JPH04291336A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the natural fogging with lapse of time and the degradation in the max. blackening density at the time of under-exposing by incorporating at least one kind of specific compds. into hydrophilic colloidal layers consisting of a silver halide. CONSTITUTION:Emulsion layers consist of the silver halide contg. the transition metal selected from group V to VIII elements of periodic table having nitrosil or thionitrosil of at least 1X10<-6> per 1mol silver and contain at least one of the compds. expressed by formula I, formula II and formula III in the hydrophilic colloidal layers. In the formulas I, II, R1 to R4 respectively denote a hydroxy group, hydroxyl amino group, amino group, etc. In the formula III, X1, X2 denote -OR1 or -NR2(R3); A denotes an arylene group. The hydrogen atom incorporated into the groups of at least one of X1, X2 and A may be substd. with a group for accelerating adsorption to the silver halide particle.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that can be handled in an environment that can be essentially called a bright room. .

0002

2. Description of the Related Art In the field of printing reproduction, there is a demand for improvement in the efficiency of the photolithography process in order to deal with the variety and complexity of printed matter. In particular, efforts have been made to improve work efficiency by performing the work in a brighter environment, especially in the collection and reversing processes. Progress has been made in the development of silver halide photosensitive materials for plate making and exposure printers. The silver halide photographic light-sensitive material for bright rooms described in this patent refers to
It refers to a photographic material that can use light with a wavelength of 0 nm or more as safelight light. Silver halide photographic light-sensitive materials for bright room use used in the collection and reversing processes use developed films on which characters or halftone images have been formed as originals, and these originals and silver halide photographic light-sensitive materials for reversing are combined. It is a photosensitive material used to convert a negative image to a positive image or a positive image to a negative image by contact exposure. , to have the ability to perform negative image/positive image conversion according to the character image width■ It is desired to have the performance to be able to adjust the tone of halftone images and the line width of characters and line images, and we have developed a bright room back that meets this demand. Silver halide photographic materials have been provided. However, when adjusting the tone of a halftone image in a bright room reversing process using a bright room silver halide photographic light-sensitive material, if underexposure occurs, the entire surface is originally developed, and the density of areas that should be blackened tends to drop significantly. It had a drawback.

[0003] As a method for obtaining high contrast and increasing Dmax, there is a method in which a developing agent is incorporated into a silver halide photographic light-sensitive material, as disclosed in US Pat. No. 4,617,258 and JP-A-5
Although these are disclosed in JP-A No. 9-171947, JP-A No. 59-206828, and JP-A-1-262533, they do not satisfy all of the performance requirements of safelight, long-term storage stability, and Dmax. In addition, a silver halide crystal containing impurities (heavy metals) is disclosed in European Patent No. 3364.
No. 27 and No. 336689, however, the storage stability is poor and fogging occurs, and the above-mentioned performances of (1) and (2) and the performance of Dm cannot be maintained stably.

0004

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to use a bright room silver halide photographic light-sensitive material that can be handled in a bright room environment, and to stably prevent density decrease during underexposure. The object of the present invention is to provide a silver halide photographic light-sensitive material that provides small and excellent reversing performance. Furthermore, a second object of the present invention is to provide a silver halide photographic light-sensitive material that exhibits excellent reversal performance without any change in photographic performance due to natural aging.

[0005]

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, in which each emulsion layer is is at least 1x per mole of silver
The hydrophilic colloid layer is made of silver halide containing a transition metal selected from the elements of groups V to VIII of the periodic table and has 10-6 moles of nitrosyl or thionitrosyl ligand, and the hydrophilic colloid layer has the following general formula [ I], [II] or [
III] This was achieved by a silver halide photographic material containing at least one compound represented by the following.

[0006]

[Chemical formula 3]

[0007]

[C4]

In the formula, R1 to R4 may be the same or different, and each represents a hydroxy group, a hydroxylamino group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy group, a phenoxy group,
It represents an alkyl group, an aryl group, an alkylthio group, a phenylthio group or a hydrazino group. General formula [III] X1 -A-X2
In the formula, X1 and X2 are -OR1 or -NR2
(R3), (R1 represents a hydrogen atom or a group that can become a hydrogen atom through hydrolysis, R2, R
3 each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group,
It represents a heterocyclic sulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a sulfamoyl group, or a carbamoyl group. ) A represents an arylene group, and at least one of X1, X2 and A may have a hydrogen atom contained in the group substituted with a group promoting adsorption onto silver halide grains.

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)
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 ligands, cyanate ligands, thiocyanate ligands. ligand, selenocyanate ligand,
Mention may be made of tellocyanate, acid and aco ligands. If an aco ligand is present, it is preferred that it occupies one or two of the ligands. Particularly preferred examples of M are rhodium, ruthenium, rhenium, osmium, and iridium.

