JPH09304857A - Sliver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To restrain occurrence of black spots without impairing sensitivity and to stabilize the photosensitive material against pH change of a developing solution by using a polymer having specified structures in the molecule as a contrast-enhancing promoter and a specified compound as a black spot preventive. SOLUTION: The photosensitive material contains in a silver halide emulsion layer or another hydrophilic colloidal layer a hydrazine derivative and as the contrast-enhancing and nucleation promoter, the polymer compound having the structures represented by formula I and II and the compound represented mainly by formula III, and in formulae I-III, each of R1 , R3 is an aliphatic or alkyl or aromatic group of the like; X in formula I is an anion; L is a bonding group; each of R21 and R22 is an H atom or an alkyl group and may combine with each other to from a ring but each is not an H atom at the same time; each of L1 and L2 is a divalent bonding group; X in formula II is an alkaline group; each of (p) and (n) is 0 or 1; (r) is 2-30; R31 is an aliphatic or aromatic or hetero ring; X1 is an O, S, or NH atom or atomic group; and X2 is an aliphatic or NH2 group.

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 light-sensitive material and a super-high contrast negative image forming method using the same, and particularly to a high contrast image processing solution having a pH of less than 11.0 which is useful in a photomechanical process. The present invention relates to a silver halide photographic light-sensitive material which can be obtained by using

[0002]

2. Description of the Related Art In recent years, colorization and complexity of printed matter have been rapidly progressing in the field of printing photoengraving. Therefore, demands for improving the quality and stabilizing the quality of the silver halide light-sensitive material for printing (hereinafter referred to as a printing light-sensitive material), which is an intermediate medium for printing, are increasing year by year. Conventionally, a general printing photosensitive material has been imparted with so-called lith development processing suitability in order to achieve high quality. However, in the lith development, it is mechanically impossible to contain a high concentration of a sulfite ion, which is a preservative, in the developing processing solution, and therefore it is not known to those skilled in the art that the stability of the developing solution is very poor. Then it is a well-known fact. As a technique for eliminating the instability of the lith development and obtaining a high-contrast image similar to the lith development processing, the disclosure of the patent document can be seen for some attempts. For example, a technique of using a hydrazine compound to obtain a high contrast image is disclosed in JP-A-53-16623, JP-A-53-20921, JP-A-53-20922, and JP-A-53-20922.
53-49429, 53-66732, 55-90940, 56-67843
No. 57, No. 57-99635, No. 62-73256, No. 62-275247, No.
62-178246, 62-180361, 63-121838, 63-
223744, 63-234244, 63-253357, 64-90
No. 439, JP-A No. 1-105943, No. 2-25843, No. 2-120736
No. 2, No. 2-37, No. 2-8834, No. 3-125134, No. 3-184039
No. 4-51143 and the like. It is necessary that the pH of the developer containing these hydrazine compounds be at a relatively high level in order to obtain a high-contrast image, and the developer having a high pH absorbs carbon dioxide in the air. PH tends to decrease, and the stability to air oxidation is not always sufficient, and the effective life of the developer is short.

To overcome these drawbacks, a lower p
In order to increase the contrast with H, for example, JP-A-60-179734,
62-948, U.S. Pat.Nos. 4,385,108, 4,269,929
No. 4,988,604, No. 4,994,365, No. 5,104,769, etc., an attempt has been made to make the hydrazine derivative more active.However, improvement of only the hydrazine derivative makes it possible to obtain high contrast at low pH. There was a limit. Therefore, the development of a contrast enhancing agent has been conventionally advanced. JP-A-56-106244, 60-218642, 61-26775
No. 9, etc., a method of adding a secondary or tertiary amino compound to a developing solution, JP-A-60-140340,
62-222241, 63-124045, U.S. Pat.No. 4,975,35
A method of adding an amino compound as disclosed in No. 4 to a light-sensitive material is known. When such an amine is added to the developing solution, there are problems of odor and waste liquid, and when it is added to the light-sensitive material, sufficient contrast cannot be obtained. Further, as described in JP-A-61-167939 and JP-A-6-313937, a method of adding a quaternary phosphonium salt compound to a developing solution or a light-sensitive material is disclosed.
Even if it is added to a light-sensitive material, it flows into a processing solution and causes a problem of environmental pollution. Even when it is added to a light-sensitive material, satisfactory contrast and photographic performance have not yet been exhibited. Further, the contrast enhancement system using hydrazine also has a problem of generation of spot-like fog called black spots which is generated in an unexposed portion, which is induced by the infectious development mechanism. Therefore, in order to suppress the generation of black spots and the thickening of halftone dots even when the composition or pH of the developer changes due to running, air oxidation, etc., improvement of the emulsion grain production method, use of various additives, etc. Is disclosed. Of these, the addition of sulfur-containing and nitrogen-containing compounds to the emulsion is described in US Pat.
Nos. 227, 5,196,292 (isothiourea compounds), 5,232,818 (thioether compounds), JP-A-5 197057 (dialkyl thiuronium compounds, mercapto group-containing heterocyclic compounds), No. 5-289226, No. 6-347935 (tetrazaindene compound), No. 6-266069 (thioamide compound), etc., but this problem has not been fully solved yet. The current situation. It is environmentally friendly and does not generate such black spots while maintaining photographic performance such as excellent halftone dot reproduction, and when the composition or pH of the developing solution as a plate-making sensitizer changes due to running or air oxidation. Also, it has been desired to develop more effective contrast enhancing agents and anti-black spot agents that retain photographic properties such as excellent halftone dot reproducibility.

