JPH049039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the generation of black dots and to maintain a high contrast by forming the silver halide in a silver halide emulsion of monodisperse particles which contain specific ratio of silver iodide and have a specific coefft. of fluctuation. CONSTITUTION:A hydrazine deriv. is incorporated into the silver halide emulsion layers on a substrate or the adjacent layers thereof and the silver halide in this silver halide emulsion is formed of the monodisperse particles which contain <=4mol% silver iodide and have <=15% coefft. of fluctuation. The particles of the type that the structure thereof has at least two layers of multilayered laminated structures are usable as the particles of the silver halide. For example, the particles consisting of the silver iodobromide particles which consist of the silver iodobromide in the core part and the silver bromide in the shell part are usable. The silver halide photographic sensitive material which is hard in contrast and has the good black dots in spite of rapid processing is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photographic material having a silver halide photosensitive layer on a support.
-Relating to silver halide photographic materials.

[Background of the invention]

The photolithography process involves converting a continuous tone original into a halftone image.

7) As a photographic technique capable of reproducing ultra-high contrast images, a technique based on contagious development has been used.
Two.

The lithium-type silver halide photographic light-sensitive material used for infectious development has, for example, an average grain size of 0.21 zm, a narrow grain distribution and a well-shaped grain, and a high silver chloride content (at least 50 mol%). Above) consists of a silver chlorobromide emulsion. By processing this Lith type developer with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called Lith type developer, an image with high contrast, high sharpness, and high resolution can be obtained. However, these Lith developers are susceptible to air oxidation and have extremely poor 1st bath stability.
It is difficult to maintain constant development quality during continuous use. Therefore, the sulfite ion concentration is high and the preservation property is good.
Techniques have been developed that aim to form ultra-high contrast images comparable to those of contagious development using a developer capable of rapid processing, and one known technique is the technique disclosed in Japanese Patent Application Laid-open No. 106244/1983. . In this technique, a hydrazine derivative is contained in a silver halide photographic light-sensitive material. According to these methods, ultra-high contrast photographic images can be obtained by processing with a developer that has good preservability and allows rapid processing. However, with these techniques, failures called black spots often occur in unexposed areas when high temperature and rapid processing is performed. In order to prevent black spots, a technique is disclosed in which a certain type of inhibitor is contained, as seen in Japanese Patent Application Laid-open No. 1-183648. However, although these techniques can suppress black spots, they often have the disadvantage of softening the tone when subjected to high-temperature and rapid processing.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that can suppress the occurrence of black spots and maintain high contrast.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or its adjacent layer. The silver halide in the silver emulsion is 4
This is achieved by a silver halide photographic light-sensitive material characterized by containing monodisperse grains containing silver iodide in an amount of mol % or less and having a coefficient of variation of 15% or less.

The present invention will be explained in detail below.

The hydrazine derivative used in the present invention has the following formula [1
], [2], and [3] are preferably used.

General formula N) In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m represents O or l, and when n is 2 or more, , each R may be the same or different.

- Formula [2] In the formula, R21 is an aliphatic group, aromatic group, or heterocyclic group, and R22 is a hydrogen atom, an optionally substituted alkoxy group, heterocycle, oxy group, amino group, or aryloxy group PI and R2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.

Formula [3] Ar-NHNH-C-R3 In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R11 represents a substituted alkyl group.

Below, Equations (1), (2), and [:3] will be specifically explained.

