JP2663042B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material (especially a negative material) used in the field of photoengraving, capable of rapidly forming an ultra-high contrast image with a highly stable processing solution. Type).

(Prior Art) In the field of photoengraving, an image forming system exhibiting ultra-high contrast (especially gamma of 10 or more) photographic characteristics in order to improve reproduction of continuous tone images or line images by halftone images. is required.

Heretofore, a special developing solution called a lithographic solution has been used for this purpose. The squirrel developer contains only hydroquinone as a developing agent, and uses a sulfite as a preservative in the form of an adduct with formaldehyde so as not to impair its infectious developability, so that the concentration of free sulfite ions is extremely low (usually 0.1%). Mol / or less). Therefore, the squirrel phenomenon liquid has a serious disadvantage that it is extremely susceptible to air oxidation and cannot withstand storage for more than three days.

U.S. Pat. Nos. 4,224,401 and 4,168,977 for obtaining high contrast photographic characteristics using a stable developer.
No. 4,166,742, No. 4,311,781, No. 4,272,60
No. 6, No. 4,221,857, No. 4,243,739, No. 4,269,9
There is a method using a hydrazine derivative described in No. 29 or the like. According to this method, photographic characteristics with ultra-high contrast and high sensitivity are obtained, and the addition of a high concentration of sulfite to the developer is allowed. Dramatically improved.

This new high contrast negative image system can increase the maximum density by adding the amount of the hydrazine derivative, thereby increasing the maximum density and achieving a remarkably high sensitivity. This can cause undesired phenomena, which is a problem in the photoengraving process.

A black spot is a black spot made of minute developed silver which is generated in a portion that should be a non-image in the future unexposed. Black potatoes frequently occur due to a decrease in sulfite ion generally used as a preservative in a developing solution and an increase in pH value, which significantly lowers the commercial value as a photosensitive material for photoengraving. Accordingly, there has been a strong need for an improved black pot system while maintaining a high maximum density and high sensitivity.

In the field of photoengraving, there is a demand for a photographic photosensitive material having good original reproducibility, a stable processing solution, a simple replenishment, and the like in order to cope with the versatility and complexity of printed matter.

In particular, a manuscript in the line drawing photographing process is created by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and line widths are mixed in an original, and a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Therefore, an image forming method having a wider latitude is required to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain photographic sensitivity with respect to these light sources, photographic photosensitive materials are usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

Although the above-mentioned image system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to be symmetric with recent print variety. A system is desired.

Examples of silver halide emulsions containing hexadentate coordination complexes of iron and cobalt with cyanide ligands are described in U.S. Pat.
No. 390, 3,890,154 and the like. EP-A-0,242,190 / A2 also discloses one or more rhodium (III) compounds having 3, 4, 5, or 6 cyanide ligands attached to each rhodium ion. Examples of silver halide emulsions formed in the presence of complex compounds are disclosed. EP-A-0,336,425 / A1 and EP-A-0,336,426 / A1 form a hexadentate coordination complex of rhenium, ruthenium, osmium or iridium having at least four cyanide ligands. Examples of the prepared silver halide emulsions are disclosed. However, there is no mention of using them in combination with a hydrazine derivative.

Examples of using hydrazine derivatives in combination with iridium are disclosed in JP-A-61-29837, JP-A-61-47942, and JP-A-61-201233. An example in which a hydrazine derivative is used in combination with rhodium is disclosed in JP-A-60-83028.

Also, an example of using a hydrazine derivative and ruthenium in combination is as follows:
JP-A-2-3032 discloses, but does not disclose, in these publications, the use of a hexadentate coordination complex containing a cyanide ligand. As for iron, an example of using a hydrazine derivative in combination with a hexadentate coordination complex containing a cyanide ligand is described in Japanese Patent Application No. 1-307362.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, high contrast (for example, γ of 10 or more), high blackening density and low black spots, and an image. It is to provide a forming method.

A second object of the present invention is to provide a very high-sensitivity and ultra-hard silver halide photographic material excellent in line image quality and having a γ of more than 10.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide photographic material has at least four emulsion layers. Ruthenium, rhodium, rhenium, osmium with cyanide ligand,
Alternatively, a halogen comprising a silver halide emulsion containing at least one of hexadentate coordination complexes of iridium, and containing at least one hydrazine derivative in the emulsion layer or another hydrophilic colloid layer. This can be achieved with a silver halide photographic material.