[0004]

The object of the present invention is to firstly provide a light-sensitive material having a high contrast and a high image density by using a developing solution which is stable at a low pH. Secondly, it occurs during hydrazine development. The third object is to provide a light-sensitive material in which the generation of black spots is suppressed, and thirdly, to provide a photographic light-sensitive material in which a change in photographic performance due to a change in composition of a developer is small.

[0005]

SUMMARY OF THE INVENTION At least one support is provided on a support.
In a silver halide light-sensitive material having a silver halide emulsion layer, the hydrazine derivative and a structural unit represented by the following general formula (1) or (2) are present in the silver halide emulsion layer or another hydrophilic colloid layer. At least one of the nucleation accelerators of the polymer compound having the following general formula (3),
It is achieved by a silver halide photographic light-sensitive material characterized by containing at least one of the compounds represented by (4), (6) and (7).

[0006]

Embedded image In the formula, R ₁ , R ₂ and R ₃ represent an aliphatic group which may have a substituent, an alkenyl group, an aromatic group or a heterocyclic group, and X
Represents an anion, and L represents a linking group.

Embedded image In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group, and may form a ring with each other. However,
R ₂₁ and R ₂₂ are not hydrogen atoms at the same time. L ₁ and L ₂ represent a divalent linking group. X represents an alkylene group which may have a substituent. p and q represent 0 or 1, and r
Represents 2 to 30.

Embedded image In the formula, R ₃₁ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X ₁
Represents any one of O, S and NH, and X ₂ represents an aliphatic group or NH ₂ .

Embedded image In the formula, R ₄₁ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X ₃
Is a hydrogen atom or a group represented by the general formula (5).

[Chemical 12] In the formula, X ₄ represents any one of O, S and NH, and X ₅
Represents an aliphatic group or NH ₂ .

Embedded image In the formula, R _{51 to} R ₅₅ represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a heterocyclic group or an acyl group, and R ₅₂ and R ₅₃ , R ₅₄ and R ₅₅ , R ₅₂ and R
₅₄ , R ₅₃ and R ₅₅ may combine with each other to form a ring. However, at least two of R _{51 to} R ₅₅ are an aliphatic group, an aromatic group, or a heterocyclic group.

Embedded image In the formula, R ₆₁ represents an acyl group or an amino group.

The polymer having the structure of the general formula (1) used in the present invention will be specifically described. R ₁ , R ₂ and R ₃ may be the same or different, and as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, 2- Ethylhexyl group, octyl group, dodecyl group,
Examples thereof include linear or branched ones such as benzyl group and phenethyl group, and cyclic alkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group. Examples of the alkenyl group include allyl group, methallyl group and cinnamyl group. As the aryl group, in addition to phenyl group, naphthyl group, etc., alkyl-substituted phenyl group (eg, methylphenyl group, ethylphenyl group, xylyl group, etc.), halogen-substituted phenyl group (eg, fluorophenyl group, chlorophenyl group, bromophenyl group, etc.) , Alkoxy-substituted phenyl groups (eg, methoxyphenyl group, ethoxyphenyl group, etc.), acyl-substituted phenyl groups (acetophenyl group, propiophenyl group, etc.), amino-substituted phenyl groups (aminophenyl group, methylaminophenyl group, dimethylaminophenyl) Group), hydroxyphenyl group,
Substituted aryl groups such as nitrophenyl groups are mentioned.
Heterocyclic groups include, for example, oxygen, nitrogen and sulfur containing 5
It is a 6-membered or 6-membered monocyclic or condensed ring, and examples thereof include a furan ring, a thiophene ring, a pyridine ring, a pyrroline ring, a quinoline ring, an oxazole ring, a thiazole ring, an imidazole ring, and a benzothiazole ring. L is a divalent linking group, for example, a linear or branched or cyclic alkylene group,
An oxyalkylene group such as an ethyleneoxy group or a propyleneoxy group, an arylene group such as a phenylene group or a naphthylene group, a carbonyl group, a sulfonyl group, an oxycarbonyl group, a sulfonyloxy group, a carboxamide group or a sulfonamide group, or these are bonded to each other. Examples thereof include organic residues, preferably divalent residues containing an oxycarbonyl group, a carboxamide group, a sulfonamide group, a phenylene group and the like.