General formula [1] In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is 0 to 6, and m is 0
Or represents 1.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R8 and R2. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R3 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, bivalylamino, benzoylamino, tetradecanoylamino, σ-(2,
(4-di-monoamylphenoxy)butyrylamino, etc.),
Sulfonylamino groups (e.g. methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g.
phenylurea, ethylurea, etc.), thiourea group (
For example, phenylthiourea L-7', edziourea), hydroxyl group, amino,! group, argylamino group (
For example, Mejiruami), ';, 14rufu'mi2no)
, a carboxyl group, an alu:l-j dicarbonyl group (eg, hydroxycarbonyl group), a carbamoyl group, a sulfo group, and the like. Examples of the divalent A' group represented by R include eva-alkylene groups (e.g., methylene, ethylene, ]-lyltylene, tetramethylene, etc.), aryμ
) groups (for example, phenylene, naphthidine, etc.), aralkylene groups, etc.Aralkylene groups include oxy groups, thio groups, seleno groups, carbony groups,
N-group (i''3 represents a hydrogen atom, an alkyl group, a j′ lyl group) may contain a sulfonyl group, etc., R0
Various substituents can be introduced into the group represented by J.

Examples of the substituent include -C0NHNHR+ (Ri has the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxyne group, an anru group, an aryl group, etc. I get kicked.

R is preferably an alkylene group.

Among the compounds represented by formula [l], preferably R1 and R2 are substituted or unsubstituted phenyl groups, and n-1
A compound in which R represents an alkylene group in η-1.

Representative compounds represented by the above-mentioned formula [1] ■-10■■0C1□11□.

■ ■ ■ ■ ■ ■ C5HII 142 ■ ■ ■ =52 =19 ■ ■ ■ ■ Next, general formula [2] will be explained. Among these, those containing a benzene ring are preferred.

The aliphatic group represented by R and ++ preferably has 6 or more carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 8 to 50 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more Lalo atoms therein. Further, this alkyl group may have a substituent such as a mono-aryl group, a nioxy group, or a sulfoxy group.

The aromatic group represented by R and l is a monocyclic or bicyclic allyl group, and j- is a saturated dicyclic group. Insatiable here (1+
Hede[) ring group is fused with a monocyclic or bicyclic aryl group.1.
may form a \-2-lowary group.

For example, to IJ: Zen ring, naphthalene ring, pyridine ring, hyrimine ring, imidazole ring, virolasol ring, quinoline ring, isoquinoline ring, pensimitazole ring, jdo/f-
Particularly preferred R2□ is an aryl group such as a monocyclic ring or a hendithiazole ring.

The aryl group or unsaturated heterocyclic group of R2□ may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monomer whose alkyl moiety has 1 to 20 carbon atoms). 2 rings spanning the rings), alkoxy groups (
(preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with argyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfonamides Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R2□ in formula [2], the optionally substituted alkoxy groups have 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

In formula [2], among the groups represented by R2゜, an optionally substituted aryloxy group or hezoro2' (ringoxy group, -C is preferably a monocyclic one, and the substituent is a halogen atom alkyl Among the groups represented by R22, such as a group, an alkoxy group, and an ano group, preferred are substituted J
-L-C is also a good alkoxy group or amino group, and
an optionally substituted 11 alkyl group, alkoxy group or -0
---5--A cyclic structure containing an N-group bond ch -) (
Good too. However, R2° is not a hydrazino group.

R2 or R2゜ in formula [l] is a coupler,
It may also incorporate a ballast group, which is commonly used in immobile photographic additives such as.

A ballast group is a group having a carbon number of 8 or more and is relatively inert with respect to photography, such as an alkyl group, an alkoxy group, an alkylphenyl group, a 7-T-, /
Rol or R2 in formula (2) may be selected from gira group, 7-alkylphenoquine group, etc. Rol or R2 in formula (2) has a group incorporated therein that enhances adsorption to the silver halide grain surface. It may be something that exists. Examples of such adsorption groups include groups described in US Pat. No. 4,355,105, such as diourea groups, heterocyclic diamide groups, mercapto heterocyclic groups, and triazole groups. -Among the compounds represented by the formula [2], the compounds represented by the following formula [2a] are particularly preferred.

