JPH09244174A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material having high γ and high sensitivity and capable of forming an ultrahigh contrast image by incorporating two kinds of specified compds. into a silver halide emulsion layer and/or other hydrophilic colloidal layer. SOLUTION: This sensitive material contains at least one kind of compd. represented by formula I and at least one of compds. represented by formulae II-VII in a silver halide emulsion layer and/or another hydrophilic colloidal layer. It is processed with an aq. alkali developer. In the formula I, R1 is optionally a substd. aryl or an optionally substd. heterocyclic group, M1 is an alkali metal atom or an alkaline earth metal atom, n1 =1 when M1 is a monovalent atom and n1 =2 when M1 is a divalent atom. In the formula II, Y1 is a group adsorbed on silver halide, X1 is an atom selected from among H, C, etc., or a divalent combining group consisting of a group of such atoms and A1 is a divalent combining 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 an image forming method, and more particularly to a super-high contrast silver halide photographic light-sensitive material and a super-high contrast image forming method used for photolithography.

2. Description of the Related Art Lith-type photosensitive materials have been used for many years to achieve ultra-high contrast photographic characteristics in the graphic arts field. Since the squirrel developer has a very low concentration of sulfite ions, it is susceptible to air oxidation, and requires various measures and efforts to maintain development quality during continuous use.
As a method of eliminating the instability of image formation by lith development and obtaining photographic characteristics of ultra-high contrast, Research Disclosure, 235, 346-351 (1983)
As disclosed in U.S. Pat. No. 4,269,929, pH 10 to 1 in the presence of a hydrazine compound.
A method of processing with a developing solution of No. 2 has been proposed. However, pH
A developer of 11.0 or more is easily oxidized by air, is unstable, and does not withstand long-term use or storage. A method of processing a silver halide photographic light-sensitive material containing a hydrazine compound with a developer having a lower pH is disclosed in U.S. Pat.
As disclosed in the specifications of US Pat. No. 365 and 4,998,604, a highly active hydrazine compound is used,
A method for obtaining a high-contrast negative image with the above developer has been proposed. However, this method is disclosed in JP-A-6-2304.
As can be seen from Japanese Patent Application Publication No. 96-96, etc., the high contrast is not sufficient and the practical requirements are not satisfied.

[0002]

SUMMARY OF THE INVENTION A first object of the present invention is to solve the above-mentioned problems of a silver halide photographic light-sensitive material containing a hydrazine compound.
Another object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and an image forming method. A second object of the present invention is to
It is an object of the present invention to provide a silver halide photographic light-sensitive material having small photographic properties and pH dependence of a developer. A third object of the present invention is to provide a silver halide photographic material which can be hardened even when processed with a developer having a pH in the range of 10.0 to 12.0.

[0003]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one other hydrophilic colloid layer on a support. Silver emulsion layer and / or
Or the other hydrophilic colloid layer has the following general formula (I)
At least one compound represented by the general formula (II),
(III), (IV), (V), (VI) and (VI)
This was achieved by a silver halide photographic material containing at least one of the compounds represented by I) and an image forming method of processing the silver halide photographic material with an aqueous alkaline developer.

[0004]

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In the formula, R ₁ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and M ₁ represents an alkali metal atom or an alkaline earth metal atom. n ₁ represents an integer of 1 or 2, ₁ when M ₁ is a monovalent atom, and M ₁ is 2
When it is a valence atom, it represents 2.

[0006]

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In the formula, Y ₁ represents a group adsorbed on silver halide. X ₁ represents a divalent linking group composed of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. A ₁ represents a divalent linking group. B ₁ represents an amino group, an ammonium group or a nitrogen-containing heterocycle, and the amino group may be substituted. m ₁ represents ₁ , 2 or 3 and n ₂ represents 0 or 1.

[0008]

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In the formula, R ₂ and R ₃ each represent a hydrogen atom or an aliphatic residue. R ₂ and R ₃ may combine with each other to form a ring. R ₄ represents a divalent aliphatic group. X ₂ represents a divalent heterocycle containing a nitrogen atom, an oxygen atom or a sulfur atom. n ₃
Represents 0 or 1. M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group.

[0010]

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In the formula, R ₅ and R ₆ are each a hydrogen atom and have 1 carbon atom.
Represents an alkyl group having from 30 to 30, an alkenyl group having from 3 to 30 carbon atoms, or an aralkyl group having from 7 to 30 carbon atoms. Also, R ₅ and R ₆
Do not represent a hydrogen atom at the same time, and may combine with each other to form a ring. n ₄ represents an integer of 2 to 50. R ₇ ,
R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0012]

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In the formula, R ₅ and R ₆ are the same as in the general formula (IV), and R ₁₁ and R ₁₂ are the same as R ₅ and R ₆ . n
₅ represents an integer of 2 to 50.

[0014]

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In the formula, X ₁ , Y ₁ and B ₁ are the same as in formula (II), and A ₂ represents a divalent linking group having at least two alkyleneoxy units. m ₂ represents 1, 2 or 3, and n ₆ represents 0 or 1.

[0016]

[Chemical 21]

In the formula, R ₁₃ , R ₁₄ and R _{15 each} represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may have a substituent. Good. m ₃ represents an integer, L represents an m ₃ -valent organic group bonded to a P atom and its carbon atom, n ₇ represents an integer of 1 to 3, X ₃ represents an n ₇ -valent anion, X ₃ may be linked to L.

