JPH07270957A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material capable of obtaining highly sensitive photographic performance having high contrast of gamma value of >10 by using a stable developer and improved in black spots by incorporating a hydrazine derivative and a specified onium compound and a specified compound in a silver halide emulsion layer. CONSTITUTION:At least one of the silver halide emulsion layers and hydrophilic colloidal layers contains a hydrazine derivative and an onium compound represented by formula I and a compound represented by formula II, and in the formula I, each of R1-R3 is an alkyl, cycloalkyl, or the like; (m) is an integer of 1-4; L is an (m)-valent organic group combining its carbon atom with P atom; and (n) is 1, 2, or 3; X is an (n)-valent anion, and in the formula II, R1 is a halogen or cyano, or the like; R2 is H, an alkyl, or the like; and R3 is H, a halogen, alkyl, or aryl.

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 more particularly to an ultrahigh-contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting super-high gradation (especially γ of 10 or more) is provided in order to improve reproduction of continuous tone images or line images by halftone dot images. is necessary. There is a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics, and one of them is US Pat. Nos. 4,166,742 and 4,16.
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
No. 272,606 and No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added is added with a sulfite preservative in an amount of 0.15 mol / liter or more. Including pH 11.0-12.
A system for forming a super-high contrast negative image having a γ value of more than 10 by treating with a developing solution of No. 3 has been proposed. This new image forming system can be used with silver iodobromide and silver iodochlorobromide, whereas the conventional ultrahigh contrast image forming system can only use silver chlorobromide with a high silver chloride content. There are features. Another feature of the conventional lith developer is that it can contain a large amount of sulfite preservative, whereas it can contain a very small amount of sulfite preservative.

However, since a developer having a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage or use, a silver halide photographic light-sensitive material containing a hydrazine compound is developed with a developer having a lower pH. However, attempts have been made to create a high contrast image. For example, Japanese Patent Laid-Open No. 1-1799
No. 39 and No. 1-179940, a nucleation development accelerator having an adsorption group for silver halide emulsion grains;
Similarly, using a light-sensitive material containing a nucleating agent having an adsorption group, p
A processing method of developing with a developing solution of H11.0 or less is described.

Further, the nucleation-hardening light-sensitive material using a hydrazine derivative has a large range of change in photographic property with a change in pH of the developing solution. The pH of the developer greatly changes due to air oxidation of the developer and increase due to concentration by evaporation of water, or decrease due to absorption of carbon dioxide in the air. Therefore, attempts have been made to reduce the dependence of photographic performance on the pH of the developer. Further, in a nucleation-hard-tone / high-tone negative image system using a hydrazine derivative, one of the points to be improved is that it causes undesired development called black spots, which is a problem in the photolithography process. ing. The black spot is a black spot made of minute developed silver that originally occurs in a portion that should be non-imaged when it is not exposed. Black spots frequently occur due to a decrease in sulfite ion, which is generally used as a preservative in a developing solution, and an increase in pH value, and the commercial value as a photosensitive material for photoengraving is remarkably reduced. For this reason, great efforts have been made to improve the black spots, but the improvement of the black spots is often accompanied by a decrease in sensitivity and gamma (γ), resulting in a high-sensitivity high-contrast (for example, 1 for γ).
There is a strong demand for a system that maintains 0 or more) and improves black spots. Further, it is known that a combination of a hydrazine compound and an onium compound provides high activation, and good photographic performance can be obtained, but it has a drawback that black spots are deteriorated with high activation. It was

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is to:
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining extremely high-contrast and high-sensitivity photographic properties with a gamma of more than 10 by using a stable developer.
A second object of the present invention is to provide a silver halide photographic light-sensitive material which has a high contrast with a developing solution having a pH of 11 or less and has little fluctuation in photographic performance due to fatigue of the developing solution.

[0006]

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, said silver halide emulsion layer or another hydrophilic colloid layer. Containing at least one hydrazine derivative and at least one onium salt compound represented by the following general formula (I), (II), (III) or (IV) in at least one layer of And a compound represented by the following general formula (V) or (VI) in the hydrophilic colloid layer.