Specific examples of transition metal coordination complexes are shown below. 1 [Ru(NO)Cl5]-22 [
Ru(NO)2 Cl4 ]-13 [Ru(N
O) (H2 O)Cl4 ]-14 [Rh(N
O)Cl5 ]-25 [Re(NO)Cl5
]-26 [Re(NO)CN5]-27
[Re(NO)ClCN4]-28 [R
h(NO)2 Cl4 ]-19 [Rh(NO)
)(H2O)Cl4 ]-110 [Ru(N
O)CN5]-211 [Ru(NO)Br5
]-212 [Rh(NS)Cl5]-21
3 [Os(NO)Cl5]-214
[Cr(NO)Cl5]-315 [Re(N
O)Cl5]-116 [Os(NS)Cl4
(TeCN)]-217 [Ru(NS)I5
]-218 [Re(NS)Cl4 (SeC
N)]-219 [Os(NS)Cl(SCN)
4]-220 [Ir(NO)Cl5]-2

[0011] 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 10-6 mol per mol of silver halide, preferably from 10-6 to 5 x 10-4 mol, especially from 1 x 10-5 to 5
x10-4 mol. There is no particular restriction on the distribution of the transition metal in the silver halide grains, but it is preferred that the transition metal be present in a larger amount outside the grains.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is preferably silver halide containing silver chloride in an amount of 90 mol% or more, and silver chlorobromide or silver halide containing 0 to 5 mol% of silver bromide. Silver chloroiodobromide. An increase in the proportion of silver bromide or silver iodide is undesirable because it deteriorates safelight safety in a bright room or lowers γ. The silver halide used in the present invention is preferably a so-called core/shell type silver halide, particularly a core/shell type silver halide in which the metal content of the shell is higher than that of the core. In order to make the above-mentioned water-soluble metal complex salt exist in silver halide grains, there is a method of adding it to the water-soluble silver salt or to the halide solution when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution. preferable. Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be prepared by a method of simultaneous mixing of three solutions as a third solution. The grain size of the silver halide emulsion of the present invention is preferably 0.20 μm or less.

[0013] In order to prepare silver halide fine grains in the present invention, the mixing conditions include a reaction temperature of 50°C or lower, preferably 40°C or lower, more preferably 30°C or lower, and a sufficiently high stirring speed to ensure uniform mixing. Silver potential below 70m
Good results can be obtained by adjusting the voltage to V or more, preferably from 80 mV to 120 mV. There are basically no restrictions on the particle size distribution, but it is preferable that it be monodisperse. Monodisperse here means at least 9 in terms of weight or number of particles.
5% is comprised of particles having a size within ±40% of the average particle size, more preferably within ±20%. The silver halide grains of the present invention preferably have regular crystal bodies such as cubes and octahedrons, and cubic shapes are particularly preferred.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too. 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. A specific example is U.S. Patent 2,44
No. 8,060, British Patent No. 618,061, etc. 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. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

Next, the general formula [I
], [II] and [III] will be explained in detail. The following general formula [I
], [II] or [III] The compound represented by [III] may be used in any layer (emulsion layer, intermediate layer, protective layer, etc.) of a silver halide photographic light-sensitive material, but is preferably used in the silver halide emulsion layer. It is more preferable. First, general formula [I]
and [II] will be explained.

[0016]

[C5]

[0017]

[C6]

In the formula, R1 to R4 may be the same or different, and each represents a hydroxy group, a hydroxylamino group, an amino group, or an alkylamino group (preferably a carbon number of 1 to 1).
5), an aralkylamino group (preferably one having 7 to 11 carbon atoms), an arylamino group (preferably an amino group substituted with an aryl group having 6 to 10 carbon atoms), alkoxy (preferably those with 1 to 5 carbon atoms), phenoxy groups, alkyl groups (preferably those with 1 to 5 carbon atoms), aryl groups (preferably those with 6 to 10 carbon atoms), alkylthio groups (preferably those with 6 to 10 carbon atoms), phenoxy groups, alkyl groups (preferably those with 1 to 5 carbon atoms), 1 to 5), a phenylthio group, or a hydrazino group. The alkyl moiety in each of the above groups is a hydroxy group, an alkoxy group (preferably one having 1 to 4 carbon atoms, especially one having 1 to 2 carbon atoms), an amino group, an alkylamino group (preferably one having 1 to 4 carbon atoms, especially one having 1 to 2 carbon atoms). The alkyl group may have a substituent such as a mono- or di-substituted amino group. Further, in each group represented by R1 to R4 above, the aryl or phenyl moiety is a hydroxy group, an amino group, an alkylamino group (preferably a mono- or di-substituted amino group of an alkyl group having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms), an alkyl It may have a substituent such as a group (preferably one having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms) and an alkoxy group (preferably one having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms). Compounds of general formulas [I] and [II] preferably used in the present invention are illustrated below.

