JPH04264545A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve running stability and to improve image quality and black spots by incorporating a hydrazine deriv. into emulsion layers consisting of silver halide particles contg. a specific transition metal. CONSTITUTION:The silver halide emulsion layers provided on a base consist of the silver halide particles contg. the transition metal selected from group V to VIII elements of periodic table having nitrosyl or thionitrosyl ligand at 10<-8> to 1X10<-6>mol per 1mol silver. At least one layer of these emulsion layers or the other hydrophilic colloidal layers contain the hydrazine deriv. A redox compd. which releases a development inhibitor when oxidized is incorporated particularly into the emulsion layers or other hydrophilic colloidal layers. The degradation in sensitivity, etc., is lessened even if the pH is decreased or the concn. of bromine ions is increased by processing a large amt. of films in this way. Image quality, such as line drawings or dot expandability or dot reducibility, is thereby improved.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to an ultra-high contrast silver halide photographic material used for photolithography.

0002

[Prior Art] In the field of photolithography, in order to deal with the diversity and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment. . Especially in the line drawing process, manuscripts are created by pasting phototypesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, in the manuscript,
There is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can reproduce images of different densities and line widths and finish these originals with good reproduction. On the other hand, in the plate making of catalogs and large posters, enlarging (stretching) or reducing (shrinking) halftone photographs is widely performed. will be photographed. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain the reproducibility of halftone gradation, an image forming method having a wider latitude is required. A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain 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. As a system that meets the demands for a wide latitude, we use a lithium-type silver halide photosensitive material made of silver chlorobromide (silver chloride content of at least 50%), with an extremely low organic concentration of sulfite ions (usually 0.1 mol/min). A known method is to obtain a line or halftone image with high contrast and blackening density, in which image areas and non-image areas are clearly distinguished, by processing with a hydroquinone developer. However, with this method, the concentration of sulfite in the developer is low;
Developing is extremely unstable to air oxidation, and various efforts and ingenuity are required to keep the liquid activity stable, and the processing speed is extremely slow, reducing work efficiency. Met.

[0003] Therefore, it is possible to solve the instability of image formation caused by the above-mentioned development method (lithographic development system), develop it with a processing solution that has good storage stability, and obtain images with ultra-high contrast photographic properties. There is a need for a forming system, one of which is U.S. Pat.
No. 77, No. 4,221,857, No. 4,224,40
No. 1, No. 4,243,739, No. 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound was added was prepared at a pH of 11.0 to 12.3 and 0.00% of a sulfite preservative. A system has been proposed for forming ultra-high contrast negative images with γ of over 10 by processing with a developer containing 15 mol/l or more and having good storage stability. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is. The above imaging system shows excellent performance in terms of sharp halftone quality, processing stability, speed, and original reproducibility, but in order to cope with the variety of printed matter in recent years, further improvements in stability and original reproducibility have been made. A system that is developed is desired.

An example of a system using hydrazine containing a redox compound that releases a development inhibitor upon oxidation for the purpose of improving image quality is disclosed in JP-A-61-213847;
It is disclosed in No. 64-72140. When a redox compound that releases a development inhibitor is used in a system that obtains high contrast using hydrazine, there is a problem that γ decreases. On the other hand, if measures are taken to achieve sufficient contrast (γ>10), such as increasing the amount of hydrazine, using highly active hydrazine, or using a chemically sensitized silver halide emulsion,
There was a problem in that black spots (black pepper) were generated.

On the other hand, an example using silver chlorobromide is disclosed in Japanese Patent Application Laid-Open No. 1986-8.
No. 3028, No. 60-112034, No. 62-235
No. 947 and No. 63-103232. Silver halide emulsions containing heavy metals having nitrosyl and thionitrosyl ligands are disclosed in European Patent Nos. 336,427 and 336,689.

[0006]

The first object of the present invention is to maintain sensitivity, γ, and Dm even if the pH decreases or the bromide ion concentration increases due to processing a large amount of film.
It is an object of the present invention to provide a silver halide photographic material with little decrease in ax. A second object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent image quality such as line drawing or suitability for stretching and shrinking. A third object of the present invention is to provide a silver halide photographic material with improved black spots.

[0007]

[Means for Solving the Problems] The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion contains 10 - characterized in that it consists of silver halide grains containing a transition metal selected from the elements of groups V to VIII of the periodic table having 8 to 1 x 10 -6 moles of nitrosyl or thionitrosyl ligands. This has been achieved by a silver halide photographic material characterized in that at least one of the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative. In particular, this has been more preferably achieved by incorporating a redox compound that releases a development inhibitor upon oxidation into the emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material.