The general formula (I) will be specifically described below. In the formula, R ₁ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and M ₁ represents an alkali metal atom or an alkaline earth metal atom. n ₁ is 1 or 2
Represents an integer. Examples of the aryl group represented by R ₁ include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, and a quinolyl group. R ₁ is preferably an aryl group. The aryl group or heterocyclic group represented by R ₁ may have various substituents. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, a urea group, a hydroxy group, an amino group, an alkylamino group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group and a sulfo group. Can be mentioned. Preferred substituents of the aryl group or heterocyclic group represented by R ₁ include silver halide adsorption promoting groups such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. Can be. Furthermore, examples of the substituent of the aryl group or heterocyclic group represented by R ₁ include a group having a quaternary ammonium cation and a group having at least 3 or more repeating ethyleneoxy units. M ₁ is not particularly limited as long as it is an alkali metal atom or an alkaline earth metal atom,
Preferable examples include sodium, potassium, lithium, calcium and magnesium. Hereinafter, specific examples of the compound represented by Formula (I) used in the present invention will be shown. However, the invention is not limited to only these specific examples.

[0019]

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[0020]

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[0021]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The method for synthesizing the compound (1) of the present invention will be described. (A) Synthesis of ethyl oxalate phenylhydrazide 29.2 g (0.2 mol) of diethyl oxalate was added at 70 ° C.
While stirring back and forth, phenylhydrazine 2
2.5 g (0.2 mol) was added dropwise over about 1 hour and 30 minutes. Next, after stirring at 80 ° C. for 30 minutes, 150 ml of n-hexane was added, and the mixture was stirred and cooled. The deposited precipitate was filtered, washed with n-hexane, and dried. Melting point 117
33 g (yield: 79.3%) of the target product having a temperature of ~ 119 ° C was obtained. (B) Synthesis of exemplary compound (1) (potassium phenylhydrazinooxalate) 10.4 g (0.05 mol) of oxalic acid ethyl ester phenylhydrazide synthesized in (A), 3.3 g of 85% aqueous potassium hydroxide solution (0.05 mol) and ethanol 1
50m were mixed and refluxed for 15 hours. The reaction solution was filtered while hot, and the precipitate was collected by filtration, washed with ethanol, and dried. Light yellow powder crystal 1 having a melting point of 241 to 246 ° C
0.3 g (yield 94.5%) was obtained. Other exemplified compounds can be synthesized in the same manner as described above. Next, the general formula (I
The compound represented by I) will be described. The group adsorbed on the silver halide represented by Y ₁ includes a nitrogen-containing heterocyclic compound. When Y ₁ represents a nitrogen-containing heterocyclic compound, the compound of the general formula (II) is represented by the following general formula (II-a).
It is represented by

[0029]

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In the formula, m ₁ represents ₁ , 2 or 3, and m ₄ is 0
Or 1, and n ₂ represents 0 or 1. [(X ₁ ) n ₂ −
A ₁ -B ₁ ] m ₁ has the same meaning as that in the general formula (II), and Q is a 5- or 6-membered heterocyclic ring composed of at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Represents an atomic group necessary for forming. Further, this heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. The heterocycle formed by Q includes, for example, substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles and tetrazoles. And azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, quinolines and the like.

These heterocycles include a nitro group, a halogen atom (eg, chlorine atom, bromine atom, etc.), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, Propyl group, t-butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.), aryl group (eg, phenyl group, 4-
Methanesulfonylamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.),
Alkenyl group (eg, allyl group), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group) , 4-methoxyphenoxy group etc.), alkylthio group (eg methylthio group, ethylthio group, methoxyethylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonyl group (eg methanesulfonyl group,
Ethanesulfonyl group, p-toluenesulfonyl group, etc.),
Carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.),
Carbonamide group (eg, acetamide group, benzamide group, etc.), Sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), Acyloxy group (eg, acetyloxy group, benzoyloxy group) Group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, etc.), ureido group (eg, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (eg, unsubstituted Thioureido group, methylureido group etc.), acyl group (eg acetyl group, benzoyl group etc.), heterocyclic group (eg 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2- Thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetra Idrofuryl group, tetrahydrothienyl group etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group etc.), oxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group etc.) ), An amino group (for example,
Unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxy group and the like.

M ₃ is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), a hydrogen atom or an alkali metal atom under alkaline conditions. Represents a group that can be (for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.). The divalent linking group represented by X ₁ is, for example, —S
-, - O -, - N (R 16) -, - C (O) O -, - OC
(O) -, - C ( O) N (R 17) -, - N (R 18) C
_{(O) -, - SO 2} N (R 19) -, - N (R 20) SO
_{2 -, - N (R 21} ) C (O) N (R 22) -, - N
_{(R 23) C (S)} N (R 24) -, - N (R 25) C (O)
_{O -, - SO 2 -,} - C (O) -, - SO 2 -O -, - O
--SO _2- , etc., and these linking groups are linear or branched alkylene groups between Q and (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene). Group, etc.). R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ ,
R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, etc.), a substituted or unsubstituted aryl group. (Eg, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted aralkyl group (eg, benzyl group, Phenethyl group).