The silver halide grains in the photographic emulsion used in the present invention may have regular crystals such as cubic or octahedral, or irregular such as spherical or plate-like. It may have a crystal or a composite 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 to
0.5 μm. The particle size distribution is preferably monodisperse.

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

The method for preparing the silver halide emulsion used in the present invention is as follows:
Various techniques known in the field of silver halide photographic materials are used. For example, Chimie et Physiqu by P. Glafkides
e Photograhique (Paul Montel, 1967) GFDu
Photographic Emulsion Chemistry (The Foca
l Press, 1966) Making an by VLZelikman et al
d Coating Photographic Emulsion (The Focal Pr
ess, 1964).

That is, any method such as an acid method, a neutral method, and an ammonia method may be used. The method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt includes a one-side mixing method, a simultaneous mixing method, and a combination thereof. Any of these may be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a control double jet method can be used. Grains can also be formed using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

According to the control double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means.

In order to make the particle size uniform, British Patent 1,
No. 535,016, JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate,
It is preferable to use a method of changing the concentration of the aqueous solution as described in JP-A-Sho 4,242,445 and JP-A-55-158124 to grow the solution quickly within a range not exceeding the critical saturation.

The monodispersed emulsion preferably has a regular crystal form such as a cubic, octahedral, or tetradecahedral, and particularly preferably a cubic or tetradecahedral.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase 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 be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide. May be.

The feature of the silver halide emulsion used in the present invention is formed in the presence of at least one of ruthenium, rhodium, rhenium, osmium or iridium hexadentate coordination complex having at least 4 cyanide ligands. It is in.

The transition metal coordination complexes satisfying the requirements of the present invention include those containing the transition metal described above as a transition metal and containing 4,5 or 6 cyanide ligands, and 4 or 5 If only the cyanide ligand is present, the remaining ligands can be any suitable conventional bridging ligand. Also, these hexadentate coordination complexes have an ionic charge in most cases. Thus, it has one or more counterions and forms a charge-neutral compound. The counterion is of little importance since the complex and its counterion dissociate when introduced into an aqueous medium such as used to form silver halide grains. Ammonium and alkali metal counterions are particularly suitable for anionic hexadentate complexes that satisfy the requirements of the present invention, as these cations are known to be well suited for silver halide precipitation operations.

In a preferred embodiment, the hexadentate coordination complex can be represented by formula (A) as follows: (A) [M (CN) _6-y L _y ] ⁿ 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.

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

[Ru (CN) ₆ ] ^-4 , [RuCl (CN) ₅ ] ^-4 , [RuBr (CN) ₅ ] ^-4 , [RuI (CN) ₅ ] ^-4 , [Ru (CN) ₅ H ₂ O] ^-4, [Ru _{(CN) 5 (SCN)]} ^-4, [Ru _{(CN) 5 (OCN)]} ^-4, [RuCl _{2 (CN) 4]} ^-4, [RuBr _{2 (CN) 4]} ^-4 , [RuI ₂ (CN) ₄ ] ^-3 , [Rh (CN) ₆ ] ^-3 , [RhCl (CN) ₅ ] ^-3 , [RhBr (CN) ₅ ] ^-3 , [RhI (CN) ₅ ] ^{- 3} , [Rh (CN) ₅ H ₂ O] ^-3 , [Rh (CN) ₅ (SCN)] ^-3 , [RhCl ₂ (CN) ₄ ] ^-3 , [RhBr ₂ (CN) ₄ ] ^-3 , [RhI ₂ (CN) ₄ ] ^-3 , [Re (CN) ₆ ] ^-4 , [ReCl (CN) ₅ ] ^-4 , [ReBr (CN) ₅ ] ^-4 , [ReI (CN) ₅ ] ^-4 , [Re (CN) ₅ H ₂ O] ^-4 , [Re (CN) ₅ (SCN)] ^-4 , [ReCl ₂ (CN) ₄ ] ^-4 , [ReBr ₂ (CN) ₄ ] ^-4 , [ ReI _{2 (CN) 4]} ^-4, [Os _{(CN) 6]} ^-4, [OsCl _{(CN) 5]} ^-4, [OsBr _{(CN) 5]} ^-4, [OSI _{(CN) 5]} ^-4, [Os (CN) ₅ H ₂ O] ^-4, [Os (CN) (SCN)] ^-4, [OsCl _{2 (CN) 4]} ^-4, [OsBr _{2 (CN) 4]} ^-4, [OsI _{2 (CN) 4]} ^-4, [Ir _{(CN) 6]} ^-3, [IrCl _{(CN) 5]} ^-3, [IrBr _{(CN) 5]} ^-3, [IrI _{(CN) 5]} ^-3, [Ir (CN) ₅ H ₂ O] ^-3, [Ir _(CN) 5 ( SCN)] ^-3, [IrCl _{2 (CN) 4]} ^-3, [IrBr _{2 (CN) 4]} ^-3, [IrI _{2 (CN) 4]} ^-3, these hexadentate coordination complexes, halides 10 per mole of silver
It is used alone in an amount corresponding to ^-8 mol to 10 ^-3 mol, or two or more compounds are used in combination.