The polymer having the structure of the general formula (2) used in the present invention will be specifically described. Examples of the alkyl group represented by R ₂₁ and R ₂₂ include a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and examples of the substituent as the substituted alkyl include a hydroxy group, a halogen atom (chlorine, bromine atom). Etc.), phenyl groups, alkyl groups (methyl, ethyl groups, etc.), cyano groups, and the like. When R ₂₁ and R ₂₂ form a ring, a piperidine ring, a morpholine ring and the like are preferable. As the linking group represented by L ₁ and L ₂ ,
-COO-, -CONH-, -NHCOO-, -NHC
An ONH-group and the like can be mentioned. Examples of X include an ethylene group, a propylene group, an isopropylene group, and a butylene group.

The polymer having the general formula (1) or (2) used in the present invention is a homopolymer or copolymer of a monomer having a polymerizable unsaturated group. Those composed of the monomer units of the system are preferred. Further, the polymerizable unsaturated monomer containing the general formula (1) in the structural formula is a (meth) acrylic acid ester derivative,
It can be supplied as a (meth) acrylamide derivative, a styrene derivative, an alkene derivative, or the like. Examples of monomers copolymerizable with these monomers include hydrophobic (meth) acrylic acid alkyl esters (C1 to C).
20), benzyl (meth) acrylate, acrylonitrile, N-isopropylacrylamide, Nt-butylacrylamide, N-dimethylaminopropylacrylamide, vinyl acetate, styrene, chloromethylated styrene, etc. Methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, hydroxyethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, N-acroylmorpholine, crotonic acid, itaconic acid, (meth) acrylic acid, styrene sulfone Examples thereof include commonly used monomers such as acid soda, vinylimidazole, maleic anhydride, N-vinylpyrrolidone and derivatives thereof.

The polymer of the present invention can be produced by a conventional vinyl polymerization method. That is, a polymerization initiator is added to a solution of a monomer having the general formula (1) or (2) or a mixture of the monomer and a monomer copolymerizable with the monomer under a nitrogen atmosphere, followed by heating or polymerization. It can be obtained by keeping the liquid containing the initiator at a high temperature and dropping the monomer mixture therein. As the solvent used for the polymerization, water, alcohols such as methanol, ethanol and isopropanol, dioxane, THF, DMF and DMSO are used, and in the case of the general formula (1), water and ethanol are preferable. A mixture of these solvents is also used. As the polymerization initiator, generally known potassium persulfate, benzoyl peroxide, azobisisobutyronitrile, 2,2′-
Azobis (2-amidinopropane) dihydrochloride, 2,2 '
-Azobis (2,4-dimethylvaleronitrile), cumene hydroperoxide and the like can be used. As another method, a polymer having a reactive group may be synthesized in advance, and a compound having a reactive group containing the general formula (1) in the structural formula may be reacted therewith to obtain the target polymer. The average molecular weight of the polymers of the present invention is between about 500 and 300,000, preferably about 1000.
~ 200,000. If the molecular weight is too high, the solubility will be reduced and the viscosity will be increased, the amount used will be restricted, and the permeation into the surface of the photosensitive material will be delayed, and it will be difficult to obtain a sufficient effect.

The polymer containing the general formula (1) or (2) of the present invention, in comparison with the low molecular weight compound, may be suppressed in diffusion in the light-sensitive material by being polymerized. The tendency to prevent the thickening of the image lines and the collapse of the halftone dots is recognized, and there is a characteristic that the deterioration of the image quality is small especially when the pH becomes too high during development. And p
If H becomes too low, there is an advantage that the pH at which the contrast is lost is lower than the corresponding low molecular weight compound, probably because the local concentration is high.

It is generally desirable for the polymers of this invention to be hydrophilic in use, and thus it is more desirable for the other monomers in the copolymer to be hydrophilic as well. The component ratio of the monomer containing the general formula (1) or (2) in the copolymer is 5 to 100% by weight, preferably 10 to 100% by weight. If the component ratio of the monomer is high, the addition amount of the polymer may be small, but it is used in an appropriate range in consideration of easiness of copolymerization with other monomer and solubilization of the polymer.

The representative polymers of the present invention are illustrated below, but the invention is not limited thereto. The value of each monomer unit is% by weight
Represents These polymers can be easily synthesized by the method described in Japanese Patent Application No. 6-278062.

[0014]

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[0015]

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[0016]

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[0017]

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The polymer compound containing the general formula (1) or (2) of the present invention has the effect of promoting the so-called high contrast for obtaining a so-called high contrast silver image, and uses a hydrazine derivative as a nucleating agent. Most effective in the system. The polymer is most preferably added to the silver halide emulsion layer, but may be contained in other non-photosensitive hydrophilic colloid layers (for example, protective layer, intermediate layer, filter layer, antihalation layer, etc.). Good. When it is added to the silver halide emulsion layer, it can be added at any time during emulsion preparation, but it is preferably added after the completion of chemical ripening and before coating. Particularly preferably, it is added to the coating solution prepared for coating. The addition amount is 1 × 10 ^-2 to 2
g / m ² is preferred.