[0019]

[C7]

[0020]

[Chemical formula 8]

[0021]

[Chemical formula 9]

[0022]

[Chemical formula 10]

[0023]

[Chemical formula 11]

[0024]

[Chemical formula 12]

[0025]

[Chemical formula 13]

[0026]

[Chemical formula 14]

[0027]

[Chemical formula 15]

[0028]

[Chemical formula 16]

These compounds are described in the Journal of the
Organic Chemistry, Vol. 27, p. 4054 (19
62), Journal of the American Chemical Society, Vol. 73, p. 2981 (1951), Japanese Patent Publication No. 10692/1980, etc. These compounds can be used as an aqueous solution, an aqueous hydrochloric acid solution, or a methanol solution to form a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer, an intermediate layer, etc., but a layer adjacent to the emulsion layer is preferable). Add to the hydrophilic colloid solution for. The timing of addition is not particularly limited, but when added to a photographic emulsion, it is convenient to add it after the second ripening and immediately before coating. The amount of these compounds added varies depending on the type of polymer used in combination, but is usually 0.01 g to 10 g, especially 0.1 g to 1 g per mole of silver.
Set to a range of

Next, the general formula [III] used in the present invention
The compound represented by will be explained. General formula [III
], A is a substituted or unsubstituted arylene group (
For example, phenylene group, naphthylene group, etc.), and substituents include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with 1 to 20 carbon atoms), and aryl groups (preferably those with 6 to 20 carbon atoms). ), alkoxy groups (preferably those having 1 to 20 carbon atoms), aryloxy groups (preferably those having 6 to 20 carbon atoms), alkylthio groups (preferably those having 1 to 20 carbon atoms), arylthio groups ( Preferably those having 6 to 20 carbon atoms), acyl groups (
Preferably those having 2 to 20 carbon atoms), acylamino groups (
(preferably an alkanoylamino group having 1 to 20 carbon atoms, a benzoylamino group having 6 to 20 carbon atoms), a nitro group, a cyano group, an oxycarbonyl group (preferably a carbon number 1 to 20 group)
alkoxycarbonyl group, aryloxycarbonyl group having 6 to 20 carbon atoms), carboxy group, sulfo group, hydroxy group, ureido group (preferably an alkylureido group having 1 to 20 carbon atoms, arylureido group having 6 to 20 carbon atoms) ), a sulfonamide group (preferably an alkylsulfonamide group having 1 to 20 carbon atoms, an arylsulfonamide group having 6 to 20 carbon atoms), a sulfamoyl group (preferably an alkylsulfamoyl group having 1 to 20 carbon atoms, a carbon number 6～
20 arylsulfamoyl group), carbamoyl group (
Preferably an alkylcarbamoyl group having 1 to 20 carbon atoms,
arylcarbamoyl group having 6 to 20 carbon atoms), acyloxy group (preferably one having 1 to 20 carbon atoms), amino group (unsubstituted amino, preferably an alkyl group having 1 to 20 carbon atoms, or an acyloxy group having 6 to 20 carbon atoms) a secondary or tertiary amino group substituted with an aryl group), a carbonate group (preferably an alkyl carbonate group having 1 to 20 carbon atoms, a carbonate group having 6 to 20 carbon atoms)
20 aryl carbonate groups), sulfonyl groups (preferably alkylsulfonyl groups having 1 to 20 carbon atoms, arylsulfonyl groups having 6 to 20 carbon atoms), sulfinyl groups (
Preferably an alkylsulfinyl group having 1 to 20 carbon atoms,
Examples include arylsulfinyl groups having 6 to 20 carbon atoms) and heterocyclic groups (pyridine, imidazole, furan, etc.).

When there are two or more substituents, they may be the same or different, and when two substituents are substituted on adjacent carbon atoms of the benzene ring, they are linked to form a 5- to 7-membered ring. Carbocycles or heterocycles may be formed, and these rings may be saturated or unsaturated. Specific ring-forming compounds include cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cycloheptadiene,
Examples include indane, norbornane, norbornene, benzene, and pyridine, which may further have a substituent. In addition, the total number of carbon atoms in the substituents is 1 to 20.
The number is preferably 1 to 10, more preferably 1 to 10.

Examples of the group represented by R1 which can become a hydrogen atom by hydrolysis include -COR4 (R4
represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group.

[0033]

[Chemical formula 17]

(J represents -CO- or -SO2 -,
Z represents a plurality of atoms necessary to form a heterocycle having at least one 5- or 6-membered ring. ).