A preferred transition metal coordination complex that achieves the object of the present invention is a hexacoordination complex represented by the general formula below. [M(NY)L5]m (wherein, M is a transition metal selected from the elements of groups V to VIII of the periodic table of elements, L is a bridging ligand, and 1
(NY) may be substituted. Y is oxygen or sulfur. m=0, -1, -2, -3. ) Preferred specific examples of L other than nitrosyl and thionitrosyl bridging ligands include halide ligands (fluoride, chloride,
bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellocyanate, azide and aco ligands. If an aco ligand is present, it is preferred that it occupies one or two of the ligands. Particularly preferred specific examples of M include rhodium, ruthenium, rhenium,
Osmium and iridium.

Specific examples of transition metal coordination complexes are shown below. 1 [Ru(NO)Cl5]-2 2 [Ru(NO)2Cl4]-13 [Ru(
NO)(H2O)Cl4 ]-14 [Rh(NO
)Cl5]-2 5 [Re(NO)Cl5]-2 6 [Re(NO)CN5]-2 7 [Re(NO)ClCN4]-28 [Rh
(NO)2Cl4 ]-19 [Rh(NO)(H2
O) Cl4 ]-110 [Ru(NO) CN5
]-211 [Ru(NO)Br5]-212
[Rh(NS)Cl5]-213 [Os(NO
)Cl5]-214 [Cr(NO)Cl5]-
315 [Re(NO)Cl5]-116 [O
s(NS)Cl4(TeCN)]-217 [Ru(
NS)I5]-2 18 [Re(NS)Cl4(SeCN)]-219
[Os(NS)Cl(SCN)4]-220
[Ir(NO)Cl5]-2

[0010] In order to incorporate the above-mentioned metal complex into silver halide, it can be added at the time of grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10-8 to 1 x 10-6 mol per mol of silver halide, but preferably 10-
The amount is 7 to 5×10 −7 mol. In the silver halide grains of the present invention, metals having different ligands can be used in combination with the metal complexes having nitrosyl and thionitrosyl ligands.

The hydrazine derivative used in the present invention as a nucleating agent is preferably a compound represented by the following general formula (1). General formula (1)

0012

[Chemical formula 1]

In the formula, R11 represents an aliphatic group or an aromatic group, and R12 represents a hydrogen atom, an alkyl group, an aryl group,
It represents an alkoxy group, an aryloxy group, an amino group or a hydrazine group, and G11 is a -CO- group, -SO2 -
group, -SO- group, -P(O)R13- group, -COCO
- group, thiocarbonyl group or iminomethylene group, A11 and A12 are both hydrogen atoms, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group,
Or represents a substituted or unsubstituted acyl group. R13 is selected from within the same range as the group defined for R12, and may be different from R12.

In the general formula (1), the aliphatic group represented by R11 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. The aromatic group represented by R11 in general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group. Preferred as R11 is an aryl group, particularly preferably one containing a benzene ring. The aliphatic group or aromatic group of R11 may be substituted, and typical substituents include 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 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, R14-NHCO-N(
R15) -CO- group (R14 and R15 are selected from the same groups as defined for R2 and may be different from each other), and preferred substituents include an alkyl group (preferably a carbon number of 1 to 20). ), aralkyl groups (preferably those with 7 to 30 carbon atoms), alkoxy groups (preferably those with 1 to 20 carbon atoms), substituted amino groups (preferably amino substituted with alkyl groups having 1 to 20 carbon atoms) basis)
, 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), phosphoric acid amide group group (preferably 1 to 3 carbon atoms)
0) etc. These groups may be further substituted. General formula (1
), the alkyl group represented by R12 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 G11 is a -CO- group, preferred among the groups represented by R12 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamide group). propyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., o-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonyl group) phenyl group, 2-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferred. R12 may be substituted, and the substituents listed for R11 can be used as substituents. G11 of general formula (1)
The most preferred is -CO- group. Also, R12 is G1
1-R12 part is split from the remaining molecule, -G11-
It may be one that causes a cyclization reaction to produce a cyclic structure containing the atom of the R12 moiety, and examples thereof include those described in JP-A No. 63-29751. Hydrogen atoms are most preferred as A11 and A12.

R11 or R12 in the general formula (1) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done. Also, as a polymer, for example, JP-A-1-10
Examples include those described in No. 0530.

R11 or R12 in general formula (1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include:
U.S. Patent No. 4,385,108 for thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
No. 4,459,347, JP-A-59-195, 2
No. 33, No. 59-200, 231, No. 59-201,
No. 045, No. 59-201, 046, No. 59-201
, No. 047, No. 59-201,048, No. 59-20
No. 1,049, No. 61-170,733, No. 61-2
No. 70,744, No. 62-948, No. 63-234,
No. 244, No. 63-234, 245, No. 63-234
, No. 246. General formula (1)
Specific examples of compounds represented by are shown below. However, the present invention is not limited to the following compounds.