Next, the general formula (3) will be described in detail. In the formula, R ₃₁ represents an aliphatic group (alkyl group, alkenyl group, alkynyl group), an aromatic group or a heterocyclic group, and the aliphatic group is a straight chain (eg, methyl group, ethyl group, n-propyl group). , N-butyl group, n-octyl group,
Allyl group, 3-butenyl group, propargyl group, butynyl group, benzyl group, etc.), branch (for example, i-propyl group,
It may be a t-octyl group or the like) or a cyclic (eg, cyclohexyl group or the like). The aromatic group is a monocyclic or bicyclic ring (phenyl, naphthyl, etc.), and the heterocyclic ring is S, N,
It contains any of O in the ring, and even if it is a monocyclic ring (eg, pyridyl group, thiadiazolyl group, etc.), it is condensed (eg, benztriazolyl group, benzthiazolyl group, benzimidazolyl group, etc.). It may be. Also,
These groups may further have a substituent. Examples of the substituent include an aliphatic group (eg, a methyl group, an ethyl group, a butenyl group, a propargyl group, an i-propyl group, etc.), an aryl group (eg, a phenyl group, a naphthyl group, etc.), a heterocyclic group ( For example, a pyridyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, etc.), a carboxy group,
Sulfo group, cyano group, alkoxy group (eg, methoxy group, ethoxy group, benzyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), hydroxy group, mercapto group, halogen atom (eg, chlorine atom, Bromine atom, etc.), alkoxycarbonyl group having 20 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p -Tolyloxy group etc.), acyloxy group (eg acetyloxy group, propionyloxy group etc.), acyl group (eg acetyl group, propionyl group, benzoyl group, mesyl group etc.), carbamoyl group (eg carbamoyl group, N, N-dimethylcarbamoyl group, morpho Nocarbonyl group, piperidinocarbonyl group etc.), sulfamoyl group (eg sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group etc.), acylamino group (eg acetylamino group) ,, propionylamino group, mesylamino group, etc.), sulfonamide group (eg, ethylsulfonamide group, p-toluenesulfonamide group, 2,4,6-triisopropylphenylsulfonamide group, etc.), ureido group (eg, methyl Ureido group, phenylureido group, etc.), amino group (eg, diethylamino group, etc.) and the like.

X ₁ represents O, S or NH, and X ₂ represents an aliphatic group (eg, methyl group, ethyl group, butenyl group, propargyl group, i-propyl group, etc.) or NH ₂ . Preferably, X ₁ is NH and X ₂ is NH _2.
Alternatively, X ₁ is O or S and X ₂ is an alkyl group (eg, methyl group, ethyl group, etc.). Particularly preferably,
X ₁ is NH and X ₂ is NH _2, or X ₁ is O and X ₂ is a methyl group. Further, the compound of the general formula (3) may form a salt with a protonic acid (for example, hydrogen chloride, hydrogen bromide, hydrogen iodide, methanesulfonic acid, p-toluenesulfonic acid, etc.).

Next, the general formula (4) will be described in detail. In the formula, R ₂ represents an aliphatic group (alkyl group, alkenyl group, alkynyl group), an aromatic group or a heterocyclic group, and the aliphatic group is a straight chain (eg, methyl group, ethyl group, n-propyl group). , N-butyl group, n-octyl group,
Allyl group, 3-butenyl group, propargyl group, butynyl group, benzyl group, etc.), branch (for example, i-propyl group,
It may be a t-octyl group or the like) or a cyclic (eg, cyclohexyl group or the like). The aromatic group is a monocyclic or bicyclic ring (phenyl, naphthyl, etc.), and the heterocyclic ring is S, N,
It has any of O in the ring, and is a condensed ring (eg, benztriazolyl group, benzthiazolyl group, benzimidazolyl group, etc.) even if it is a monocyclic ring (eg, pyridyl group, thiadiazolyl group, etc.) May be. Also,
These groups may further have a substituent, and examples of the substituent include the substituents mentioned in the description of R ₃₁ . X ₃ is a hydrogen atom or a group represented by the general formula (5).

In the general formula (5), X_FourIs O, S, N
Represents either H or X_FiveIs NH_Two Or aliphatic groups (eg
For example, methyl, ethyl, butenyl, propargyl
Group, i-propyl group, etc.). Preferred general formula (4)
The compound is X_ThreeIs a hydrogen atom, or a general formula
X on the basis of (5)_FourBut NH is X_FiveIs NH_Twobelongs to. Ma
Further, the compound of general formula (4) is the same as the compound of general formula (3)
Similarly, it may form a salt with a protonic acid. Less than
Specific examples of the compounds represented by the general formulas (3) and (4)
, But of course the following compounds are not limited to
Absent.

[0023]

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[0024]

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[0025]

[Chemical 21]

[0026]

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The compound represented by formula (3) or (4) in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers. . Since the content of the compound of the general formula (3) or (4) of the present invention in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the developing conditions, a suitable content is wide. Can vary over a range but is about 5 × 1 per mole of silver in the silver halide emulsion
The range of 0 ^{-6 to} 5 × 10 ^-2 mol is preferable. More preferably, the range is from 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol.