R2 and R3 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted aryl group Sulfonyl group, substituted or unsubstituted heterocyclic sulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted heterocyclic carbonyl group, substituted or unsubstituted sulfamoyl group, substituted Alternatively, it represents an unsubstituted carbamoyl group, and R2 and R3 may be the same or different, or may be linked to form a nitrogen-containing heterocycle. (For example, morpholino group, piperidino group, pyrrolidino group, imidazolyl group, piperazino group, etc.) R2, R3
Examples of the substituent include the same substituents as those listed for A.

The adsorption-promoting group to silver halide can be represented by the following formula: Y-(L)m - Y is the adsorption-promoting group to silver halide, and L is a divalent linking group. m is 0 or 1. Preferred examples of the adsorption promoting group to silver halide represented by Y include a thioamide group, a mercapto group, a group having a disulfide bond, or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group represented by Y is a divalent group represented by -CS-amino, and may be a part of a ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
No. 30,925, No. 4,031,127, No. 4,08
No. 0,207, No. 4,245,037, No. 4,255
, No. 511, No. 4,266,013, and No. 4,27
No. 6,364 and “Research Disclosure”
Magazine Volume 151 No. 15162 (November 1976)
, and Volume 176 No. 17626 (1978
You can choose from those disclosed in February). Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc. Specific examples of cyclic thioamide groups 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-thiadiazolin-2-thione, 1,3,4-oxadiazolin-2
-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione, which may be further substituted.

The mercapto group of Y is an aliphatic mercapto group,
An aromatic mercapto group or a heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group that has a tautomeric relationship with this group, and specific examples of this group are the same as those listed above).

The 5- to 6-membered nitrogen-containing heterocyclic group represented by Y includes a 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur, and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole,
Examples include benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These may be further substituted with a suitable substituent.

[0039] As the substituent, those mentioned as the substituent for A can be mentioned. Among those represented by Y, preferred are cyclic thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles, such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group,
5-mercaptotetrazole group, 2-mercapto-1,
3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g.
(benzotriazole group, benzimidazole group, indazole group, etc.). Y-(L)m- group is 2
More than one may be substituted, and may be the same or different.

The divalent linking group represented by L is C
, N, S, and O. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S
-, -NH-, -N=, -CO-, -SO2 - (these groups may have a substituent), etc., alone or in combination.

As a specific example, -CONH-
, -NHCONH- , -SO2NH- , -COO
-, -NHCOO-, -CH2-, -(CH2)-
, -(CH2)3-, -NHCONHCH2CH2
CONH- , -CH2CH2SO2NH- , -CH
2CH2CONH-,

[0042]

[Chemical formula 18]

[0043]

[Chemical formula 19]

[0044] etc. These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent for A.

Next, preferred specific examples of the compound represented by the general formula [III] will be shown, but the scope of the present invention is not limited thereto.

[0046]

[C20]

[0047]

[C21]

[0048]

[C22]

[0049]

[C23]

[0050]

[C24]

[0051]

[C25]

[0052]

[C26]

[0053]

[C27]

[0054]

[C28]

[0055]

[C29]

[0056]

[C30]

[0057]

[Chemical formula 31]

[0058]

[C32]

Typical methods for synthesizing the compound of general formula [III] will be described below with reference to synthetic examples. Synthesis Example Synthesis of Compound III-55 23.8 g (0.1 mol) of 5-phenylbenztriazole carbonate, 25.2 g (0.11 mol) of 2-(4-aminophenyl)-ethylhydroquinone, and 100 ml of DMAC were mixed in a nitrogen stream. The mixture was heated and stirred in an oil bath at 120° C. (external temperature) for 5 hours. Next, DMAC was distilled off under reduced pressure, and methanol
When ml was added, a trace amount of black crystal by-product remained as an insoluble matter. Insoluble matter was removed by suction filtration, methanol was distilled off under reduced pressure, and the resulting reaction mixture was isolated and purified using a silica gel column (chloroform/methanol = 4/1). After washing with methanol, the target product I-11 was isolated. Obtained. Yield 14.4 (38
．． 5%) melting point: 256-7°C, and the compound represented by the general formula [III] has a melting point of 1 x 10-5 per mole of silver halide.
It is preferably added in an amount of from 1.times.10@-1 mol to 1.times.10@-1 mol, particularly from 1.times.10@-4 to 5.times.10@-2 mol. When these compounds of general formula [III] are incorporated into a photographic light-sensitive material, they may be contained in an aqueous solution if they are water-soluble, or as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), or ketones if they are water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution in a water-miscible organic solvent such as (for example, acetone). When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after chemical ripening, especially when the coating is prepared for coating. It is preferable to add it to the liquid.

In the photographic material produced using the present invention, it is preferable that the hydrophilic colloid layer located above the emulsion layer contains a dye dispersed in solid form as a filter dye. Specific examples of preferred dyes are shown below, but the invention is not limited thereto. Furthermore, solid dispersed dyes are described in International Application Publication (WO) No. 88/04794, European Patent No. 0276566, and the like.