[0018]

[Case 2]

[0019]

[Chemical formula 3]

[0020]

[C4]

[0021]

[C5]

[0022]

[C6]

[0023]

[C7]

[0024]

[Chemical formula 8]

In addition to the above-mentioned hydrazine compounds as nucleating agents used in the present invention, RESEAR
CH DISCLOSURE Item 23516
(November 1983, p. 346) and the documents cited therein, as well as U.S. Pat.
, No. 269,929, No. 4,276,364, No. 4.
No. 278,748, No. 4,385,108, No. 4,4
No. 59,347, No. 4,560,638, No. 4,47
No. 8,928, British Patent No. 2,011,391B, Japanese Patent Application Publication No. 60-179,734, No. 62-270,948, No. 63-29,751, No. 61-170,733, No. 61 -270,744, 62-270,948
No., EP 217,310, EP 356,898, U
No. S4,686,167, JP-A-62-178,246
No. 63-32,538, No. 63-104,047
No. 63-121,838, No. 63-129,33
No. 7, No. 63-223,744, No. 63-234,2
No. 44, No. 63-234, 245, No. 63-234,
No. 246, No. 63-294, 552, No. 63-306
, No. 438, JP-A-1-100,530, JP-A No. 1-10
No. 5,941, No. 1-105,943, JP-A No. 1983-
No. 10,233, JP-A-1-90,439, JP-A-1
-276,128, 1-280,747, 1-
No. 283,548, No. 1-283,549, No. 1-2
No. 85,940, No. 2-2541, No. 2-139,5
No. 38, No. 2-77057, Patent Application No. 1-18,377
No. 1-18,378, No. 1-18,379, No. 1-15,755, No. 1-16,814, No. 1-4
No. 0,792, No. 1-42,615, No. 1-42,6
No. 16, No. 1-123,693, No. 1-126,28
Those described in No. 4 can be used. The additive of the hydrazine compound as a nucleating agent in the present invention is 1 x 10-6 mol to 5 mol per mol of silver halide.
It is preferable to contain ×10 −2 mol, especially 1 × 10
The preferred addition amount is in the range of -5 mol to 2 x 10-2 mol.

The redox compound of the present invention which can release a development inhibitor upon oxidation will be explained. The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, 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), represented by the general formula (R-3). General formula (R
A compound represented by -1) is particularly preferred.

[0028]

[Chemical formula 9]

In these formulas, R1 represents an aliphatic group or an aromatic group. G1 is -CO- group, -COCO- group, -CS- group, -C(=NG2R2)- group, -SO
- group, -SO2 - group or -P(O)(G2 R2
) - represents a group. G2 is just a bond, -O-, -S
- or -N(R2)-, 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), A1
, A2 is a hydrogen atom. A3 has the same meaning as A1 or -CH2 -CH(A4)-(T
ime)t-PUG.

A4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G1 -G2 -R1. Time represents a divalent linking group, t is 0 or 1
represents. PUG stands for development inhibitor. General formula (R-
1), (R-2), and (R-3) will be explained in more detail. In general formulas (R-1), (R-2), and (R-3), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. straight chain,
It is a branched or cyclic alkyl group. This alkyl group may have a substituent.

General formula (R-1), (R-2), (R-3
), the aromatic group represented by R1 is monocyclic or bicyclic.
It is a ring 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:
For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Ureido group, urethane group, aryloxy group, asfamoyl 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, carbonamide group, sulfonamide group,
Examples include a carboxyl group, a phosphoric acid amide group, etc. Preferred substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (
(preferably one having 7 to 30 carbon atoms), an alkoxy group (preferably one having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), and an acylamino group (preferably one substituted with an alkyl group having 1 to 30 carbon atoms). (preferably one having 2 to 40 carbon atoms), a sulfonamide group (preferably one having 1 to 4 carbon atoms)
0), ureido group (preferably 1 to 4 carbon atoms)
0, a phosphoric acid amide group (preferably a carbon number of 1 to
40) etc.

General formula (R-1), (R-2), (R-3
) is preferably a -CO- group or a -SO2- group, most preferably a -CO- group. A1 and A2 are preferably hydrogen atoms, and A3 is a hydrogen atom, -
CH2-CH(A4)-(Time)t-PUG
is preferred. General formula (R-1), (R-2), (R-3
), Time represents a divalent linking group and may have a timing adjustment function. The divalent linking group represented by Time is T released from the oxidized product of the redox mother nucleus.
It represents a group that releases PUG from ime-PUG through one or more reaction steps.