Next, the general formulas (6) and (7) will be described in detail. R ₅₁ to R ₅₅ represents a hydrogen atom, an aliphatic group (an alkyl group, an alkenyl group, an alkynyl group), an aromatic group or a heterocyclic group. As the aliphatic group, straight chain (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, propargyl group, butynyl group, benzyl group, etc.), It may be branched (for example, i-propyl group, t-octyl group, etc.) or cyclic (for example, cyclohexyl group, etc.), and is R ₅₂ and R ₅₃ , R ₅₄ and R ₅₅ , R ₅₂ and R ₅₄ , R ₅₃ and R. ₅₅ may be linked to each other to form a ring (eg, pyrrolidyl ring, piperidyl ring, morpholyl ring, etc.). The aromatic group is a part or bicycle (phenyl group, naphthyl group, etc.),
Further, it may be a heteroaromatic ring having a hetero atom (eg, S, N, O, etc.) in the ring (eg, pyridyl group, thiadiazolyl group, benztriazolyl group, etc.). The heterocyclic group contains any one of S, N and O in the ring, and may be a monocyclic ring (eg, pyridyl group, thiadiazolyl group, etc.) or a condensed ring (eg, benztriazolyl group). , Benzthiazolyl group, benzimidazolyl group, etc.)
You can do it. Moreover, these groups may further have a substituent. R ₅₂ and R ₅₄ , and R ₅₃ and R ₅₅ may be linked to each other to form a ring (for example, an imidazolidine ring or the like) so as to contain two nitrogens of a guanidyl group,
These may further have a substituent. Examples of these substituents include an aliphatic group (eg, methyl group, ethyl group, butenyl group, propargyl group, i-propyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group Group (for example, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, etc.), carboxy group,
Sulfo group, cyano group, alkoxy group (eg, methoxy group, ethoxy group, benzyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), hydroxy group, mercapto group, halogen atom (eg, chlorine atom, Bromine atom, etc.), alkoxycarbonyl group having 20 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p -Tolyloxy group etc.), acyloxy group (eg acetyloxy group, propionyloxy group etc.), acyl group (eg acetyl group, propionyl group, benzoyl group, mesyl group etc.), carbamoyl group (eg carbamoyl group, N, N-dimethylcarbamoyl group, morpho Nocarbonyl group, piperidinocarbonyl group etc.), sulfamoyl group (eg sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group etc.), acylamino group (eg acetylamino group) ,, propionylamino group, mesylamino group, etc.), sulfonamide group (eg, ethylsulfonamide group, p-toluenesulfonamide group, 2,4,6-triisopropylphenylsulfonamide group, etc.), ureido group (eg, methyl Ureido group, phenylureido group, etc.), amino group (eg, diethylamino group, etc.) and the like. Further, the compounds represented by the general formulas (6) and (7) are protic acids (for example, hydrogen chloride, hydrogen bromide, hydrogen iodide, methanesulfonic acid, p
-Toluenesulfonic acid, etc.) may form a salt.

In the general formula (7), R ₆₁ represents an acyl group or an amino group. Examples of the acyl group include an acetyl group, a propionyl group, a butyroyl group and a benzoyl group. The amino group is preferably a substituted amino group, and examples thereof include a methylamino group, a butylamino group, a benzylamino group and a 3-phenylpropylamino group. Specific examples of the compounds represented by the general formulas (6) and (7) are shown below, but the invention is not limited to the following compounds.

[0030]

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[0031]

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[0032]

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[0033]

[Chemical formula 26]

Examples of the hydrazine derivative used in the present invention include compounds represented by the following general formula (8).

[0035]

Embedded image In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfonyl group or an acyl group, R _a is an aliphatic group, an aromatic group or a heterocyclic group, and G ₁ is It represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group, or an iminomethylene group, and R _b represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, an amino group, or the general formula (9 ) Represents.

[0036]

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In the general formula (9), Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.