[0061]

[Chemical formula 33]

[0062]

[C34]

Furthermore, a water-soluble dye may be used in combination with the hydrophilic colloid layer or emulsion layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. The photographic emulsion and non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardening agent. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, N,N-methylenebis-[β-
(vinylsulfonyl)propionamide], active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-
morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A No. 53-41220, No. 53-57257, No. 59-162546, No. 60-8
0846 and U.S. Pat.
325,287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (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 glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonic acids salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylborioxyethylene 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. 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 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 acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, etc. as monomer components can be used. Gelatin is advantageously used as a condensing agent or protective colloid in 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-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyvinylpyrazole. 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. The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate. Supports for the photosensitive material of the present invention include cellulose triacetate,
Cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, etc. can be used.

There is no particular restriction on the developing agent used in the developing solution used in the present invention, but it is preferable that it contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl are preferred because they facilitate obtaining good halftone quality. A combination of -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,
, 5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred. 1-phenyl-3 used in the present invention
- As a developing agent for pyrazolidone or its derivative, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and so on. Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-
(β-hydroxyethyl)-p-aminophenol, N
-(4-hydroxyphenyl)glycine, 2-methyl-
Among them, p-aminophenol, p-benzylaminophenol and the like are preferred, among which 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 should be mixed at 0.05 mol/liter to 0.05 mol/liter.
5 mol/l, the latter preferably in an amount of up to 0.06 mol/l. Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably at least 0.3 mol/liter, particularly preferably at least 0.4 mol/liter. Further, the upper limit is preferably up to 2.5 mol/liter, particularly up to 1.2 mol/liter. Alkaline agents used to set pH include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate, and potassium silicate. Contains buffering agent. Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , hexylene glycol, ethanol, methanol and other organic solvents: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-
Mercapto compounds such as sulfonic acid sodium salt, 5-
It may contain antifoggants such as indazole compounds such as nitroindazole, benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, antifoaming agents, water softeners, hardeners, etc. as necessary. membrane agent,
It may also include. In particular, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-48-35493 are preferred from the standpoint of accelerating development or increasing sensitivity. The developing solution used in the present invention contains a compound described in JP-A No. 56-24347 as a silver stain preventive agent, and a compound described in JP-A-62-212,6 as an agent for preventing uneven development.
No. 51), as a solubilizing agent, JP-A-61-
Compounds described in No. 267759 can be used. In the developing solution used in the present invention, a buffering agent is used.
Boric acid described in No. 2-186259, JP-A-60-93
Saccharides (e.g., saccharose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalcylic acid), tertiary phosphates (e.g., sodium salt, potassium salt), etc. described in 433 are used, and preferably Boric acid is used.