[0007]

[Chemical 5]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0009]

[Chemical 6]

In the formula, A represents an organic group for completing the heterocycle. B and C each represent a divalent group. R ₁ ,
R ₂ represents an alkyl group or an aryl group, and R ₃ ,
R ₄ represents a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but in the case of an inner salt, X
Is not necessary. General formula (V)

[0011]

[Chemical 7]

In the formula, R ₁ is a halogen atom, --CN, --C
_{OOR, -CONH 2, -CONHR, -CONR} 2,
_{-SO 2 R, -SO 2 NH 2} , -SO 2 NHR or -
It represents SO ₂ NR ₂ . R ₂ represents a hydrogen atom, an alkyl group, an aryl group, —OR, —SR or —SeR, and R ₃
Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. R represents an alkyl group or an aryl group, and when the compound of the general formula (V) contains a plurality of Rs, they may be the same or different, and further -CO
In NR ₂ and —SO ₂ NR ₂ , two Rs may combine to form a cyclic structure. General formula (VI)

[0013]

[Chemical 8]

In the formula, R ₄ and R ₆ have the same definition as R _{1 in the} general formula (V) and may be the same or different.
₅ , R ₇ have the same definition as R _{3 in the} general formula (V), and may be the same or different. X ₁ and X ₂ are oxygen atoms,
It represents a sulfur atom or a selenium atom and may be the same or different, and n and m represent 0 or 1. L represents a divalent organic acid.

The general formula (I) will be described in detail.

[0016]

[Chemical 9]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group and a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have.

Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-group.
A linear or branched alkyl group such as a butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; a cyclopropyl group, a cyclopentyl group Group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group, naphthyl group, phenanthryl group; alkenyl group such as allyl group, vinyl group, 5-hexenyl group; cycloalkenyl such as cyclopentenyl group, cyclohexenyl group Group; pyridyl group, quinolyl group,
Furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group,
Heterocyclic residues such as a morpholyl group, a pyrimidyl group and a pyrrolidyl group are mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 2, a tertiary amino group, an alkyl or aryl ether group, an alkyl or aryl thioether group, a carbonamido group, a carbamoyl group,
Examples thereof include sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group and carbonyl group. Examples of the group represented by L include a group having the same meaning as R ₁ , R ₂ and R ₃ , as well as a trimethylene group, a tetramethylene group,
Polymethylene group such as hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, divalent aromatic group such as phenylene group, biphenylene group and naphthylene group, polyvalent fat such as trimethylenemethyl group and tetramethylenemethyl group Examples thereof include polyvalent aromatic groups such as group groups, phenylene-1,3,5-toluyl group, and phenylene-1,2,4,5-tetrayl group. Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion, p-toluene sulfonate and methane sulfonate. Examples thereof include sulfonate ion such as butane sulfonate and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion and nitrate ion.

In the general formula (I), R ₁ , R ₂ , R ₃
Is preferably a group having 20 or less carbon atoms, and an aryl group having 15 or less carbon atoms is particularly preferable. m is preferably 1 or 2, and when m is 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. , -O- group, -N
R ₄ — group (provided that R ₄ is a hydrogen atom or R ₁ , R ₂ , R
₃ represents a group having the same meaning as _3, and when a plurality of R _4's are present in the molecule, they may be the same or different and may be bonded to each other), —S— group, — SO-
It is a divalent group formed by combining a group and a —SO ₂ — group. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more, R ₁ in the molecule,
R _2, R ₃ are each plurality of, the plurality of R _1, R _2, R ₃ may be different even in the same, respectively. n is preferably 1 or 2 and m is 1 or 2
Is preferred. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt.

Many of the compounds represented by formula (I) of the present invention are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

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

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

[0029]

[Chemical 17]

[0030]

[Chemical 18]

Next, the general formulas (II), (III) and (IV) will be described in more detail.