Next, the general formulas (8) and (9) will be described in detail. In the general formula (8), A ₁ and A ₂ are hydrogen atoms, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group, or the sum of Hammett's σ _p is -0.5 or more). A substituted phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's σ _p is −0.5 or more), or A straight-chain, branched or cyclic, unsubstituted or substituted aliphatic acyl group (the substituent includes, for example, a halogen atom, an ether group, a sulfonamide group, an amide group, a hydroxy group, a carboxy group, and a sulfo group). It is most preferable that A ₁ and A ₂ are hydrogen atoms. The aliphatic group represented by _Ra is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by _Ra is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.
The heterocyclic group for R _a is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, and S atoms, which may be a monocycle, You may form a condensed ring with the aromatic ring or heterocycle of. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolyl group, a thiazolyl group, and a benzothiazolyl group. Are preferred. R _a may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example,
Alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group , Hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, ammonium group, pyridinium group, thiuronium group, isothioureido group and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R _a is an aromatic group, more preferably an aryl group. Further, R _a may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. be able to. Q ⁺ in the general formula (9) is a group containing a cationic group having at least one quaternary nitrogen atom, and is G ₁ through a linear or branched hydrocarbon chain having 1 to 4 carbon atoms. And part or all of this chain may form part of a heterocycle having a quaternary nitrogen atom. Preferred examples of Q ⁺ include a trialkylammonioalkyl group, a pyridinium-1-ylalkyl group, a 1-alkylpyridinium-2-yl group, a 1-alkylpyridinium-3-yl group, and a 1-alkylpyridinium-4-yl group. Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and as the substituent, those mentioned as the substituent for R _a are preferable.
Further, when these groups form a ring structure, they may be condensed with another ring. A ^- is a counter anion of Q ^+, Cl preferred examples ^-, Br -, ^{p-toluenesulfonate,} but like methyl sulfonate, having a sulfo group as a Q ⁺ substituents, inner salt Is not present when forming

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R _b is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). When G ₁ is a carbonyl group, R _b
Preferred among the groups represented by are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group,
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, 2-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2-methane) Sulfonamidophenyl group, 4-methanesulfonamidophenyl group, 2-hydroxymethylphenyl group, etc.), the general formula (9) and the like, particularly a hydrogen atom,
Formula (9) is preferred. R _b may be substituted, and as the substituent, the substituents listed for R _a can be applied. When G ₁ is an oxalyl group, preferred as R _b are an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-hydroxymethylphenoxy group). Group, 4-chlorophenoxy group, etc.),
An amino group (for example, a 3-hydroxypropylamino group,
2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group and the like), general formula (9) and the like, with an amino group being particularly preferable. R _a and R _b may be those in which a group that enhances adsorption to the surface of the silver halide grain is incorporated.
Examples of the adsorptive group include groups described in US Pat. No. 4,355,105 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
R _b splits the G ₁ -R _b portion from the residual molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing atoms of the G ₁ -R _b portion, and examples thereof include those described in JP-A-63-29751. Can be mentioned. Specific examples of the compound represented by the general formula (8) are shown below, but the present invention is not limited to the following compounds.

[0040]

[Chemical 29]

[0041]

Embedded image

[0042]

[Chemical 31]

[0043]

Embedded image

[0044]

[Chemical 33]

The hydrazine compound of the present invention is disclosed in, for example, JP-A-61-213847, JP-A-62-178246, JP-A-62-180361, JP-A-62-260153, and JP-A-6-260153.
No. 3-253357, U.S. Pat. No. 4,684,604
No. 3,379,529 and 4,377,63
No. 4, No. 4,332,878, No. 4,937,1
No. 60, Japanese Patent Application No. 63-98803, Japanese Patent Application No. 7-476
It can be synthesized by utilizing the method described in No. 24, No. 7-182342 and the like.

The hydrazine compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethyl sulfoxide,
It can be used by dissolving it in methylcellosolve or the like.
Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, glyceryl triacetate or an oil such as diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Things can be created and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

In the light-sensitive material of the present invention, the hydrazine compound is preferably contained in the silver halide emulsion layer.
It may be contained in a hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer is a layer having any function, such as a subbing layer, an intermediate layer, a filter layer, a protective layer, or an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. Good. Since the content of the hydrazine compound in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range, but for the hydrazine compound the surface can be varied. About 1 x 10 per mol of silver in latent image type silver halide emulsion
A range of ^-6 to 1 x 10 ^-2 mol is practically useful.

The silver halide used in the light-sensitive silver halide emulsion of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferable, and the silver halide is selected from silver chloride and salts. Although silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide or the like can be used, when silver chloroiodobromide or silver iodobromide is used, the content of silver iodide is 5 It is preferably in the range of mol% or less. The form, crystal habit, size distribution and the like of the silver halide grains are not particularly limited, but the grain size is 0.7
Those having a size of μm or less are preferred. Silver halide emulsions include gold compounds such as chloroaurate and gold trichloride, sulfur compounds which form silver sulfide by reacting with salts of noble metals such as rhodium and iridium and silver salts, stannous salts, Sensitivity can be increased without reducing particles with a reducing substance such as an amine. Also, salts of precious metals such as rhodium and iridium,
An iron compound such as a red blood salt may be present during physical ripening or nucleation of silver halide grains. In particular, the addition of a rhodium salt or a complex salt thereof is preferable because the effect of the present invention of achieving ultra-high contrast photographic properties in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion means an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of No. 401. It is desirable that the silver halide emulsion be monodisperse, and in particular, the above-mentioned US Pat.
An emulsion having the monodispersity defined in No. 224,401 is preferable. It is preferable that the silver halide emulsion used in the present invention contains a water-soluble rhodium salt (eg, rhodium dichloride, rhodium trichloride, potassium hexachloride rhodium (III) acid, ammonium hexachloride rhodium (III) acid). The rhodium salt is preferably added before the first ripening at the time of emulsion production. The addition amount of the rhodium salt is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, particularly preferably 0.1 to 0.4 μm. The shape of the silver halide grains may be a regular one such as cubic or octahedral, or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The term "monodisperse emulsion" as used herein means an emulsion in which 90%, more preferably 95%, of the total number of grains falls within a grain size range of ± 40% of the average grain size. The method of reacting the soluble silver salt and the soluble halogen salt for the preparation of the silver halide emulsion in the present invention may be a single jet method, a double jet method, a reverse mixing method of forming in the presence of excess silver ions, or the like. However, for the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form particles is particularly preferable. The silver halide emulsion thus prepared may or may not be chemically sensitized. From the viewpoint of improving the handleability, it is rather preferable that the so-called bright room light-sensitive material to be handled in a safe light environment, which can be substantially called a bright room, is not chemically sensitized. For chemical sensitization, ordinary sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and the like are used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. These sensitizing dyes may be used alone or in combination.
A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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 hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles,
For example, benzothiazolium salt, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles; mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, etc. Many compounds, more known as antifoggants or stabilizers, can be added. Of these, particularly preferred are
Benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole). These compounds may be contained in the processing solution.