-Formula C2-a] In the above-mentioned formula (2-a), R23 and R24 are hydrogen atoms, optionally substituted alkyl groups (for example, methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group) , 2-anoethyl group,
2-taloloyutyl group), an optionally substituted phenyl group,
Naphthyl group, nclohex.

group, pyridyl group, pyrrolidyl group (e.g. phenyl group,
p-Methyl group: nyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl 2-pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group) , R25 is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), R16 and R2a represent a divalent aromatic group (e.g. phenylene group or naphthylene group),
Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -5O2CH2CH2N) I-3o2NH,
-0CH2So2NH, -0CH=N-), R2B represents -R/ R/ / or -0R2, R
/R// and R29 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodenyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group,
p-methoxyphenyl group), naphthyl group (e.g. σ-naphthyl group, β-naphthyl group) or heterocyclic group (e.g.
unsaturated heterocyclic groups such as pyridine, thiophene, and furan;
Alternatively, it represents a saturated heterocyclic group such as tetrahydrofuran or sulfolane, and R' and R//R may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

m and n represent 0 or 1. When representing R2aOR2s, Y preferably represents a sulfur atom.

Above - representative general formula represented by formula [2] and (2-a) [
2] Specific example O tL -(L)CsH1+ CH.

C1oH21n ■ *-NHNHCCOCH2CH2SO2CH2CH20
HO ■ *-NHNHCCOCI (2CH2SCH2CH□OH
On δ O 4;3 H3 ・To1 ・15 1,) ■ *-NHN11CCNHCH,C1,5CH2CH2S
CH2C)120H=51 *(a) 1l NHNHCCNHC,2H2゜shi113 shi+13 Next, among the above specific compounds, compound 2-45゜2-4
7 will be used as an example to show its synthesis method.

Synthesis of Compound 2-45Synthetic Scheme (A) (B) 1st F12-45 Compound 4-nitrophenylhydrazine 153g and 500g
Mix mQ of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 of the obtained crystals (A)
Dissolve g in 1000 m12 of methanol by heating, and make pd/
Compound (B) is obtained by reduction under a C (palladium/carbon) catalyst in a pressurized H2 atmosphere of 50 Psj.

22g of this compound (B) was added to 200ml of acetonitrile.
Compound (C) 2 was dissolved in a solution of 16 g of pyridine at room temperature.
4 g of acetonitrile solution was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

10g of compound (E) was dissolved in 100ml of acetonitrile, 360g of ethyl isothiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound CF)7 was purified by crystallization.
．． 0. I got it. Compound (F) 5.0g was mixed with 5.0g of methanol.
Methylamine (40% aqueous solution 8ml +
2) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (B) (C) (D) (E) Compound 2-47 22 g of Compound (B) was dissolved in 200 m of Bilysin (+) and poured into a stirring sieve, p-nitrobence>sulfonyl chloride 22 g was added. The reaction mixture was poured with water, and the precipitated solid was then taken out to obtain compound (C). Compound (C) was subjected to the same reaction as compound 2-45 according to the synthesis scheme to obtain compounds 2-47. Ta.

Next, general formula [3] will be explained.

Formula [3] Ar NHNH-CR3 In formula [;3], Ar is an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. A ballast group is a -C group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an argylphenoxy group, etc. You can choose from among them.

Examples of silver halide adsorption promoting groups include thiourea group, di-primary cretane group, heterocyclic thioamide group, mercapto heterocyclic group,
Mention may be made of the groups described in US Pat. No. 4,385,108, such as triazole groups.

R31 represents a substituted alkyl group, and the argyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, inglovil, pendel, cyclohegycyl, and the like.