[0035] As the divalent linking group represented by Time, for example, US Pat.
No. 4-145,135), which releases PUG through an intramolecular ring-closing reaction of p-nitrophenoxy derivatives; US Pat.
U.S. Pat. No. 4,330,617 and U.S. Pat. No. 4,446, which release PUG by an intramolecular ring-closing reaction after ring cleavage as described in U.S. Pat.
, No. 216, No. 4,483,919, JP-A-59-1
No. 21,328, etc., which releases PUG with the production of acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analog; US Pat. No. 4,409,323; No. 4,421,845,
Research Disclosure Magazine No. 21,228
(December 1981), U.S. Patent No. 4,416,977
No. (JP-A No. 57-135,944), JP-A No. 58-2
No. 09,736, No. 58-209,738, etc., in which quinomonomethane or an analog thereof is generated by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group, and PUG is released. U.S. Patent No. 4,420,554
No.), JP-A-57-135,945, JP-A No. 57-188
, No. 035, No. 58-98,728 and No. 58-2
P from the γ-position of the enamine by electron transfer of the enamine structure-containing part of the nitrogen-containing heterocycle described in No. 09,737, etc.
Those that release UG; those that release PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle described in JP-A No. 57-56,837 ; U.S. Patent No. 4,146,
No. 396 (JP-A-52-90932), JP-A-59-
No. 93,442, JP-A-59-75475, JP-A-6
0-249148, JP-A-60-249149, etc., which release PUG with the production of aldehydes; JP-A-51-146,828, JP-A-57-179,
842 and 59-104,641 which releases PUG with decarboxylation of the carboxyl group; -O-
COOCRa has the structure of Rb-PUG (Ra and Rb represent monovalent groups) and releases PUG with decarboxylation and subsequent generation of aldehydes; disclosed in JP-A-60-7,429 which releases PUG with the formation of isocyanates as described; US Pat. No. 4,438,1
Examples include those that release PUG through a coupling reaction with an oxidized product of a color developer described in No. 93 and the like.

Specific examples of these divalent linking groups represented by Time can be found in JP-A No. 61-236,549;
It is also described in detail in Japanese Patent Application No. 63-98,803. PUG represents a group having a development inhibiting effect as (Time)t-PUG or PUG. PUG or (
The development inhibitor represented by 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.Mies (C.E.Mies). K.Mess) and T.H.
“The Theory of the Photographic Process” by T.H. James
Theory of Photographic Pr
3rd edition, 1966 Macmillan
Cmillan), 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.

Further, general formulas (R-1), (R-2), (R
-3), R1 or -(Time)t -P
UG contains ballast groups commonly used in immobile photographic additives such as couplers, general formulas (R-1), (
A group that promotes adsorption of the compound represented by R-2) or (R-3) to silver halide may be incorporated.

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 from diffusing into other layers or processing liquids, and includes alkyl groups, aryl groups, heterocyclic groups, and ethers. group, thioether group, amide group, ureido group, urethane group, 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.

Examples of the adsorption promoting group to silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, then It has the same meaning as a cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), a group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz imidazole, imidazole,
5- to 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur and carbon, such as benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene, and benz Examples include heterocyclic quaternary salts such as imidazolinium.

[0040] These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent for R1. Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0041]

[Chemical formula 10]

[0042]

[Chemical formula 11]

[0043]

[Chemical formula 12]

[0044]

[Chemical formula 13]

[0045]

[Chemical formula 14]

[0046]

[Chemical formula 15]

[0047]

[Chemical formula 16]

[0048]

[Chemical formula 17]

In addition to the above-mentioned redox compounds, examples of the redox compounds used in the present invention include those described in Japanese Patent Application Laid-Open No. 61-213, 8
No. 47, No. 62-260, 153, Patent Application No. 1-102
, No. 393, 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 described in, for example, JP-A No. 61-213,847.
No. 62-260,153, U.S. Patent No. 4,684,6
No. 04, Japanese Patent Application No. 63-98,803, U.S. Patent No. 3,
No. 379,529, No. 3,620,746, No. 4,3
No. 77,634, No. 4,332,878, Japanese Unexamined Patent Publication No. 1977
-129,536, 56-153,336, 5
6-153,342, etc.

The redox compound of the present invention is used in an amount of 1 x 10-6 to 5 x 10-2 mol, more preferably 1 x 10-5 to 1 x 10-2 mol, per mol of silver halide. . The redox compounds of the present invention can be dissolved in suitable water-miscible organic solvents, such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used after being dissolved. In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things. Alternatively, a powder of a redox compound can be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave, using a method known as a solid dispersion method.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, but preferably has a silver chloride content of 50 mol % or more and is either silver chlorobromide or silver iodochlorobromide. The silver iodide content is 3 mol% or less, more preferably
It is 0.5 mol% or less. Various methods known in the field of silver halide photographic materials can be used to prepare the monodisperse silver halide emulsion used in the present invention. For example,
“Shimmy” by P. Glafkides
Chimie e Physique Photographic (Chimie e
t Physique Photographique
)” (Paul Montel
), G.F. Dufin (1967), G.F.
．． Photographic Emulsion Chemistry (Photographic Emulsion Chemistry) by Duffin
lsion Chemistry) (The Focal Press) 19
1966), V.L. Zelikman
Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions) by Ikman et al.
King and Coating Photogra
phic Emulsion” (The Focal Press) 1964
It can be prepared using the method described in 2010).

The silver halide emulsion used in the present invention is preferably a monodisperse emulsion with a variation coefficient of preferably 20% or less, particularly preferably 15% or less. Here, the coefficient of variation (%) is the value obtained by dividing the standard deviation of the particle size by the average value of the particle size and multiplying it by 100. The average grain size of grains in a monodisperse silver halide emulsion is 0.
．． 5 μm or less, particularly preferably 0.1 μm to 0.1 μm.
It is 4 μm.