Preferably, it is used in the range of 10 ^-7 mol to 10 ^-4 mol.

The addition of these hexadentate coordination complexes can be appropriately performed during the production of a silver halide emulsion and at each stage before coating the emulsion. During the production of silver halide grains, it may be added during grain formation or physical ripening, and also during chemical ripening of the silver halide emulsion. In particular, it is preferably incorporated into silver halide grains.

In order to add the complex at the time of grain formation, it is preferable to add the complex to the water-soluble silver salt or the halide solution when the water-soluble silver salt and the water-soluble halide solution are simultaneously mixed. Alternatively, when the silver salt and the halide solution are mixed simultaneously, the third
May be used to prepare silver halide grains by a three-liquid simultaneous mixing method. Further, a required amount of the above-mentioned aqueous solution of the complex may be added to the reaction solution during the formation of the particles.

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

The amount of the iridium salt or its complex used is 1
It is preferably from 10 ^-8 to 10 ^-5 mol per mol.

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

The “iridium salt other than the hexadentate coordination complex having at least four cyanide ligands” used herein is a water-soluble iridium salt or an iridium complex salt. Preferably trivalent or tetravalent iridium halide or trivalent or tetravalent
Hexavalent iridate, hexabromoiridate, and hexaiodoiridate. In particular, iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), hexachloroiridium (I
V) Potassium acid, ammonium hexachloroiridate (III) and the like are preferred.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
Sulfites, lead salts and thallium salts may coexist.

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

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Preferred sulfur compounds are thiosulfates and thiourea compounds, and preferably have a pAg at the time of chemical sensitization.
8.3 or less, more preferably in the range of 7.3 to 8.0. Moisar, Klein Gelatine.Proc. Symp. 2nd, 301-309
The method of using polyvinylpyrrolidone and thiosulfate in combination as reported by (1970) also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

In the present invention, the silver halide emulsion layer is described in JP-A-61-2237.
No. 34 and No. 62-90646 preferably contain two types of monodispersed emulsions having different average grain sizes from the viewpoint of increasing the maximum density (Dmax). The chemical sensitization method is most preferably sulfur sensitization. The large-size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Since large-sized monodispersed particles generally tend to generate black spots, it is particularly preferable not to perform chemical sensitization, or to apply the chemical sensitization so shallow that black spots do not occur. Here, "shallow application" refers to shortening the time for applying chemical sensitization, lowering the temperature, or reducing the amount of chemical sensitizer added as compared with chemical sensitization of small-sized grains. The sensitivity difference between the large-sized monodispersed emulsion and the small-sized monodispersed emulsion is not particularly limited, but ΔlogE is 0.1 to 1.1, more preferably 0.2 to 0.7, and the larger large-sized monodispersed emulsion is more preferable.

Here, the sensitivity of each emulsion is obtained when the emulsion is coated with a hydrazine derivative, coated on a support, and processed using a developer having a pH of 10.5-12.3 containing sulfite ions in an amount of 0.15 mol / or more. More specifically, it conforms to the evaluation method described in Example 1.

The average grain size of the small-sized monodispersed grains is 90% or less, preferably 80% or less of the average size of the large-sized silver halide monodispersed grains. The average grain size of the silver halide emulsion grains is preferably from 0.02 μm to 1.0 μm, more preferably from 0.1 μm to 0.5 μm, and the average grain size of the large size and small size monodispersed grains is included in this range. preferable.

When two or more kinds of emulsions having different sizes are used in the present invention, the silver coating amount of the small-size monodispersed emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total silver coating amount. is there.