The photographic light-sensitive 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 (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6). −
Hydroxy-S-triazine, etc.) or the like can be used alone or in combination. The photosensitive silver halide emulsion layer or an adjacent layer may be provided with a research disclosure (R) for the purpose of increasing sensitivity, increasing contrast, or accelerating development.
The compounds described in Esearch Disclosure No. 17465, Item XXI, Item B to D can be added, and it is particularly preferable to add polyethylene glycol or a derivative thereof.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention can be coated with a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development). A surfactant may be included for various purposes such as acceleration, contrast enhancement, and sensitization. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy group, such as alkyl phosphates,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate groups, and phosphate groups, amino acids,
Amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium Can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide photographic light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ions (especially 0.15 mol / l or more) as a preservative can be used, and a pH of 9.5 or more, especially 10 With a developing solution of about 11.0, a sufficiently high-contrast negative image can be obtained. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0057]

【Example】

[Example 1] [Preparation of coating sample] 1.0 x 10 ^-7 mol of (NH4) ₃ RhC per mol of silver was added to a gelatin aqueous solution kept at 40 ° C.
1 ₆ and 2.0 × 10 ^-7 mol of K ₃ IrCl _{6 in} the presence of an aqueous solution of silver nitrate and an aqueous solution containing sodium chloride and potassium bromide into an aqueous gelatin solution containing 1,3-dimethyl-2-imidazolinethione. Mix by jet method,
60 mol% silver chloride content with an average grain size of 0.2 μm
A core consisting of silver chlorobromide grains was obtained. Subsequently, an aqueous silver nitrate solution and an aqueous solution containing sodium chloride and potassium bromide were similarly added by the double jet method. After that, 1.0 × 10 ⁻³ mol of potassium iodide solution was added per mol of silver and gelatin was added after removing soluble salts by a method well known in the art to adjust pH to 6.5 and pAg to 7.5. It was adjusted and further chemically ripened by adding 7 mg of sodium toluenethiosulfonate, 5 mg of sodium thiosulfate and 7 mg of chloroauric acid per 1 mol of silver, and 170 mg of 2-methyl-4-hydroxy-1,3 as a stabilizer. , 3a, 7-Tetraazaindene was added. This emulsion has an average grain size of 0.25
It was a monodisperse emulsion having a cubic crystal shape of μm. 5,5'-dichloro-9-ethyl-3, a sensitizing dye, was added to this emulsion.
3′-bis- (4-sulfobutyl) oxacarbocyanine was expressed as 3 × 10 ⁻⁴ mol / Agmol and the general formula (8) shown in Table 1 was used as 7 × 10 ⁻⁴ mol / Agmol and the general formula (1), respectively. 100 mg / m ^{2 of the} polymer containing (2) and 0.05 mmol / Agmol of the general formulas (3) to (7).
added. Subsequently, polyethyl acrylate latex was added as solid content to gelatin in an amount of 30 wt%, and 1,3-divinylsulfonyl-2-propanol was added as a hardening agent to give an Ag amount of 3.8 g / m ² on the polyester film. Like so. Gelatin was 1.8 g / m ² . On top of this, 1.5 g / m ² of gelatin and 0.3 g / m ^{2 of} polymethyl methacrylate having a particle size of 2.5 μm as a protective layer.
Layers were applied. Further, the comparative nucleation accelerator shown below was 20 mg / m ² and the black spot inhibitor was 0.05 mmol / A.
A comparative sample containing gmol was also prepared.