Examples of substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, oxy, etc.), aryloxy (e.g., fenoquine, p-chlorophenoxy, etc.),
peterocyclic oxy (e.g. pyridyloxy, etc.), mercapto, alkylthio (methylthio, ethylthio, etc.), arylthio (e.g. phenylthio, p-chlorophenylthio, etc.), peterocyclic thio (e.g. pyridylthio, birimidyldio, thiacyazolylthio, etc.), Alkylsulfonyl (e.g. methanesulfonyl, butanesulfonyl, etc.),
arylsulfonyl (e.g. benzenesulfonyl etc.),
Heteryl 21-ring sulfonyluphorinosulfonyl, etc.), acyl (e.g., acedel, benzoyl, etc.), n-a, no, chloro, bromine, alkylsulfonyl (e.g., ethoxycarbonyl, carbonyl, etc.), aryloxycarbonyl ( (e.g., phenogidicarponyl, etc.), carboxy, carbamoyl, argylcarbamoyl (e.g., eva, N-methylcarbamoyl, N,
N-dimethylcarbamoyl, etc.), arylsulfonyl (
For example, N-7 enylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino, naphthylamino, etc.), anrylamino (e.g., acetyl (amino, pensoylamino, etc.), alkoxycarpolamino (e.g., etogine carbonylamino, etc.), aryloxycarbonylamino (e.g., ) 1/f
turbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, Six groups include alkylsulfamoyl (eg, methylsulfamoyl, etc.), arylsulfamoyl (eg, phenylsulfamoyl, etc.).

The hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.). Good too.

Above - Representative compound represented by formula [3] = 7 ;3 Go 3 =48 5hn (L) Next, a synthesis example of compound 3-5 will be described.

Synthesis of Compound 3-5 Compound 3-5 was obtained according to the synthesis scheme of Compound 2-45.

General formula [
1], [:2:l, I:3:] is 5×10-' to 5×10-1 per mole of silver halide contained in the silver halide photographic material of the present invention. Preferably up to mol, more preferably 5 x l0-6 to l
X 10-'' mole range.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer. In other words, if at least one silver monotinide emulsion layer is provided on one side of the support,
, or at least one layer on both sides 6 of the support.

Then, this .
Additionally, a hydrophilic phytolayer such as a protective layer may be coated on the silver halide emulsion layer. The silver halide emulsion layer is divided into two silver halide emulsion layers of different sensitivities, e.g. high sensitivity and low sensitivity.
It may also be coated. In this case, an intermediate layer may be provided between each silver halide emulsion layer.

That is, an intermediate layer made of a hydrophilic colloid may be provided if necessary, and an intermediate layer, a protective layer, an anti-halation 5-112 layer, etc. may be provided between the silver halide emulsion layer and the protective layer.
2. A non-photosensitive i8' hydrophilic colloid layer such as a king layer is provided.・T〉' Halo 77 in silver oxide photosensitive H material
The silver oxide layer or t- is contained in the hydrophilic colloid layer adjacent to the silver emulsion layer.

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. As for the composition of the silver halide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide containing 4 mol % or less of silver iodide are used.

Preferably, silver halide containing 0.1 to 3 mol % of silver iodide is used. The average particle size of the silver halide particles is preferably in the range of 0.05 to 0.50 .mu.I11, with 0.10 to 0.40 .mu.m being particularly preferred.

Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the immediate dispersion value defined below is in the range of 1 to 15, more preferably in the range of 5 to 12.

Here, the monodispersity is defined as a value (%) obtained by multiplying by 100 the value obtained by dividing the standard deviation of particle diameter by the average particle diameter (coefficient of variation). For convenience, the grain size of silver halide grains is expressed by the edge length in the case of cubic grains, and is expressed by the edge length for other grains (8
(hedron, tetradecahedron, etc.) is calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver halide grains having a multilayer structure of at least two layers, for example, iodobromide particles in the core part. It is possible to use silver iodobromide grains in which the shell portion is silver or silver bromide5.Nowadays, it is possible to incorporate iodine into any layer within 5 mol%.

The silver halide grains used in the halo'7] silver emulsion of the present invention are prepared in the process of forming and/or growing grains such as cadmium salt, zinc salt, lead salt, tali I'7m salt, Metal ions are added using at least one selected from rhizium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing), into the inside of the particles and/or on the particle surfaces. By incorporating these metal core elements and placing them in a suitable reducing atmosphere, back-light sensitization can be applied to the interior of the particles and/or the surface of the particles.