[0032]

[Chemical 19]

In the formula, A represents an organic group for completing the heterocycle, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A may be a 5- to 6-membered ring, and a more preferred example is a pyridine ring,
Examples thereof include a quinoline ring and an isoquinoline ring. In addition, A may be substituted, and as a preferable substituent,
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.), A substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, furyl group,
Thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group) Group), an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. Particularly preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group,
A hydroxy group may be mentioned. The divalent group represented by B and C includes alkylene, arylene, alkenylene, and
_{SO 2 -, - SO -,} - O -, - S -, - N (R 6) - those constituted singly or in combination are preferred. However, R ₆ represents an alkyl group, an aryl group, or a hydrogen atom. As a particularly preferred example, B and C include alkylene, arylene, -O-, and -S-, which may be constituted alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group). ,
Furyl group, thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group) Group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group,
It represents an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. In particular,
As a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group.

R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. R ₅ has 1 to 2 carbon atoms
An alkyl group of 0 is preferable, and whether it is linear or branched,
Further, it may be a cyclic alkyl group. The alkyl group may be substituted with a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . X represents an anion group, but X is not necessary in the case of an inner salt. Examples of X are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The compounds represented by the general formulas (II), (III) and (IV) of the present invention can be easily synthesized by well-known methods. Refer to the following documents. You can (See Quart. Rev., 16, 163 (196
2).)

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

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

The amount of the compounds of the general formula (I), general formula (II), general formula (III) and general formula (IV) of the present invention added is
There is no particular limitation, but 1 × 10 1 per mol of silver halide
^-5 to 2 × 10 ^-2 mol is preferable, and a particularly preferable range is 2 × 10 ^-5 to 1 × 10 ^-2 mol.

The general formula (I) and the general formula (I
I), the compounds of the general formula (III) and the general formula (IV) are contained in the photographic light-sensitive material as an aqueous solution in the case of being water-soluble, and alcohols (eg methanol, ethanol) in the case of being insoluble in water, It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (eg ethyl acetate) and ketones (eg acetone). Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

General formulas (V) and (VI) used in the present invention
The compound will be described in detail. General formula (V), (V
In I), R ₁ , R ₄ , and R ₆ are each a halogen atom, —CN, —CONHR, —CONR ₂ , or —SO ₂ R.
Is preferred. R ₂ is preferably a group having a total carbon number of 6 or more, an alkyl group (for example, C ₇ H ₁₅ —, C ₉ H ₁₉ —, etc.), —S.
R (e.g. _{C 6 H 13 S-, C 8} H 17 S-, C 6 H 5 S-
Etc.) and aryl groups (eg C ₆ H ₅ — etc.) are particularly preferred. R ₃ , R ₅ , and R ₇ are hydrogen atoms, halogen atoms, and alkyl groups having 8 or less carbon atoms (for example, CH ₃ —, i-C ₃ H ₇
-Etc.), An aryl group having 6 to 10 carbon atoms (for example, C
₆ H ₅ — and the like) are preferable, and a hydrogen atom or a methyl group is particularly preferable. X ₁ and X ₂ are preferably sulfur atoms. L is alkylene, phenylene, -O-, -NH-, -NR-,
A divalent group that can be formed by combining —CO— and —SO ₂ — is preferable, and both ends thereof are preferably carbon atoms. Particularly preferably, L is a divalent group having a total carbon number of 2 or more and 10 or less. In the above, each R represents an alkyl group or an aryl group.

In the general formulas (V) and (VI), R ₁ ,
R < ₂ >, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ >, R < ₇ > and L may each be substituted, and typical examples of the substituent include an alkyl group, an aryl group, a halogen atom, -OR, -SR, -S
_{O 2 R, -NHR, -NR 2} , -COOH or salts _{thereof, -COOR, -CONH 2, -CONHR,} -CO
_{NR 2, -NHCOR, -OCOR, -SO} 3 H or a salt _{thereof, -SO 2 OR, -SO 2 NH} 2, -SO 2 NH
_{R, -SO 2 NR 2, -NHSO} 2 R, -NO 2, -C
N, etc. may be mentioned, and these groups may be further substituted. Specific examples of formulas (V) and (VI) are shown below, but the invention is not limited thereto.