The fixing solution is an aqueous solution containing, in addition to the fixing agent, a hardening agent (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof) as necessary. , has a pH of 3.8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0.1
~about 5 mol/liter. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, and includes, for example, aluminum chloride, aluminum sulfate, and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective to use these compounds in a content of 0.005 mol or more per liter of the fixing solution, particularly 0.01 mol/liter to 0.03 mol/liter. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, and the like. Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate. The fixer further contains a preservative (e.g. sulfite, bisulfite), if desired.
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Here, since the pH of the developer is high, the pH buffer is used in an amount of about 10 to 40 g/liter, more preferably about 18 to 25 g/liter. The fixing temperature and time are the same as for development, about 20
℃ to about 50℃ for 10 seconds to 1 minute is preferred. Also, use anti-mold agents in the washing water (for example, from Horiguchi's ``Chemistry of Bacteria and Prevention'').
, the compound described in JP-A-62-115154)
, a water washing accelerator (such as sulfite), a chelating agent, etc. may be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out to almost completely remove the silver salt dissolved during fixing, and is preferably carried out at about 20° C. to about 50° C. for 10 seconds to 3 minutes. Drying is carried out at a temperature of about 40° C. to about 100° C., and the drying time can be changed as appropriate depending on the surrounding conditions, but is usually about 5 seconds to 3 minutes and 3 seconds. U.S. Patent No. 3025 regarding roller conveyance type automatic developing machine
It is described in Japanese Patent No. 779 and Japanese Patent No. 3,545,971, and is simply referred to herein as a roller conveyance type processor. A roller conveyance type processor consists of four steps: development, fixing, washing, and drying, and although the method of the present invention does not exclude other steps (for example, a stopping step), it is most preferable to follow these four steps. . Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method. The developer used in the present invention is preferably stored in a packaging material with low oxygen permeability as described in JP-A-61-73147. Further, the developer used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 62-9193.
The replenishment system described in No. 9 can be preferably used. The silver halide photographic material of the present invention has a high Dm
ax, and therefore, when subjected to power reduction processing after image formation, a high density is maintained even if the halftone dot area is reduced. There are no particular restrictions on the reducing fluid used in the present invention;
For example, "The Theory of th
e Photographic Process”73
Pages 8-744 (1954, Macmillan)
, Tetsuo Yano, “Photo Processing Theory and Practice” 166-16
In addition to published works such as 9 pages (1978, Kyoritsu Shuppan), Japanese Patent Publication Nos. 50-27543, 52-68429, and 55-
No. 17123, No. 55-79444, No. 57-101
No. 40, No. 57-142639, JP-A No. 61-611
Those described in No. 55 etc. can be used. That is, permanganates, persulfates, ferric salts, cupric salts, ceric salts, red blood salts, dichromates, etc. are used alone or in combination as oxidizing agents, and if necessary, Inorganic acids such as sulfuric acid,
A reducing solution containing alcohol, or an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetic acid salt, and a silver halide solvent such as thiosulfate, rhodan salt, thiourea or a derivative thereof, and as necessary. Depending on the situation, a reducing fluid containing an inorganic acid such as sulfuric acid is used. Typical examples of the reducing fluid used in the present invention include so-called Farmer reducing fluid, ferric salt of ethylenediaminetetraacetic acid, potassium permanganate, and ammonium persulfate reducing fluid (Kodak R-
5), ceric salt reducing liquid. The conditions for the force reduction treatment are generally 10 DEG C. to 40 DEG C., particularly 15 DEG C. to 30 DEG C., and preferably can be completed within several seconds to several tens of minutes, particularly several minutes. By using the photosensitive material for plate making of the present invention, a sufficiently wide reduction width can be obtained within the range of these conditions. The reducing solution acts on the silver image formed in the emulsion layer through the non-photosensitive upper layer containing the compound of the present invention. Specifically, there are various methods, such as immersing the sensitizer for plate making in a reducing solution and stirring the solution, or applying the reducing solution to the surface of the sensitizing agent for plate making with a brush, roller, etc. method is available.

[0069] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. In the Examples, a developer having the following formulation was used.・Potassium sulfite

67g・Ethylenediamine-4-acetic acid-2-sodium
3.0g・Hydroquinone

23g・4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone
0.4
Sodium g.2-mercaptobenzimidazole-5-sulfonic acid

0.3g・Potassium hydroxide

11g
・5-methylbenzotriazole
0
．． 1g/sodium carbonate

11g/potassium bromide

3.0g
Add water to make 1 liter. (Adjusted to pH 10.7)

[0070]

[Example] Example 1 Preparation of emulsion Silver nitrate aqueous solution and silver 1 were added to gelatin aqueous solution kept at 40℃.
A sodium chloride aqueous solution containing 5 x 10-5 moles of metal per mole as shown in Table 1 was added at the same time for 3 and a half minutes, and the potential during that time was controlled at 95 mV to prepare core particles of 0.11 μm. . Thereafter, a silver nitrate aqueous solution and a sodium chloride aqueous solution containing 1.5 x 10-4 mol of metal as shown in Table 1 per mol of silver were added at the same time for 7 minutes, and the potential was controlled at 95 mV to reduce the average particle size to 0. .14 μm cubic silver chloride grains were prepared. Preparation of coating sample The above emulsion was mixed with 2.5 mg/m2 of 1-phenyl-5-mercaptotetrazole and ethyl acrylate latex (
The compound of the present invention was added as shown in Table 1, and 126 mg/m2 of 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent.
g/m2 plus 3.0 g/m silver on polyester support
It was applied so that it became 2. Gelatin was 1.5 g/m2. Gelatin 0.8g/m as a lower protective layer on top of this
2. Apply 8 mg/m2 of lipoic acid and 230 mg/m2 of ethyl acrylate latex (average particle size 0.05 μm), and then apply 0.7 g/m2 of gelatin as an upper layer of a protective layer.
m2, the dye 11 was applied in a solid dispersion state. At this time, matting agent (silicon dioxide, average particle size 3.5 μm) 5
5mg/m2, methanol silica (average particle size 0.02μ
m) 135 mg/m2, sodium dodecylbenzenesulfonate 25 mg/m2 as a coating aid, 20 mg/m2 sodium salt of sulfuric ester of poly(degree of polymerization 5) oxyethylene nonylphenyl ether, N-perfluorooctanesulfonyl-N-propylglycine A sample was prepared by simultaneously applying 3 mg/m2 of potassium salt. Note that the base used in this example has a back layer and a back protective layer having the following compositions. (The swelling rate on the back side is 110%.) (Back layer) Gelatin