[0053] The water-soluble silver salt (silver nitrate aqueous solution) and the water-soluble halogen salt may be reacted by any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetrasubstituted thiourea. More preferred are tetrasubstituted thiourea compounds, which are described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethinithiourea, 1,3-dimethyl-2-imidazolidinethione. 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. The monodisperse emulsion preferably has a regular crystal shape such as a cube, an octahedron, or a tetradecahedron, and a cubic 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 monodispersed emulsion of the present invention is preferably chemically sensitized, and known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used, and these methods may be used alone or in combination. A preferred chemical sensitization method is gold 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. Specific examples are U.S. Patent Nos. 1,574,944 and 2,27
No. 8,947, No. 2,410,689, No. 2,728
, No. 668, No. 3,501,313, No. 3,656,
It is described in No. 955. 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. More Moisar
, Klein Gelatine. Proc. Syme
．． 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, such as platinum, palladium, and iridium. Specific examples thereof are described in US Pat. No. 2,448,060, British Patent No. 618,061, etc.

Gelatin is advantageously used as a binder or protective colloid for photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N-
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

[0056] In the present invention, Japanese Patent Application Laid-Open No. 55-52050
Sensitizing dyes having an absorption maximum in the visible range (for example, cyanine dyes, merocyanine dyes, etc.) described on pages 45 to 53 of the present invention may also be added. This allows spectral sensitization to be performed on the longer wavelength side than the inherent sensitivity region of silver halide. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure.
closure ) Volume 176 17643 (1978
(February issue) Page 23, Section IV, J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro benzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4
-Hydroxy-substituted (1,3,3a,7)tetrazaindenes), pentaazaindenes, etc. Known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, Many other compounds can be added. Among these, preferred are benzotriazoles (e.g.
-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Also,
These compounds may 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 developing agents such as hydroquinone derivatives and phenidone derivatives for various purposes such as stabilizers and accelerators. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.),
Dioxane derivatives, 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-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. For example, saponin (
steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines, amides, polyethylene oxide adducts of silicone),
Nonionic surfactants such as alkyl esters such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonic acids salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters amphoteric surfactants such as alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or hetero Cationic surfactants such as ring-containing phosphonium or sulfonium salts can be used. In particular, the surfactant preferably used in the present invention is
These are polyalkylene oxides with a molecular weight of 600 or more described in Japanese Patent No. 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 a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in accordance with the density of the image during development in the photographic emulsion layer and other hydrophilic colloid layers. It's okay. Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat. No. 4,377,634, U.S. Pat.
, No. 536, JP-A-54-67,419, JP-A-56
-153,336, JP-A-56-153,342,
Examples include compounds described in JP-A-59-278,853, JP-A-59-90435, JP-A-59-90436, and JP-A-59-138808.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, or polymethyl methacrylate in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example alkyl (meta)
Polymers containing as monomer components acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. 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 compounds having acid groups include polymers or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, JP-A No. 61-22383
No. 4, No. 61-228437, No. 62-25745, and No. 62-55642 can be referred to. 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.

The emulsions used in this invention are coated onto a suitable support such as glass, acetic acid, cellulose film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin-coated paper, and the like.

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a pH 13 developer described in US Pat. No. 2,419,975.
It is not necessary to use a highly alkaline developer close to that of 100%, and a stable developer can be used. That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0.
Contains 15 mol/liter or more, pH 10.5-12.3
In particular, a sufficiently high contrast negative image can be obtained using a developer having a pH of 11.0 to 12.0. Although there are no particular restrictions on the developing agent used in the developer used in the present invention, it is preferable that it contains dihydroxybenzenes, since it is easy to obtain good halftone dot quality, and dihydroxybenzenes and 1-
A combination of phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5- Examples include dimethylhydroquinone, and hydroquinone is particularly preferred.

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, and 1-phenyl-4-pyrazolidone. Methyl-4-
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone,
Examples include 1-p-tolyl-4,4-dimethyl-3-pyrazolidone. The p-aminophenol developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, p-aminophenol, and p-aminophenol.
-aminophenol, N-(β-hydroxyethyl)-
p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, p-
Among them, N-methyl-p-aminophenol is preferred. The developing agent is preferably used in an amount of usually 0.05 mol/liter to 0.8 mol/liter. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is 0.
05 mol/liter to 0.5 mol/liter, the latter being 0
．． It is preferable to use it in an amount of 0.6 mole/liter or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfites are 0.15 mol/liter or more, especially 0.
．． It is preferably 5 mol/liter or more. Also, the upper limit is 2.5
Preferably up to mol/liter. Alkaline agents used for setting pH include pH adjusting agents and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. The pH of the developer is set between 10.5 and 12.3. Additives used in addition to the above components 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 organic solvents; 1-phenyl-5-mercaptotetrazole, 5-
Antifoggants such as indazole compounds such as nitroindazole, benztriazole compounds such as 5-methylbenztriazole, or black pep
per) inhibitor; and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, an amino compound described in JP-A-56-106244, etc., as necessary. . In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. JP-A-61-2677 as a dissolution aid added to the developer
Compounds described in No. 59 can be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,43
Compounds described in No. 3 or JP-A-62-186259
Compounds described in this issue can be used.