A ₁ represents a divalent linking group, and as the divalent linking group, a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group). Group), a linear or branched alkenylene group (eg, vinylene group, 1-methylvinylene group, etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), an arylene group (eg, phenylene group, naphthylene group) Etc.) can be mentioned. The substituted or unsubstituted amino group of B ₁ is represented by formula (II-b).

[0034]

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In the formula, R ₂₆ and R ₂₇ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aralkyl group, These groups are straight chain (eg, methyl,
It may be ethyl group, n-propyl group, allyl group, 3-butenyl group, benzyl group, 1-naphthomethyl group, etc.), branched (for example, isopropyl group, t-octyl group, etc.) or cyclic (for example, cyclohexyl group, etc.). . Also, R ₂₆ and R ₂₇
May combine to form a ring, which is cyclized to form a saturated heterocycle containing one or more heteroatoms (eg, oxygen, nitrogen, sulfur, etc.). It may be included, and examples thereof include a pyrrolidyl group, a piperidyl group, and a morpholino group. Also, R ₂₆ ,
Examples of the substituent of R ₂₇ include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 20 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 20 or less carbon atoms (eg, Methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), carbon number 20
The following monocyclic aryloxy groups (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy groups having 20 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), acyl groups having 20 or less carbon atoms ( For example, acetyl group, propionyl group, benzoyl group, etc., carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N , N-dimethylsulfamoyl group, morpholinosulfamoyl group, piperidinosulfamoyl group, etc.), acylamino group having 20 or less carbon atoms (eg, acetylamino group, propionylamino group, benzoylamino group, etc.), sulfonamide Group (eg, ethylsulfonamide group, P- Toluene sulfonamide group, etc.), of 20 or less carbonamido group having a carbon (e.g., methyl carbonamido group, a phenyl carbonamido group, etc.), 2 carbon atoms
Examples thereof include ureido groups of 0 or less (eg, methylureido group, phenylureido group, etc.), amino groups, and the like. B ₁
The ammonium group of is represented by the general formula (II-c).

[0036]

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In the formula, R ₂₈ , R ₂₉ and R ₃₀ are the same groups as R ₂₆ and R _{27 in the} above-mentioned general formula (II-b), Z ⁻ represents an anion, for example, a halide ion (eg, C
l ⁻ , Br ⁻ , I ^−, etc.), a sulfonate ion (eg,
Trifluoromethane sulfonate, p-toluene sulfonate, benzene sulfonate, p-chlorobenzene sulfonate, etc.), sulfato ion (eg, ethyl sulfate, methyl sulfate, etc.), perchlorate, tetrafluoroborate and the like can be mentioned. p represents 0 or 1, and is 0 when the compound forms an intramolecular salt. The nitrogen-containing heterocycle represented by B ₁ is a 5- or 6-membered ring containing at least one nitrogen atom, and these rings may have a substituent or are condensed with another ring. May be. As the nitrogen-containing heterocycle, for example, an imidazolyl group,
Examples thereof include a pyridyl group and a thiazolyl group. The general formula (I
Preferred among I) is the following general formula (II-
Examples thereof include compounds represented by d), (II-e), (II-f) or (II-g).

[0038]

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[0039]

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In the formula,-(X ₁ ) n ₂ -A ₁ -B ₁ , M ₃ , m ₁
Is the same as that of the general formula (II-a). Z ₂ ,
Z ₃ and Z ₄ are the same as in the general formula (II-a).
(X ₁ ) n _2- A ₁ -B ₁ has the same meaning, or a halogen atom, an alkoxy group having 20 or more carbon atoms (eg, a methoxy group), a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group. It represents an amino group, and the substituent thereof can be selected from the substituents of R ₂₆ and R _{27 in} the above (II-b). However, at least one of Z ₂ , Z ₃ and Z ₄
One is - (X ₁₎ is synonymous with n ₂ -A ₁ -B _1. Further, these heterocycles may be substituted with a substituent applied to the heterocycle of the general formula (II). Next, the compounds represented by the general formula (II) are shown, but the present invention is not limited thereto.

[0041]

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[0044]

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[0045]

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[0046]

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[0047]

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Next, the compound represented by formula (III) will be described. In the formula, R ₂ and R ₃ each represent a hydrogen atom or an aliphatic residue. R ₂ and R ₃ may combine with each other to form a ring. R ₄ represents a divalent aliphatic group. X ₂ represents a divalent heterocycle containing a nitrogen atom, an oxygen atom or a sulfur atom. n ₃ represents 0 or 1. M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group. As the aliphatic residue of R ₂ and R ₃ , an alkyl group, an alkenyl group and an alkynyl group each having 1 to 12 carbon atoms are preferable, and each of them may be substituted with an appropriate group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, dodecyl group, isopropyl group, se
Examples thereof include c-butyl group and cyclohexyl group. Examples of the alkenyl group include an allyl group, a 2-butenyl group, a 2-hexenyl group, a 2-octenyl group and the like. Examples of the alkynyl group include a propargyl group and a 2-pentynyl group. Examples of the substituent include a phenyl group, a substituted phenyl group, an alkoxy group, an alkylthio group, a hydroxy group, a carboxyl group, a sulfo group, an alkylamino group and an amide group.