170mg/m2 Sodium dodecylbenzenesulfonate
32mg/m2 dihexyl-α-
Sulfosacnate sodium
35mg/m2 SnO2/Sb(9
/1 weight ratio, average particle size 0.25 μm) 31
8mg/m2 (back protective layer) gelatin

2.7g silicon dioxide matting agent (average particle size 3.5μm)
26mg/m2 Sodium dihexyl-α-sulfosacnate
20mg/m2 Sodium dodecylbenzenesulfonate
67mg/m2

[0071]

[C35]

[0072]

[C36]

Ethyl acrylate latex (average particle size 0.05 μm) 260 mg/m21,3-
Divinylsulfonyl-2-propanol 149mg/m
2

Photographic performance The sample thus obtained was exposed to light through a light wedge using a P-627FM printer (mercury) manufactured by Dainippon Screen Co., Ltd., using a developer LD-835 manufactured by Fuji Photo Film Co., Ltd. and an automatic processing machine FG800RA. The film was developed for 20 seconds at 38° C., fixed, washed with water, and dried. The following items were evaluated for these samples. 1) γ; (1.5-0.1)/-{log(concentration 0.1
(exposure amount that gives a density of 1.5) - log (exposure amount that gives a density of 1.5)}2) Dmax, Dmax (-1%); Glue the film (halftone original) on which the halftone image is formed on the pasting base The protective layer of each film sample and the halftone dot original were fixed with tape and brought into close contact so that they overlapped face-to-face.
The maximum blackening density when exposure is given so that the halftone dot area becomes 50% and 49% on the film sample are respectively D.
max and Dmax (-1%). 3) Storage stability over time (△fog); film at 60°C 30%
After being left under these conditions for 5 days, the Dmin of the 5-layer stack of developed samples was evaluated based on the increase in fresh performance. As is clear from Table 1, the samples of the present invention have little fogging over time, hard toe gradation, and high Dmax, indicating excellent return performance.

[0075]

[Table 1]

Example 2 Preparation of emulsion Silver nitrate aqueous solution and silver 1 were added to a gelatin aqueous solution kept at 38°C.
A sodium chloride aqueous solution containing 5 x 10-5 moles of metal per mole as shown in Table 2 was simultaneously added for 3 and a half minutes, and the potential during that time was controlled at 95 mV to prepare core particles of 0.08 μm. . Thereafter, a silver nitrate aqueous solution and a sodium chloride aqueous solution containing 1.5 x 10-4 mol of metal as shown in Table 2 per mol of silver were added at the same time for 7 minutes, and the potential during the period was controlled at 95 mV.
6-trimethylene-7-hydroxy-s-triazolo(
2,3-a) Pyrimidine was added at 5 x 10-3 moles per mole of silver. The obtained particles have an average particle size of 0.10 μm
were silver chloride cubic particles. Preparation of coating sample The above emulsion was mixed with 2.5 mg/m2 of 1-phenyl-5-mercaptotetrazole and 1 g/m of 5,6-trimethylene-7-hydroxy-s-triazolo(2,3-a)pyrimidine.
2 mg/m2, 770 mg/m2 of ethyl acrylate latex (average particle size 0.05 μm), the compound of the present invention as shown in Table 2, and 126 mg of 2-bis(vinylsulfonylacetamido)ethane as a hardening agent. /m
2 and coated on a polyester support at a silver content of 3.0 g/m2. Gelatin was 1.5 g/m2. On top of this, 0.8 g/m2 of gelatin, 8 mg/m2 of lipoic acid, and 230 mg/m2 of ethyl acrylate latex (average particle size 0.05 μm) were applied as a lower protective layer, and 0.8 g/m2 of gelatin was applied as an upper protective layer. 7g/m2,
The dye 11 was applied in the form of a solid dispersion. At this time, 55 mg of matting agent (silicon dioxide, average particle size 3.5 μm)
/m2, methanol silica (average particle size 0.02 μm) 1
35mg/m2, sodium dodecylbenzenesulfonate 25mg/m2 as a coating aid, sodium salt of sulfuric acid ester of poly(degree of polymerization 5) oxyethylene nonylphenyl ether 20mg/m2, N-perfluorooctanesulfonyl-N-propylglycinepotadium 3mg salt
/m2 was applied at the same time to prepare a sample. The back layer is the same as in Example 1. The obtained sample was tested in the same manner as in Example 1, and the results are shown in Table 2. As is clear from Table 2, the samples of the present invention have hard toe gradation, high Dmax, and excellent return performance with little fogging over time.