[0067] As the fixing agent, one having a commonly used composition can be used. As a fixing agent, thiosulfate,
In addition to thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain water-soluble aluminum (eg, aluminum sulfate, alum, etc.) as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0.4 to 2.0 g-Al/
It is a liter. Furthermore, a trivalent iron compound can also 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.

[0068]

EXAMPLES Next, the present invention will be explained in more detail based on examples. The developer used had the formulation described below. (Developer formulation) Hydroquinone

50.0g N-methyl-p-aminophenol
0.3g sodium hydroxide

18.0g 5-sulfosalicylic acid
55.0g Potassium sulfite
110.
0g Disodium ethylenediaminetetraacetate
1.0
g potassium bromide

10.0g 5-methylbenzotriazole
0.4g 2-mercaptobenzimidazole-5-sulfonic acid
0.3g 3-(5-mercaptotetrazole)benzenesulfonic acid 0.2g Sodium N-n-butyldiethanolamine
15.0g
Sodium toluene sulfonate
8.0
g Add water

1 liter Adjust to pH=11.6 (add potassium hydroxide) pH 11
．． 6

Example 1 An emulsion was prepared in the following manner. Emulsion A: 0.13 M aqueous silver nitrate solution containing K2 Ru(NO)Cl5 corresponding to 1 x 10-7 mol and K2 IrCl6 corresponding to 2 x 10-7 mol per mole of silver and 0.04 M bromide. A halogen salt aqueous solution containing potassium and 0.09M sodium chloride was mixed with sodium chloride and 1,3-dimethyl-2
- In an aqueous gelatin solution containing imidazolidinethione,
It was added by double jet method for 12 minutes at 38°C with stirring, and the average particle size was 0.15 μm, and the silver chloride content was 7.
Nucleation was performed by obtaining 0 mol% silver chlorobromide grains. Subsequently, 0.87M silver nitrate aqueous solution and 0.87M silver nitrate aqueous solution were added in the same manner.
A halogen salt aqueous solution containing 26M potassium bromide and 0.65M sodium chloride was prepared by a double jet method.
Added over 0 minutes. Then 1 x 10-3 mol of KI
Add the solution and perform conversion, wash with water by flocculation method according to the usual method, add 40 g of gelatin, adjust to pH 6.5 and pAg 7.5, and further add 8 mg of sodium benzenethiosulfonate and 5 mg of sodium thiosulfate per mole of silver. and 8 mg of chloroauric acid, and 6
The mixture was heated at 0° C. for 60 minutes to undergo chemical sensitization treatment, and 150 mg of 1,3,3a,7-tetrazaindene was added as a stabilizer. The obtained particles had an average particle size of 0.27 μm,
They were silver chlorobromide cubic particles with a silver chloride content of 70 mol%. (Coefficient of variation 10%) Emulsions B to J having different types and contents of heavy metals were prepared in the same manner.

Emulsions A to J were divided into silver 1 as a sensitizing dye.
1×10 −3 mol per mole of 5-[3-(4-sulfobutyl)-5-chloro-2-oxazolidylidene]-1
-Hydroxyethyl-3-(2-pyridyl)-2-thiohydantoin was added, and further 2 x 10-4 mol of 1-phenyl-5-mercaptotetrazole and 5 x 10-4 mol of the following structural formula (a) were added. shortwave cyanine dye expressed,
Water-soluble latex (200 mg/m
2) and polyethyl acrylate dispersion (200 m
g/m2) 1,3-divinylsulfonyl- as a hardening agent
2-propanol (200 mg/m2), hydrazine compound (c) of the present invention (1 x 10-4 mol/mol Ag),
and other hydrazine compounds were added as shown in Table 1.

[0071]

[Chemical formula 18]

[0072]

[Table 1]

[0073] On top of this, 1.0 g of gelatin was added as a protective layer.
m2, amorphous SiO2 with a particle size of approximately 3.5μ, matting agent 40mg/m2, methanol silica 0.1g/m2
, polyacrylamide 100mg/m2, hydroquinone 200mg/m2 and silicone oil (20mg/m2).
2) and a fluorine surfactant (5 mg/m2) represented by the following structural formula as a coating aid.

[0074]

[Chemical formula 19]

A layer containing sodium dodecylbenzenesulfonate (100 mg/m2) was simultaneously coated and
A sample like this was prepared. The evaluation results are shown in Table 2. The back layer and back layer protective layer were coated using the following formulations.