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

[Chemical 30]

General formulas (V) and (VI) in the present invention
The addition amount of the compound is 1 × 10 ⁻⁴ per mol of silver
To 2.5 × 10 ⁻² mol, preferably 2 × 10 ⁻⁴ to 5 × 10 ⁻³ .

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

[0054]

[Chemical 31]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ - group, -SO- group,

[0056]

[Chemical 32]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (VII), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (VII),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group,
Sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having hydrazide structure, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group , Carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, selenium atom or Examples thereof include a group containing a tellurium atom, a group having a tertiary sulfonium structure or a group having a quaternary sulfonium structure, and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having a carbon number of 1).
~ 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably Amino group substituted with alkyl group having 1 to 20 carbon atoms, acylamino group (preferably having 2 carbon atoms)
To 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

In the general formula (VII), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), Aryl groups (eg phenyl groups, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom and trifluoromethyl group are particularly preferable. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G in the general formula (VII), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. Also, R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (VII) may be further substituted, and preferred examples thereof include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (VII) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (VII) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,34.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivative in the present invention is that R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, Or a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (as a substituent, an electron-withdrawing group or a hydroxymethyl group at the 2-position is used. Preferred) hydrazine derivative. Note that any combination of the above R ₁ and R ₂ options is possible and preferred.

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

[0066]

[Chemical 33]

[0067]

[Chemical 34]

[0068]

[Chemical 35]

[0069]

[Chemical 36]

[0070]

[Chemical 37]

[0071]

[Chemical 38]

[0072]

[Chemical Formula 39]

[0073]

[Chemical 40]

[0074]

[Chemical 41]

[0075]

[Chemical 42]

[0076]

[Chemical 43]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative 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, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide, silver iodobromide. However, silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol% or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is 0.1 μm
0.7 μm is preferable, but 0.2 to 0.
5 μm, {(standard deviation of particle size) / (average particle size)}
The coefficient of variation represented by × 100 is preferably 15% or less, more preferably 10% or less and having a narrow particle size distribution. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is a Chimie et Physique Ph by P. Glafkides.
otographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (The Forca by Dufin
Press, 1966), by VL Zelikman et al Maki
ng nd Coating Photographic Emulsion (The Focal Pre
ss, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Preferably. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, and more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545 and JP-A-4-167453.
No. 76534, Japanese Patent Application Nos. 4-68305 and 4-258.
No. 187, etc., it may be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having halogen, amines, oxalate, etc. as a ligand, for example, hexachlororhodium (III)
Examples thereof include complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by being dissolved in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the rhodium compound,
That is, a method of adding an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of forming the emulsion and incorporated into the silver halide grains. It is preferable.

The rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1.
-2859451, 2-20852, 2-208
It is added in the form of a water-soluble complex salt described in No. 55, etc. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands and thionitrosyl ligands. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (CN) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) ₆ ] ^-4 [Ru (CO) ₃ Cl ₃ ] ^-2 [Ru (CO) Cl ₅ ] ^-2 [Ru (CO) Br ₅ ] ^-2 [OsCl ₆ ] ^-3 [OsCl ₅ (NO)] ^-2 [Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of forming the emulsion and incorporated into the silver halide grains. It is preferable. To incorporate these compounds into the silver halide grains by adding them during the formation of silver halide grains, a powder of a metal complex or an aqueous solution dissolved together with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which a silver halide grain is prepared by adding it into a water-soluble halide solution, or by adding as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-liquid simultaneous mixing method, or grain formation There is a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like.
These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg KCl,
NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The silver halide grains in the present invention may be doped with another heavy metal salt. Especially K ₄ [Fe (C
Doping with Fe salts such as N) ₆ is advantageous. Further, in the silver halide grain used in the present invention, cobalt,
It may contain a metal atom such as nickel, palladium, platinum, gold, thallium, copper or lead. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide.
Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is preferably chemically sensitized, and sulfur sensitization, selenium sensitization, tellurium sensitization,
Known methods such as reduction sensitization and noble metal sensitization can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, thiazoles, rhodanins, etc. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher, for a certain period of time. Unstable selenium compounds are disclosed in Japanese Examined Patent Publications Nos. 44-15748 and 43-43
13489, Japanese Patent Application Nos. 2130976 and 2-22
The compounds described in No. 9300, No. 3-121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patents 235,211 and 1,121,496. No. 1,295,462, No. 1,396,696
No., Canadian Patent No. 800,958, Japanese Patent Application No. 2-333.
No. 819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Comm.
un., 635 (1980), ibid. 1102 (1979), ibid.645 (1979), J. Che
m.Soc. Perkin.Trans., 1,2191 (1980), edited by S.Patai, T
he Chemistry of Organic Serenium and Tellurium Com
The compounds described in pounds, Vol1 (1986) and Vol2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use molar amounts. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. A degree can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in European Patent (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions) may be used together.