When R ₂ and R ₃ form a ring,
A 5- or 6-membered carbon ring or hetero ring consisting of a carbon atom or a combination of a nitrogen atom and an oxygen atom, particularly preferably a saturated ring, for example, pyrrolidyl, piperidyl, morpholyl,
Examples thereof include piperazil and 4-methylpiperazyl. R
Particularly preferred as ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, and more preferably ethyl groups. As the divalent aliphatic group for R ₄ , —R ₃₁ — or —R ₃₁ S— is preferable. Here, R ₃₁ is a divalent aliphatic residue, preferably a saturated or unsaturated one having 1 to 6 carbon atoms, for example,-
_{CH 2 -, - CH 2 CH} 2 -, - (CH 2) 3 -, - (C
_{H 2) 4 -, - (} CH 2) 6 -, - CH 2 CH = CHCH
_{2 -, - CH 2 CH (} CH 3) CH 2 - , and the like. R ₃₁ preferably has 2 to 4 carbon atoms, more preferably —CH ₂ CH ₂ — and — (CH ₂ ) ₃ —. In addition,
(X ₂₎ R ₄ when n ₃ of n ₃ is 0, -R ₃₁ - represents only.
The hetero ring of X ₂ may be a 5- or 6-membered hetero ring containing a nitrogen atom, an oxygen atom or a sulfur atom, which may be condensed with the benzene ring. Preferred heterocycles are aromatic ones, such as tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole and benzoxazole. Of these, tetrazole and thiadiazole are particularly preferred.

M_TwoAs the alkali metal of⁺,
K⁺, Li⁺And so on. As the alkaline earth metal, Ca
⁺⁺, Mg⁺⁺Etc. As a quaternary ammonium salt, charcoal
It is composed of 4 to 30 prime numbers and is, for example, (CH_Three)
_FourN⁺, (C_TwoH_Five)_FourN⁺, (C_FourH₉)_FourN ⁺, C₆H_FiveCH_Two
N⁺(CH_Three)_Three, C₁₆H₃₃N⁺(CH_Three)_ThreeAnd so on. Fourth grade
As the phosphonium salt, (C_FourH₉)_FourP⁺, C₁₆H₃₃P
⁺(CH_Three)_Three, C₆H_FiveCH_TwoP⁺(CH_Three)_ThreeAnd so on. one
As the inorganic acid salt of the compound represented by the general formula (III),
For example, there are hydrochlorides, sulfates, phosphates, etc.
As, for example, acetate, propionate, methane
Ruphonate, benzene sulfonate, P-toluene sulphate
There are phonates, etc. Represented by general formula (III) below
Specific examples of the compounds will be given.

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[0057]

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Next, the compounds represented by formulas (IV) and (V) will be described. R ₅ and R ₆ may be the same or different and each is a hydrogen atom or an alkyl group which may have a substituent having 1 to 30 carbon atoms (eg, methyl group, ethyl group, n-butyl group). Group, n-hexyl group, n-octyl group, 2-ethylhexyl group, methoxyethyl group,
Ethylthioethyl group, dimethylaminoethyl group, n-decyl group, n-dodecyl group, phenoxyethyl group, 2,4
-Di-t-amylphenoxyethyl group, n-octadecyl group, etc.), an alkenyl group having 3 to 30 carbon atoms and optionally having a substituent (for example, an allyl group, butenyl group, pentenyl group, etc.), or carbon Aralkyl group optionally having a substituent of formula 7 to 30 (for example, phenethyl group, benzyl group, 4-methoxybenzyl group, 4-t-butylbenzyl group, 2,4-di-t-amylphenethyl group Etc.).
Further, R ₅ and R ₆ are integrated and become an optionally substituted alkylene, and may form a ring together with a nitrogen atom. For example, a pyrrolidine ring, a piperidine ring, a 2-methylpiperidine ring, a hexamethyleneimine ring and the like. R ₇ , R ₈ ,
R ₉ and R ₁₀ may be the same or different and each is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (preferably a lower alkyl group having no substituent, for example, a methyl group,
(Ethyl group, n-butyl group, etc.).

Here, when R ₅ and R ₆ have a substituent,
As the substituent, for example, a halogen atom (for example,
Chlorine atom, bromine atom, etc.), cyano group, nitro group, hydroxy group, alkoxy group (eg, methoxy group), aryloxy group (eg, phenoxy group, 2,4-di-t)
-Amylphenoxy group, etc.), alkylthio group (eg,
Methylthio group etc.), arylthio group (eg phenylthio group etc.), acyloxy group (eg acetyloxy group, benzoyloxy group etc.), amino group (eg unsubstituted amino group, dimethylamino group etc.), carbonamide group ( For example, acetamide group etc.), sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), oxycarbonylamino group (eg methoxycarbonylamino group etc.), ureido group (eg unsubstituted ureido group, 3 , 3-dimethylureido group etc.), thioureido group (eg unsubstituted thioureido group, 3-phenylthioureido group etc.), acyl group (eg acetyl group, benzoyl group etc.), oxycarbonyl group (eg,
Methoxycarbonyl group, etc.), carbamoyl group (eg,
Methylcarbamoyl group, 4-methylphenylcarbamoyl group etc.), sulfonyl group (eg methanesulfonyl group etc.), sulfamoyl group (eg methylsulfamoyl group, 4-methoxyphenylsulfamoyl group etc.), carboxylic acid or its Examples thereof include salts, sulfonic acids and salts thereof.