[0058]

Embedded image

[0059]

Embedded image

<Evaluation of Photographic Property> The obtained coated sample was exposed to xenon flash light having an emission time of 10 ⁻⁵ sec through an interference filter having a peak at 633 nm and a step wedge, and then [Developer-1] having the following composition. At 35 ° C
Develop processing for 30 seconds and fixer PURCF9 from Mitsubishi Paper Mills Ltd.
It was fixed at 01, washed with water and dried. Table 1 shows the results of evaluation of the relative sensitivity, contrast and black spots of each sample. The relative sensitivity was calculated as the reciprocal of the exposure amount required to obtain a transmission density of 3.0. It is a relative value when the sensitivity value of Sample 7 is 100. The contrast indicating the degree of contrast of an image is the slope of the linear portion of the characteristic curve (optical density 1.0 to
It is represented by tan Θ) of 2.5, and if it is 10 or less, the hardness is insufficient and it is not practical. Also, black spots (black spots) that cause fog in the unexposed area are observed with a magnifying glass of 100 times, and the number of occurrences is evaluated on a scale of 5, and those without black spots are set to 5 and 3 or more. Is a relative level that is practically usable.

[Developer-1] Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-plaseridine 0.3 g Sodium sulfite 75.0 g EDTA.2Na 1.0 g Tripotassium phosphate 80.0 g Potassium bromide 2.0 g Sodium hydroxide 13.0 g 5-Methylbenzotriazole 0.3 g Sodium p-toluenesulfonate 7.0 g Water is added to adjust the pH to 10.5 with 1 liter potassium hydroxide.

[0062]

[Table 1]

As can be seen from the results shown in Table 1, the addition of the hydrazine compound of the present invention, the polymer contrast-increasing accelerator, and the black spot inhibitor suppresses the number of black spots while maintaining a high contrast as compared with the comparison. It shows good results.

[Example 2] Next, the developers shown in Table 2 were prepared from the sample prepared in Example 1 in order to see the change in the halftone dot image quality due to the change in the pH of the developer. Halftone dot image quality is 150
50% halftone original is exposed to 50% through a line gray contact screen, the halftone dot developed at pH 10.5 is used as standard 50, and the same exposure amount is used to obtain pH 10.0. The image quality was evaluated by developing at 11.0. Observe the halftone image quality with a magnifying glass of 100 times,
The one with extremely high halftone image quality is set to 10, and the following is 9, 8, and 7
・ ・ ・ 3, 2, and 1 are ranked, and those of 8 or more have no problem in practical use, 4 to 7 are levels that can withstand practical use but are not preferable, and 1 to 3 are practical. Is unbearable. Table 3 shows the results.

[0065]

[Table 2]

[0066]

[Table 3]

From the results shown in Table 3, it can be seen that the present invention is superior to the change in pH during the development processing in that the image quality of the halftone dot is less varied and stable image quality is maintained as compared with the comparison.

[0068]

As described above, in the super-high contrast image forming method using a hydrazine compound in a silver halide photographic light-sensitive material, a polymer having a structural part represented by the general formula (1) or (2) in its molecule is used as a high-contrast accelerator. By using the general formula (3), (4), (6) or (7) as an anti-black spot agent, generation of black spots can be suppressed without impairing sensitivity while maintaining high contrast, and a developer can be used. It is possible to obtain a stable contrast and halftone dot quality even when the pH is changed, and to provide a good light-sensitive material with less black spots.

Claims (1)

[Claims] 1. In a silver halide light-sensitive material having at least one silver halide emulsion layer on a support, the hydrazine derivative and the following general formula (1) are contained in the silver halide emulsion layer or another hydrophilic colloid layer. ) Or at least one of the nucleation accelerators of the polymer compound having the structural part represented by (2) and at least the compounds represented by the following general formulas (3), (4), (6) and (7) A silver halide photographic light-sensitive material containing one kind. Embedded image In the formula, R ₁ , R ₂ and R ₃ represent an aliphatic group which may have a substituent, an alkenyl group, an aromatic group or a heterocyclic group,
X represents an anion and L represents a linking group. Embedded image In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group, and may form a ring with each other. However,
R ₂₁ and R ₂₂ are not hydrogen atoms at the same time. L ₁ and L ₂ represent a divalent linking group. X represents an alkylene group which may have a substituent. p and q represent 0 or 1, and r
Represents 2 to 30. Embedded image In the formula, R ₃₁ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X ₁
Represents any one of O, S and NH, and X ₂ represents an aliphatic group or NH ₂ . Embedded image In the formula, R ₄₁ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X ₃
Is a hydrogen atom or a group represented by the general formula (5). Embedded image In the formula, X ₄ represents any one of O, S and NH, and X ₅
Represents an aliphatic group or NH ₂ . [Chemical 6] In the formula, R _{51 to} R ₅₅ represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a heterocyclic group or an acyl group, and R ₅₂ and R ₅₃ , R ₅₄ and R ₅₅ , R ₅₂ and R
₅₄ , R ₅₃ and R ₅₅ may combine with each other to form a ring. However, at least two of R _{51 to} R ₅₅ are an aliphatic group, an aromatic group, or a heterocyclic group. [Chemical 7] In the formula, R ₆₁ represents an acyl group or an amino group.