy dot performance were evaluated.

Here, the sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of 1.5 when developed at 34° C. for 30 seconds, and the value of sample-1 of each example was set to 100.

Dmax is expressed as a concentration equivalent to Dmax in practical skill.

(On the characteristic curve, fogE for the sensitivity point of density 0.1
(density at +0.5 exposure) 2. Evaluation of copy dots (1) Manuscript creation Monochrome scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special paper SP-1oowp, a step wedge in which the dot percentage was changed in stages was created. The number of screen lines during exposure was 150 lines and 1 inch.

(2) ↑Maximum Dai Nippon Screen■ The above manuscript and sample were set in predetermined positions in a plate making camera C-690 (auto companie), and a Xe lamp was irradiated onto the reflective manuscript to take a photograph.

At this time, the exposure time is 80% of the step wedge on the original.
It was adjusted so that the portion was 10% on the sample.

Evaluation of 3.7% Bottle The photographic properties of Black Bottle were determined by aging the above-mentioned developer over time without replenishment for one week, with the pH increasing by 0.1 and the sulfite ion concentration decreasing to 30% of that of the new solution. After processing in the same manner as above, the quality was evaluated by microscopic observation on a five-point scale, with "5" representing the best quality and "1" representing the worst quality.

"5" or "4" is practical, "3" is poor but barely practical, and "2" or rlJ is impractical.

(Example 1) Emulsions (A) to (K) were prepared by the following method.

[Emulsion A]

A monodisperse silver iodobromide emulsion (average grain size 0.28μ, silver iodide amount 0.
4 mol%) was prepared.

This emulsion was washed with water according to a conventional method to remove soluble salts, and then potassium iodide was added to the emulsion to convert the grain surface, so that the grain average silver iodide content/grain surface silver iodide content = 173. A silver iodobromide emulsion was obtained. Phenoxyethanol was added to this as a preservative.

[Emulsion B]

Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution kept at 50℃
An aqueous solution of potassium iodide and potassium bromide containing 1×10−6 mol of KaRu C12° per mol was simultaneously added to 60
A monodisperse silver iodobromide emulsion (average grain size 0.28 μm, silver iodide content 0.4 mol %) was prepared by adding the mixture for 1 minute and maintaining the pAg at 7.5.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then potassium iodide was added to the emulsion to convert the grain surface, resulting in grain average silver iodide content/grain surface silver iodide content -1/ A silver iodobromide emulsion of No. 3 was obtained. Phenoxyethanol was added to this as a preservative.

[Emulsion C]

In emulsion B, I X 10-' moles of K a Ru C/! per mole of silver. Emulsion C was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing h was used.

[Emulsion D]

In emulsion B, lXl0-S mol (D
An emulsion was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing K4Ru(CN)b was used.

[Emulsion E]

In emulsion B, lXl0-' moles of K per mole of silver
Emulsion E was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing a Ru (CN ) b was used.

[Emulsion F]

Emulsion F was prepared in exactly the same manner as in Emulsion B, except that an aqueous solution of potassium iodide and potassium bromide containing 40 scIlb per 1 mole of silver was used.

[Emulsion G] Emulsion G was prepared in exactly the same manner as in Emulsion B, except that an aqueous solution of potassium iodide and potassium bromide containing I x 10-' mol of KaOs C16 per mol of silver was used.
was prepared.

[Emulsion H]

Emulsion G was prepared in exactly the same manner as in Emulsion B, except that an aqueous solution of potassium iodide and potassium bromide containing 40s(CN)6 at 10@-5 moles of I.sub.x per mole of silver was used.

[Emulsion I]

In emulsion B, 5X10-' moles of K per mole of silver
Emulsion (2) was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing s (2) rCItb was used.

[Emulsion J]

In emulsion B, 5X10-h moles of K per mole of silver
Emulsion J was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing sIrC and the like was used.

[Emulsion K]

In emulsion B, 5X10-' moles of K per mole of silver
Emulsion K was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing sIr(CN)h was used.

These emulsions contain 3X10 per mole of silver as a sensitizing dye.
-'moles of 5,5'-dichloro-9-ethyl-3,3'
-Bis(3-sulfoprobyl)oxacarbocyanine is added, and the following compounds (a) and (b) was added at a coating rate of 5 cm/box.

As SOsH-N(CzHs) y Sow 0 hydrazine compounds, ■-19 was added at 2X10-' mol/silver mol and I-7 was added at 7X10-' mol/silver mol. Furthermore, polyethylene glycol with an average molecular weight of 600 is added to 75
■/rrl, a solid content of a polyethyl acrylate dispersion of 30 wt% to gelatin, 1,3-divinylsulfonyl-2-propanol as a hardening layer, and 3.5 g of silver on a polyethylene terephthalate film.
/m to obtain samples 1 to 11. (Gelatin zgi=> Gelatin 1.2 g/m as a protective layer on this, amorphous SiO□ matting agent 40*/rd with a particle size of about 3 μm, methanol silica 0.Ig/rrr, polyacrylamide 100 μ/d, Hydroquinone 200/M and silicone oil, Proxel and phenoxyethanol as preservatives, and fluorine surfactant represented by the following structural formula as coating aid Cs F +?S O! N CHz C
A layer containing O○KC3H) and sodium dodecylbenzenesulfonate was simultaneously coated to prepare samples as shown in Table 1.

The back layer was coated using the following recipe.