In the general formulas (IV) and (V), preferred R ₅
And R ₆ each represent an alkyl group having 1 to 30 carbon atoms or an aralkyl group having ₇ to 30 carbon atoms, and R ₇ , R ₈ , R ₉ and R
₁₀ represents a hydrogen atom, and n ₄ represents an integer of 3 to 20. In formulas (IV) and (V), more preferably R ₅ and R ₆ each represent an alkyl group having 5 to 20 carbon atoms. R ₁₁ and R ₁₂ are R
Same as ₅ and R ₆ . n ₅ represents an integer of 2 to 50. Specific examples of the compounds represented by formulas (IV) and (V) are shown below, but the compounds of the present invention are not limited thereto.

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Next, the compound of the general formula (VI) will be described. In the formula, X ₁ , Y ₁ and B ₁ are the same as those in the general formula (II), m ₂ represents 1, 2 or 3 and n ₆ represents 0 or 1. . A ₂ represents a divalent linking group having at least two alkyleneoxy units, preferably

[0074]

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Represents In the formula, R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅
Each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), and q represents an integer of 2 to 50. Specific examples of the compound represented by formula (VI) are shown below, but the invention is not limited thereto.

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Next, the general formula (VII) will be described.
Specific examples of the groups represented by R ₁₃ , R ₁₄ and R ₁₅ include linear or branched alkyl groups (eg, methyl group, ethyl group,
Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), cycloalkyl group (for example,
Cyclopropyl group, cyclopentyl group, cyclohexyl group etc.), aryl group (eg phenyl group, naphthyl group, phenanthryl group etc.), alkenyl group (eg allyl group, vinyl group, 5-hexenyl group etc.), cycloalkenyl group ( For example, cyclopentenyl group, cyclohexenyl group, etc., heterocyclic residue (for example, pyridyl group, quinolyl group, furyl group, imidazolyl group, thiabenzolyl group, thiazodiazolyl group, benzotriazolyl group, benzothiazolyl group, morpholino group, pyrimidyl) Group, pyrrolidyl group, etc.). Examples of the substituents substituted with these groups include, in addition to the groups represented by R ₁₃ , R ₁₄ and R ₁₅ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 2, a tertiary amino group,
Alkyl or aryl ether group, alkyl or aryl thioether group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxy group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group or carbonyl group. You can Examples of the group represented by L include R ₁₃ , R ₁₄ and R
_In addition to the groups synonymous with ₁₅ , polymethylene groups such as trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, divalent aromatic compounds such as phenylene group, biphenylene group and naphthylene group. Group, trimethylenemethyl group, polyvalent aliphatic group such as tetramethylmethyl group, phenylene-1,3,5-toluyl group,
Examples thereof include polyvalent aromatic residues such as phenylene-1,2,4,5-tetrayl group.

Examples of the anion represented by X ₃ include halogen ions such as chlorine ion, bromine ion and iodine ion, carboxylate ions such as acetate ion, oxalate ion, fumarate ion and benzoate ion, p -Sulfonate ions such as toluene sulfonate ion, methane sulfonate ion, butane sulfonate ion, benzene sulfonate ion, sulfate ion, perchlorate ion, carbonate ion, nitrate ion and the like. In the general formula (VII), R ₁₃ , R ₁₄ , and R ₁₅
Is preferably a group having 20 or less carbon atoms, and having 15 carbon atoms.
The following aryl groups are particularly preferred. m ₃ is preferably 1 or 2, and when m represents 1, L preferably has 20 carbon atoms.
Of the following groups, an alkyl group or an aryl group having a total carbon number of 15 or less is particularly preferable. When m ₃ represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group, or a divalent group formed by bonding these groups, and further, CO- group, -O- group, -N
R ₃₆ - group (R ₃₆ represents a hydrogen atom or R _13, R _14, R ₁₅ group having the same meaning as, when a plurality of R ₃₆ are present, it may be different even in the same , And may be bonded to each other), an —S— group, and a —SO ₂ — group. When m ₃ represents 2, L is the total number of carbon atoms bonded to P atoms at that carbon atom is 20
The following divalent groups are particularly preferable. When m ₃ is an integer of 2 or more, but R _13, R _14, R ₁₅ are present in plural in the molecule, the plurality of R _13, R _14, R ₁₅ is optionally substituted by one or more identical respectively Good. n ₇ is preferably 1 or 2, and X ₃ may combine with R ₁₃ , R ₁₄ , R ₁₅ or L to form an inner salt. The general formula (VI
Many of the compounds represented by I) are known and commercially available as reagents. As a general synthesis 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 converting a counter anion of a phosphonium salt by a conventional method. Specific examples of the compound represented by the general formula (VII) are shown below. However, the compound of the present invention is not limited to these.

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The addition amount of the compound of the formula (I) of the present invention is preferably 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, particularly 1 × 10 ^-5 mol to 3 × 10 ^-2 mol per mol of silver is the preferred amount. The compound of the formula (I) of the present invention can be used by dissolving it in a suitable water-miscible organic solvent, for example, alcohols, ketones, dimethylformamide, methyl cellosolve and the like. Formulas (II) and (II
The optimum addition amount of the compounds I), (IV), (V), (VI) and (VII) varies depending on the kind of the compound, but is 1.0 × 10 ^{−3 to} 0.5 g / m 2. ² , preferably 5.0 × 10 ^{−3 to} 0.3 g / m ² . These accelerators are dissolved in a suitable solvent, for example, water, alcohols such as methanol and ethanol, acetone, dimethylformamide, methyl cellosolve and the like, and added to the coating solution. A plurality of these additives may be used in combination.