[Back layer formulation] Gelatin

3g/m2 latex polyethyl acrylate
2g/m2 Surfactant p-
Sodium dodecylbenzenesulfonate 4
0mg/m2

[0077]

[C20]

Dye Mixture of dyes [a], [b] and [c] Dye [a]

50mg/m2 dye [b]

100mg/m2
Dye [c]

50mg/m2

[0079]

[C21]

[Back protective layer] Gelatin

0.8mg/m2 Polymethyl methacrylate fine particles (average particle size 4.5μ) 30m
g/m2 Dihexyl-α-sulfosacnate sodium salt 15mg/m2
Dodecylbenzenesulfonic acid sodium salt
15mg/m2 Sodium acetate

40mg/m2

[0081]

[C22]

As is clear from Table 2, samples 1 to 1 of the present invention
6 has good photographic characteristics of 2 and black spots. In addition,
Evaluation was performed using the following test method. (Photographic properties) The photographic properties are FG-6 with the developer of the above formulation.
These are the results of 30" processing at 34°C using a 60F automatic processor (manufactured by Fuji Photo Film Co., Ltd.). GR-F1 was used as the fixer. Here, the sensitivity is a density of 1 when developed for 30 seconds at 34°C. The value of sample 1 was set to 100 with the relative value of the reciprocal of the exposure amount giving .5.Here, γ is expressed by the following formula.

[0083]

[Formula 1]

It is defined as follows. Black spots are evaluated by microscopic observation of the developed area after developing at 34° C. for 40 seconds, 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 "1" is impractical. Those between "4" and "3" were evaluated as "3.5."

[Evaluation of line image quality] Reflection density is 0.5 to 1
．． A manuscript consisting of 7th grade Mincho typeface and Gogic typeface typeface in the 2nd grade range was scanned using a Dainippon Screen camera (DSC3).
After photographing with 51), development processing (
The results are the results obtained at 34° C. 30″).Evaluation is performed on a 5-level 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 "1" is impractical.

[0086]

[Table 2]

Example 2 Emulsions K, L and M were prepared in the following manner. Emulsion K: 0.
13M silver nitrate aqueous solution and 1 x 10-7 per mole of silver
molar equivalent of K2 Ru(NO)Cl6 and 2×
Contains K3IrCl6 equivalent to 10-7 moles and 0.0
A halogen salt aqueous solution containing 52M potassium bromide and 0.078M sodium chloride was mixed with sodium chloride and 1,3
It was added to an aqueous gelatin solution containing dimethyl-2-imidazolidinethione at 45°C for 12 minutes with stirring, and the average particle size was 0.15 μm.
Nucleation was performed by obtaining silver chlorobromide grains with a silver chloride content of 60 mol %. Subsequently, a halogen salt aqueous solution containing 0.87M silver nitrate aqueous solution, 0.34M potassium bromide, and 0.52M sodium chloride was similarly added over 20 minutes by the double jet method. then 1×10
- Conversion was performed by adding 3 mol of KI solution, washing with water by the flocculation method according to a conventional method, adding 40 g of gelatin, and adjusting the pH to 6.5 and pAg to 7.5.
In addition, per mole of silver 8 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid.
1,3,3a,7-tetrazaindene was added as a stabilizer. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10%).

Emulsion L: 0.13M silver nitrate aqueous solution and K2 Ru (corresponding to 1 x 10-7 mol per mol of silver)
NO) Cl6 and K3 equivalent to 2 x 10-7 mol
Contains IrCl6 with 0.078M potassium bromide and 0
．． A halogen salt aqueous solution containing 052M sodium chloride was added to an aqueous gelatin solution containing sodium chloride by a double jet method at 45°C for 12 minutes while stirring to obtain an average particle size of 0.15 μm and a silver chloride content of 70 mol%. Nucleation was carried out by obtaining silver chlorobromide grains. Subsequently, in the same manner, 0.87M silver nitrate aqueous solution and 0.522
A halogen salt aqueous solution containing M potassium bromide and 0.348 M sodium chloride was mixed with 20
It was added over a period of minutes. After that, 1 x 10-3 mol of KI solution was added to carry out conversion, followed by washing with water by the flocculation method according to a conventional method, and 40 g of gelatin was added.
The pH was adjusted to 6.5 and the pAg was adjusted to 7.5, and 8 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate, and 8 mg of chloroauric acid were added per mole of silver.
The mixture was heated at .degree. C. for 60 minutes to undergo chemical sensitization treatment, and 150 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added as a stabilizer. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.27 μm and a silver chloride content of 40 mol%. (Variation coefficient 11%)

Emulsion M: In the presence of ammonia, 1 mol of silver nitrate aqueous solution and 1.2 x 10-7 mol of K2Ru(NO)Cl6 per 1 mol of silver were added to an aqueous gelatin solution kept at 50°C.
Potassium iodide and potassium bromide aqueous solutions containing 60
A cubic monodisperse emulsion with an average grain size of 0.25 μm and an average silver iodide content of 1 mol % was prepared by adding 40 g of gelatin for 1 minute and maintaining the pAg at 7.8. Added pH=6.0 pA
g = 8.5, added 5 mg of sodium thiosulfate and 6 mg of chloroauric acid, heated at 60°C for 60 minutes, subjected to chemical sensitization treatment, and added 4-hydroxy-6-methyl-1,3, 150 mg of 3a,7-tetrazaindene was added. (variation coefficient 9%)