In the present invention, as a method for introducing monodisperse emulsions having different grain sizes, they may be introduced into the same emulsion or into different layers. When introduced into separate layers, it is preferred that the large size emulsion be the upper layer and the small size emulsion be the lower layer.

The emulsion used in the present invention is described in JP-A-61-219948,
61-219949, 62-240951, 63-40137, 63
As shown in -40139 and the like, it is preferable to use a silver halide emulsion treated with a porous adsorbent or an ion exchange resin during the production process. In particular, it is preferable to use a silver halide emulsion treated with a porous adsorbent.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (I).

General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, -SO ₂ -group, -SO- group, Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. This alkyl group may have a substituent.

In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with the aryl group.

Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring.

The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, And the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), and an alkoxy group (preferably having 1 to 20 carbon atoms). ), A substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In formula (I), the alkyl group represented by R ₂ 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, those containing a benzene ring ).

In the case of, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group and the like). ), Aralkyl groups (eg, o-hydroxybenzyl group), aryl groups (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl) And the like), and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

As G in the general formula (I), Is most preferred.

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be such as to occur a cyclic structure cyclization reaction to form a containing, include those described in, for example, JP 63-29751 as an example.

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in JP-A Nos. 62-67,510.

Specific examples of the compound represented by the general formula (I) are shown below. However, the present invention is not limited to the following compounds.

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
Nos. 61-170,733, 61-270,744, 62-948
No., EP217,310, or US 4,686,167, JP-A-62-17
No. 8,246, No. 63-32,538, No. 63-104,047, No. 63-12
Nos. 1,838, 63-129,337, 63-223,744, 63-2
Nos. 34,244, 63-234,245, 63-234,246, 63-
294,552, 63-306,438, JP-A-1-100,530,
No. 1-105,941, No. 1-105,943, JP-A-64-10,233
No., JP-A-1-90,439, Japanese Patent Application No. 63-105,682, 63
-114,118, 63-110,051, 63-114,119, 6
3-116,239, 63-147,339, 63-179,760,
63-229,163, Japanese Patent Application No. 1-18,377, 1-18,378
Nos. 1-18,379, 1-15,755, 1-16,814
Nos. 1-40,792, 1-42615, 1-42616
And those described in Nos. 1-123,693 and 1-126,284 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1.times.10.sup.- ⁶ mol to 5.times.10.sup.- ² mol, more preferably 1.times.10.sup.- ⁵ mol to 2.times.10.sup.- ⁵ mol per mol of silver halide.
A range of × 10 ^-2 mol is a preferable addition amount.

The hydrazine derivative of the present invention may be used alone,
Two or more types may be used in combination.

In the present invention, the use of a compound that releases a development inhibitor by being oxidized further improves the image quality of the obtained image, which is preferable.

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

The redox group of the redox compound is preferably a hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a hydroxyamine, or a reductone, and more preferably a hydrazine.

The hydrazines used as a redox compound capable of releasing a development inhibitor by being oxidized according to the present invention are preferably those represented by the following general formulas (R-1) and (R-2).
It is represented by the general formula (R-3). The compound represented by formula (R-1) is particularly preferred.

In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ .

A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or Represents

A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1.

Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

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

In the general formulas (R-1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 20 carbon atoms. Is a linear, branched or cyclic alkyl group. This alkyl group may have a relaxing group.

In formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ 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 benzene rings, naphthalene rings, pyridine rings, quinoline rings, isoquinoline rings, etc., those containing a benzene ring are particularly preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl Groups, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like. Preferred substituents are a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms). Aralkyl group (preferably having 7 to 30 carbon atoms), aralkyl group Coxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with 30 alkyl groups), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having A compound having 1 to 40, a phosphoric acid amide group (preferably having 1 to 40 carbon atoms) and the like.

As G _{1 in the} general formulas (R-1), (R-2) and (R-3), Is most preferred.

A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, Is preferred.

In the general formulas (R-1), (R-2) and (R-3)
Time represents a divalent linking group, and may have a timing adjusting function.