In the silver halide emulsion used in the present invention, various spectral sensitizing dyes can be used for the purpose of imparting desired spectral sensitivity. The 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 those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Useful sensitizing dyes used in the present invention are, for example,
RESEARCH DISCLOSURE Item 17643 IV-A item (Dec. 1978, p. 23) and Item 1831X item (Aug. 1978, p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-162247 and JP-A-2-
No. 48653, US Pat. No. 2,161,331, West German Patent No. 936,071, and Japanese Patent Application No. 3-189532, the simple merocyanines, B) helium-neon laser light source are disclosed in JP-A-50-62425. Issue 54
For the trinuclear cyanine dyes shown in Nos. 18726 and 59-102229, C) LED light source and red semiconductor laser, Japanese Patent Publication Nos. 48-42172 and 51-9.
No. 609, 55-39818, JP-A-62-284
343, thiacarbocyanines described in JP-A-2-105135, and D) infrared semiconductor laser light source, JP-A-59-191032 and JP-A-60-808.
No. 41, tricarbocyanines, JP-A-59
-192242 and the general formula (I
IIa), dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIb), etc. are advantageously selected.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176 Vol.
7643 (issued in December 1978), page 23, IV, paragraph J. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, preferably 10 ^-7 to 1 × 10 ^-2 mol per mol of silver halide,
In particular, it is used in the range of 10 ⁻⁶ to 5 × 10 ⁻³ mol.

As the binder or protective colloid for the photographic emulsion, 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol-
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polyacrylic acid, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl butyral and the like can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage during storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Hydroquinone and its derivatives; Disulfides, such as thioctic acid; Antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Alternatively, many compounds known as stabilizers can be added. Among these, preferred are benzotriazoles (eg, 5
-Methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Also,
These compounds may be contained in the treatment liquid.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formulas (II-m) to (II-p) and compounds II-1 to II-22, The compounds described in Kaihei 1-179939. 2) Surfactant JP-A-2-12236, page 9, right upper column, line 7 to antistatic agent, right lower column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to 4 Lower right column, line 18 3) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 Stabilizer, page 18 to upper right column, line 4 and lower right column, line 1 to line 5 Furthermore, the thiosulfinic acid compounds described in JP-A-1-237538. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compounds having an acid group JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 From page 11, page 11, upper left column, line 8. 6) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 8) Dyes, JP-A-2-103536, page 17, lower right column, line 1 to line 18, and JP-A-2-39042, page 4, upper right column, column 1 line to page 6, upper right column, line 5. Further, the solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 11) Redox compounds Compounds represented by formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), and general formulas described in pages 3 to 20 of JP-A 3-1 74143. (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 13) Hydroxybenes Compounds described in JP-A-3-39948, page 11, upper left column to page 1, zens, page 2, lower left column, and EP 452,772A.

The developer for developing the silver halide photographic light-sensitive material of the present invention has a pH of 1 which is used when processing a conventional light-sensitive material utilizing the hydrazine nucleation infectious development effect.
It is not necessary to use a developing solution of 1.0 or more, and a stable developing solution having a pH of 9.6 or more and 11.0 or less can be preferably used.