Furthermore, maj-, halo',, +, silver oxide can be sensitized by various chemical sensitizers. Examples of the sensitizers include active seratin, sulfur sensitizers (thiosulfate sorta, IJ ruthiocarbamide, thiourea, allyl isothiacine-1□, etc.), selenium sensitizers (N, N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, etc.), potassium chloroolite, potassium chloride, I
Thionanate, potassium chloroole-1, 2-
Various noble metal sensitizers such as aurosulbobenzothiazole methyl chloride, ammonium chloroparade-1, potassium chloroplatinum-1, and nalium chloroparadite may be used alone or in combination. Can be used in combination. When using a metal sensitizer, rotammonium can also be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than that of their internal sensitivity, or silver halide grains which give so-called ineffective images. It is possible to increase

In addition, the silver halide emulsions used in the present invention include Norcaf I-class compounds (1-phenyl-5-mercaptothi-I-usole, 2-mercaptothiazole), Benz-I-lyasole classes (5-bromobenzotriazole), 5-Meboulhensotriazol), Penzimidazoles (6
C stabilization or capri suppression can be carried out using compounds such as -2I-lobenzimidazole).

The photosensitive silver halide emulsion layer or its adjacent layer has a sensitivity of 1
Research Disclosure (Re5earch1"1i) for the purpose of increasing contrast 1-1 or promoting development.
Section XXI B-D of No. 17463
Compounds described in Section 2.1 can be added.

Ff is a compound represented by the following formula [4].

General formula [・1] R1-0 CH, CH2O crucible H For example, ・4 Not limited to these 5, IO(CH, Ct120) n HHO(CH2C
H20) nH HO(CI2CH,0)nH HO(CH2CH20)nH HP(CH2CH20)nH HO(CH7CH20)nH n・10 −3O n=5O n・70 n=I 50 n=200 [In the formula, R1 is hydrogen It represents an aromatic ring that is unsubstituted or has a substituent, and n represents an integer from 10 to 200. ] More preferable example than the compound represented by the formula [4] is i17 .1 and 113 These compounds are commercially available and can be easily obtained. These compounds have a content of 0.0% per mole of silver halide. It is preferable to add 1 to 4.0 moles of O.0.02
-2 mol is more preferred.

In addition, it is possible to include two kinds of son compounds having different values of l].

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardening agent, etc. can also be added to the 4''l silver halide emulsion used in the present invention.
), [:3], gelatin is suitable as the binder for the hydrophilic colloid layer, or hydrophilic colloids other than gelatin can also be used.

These hydrophilic binders are coated on each side of the support.
It is preferable to apply the coating at a temperature of 0g, .11)° or less. Supports that can be used in carrying out the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene 7 synthetic paper, glass board, cellulose acetate,
S
Yu L-1-Nato's polyester film listed 5)-
I can do it. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material. For example, the following developing agents are used.

HO-((:H=CH)n is a typical type of -OH type developing agent, and -C is hytroki, /n or Auri, and others include kadel, bi-1-1 calol, etc. .

In addition, typical HO-(CI-C)I)n-NH2 type developers include ortho- and pela-aminophenol or aminopyrasolole, N-methyl-p-aminoferol, Nβ-hydroxyl, 2-
There is an Ami y-j 71--le exclusive.

・＼゛“As a 1-ring type developer, 1-phenyl-3-
bitzjl ln, ■-7-nyl-4, 4-dimedyl 3-hydrasolide], 1=-tu-unyl-1-medyl-4-cyto, 3-pyrazolidone, ■-phenyl-4 -Methyl-4-hydroxymethyl-
Examples include 3-pyrazolidones such as 3-birasoliton.