The silver halide emulsion used in the present invention is
Any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver iodochlorobromide can be used. Various known techniques are used for preparing the silver halide emulsion used in the present invention. For example, P. Grafkiddes, "Simmy e Physique Photographic", published by Paul Montell, 1967, GFF Duffin, "Photographic Emulsion Chemistry", published by The Focal Press, 1966, etc. Can be prepared using the method described in The form, crystal habit, size distribution and the like of silver halide grains are not particularly limited, but those having a grain size of 0.5 μm or less are preferred. Further, those having a narrow particle size distribution are preferred, and so-called monodispersed emulsions are preferred. As a method for reacting a water-soluble silver salt (for example, an aqueous solution of silver nitrate) with a water-soluble halogen salt (for example, sodium chloride or potassium bromide), a simultaneous mixing method, in particular, a double jet method or a triple jet method in which pAg is controlled is used. preferable. The silver halide emulsion used in the present invention is preferably an emulsion containing an iridium salt or a rhodium salt.
In particular, a combination of both is preferred. Examples of the rhodium salt include rhodium trichloride and ammonium hexachloride (III). Examples of the iridium salt include iridium trichloride, iridium tetrachloride, potassium hexachloride iridate (III), potassium hexachloride iridium (IV), and the like.

The silver halide emulsion of the present invention may be subjected to gold sensitization and sulfur sensitization. Examples of the gold sensitizer include potassium chloroaulite, potassium aurithiocyanate, and auric chloride. Examples of the sulfur sensitizer include thiosulfates, thioureas, rhodanines and the like, in addition to sulfur compounds in gelatin. A spectral sensitizing dye can be added to the silver halide emulsion of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes, oxonol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dye and merocyanine dye systems. These sensitizing dyes may be used alone, but may also be used in combination for the purpose of supersensitization in order to obtain spectral sensitivity according to the purpose. Various dyes and ultraviolet absorber dyes can be added to the silver halide emulsion layer or other hydrophilic colloid layer of the present invention for the purpose of preventing halation and irradiation.

Gelatin is mainly used as the binder or protective colloid that can be used in the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, but other than that, for example, gelatin derivatives, Proteins such as albumin and casein, cellulose derivatives such as ethyl cellulose and carboxymethyl cellulose, sugar derivatives such as starch derivatives, hydrophilicity such as polyvinyl alcohol, polyacrylic acid, polyacrylamide and polymethacrylic acid such as single or copolymer Polymers can be used. The emulsion layer and the other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may have various types of materials for the purpose of preventing fogging during the production process, storage or development processing, or stabilizing photographic performance. Compounds can be added. As this compound,
For example, benzothiazolinium salts, nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptothiadiazoles, benzotriazoles, azoles such as mercaptotetrazole, azaindene and the like, conventionally antifoggants or stabilizers Can be mentioned. Of these, particularly preferred are benzotriazoles and nitroindazoles. These compounds may be contained in a processing solution used for the development processing.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention can contain an inorganic or organic hardener. Examples of the hardener include chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives, and active vinyl compounds. They can be used alone or in combination. The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention include coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization, etc.). ) Etc. can be contained for various purposes. Examples of the surfactant include saponins, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols, and sugars. Nonionic surfactants such as alkyl esters, anions having an acidic group such as carboxy group, sulfo group, sulfate group, phosphate group such as alkyl carboxylate, alkyl sulfate, alkyl phosphate, etc. Amphoteric surfactants, amino acids, aminoalkylsulfonic acids, amphoteric surfactants such as aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, or heterocyclic quaternary ammonium salts Etc. It can be exemplified emissions surfactant.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, It can be used in combination with a polymer having a combination of α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like as a monomer component. Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, an intermediate layer, a filter layer, an antihalation layer, and an antistatic layer. A matting agent can be contained in a hydrophilic colloid layer such as a surface protective layer for the purpose of preventing adhesion and the like. Examples of the matting agent include polymethyl compounds described in U.S. Pat. Nos. 2,701,245, 2,992,101, 4,142,894, and 4,396,706. A methacrylate homopolymer, a copolymer of methyl methacrylate and methacrylic acid, and fine particles of starch, silica, magnesium oxide and the like can be used. The surface protective layer may be formed of a silicone compound described in the specifications of U.S. Pat. Nos. 3,489,576 and 4,047,958.
No. 3,139, colloidal silica, other paraffin waxes, higher fatty acid esters and the like can be added.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers in the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention. Further, a fluorescent whitening agent, a development accelerator, a pH adjuster, a thickener, an antistatic agent and the like can be added to the emulsion layer and other hydrophilic colloid layers. As a support of the photographic light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate and the like can be used. Particularly preferred is a polyethylene terephthalate film. These supports may be subjected to a corona treatment by a known method, or may be subjected to a subbing treatment by a known method as necessary. In addition, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to increase the so-called dimensional stability, in which dimensions change due to changes in temperature or humidity.