[0102]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 <Preparation of silver halide light-sensitive material> Emulsion preparation An emulsion was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride, and K ₃ IrCl corresponding to 3.5 × 10 ^-7 mol per mol of silver
₆ and 2.0 × 10 ^-7 mols of an aqueous solution of a halogen salt containing K ₂ Rh (H ₂ O) Cl ₅ equivalent to a mixture of sodium chloride and an aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione was stirred. While being added by the double jet method, silver chlorobromide grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol% were prepared.

After that, the product was washed with flocculation according to a conventional method, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol%.
(Variation coefficient 10%)

<Preparation of Coating Sample> On a polyethylene terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride, a UL layer, an EM layer, and a support layer were sequentially formed from the support side.
A sample was prepared by coating so as to have a PC layer and an OC layer. The preparation method and coating amount of each layer are shown below. As the (UL) UL layer, 0.5 g / m ^{2 of} gelatin and 150 mg / m ² of a dispersion of polyethyl acrylate were applied.

(EM) The following compound S-1 as a sensitizing dye was added to the above emulsion in an amount of 5 × 10 ^-4 mol per mol of silver and S-2.
5 × 10 ⁻⁴ mol, and further 3 × 10 per mol of silver
^-4 mol of mercapto compound represented by the following (a), 4x
10 ⁻⁴ mol of the mercapto compound represented by (b), 4 ×
10 ⁻⁴ mol of the triazine compound represented by (c), 2 ×
10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added, and 4 × 1 of the following compound H-1 was used as a hydrazine nucleating agent.
0 ^-4 mol was added, and the onium salt compound of the present invention and the tetraazaindene compound of the present invention were added as shown in Table 1. Furthermore, hydroquinone 100 mg, N-
30 mg of oleyl-N-methyltaurine sodium salt
/ M ² and the compound represented by (d) are added so as to be coated by 20 mg / m ² , the water-soluble latex represented by (e) is 200 mg / m ² , and the dispersion of polyethyl acrylate is 200 mg / m ^2. , 200 mg / l of a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7).
20 m ² of colloidal silica with an average particle size of 0.02 μm
0 mg / m ² , and 200 mg / m ² of 1,3-divinylsulfonyl-2-propanol was added as a hardening agent. The pH of the solution was adjusted to 5.6 with acetic acid. They were coated so that the coated silver amount was 3.6 g / m ² .

(PC) Gelatin 0.5 g / m ² , polyethyl acrylate dispersion 250 mg / m ² , sodium ethylsulfonate 5 mg / m ² , 1,5-dihydroxy-2-benzaldoxime 10 mg / m 2. ² applied. (OC) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm 40 mg /
m ² and colloidal silica 100 having an average particle size of 0.02 μm
mg / m ² , methanol silica 100 mg / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (f) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0107]

[Chemical 44]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound [a] 110 mg / m ²

[0109]

[Chemical formula 45]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² dye [B] 70 mg / m ² dye [c] 90 mg / m ²

[0111]

[Chemical formula 46]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

[0113]

[Table 1]

<Exposure and development> (1) Evaluation of photographic performance The above sample was passed through an interference filter having a peak at 488 nm and passed through a step wedge to emit light for 10 ^-5 se.
It is exposed with a xenon flash light of c, and developed (3) using an FG-680AG automatic developing machine manufactured by FUJIFILM Corporation.
5 ° C. for 30 seconds), fixing, washing with water, and drying. As the developing solution and the fixing solution, the developing solution and the fixing solution having the following compositions were used.

Developer Formulation Developer 1 Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium metabisulfate 40.0 g Potassium carbonate 12.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.06 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.15 g hydroquinone 25.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g Sodium erythorbate 3.0 g Potassium hydroxide is added, water is added to 1 liter and the pH is adjusted to 10.5. 1 liter

Fixing solution formulation Concentrating solution Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 75.0 g NaOH (pure content) 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g Add sulfuric acid or sodium hydroxide to adjust the pH to 5.05, and add water to make 1 liter concentrate. Use 1 liter with 2 liters of water.

The sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the higher the value, the higher the sensitivity. As an index (γ) representing the contrast of the image, fog + density of 3.
The point of 0 was connected by a straight line, and the slope of this straight line was expressed as a γ value. That is, γ = (3.0-0.3) / [log (exposure amount that gives a density of 3.0) -log (exposure amount that gives a density of 0.3)], and the higher the γ value, the harder the image. It shows that it is a characteristic. (2) Evaluation of black spots The black spots were evaluated by microscopic observation of the actual spots. “5” indicates the best level without black spots, and “1” indicates the occurrence of black spots. Remarkably and also represents poor quality. “3” is the limit level at which the generation of black spots is practically acceptable.

(3) PDM, PDS (actual concentration) Here, the actual concentration means Magnascan M65 for the above sample.
6 (manufactured by Crossfield) was used to output a 500 lpi test pattern, and the solid density at the exposure amount (current value) at which 50% halftone dots of the test pattern were 50% on the sample was defined as the practical density PD _M. . In addition, SG-757 (manufactured by Dainippon Screen Co., Ltd.) was used to output a 490 lpi test pattern, and the solid density at the exposure amount (current value) at which 50% halftone dots of the test pattern were 50% finished on the sample was practically used. The concentration was PD _S.

(4) Evaluation of processing stability Processing was carried out and evaluated in the same manner as in (1) Evaluation of photographic property except that the developing solutions 2 to 4 having the following formulations were used.

Developer 2 Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium metabisulfate 40.0 g Potassium carbonate 40.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.08 g 2,3,5,6,7,8-Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.15 g hydroquinone 25.0 g 4-hydroxy Methyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g Sodium erythorbate 3.0 g Diethylene glycol 20.0 g Potassium hydroxide is added, water is added to 1 liter and the pH is adjusted to 10.45. 1 liter Developer 3 Developer 1 with 5% of each sample with a blackening rate of 80%
0 m ² treatment was performed, and running for 5 days while replenishing 300 ml of developer ² per 1 m ² , a developer 3 was prepared. Developing solution 4 Using developing solution 1, each sample with a blackening rate of 20% is 5
m ² treatment and running for 28 days while replenishing 300 ml of developer ² per 1 m ^{2 to} prepare developer 4.

The results are shown in Tables 1 and 2. It is understood that the sample of the present invention has high contrast, little black spots are generated, the change in photographic performance after running is small, and deterioration of black spots is small.

[0122]

[Table 2]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one hydrazine derivative is present in at least one of said silver halide emulsion layer or other hydrophilic colloid layer. And the following general formula (I), (II), (III) or (IV)
Characterized by containing at least one onium salt compound represented by the formula (1), and containing the compound represented by the following general formula (V) or (VI) in the emulsion layer or another hydrophilic colloid layer. Silver halide photographic light-sensitive material. [Chemical 1] In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. m is an integer of 1 to 4, L is P
Represents an m-valent organic group that is bonded to an atom and its carbon atom,
n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L. [Chemical 2] In the formula, A represents an organic group for completing the heterocycle.
B and C each represent a divalent group. R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt.
General formula (V) In the formula, R ₁ is a halogen atom, —CN, —COOR, —C
_{ONH 2, -CONHR, -CONR 2,} -SO 2 R,
-SO ₂ NH _2, -SO ₂ NHR or -SO ₂ NR ₂
Represents R ₂ is a hydrogen atom, an alkyl group, an aryl group,
Represents OR, -SR or -SeR, R ₃ is a hydrogen atom,
Represents a halogen atom, an alkyl group or an aryl group. R represents an alkyl group or an aryl group, and when the compound of the general formula (V) contains a plurality of Rs, they may be the same or different, and in —CONR ₂ and —SO ₂ NR ₂ , Two Rs may combine to form a ring structure. General formula (VI) In the formula, R ₄ and R ₆ have the same definition as R _{1 in the} general formula (V), and may be the same or different, and R ₅ and R ₇ are the same as R _{3 in the} general formula (V). It is a definition and may be the same or different. X ₁ and X ₂ represent an oxygen atom, a sulfur atom or a selenium atom, and may be the same or different, and n and m represent 0 or 1. L represents a divalent organic acid. 2. The silver halide emulsion grains have a silver chloride content of 5
The silver halide photographic light-sensitive material according to claim 1, wherein the content is 0 mol% or more.