The Photographic Process, 4th Edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pp. 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
Developers such as those described on page 3.100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. Other than that, such as caustic alkali, carbonate alkali, or amide 7 used in general black and white developers, J:6 pH adjustment and basso? - functions (also functions), -, and fluorocarbons, inorganic development inhibitors, and 5
-Methyl\sotriazole, 5-methylbenz1'
E-1 development inhibitors such as Mi-9zole, 5-nitrointasole, adenine, 'noani', ■-phenyl-5-mercabutodetrazole, and metal/ion scavengers such as J-dienediaminetetraacetic acid. , methanol, ethanization, ben-ε-alcohol, polyalkylene oxide and other development accelerators, alkylaryl sulfonic acid triuno, the power of nature - bonine, saccharides or alkylene oxides of the above compounds.
Surfactants such as glutamate, glutamate, glutamate, hol,
It is optional to add a hardening agent such as marine or glyoxanoate, an ionic strength adjusting agent such as sulfuric acid, etc.

The developer used in the present invention includes organic solvents, alkanolamines such as diene-9-nolamine and l-ethanolamine, and adhesives such as diethylene glycol and triethylene glycol. may also be contained.Also for diethylamino, 2 so 171 c]/'
Alkylamino alcohols such as y'ol and butylamino 70 panol are particularly preferred [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsion A) A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous silver nitrate solution were mixed in an aqueous gelatin solution at 50° C.
The stirring conditions and the addition flow rate were adjusted such that the pI was 42.0. During this mixing, 21rCC6 was added at 8 x 1 per mole of silver.
0-'mol was added.

After adding 6.5 cc of a 1% aqueous potassium iodide solution per mole of silver to this emulsion, modified gelatin (Japanese Patent Application No. 1996-1)
By adding exemplified compound G-8) of No. 80787,
It was washed with water and desalted in the same manner as in Example 1 of No. 1890787. r)Ag at 40°C after desalting was 8.0.

Furthermore, during redispersion, a mixture of the following compounds [A], [B], and [CI] was added.

The final emulsion was a silver iodobromide emulsion (2 silver iodide per mole of silver) consisting of cubic grains with an average grain size of 020 JIm.
(mol%) was rated A5.

In the above method for preparing emulsion A, an emulsion with a larger dispersion coefficient than emulsion A and emulsions B-F with different silver iodide contents were prepared by changing the amounts of potassium iodide and potassium bromide, stirring conditions, and addition flow rate. did. Table 1 shows the characteristics of emulsions A-F.

[A] [B] [CI (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (Japanese Patent Application Laid-open No. 59-1994
'i
5. Apply the halogen silver oxide emulsion layer of prescription (1) in F so that the amount of gelatin is 2.0 g/m2 and the amount of silver is 3.3 g/m2, and then apply the following recipe. The protective layer in (2) is determined by the amount of gelatin (1). og/m2, and on the other undercoat layer on the opposite side, apply a banking layer according to the following recipe (3) so that the amount of gelatin is 2.4 g/m''5. Further, a protective layer of the following formulation (4) was applied on top of it so that the amount of gelatin was 1.0g/m2, and sample No.
I got 1 to 8.