In order to obtain ultrahigh contrast photographic characteristics using the silver halide photographic light-sensitive material of the present invention, the conventional lith developer or the pH described in US Pat. No. 2,419,975 is used.
It is not necessary to use a high alkali developer close to 13, and a stable developer 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 (particularly 0.15 mol / l or more) can be used as a preservative, and the pH is 10.0 to 10. A developer in the range of 12.0 can sufficiently obtain a super-high contrast negative image. As the developing agent used in the processing of the photographic light-sensitive material of the present invention, dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. In addition to the above, the developing solution also includes pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (preferably nitroindazoles or benzotriazoles). ) Etc. can be included. Also, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a film silver stain inhibitor (for example, 2-mercaptobenzimidazoles). Etc. may be included. As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. or,
The fixer may contain a water-soluble aluminum salt or the like as a hardening agent.

[0112]

EXAMPLES The present invention will be described below based on examples. Example 1 An aqueous solution of silver nitrate in an aqueous solution of gelatin maintained at 55 ° C.
Double mixed solution of sodium chloride and potassium bromide (containing 5 × 10 ^-7 mole of potassium hexachloride iridate (III) and 2 × 10 ^-7 mole of ammonium hexachloride rhodium (III) per mole of silver) The mixture was added and mixed by a jet method over 60 minutes to prepare a silver chlorobromide emulsion (silver bromide content: 30 mol%) composed of a monodisperse cube having an average particle size of 0.3 μm. After the particles were formed, the particles were washed with water by a conventional method to remove soluble salts. Next, gelatin was added, and further, sodium chloride, potassium bromide, and sodium hydroxide were added to adjust the pAg to 7.6 and the pH to 6.0, and then sodium thiosulfate was added per mole of silver. 2 × 10
^-5 mol, 3 × 10 ^-5 mol of potassium chloroaulite was added, and the mixture was subjected to chemical sensitization at 60 ° C. for 40 minutes. 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer
-5 × 10 ^-3 mole per mole of silver of tetrazaindene was added. Further, the compounds of the present invention were added as shown in Table 1.

Further, 5-methylbenzotriazole is 3 × 10 ^-3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole is 4 × 10 ^-4 mol per mol of silver,
The polyethyl acrylate compounds 1 m ² per 0.8g described in Preparation Formulation 3 of Japanese Patent Publication 45-5331 discloses a polymer latex, a p- sodium dodecylbenzenesulfonate as a coating aid 1 m ² per 40 mg,
As a hardening agent, 1,3-divinylsulfonyl-2-propanol was added so as to be 100 mg / m ² . The prepared emulsion was coated on a polyethylene terephthalate support simultaneously with the following protective layer so that the amount of silver was 3.2 g per 1 m ² . The protective layer overlying the silver halide emulsion layer had a gelatin content of 1.2 g / m ² , and the protective layer had a mean particle size of 3.4 as a matting agent.
μm polymethyl methacrylate, silicone oil,
Sodium p-dodecylbenzenesulfonate and the like were contained. Thus, Samples 1 to 7 shown in Table 1 were produced.

[0114]

[Table 1]

These samples were exposed under a light wedge, developed with a developer having the following composition at 35 ° C. for 30 seconds, fixed, washed with water,
Drying was performed. Water 700 ml EDTA · 2Na salt 0.6 g Phenidone 1.2 g Potassium sulfite (55% aqueous solution) 120 ml Hydroquinone 18 g Benzotriazole 0.3 g Potassium bromide 2.5 g Potassium carbonate 7.0 g Potassium hydroxide 35.0 g Add water to 1000 ml And pH = 11.75 The results obtained are shown in Table 2. As an index indicating the contrast of the image, a point at a density of fog + 3.0 was connected to a point at a density of fog + 3.0 by a straight line from a point at a density of fog + 0.3 on the characteristic curve, and the slope of this straight line was represented as a γ value. As for the relative sensitivity, the relative value of the reciprocal of the exposure amount giving a density of 1.5 was represented by setting Sample 1 to 100.

[0116]

[Table 2]

From the results of Table 2, Samples 4 to 7 of the present invention are
It can be seen that the relative sensitivity and the γ value are high. Example 2 In Example 1, the compounds of the present invention were added as shown in Table 3 to prepare Samples 8 to 13.

[0118]

[Table 3]

These samples were exposed under an optical wedge to obtain the following composition.
Develop at 35 ° C for 30 seconds with a developing solution, fix, wash with water,
Drying was performed. Water 700 ml potassium sulfite (55% aqueous solution) 125 ml EDTA / 4Na salt 1.2 g potassium hydroxide (48% aqueous solution) 9.2 ml potassium bromide 3.3 g diethylene glycol 50 ml hydroquinone 20 g anhydrous potassium carbonate 23 g potassium hydroquinone sulfonate 1.7 g dimesone S 1.0 g 5-methylbenzotriazole 0.15 g Sludge inhibitor (Compound A)   2.7 g 1-phenyl-5-mercaptotetrazole 0.02 g Add water to make 1000 ml. pH = 10.50

[0120]

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The results obtained are shown in Table 4.

[0122]

[Table 4]

From the results of Table 4, Samples 10 to 13 of the present invention
Indicates that the relative sensitivity and the γ value are high.