[Back layer prescription]

Gelatin 4 g/m Mantle agent Polymethyl methacrylate (particle size 3.0 to 4.0 μ) 10 μ/Iratesox polyethyl acrylate) 2 g/n
(Surfactant p-dodecylhenzenesulfonate sodium 40■/d Fluorine surfactant Cm F I,s Ox N CHz COOKCsH
v 5■/, (gelatin hardening side CHz = CHS Ox CHz dye dye (a
), [b) Dye (a) Dye (b) Dye (C) 0NH- 110■/n (Mixture of and (C) 50■/d 100■/d 50■/d Dye (a) CH, -C -C=CH-C-C-CH.

II I II
II02K SO, Dye (b) CJsOOCCC=CH CH""'CHCCC00CzHs In addition, Proxel and phenoxyethanol were added as preservatives to the back layer coating solution.

Sample 1-11 thus obtained was subjected to the above-mentioned test and evaluated. The results are shown in Table 1.

As is clear from Table 1, the sample of the present invention using an emulsion formed in the presence of a hexacoordination complex having a cyanide ligand had a lower sensitivity, r, and D□8 compared to the comparative sample. The color is high and the black spots are good.

Dye (C) SO,K 03K SO,K To SOL (Example 2) Emulsions (L) to (S) were prepared by the following method.

[Emulsion L] 0.37 mol of silver nitrate aqueous solution and 1Xl per mol of silver
(NH4)zRhC1ho, corresponding to 0-'mol;
A halogenated salt aqueous solution containing 11 mol of potassium bromide and 0.27 mol of sodium chloride is mixed with sodium chloride and 1
, 3-dimethyl-2-imidazolidine was added to an aqueous gelatin solution containing 1,000 ions at 45° C. for 12 minutes with stirring using the double die method, and the average particle size was 0.20.
Nucleation was performed by obtaining silver chlorobromide grains with a diameter of 70 mol % and a silver chloride content of 70 mol %. Subsequently, in the same manner, 0.63 mol of silver nitrate aqueous solution, 0.19 mol of potassium bromide, and 0.
．． A halogen salt aqueous solution containing 47 mol of sodium chloride was added over 20 minutes by a double jet method. Thereafter, conversion was carried out by adding 1X10-' mol of Kl solution, followed by washing with water by flocculation according to a conventional method, and 40 g of gelatin was added, pH 6.5, pAg 7.
5, and further added 7μ of sodium Hensensulfonate, 5μ of sodium thiosulfate, and 8μ of chloroauric acid per mole of silver, heated at 60°C for 45 minutes, chemically sensitized, and used as a stabilizer. 1.3.3a7 150 μl of tetrazaindene and Proxel as preservative were added. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%) [Emulsion M] ~ [Emulsion S] When performing nucleation in emulsion, 1 mole of silver
x 10-'-T-runi equivalent (NH4)! Rh
Emulsions M~ Emulsion S was prepared.

Thus i) Add 104 moles of 5-(3-(4-sulfobutyl)-
5-chloro-2-oxazuridylidene)-1-hydroquinoethyl-3-(2-pyridyl)-2-thiohydantoin and an additional 2 x 10-4 moles of 1-phenyl-5
- mercaptotetrazole, 5 x 10-' moles of a short-wave cyanine dye represented by the following structural formula (a), a polymer represented by (b) (200 μ/=> and a dispersion of polyethyl acrylate (200 μ/m′)) As a membrane agent 1
, 3-divinyl-sulfonyl-2-propatol (20
0■/d), l-19 which is the hydrazine compound of the present invention
5X10-'' mole/silver mole and I-7 at 8X10-''
'mole/mole of silver was added and coated on a polyethylene terephthalate film at a weight of 113.8 g/mole. (
Gelatin 2g 10f) Compound (a) Compound (b) CHl 1 tip is good. Sample 15 containing an iridium compound.
No. 19 has even better image quality.

/ / Thousand C-CH2÷ C1l.

A protective layer was applied thereon in the same manner as in Example 1 to prepare a sample.

Further, the back layer was also coated using the same recipe as in Example 1.

The sample thus obtained was evaluated in the same manner as in Example 1. The devil set the value of sample 12 to 100.

As is clear from Table 3, compared to the comparative sample, the sample with the structure of the present invention had a lower score of 7. Dmax is high and black po was added and applied to prepare a sample. These samples were evaluated in the same manner as in Example 1. Sensitivity is sample 2
The value of 0 was set as 100. The results are shown in Table 4.

As is clear from the table, the presence of the compound of general formula (I[) of the present invention further improves the image quality.

Example 4 In Examples 1 to 3, when developer B or C was used instead of developer A, the samples of the present invention showed excellent characteristics similar to Examples 1 to 3.

Claims (3)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, the emulsion layer has at least four cyanide ligands containing ruthenium, rhodium, rhenium, osmium, or a silver halide emulsion containing at least one type of hexacoordination complex of iridium, and the emulsion layer or other hydrophilic colloid layer contains at least one type of hydrazine derivative. Silver chemical photographic material. (2) The silver halide emulsion is characterized in that it contains at least an iridium salt other than a hexacoordination complex having at least 4 cyanide ligands of 1×10^-^8 moles per mole of silver. A silver halide photographic material according to claim (1). (3) The silver halide photographic material according to claim (1), wherein the emulsion layer or other hydrophilic colloid layer contains a redox compound that releases a development inhibitor upon oxidation.