[0077]

[Table 2]

Example 3 Preparation of emulsion Silver nitrate aqueous solution and silver 1 were added to a gelatin aqueous solution kept at 40°C.
A sodium chloride aqueous solution containing 5 x 10-5 moles of metal per mole as shown in Table 3 was simultaneously added for 3 and a half minutes, and the potential during that time was controlled at 95 mV to prepare core particles of 0.11 μm. . Thereafter, a silver nitrate aqueous solution and a sodium chloride aqueous solution containing 1.5 x 10-4 mol of metal as shown in Table 1 per mol of silver were added at the same time for 7 minutes, and the potential was controlled at 95 mV to reduce the average particle size to 0. .14 μm cubic silver chloride grains were prepared. Other conditions were the same as in Example 1, and each sample was prepared. Each sample was evaluated in the same manner as in Example 1, and the results shown in Table 3 were obtained. As is clear from Table 3, the samples of the present invention have little fogging over time, hard toe gradation, and high Dmax, indicating excellent return performance.

[0079]

[Table 3]

Example 4 Preparation of emulsion Silver nitrate aqueous solution and silver 1 were added to a gelatin aqueous solution kept at 38°C.
A sodium chloride aqueous solution containing 5 x 10-5 moles of metal per mole as shown in Table 2 was simultaneously added for 3 and a half minutes, and the potential during that time was controlled at 95 mV to prepare core particles of 0.08 μm. . Thereafter, a silver nitrate aqueous solution and a sodium chloride aqueous solution containing 1.5 x 10-4 mol of metal as shown in Table 4 per mol of silver were simultaneously added for 7 minutes, the potential during the period was controlled at 95 mV, and 5.
6-trimethylene-7-hydroxy-s-triazolo(
2,3-a) Pyrimidine was added at 5 x 10-3 moles per mole of silver. The obtained particles have an average particle size of 0.10 μm
were silver chloride cubic particles. Preparation of coating sample The above emulsion was mixed with 2.5 mg/m2 of 1-phenyl-5-mercaptotetrazole and 1 g/m of 5,6-trimethylene-7-hydroxy-s-triazolo(2,3-a)pyrimidine.
2 mg/m2, 770 mg/m2 of ethyl acrylate latex (average particle size 0.05 μm), the compound of the present invention as shown in Table 4, and 126 mg of 2-bis(vinylsulfonylacetamido)ethane as a hardening agent. /m
2 and coated on a polyester support at a silver content of 3.0 g/m2. Gelatin was 1.5 g/m2. On top of this, 0.8 g/m2 of gelatin, 8 mg/m2 of lipoic acid, and 230 mg/m2 of ethyl acrylate latex (average particle size 0.05 μm) were applied as a lower protective layer, and 0.8 g/m2 of gelatin was applied as an upper protective layer. 7g/m2,
The dye 11 was applied in the form of a solid dispersion. At this time, 55 mg of matting agent (silicon dioxide, average particle size 3.5 μm)
/m2, methanol silica (average particle size 0.02 μm) 1
35mg/m2, sodium dodecylbenzenesulfonate 25mg/m2 as a coating aid, sodium salt of sulfuric acid ester of poly(degree of polymerization 5) oxyethylene nonylphenyl ether 20mg/m2, N-perfluorooctanesulfonyl-N-propylglycinepotadium 3mg salt
/m2 was applied at the same time to prepare a sample. The back layer is the same as in Example 1. The obtained sample was tested in the same manner as in Example 1, and the results are shown in Table 4. As is clear from Table 4, the samples of the present invention have hard toe gradations, high Dmax, and little fogging over time, indicating excellent return performance.

[0081]

[Table 4]

[0082]

Effects of the Invention The present invention provides silver halide emulsions containing transition metal coordination complexes having the general formula (I), (II) or (III).
) By using the compound represented by (2), it was possible to prevent natural aging fogging of photosensitive materials handled in a bright room and a decrease in maximum blackening density during underexposure.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer comprising at least one light-sensitive silver halide emulsion layer on a support, each emulsion layer containing at least 1 x 10-6 per mole of silver. The hydrophilic colloid layer is made of silver halide containing a transition metal selected from elements of groups V to VIII of the periodic table and has a mole of nitrosyl or thionitrosyl ligand, and the hydrophilic colloid layer has the following general formula [I],
A silver halide photographic material containing at least one compound represented by [II] or [III]. [Chemical 1] [Chemical 2] In the formula, R1 to R4 may be the same or different, and each represents a hydroxy group, a hydroxylamino group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy group, or a phenoxy group. group, alkyl group,
It represents an aryl group, an alkylthio group, a phenylthio group or a hydrazino group. General formula [III]
X1 -A-X2 In the formula, X1 and X2 are -OR1
or -NR2 (R3), (R1 represents a hydrogen atom or a group that can become a hydrogen atom by hydrolysis, and R2 and R3 are each a hydrogen atom, an alkyl group,
It represents an aryl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a sulfamoyl group, or a carbamoyl group. ) A represents an arylene group, and at least one of X1, X2 and A may have a hydrogen atom contained in the group substituted with a group promoting adsorption onto silver halide grains.