Emulsions A, K, L, and M were divided to contain 5-[3-(4
-sulfobutyl)-5-chloro-2-oxazolidylidene]-1-hydroxyethyl-3-(2-pyridyl)-
2-thiohydantoin was added, followed by 2 x 10-4 moles of 1-phenyl-5-mercaptotetrazole, 5 x 1
0-5 mol ethylthiosulfonic acid sodium salt, 5x
10 −4 mol of a short-wave cyanine dye represented by the following structural formula (a), a water-soluble latex represented by (b) (20
0 mg/m2) and a dispersion of polyethyl acrylate (200 mg/m2), 1,3-divinylsulfonyl-2-propanol (200 mg/m2) as a hardening agent, hydrazine compound (c) of the present invention (1 x 10-4 mol/mol Ag), (d) (1 x 10-6 mol/mol Ag).

[0091]

[C23]

(Preparation of redox compound-containing layer emulsion) 1
．． 0M silver nitrate aqueous solution and 3 x 10-7 per mole of silver
An aqueous halogen salt solution containing 0.3M potassium bromide and 0.74M sodium chloride, containing mol of (NH4)3RhCl6, was mixed with sodium chloride and 1,3-dimethyl-
In an aqueous gelatin solution containing 2-imidazolinthione,
It was added by double jet method for 30 minutes at 45°C with stirring, and the average particle size was 0.28 μm, and the silver chloride content was 7.
0 mol % silver chlorobromide particles were obtained. Thereafter, it was washed with water by the flocculation method according to a conventional method, and 40 g of gelatin was added to adjust the pH to 6.5 and pAg to 7.5, and further 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per mole of silver.
was added, heated at 60°C for 60 minutes, subjected to chemical sensitization treatment, and 4-hydroxy-6-methyl-1,3,
150 mg of 3a,7-tetrazaindene was added. The obtained grains had an average grain size of 0.28 μm and a silver chloride content of 7.
It was 0 mol% silver chlorobromide cubic particles. (coefficient of variation 1
0%). This emulsion was divided and used as a sensitizing dye at a concentration of 1 x 10-3 mol of 5-[3-(4-sulfobutyl)-5-chloro-2-oxazolidylidene]-1-hydroxyethyl-3 per mol of silver. -(2-pyridyl)-2-thiohydantoin was added, and a dispersion of 2 x 10-4 mol of 1-phenyl-5-mercaptotetrazole and polyethyl acrylate was added at 50 mg/m2 of 1,2-bis(vinylsulfonyl). 40 mg/m2 of acetamido)ethane and the redox compound of the present invention were added as shown in Table 3.

[0093] The hydrazine-containing layer is the bottom layer (Ag3.6g
/m2, gelatin 2g/m2), a layer containing a redox compound (Ag0.4g/m2, gelatin 0.5g/m2) via an intermediate layer (gelatin 0.5g/m2), and a protective layer thereon. Gelatin 1.0g/m2, amorphous SiO2 matting agent 40 with a particle size of approximately 3.5μ
mg/m2, methanol silica 0.1g/m2, polyacrylamide 100mg/m2, hydroquinone 200
mg/m2, silicone oil, and a fluorine surfactant (5 mg/m2) represented by the following structural formula as a coating aid, and sodium dodecylbenzenesulfonate (40 mg/m2).
A layer containing 2) was simultaneously coated to prepare samples as shown in Table 3. The evaluation results are shown in Table 3. Further, the back layer and the back layer protective layer were coated using the same formulation as in Example 1.

[0094]

[C24]

[0095]

[Table 3]

As is clear from Table 3, the sample containing the redox compound of the present invention shows good dependence on the processing solution composition and black spots, and exhibits excellent line image quality.

[0097]

Effects of the Invention The present invention improves running stability and image quality by using an ultra-high contrast silver halide photographic material containing a transition metal having 10-8 to 10-6 moles of nitrosyl or thionitrosyl ligand and a hydrazine nucleating agent. And it was possible to improve black spots.

Claims (3)

[Claims] Claim 1: In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion has a concentration of 10 -8 to 1 x 1 per mole of silver.
A silver halide photographic photosensitive material comprising silver halide grains containing a transition metal selected from elements of Groups V to VIII of the Periodic Table having 0 to 6 moles of nitrosyl or thionitrosyl ligands. A silver halide photographic material containing a hydrazine derivative in at least one of the emulsion layer or other hydrophilic colloid layer. 2. The silver halide photographic material according to claim 1, wherein the silver halide in the emulsion layer has a silver chloride content of 50 mol % or more. 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.