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

As the divalent linking group represented by Time, for example, an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135) and the like can be used.
U.S. Pat. No. 4,310,612 (Japanese Unexamined Patent Publication No.
Which release PUG by an intramolecular ring-closure reaction after ring opening described in, for example, US Pat. Nos. 4,330,617, 4,446,216, 4,483,919, and JP-A-59-121,328. No. 4,409,323, U.S. Pat. No. 4,421,845, which releases PUG with the formation of an acid anhydride by an intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or an analog thereof described in Research Disclosure No. 21,228 (December 1981), U.S. Patent No.
4,416,977 (JP-A-57-135,944), JP-A-58-209,
No. 736, No. 58-209,738, etc., which produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. No. 4,420,554 (Japanese Unexamined Patent Publication No.
57-136,640), JP-A-57-135,945 and JP-A-57-188,03.
No. 5,58-98,728 and 58-209,737, which release PUG from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring;
7-56,837 which releases PUG by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocyclic ring; U.S. Pat. -90932), JP-A-59-93,4
No. 42, JP-A-59-75475, JP-A-60-249148, with formation of aldehydes described in JP-A-60-249149 and the like.
Those which release PUG; JP-A-51-146,828, 57-179,
No. 842, No. 59-104,641, which release PUG with decarboxylation of carboxyl group; -O-COOCR _a R _b -PUG
(R _a and R _b represent monovalent groups), which release PUG with decarboxylation and subsequent formation of aldehydes; isocyanates described in JP-A-60-7,429 And PUG is released by the coupling reaction of a color developer with an oxidized product described in U.S. Pat. No. 4,438,193.

Specific examples of the divalent linking group represented by Time are described in detail in JP-A-61-236,549 and Japanese Patent Application No. 63-98,803.

PUG represents a group having a development inhibiting effect as (Time _t PUG or PUG).

The development inhibitors represented by PUG or (Time _t PUG are known development inhibitors having a heteroatom and bonded through a heteroatom, such as CEKMess and "The Theory of Photographic Process" by THJames
Processes), 3rd Edition, 1966 Macmillan
It is described in company publications, pages 344 to 346.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those exemplified as the substituent of R ₁ , and these groups may be further substituted.

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

In the general formulas (R-1), (R-2), and (R-3), R ₁ or Time _t PUG is a ballast group commonly used in immobile photographic additives such as couplers. A group which promotes the compounds represented by formulas (R-1), (R-2) and (R-3) to be adsorbed to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-
An organic group that gives a molecular weight sufficient to prevent the compound represented by 3) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, It comprises one or more combinations of an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the group that promotes adsorption to silver halide include-
Thiazoline-2-thione, 4-imidazoline-2-thione-, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4 Cyclic thioamide groups such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, and chain thioamides Group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, this is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo Le, indazole, benzimidazole, imidazole, benzothiazole,
Nitrogen, oxygen, such as thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples thereof include a 5- or 6-membered nitrogen-containing heterocyclic group composed of a combination of sulfur and carbon, and a heterocyclic quaternary salt such as benzimidazolinium.

 It may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent of R ₁ .

Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

As the redox compound used in the present invention, in addition to the above, for example, JP-A-61-213,847 and JP-A-62-260,1
No. 53, Japanese Patent Application No. 1-102,393, No. 1-102,394, No. 1-
Nos. 102,395 and 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A-61-213,847 and JP-A-62-260,153, U.S. Pat.
No. 4,684,604, Japanese Patent Application No. 63-98,803, U.S. Pat.
No. 29, 3,620,746, 4,377,634, 4,332,878
No., JP-A-49-129,536, JP-A-56-153,336, JP-A-56-15
No. 3,342.

The redox compound of the present invention is used in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ per mol of silver halide.
It is used in the range of １1 × 10 ^-2 mol.

The redox compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

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 hydrophilic colloid layer.

Examples of the case where the photosensitive emulsion layer contains a hydrazine derivative and the other hydrophilic colloid layer contains the redox compound of the present invention are Japanese Patent Application Nos. 1-108215 and 1-240967.

At this time, the layer containing the redox compound of the present invention may be either the upper layer or the lower layer of the photosensitive emulsion layer containing the hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain light-sensitive or light-insensitive silver halide emulsion grains. 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 a hydrazine nucleating agent.

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

To the light-sensitive material used in the present invention, sensitizing dyes (for example, cyanine dyes, merocyanine dyes and the like) described in JP-A-55-52050, pp. 45-53 can be added for the purpose of increasing the light sensitivity. .

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with sensitizing dye,
A dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
arch Disclosure) Volume 176 17643 (Issued December 1978) No. 23
It is described in section J on page IV.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. Of these, preferably benzotriazole (eg, 5-methyl-benzotriazole)
And nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during development described in JP-A-62-30243 can be contained for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive 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 hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-) Tricoazines and the like, and mucohalogenic acids (such as mucochloric acid) can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

It is preferable to use a fluorinated surfactant described in JP-A-60-80849 or the like for antistatic.