[0124]

EFFECT OF THE INVENTION Containing a compound of the general formula (I) of the present invention and a compound selected from compounds of the general formulas (II), (III), (IV), (V), (VI) and (VII) The silver halide photographic light-sensitive material has a high γ value and high sensitivity, and a super-high contrast image can be formed by using the silver halide photographic light-sensitive material of the present invention.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one other hydrophilic colloid layer on a support, the silver halide emulsion layer and / or the other hydrophilic layer. The colloidal layer comprises at least one compound represented by the following general formula (I) and general formulas (II), (III), (IV), (V),
A silver halide photographic material comprising at least one of the compounds represented by (VI) and (VII). Embedded image In the formula, R ₁ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and M ₁ represents an alkali metal atom or an alkaline earth metal atom. n ₁ represents an integer of 1 or 2, when when M ₁ is a monovalent atom 1, M ₁ is a divalent atom represents 2. Embedded image In the formula, Y ₁ represents a group adsorbed on silver halide. X ₁ represents a divalent linking group composed of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom.
A ₁ represents a divalent linking group. B ₁ represents an amino group, an ammonium group or a nitrogen-containing heterocycle, and the amino group may be substituted. m ₁ represents ₁ , 2 or 3, and n ₂ is 0 or 1
Represents Embedded image In the formula, R ₂ and R ₃ each represent a hydrogen atom or an aliphatic residue.
R ₂ and R ₃ may combine with each other to form a ring. R ₄ represents a divalent aliphatic group. X ₂ represents a divalent heterocycle containing a nitrogen atom, an oxygen atom or a sulfur atom. n ₃ is 0 or 1
Represents M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group. Embedded image In the formula, R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 3 to 30 carbon atoms or 7 to 7 carbon atoms.
Represents 30 aralkyl groups. Further, R ₅ and R ₆ do not represent hydrogen atoms at the same time, and may be bonded to each other to form a ring. n ₄ represents an integer of 2 to 50. R ₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Embedded image In the formula, R ₅ and R ₆ are the same as in the general formula (IV), and R ₁₁ and R ₁₂ are the same as R ₅ and R ₆ . n ₅ is 2-5
Represents an integer of 0. [Chemical 6] In the formula, X ₁ , Y ₁ and B ₁ are the same as in the general formula (II), and A ₂ represents a divalent linking group having at least two alkyleneoxy units. m ₂ is 1, 2 or 3
And n ₆ represents 0 or 1. Embedded image In the formula, R ₁₃ , R ₁₄ and R ₁₅ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
It represents a heterocyclic residue, which may further have a substituent. m ₃ represents an integer, L represents an m ₃ -valent organic group bonded to a P atom and its carbon atom, n ₇ represents an integer of 1 to 3, X ₃ represents an n ₇ -valent anion, X ₃ may be linked to L. 2. A support having at least one silver halide emulsion layer and at least one other hydrophilic colloid layer, wherein the silver halide emulsion layer and / or the other hydrophilic colloid layer are as follows: At least one compound represented by general formula (I) and general formulas (II), (III),
An image forming method comprising processing a silver halide photographic material containing at least one of the compounds represented by (IV), (V), (VI) and (VII) with an aqueous alkaline developer. Embedded image In the formula, R ₁ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and M ₁ represents an alkali metal atom or an alkaline earth metal atom. n ₁ represents an integer of 1 or 2, when when M ₁ is a monovalent atom 1, M ₁ is a divalent atom represents 2. Embedded image In the formula, Y ₁ represents a group adsorbed on silver halide. X ₁ represents a divalent linking group composed of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom.
A ₁ represents a divalent linking group. B ₁ represents an amino group, an ammonium group or a nitrogen-containing heterocycle, and the amino group may be substituted. m ₁ represents ₁ , 2 or 3, and n ₂ is 0 or 1
Represents Embedded image In the formula, R ₂ and R ₃ each represent a hydrogen atom or an aliphatic residue.
R ₂ and R ₃ may combine with each other to form a ring. R ₄ represents a divalent aliphatic group. X ₂ represents a divalent heterocycle containing a nitrogen atom, an oxygen atom or a sulfur atom. n ₃ is 0 or 1
Represents M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group. Embedded image In the formula, R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 3 to 30 carbon atoms or 7 to 7 carbon atoms.
Represents 30 aralkyl groups. Further, R ₅ and R ₆ do not represent hydrogen atoms at the same time, and may be bonded to each other to form a ring. n ₄ represents an integer of 2 to 50. R ₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Embedded image In the formula, R ₅ and R ₆ are the same as in the general formula (IV), and R ₁₁ and R ₁₂ are the same as R ₅ and R ₆ . n ₅ is 2-5
Represents an integer of 0. Embedded image In the formula, X ₁ , Y ₁ and B ₁ are the same as in the general formula (II), and A ₂ represents a divalent linking group having at least two alkyleneoxy units. m ₂ is 1, 2 or 3
And n ₆ represents 0 or 1. Embedded image In the formula, R ₁₃ , R ₁₄ and R ₁₅ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
It represents a heterocyclic residue, which may further have a substituent. m ₃ represents an integer, L represents an m ₃ -valent organic group bonded to a P atom and its carbon atom, n ₇ represents an integer of 1 to 3, X ₃ represents an n ₇ -valent anion, X ₃ may be linked to L. 3. The image forming method according to claim 2, wherein the pH of the aqueous alkaline developer is in the range of 10.0 to 12.0.