Prescription (1) (c) Silver cogenide emulsion layer composition Gelatin
20g/lη2 Silver halide emulsions of the present invention and comparison 1. Silver amount 3.3g/m2 Anti-fog agent/adenine 10 mg/m2 Stabilizer 4-mej-6-hydroquine! , 3.3a, 7-tel-razai〉'den 30
mg/m2 Surfactant: Chiboni〉O, 1g/m2 S-18, 0mg/m2 Hydrazine derivative Amount shown in Table 2 Polyethylene glyco molecular weight 4000 01f;/m2 Latinx volima 1 g/'m2 Sensitizing dye: SO, ○ 5OxN(CzHs)s Hardener r (60mg/m2 nN; l Prescription (2) [Emulsion protective layer composition] Gelatin 0-9g/m" Gel) 11 Gluing force surfactant with average particle size of 35 μm Agent S-2 C112COOCII□(C21b)CtHi3mg/
m2 Hardener: C(C)lzso:CH-CH2), NH2
50mg/m in CHzCHZSO3: Polmarine 30mg/m2 Surfactant S -31,0mg/m2 NaO, 5-CHCOOCH2 (CF2), HCH7C
OOCH2 (CF 2 ) 6 H prescription (3) (Hasoking layer composition) Gelatin surfactant: s-1 Prescription (4) Gelatin maso) agent, average particle size 3.0-5 Methacrylate surfactant s-2 Dura film Agent: Glyoxal [Backing protective layer composition] 03Na 2.4g/m2 6.0mg/m2 14/m2 0 μnl polymethyl 50mg/m' 10mg/m2 25mg/m2 :H-135mg/m' Step the sample again. Close the wedge, 320
After exposure for 5 seconds to tungsten light at a temperature of 0.0, processing was carried out under the following conditions using an automatic developing machine for rapid processing into which a developer and a fixer having the compositions shown below were introduced.

Detection liquid prescription Ethylenediamine) Tetraacetic acid disodium salt g Sodium sulfite 60 g Tripotassium phosphate 30 g Hydroquinone 22.5 g Sodium hydroxide 8.0 g N,N-diethylethanolamine 15 g Bromide] Lithium
3.0g 5-Sodylbenzo I Riazole 0.25g 1-Tubonyl-5-mercaptotetrazole 0.08g Metric

0 Add 25 g of water to make the IQ, and adjust the pH to 11.7 with sodium hydroxide.

Fixer formulation composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 2
4On+f2 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g (composition) Pure water (ion exchange water) 17mQ sulfuric acid (50% w/w aqueous solution) 4.7g aluminum sulfate (AM203 equivalent content 8.1% w/w) aqueous solution) 26
．． 5g When using the fixer, dissolve the above composition A in the order of composition in 500mQ of water, 10. It was finished and used. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
40°0 15 seconds fixed
Wash with water at 35℃ for 15 seconds
Dry for 10 seconds at 30℃
50 °0 10 seconds The obtained sample was measured with a Konica digital densitometer FDP-65, and sample No.
,] at a density of 3.0 is expressed as 100, and a comma is expressed as a tangent with the density of 0.37 and 3.0. A comma value of less than 6 is unusable, and a comma value of 6 or more and less than -4-1O still provides insufficient high contrast performance. With a gamma value of 10 or higher, the image becomes extremely high contrast, making it fully practical.

Furthermore, the unexposed portions of the developed samples were observed under a 40x magnifying glass, and the performance of the black spots was evaluated on a five-point scale. Rank 4 and above are usable levels.

Table 2 As is clear from Table 2, it can be seen that the sample according to the present invention has higher contrast and better black-tone performance than the comparison.

Example 2 A sample prepared in the same manner as in Example 1 was exposed in the same manner as in Example 1, processed in exactly the same manner except that the developer was changed to the following formulation, and evaluated.

L±Izumi View High 1-Loginon 35
l・-le
0.25
gJ Dilenediaminetetraacetic acid 1.0g Sodium sulfite 60.0g Sodium hydroxide 8.0g 3-(diethylamino)-1,2-propanediol 0g Sodium bromide 3,0g 5-Methylbenzotriazole O, Igl -Phenyl-5-mercaptotetrazole 0.08g ■-Funiru4,4-::Methyl-3-pyrazolidone 0.2g Phenylpicolinium bromide 2.5g Water was added to give an IQ, and the pH was adjusted to 1O18.

The results of the above examples are shown in Table 3.

As is clear from the results in Table 3, the sample according to the present invention, similar to Example 1, has higher contrast and better black spot performance than the comparison.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic light-sensitive material with high contrast and good black shading even through rapid processing.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or its adjacent layer, the silver halide in the silver halide emulsion 1. A silver halide photographic material comprising monodispersed grains containing 4 mol % or less of silver iodide and having a coefficient of variation of 15% or less.