The photographic light-sensitive material of the present invention includes a hydroquinone derivative (a so-called DIR-) which releases a development inhibitor in a photographic emulsion layer or other hydrophilic colloid layer in accordance with the density of an image during development.
(Hydroquinone).

Examples thereof are U.S. Pat.No. 3,379,529 and U.S. Pat.
20,746, U.S. Patent 4,377,634, U.S. Patent 4,332,878
JP-A-49-129,536, JP-A-54-67,419, JP-A-56-153,336, JP-A-56-153,342, JP-A-59-27
No. 8,853, No. 59-90435, No. 59-90436, No. 59-13880
No. 8 and the like.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, or polymethyl methacrylate for the purpose of preventing adhesion to a photographic emulsion layer or other hydrophilic colloid layers.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, use is made of a polymer having a monomer component of alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like alone or in combination, or a combination of acrylic acid, methacrylic acid, or the like. be able to.

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 salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit.

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

In order to obtain high-sensitivity and high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in U.S. Pat.No. 2,419,975. And a stable developer can be used.

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

The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used.

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

Examples of the developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-4-pyrazolidone.

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

The developing agent is preferably used usually in an amount of 0.05 mol / to 0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol /, and the latter is used in an amount of 0.06 mol / or less. preferable.

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.
The amount of the sulfite is preferably 0.15 mol / or more, particularly preferably 0.5 mol / or more. The upper limit is preferably up to 2.5 mol /.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters and buffers. The pH of the developer is set between 10.5-12.3.

Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve Organic solvents such as hexylene glycol, ethanol and methanol: antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole; Potato (black pepper) inhibitor: may be further contained, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, JP-A-56-106244, and Japanese Patent Application No. Hei 1-106. It may contain an amino compound described in No. 29418 and the like.

The developer of the present invention contains a silver stain inhibitor as disclosed in JP-A-56-24,3.
The compound described in No. 47 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Further, compounds described in JP-A-60-93,433 or compounds described in JP-A-62-186259 can be used as a pH buffer used in the developer.

As the fixing agent, those having a commonly used composition can be used. As a fixing agent, thiosulfates and thiocyanates, and organic sulfur compounds known to have an effect as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, bright bun, etc.) as a hardener. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al /. Further, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent.

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

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

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

The evaluation in each example was performed by the following test methods.

Test method 1. Evaluation of enlargement image quality (1) Creation of manuscript Fuji Photo Film Co., Ltd. monochrome scanner SCAN
Using ART30 and the special photosensitive material SF-100, a transmission image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise were created. At this time, the screen frequency was set to 150 lines / inch.

(2) Photographing The original was set on a plate making camera C-440 manufactured by Dainippon Screen Co., Ltd. so that the magnification was equal, and the sample was exposed to an Xe lamp to expose the evaluation sample.

At this time, the exposure was performed such that 95% of the step wedge of the original became 5%.

(3) Evaluation The exposure time was adjusted as described in (2), and the sample whose dot percentage on the small dot side was 10% and which had good tone reproducibility (the difficulty of dot destruction) in the shadow portion was evaluated as 5, A five-step relative evaluation was performed with the bad one as one.

The obtained sample was exposed to light using a xenon light source. The developer was used as a developer and a fixing solution at a temperature of 34 ° C. using a developer of developer formulation A and GR-F1 manufactured by Fuji Photo Film Co., Ltd. and an automatic developing machine FG-710F. Second development was performed to evaluate the elongation performance and copy dot performance.

Here, the sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5 in development at 34 ° C. for 30 seconds, and the value of Sample-1 in each Example is 100.
And

Dmax was indicated by a density corresponding to Dmax of the practical skill. (On the characteristic curve, the density at an exposure of +0.5 in logE against a sensitivity point of density 0.1) 2. Evaluation of copy dots (1) Original creation Fuji Photo Film Co., Ltd. monochrome scanner SCAN
ART30 and special paper SP-100WP were used to make a step wedge with a step change of net percent. The exposure was performed with a screen ruling of 150 lines and 1 inch.

(2) Photographing The original and the sample were set at predetermined positions on a plate making camera C-690 (Auto Companica) manufactured by Dainippon Screen Co., Ltd., and an Xe lamp was irradiated on the reflective original to photograph.

At this time, the exposure time is 80% of the step wedge on the original
Was adjusted to be 10% on the sample.

3. Evaluation of black pot Black pot was fatigued over time without replenishing the developer of the above formulation for one week, the pH increased by 0.1, and the sulfite ion concentration became 30% of the new solution.
%, Processed in the same manner as the photographic characteristics in a state reduced to 5%, and evaluated by a microscopic observation in five stages.
"5" represents the best and "1" represents the worst quality.
"5" or "4" is practical and "3" is bad, but practically available, "2" or "1" is practically impossible.

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

[Emulsion A]

A monodispersed silver iodobromide emulsion (average grain size 0.28 μ, silver iodide content 0.4 mol%).

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 to obtain a grain average silver iodide content / silver iodide content of grain surface = 1. / 3 silver iodobromide emulsion was obtained. To this was added phenoxyethanol as a preservative.

[Emulsion B]

Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution maintained at 50 ° C
Added per mole 1 × 10 ^-6 mol of K ₄ RuCl ₆ simultaneously 60 minutes of potassium iodide and aqueous solution of potassium bromide containing, monodispersed silver iodobromide emulsion (average by keeping during the pAg at 7.5 (Grain size: 0.28 μm, silver iodide content: 0.4 mol%).

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 to obtain a grain average silver iodide content / silver iodide content of grain surface = 1. / 3 silver iodobromide emulsion was obtained. To this was added phenoxyethanol as a preservative.

[Emulsion C]

In emulsion B, 1 × 10 ^-5 mol of K ₄ Ru per mol of silver
Emulsion C was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing Cl ₆ was used.

[Emulsion D]

In emulsion B, 1 × 10 ^-5 mol of K ₄ Ru per mol of silver
Emulsion D was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing (CN) ₆ was used.

[Emulsion E]

In emulsion B, 5 × 10 ⁻⁵ mol of K ₄ Ru per mol of silver
Emulsion E was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing (CN) ₆ was used.

[Emulsion F]

In emulsion B, 1 × 10 ^-6 mole of K ₄ Os per mole of silver
Emulsion F was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing Cl ₆ was used.

[Emulsion G]

In emulsion B, 1 × 10 ^-5 mole of K ₄ Os per mole of silver
Emulsion G was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing Cl ₆ was used.

[Emulsion H]

In emulsion B, 1 × 10 ^-5 mole of K ₄ Os per mole of silver
Emulsion G was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing (CN) ₆ was used.

[Emulsion I]

In emulsion B, 5 × 10 ⁻⁷ mol of K ₃ Ir per mol of silver
Emulsion I was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing Cl ₆ was used.

[Emulsion J]

In emulsion B, 5 × 10 ^-6 mol of K ₃ Ir per mol of silver
Emulsion J was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing Cl ₆ was used.

[Emulsion K]

In emulsion B, 5 × 10 ^-6 mol of K ₃ Ir per mol of silver
Emulsion K was prepared in exactly the same manner except that an aqueous solution of potassium iodide and potassium bromide containing (CN) ₆ was used.

These emulsions were used as sensitizing dyes in an amount of 3 × 10
^-4 mol of 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine sodium salt was added, and 4-hydroxy-6 was added as a stabilizer.
-Methyl-1,3,3a, 7-tetrazaindene, 5-methylbenzotriazole, and the following compounds (a) and (b) were added so as to be applied at 5 mg / m ² .

As a hydrazine compound, I-19 was added at 2 × 10 ^-5 mol / silver mol and I-7 was added at 7 × 10 ^-4 mol / silver mol. Further, polyethylene glycol having an average molecular weight of 600 was added to a concentration of 75 mg / m ^2, and a dispersion of polyethyl acrylate was added at a solid content of 30 wt% to gelatin, and 1,3-divinylsulfonyl-2-propanol was added as a hardening agent. Samples 1 to 11 were obtained by coating on a polyethylene terephthalate film so that silver became 3.5 g / m ² . (Gelatin 2 g / m ² ) On top of this, gelatin 1.2 g / m ² as a protective layer, amorphous SiO ₂ matting agent 40 mg / m ^{2 with} a particle size of about 3 μm, methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , 200 mg / m ^{2 of} hydroquinone and silicone oil, proxel and phenoxyethanol as preservatives, and a fluorine-based surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare samples as shown in Table 1.

 The back layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4g / m ² Matting agent polymethyl methacrylate (particle size 3.0
4.0μ) 10mg / m ² Latex Polyethyl acrylate 2g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40mg / m ² Fluorine surfactant Gelatin effect agent Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² Proxel and phenoxyethanol were added as preservatives to the back layer coating solution.

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

As is clear from Table 1, the sample of the constitution of the present invention using the emulsion formed in the presence of the hexadentate coordination complex having a cyanide ligand has higher sensitivity, γ, Dmax, and black pot than the comparative sample. Is good.

(Example 2) Emulsions (L) to (S) were prepared by the following method.

[Emulsion L]

0.37 mol silver nitrate aqueous solution and 1 × 10 ^-7 per mol of silver
Mol of (NH ₄ ) ₃ RhCl _{6 An} aqueous halide solution containing 0.11 mol of potassium bromide and 0.27 mol of sodium chloride is added to an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione. The mixture was added at 45 ° C. for 12 minutes with stirring by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Then likewise 0.
63 mol silver nitrate aqueous solution, 0.19 mol potassium bromide,
A halogen salt aqueous solution containing 0.47 mol of sodium chloride was added by a double jet method over 20 minutes. Thereafter, 1 × 10 ⁻³ mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, and added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5. 7 mg of sodium silicate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added, heated at 60 ° C. for 45 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer. Tetrazaindene 150m
g and proxel as a preservative. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation: 9%) [Emulsion M] to [Emulsion S] In the emulsion L, when nucleation is performed, bromide containing (NH ₄ ) ₃ RhCl ₆ equivalent to 1 × 10 ⁻⁷ mol per mol of silver. Emulsions M to S were prepared in exactly the same manner, except that instead of using a halogen salt aqueous solution containing potassium and sodium chloride, a halogen salt aqueous solution containing a metal salt and a metal complex shown in (Table 2) was used.

The emulsion thus obtained was used as a sensitizing dye in an amount of 1.times.10.sup.- ³ mol of 5- [3- (4-sulfobutyl) -5 / mol of silver.
-Chloro-2-benzoxazolidylidene] -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt, and 2 × 10 ^-4 mol of 1-phenyl-5-mercapto was further added. Tetrazole, 5 × 10
^-4 mol of a short-wave cyanine dye represented by the following structural formula (a), a polymer represented by (b) (200 mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ) -Divinyl-sulfonyl-2-propanol (200
mg / m ² ), the hydrazine compound of the present invention I-19
× 10 ^-6 mol / silver mol and I-7 were added at 8 × 10 ^-4 mol / silver mol, and silver was added to the polyethylene terephthalate film.
The coating was performed so as to be 3.8 g / m ² . Gelatin 2g / m ²⁾ A protective layer was applied thereon similarly as in Example 1 to prepare a sample.

 The back layer was also applied according to the same formulation as in Example 1.

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

As is apparent from Table 3, the sample of the present invention has higher sensitivity, γ, Dmax and better black spots than the comparative sample. Samples 15 and 19 containing the iridium compound have better image quality.

Example 3 Emulsions O and S used in Example 2 were replaced by the general formula (II) of the present invention.
Was added as shown in Table 4, and the same compound as in Example 2 was further added, followed by coating to prepare a sample. These samples were evaluated in the same manner as in Example 1. Sensitivity is sample
The value of 20 was set to 100. Table 4 shows the results.

As is clear from the table, the image quality is further improved by the presence of the compound of the general formula (II) of the present invention.

Example-4 In Examples 1 to 3, instead of using the developer A,
When the developer B or C was used, the sample of the present invention showed excellent characteristics as in Examples 1 to 3.

Claims (3)

(57) [Claims] 1. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer contains ruthenium, rhodium, rhenium having at least four cyanide ligands. A silver halide emulsion containing at least one of osmium or iridium hexadentate coordination complexes, and the emulsion layer or another hydrophilic colloid layer contains at least one hydrazine derivative. Silver halide photographic light-sensitive material. 2. The silver halide emulsion according to claim 1, wherein the silver halide emulsion contains at least 1 × 10 ^-8 mol of iridium salt other than hexadentate complex having at least 4 cyanide ligands per mol of silver. The silver halide photographic material according to claim (1). 3. The silver halide photographic material according to claim 1, further comprising a redox compound which releases a development inhibitor by being oxidized into an emulsion layer or another hydrophilic colloid layer.